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I. spuria I. ensata I. crocea I. hookeriana

I. germanica

DART-MS

I. kashmiriana

Chemical ProďŹ ling and Discrimination of Medicinal Himalayan Iris Species Using Direct Analysis in Real Time Mass Spectrometry Combined with Principal Component Analysis Pratibha Singh, Vikas Bajpai, Abha Sharma, Bikarma Singh, Brijesh Kumar

October - December 2019 Volume 6 Number 25


VISÃO FOKKA - COMUNICATION AGENCY


About Br. J. Anal. Chem. The Brazilian Journal of Analytical Chemistry (BrJAC) is a peer-reviewed scientific journal intended for professionals and institutions acting mainly in all branches of analytical chemistry. BrJAC is an open access journal which does not charge authors an article processing fee. Scope BrJAC is dedicated to the diffusion of significant and original knowledge in all branches of Analytical Chemistry. BrJAC is addressed to professionals involved in science, technology and innovation projects in Analytical Chemistry at universities, research centers and in industry. BrJAC publishes original, unpublished scientific articles and technical notes that are peer reviewed in the double-blind way. In addition, it publishes reviews, interviews, points of view, letters, sponsor reports, and features related to analytical chemistry. Manuscripts submitted for publication in BrJAC cannot have been previously published or be currently submitted for publication in another journal. For manuscript preparation and submission, please see the Guidelines for the Authors section at the end of this edition. When submitting their manuscript for publication, the authors agree that the copyright will become the property of the Brazilian Journal of Analytical Chemistry, if and when accepted for publication. BrJAC is Published by: VisĂŁo Fokka Communication Agency Publisher Lilian Freitas MTB: 0076693/ SP lilian.freitas@visaofokka.com.br Advertisement Luciene Campos luciene.campos@visaofokka.com.br ISSN 2179-3425 printed

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Editorial Board Editor-in-Chief

Marco Aurélio Zezzi Arruda Full Professor / Institute of Chemistry, University of Campinas, Campinas, SP, BR

Associate Editors

Cristina Maria Schuch Analytical Department Manager / Solvay Research & Innovation Center, Paris, FR Elcio Cruz de Oliveira Technical Consultant / Technol. Mngmt. at Petrobras Transporte S.A. and Aggregate Professor at the Post-graduate Program in Metrology, Pontifical Catholic University, Rio de Janeiro, RJ, BR Fernando Vitorino da Silva Chemistry Laboratory Manager / Nestle Quality Assurance Center, São Paulo, SP, BR Mauro Bertotti Full Professor / Institute of Chemistry, University of São Paulo, São Paulo, SP, BR Pedro Vitoriano Oliveira Full Professor / Institute of Chemistry, University of São Paulo, São Paulo, SP, BR Renato Zanella Full Professor / Dept. of Chemistry, Federal University of Santa Maria, Santa Maria, RS, BR

Advisory Board

Adriano Otávio Maldaner Criminal Expert / Forensic Chemistry Service, National Institute of Criminalistics, Brazilian Federal Police, Brasília, DF, BR Auro Atsushi Tanaka Full Professor / Dept. of Chemistry, Federal University of Maranhão, São Luís, MA, BR Carlos Roberto dos Santos Director of Engineering and Environmental Quality of CETESB, São Paulo, SP, BR Gisela de Aragão Umbuzeiro Professor / Technology School, University of Campinas, Campinas, SP, BR Janusz Pawliszyn Professor / Department of Chemistry, University of Waterloo, Ontario, Canada Joaquim de Araújo Nóbrega Full Professor / Dept. of Chemistry, Federal University of São Carlos, São Carlos, SP, BR José Anchieta Gomes Neto Associate Professor / São Paulo State University (UNESP), Inst. of Chemistry, Araraquara, SP, BR José Dos Santos Malta Junior Pre-formulation Lab. Manager / EMS / NC Group, Hortolandia, SP, BR Lauro Tatsuo Kubota Full Professor / Institute of Chemistry, University of Campinas, Campinas, SP, BR Luiz Rogerio M. Silva Quality Assurance Associate Director / EISAI Lab., São Paulo, SP, BR Márcio das Virgens Rebouças Global Process Technology / Specialty Chemicals Manager - Braskem S.A., Campinas, SP, BR Marcos Nogueira Eberlin Full Professor / School of Engineering, Mackenzie Presbyterian University, São Paulo, SP, BR Maria das Graças Andrade Korn Full Professor / Institute of Chemistry, Federal University of Bahia, Salvador, BA, BR Ricardo Erthal Santelli Full Professor / Analytical Chemistry, Federal University of Rio de Janeiro, RJ, BR


Contents

Br. J. Anal. Chem., 2019, 6 (25)

Editorial BrJAC celebrating 10 years...............................................................................................................2-2 Pedro Vitoriano Oliveira

Interview Professor Matthieu Tubino, a researcher with a long academic career and strong humanist profile, exposed his ideas and memories to BrJAC......................................................................................3-7 Point of View Current Elemental Speciation Analysis from a Green Chemistry Perspective..................................8-9 Rodolfo G. Wuilloud

Letter Chemical Approach for Identification of PVC and PVDC in Pharmaceutical Packaging Materials.................10-12 Renan Marcel Bonilha Dezena, Renan Cicero Coelho Silva, Gabriel Ferreira Luiz

Articles Accumulation and Fractionation of Iron and Copper in Urban and Rural Soil from Brazilian City...................13-23 Aline Pereira de Oliveira, Caíque Matheus Santos Pereira Noda, Juliana Naozuka

Chemical Profiling and Discrimination of Medicinal Himalayan Iris Species Using Direct Analysis in Real Time Mass Spectrometry Combined with Principal Component Analysis.........................24-39 Pratibha Singh, Vikas Bajpai, Abha Sharma, Bikarma Singh, Brijesh Kumar

Review Production, Characterization and Application of Ferrate(VI) in Water and Wastewater Treatments...............40-57 Alexis Munyengabe, Caliphs Zvinowanda

Technical Note Point-of-use Determination of Fluoride and Phosphorus in Water through a Smartphone using the PhotoMetrix® App...................................................................................................................58-66 Cristiane Pappis, Marcia Librelotto, Luiza Baumann, Alessandra Betina Parckert, Roberta Oliveira Santos, Iberê Damé Teixeira, Gilson Augusto Helfer, Eduardo Alexis Lobo, Adilson Ben da Costa

Features 6 Analitica Latin America Conference Addressed Topics that are Directly Connected to Industry Demands.......................................................................................................................................67-73 th

6th EspeQBrasil Brought Together Leading Researchers to Reflect on Chemical Speciation..............74-76 Sponsor Reports Analysis of Elemental Impurities in Drug Products using the Thermo Scientific iCAP 7400 ICP-OES Duo....77-85 Thermo Scientific

Tomorrow’s Quantitation with the TSQ Fortis Mass Spectrometer: Robust, Reproducible Quantitation Workflows of Haloacetic Acids, Bromate, and Dalapon in Water According to EPA Method 557.....................................86-94 Thermo Scientific

Sample Preparation of Polymers for Trace Metal Analysis...........................................................95-98 Milestone


Contents

Releases BrJAC Editor-in-Chief Prof. Dr. Marco Aurélio Zezzi Arruda was recently honored as Fellow of the Royal Society of Chemistry................................................................................................................ 99 Thermo Scientific iCAP 7000 Plus Series ICP-OES: Powerful, easy-to-use, solution for multielement analysis............................................................................................................................... 100 Thermo Scientific TSQ Fortis triple quadrupole mass spectrometer — Fast and robust quantitation for every Environmental and Food Safety workflow......................................................................... 102 Ethos UP and Milestone Connect: High Performance Microwave Digestion Systems..................... 104 Pittcon Conference & Expo — Be Amongst the best in PITTCON 2020... The Future of Laboratory Sciences........................................................................................................................................... 106 SelectScience® Pioneers Online Communication and Promotes Scientific Success since 1998................................................................................................................................................. 108 CHROMacademy Helps Increase your Knowledge, Efficiency and Productivity in the Lab............. 110 Notices of Books

........................................................................................................... 112

Periodicals & Websites ........................................................................................................... 113 Events Acknowledgments

.................................................................................................... 114-115 ............................................................................................... 116-117

Guidelines for the Authors ............................................................................................... 118-120


Editorial

Br. J. Anal. Chem., 2019, 6 (25) pp 2-2 DOI: 10.30744/brjac.2179-3425.editorial.pvoliveira.N25

BrJAC celebrating 10 years

Pedro Vitoriano Oliveira Departamento de Química Fundamental – Instituto de Química Universidade de São Paulo São Paulo, SP, Brazil

In the year 2020 BrJAC – the Brazilian Journal of Analytical Chemistry – celebrates its 10th anniversary. It is gratifying for me to have participated in this project from the beginning. It is also satisfying to see, 10 years later, that BrJAC can be accessed all over the world from different scientific databases (Web of Science, Scopus, CAplus and Google Scholar). For this, it is essential to express our gratitude to the Editor-in-Chief, Associate Editors, Advisory Board, the outstanding reviewers as selected by the Editorial Group and also the Authors for their significant contributions and believing in this scientific journal; the success of BrJAC has been driven by all these players. BrJAC maintains its original proposal, which is publishing articles, technical notes, reviews, interviews with senior researchers, letters, points of view and sponsor reports. The main focus of the interviews is directed at the illustrated trajectories, experiences, difficulties and achievements of senior researchers, whose stories serve as encouragement and reference for young scientists and professionals in related fields. With the letters and points of view, the objective is communication and discussion between different readers in the academic and industrial sectors. Over these 10 years, multidisciplinary subjects involving analytical chemistry have been published, directed at the qualitative and quantitative demands required every day in our modern world, either by the fast action of high-tech industries, which seek quality in processes and products, or by successful insertion of proposed modern methods using new instrumentation in the fields of medicine, biology, biochemistry, pharmaceuticals, food, agriculture and the environment, etc. A new decade begins for BrJAC and, with due responsibility, we will help to disseminate quality analytical chemistry to Brazil and other parts of the world. We hope you enjoy the contributions of this 25th volume of BrJAC.

2


Interview

Br. J. Anal. Chem., 2019, 6 (25) pp 3-7 DOI: 10.30744/brjac.2179-3425.interview.tubino

Professor Matthieu Tubino, a researcher with a long academic career and strong humanist profile, exposed his ideas and memories to BrJAC Matthieu Tubino

Full Professor Institute of Chemistry, University of Campinas - Unicamp Campinas, SP, Brazil Matthieu Tubino has been a professor at the Institute of Chemistry of the University of Campinas (Unicamp) since 1971. He began his teaching career as an Instructor MS-1 (level 1 university professor) and attained the position of Full Professor (MS-6). He graduated from the University of São Paulo with a degree in chemistry and holds master’s and doctorate degrees from Unicamp and a postdoctoral degree from the Institut de “Chimie Minérale et Analytique” of the Université de Lausanne, Switzerland. His chemistry background covers the areas of chemical reaction kinetics, reaction mechanisms, qualitative and quantitative spot test analysis, flow injection analysis, ultraviolet–visible diffuse reflective chemical analysis, the development of experiments for chemistry teaching, and analytical methods for application in industrial matrices, including biodiesel and raw materials. Dr. Tubino has been honored with several awards, such as the “Peróxidos do Brasil” award in 1989, 1997, and 1998; the “Governador do Estado” award, offered by the Secretariat of Science and Technology of the State of São Paulo, Brazil, in 1990; the Fritz Feigl award, offered by the Regional Chemistry Council, IV Region, in 2007; and the Honorable Mention for Licensed Technology award and the Inventors Award by the Inova Unicamp Innovation Agency in 2010. What early influences encouraged you to study science? Did you have any influencers, such as a teacher? My interest in chemistry came when I was about 13 because of my curiosity to understand the properties of matter and its transformations. Also, the fact that I had excellent chemistry and physics teachers in secondary school motivated me further toward choosing a science profession, in this case, chemistry. As for the professional quality of my secondary school science teachers, I should add that they were all graduates of the University of São Paulo (USP), which is a public university and a top university in Brazil. How was the beginning of your career in chemistry? When I was in the fourth year of my chemistry course, in 1970, in the so-called Department of Chemistry of the Faculty of Philosophy, Sciences and Languages of the University of São Paulo (shortly thereafter, this department became the Institute of Chemistry from USP), three colleagues and I were invited to work at the then-beginning Institute of Chemistry of the State University of Campinas (at that time, the acronym of this university was UEC; soon after, it became University of Campinas, Unicamp). Shortly after the invitation, which was made in June 1970, the four of us went to the city of Campinas, SP, to visit the campus of that university. I can say that this campus was a vast cane field, no longer 3


Interview

cultivated, but some sugarcane clumps were still there. There was only the building of the university rectory and two more sheds. In one of the sheds, the Institute of Chemistry was located, along with other institutes and colleges. The building of the Institute of Chemistry was still under construction, and its occupation began in 1971. Given the conditions at that time, two of my colleagues gave up, but Professor José Augusto Rosário Rodrigues, deceased on October 11, 2019, and I agreed to stay in Campinas. Prof. José Augusto has since specialized in organic chemistry. At that time, we were hired as instructors, that is, at the 1st level of the professor career, and we started our activities on March 1st, 1971. Although we were at the very beginning of our careers, we taught practical classes in the laboratory and also theoretical classes on general chemistry. Those were hard years, both in terms of working conditions, as everything had to be done, and in political terms because the political regime in Brazil was dictatorial and no one felt safe, even those who had no involvement with politics. At this point, I would like to “Those were hard years, both pay a simple tribute to the memory of Professor Ana Rosa Kucinski in terms of working conditions, Silva, from the Department of Analytical Chemistry of the Institute of as everything had to be done, Chemistry of the University of São Paulo (IQ-USP), who disappeared and in political terms because in 1974, a victim of the dictatorial government. I can testify about her the political regime in Brazil was professional competence and, above all, about her intelligence and dictatorial and no one felt safe...” sensitivity in dealing with people. In Campinas, UEC at that time, everything had to be done. We barely had any lab supplies. There was no library, so periodically we had to travel to São Paulo to consult with the IQ-USP library. This situation, at that time, brought difficulties for most beginners in their college career, causing some to give up. For another group, which I include myself in, this served as a stimulus to continue with building something new. We “got blood out of stone”, as everything was difficult. My master’s and doctoral works were on the kinetics of decomposition of iron II complexes with diimines. Shortly after I completed my doctorate, I guided a master’s dissertation (at the time, called master’s thesis) in analytical chemistry, which made me decide to focus primarily on this area of research in chemistry. However, as can be seen from my publications, I have always tried to act broadly, having worked in various areas of chemistry, including chemistry teaching, which I consider of utmost importance. What has changed in your profile, ambitions and performance since the beginning of your career? Throughout my career, as with everyone, I matured both in terms of understanding society and the profession. What I understood most is that no matter how much one learns, there is much more to learn. The increase in knowledge opens doors and windows to other paths and to other views. And as this process progresses, it repeats itself ad infinitum. Looking back, we see that we walked a lot, but looking ahead, we see the road of knowledge merging with the horizon. Thus, my possible ambitions of youth have gradually become a simple desire to know and, as far as possible, to help others in the acquisition of knowledge, wherever possible, including in the field of analytical chemistry. Could you briefly comment on recent developments in analytical chemistry, considering your contributions? Analytical chemistry has changed a lot in recent decades because of the evolution of electronics, to which chemistry as a whole has also contributed. Despite the importance of this evolution in analysis techniques, which is very desirable, it is not accurate to say, in my view, that there was a great evolution of analytical chemistry, but rather of the instrumentation available to perform analysis of matter. This advance was very great since it allowed us to not only reach increasingly lower concentration levels, 4


Interview

but also to perform a greater number of simultaneous determinations, even in complex matrices. It also provided the possibility of automation, etc. I am concerned that in the teaching of analytical chemistry emphasis is no longer being placed on the content of chemistry as a whole, so as to provide the student with insights into a larger and better view of this broad science. However, despite this regret, I remain optimistic. I think that in the not-toodistant future a lot will change in terms of human knowledge and, certainly on another level, there will be a broad reevaluation of scientific knowledge. What are your lines of research? You have published many scientific papers. Would you highlight any? Through the paths that life leads us and because analytical chemistry is very important for the study and understanding of chemical processes, I dedicated myself, one way or another, to analytical subjects, whether they were direct, i.e., the development of new analytical methods, or indirect, in the application of analytical work, already known or even new, for the study of chemical systems of interest. I do not think much about highlighting any of my papers. They were all made with great dedication. Just to illustrate, I mention the one referring to the oxidation of metallic mercury in nature. The idea of ​​such a study arose when watching a report on television about “The idea of ​​ such a study gold prospectors who used mercury in gold mining. Many of them arose when watching a developed diseases that affect the nervous system. It was clear to report on television about me that, contrary to what was believed about the “chemical inertia” of gold prospectors who used metallic mercury, oxidation of mercury occurs easily in the prospector’s mercury in gold mining.” body. This resulted in a doctoral thesis and two publications, one in a specialized journal and another in a cultural journal. In the case of this work on mercury, the insertion of the researched subject in various sectors of knowledge, i.e., in environmental chemistry, toxicology, chemical kinetics, and analytical chemistry, is reflected. Regarding the dissemination of my work in general, I have published, to this day, about 160 papers in Brazilian and foreign journals, as well as book chapters on college admission exams, and I have also filed some patent applications. In fact, I was never concerned with the volume of publications, but with the subjects concerning them. Do you keep yourself informed about the progress of scientific research in your area? What is your opinion about the current progress of this research in Brazil? What are the recent advances and challenges in scientific research in Brazil? I have been trying to keep myself up to date on the progress of science as a whole. Chemistry is part of human knowledge; therefore, we cannot just look at chemistry, otherwise, we would risk positioning ourselves only in the technological sector. True science is broad and impregnated by philosophy. Science, artificially divided by methodological questions, interrelates; science is one. Science in Brazil is very misunderstood with regard to its importance for the development of society, both generally and individually. Without being aware of existing knowledge and without working for the evolution of knowledge, a society has no future. This is the biggest challenge: clarifying the importance of knowledge, which is acquired through its dissemination to the people as a whole, in a broad process, especially by the school, at all levels, for everyone, regardless of skin color, color of eyes, height, or social status. In the world, the societies of the future will be more intellectualized, and knowledge will be more widely disseminated and taught. If the same is not done in our country, its future will be obscure. In scientific terms, at the present time in the world, we are waiting for something that will supplant the current knowledge. I am convinced that there will be paradigm shifts, similar to what happened in the late nineteenth century and the first half of the twentieth century. I think this should start in the coming decades because the current state of scientific ideas is trending towards stagnation, a fact that indicates that a restlessness will soon manifest itself, timid at first, but vigorous thereafter. 5


Interview

For you, what have been the most important recent achievements in the analytical chemistry research? What are the landmarks? Advances in the field of ​​chemical analysis have essentially taken place in terms of instrumentation, as I said earlier. Undoubtedly, developments in this regard have been enormous, with great benefits to society at large. Such progress was greatly influenced by the development of electronics (which was greatly influenced by chemistry and physics) and informatics, which clearly shows the importance of the interaction of different fields of knowledge that constitute human knowledge. There are in Brazil and in the world several meetings on chemistry. To you, how important are these meetings to the scientific community? How do you see the development of national chemistry meetings in Brazil? Scientific meetings in all areas have always been, and still are, of great importance for the dissemination and exchange of ideas. Nowadays, however, with the growing power of the means of communication, we must pay particular attention to the possibilities they offer to the world of science in order to increase the exchange of scientific information and its dissemination. In addition, these means of communication offer us a great opportunity to increase our contribution to society as a whole through the knowledge we can offer, aiming to promote its progress. You have already received some awards. What is it like to receive this kind of recognition? What is the importance of these awards in the development of science and new technologies? For anyone, it is always rewarding to have your work recognized. However, I do not think that the prizes awarded could have an important influence on the development of science. I believe that the application of knowledge developed in favor of humanity can be a much greater stimulus for the scientist. In some ways, the award process creates an atmosphere of competition. Little by little, human society and, therefore, the scientific community are replacing competition with cooperation. This change of attitude will greatly favor the move of science and the improvement of human society. For you, what is the importance of the funding support for the scientific development of Brazil? Support from funding agencies is fundamental for the development of national scientific knowledge. Without such funding, scientific activity in Brazil would tend to disappear. The argument that some people make about private scientific funding, in my view, is not valid since the private sector is focused on the profits it can make from technological innovation. At the moment, the situation for scientific research in Brazil is one of decreasing investment. How do you see this situation, and what would you say to young researchers? Current events in Brazil are very worrying as they tend to greatly undermine scientific research in the country. However, I would like to encourage young researchers not to give up on the scientific ideal. Using creativity, it is possible to do good scientific work, focusing their interest, curiosity, and effort on practical or theoretical subjects that are often not studied in other countries. What advice would you give to a young scientist who wants to pursue a career in chemistry? To pursue a career in chemistry, it is necessary to enjoy and be curious about matter, its constitution and transformations, within a universal context, including not only the material phenomenological aspects, but also its reflexes in society and nature. To give a solid foundation to these activities, the 6


Interview

professionals can never neglect to develop their general culture as well, in order to avoid narrowing their vision of the Universe. In fact, this thinking can be applied to all professions, especially those of an investigative nature. How would you like to be remembered? In terms of professional experience, I would like to be remembered as a person who has sought to perform his duties with seriousness and dedication. In this same professional environment, it would be good for me to be remembered as someone who has always strived to maintain good relations with all the people with whom I lived with.

7


Point of View

Br. J. Anal. Chem., 2019, 6 (25) pp 8-9 DOI: 10.30744/brjac.2179-3425.pointofview.rgwuilloud.N25

Current Elemental Speciation Analysis from a Green Chemistry Perspective

Rodolfo G. Wuilloud Associate Professor Laboratory of Analytical Chemistry for Research and Development (QUIANID) Interdisciplinary Institute of Basic Sciences (ICB-CONICET UNCUYO) Faculty of Exact and Natural Sciences National University of Cuyo Mendoza, Argentina There is no doubt that elemental speciation is a concept that is extremely relevant in nutritional, toxicological and environmental studies, as it generates crucial information enabling the full understanding of the bioavailability and toxicity of an element. However, high selectivity and sensitivity are the main demands to be covered by analytical methods for trace element speciation studies. To accomplish these goals, the combination of a selective separation technique with highly sensitive detectors has been the main strategy. Although any kind of separation technique is feasible, chromatographic techniques are easily coupled to elemental-specific detectors. Likewise, non-chromatographic separation techniques can also be used for speciation analysis, but with a more limited separation power. In any case, both methodological approaches require constant improvements due to the high complexity of analyzing the speciation of some elements and the difficulty imposed by sample matrices. Among these general strategies, the use of the so-called hyphenated instrumental techniques has gained much terrain in the speciation arena over the years with respect to those methods involving nonchromatographic techniques for the separation of chemical species. This is mainly due to the greater practicality, automation and analytical frequency that is generally provided by the former. However, and although increasing research is currently being carried out on green analytical chemistry, there is still little critical reflection in the scientific community regarding the environmental sustainability of the practices involved in elemental speciation analysis and the need to address this concept during the development of this type of analytical method. For example, the HPLC-ICP-MS instrumental coupling has been heavily applied as a tool in speciation studies, but it can be criticized from an environmental point of view if we consider the fact that significant amounts of solvents and chemical reagents are used to separate the species of a particular element or a group of elements. Likewise, the low efficiency of the nebulization process required for sample introduction into ICP-MS is responsible for significant waste generation after several samples analyzed with this instrument. Also, this instrumentation has a high demand of energy for its operation, a relatively high cost and the need for highly trained personnel, issues that sometimes pose great challenges in Latin American countries due to the usual economic difficulties. At this point, a first reflection arises about the need to involve the concept of green chemistry during the design of analytical instrumentation, so that the equipment developed promotes the care of the environment and not only prioritizes the productivity of laboratories. In this sense, without a doubt, the companies that manufacture analytical instrumentation have a great responsibility and will only 8


Point of View

change their priorities if there is a regulatory framework derived from the policies imposed by each country and its commitment to preserve our environment. In contrast, it can be considered that elemental speciation analysis based on the application of non-chromatographic separation techniques has had greater development in the sense of including the concept of green or sustainable chemistry. In this way, the emergence of liquid or solid phase microextraction techniques, where the use of solvents is avoided or at least minimized significantly, implies great environmental benefits, in addition to the possibility of separating chemical species and even increasing analytical sensitivity through the pre-concentration advantage. In addition, reducing the scale of analytical operations has allowed small volumes of solvents resulting from techniques such as LLME and SPME to be completely injected into elemental detectors such as ETAAS, which can also decompose the injected solvents during the pyrolysis stage. This vast universe of microextraction techniques has also addressed the concept of green chemistry through innovations regarding the use of more ecological solvents, more efficient sorbent materials that pose a lower need for their use and the possibility of their recycling. Obviously, non-chromatographic techniques have a limited separation capacity when compared to HPLC or others. With these few words, I do not intend to position one above the other, but they can be considered a very attractive option for laboratories that have a high requirement for analysis and the need to determine few species, since they avoid the generation of significant amounts of waste, demand a smaller volume of solvents and may require less expensive analytical instrumentation. The choice of a specific technique from a group of elemental speciation analysis techniques will depend on several factors, among which the complexity of the speciation and the required analytical sensitivity will play a crucial role. However, when choosing, I also appeal to analysts to consider how much environmental sustainability is implicit in our daily practices, if not for us, at least for future generations.

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Letter

Br. J. Anal. Chem., 2019, 6 (25) pp 10-12 DOI: 10.30744/brjac.2179-3425.letter.rmbdezena.N25

Chemical Approaches for the Identification of PVC and PVDC in Pharmaceutical Packaging Materials

Renan M. B. Dezena*

Renan C. Coelho Silva

Gabriel Ferreira Luiz

Rua Lousiana, 450, Chácara Campos Elíseos, Campinas, SP, Brazil

Rua Dr. Solon Fernandes, 729, Vila Rosália, Guarulhos, SP, Brazil

Av. Guarulhos, 4329, Guarulhos, SP, Brazil

Preformulation Researcher Pharmaceutical Industry

Preformulation Specialist Pharmaceutical Industry

Analytical Dev. Analyst Pharmaceutical Industry

For the proper packaging of a drug to ensure its integrity and protection from external factors such as oxygen, moisture and light, it is essential to choose the correct packaging material [1]. Until the 19th century, medicines were mostly stored in glass containers and cotton agglomerates, as shown in Figure 1.

Figure 1: Drug packaging until the 19th century [2].

In the early 1960s, with the launch of the first contraceptives, in order to increase women’s adherence and facilitate their correct use, the first blister packs for drug packaging began to emerge [3]. Currently, in Europe, 85% of solid medicines are packaged in blister packs, while the blister pack is the most frequently used packaging in all pharmaceutical follow-up in Brazil [3]. In most blisters, two main polymers are used: polyvinyl chloride (PVC) and polyvinylidene chloride (PVDC) [4]. 10


Letter

Polyvinyl Chloride (PVC) This is a transparent, low cost material with high thermoforming, physical and chemical resistance, low permeability to oils, fats and aromatic substances and a low permeability index to air humidity [5]. PVC is the most commonly used material for blister packaging, being used in 80% of cases; however, among all of the materials used, this is the one that offers the least protection. Within the remaining 20% are PVC/PVDC, AclarŽ and ALU/ALU [5]. The thickness of the rigid PVC film that is generally used by the pharmaceutical industries is 0.2 mm to 0.8 mm. The thickness has a great influence on the light barrier property, because the higher the thickness, the lower the percentage of light that passes through the material [5]. As for the application, transparent PVC, which is the simplest type of material, has a limited barrier and will only be used for more stable drugs in the presence of moisture or light, such as paracetamol and cotrimoxazole, although some manufacturers can add barrier enhancing additives such as UV light absorbers [5]. In the manufacture of PVC, there is a release of toxins during its combustion; this has led to its replacement by polypropylene (PP) for blister packs in Europe. Polyethylene terephthalate (PET) and polystyrene (PS) can replace PVC; however, their high moisture permeability compared to PVC restricts their use [5]. PP has a high shrinkage rate during thermoforming, which makes it one of the most difficult to shape. PP is most often used for suppository packaging [5]. In addition, it is unsuitable for the packaging of photosensitive pharmaceutical products, as it has a transmittance of up to 80% between 300 and 400 nm, differing from that which is currently required in Pharmacopoeia, a transmittance of at most 25% and 20%, respectively, within a wavelength range between 290 and 450 nm [5]. Polyvinylidene Chloride (PVDC) PVDC is used in PVC-laminated or coated packaging, reducing the permeability of PVC to oxygen and moisture by 5–10 times [5]. Moldable film is usually colorless and transparent, but may be darkened to protect light-sensitive products. PVDC cannot be used as a sole material due to its relatively high cost and mechanical properties. The best properties are obtained by combining PVDC with a PVC base coat, which is used for products that are not very sensitive to external factors and have a long shelf life, such as capsules or multivitamin tablets [5]. Different blister formats are shown in Figure 2.

Figure 2: Drug blisters [6].

It is important to correctly identify the materials used for the construction of the blister in order to ensure its quality and efficiency in the protection of the drug. A safe and effective way to make this identification is through a chemical indicator solution [7]. 11


Letter

This chemical indicator solution should be prepared as follows:

After preparing the chemical indicator solution, the PVC and/or PVDC samples should be prepared for identification by cutting a piece that is approximately 5 cm wide and 5 cm long; in fact, a bubble is sufficient, as shown in Figure 4. The identification solution should be added throughout the surface of the material to be identified and then left for about 30 seconds for the solution to change color. Initially, the solution is colorless, but will turn brown on contact with PVC, and black on contact with PVDC, as shown in Figures 3 and 4 [7,8].

Figure 3. PVC blister. Left: before addition of the identification solution; Right: 30 seconds after addition of the identification solution.

Figure 4. PVDC blister. Left: before addition of the identification solution; Right: 30 seconds after addition of the identification solution.

It is important to photograph the samples before and after adding the identification solution for future comparisons of color changes. In the case of drug blisters, it is common to use PVC on one side and PVDC on the other; therefore, it is also important to identify both the inner and outer faces of the blister. REFERENCES 1. Zadbuke, N.; Shahi, S.; Gulecha, B.; Padalkar, A.; Thube, M. J Pharm Bioallied Sci., 2013, 5 (2), pp 98-110 (http://dx.doi.org/10.4103/0975-7406.111820). 2. https://pixabay.com/photos/molfsee-open-air-museum-building-851316/ [Accessed Nov. 6, 2019]. 3. https://www.montesino.com/resources/early-blister-packaging/ [Accessed November 6, 2019]. 4. Wypych, G. Handbook of Polymers. ChemTec Publishing, Toronto, 2016, pp 618-629. 5. Pereira, D. A. C.; Ferreira, L. A. Visao Acad., 2016, 17 (3), pp 91-100 (http://dx.doi.org/10.5380/acd.v17i3.48422). 6. https://pixabay.com/photos/tablets-medical-health-ill-pills-2148890/ [Accessed Nov. 6, 2019]. 7. Urzendowski, I. R.; Pechak, D. G. Food Struct., 1992, 11 (4) pp 301-314. 8. http://www.celplast.com/packaging-insight/top-tips-for-checking-treat-side-of-substrates/ [Accessed November 6, 2019]. 12


Br. J. Anal. Chem., 2019, 6 (25) pp 13-23

Article

DOI: 10.30744/brjac.2179-3425.AR-20-2019

Accumulation and Fractionation of Iron and Copper in Urban and Rural Soil from Brazilian City Aline Pereira de Oliveira, Caíque Matheus Santos Pereira Noda, Juliana Naozuka Departamento de Química, Universidade Federal de São Paulo, Rua Prof. Arthur Riedel, 275, 09972-270, Diadema, SP, Brasil

Graphical Abstract

The anthropic action effects on soil contamination with regard to Fe and Cu accumulation were evaluated through procedures to determine the pseudo-total concentration and fractionation based on elemental mobility and bioaccessibility in soils from rural and urban area collected in different depths.

Iron (Fe) and copper (Cu) are essential elements and naturally present in soils. However, these metals content can be altered by natural phenomena and/or anthropic actions, causing changes in the ecological balance. The anthropic actions effects on soil contamination with respect to Fe and Cu accumulation were evaluated through procedures to determine the pseudo-total concentration and fractionation by sequential extraction procedure in soils from a rural and urban area collected in different depths, which the fractions were experimentally defined as exchangeable, carbonate-, reducible (Fe– Mn oxide-), oxidizable (organic matter and sulfites-bound) and residual. Results showed that pseudototal Cu concentrations were 13.7 and 10.5 times and Fe concentrations were 2.8 and 1.5 times higher in the urban area at depths of 5 and 15 cm, respectively, than rural area. The fractionation evidenced the anthropic effects in the different elemental species. In general, the Cu and Fe distribution into the various solid phases showed similar patterns for each sample, which followed order: residual > bound to organic matter > bound to Fe-Mn oxides > bound to carbonates > exchangeable. Nevertheless, the Cu concentration in the fractions exchangeable and bound to carbonates in the rural soil collected at the depth of 15 cm were significantly higher in relation to the depth of 5 cm, while there was no significant difference between Cu concentrations in other fractions at both depths evaluated. On the other hand, unlike that observed in the rural area, in the urban area the fractions of Cu exchangeable (fraction 1) and bound to carbonates (fraction 2) decreased significantly with increasing depth from 5 to 10 cm. In 13


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Accumulation and Fractionation of Iron and Copper in Urban and Rural Soil from Brazilian City

addition, it was observed that significant Cu and Fe amounts were associated with the residual fraction in the soil from both regions, ranging from 20% (Cu: rural, 15 cm) to 91% (Fe: urban, 15 cm) in relation to the pseudo-total concentration. Keywords: Iron, copper, fractionation, soil, urban, rural INTRODUCTION In addition to several other components, such as quartz, feldspar, sand, silt and clay, the soil is composed of essential micro and macronutrients essential for living organism. However, soils of urban origin have meanwhile a variable composition, due to the significant amount of anthropogenic activities in urbanized areas and consequently higher contaminants levels in relation to soils of rural origin [1]. Nowadays, the soil contamination by metals, such as Cu, Fe, Ni, Cd, Cr, Pb, Zn, is one of the main environmental problems [2,3]. Anthropogenic contamination of soils from industrial activities has been highlighted in recent years, in which metals are believed to be easily accumulated at the soil surface resulting in problems, such as toxicity to living organisms, food chain and ecosystem disruption [4,5]. Among the micronutrients present in the soil are iron (Fe) and copper (Cu), which may be naturally present due to weathering and other soil formation processes [6]. However, the concentration of these metals in the soil can be altered by natural phenomena, such as elemental redistribution by wind and water or anthropic actions by residues burning and industrial dust deposition [2,5-8]. According to Brazilian legislation in the CONAMA resolution 420/2009 guideline values for Cu range from 200 (agricultural area) to 600 (industrial area) mg kg-1 (dry mass), while for Fe there are no established data [9]. Indeed, high amounts of these metals may result in inhibition of plant growth causing changes in flora and microorganisms [10-12]. The high concentrations of Fe may be hazardous by catalyzing the production of oxygen radicals and stimulating the growth of bacteria, whereas Cu has high affinity for sulfur and nitrogenous ligands and in high concentrations can bind to important proteins sites [13,14]. Considering the information, it is necessary to improve understanding of the metal behavior in soils and the anthropic action effects on the metal distribution. Furthermore, the knowledge of the metals pseudototal concentration in soils is not enough in the evaluation of the their mobilities and bioavailabilities for living organisms. The mobility, bioavailability and toxicity of the pollutants depend on the chemical form and its binding state, in which fractionation methods from sequential extraction procedures can provide information on the metal associations with different soil geochemical phases [15-17]. Even with a wide variety of sequential extraction procedures currently available [18], Tessier’s procedure [15] can be highlighted, which has been applied successfully in studies of soils and sediments [19-23]. The elemental fractionation procedure proposed by Tessier indicates that metals can be associated with different soil fractions and after sequential extraction procedures exchangeable, carbonate-related, reduced (associated with Fe or Mn oxides), oxidized (associated with organic matter) and residual fractions are obtained [15]. In general, the exchangeable form was considered readily mobile and bioavailable species, while the residual form was considered to incorporate into soil minerals and appeared to be the most inactive species. Bound to carbonate, Fe-Mn oxide and organic matter fractions can be considered relatively active depending on the physical-chemical properties of the soil [15,18]. Although several single and sequential extractions methods have been proposed, the soil fractionation schemes were not standardized, and the results of different procedures are not always comparable, due to the lack of uniformity of the experimental conditions. On the other hand, a certain procedure can be applied successfully for comparison of soils from different areas to evaluate the anthropic actions effect on the metal species distribution and, consequently, elemental mobility and bioavailability in the environment. Thus, the aim of this study was to apply sequential extraction procedure (Tessier’s procedure) to fractionate Cu and Fe content in rural soil, from an area of environmental preservation, and urban soil near to an industrialized area. 14


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MATERIALS AND METHODS Instrumentation For quantification of Fe (pseudo-total and fractionated) and Cu (pseudo-total), an atomic absorption spectrometer (Model AAS Vario 6, Analytik Jena AG, Jena, Germany), equipped with a hollow cathode lamp of Cu (324.8 nm, 4 mA, and slit 0.8 nm) and Fe (248.3 nm, 4 mA, and 0.8 nm), and a deuterium lamp for background correction, was used. For elemental determination by flame atomic absorption spectrometry (F AAS), flame composition and observation height were optimized. The instrumental parameters were: for Fe, 70 L h-1 acetylene flow, 430 L h-1 air flow, and 5 mm observation height; and for Cu, 50 L h-1 acetylene flow, 430 L h-1 air flow, and 5 mm observation height. For the Cu quantification in (i) exchangeable, (ii) bound to carbonates, (iii) bound to Fe-Mn oxides, (iv) bound to organic matter, and (v) residual fractions, a ZEEnit 60 model atomic absorption spectrometer (Analytikjena AG, Jena, Germany) equipped with a transversely heated graphite atomizer, pyrolytically coated graphite tube, and transversal Zeeman-effect background correction was used. The spectrometer was operated with a hollow cathode lamp operated by a wavelength lamp current and slit equal to 324.8 nm, 4 mA, and 0.8 nm, respectively. All measurements were based on integrated absorbance values. A 10 µL aliquot of different supernatants was introduced into the graphite tube without adding a chemical modifier. The instrumental conditions for the spectrometer and the heating program are shown in Table I. Argon 99.998%, v v-1 (Air Liquide Brazil, SP, Brazil) was used as a protective and purging gas. Table I. Heating program for Cu determination by GF AAS Step

Temperature (ºC)

Ramp (ºC s-1)

Hold (s)

Argon flow (mL min-1)

Drying

130

5

20

1000

Pyrolysis

1200

100

15

1000

Atomization

2300

2300

5

0

Cleaning

2500

200

2

1000

The samples were dried using an oven (model 515, FANEM, Brazil). An orbital shaker (Quimis, Brazil) was used to mix the samples and extractants. Phase separation was performed by centrifugation (Spectrafuge 6C Compact model, Labnet International, USA). The digestion of samples was carried out in a thermostatic water-bath (Q226M2 model, Quimis, Brazil). Reagents and samples The soil samples were collected in two different regions (urban or rural) and depths (5 and 15 cm) from the city of Campo Limpo Paulista, SP, Brazil. Souza (2018) previously described the soil characteristics of a region close to our experimental area. It is a red clay soil, with loamy texture composed of sand (45% w w-1), silt (25% w w-1) and clay (30% w w-1), 2.82% (w w-1) of organic matter with pH = 4.9 [24]. All solutions were prepared using analytical reagent-grade chemicals, with high-purity deionized water obtained from a Milli-Q water purification system (Millipore, USA). Analytical grade 65% (w v-1) HNO3 (Merck, Germany), distilled in a quartz sub-boiling still (Marconi, Brazil), 30% (w v-1) H2O2 (Merck, Germany), and 37% (v v-1) HCl (Merck, Germany), were used for sample digestion and analytical solutions. Analytical-grade Tritisol solutions (Merck, Germany) of 1000 mg L-1 for Cu (CuCl2) and Fe (FeCl3) were applied to prepare the reference analytical solutions, after dilution in HNO3 0.1% (v v−1) for determining the Fe and Cu content by F AAS and graphite furnace atomic absorption spectrometry (GF AAS). For the fractionation procedure solutions of MgCl2.6H2O (Merck, Germany), CH3COONa.3H2O (Merck, Germany), CH3COOH (Sigma Aldrich, USA), NH2OH.HCl (Synth, Brazil), and CH3COONH4 15


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Accumulation and Fractionation of Iron and Copper in Urban and Rural Soil from Brazilian City

(Merck, Germany) were used. Soil sampling and preliminary sample preparation For soil sampling two different regions were sampled: rural (environmental preservation region) and urban (industrialized region) areas of the city of Campo Limpo Paulista (23º12’S, 46º47’W) in the state of Sao Paulo, Brazil, in which soil samples (six sub-samples) were randomly collected in an area of 2 x 2 m² at depths of 5 and 15 cm in rural and urban regions. The soil samples were dried in an oven at 60 ºC, ground and homogenized using a pestle and mortar (decontaminated). Extraction of pseudo-total Cu and Fe For pseudo-total Cu and Fe determination by F AAS, the soil samples were submitted to two different extraction procedures in thermostatic bath (HNO3 + H2O2 or HNO3 + 3HCl) to evaluate the efficiency of Cu and Fe extraction. In the first extraction procedure evaluated, 50 mL of HNO3 + 3HCl solution was prepared adding 12.5 mL of HCl 37% (v v-1) and 3.6 mL of HNO3 65% (w v-1) to a polypropylene tube and filled with deionized water. The HNO3 + 3HCl solution was stored at 4 °C for later use for sample digestion. In this way, 7 mL of HNO3 + 3HCl and 0.5 mL of deionized water were added to 0.750 g of samples and heated in a thermostatic bath at 90 °C for 2 hours, followed by centrifugation at 4000 rpm for 10 min [25,26]. After the extraction, the final volume was completed to 15 mL with deionized water. In the second extraction procedure evaluated, a volume of 3 mL of HNO3 was added to 0.750 g of samples. The mixture was heated in a thermostatic bath at 80 °C for 30 minutes, followed by addition of 2 mL of H2O2, heating for 30 minutes, and centrifugation at 4000 rpm for 10 min. After the extraction, the final volume was completed to 10 mL with deionized water. Fractionation of Cu and Fe For the Fe and Cu fractionation in different soil samples, the Tessier’s extraction method [15] was performed in five sequential extractions steps described below. At the end of each step of the sequential extraction procedure, the samples were submitted to centrifugation at 4000 rpm for 10 min for separation of residue and supernatant. The supernatants were subjected to elemental determination by F AAS or GF AAS. (i) Exchangeable: The soil samples (ca. 1.0 g) were subjected to extraction with 8 mL of MgCl2 (1 mol L-1, pH 7.0) under shaking for 1 hour at room temperature, and centrifugation at 4000 rpm for 10 min. After the extraction, the final volume was completed to 10 mL with deionized water. (ii) Bound to carbonates: To the residue from step (i), 8 mL of CH3COONa.3H2O (1 mol L-1, pH 5.0 adjusted with CH3COOH) was added under continuous agitation for 5 hours at room temperature, and centrifugation at 4000 rpm for 10 minutes. After the extraction, the final volume was completed to 10 mL with deionized water. (iii) Bound to Fe-Mn oxides: The residue from step (ii) was extracted with 20 mL of NH2OH.HCl in 25% (v v-1) CH3COOH, under continuous agitation for 6 hours at 96 °C, and centrifugation at 4000 rpm for 10 min. After the extraction, the final volume was completed to 15 mL with deionized water. (iv) Bound to organic matter: To the residue from step (iii), HNO3 (3 mL, 0.02 mol L-1) and H2O2 (5 mL, 30 % (v v-1)) were added, adjusted to pH 2 with HNO3, and the mixture was heated to 85 °C for 2 hours under continuous agitation. A second aliquot of 3 mL of 30% (v v-1) H2O2 (pH 2.0 adjusted with HNO3) was then added and the sample was heated again to 85 °C for 3 hours under continuous agitation. After cooling, CH3COONH4 (5 mL, 3.2 mol L-1) in 20% (v v-1) HNO3 was added and the sample was diluted to 20 mL and agitated continuously for 30 minutes, and centrifuged at 4000 rpm for 10 min. After the extraction, the final volume was completed to 10 mL with deionized water. (v) Residual: The residue from step (iv) was digested with HNO3 and H2O2 mixture according to the 16


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Article

procedure previously described for pseudo-total Fe and Cu determination. After the extraction, the final volume was completed to 6 mL with deionized water. Cu and Fe determination The determination of Cu (pseudo-total) and Fe (pseudo-total and fractioned) was carried out by F AAS, and Cu (fractioned) by GF AAS. For elemental determination by F AAS, acetylene flow was optimized, ranging from 50 to 80 L h-1 in increments of 5 L h-1, with constant air flow (430 L h-1) and observation height (6 mm). The observation height was evaluated (5, 8, 10, 12, and 15 mm) in the best acetylene flow for each element. Under each condition, absorbance signals were obtained in triplicate, using analytical solutions of 0.75 and 1.0 mg L-1 of Fe and Cu, respectively. Instrument calibration was performed using analytical solutions with concentrations ranging from 0.25 to 3.0 mg L-1 and 0.1 to 4.0 mg L-1 in 0.1% (v v-1) HNO3 for Fe and Cu, respectively. For the Fe determination, further dilutions with deionized water were necessary, ranging from 2 (bound to carbonates fraction) to 500-fold (residual fraction). The fractionated Cu determination was carried out by GF AAS in different extracts. The instrument calibration was performed using analytical solutions with concentrations ranging from 10 to 80 µg L−1 of Cu in 0.1% v v−1 HNO3. For the Cu determination, the supernatants were diluted 2- to 100-fold in deionized water and no chemical modifier was used. The chemical interferences during Cu and Fe determination were verified by an addition and recovery test, adding 0.4 mg L-1 of Fe (pseudo-total and different extracts) or Cu (pseudo-total), and 20 µg L-1 of Cu (different fractionation extracts). Statistical analyses The determination of the pseudo-total concentration and fractionated was done in triplicate for the soil from the rural and urban areas with different depths. Statistically significant differences (p < 0.05) between the soil origin or depth in a given element and extraction procedure were detected using two-way analysis of variance (ANOVA). Differences between means were compared by Student’s t-test at the 95% confidence limit. Similarly, the statistically significant differences (p < 0.05) between the soil origin or depth in a given element and step of the fractionated extracts were detected using Student’s t-test at the 95% confidence limit. RESULTS AND DISCUSSION Optimization of flame conditions for Fe and Cu determination by F AAS A suitable chemical environment of the air-acetylene flame is required for proper formation of the atomic precursors, since different flame compositions may favor the refractory species formation of the elements [27]. The effects of the acetylene flow variation on Cu and Fe atomization are shown in Figure 1. In general, it was verified that increased fuel flow altered Cu atomization and its absorbance decreased significantly taking into account the profile and standard deviation of the absorbance value (n=3). On the other hand, Fe showed significant increase in absorbance value from 70 L h-1. Thus, the acetylene flow of 50 and 70 L h-1 were applied in the Cu and Fe determination, respectively. After fuel flow optimization, observation height was also optimized to obtain the highest values of absorbance, which represent the interaction of the electromagnetic radiation from the hollow cathode lamp with gaseous atoms in the fundamental state formed in the atomizer [27]. The effects of the observation height variation on the Cu and Fe absorbance values are shown in Figure 1. It was found that the absorbance value decreased with increasing observation height, thus, the observation height of 5 mm was applied in the Cu and Fe determination in the samples considering the profile and standard deviation of the absorbance signal (n=3).

17


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Accumulation and Fractionation of Iron and Copper in Urban and Rural Soil from Brazilian City

(A)

(B)

Figure 1. Optimization of flame chemical composition (acetylene flow) (A) and observation height (B) using analytical solutions of 1.0 mg L-1 Cu (▲) and 0.75 mg L-1 Fe (■).

Characteristic parameters of the analytical calibration curve for Cu and Fe determination by F AAS, such as linear range, correlation coefficient (R2), limit of detection (LOD), and limit of quantification (LOQ), are presented in Table II. The LOD was calculated using the standard deviation of 10 measurements of the analytical blank sample (3 × σblank, where σ is the standard deviation) and the LOQ was calculated as 3.3 × LOD. The LOD and LOQ values were obtained in µg g−1, considering a sample mass of 0.75 g and a final volume of 10 mL for the solutions. The influence of concomitants in pseudo-total Cu and Fe determination by F AAS was investigated through addition and recovery test, adding to the samples 0.4 mg L-1 of Fe and Cu after the extraction procedures (HNO3 + H2O2 or HNO3 + 3HCl). The Cu and Fe recovery percentages in different extractants are shown in Table II. The recoveries showed absence of matrix influence in Cu and Fe determination with recovery percentages ranging from 98 to 107%. According to NBR ISO/IEC 17025, guidelines for elemental determination by spectrometric techniques, the recovery tolerance should range from 70 to 120% [28]. Table II. Characteristics method for Cu and Fe determination by F AAS Linear range (mg L-1)

Cu

0.1 – 4.0

0.9995

Fe

0.25 – 3.0

0.9993

Element

Analytical blank

LOD (µg g-1)

LOQ (µg g-1)

Recovery (%)

HNO3+ 3HCl

5

15

101

HNO3 + H2O2

0.04

0.1

107

HNO3+ 213HCl

0.03

0.1

99

HNO3 + H2O2

0.4

1.2

98

Accumulation Fe and Cu in rural and urban soils The Fe and Cu concentrations in soil samples from the rural and urban areas, and at depths of 5 and 15 cm obtained after the different extraction procedures are shown in Table III.

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Table III. Fe and Cu concentrations in soils submitted to different extraction procedures Elemental concentration ± standard deviation (n=3)

Soil Origin / Depth

Copper*

Iron**

HNO3 + H2O2

HNO3 + 3HCl

HNO3 + H2O2

HNO3 + 3HCl

rural / 5cm

0.7 ± 0.1a

2.1 ± 0.4a

4.8 ± 0.1a

13 ± 1a

rural / 15cm

0.9 ± 0.1a

3.4 ± 0.2a

6.7 ± 0.2a

14 ± 1a

urban / 5cm

9.6 ± 0.6b

10 ± 2b

10 ± 1b

25 ± 2b

urban / 15cm

9.5 ± 0.5b

13 ± 1b

10 ± 1b

25 ± 2b

*mg kg-1; **g kg-1;

a-b

Different superscripted letters in a given element and extraction procedure indicate significant differences in elemental concentration between depths and origins (p<0.05).

The extraction procedures for pseudo-total Cu and Fe determination may have promoted the Cu and Fe partial extraction, since that the solubilization was not complete. It was observed that the concentrations obtained using HNO3 + 3HCl were significantly higher when compared to the mixture HNO3 + H2O2, since that more acidic medium and the HCl presence has complexing character, resulting in a greater solubility of compounds bound to Cu and Fe [29]. On the other hand, the procedure with HNO3 + H2O2 was more feasible, because the mixture HNO3 + 3HCl promoted several problems in the control of the solution boiling in thermostatic bath, due to violent reaction with great gas generation and possible sample losses during the process. Therefore, the residual fraction from fractionation procedure by the Tessier’s method was solubilized using HNO3 + H2O2 and only this extraction procedure for pseudo-total elemental determination was considered. The different depths were evaluated aiming to analyze recent changes (5 cm), as well as, environmental changes in other periods (15 cm) and according to the Table III there were no significant differences in the pseudo-total Fe and Cu concentration in soils collected at different depths. However, the average Cu and Fe concentration in the soil from the urban area were significantly higher than rural area, varying from approximately 12 (Fe) to 2 (Cu) times higher. The rural area is remote and environmental preservation region, while urban region has become a storage area for building materials and other wastes with sewage passage. In this way, anthropogenic actions may be a determining factor for the increase of total Fe and Cu concentration in the urban area evaluated. The Cu concentrations in the urban region were 13.7 and 10.6 times higher than in the rural region at depths of 5 cm and 15 cm, respectively, while Fe concentrations were 2.0 and 1.5 times higher than in the rural region. Therefore, these results in urban soils showed the effects of anthropic action and industrial activities on the accumulation of Fe and Cu in the soil [30]. In addition, although Cu concentrations are below the values established by CONAMA resolution 420/2009 (600 mg kg-1 in industrial areas), it was verified that the anthropic actions in region are favoring the increase in the these metals concentration in the soil, which can be easily accumulated and, in the future, may result in potential problems such as toxicity to plants and animals [4]. Fractionation of Fe and Cu in rural and urban soils Characteristic parameters of the analytical calibration curve for Cu and Fe determination by GF AAS and F AAS, respectively, are presented in Table IV. The LOD and LOQ values were obtained in ng g−1, considering a sample mass of 1.0 g and a final volume of 10 mL (step 1 and 2 of the sequential extraction) and 15 mL (step 3 and 4 of the sequential extraction) for the solutions. The concomitants influence in fractionated Cu and Fe determination was investigated through addition and recovery test. The Cu and Fe recovery percentages in different extractants are shown in Table IV. The recoveries showed absence of matrix influence in Cu and Fe determination with recovery 19


Accumulation and Fractionation of Iron and Copper in Urban and Rural Soil from Brazilian City

Article

percentage ranging from 87 to 115% [28]. Table IV. Characteristics method for fractionated Cu and Fe determination and recovery evaluation in different steps of Tessier’s method Element

Linear range

Cu*

10 – 80

Fe**

0.25 – 3.0

0.9998

0.9961

Analytical blank

LOD

LOQ

Recovery (%)

Step 1

3.7

12.1

93

Step 2

1.5

4.9

115

Step 3

6.6

21.8

98

Step 4

19.3

66.7

99

Step 5

21.3

70.4

114

Step 1

0.8

2.6

87

Step 2

1.7

5.1

91

Step 3

0.5

1.5

88

Step 4

0.6

1.7

92

Step 5

0.4

1.2

98

*Linear range (µg L ); LOD and LOQ (ng g ) **Linear range (mg L-1); LOD and LOQ (µg g-1) -1

-1

The Cu and Fe concentrations in five fractions of the sequential extraction of the Tessier’s method applied to the soil samples from rural and urban areas at different depths are presented in Table V, as well as, the elemental concentration in the residual fraction after the extraction procedure with HNO3 + H2O2 and the sum of the elemental concentration at all steps. Table V. Fe and Cu concentrations in soils submitted to sequential extraction procedures of Tessier’s method Soil origin/ Depth

Cu*

Fe**

Concentration ± standard deviation (n=3) Step 1

Step 2

Step 3

Step 4

Step 5

Sum

Rural 5 cm

< LOD

< LOQ

28 ± 2a

0.40 ± 0.04a

0.19 ± 0.04a

0.6 ± 0.2a

Rural 15 cm

330 ± 10a

110 ± 1a

29 ± 2a

0.34 ± 0.05a

0.18 ± 0.02a

0.9 ± 0.1a

Urban 5 cm

310 ± 13a

570 ± 2b

919 ± 28b

2.5 ± 0.2b

4.7 ± 0.1b

8.9 ± 0.2b

Urban 15 cm

212 ± 7b

410 ± 4c

902 ± 9b

2.4 ± 0.1b

4.9 ± 0.3b

8.8 ± 0.3b

Rural 5 cm

6.7 ± 0.6a

60 ± 5a

230 ± 10a

420 ± 10a

3.4 ± 0.1a

4.2 ± 0.1a

Rural 15 cm

4.7 ± 0.5b

40 ± 2b

190 ± 10b

410 ± 10a

4.9 ± 0.2b

5.6 ± 0.2b

Urban 5 cm

4.7 ± 0.5b

20 ± 3c

280 ± 10c

740 ± 20b

9.6 ± 0.4c

11 ± 1c

Urban 15 cm

5.9 ± 0.4a

30 ± 2d

380 ± 10d

710 ± 20b

10 ± 1c

11 ± 1c

*Cu concentration in steps 1, 2, and 3 (µg kg-1) and steps 4, 5 and sum (mg kg-1) **Fe concentration in steps 1, 2, 3, and 4 (mg kg-1) and step 5 and sum (g kg-1) a-d Different superscripted letters in a given element and step indicate significant differences in elemental concentration between depths and origins (p < 0.05) 20


de Oliveira, A. P.; Noda, C. M. S. P.; Naozuka, J.

Article

Firstly, comparing the sum of the Cu or Fe concentrations of all fractions with the pseudo-total concentration obtained after the extraction procedure with HNO3 + H2O2 (Table III), it was verified that Cu and Fe pseudo-total concentrations were satisfactorily fractionated by Tessier’s method. In addition to indicating a higher solubility of the species bound to Cu and Fe in more acidic media comparing different extraction procedures, it was possible to infer about each elemental species concentration in the soil through elemental fractionation. The Cu and Fe distribution showed similar patterns for each sample, which followed order residual > bound to organic matter > bound to Fe-Mn oxides > bound to carbonates > exchangeable. However, rural soil (15 cm) was an exception to the observed pattern, which contained 200% more Cu exchangeable species than bound to carbonates species. Besides that, the Cu species concentration bound to organic matter in rural soil was 110% (5 cm) and 89% (15 cm) higher than residual fraction. In contrast to that observed for the rural soil, in the urban soil the residual fraction presented the highest Cu concentration. The Tessier’s method fractionation allows to evaluate the metals extraction from different geochemical fractions of the soils and sediments. The first steps of the method extract from the sample the weakly associated and most available metals, while in the residual fraction, it is possible to assess the metal fraction that is not potentially available to the environment and is accumulated in the soil under natural conditions, such as metals included in clays [15,18]. Thus, it is possible to infer that soil samples from urban areas are polluted samples, since that in polluted soils there are high residual content, evidencing by incomplete dissolution during previous steps of the Tessier’s method [15,18] and the residual fraction (Table V, step 5) shows the high metals accumulation and low reactivity of Cu species present in urban soil. The Cu concentration exchangeable and bound to carbonates in the rural soil collected at the depth of 15 cm is significantly higher in relation to the depth of 5 cm, while there is no significant difference between Cu concentrations bound to Fe-Mn oxides, bound to organic matter, and residual at both depths evaluated. Furthermore, with increasing Cu concentrations exchangeable and bound to carbonates (fractions 1 and 2) in 15 cm, it is possible to infer that weathering, such as changes in the local vegetation or Cu redistribution by wind or water action promoted a decrease in concentration of mobile and bioavailable Cu species in upper layers of rural soil. On the other hand, unlike that observed in the rural area, in the urban area the fractions of Cu exchangeable (fraction 1) and bound to carbonates (fraction 2) decreased significantly with the depth increase, in which it was possible to infer that current anthropic activities favor the increase of Cu species concentration more mobile and bioavailable in the topsoil. In the residue (fraction 5) there is Cu species incorporated into soil minerals and appeared to be the most inactive did not change significantly with depth in both soils [19]. In contrast to that observed for Cu in rural soils, at greater depths there is a significant decrease in the exchangeable, bound to carbonates, and bound to Fe-Mn oxides Fe concentration, while there is an increase of 44% in residual Fe concentration with increasing depth. These results indicate that factors related to weathering have probably increased the concentration of more mobile and bioaccessible species in the topsoil of rural region. The increase in residual Fe concentration corresponds to less mobile and reactive species indicates the Fe accumulation in lower layers of the soil. However, in the urban soil there was a significant increase in the concentration of exchangeable Fe, bound to carbonates and bound to Fe-Mn oxides with increasing depth. The increase in the concentration of these more mobile species in lower layers of the urban soil indicates that anthropic activities in the past favored the increase of these mobile and bioavailable species, which can crystallize into crystalline lattice of soil minerals and compose the residual fraction [18,19]. Additionally, it was observed that significant Cu and Fe amounts were associated with the residual fraction, ranging from 20% (Cu: rural, 15 cm) to 91% (Fe: urban, 15 cm) in relation to the pseudo-total concentration. Therefore, Fe fractionation was dominated by residual species as might be expected for an element whose minerals constitute a major structural component of soil [1], ranging from (3.4 ± 0.1) (rural, 5 cm) to (10 ± 1) (urban, 15 cm) g kg-1 with lower concentrations of exchangeable species ranging from (4.7 ± 0.5) (rural, 15 cm) to (6.7 ± 0.6) (rural, 5 cm) mg kg-1. Indeed, the variable pseudo-total Fe 21


Article

Accumulation and Fractionation of Iron and Copper in Urban and Rural Soil from Brazilian City

and Cu concentrations were found in the rural and urban soils at different depths, but the exchangeableCu and Fe concentrations were relatively low (average < 5%), indicating the predominant presence of recalcitrant fractions (associated with Fe-Mn oxides, organic matter, and residual) with low mobile and strongly bound species that favor the accumulation of these elements in the soils, since that Cu and Fe bound to residual fraction is often consider unreactive and not affected by environmental changes [18,23]. CONCLUSIONS The evaluation of the pseudo-total Cu and Fe concentration in the soils through procedures of partial solubilization showed that there is a significant difference in the content of these elements between different studied soils. The Cu and Fe concentration in the soil from the urban area were significantly higher than rural area. The high levels of these elements from the urban area must be related to the anthropic activities practiced in this area, which has become a place where the sewage water passes besides being a deposit of construction materials and garbage, while the rural area evaluated is a place of environmental preservation. Therefore, it was possible to evaluate the potential effects of anthropic activities on the heavy metal concentrations in the soil through fractionation, in which the concentration of exchangeable species of both metals was significantly lower when compared to the concentrations of species bound to organic matter and residual fraction. The results indicated that in addition to be a determining factor and increasing the Cu and Fe pseudo-total concentration in the soil, the anthropic actions increased the concentration of these metals associated to residual fraction where metals most strongly associated with soil components, such as metals included in clays. Finally, in the urban area, the metals evaluated presented lower mobility in the environment and possibly are accumulated in soil under natural conditions. The strong interaction of these metals with soil components and low availability may cause changes in the microorganisms and plant community that share the common environment and interact with each other, animal populations, and the physical environment. Acknowledgments Aline Pereira de Oliveira (2015/01128-6, 2017/05009-7 and 2019/00663-6) and Juliana Naozuka (2015/15510-0 and 2018/06332-9) thank the “Fundação de Amparo à Pesquisa do Estado de São Paulo”/FAPESP for the fellowship provided and financial support, respectively. The authors also thank the “Coordenação de Aperfeiçoamento de Pessoal de Nível Superior”/CAPES for financial support to Graduate Program in Chemistry Sustainability Science and Technology. Compliance with Ethics Requirements The authors declare that they have no conflict of interest. This article does not contain any studies with human or animal subjects. Manuscript received: June 4, 2019; revised manuscript received: September 6, 2019; manuscript accepted: September 12, 2019; published online: October 18, 2019. REFERENCES 1. Wu, S.; Peng, S.; Zhang, X.; Wu, D.; Luo, W.; Zhang, T.; Wu, L. J Geochem Explor., 2015, 148, pp 71-78. 2. Nazir, R.; Khan, M.; Masab, M.; Rehman, H. U.; Rauf, N. U.; Shahab, S.; Shaheen, Z. J. Pharm. Sci. Res., 2015, 7 (3), pp 89-97. 3. Cui, J. L.; Luo, C. L.; Tang, C. W. Y.; Chan, T. S.; Li, X. D. J. Hazard. Mater., 2017, 329, pp 150-158. 22


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4. Pandey, G.; & Madhuri, S. Research Journal of Animal, Veterinary and Fishery Sciences, 2014, 2 (2), pp 17-23. 5. Fujimori, T.; Takigami, H. Environ. Geochem. Health., 2014, 36 (1), pp 159-168. 6. Antoniadis, V.; Levizou, E.; Shaheen, S. M.; Ok, Y. S.; Sebastian, A.; Baum, C.; Rinklebe, J. EarthSci. Rev., 2017, 171, pp 621-645. 7. Ghazban, F.; Parizanganeh, A.; Zamani, A.; Baniardalan, S. Int. J. Environ. Res., 2018, 12 (6), pp 843-860. 8. Tóth, G.; Hermann, T.; Da Silva, M. R.; Montanarella, L. Environment international, 2016, 88, pp 299-309. 9. http://www.mma.gov.br/port/conama/legiabre.cfm?codlegi=620 [Accessed 30 June 2018]. 10. Mishra, J.; Singh, R.; Arora, N. K. Front. Microbiol., 2017, 8, p 1706. 11. Roy, M.; McDonald, L. M. Land Degradation & Development, 2015, 26 (8), pp 785-792. 12. Alloway, B. J. Heavy metals in soils. Springer, Dordrecht, 2013, p 11. 13. Du, H. Y.; Yu, G. H.; Sun, F. S.; Usman, M.; Goodman, B. A.; Ran, W.; Shen, Q. R. Biogeosciences, 2019, 16 (7), pp 1433-1445. 14. Guigues, S.; Bravin, M. N.; Garnier, C.; Masion, A.; Chevassus-Rosset, C.; Cazevieille, P.; Doelsch, E. Metallomics, 2016, 8 (3), pp 366-376. 15. Tessier, A.; Campbell, P. G.; Bisson, M. Anal. Chem., 1979, 51 (7), pp 844-851. 16. Kim, R. Y.; Yoon, J. K.; Kim, T. S.; Yang, J. E.; Owens, G.; Kim, K. R. Environ. Geochem. Health., 2015, 37 (6), pp 1041-1061. 17. Essington, M. E. Soil and water chemistry: an integrative approach. CRC press. 2015. 18. Bacon, J. R.; Davidson, C. M. Analyst, 2008, 133 (1), pp 25-46. 19. Fajkovic, H.; Roncevic, S.; Nemet, I.; Prohic, E.; Leontic-Vazdar, D. Fractionation of metals by sequential extraction procedures (BCR and Tessier) in soil exposed to fire of wide temperature range. In: EGU General Assembly Conference Abstracts, 2017, 19, p 424. 20. Liu, Y.; Zhang, J.; He, H. Acta Oceanol. Sin., 2018, 37 (5), pp 22-28. 21. Orecchio, S.; Amorello, D.; Barreca, S.; Pettignano, A. Environ. Sci.: Processes Impacts, 2016, 18 (3), pp 323-329. 22. Gabarrón, M.; Zornoza, R.; Martínez-Martínez, S.; Muñoz, V. A.; Faz, Á.; Acosta, J. A. Chemosphere, 2019, 218, pp 266-272. 23. Sungur, A.; Soylak, M.; Yilmaz, E.; Yilmaz, S.; Ozcan, H. Soil and Sediment Contamination: An International Journal, 2015, 24 (1), pp 1-15. 24. Souza, W. M. Influência dos atributos do solo na sorção e lixiviação do indaziflam em solos tropicais. Master’s thesis, 2018, Universidade Federal de Viçosa, Minas Gerais, Brazil. 25. Inboonchuay, T.; Suddhiprakarn, A.; Kheoruenromne, I.; Anusontpornperm, S.; Gilkes, R. J. Geoderma Regional, 2016, 7, pp. 120-131. 26. Ferri, R.; Hashim, D.; Smith, D. R.; Guazzetti, S.; Donna, F.; Ferretti, E.; Curatolo, M.; Moneta, C.; Beone, G. M.; Lucchini, R. G. Sci. Total Environ., 2015, 518, pp. 507-517. 27. Skoog, D. A.; West, D. M.; Holler, F. J.; Stanley, R. C. Fundamentos da Química Analítica, Translation of the 8th North-American edition. Ed. Thomson, São Paulo, 2007, p 807. 28. Associação Brasileira de Normas Técnicas. NBR ISO/IEC 17025: Requisitos Gerais para Competência de Laboratórios de Ensaio e Calibração, 2005. 29. Hsu, L. C.; Liu, Y. T.; Tzou, Y. M. J. Hazard. Mater., 2015, 296, pp 230-238. 30. Karim, Z.; Qureshi, B. A.; Mumtaz, M.; Qureshi, S. Ecol. Indic., 2014, 42, pp 20-31.

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Article

Br. J. Anal. Chem., 2019, 6 (25) pp 24-39 DOI: 10.30744/brjac.2179-3425.AR-22-2019

Chemical Profiling and Discrimination of Medicinal Himalayan Iris Species Using Direct Analysis in Real Time Mass Spectrometry Combined with Principal Component Analysis Pratibha Singh1,2, Vikas Bajpai1, Abha Sharma3, Bikarma Singh4, Brijesh Kumar1,2* Sophisticated Analytical Instrument Facility, CSIR-Central Drug Research Institute, Sitapur road, Lucknow, Uttar Pradesh, 226031, India 2 Academy of Scientific and Innovative Research (AcSIR), New Delhi, 110025, India 3 National Institute of Pharmaceutical Education and Research, Raebareli, Lucknow, Uttar Pradesh, 226301, India 4 Biodiversity and Applied Botany Division, CSIR-Indian Institute of Medicine, Jammu, 180001, India 1

Graphical Abstract

Metabolic profiling of I. crocea, I. ensata, I. germanica, I. hookeriana, I. kashmiriana and I. spuria, was carried out using direct analysis in real-time mass spectrometry (DART-MS) to generate the chemical fingerprints for the differentiation. Phytochemical analysis showed presence of twenty-two flavonoids and isoflavonoids in the intact leaf and root of these species. The DART-MS data have been subjected to principal component analysis (PCA) which showed clear differentiation among the species and plant parts. It clearly indicated that the DART-MS technique followed by PCA is a quick and reliable method for the direct profiling and discrimination of Iris species and their plant parts.

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Chemical Profiling and Discrimination of Medicinal Himalayan Iris Species Using Direct Analysis in Real Time Mass Spectrometry Combined with Principal Component Analysis

Article

Keywords: DART-MS, flavonoids, isoflavonoids, Iris species, Principal Component Analysis (PCA). INTRODUCTION Traditional health care system involved the medicinal use of plants throughout the world. In India the practice of ethno medicine by rural and tribal communities evolved through the system of Ayurveda, Siddha and Unani [1]. The Indian Himalayan region is a biodiversity hotspot hosting a remarkably rich variety of medicinal plants [2]. The genus Iris belongs to the family Iridaceae which comprises over 300 species, of which twelve are reported in India, mostly in the Kashmir, Himalaya from the valley to high alpines [3,4]. The most common Iris species found in India include I. crocea, I. ensata, I. germanica, I. hookeriana, I. kashmiriana and I. spuria. Iris plants are widely used in traditional medicine to treat liver bacterial, dysfunction, inflammation, and viral infections [5,6]. They are also used as antispasmodic, emetic, haemostasis and laxative agents [6]. The rhizomes of I. germanica and I. spuria have been used as aperient, blood purifier, diuretic, and stimulant to treat gall bladder, venereal diseases and cancer [7]. Because of the violetlike scent of their flowers Iris species also find use in the perfume and cosmetic industries [8]. They are considered rich sources of secondary metabolites. The phytochemicals isolated from Iris species possess antibacterial [9], anticancer, anticholinesterase, antihelmintic, antiinflammatory, antimicrobial, antioxidant, antiplasmodial, antituberculosis, antiulcer, cytotoxic, free radical scavenging [10,11], hepatoprotective, hypolipidemic, immunomodulatory, molluscicidal and pesticidal activities [5,6,9,12,13]. A variety of secondary metabolites including flavonoids, isoflavonoids, iridal type triterpenoids, irones, phenolics, quinines, stilbenes glycosides and xanthones have been isolated from Iris plants [9,13-15]. The Iris rhizomes showed characteristic isoflavonoids and iridals (mono and bicyclic triterpenoids), whereas the leaves contained C-glycosylflavones, flavonoid aglycones, isoflavones, phenolics and xanthone glycosides [16]. About 50 different isoflavonoids in the form of diglucosides, triglucosides or aglycones are reported from the Iris plants [17]. The preventive role of isoflavones is well-known in diseases like cancer, cardiovascular, osteoporosis, and menopausal symptoms [18,19]. Since the genus Iris is rich in bioactive flavonoids, isoflavonoids, phenolics and several Iris species having different contents of these components are used in traditional medicine, their metabolite analysis is essential for the quality control of herbal drugs [20-22]. Earlier reports showed the metabolite profiling of Iris species using gas chromatography-mass spectrometry (GC-MS) [23] for volatile components, highperformance liquid chromatography (HPLC) [24,25] and high-performance thin layer chromatography (HPTLC) [25]. Electrospray ionization mass spectrometry (ESI-MS) combined with high performance liquid chromatography and diode array detector (HPLC-DAD) was used to identify the flavonoids and other constituents in the rhizomes of three Iris species namely I. crocea, I. germanica and I. spuria [6,13,25]. The flavonoids and isoflavonoids of Iris species were also identified by 1H-NMR [5,15,26], 13 C-NMR [27], IR [28], UV [16,29]. But all these techniques require elaborate sample preparation and are time and labor consuming. Direct analysis in real-time mass spectrometry (DART-MS)-based metabolic profiling is quicker profiling strategy as there is no need of sample preparation [30-34]. It is therefore an appropriate technique for the metabolic profiling of plant species [35,36]. Besides DART, there are others ambient ionization technique like Desorption electrospray ionization (DESI), Desorption atmospheric pressure chemical ionization (DAPCI), Atmospheric solids analysis probe (ASP) employed to access metabolic profiles of plants [37]. Metabolic profiling followed by statistical analysis is a preferred method for the differentiation of plants [37-40]. Hence, it was decided to profile the chemical constituents in the roots and leaves of six Iris species namely I. crocea, I. ensata, I. germanica, I. hookeriana, I. kashmeriana and I. spuria collected from Kashmir Himalaya using DART-MS and utilize the chemical fingerprint data to run principal component analysis (PCA) for discrimination.

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Article

Singh, P.; Bajpai, V.; Sharma, A.; Singh, B.; Kumar, B.

MATERIALS AND METHODS Plant Materials The leaf and root of I. crocea, I. ensata, I. germanica, I. hookeriana, I. kashmiriana and I. spuria were collected in June 2015 from Kashmir Himalaya. Voucher specimens of all collected Iris species were deposited in Plant Herbarium of CSIR-IIIM, Jammu India. Details are available in supplementary Table SI. Samples for DART MS analysis Intact plant parts (leaf and root) were thoroughly washed with tap water followed by distilled water in order to remove foreign particles from the surface and dried at room temperature. DART MS Analysis The mass spectrometer used was a JMS-T100LC, Accu Tof atmospheric pressure ionization timeof-flight mass spectrometer (Jeol, Tokyo, Japan) fitted with a DART ion source. The mass spectrometer was operated in positive-ion mode with a resolving power of 6000 (full-width at half-maxima). The orifice 1 potential was set to 28 V, resulting in minimal fragmentation. The ring lens and orifice 2 potentials were set to 13 and 5 V, respectively. Orifice 1 was set at 100 °C and RF ion guide potential at 300 V. The DART ion source was operated with helium gas flowing at approximately 4.0 L min-1 and gas heater was set at 300 °C. The potential on the discharge needle electrode of the DART source was set to 3000 V, electrode 1 at 100 V and the grid at 250 V. Data acquisition was from m/z 10 to 1050. All the leaf and root samples were analyzed in 15 repeats to check the reproducibility of spectra. Mass calibration was accomplished by including a mass spectrum of neat polyethylene glycol (PEG) (1:1 mixture PEG 200 and PEG 600) in the data file. The mass calibration was accurate to within ±0.002 u. Using the Mass Centre software, the elemental composition was determined on selected peaks. Statistical analysis Principal component analyses (PCAs) was performed with the STATISTICA software, Windows version 7.0 (Stat Soft, Inc., USA). Data for PCA analysis was extracted from DART-MS spectra of fifteen repeats of each sample. All ions having ≥5% peak intensity were selected for principal component analysis. RESULTS AND DISCUSSION Comparison of DART-MS fingerprints of Iris species Comparative DART-MS fingerprints of the leaf and root of I. crocea, I. ensata, I. germanica, I. hookeriana, I. kashmiriana and I. spuria are shown in Figures 1 and 2 respectively. The structures of detected compounds are given in Figure 3.

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Chemical Profiling and Discrimination of Medicinal Himalayan Iris Species Using Direct Analysis in Real Time Mass Spectrometry Combined with Principal Component Analysis

Article

Figure 1. Comparative DART-MS fingerprint spectra of the leaf of six Iris species.

27


Singh, P.; Bajpai, V.; Sharma, A.; Singh, B.; Kumar, B.

Article

Figure 2. Comparative DART-MS fingerprint spectra of the root of six Iris species.

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Chemical Profiling and Discrimination of Medicinal Himalayan Iris Species Using Direct Analysis in Real Time Mass Spectrometry Combined with Principal Component Analysis

Article

Figure 3. Structures of identified compounds in Iris species.

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Singh, P.; Bajpai, V.; Sharma, A.; Singh, B.; Kumar, B.

Table I. Exact mass data for the identified constituents and their distribution in the roots and leaves of six Iris speciesa

S. Nº

Class of Compounds

Compounds

Cal. mass [M+H]+

Meas. mass [M+H]+

M. formula

Root

Leaf

Error (ppm)

Ic

Ie

Ig

Ih

Ik

Is

Ic

Ie

Ig

Ih

Ik

Is

Biological activity

Ref.

Free radical scavenging activity

[14]

1

Alkylphenylketones

Acetovanillone

167.0708

167.0701

C9H10O3

-4.2

-

-

+

-

-

-

-

+

+

+

+

-

2

Iron oxide

β-Irone

207.1991

207.1960

C14H22O

-15.0

-

-

-

-

-

-

-

+

+

-

+

+

[10]

3

Isoflavonoids

Alpinone

287.2724

287.2739

C16H14O5

5.2

-

+

+

-

-

-

-

+

-

-

-

-

[14]

4

Isoflavonoids

Irilone

299.0602

299.0556

C16H10O6

-15.4

-

+

+

+

+

+

+

+

-

+

+

-

Cancer chemo preventive potential, free radical scavenging activity

5

Isoflavonoids

Tectorigenin

301.9810

301.9773

C16H12O6

-12.3

+

+

+

+

+

-

-

+

-

-

-

-

Antibacterial, antiinflamentry, antioxidative and antitumor

6

Isoflavonoids

5,2’,3’-Trihydroxy7-methoxyflavone

303.1251

303.1233

C16H14O6

-5.9

-

-

-

-

-

-

-

+

-

-

+

+

7

Isoflavonoids

5-Methoxy-4’-hydroxy-6,7methylenedioxyisoflavone

313.0579

313.0581

C17H12O6

0.6

+

+

+

-

+

+

+

+

-

-

-

+

Free radical scavenging activity

[6]

8

Isoflavonoids

5,7-Dihydroxy-4’6dimethoxyisoflavone

315.0732

315.0716

C17H14O6

-5.1

+

+

+

+

+

+

-

+

-

-

-

-

Cancer chemo preventive potential

[14]

9

Isoflavonoids

Irisoid A

329.2042

329.2038

C17H12O7

-1.2

+

+

+

+

+

-

-

-

-

-

-

-

Free radical scavenging activity

[14]

10

Isoflavonoids

Iristectorigenin A

331.0793

331.0818

C17H14O7

7.6

+

+

+

+

-

-

+

+

-

+

+

-

[6]

[6]

[20]

[14]

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Chemical Profiling and Discrimination of Medicinal Himalayan Iris Species Using Direct Analysis in Real Time Mass Spectrometry Combined with Principal Component Analysis

Article

Table I. Exact mass data for the identified constituents and their distribution in the roots and leaves of six Iris species (Cont.)a

S. Nº

Class of Compounds

Compounds

Cal. mass [M+H]+

Meas. mass [M+H]+

M. formula

Root

Leaf

Error (ppm)

Ic

Ie

Ig

Ih

Ik

Is

Ic

Ie

Ig

Ih

Ik

Biological activity

Ref.

Cancer chemo preventive potential

[10]

Is

11

Isoflavonoids

Iriskashmirianin

343.2637

343.2683

C18H14O7

13.4

+

+

+

+

+

+

+

+

-

+

+

-

12

Isoflavonoids

Irisflavone C

361.0923

361.0917

C18H16O8

-1.7

-

-

+

-

+

+

-

+

-

-

-

-

[28], [43]

13

Xanthonoid

Mangiferin

423.3591

423.3627

C19H18O11

8.5

-

-

-

-

-

-

-

-

-

+

+

-

[43]

14

Xanthonoid

7-O-methylmangiferin

437.3632

437.3631

C20H20O11

-0.2

-

-

-

-

+

-

-

+

-

-

-

-

[14]

15

Flavonoids

Swertisin

447.3287

447.3267

C22H22O10

-4.5

-

-

-

-

-

-

-

+

+

+

-

-

[8] [14]

16

Isoflavonoid o-glycosides

Irilone 4’-O-glucoside

461.1401

461.1448

C22H20O11

10.2

+

+

+

+

+

+

+

-

-

-

+

+

[6]

17

Flavonoids

Tectoridin

463.3205

463.3212

C22H22O11

1.5

+

+

+

-

+

+

+

+

+

+

+

+

18

Flavonoids

Germanaism B

475.1392

475.1380

C23H22O11

-2.5

-

+

+

+

-

+

+

+

-

-

-

-

19

Flavonoids

Iriflogenin 4’-O-glucoside

491.4783

491.4828

C23H22O12

9.2

+

+

-

-

-

-

+

-

-

-

-

-

20

Flavonoids

Iristectorigenin B 7-O-glucoside

493.4984

493.4972

C23H24O12

-2.4

-

+

+

-

+

+

+

+

-

-

-

+

[6]

21

Flavonoids

Iridin

523.4028

523.4018

C24H26O13

-1.9

-

-

-

-

-

-

-

-

+

-

-

-

[6]

22

Flavonoids

Germanaism D

611.3387

611.3373

C27H30O16

-2.3

-

-

-

-

-

-

+

+

-

-

-

-

[11]

a

(+): detected, (-) not detected, Ic: Iris crocea, Ie: Iris ensata, Ig: Iris germanica, Ih: Iris hookeriana, Ik: Iris kashmiriana and Is: Iris spuria.

Antibacterial, antiinflamentry, antioxidative and antitumor

[6] [14]

[14] Cancer chemo preventive potential

[6]

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Article

Singh, P.; Bajpai, V.; Sharma, A.; Singh, B.; Kumar, B.

The variation and distribution of bioactive compounds in the leaves and roots of six Iris species could be observed from their fingerprints. Twenty-two constituents were tentatively identified based on their exact mass and molecular formula (Table I). These constituents were directly ionized from the leaves and roots during analysis and appeared as protonated molecular ions [M+H]+ in the resulting spectra. Phytochemical analysis of Iris species showed mainly the presence of flavonoids and isoflavonoids. The major isoflavonoids obtained in the DART-MS of Iris species at m/z 299.0556 (C16H10O6), 301.9773 (C16H12O6), 313.0581 (C17H12O6), 315.0716 (C17H14O6), 329.2038 (C17H12O7) and 343.2683 (C18H14O7), could be due to irilone (4) [6], tectorigenin (5) [6], 5-methoxy-4’-hydroxy-6,7methylenedioxyisoflavone (7) [6], 5,7-dihydroxy-4’6-dimethoxyisoflavone (8) [14], irisoid A (9) [14] and iriskashmirianin (11) [10] respectively. Compounds irilone (4), tectorigenin (5), 5-methoxy-4’hydroxy-6,7-methylenedioxyisoflavone (7) and irisoid A (9) are reported for their anticancer activity were detected in the roots of all the species except (4) in I. crocea, (5) and (9) in I. spuria, and (7) in I. hookeriana. Compound irilone 4’-O-glucoside (16) [6] was detected in the roots of all the species. While compound tectoridin (17) [6,14] m/z 463.3212 (C22H22O11) was present in all the roots and leaves except I. hookeriana. Compound iriflogenin 4’-O-glucoside (19) [6] m/z 491.4828 (C23H22O12) was detected only in the roots and leaves of I. crocea and I. ensata. Compound mangiferin (13) [43] m/z 423.3627 (C19H18O11) was found only in the leaf of I. hookeriana and I. kashmiriana, while swertisin (15) [8,14] m/z 447.3267 (C22H22O10) was detected in the leaves of I. ensata, I. germanicaand I. hookeriana. The compounds iridin (21) [6] m/z 523.4018 (C24H26O13) and germanaism D (22) [11] m/z 611.3373 (C27H30O16) were detected in the leaves of I. germanica, I. crocea and I. ensata as shown in Table I. The relative content of nine bioactive compounds was tentatively converted in terms of percent ionization, which was obtained as the ratio of the expression of the peak to the sum of all the expressions within the spectra ranging from m/z 100–800. All the ions with the relative intensity above 5% were taken and compared based on the percent ionization. Fifteen repeats of each sample were carried out and the averaged value was utilized for the comparison as shown in Figure 4 and in supplementary Figure S1. The relative content is given in Table II.

Figure 4. Comparison of nine bioactive compounds in roots of six Iris species.

32


Chemical Profiling and Discrimination of Medicinal Himalayan Iris Species Using Direct Analysis in Real Time Mass Spectrometry Combined with Principal Component Analysis

Article

Table II. Relative percent ionization of nine bioactive compounds in Iris species Peaks

I. crocea

I. ensata

I. germanica

I. hookeriana

I. kashmiriana

I. spuria

Root

Leaf

Root

Leaf

Root

Leaf

Root

Leaf

Root

Leaf

Root

Leaf

287 (3)

nd

nd

43.7

nd

24.7

nd

nd

nd

nd

nd

nd

nd

299 (4)

nd

29.4

63.1

39.6

17.1

nd

16.3

43.1

23.7

51.4

23.3

nd

301 (5)

79.9

nd

42

27.9

nd

nd

28.1

nd

20.2

nd

nd

nd

313 (7)

98.6

54.7

36

40

96.1

nd

89.4

nd

78.9

nd

44.6

76

315 (8)

68.5

nd

31.5

25.7

28.1

nd

24.7

nd

39

nd

95.2

nd

329 (9)

27.5

nd

25

nd

22.5

nd

29.8

nd

29.2

nd

nd

nd

343 (11)

32.7

30.6

30.6

14

32.3

nd

42.6

51.1

24.2

23.3

39.4

nd

463 (17)

31.1

25.7

95

23.6

39.5

43.5

nd

53.3

32.3

42.1

49.3

58.7

491 (19)

26.5

21.8

27.5

nd

nd

nd

nd

nd

nd

nd

nd

nd

nd: not detected

Highest abundance of cancer chemo preventive compound, irilone (4) [41] was detected in the root of I. ensata (63.1%) followed by leaf of I. kashmiriana (51.4%), I. hookeriana (43.1%) and I. ensata (39.6%). Similarly, 5,7-dihydroxy-4’6-dimethoxyisoflavone (8) was relatively high in the roots of I. spuria (90%) and I. crocea (68.5%). Compound iriskashmirianin (11) was detected relatively more in the leaf of I. hookeriana (50.1%) and roots of I. hookeriana (42.6%) and I. spuria (39.4%) whereas iriflogenin 4’-O-glucoside (19) was found high in the roots of I. ensata (27.5%) and I. crocea (26.5%). High content of irisoid A (9) was found in the roots of I. hookeriana (29.8%), I. kashmiriana (29.2%) and I. crocea (27.5%). The compounds alpinone (3) and 5-methoxy-4’-hydroxy-6,7-methylenedioxyisoflavone (7) were detected high in the roots of I. crocea (98.6%), I. germanica (96.1%), I. hookeriana (89.4%), I. kashmiriana (78.9%) and I. ensata (43.7%) respectively. Similarly, tectorigenin (5) and tectoridin (17) were found high in the roots of I. ensata (95%) and I. crocea (79.9%) respectively. This observation could be helpful in selecting the most suitable plant/parts of Iris species for their medicinal purposes and quality control. Discrimination of root and leaf of six Iris species using principal component analysis The chemical fingerprint data when combine with principal component analysis serves as an effective means for identifying the natural components as markers which can be used to discriminate among the species [38-40,42]. PCA is an unsupervised procedure that determines the directions of the largest variations in the data set and the data are generally presented as a two-dimensional plot (score plot) where the coordinate axis represents the directions of two largest variations [38-40,42]. The DART MS data obtained from root and leaf of I. crocea, I. ensata, I. germanica, I. hookeriana, I. kashmiriana and I. spuria was subjected to PCA. The scores and loading plots (PC1 vs. PC2) are given in Figures 5 and 6. The data for PCA analysis was taken from the m/z 100 to 800 Da. All the m/z considered for PCA analysis were pseudo molecular [M+H]+ ions with defined isotopic peak patterns. Fifty-three peaks were identified from fifteen repeats of each sample of the six Iris species. Averages of 15 repeats of all the samples were used for PCA analysis. In the case of leaf samples of six Iris species, 71 peaks were taken for analysis. These extracted 53 and 71 peaks of roots and leaves respectively were used as variables for PCA analysis using correlation matrix of data. The PCA scores plots of the roots of I. crocea, I. ensata, I. germanica, I. hookeriana, I. kashmiriana and I. spuria (Figure 5a) showed clustering of the data according to the plant species. 33


Article

Singh, P.; Bajpai, V.; Sharma, A.; Singh, B.; Kumar, B.

Figure 5a. PCA Score plot discriminating the root of six Iris species.

Figure 5b. PCA loading plot of root of six Iris species.

The PCA extracted 18 marker peaks out of 53 peaks at m/z 133, 163, 237, 261, 271, 297, 299, 377, 387, 393, 427, 439, 441, 443, 475, 491, 499 and 507 which were contributing for discrimination of roots. These 18 marker peaks clearly separated roots of all the plants, which accounted for total 78.86% variance as shown in Figure 5a and 5b. Similar, clustering and differentiation was clearly observed among the leaves of I. crocea, I. ensata, I. germanica, I. hookeriana, I. kashmiriana and I. spuria. The principal component analysis was initially done for 71 variables (m/z) detected in the fingerprints of leaves. The PC1 vs PC2 plot showed that the first two principal components were able to explain highest variance of 73.71% information contained in the 16 marker peaks at m/z 123, 153, 167, 183, 237, 277, 313, 327, 331, 343, 397, 415, 441, 493, 557 and 638 which discriminated among the leaves Figure 6a and 6b. By using the PCA as a chemometric tool, the number of PCs were identified which were able to differentiate among the leaves and roots of six Iris species. It is, therefore, clear that DART MS followed by PCA is an appropriate method for the clear identification of different Iris species.

Figure 6a. PCA Score plot discriminating the leaf of six Iris species.

34

Figure 6b. PCA loading plot of root of six Iris species.


Chemical Profiling and Discrimination of Medicinal Himalayan Iris Species Using Direct Analysis in Real Time Mass Spectrometry Combined with Principal Component Analysis

Article

CONCLUSION The DART-MS method has been developed and applied successfully for the first time for the chemical profiling of flavonoids and isoflavonoids in the roots and leaves of I. crocea, I. ensata, I. germanica, I. hookeriana, I. kashmiriana and I. spuria. Significant difference in the mass spectra was observed. A total of twenty-two phyto-constituents were tentatively identified and their variations were studied. Compounds acetovanillone (1), irilone (4), tectorigenin (5), 5-methoxy-4’-hydroxy-6,7-methylenedioxyisoflavone (7), 5,7-dihydroxy-4’6-dimethoxyisoflavone (8), irisoid A (9), iriskashmirianin (11), tectoridin (17), and iriflogenin-4’-O-glucoside (19) reported to possess several biological activities are among the main identified bioactive compounds. PCA analysis was able to classify and identify marker peaks for discrimination among roots and leaves of Iris species. This analysis underscores the importance of DART-MS method for high throughput analysis and identification of bioactive compounds for selection of the best plant/part according to need, authentication and quality control of these Iris species. Acknowledgements Grateful acknowledgement is made to the Sophisticated Analytical Instrument Facility (SAIF), Central Drug Research Institute, Lucknow, where all the mass spectral studies were carried out. Pratibha Singh is also thankful to ICMR New Delhi. CDRI communication no. 10021. Manuscript received: July 11, 2019; revised manuscript received: Nov. 4, 2019; accepted: Nov. 19, 2019; published online: Dec. 30, 2019. REFERENCES 1. Gadgil, M. Current Science (Bangalore), 1996, 70 (1), pp 36-44. 2. Myers, N.; Mittermeier, R. A.; Mittermeier, C. G.; da Fonseca, G. A. B.; Kent, J. Nature, 2000, 403, pp 853-858 (https://doi.org/10.1038/35002501). 3. Bhattacharjee, S. K. Handbook of Medicinal Plants. Pointer Publishers, Jaipur, India, 1998, pp 118-132. 4. Chesfeeda, A.; Khuroo, A. A.; Malik, A. H.; Dar, G. H. Iran. J. Bot., 2013, 19 (2), pp 119–126. 5. Rahman, A.; Nasim, S.; Baig, I.; Jalil, S.; Orhan, I.; Sener, B.; Choudhary, M. I. J. Ethnopharmacol., 2003, 86 (2), pp 177-180 (https://doi.org/10.1016/S0378-8741(03)00055-2). 6. Bhat, G.; Shawl, A. S.; Shah, Z.; Tantry, M. J. Anal. Bioanal. Tech., 2014 (https://doi.org/10.4172/2155-9872.1000223). 7. Uzair, A.; Bakht, J.; Iqbal, A.; Naveed, K.; Ali, N. Pak. J. Pharm. Sci. 2016, 29 (1), pp 145-150. 8. Kukula-Koch, W.; Sieniawska, E.; Widelski, J.; Urjin, O.; Głowniak, P.; Skalicka-Woźniak, K. Phytochem. Rev., 2015, 14 (1), pp 51-80. 9. Woźniak, D.; Matkowski, A. Fitoterapia, 2015, 107, pp 1-14 (https://doi.org/10.1016/j.fitote.2015.08.015). 10. Choudhary, M. I.; Hareem, S.; Siddiqui, H.; Anjum, S.; Ali, S.; Zaidi, M. I. Phytochemistry, 2008, 69 (9), pp 1880-1885 (https://doi.org/10.1016/j.phytochem.2008.03.011). 11. Nazir, N.; Koul, S.; Qurishi, M. A.; Taneja, S. C.; Purnima, B.; Qazi, G. N. J. Asian Nat. Prod. Res., 2008, 10 (12), pp 1137-1141 (https://doi.org/10.1080/10286020802413296). 12. Wang, H.; Cui, Y.; Zhao, C. Mini-Rev. Med. Chem., 2010, 10 (7), pp 643-661 (https://doi.org/10.21 74/138955710791384027). 13. Singaba, A. N. B.; Ahmed, A. H.; Sinkkonen, J.; Ovcharenko, V.; Pihlaja, K. Z. Naturforsch., C: J. Biosci., 2006, 61 (1-2), pp 57-63 (https://doi.org/10.1515/znc-2006-1-211). 14. Kassak, P. Acta Univ. Agric. et Silvic. Mendel. Brun., 2012, 60 (8), pp 119-126 (https://doi. org/10.11118/actaun201260080119). 15. Miyake, Y.; Ito, H.; Yoshida, T. Can. J. Chem., 1997, 75 (6), pp 734-741 (https://doi.org/10.1139/v97-089). 16. Williams, C. A.; Harborne, J. B.; Goldblatt, P. Phytochemistry, 1986, 25 (9), pp 2135-2154 (https://doi.org/10.1016/0031-9422(86)80079-6). 35


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Chemical Profiling and Discrimination of Medicinal Himalayan Iris Species Using Direct Analysis in Real Time Mass Spectrometry Combined with Principal Component Analysis

Article

Supplementary Material Table SI. The sample code, voucher specimen number and collection location of Iris species from J&K, India Sample Voucher Place of S. Nยบ Iris species Specimen Nยบ collection Code 1

RRLH 8643

Iris crocea Jacq. ex R.C. Foster

Ic

Srinagar

2

RRLH 52992

Iris ensata Thunb.

Ie

Bandipora

3

RRLH 52990

Iris x germanica L.

Ig

Pahalgam

4

RRLH 53176

Iris hookeriana Foster

Ih

Razdhan Pass

5

RRLH 52991

Iris kashmiriana Baker

Ik

Srinagar

6

RRLH 8642

Iris spuria L.

Is

Srinagar

Table SII. Variance contributions of each principal component in the root of six Iris species Variable contributions based on correlations Factor 1

Factor 2

Factor 3

Factor 4

Factor 5

133

0.092791

0.004990

0.017997

0.050937

0.033285

163

0.036368

0.044221

0.113450

0.135111

0.091540

237

0.042414

0.099133

0.008150

0.074854

0.037519

261

0.092791

0.004990

0.017997

0.050937

0.033285

271

0.013311

0.071328

0.210276

0.039550

0.041972

297

0.092791

0.004990

0.017997

0.050937

0.033285

299

0.092791

0.004990

0.017997

0.050937

0.033285

377

0.051031

0.082844

0.034164

0.035257

0.010497

387

0.051031

0.082844

0.034164

0.035257

0.010497

393

0.051031

0.082844

0.034164

0.035257

0.010497

427

0.023319

0.068255

0.088416

0.151777

0.173980

439

0.059184

0.045572

0.063246

0.006869

0.164783

441

0.051031

0.082844

0.034164

0.035257

0.010497

443

0.013311

0.071328

0.210276

0.039550

0.041972

475

0.042414

0.099133

0.008150

0.074854

0.037519

491

0.059184

0.045572

0.063246

0.006869

0.164783

499

0.042414

0.099133

0.008150

0.074854

0.037519

507

0.092791

0.004990

0.017997

0.050937

0.033285

37


Article

Singh, P.; Bajpai, V.; Sharma, A.; Singh, B.; Kumar, B.

Table SIII. Variance contributions of each principal component in the leaf of six Iris species Variable contributions based on correlations Factor 1

Factor 2

Factor 3

Factor 4

Factor 5

123

0.071466

0.057625

0.086823

0.013097

0.041480

153

0.120635

0.001805

0.009805

0.079409

0.004345

167

0.052878

0.089544

0.054694

0.076012

0.000327

183

0.021815

0.158362

0.024677

0.005847

0.054842

237

0.103264

0.020605

0.001516

0.109099

0.016853

277

0.031894

0.002110

0.166062

0.305526

0.038281

313

0.048839

0.101673

0.038750

0.072000

0.008419

327

0.018637

0.101194

0.042743

0.021079

0.295006

331

0.001706

0.175003

0.044722

0.005172

0.085057

343

0.002482

0.160381

0.000066

0.041501

0.185119

397

0.120450

0.011834

0.005839

0.052407

0.002905

415

0.000269

0.057402

0.253889

0.179570

0.011065

441

0.101471

0.004826

0.130796

0.000204

0.006385

493

0.106080

0.038860

0.004805

0.038459

0.000597

557

0.096643

0.013952

0.004016

0.000413

0.242934

638

0.101471

0.004826

0.130796

0.000204

0.006385

Figure S1. Comparison of nine bioactive compounds in leaves of six Iris species.

38


Chemical Profiling and Discrimination of Medicinal Himalayan Iris Species Using Direct Analysis in Real Time Mass Spectrometry Combined with Principal Component Analysis

Figure S2. PCA Score plot (PC1 x PC3) of root of six Iris species

Article

Figure S3. PCA Score plot (PC1 x PC4) of root of six Iris species

Figure S4. PCA Score plot (PC1 x PC3) of leaf of six Iris species

Figure S5. PCA Score plot (PC1 x PC4) of leaf of six Iris species

39


Br. J. Anal. Chem., 2019, 6 (25) pp 40-57

Review

DOI: 10.30744/brjac.2179-3425.RV-19-2019

Production, Characterization and Application of Ferrate(VI) in Water and Wastewater Treatments Alexis Munyengabe

Caliphs Zvinowanda*

Department of Chemical Sciences, Faculty of Science, Doornfontein Campus, University of Johannesburg Corner Nind and Beit Streets, P.O. Box 17011, Johannesburg, South Africa, 2028

Graphical Abstract

Investigation into the production, characterization and application of ferrate(VI) in water and wastewater treatment to enable metal removal through oxidation and coagulation processes and recommended in perspective for AMD treatment as a sustainable process.

This paper aimed at reviewing different research work done on the synthesis of ferrate(VI) salts of potassium and or sodium, their applications in industrial wastewater, municipal sewage and water treatment. In this review, it was found that ferrate(VI) salt can exhibit more than one function in water and wastewater treatment as this chemical can take the roles of coagulants, flocculants, antioxidant, bactericide or disinfectant, and oxidant. Despite these properties, its availability on the market in a solid state is still a big problem due to its high cost and difficulties during its production as well as its chemical instability. Furthermore, suitable methods or procedures for manufacturing pure and stable ferrate(VI) salts were established in the past decades but are too expensive to produce sufficient quantities required for a large-scale water and wastewater treatment. Current ferrate synthesis methods include wet chemical oxidation, dry and electrochemical techniques. Among them, the wet oxidation method is the most applicable and safe to generate ferrate(VI) as dry and electrochemical methods can provoke detonation due to elevated temperatures and high concentration of electrolytes used, respectively. Some analytical techniques used to characterise and to quantify the ferrate(VI) products are scanning electron microscope, X-ray diffraction, infrared spectrometry, Mรถssbauer, ultraviolet-visible spectroscopy, thermogravimetric analysis, and volumetric methods. Several studies have been conducted to evaluate ferrate stability and its effective application in water and wastewater treatment. However, these studies showed that ferrate(VI) can oxidise or degrade organic pollutants such as pharmaceuticals, illicit drugs, and can also destroy or eliminate suspended particulate organic matter in a single mixing and dosing unit procedure. The stability of ferrate(VI) was found to depend on concentration, pH, and temperature of the solution, and coexistence of ions in the solution. Lately, most researchers stated that ferrate(VI) can also be applied to treat different emerging micro-pollutants, viz., personal care products, industrial 40


Production, Characterization and Application of Ferrate(VI) in Water and Wastewater Treatments

Review

organic chemicals, endocrine disrupting chemicals, heavy metals, metal-complexed species, and others in water decontamination processes. Studies also showed that ferrate(VI) salt can be classified as a green chemical which can replace different disinfectants and oxidants producing toxic disinfectant by-products generated by the use of chemicals such as chlorine and chlorine dioxide. Mining industry is another sector, which still has a problem of high energy consumption during acid mine drainage (AMD) treatment. This is due to extensive stirring and aeration which required to facilitate the oxidation of Fe(II) ions. However, the authors recommend the use of ferrate(VI) salt for AMD treatment as it can work as a powerful oxidant converting Fe(II) to Fe(III) and act as a coagulant in a single treating unit, hence, thus reducing energy consumption and environmental pollution problems. Keywords: green chemical; coagulant; flocculant; oxidant; chemical stability; ferrate(VI) salts; water; wastewater INTRODUCTION Drinking water, domestic sewage and industrial effluent treatments are generally performed distinctively where different pollutants or contaminants are partially eliminated or completely degraded by the application of progressive modern technologies. There are various ways of water and wastewater treatments, which are based on different criteria. Conventional wastewater treatment consists of preliminary, primary, secondary and tertiary treatments that are based on biological, physical and chemical processes. For example, suspended solids, oil and small debris are removed during the primary treatment for municipal wastewater treatment while some physical parameters and phenols are reduced or removed in the secondary treatment. The most common biological process of wastewater treatment is a treatment with activated sludge. Bacteria, protozoa and microscopic metazoa use organic matter from wastewater as food and enhancement of biomass. Biological treatment offers high quality removal of suspended solids, 5-day biochemical oxygen demand (BOD5) and nutrients and waste sludge can be used in composting. Conventional biological treatment is highly efficient, uses less space compared to non-conventional treatments and their functioning is not dependent on outdoor conditions. Some of the disadvantages of these treatments are the constant high electrical energy requirements and the design, supervision, maintenance, and the general cost of construction that would require highly skilled workers [1]. The chemical pollution purification and subsequent reuse of treated water is performed in the tertiary treatment using electrodialysis, ion-exchange, oxidation, membrane ultrafiltration and reverse osmosis techniques [2]. These stages for conventional wastewater treatment to generate potable water consume a huge amount of energy through constant stirring, aeration and pumping at high pressure to generate treated water of either industrial or potable quality. Other wastewater treatment stages such as flocculation, coagulation and neutralisation are also characterised by limited effectiveness as they do not completely remove different pollutants usually found in environmental matrices. Although these techniques are commonly applied in water and wastewater treatment, some of them are known to produce toxic by-products, use too much and expensive neutralising agents (e.g. lime) especially in the case of acid mine drainage treatment. To solve this problem, however, advanced oxidation processes (AOPs) were being given serious consideration as an alternative to the existing water treatment procedures [3]. However, these AOPs normally use free radicals produced by various methods [4-6]. These free radicals contain unpaired valence electrons, which react to oxidize a wide range of microcontaminants, making them useful in water and wastewater treatment. One of the earliest methods of producing hydroxyl radicals in industrial waters was the use of Fentonâ&#x20AC;&#x2122;s reagent, using ferrous iron (Fe2+) to decompose hydrogen peroxide (H2O2) to form OH before being reduced back to ferrous iron to produce another radical and water [7]. However, the use of AOPs involving the hydroxyl radical can increase oxidation of contaminants due to the radicalâ&#x20AC;&#x2122;s higher reactivity when compared to ozone or other conventional oxidants. Hydroxyl free radicals are strong oxidants with an oxidation potential of 2.80 V compared to ozone (2.07 V) and chlorine (1.36 V) and can oxidize organics including 41


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those resistant to ozone such as some pesticides and volatile organic compounds. Methods commonly used to generate hydroxyl radical now include combinations of ozone and ultraviolet radiation with hydrogen peroxide. Ozone can react with hydrogen peroxide or, through a series of reactions involving hydroxide ions, form the hydroxyl radical [7]. Nowadays, researchers are no longer using free radicals because of expensive reagents such as ozone and long process to produce them. Another promising AOP that has been currently investigated to treat water and industrial wastewater is ferrate(VI) in the form of either potassium ferrate(VI) or sodium ferrate(VI). This AOP can concurrently act either as a disinfectant, coagulant or oxidant in a single mixing and dosing unit procedure [8]. The ferrate(VI) ion (FeO42-) is a typical oxyanion of iron with an oxidation state +6, which has an orthorhombic structure and a tetrahedral form when different ferrate(VI) salts are dissolved in water [9]. Its structure is very close to those of chromate and permanganate oxyanions, wherein four oxygen atoms are covalently attached to a central iron atom [10,11]. Even if chromate and permanganate can also be used as strong oxidants, researchers reported them to generate hazardous by-products (chromium and manganese) in water and wastewater treatment. In general, iron usually exists as a metallic iron with zero valence, +2 and +3 in ferrous and ferric forms. The most known of these ferric or ferrous oxides include hematite, wuestite, magnetite, hypoferrite, ferrite, goethite, and akageneite [12]. Some of them such as magnetite and akageneite are currently utilised as powerful adsorbents in water, brine water and industrial wastewater treatment [13,14]. Iron can also appear in different forms with high oxidation states such as ferrate(IV) [FeO4]4-, ferrate(IV) [FeO3]2-, ferrate(V) [FeO4]3-, ferrate(VI) [FeO4]2-, ferrate (VII) [FeO4]â&#x20AC;&#x201C;, and ferrate(VIII) [FeO5]2- [15,16]. However, the ferrate(VI) ion has been studied progressively in the past years amongst other ferrate salts as a powerful flocculant, coagulant and disinfectant of emerging micropollutants [9,17-19] and also as a strong oxidant of inorganic and organic compounds in water and industrial wastewater treatment processes due to its high oxidation potential in wide range of pH values [20-27]. Over this entire pH range, ferrate(VI) can oxidise different pollutants by substituting existing oxidants of environmental concern (chlorine, chromate, permanganate, chloramines and ozone), that can cause the production of many disinfectant by-products (DBPs) of concern [9,19,28,29]. Some occurrences of generated lethal DBPs that have been revealed to be cancer-causing in humans and animals include trihalomethanes [30]. These pollutants are normally generated when chlorinated disinfectants and chlorine are utilised to remove microbial pollutants from water by reacting with naturally-occurring inorganic and organic materials [21,31,32]. Epidemiological studies also recommended some relationship between the drinking water treated with the chlorine and the prevalence of colon, bladder and rectal cancer [30,33]. Comparing with chlorination treatment, the by-products being generated through the application sequestration of ferrate(VI) salts are environmentally-friendly ferric-based chemicals, that can also be served as an effective coagulant in water and wastewater treatment [22,24,34]. Ferrate(VI) has also been applied in different fields such as non-chlorine oxidation for pollutant remediation, catalyst in the green chemistry synthesis and in the fabrication of a super iron battery [34,35]. Moreover, the ferrate(VI) can also provide an environmentally-friendly high energy density cathode for battery and exhibits different properties such as high functional group selectivity as well as high oxidising power [21]. The redo potentials of ferrate(VI) vary from +2.20 V (EÂş FeO42-/Fe3+) to +0.72 V [EÂş FeO42-/Fe(OH)3] in acidic (pH=1) and alkaline (pH=14) solutions, respectively (30,36,37]. Application of ferrate(VI) as a powerful steriliser in water and industrial waste effluent treatments has been widely reviewed by Machala et al. [38]. The oxidization and disinfection capacities of commonly used compounds in water and wastewater treatment are presented in Figure 1, which is easily comparable to ferrate(VI).

42


Production, Characterization and Application of Ferrate(VI) in Water and Wastewater Treatments

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Figure 1. Comparison of current disinfectants and oxidant ability to use for treatment of water and wastewater.

In some studies, the results suggested a permanent inactivation of bacteria by ferrate(VI) with a kill rate of 99.9%, while a significant resistance of bacteria to chlorination treatment was highlighted [39,40]. Ferrate(VI) is also beneficial in the coagulation process where it can be used in a pre-oxidation stage of the water treatment [41]. Notably, all the above properties of ferrate(VI) can thus made it be utilised in a single dose for reuse and recycling of water and wastewater [38]. According to its exceptional properties, ferrate(VI) have encouraged several investigators to examine its effectiveness in water and wastewater treatment in comparison with other coagulants and oxidants such as ferric sulphate, chlorine, sodium hypochlorite, aluminum sulphate, ozone, ferric chloride, and chlorine dioxide [40]. However, the challenges have been raised for the application of ferrate(VI) technology in practice due to the high production cost of solid ferrate(VI) products or chemical instability of a ferrate(VI) solution [42]. To reach an effective treatment, research has been focused on the production and application of ferrate(VI) salts in-situ to avoid its degradation through transportation [17,43]. This paper reviewed the progress made in the production of ferrate(VI) salts based on electrochemical, wet oxidation and dry methods, stability and characterization methods of the product as well as its application in water and wastewater treatment. Analytical techniques currently used to characterise and to quantify the ferrate(VI) ion have also been reviewed, namely: infrared spectrometry, X-ray diffraction, scanning electron microscopy, Mรถssbauer and ultraviolet-visible spectroscopy, thermogravimetric analysis and volumetric titration method [44,45]. Different studies carried out on the application of ferrate(VI) in water, domestic sewage and wastewater treatment are also presented in this review. The authors concentrated on the current processes made in the potential use of ferrate(VI) in water treatment, decomposition of organic and inorganic contaminants, emerging micropollutants and the analysis of the toxicity organic by-products generated from ferrate(VI) salts in treated water and wastewater. Lastly, the authors recommend continuing to implement this multifunction chemical (disinfectant, coagulant, oxidant, and flocculant) in practice for the future research, especially in water and wastewater as well as in acid mine drainage treatment. PRODUCTION OF FERRATE(VI) SALTS Different ferrate(VI) salts are now being produced by mixing potassium nitrate and iron filings at high temperature [17]. After dissolving the molten residue in water, an unstable red-purple compound 43


Munyengabe, A.; Zvinowanda, C.

Review

appears by revealing the existence of potassium ferrate (K2FeVIO4) in the solution. Moreover, some methods have been successfully confirmed during the production of different ferrate(VI) salts, viz., wet oxidation, dry oxidation or thermal and electrochemical methods [22,46]. Among these methods, the electrochemical method was the one which attracted many researchers in the 20th century. Normally, the ferrate(VI) salts can be formed with the chemical formula MxFeO4, where M stands for two atoms of K, Na, Ag, Cs or one atom of Ba or Ca [47]. Ferrate(VI) salts may be prepared using iron(III) salts either in solid state or liquid solutions such as ferric chloride, ferric nitrate, ferric sulphate or ferrous salts with an oxidant containing chloride ion (e.g. hypochlorite) in a strong base such as sodium carbonate and sodium hydroxide for wet oxidation method and the reaction of ferric oxides with sodium peroxide for dry method [48-50]. Other mixed cation ferrates such as potassium-sodium double ferrate and potassiumstrontium double ferrate(VI) salts can also be synthesised. For example, potassium-sodium double ferrate can be synthesised by adding potassium hydroxide to 40% sodium hydroxide containing 0.1 M ferrate ions [51]. However, the crystals that precipitated out of the reaction are collected and washed and dried under a vacuum while potassium-strontium double ferrate(VI) is produced by precipitating with an alkaline solution of nitrate from a slightly alkaline solution of potassium ferrate [51]. These promising methods for synthesising ferrate(VI) are briefly described in the next paragraphs. Wet oxidation method for ferrate production The wet oxidation method for ferrate production has been extensively used by several researchers to produce solid or liquid ferrate, especially sodium and potassium ferrate(VI) [52-54]. Generally, this method uses cheap and less toxic chemicals such as sodium hypochlorite, any source of ferric ions, and alkalis such as sodium hydroxide, potassium hydroxide, calcium hydroxide, which are also familiarly used in the treatment of water and industrial wastewater. Researchers have preferred to utilise either ferrous or ferric salts as a main source of iron to be oxidised into ferrate(VI), calcium or sodium hypochlorite preferably with higher concentrations greater than 12% or sodium thiosulphate or chlorine as oxidisers, and sodium hydroxide or carbonate or potassium hydroxide to increase the pH of the medium [17]. For instance, Thompson et al. [52] reacted liquid FeCl3 with NaOCl in the presence of NaOH to yield a sodium ferrate (Na2FeVIO4) as shown in Equation 1.

2FeCl3(l) + 3NaOCl(l) + 10NaOH(l) → 2Na2FeO4(l) + 9NaCl(s) + 5H2O(l)

(1)

From equation 1, ferric chloride is the iron source and can be replaced by other ferrous or ferric salts such as ferrous sulphate heptahydrate, ferric nitrate nonahydrate, ferric hydroxide or oxide, and ferric sulphate nonahydrate, etc. In some case, the mentioned oxidisers can also be replaced by a chlorine gas. Numerous measures have been set to synthesise solid Na2FeO4, though, there were many complications in separating any solid products from the resulting solutions, as this ferrate salt has a high solubility in a concentrated NaOH solution [28]. For the purpose of raising the ferrate(VI) production efficiency, KOH replaced NaOH and thus the transitional formation of Na2FeO4 in the synthesis was stopped. Therefore, the yield of K2Fe(VI)O4 salt increased up to 75%. The high purity of the solid product can be made up to 99%, by a precipitation process where K2FeO4 can be isolated or precipitated out from the potassium hydroxide solution as shown in Equation 2 and by carrying out numerous dissolution and precipitation steps [55,56]. Though, the process consumes a lot of alkali solutions and thus, has made the high purity ferrate(VI) salts very expensive [17,53,57].

Na2FeO4(l) + 2KOH(l) → K2FeO4(s)↓ + 2NaOH(l)

(2)

The preparation of other alkali metal ferrate(VI) salts such as rubidium or caesium ferrate(VI) can also follow the same procedure of sodium and potassium. In addition, through this wet method, alkaline earth metal ferrate(VI) salts such as strontium or barium can also be prepared in a highly alkaline 44


Production, Characterization and Application of Ferrate(VI) in Water and Wastewater Treatments

Review

potassium ferrate(VI) as shown in Equation 3 [48,49,57].

K2FeO4(s) + BaCl2(s) â&#x2020;&#x2019; BaFeO4(s) + 2KCl(s)

(3)

However, the application of barium ferrate in water and wastewater treatment is constrained by the toxicity of barium ion released. Hence, ideally ferrate salts should include counter ions such as sodium, potassium, magnesium and calcium with no toxicity in product water. The production of ferrate by wet methods is widely reported in literature, however, the solution of ferrate produced is highly unstable. Hence, more studies need to be done to produce either solid or liquid ferrate of high stability at high concentrations in order to use it in water and wastewater treatment conveniently. Thermal method for ferrate production The thermal method for ferrate production which is also known as the dry oxidation method has been intensively used in the beginning as a trial method by many researchers to synthesise solid ferrate salts [58]. These researchers produced ferrate salts by calcinating together iron filings with nitrates or by mixing iron oxides with alkali and nitrates at high temperature [58,59]. Ferrate salts can also be prepared using the thermal method by calcinating a mixture of K2O2 with Fe2O3 or by heating Fe2O3 with Na2O2 at elevated temperature and pressure with a continuous flow of dry oxygen [17,58]. However, the resulting products were considered to contain Fe4O54- anions, which can be further hydrolysed to form a tetrahedral FeO42- ion as shown in Equation 4, resulting in a red-violet solution [60].

Fe4O54-(s) + H2O(l) â&#x2020;&#x2019; FeO42-(aq) + 2OH- (aq) (4)

To avoid detonation, this method has been tried at room temperature by several [23,61,62]. For example, Evrard et al. [61] combined ferrous sulphate heptahydrate with calcium hypochlorite to produce potassium sulphatoferrate as shown in Equation 5.

2FeSO4.7H2O(s)+Ca(ClO)2(aq)+6KOH(s) â&#x2020;&#x2019; 2K2(Fe,S)1/2O4(aq)+2KCl(aq)+ Ca(OH)2(aq) +9H2O(l) (5)

Even though this process has been comparatively recognised as high production efficiency of ferrate(VI), it has been considered as non-economic since calcium hypochlorite is still an expensive oxidant [23]. Therefore, Kanari et al. [62] substituted calcium hypochlorite by chlorine for the oxidation of ferrous sulphate. The dry synthesis at high temperature is an advantageous process compared to the wet method, which may cause the decomposition of the final product in an aqueous medium. At the same time, the thermal method has got its own limitation, showing a lower thermal stability. Even if this method can look to be a green technology because of recycling various iron waste materials, it is no longer being used to prepare ferrate(VI) salts due to the fact that elevated temperatures can enhance detonation, which is considered dangerous and too difficult to control. There is no or little evidence in literature to support the use of thermal method for mass production of ferrate to meet the needs of water and wastewater treatment sectors. Hence, there is still a huge opportunity to develop commercially viable ferrate production technologies capable of producing quantities which will meet water and wastewater treatment sectors cost-effectively. Electrochemical method for ferrate production The last method used to prepare ferrate(VI) salts in this review is the electrochemical process. Through this method, ferrate(VI) salts can be produced by anodic oxidation of iron(II) electrode in an electrolysis cell comprising of a concentrated solution of KOH(aq) or NaOH(aq) [43,45]. The main cathodic and anodic reactions involved in this method are represented by equations 6-9.

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Cathodic reaction: 6H2O(aq) + 6e- → 3H2(g) + 6OH-(aq)

(6)

Anodic reaction: Fe2+(aq) + 8OH-(aq) → FeO42-(aq) + 4H2O(l) + 6e-

(7)

Overall reaction: Fe2+(aq) + 2OH-(aq) + H2O(l) → FeO42-(aq) + 3H2(g)

(8)

And: FeO42-(aq) + 2K+(aq) (or 2Na+) → K2FeO4(s) (or Na2FeO4(aq) )

(9)

The electrochemical synthesis of ferrate(VI) can generate a pure product with respect to other preparation methods. Moreover, the anodic polarisation of the iron electrode in the molten hydroxide is more reasonable when compared to the conventional electrolysis in an aqueous medium since ferrate(VI) is decomposed by water and passivation significantly is reduced in this environment [63]. However, there exists some drawbacks related with electrochemical method of ferrate(VI) salt production, including the production of a residual passive film on the surface of the electrode and the level to which the competitive oxygen evolution reaction is present, at the ferrate(VI) formation potential to room temperature. All of this can decrease the efficiency of the ferrate(VI) synthesis procedure [9]. It also involves high concentrations of electrolytes and can encounter some difficulties with the current. Furthermore, the use of potassium hydroxide for the synthesis of K2FeO4 and applications in water treatment will also have the same restrictions. The separation of solid or dry K2FeO4 can also involve several procedures; causing economic disadvantages. However, to reduce the cost of synthesis of ferrate(VI), sodium hydroxide was proposed as the best alkaline medium during this electrochemical method [45]. Electrochemical techniques of ferrate production are still too expensive to produce enough quantities which will meet the needs of water and wastewater treatment sectors. CHARACTERISATION OF SYNTHESISED FERRATE(VI) As usual, once the product is synthesised, it needs to be physically and chemically characterised to confirm if the expected product was formed. However, there are many techniques which are utilised to characterise the produced ferrate(VI) according to its physical and chemical properties [64]. These analytical techniques are described in the following paragraphs. Quantitative estimation of ferrate(VI) Ferrate(VI) may be analysed quantitatively by the methods described in the following subsections. Volumetric analysis method In this method, the prepared ferrate(VI) solution is allowed to oxidise the chromite salt (in excess) as a shown in Equation 10:

FeO42- + Cr(OH)4- + 3H2O → CrO42- + Fe(OH)3(H2O)3 + OH-

(10)

However, the oxidised chromate can be then titrated with an iron(II) salt solution in an acidic medium. The sodium diphenylamine sulfonate can further be served as a suitable indicator [44,65,66]. Even if the volumetric analysis technique is used for quantitative analysis of ferrate(VI) salts, degradation of these salts is very rapid in aqueous solution. Thus, phosphate buffer solution is highly needed to keep pH of the ferrate(VI) solution at 8. The other biggest disadvantage of this method is that the generated waste needs to be kept and treated before being discarded as it normally produces chromium residual, which is highly a toxic metal for both humans and the environment [44]. UV-Visible (UV-Vis) spectroscopy The UV-Vis technique also known as a direct colorimetric method is suitable for quantification of 46


Production, Characterization and Application of Ferrate(VI) in Water and Wastewater Treatments

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liquid ferrate(VI) solution. It is founded on determining the concentration of a given solution due to the intensity of the colour absorbed. In the case of ferrate(VI), the characteristic darkish purple colour corresponds to the visible spectrum between 500 and 800 nm [67]. Bielski and Thomas [68] observed a valuable peak at 510 nm at pH 10 with a shoulder of 275 and 320 nm. Denvir and Pletcher [69] also reported the absorption spectrum of ferrate(VI) at 505 nm. Two minima of absorbance at 400 and 678 nm and another absorption shoulder at 570 nm have been observed [60,70]. The molar absorptivity of ferrate(VI) salt was confirmed to vary between 1150 and 1170 M-1 cm-1, which can help to determine quantitatively the concentration of ferrate(VI) at pH 9 [44,71]. Like other methods in analytical chemistry, this method presented some drawbacks because some salts such as barium ferrate(VI) are characterised by low solubility especially in aqueous solution. Moreover, most ferrate(VI) salts tend to decompose in aqueous solution into ferric hydroxides, which can provoke some noise peaks during UV-Vis analysis. This can be avoided by mixing phosphate buffer with ferrate(VI) solution to make complexes with these ferric hydroxides. This technique can also be applied to determine the rate constants of reactions of ferrate(VI) [72]. Indirect method of ferrate(VI) determination using ABTS Lee, Yoon and von Gunten [72] proposed an indirect method to find out even the lower concentration of ferrate(VI) that can be difficult to measure using 2,2â&#x20AC;&#x2122;-azino-bis(3-ethylbenzo-thiazoline-6-sulfonate) (ABTS). However, the colourless ABTS interacts with ferrate(VI) to generate ABTSâ&#x20AC;˘+ (a green radical cation of ABTS), which normally shows a representative peak at 415 nm [44,72,73]. Fourier transform-infrared (FT-IR) spectroscopy The FT-IR is a method which is frequently used by many researchers to characterise different ferrate salts in a powder form. It normally uses two types of methods, which are diffuse reflection method and Nujol method. When measuring an infrared spectrum using the diffuse reflection method, the sample powder is normally not measured directly, but diluted in an alkali halide, such as KBr by forming a sheet that is transparent in the infrared region. For the Nujol method, the sample is distributed in a liquid of approximately equal refractive index, and the infrared spectrum is further measured. Generally, the powder is dispersed in non-volatile liquid paraffin (Nujol) that has low absorption in the infrared region. FT-IR provides a primary peak for ferrate salt around 808 cm-1 and a shoulder peak can also be observed approximately at 780 cm-1, which point out to the asymmetric stretching vibrations of the ironoxygen bond in the ferrate(VI) compound [74]. The more the intensity of the characteristic vibrational peak of ferrate(VI) is strong, more the purity of the prepared ferrate(VI) is also higher. FT-IR can also be used to study the structures of degraded pollutants after being exposed to ferrate as an oxidant [8]. Scanning electron microscopic study The Scanning electron microscopy (SEM) is currently used to characterise the ferrate(VI) salts in the powder form by providing some micrographs or structural images of the product. For example, Lei, Zhou, Cheng & Du [60] characterised the potassium ferrate(VI) using the SEM analysis where the crystals obtained were plump, columnar and had cone-shaped growth surface at the two ends of the crystalline grains. X-Ray powder Diffraction (XRD) method The XRD is another method which goes together with FT-IR and SEM analyses in order to confirm the crystallinity, structures and magnetic properties of the ferrate(VI) salts. The XRD is one of the analytical facilities used to indicate the presence of ferrate(VI) by demonstrating the isomorphism with other ferrate salts obtained in the literature [45,60]. For example, in the study conducted by Lei, Zhou, Cheng and Du [60], their XRD pattern results indicated an orthorhombic crystal structure of ferrate(VI) salt. 47


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Mössbauer spectroscopy Mössbauer spectroscopy allows detecting the oxidation state of iron. Thus, it can help to determine the degradation rate of Fe(VI) in ferrate(VI) ion over time. It also helps to check the presence of a magnetic order at low temperature [44,45]. STABILITY STUDIES OF FERRATE(VI) SALTS Stability of ferrate(VI) solution depends on factors such as coexisting ions in the solution, temperature, pH and concentration of the solution. About the temperature of the solution, research showed that are more stable at a low temperature approximately at 0.5 ºC. For example, a solution of 0.01 M ferrate(VI) remained almost unaffected for a period of 2 hours at 0.5 ºC while a reduction of 10% was observed when was increased to 25 ºC [75]. About the concentration of the solution, studies revealed that highly concentrated solutions of ferrate(VI) are unstable compared to their serial dilutions. For conservation or coexistence of ions and pH of the solution, coexistence of ions such as Fe2+, Mn2+, CO32- has been reported to affect the stability of Fe(VI) in previous studies and spontaneous decomposition was shown to be directly proportional to the decrease of pH value [55]. Phosphate buffer solution and high concentration of potassium hydroxide (more than 10 M) were found to retard the ferrate(VI) degradation. Nitrate ions and diatomite can also be used for the conservation of ferrate(VI) salts [75]. In another study, sodium ferrate(VI) in 50% of sodium hydroxide degrades gradually at ambient temperature and can be preserved with slight degradation for a period of one month at 0 ºC [76]. Solid ferrate(VI) salts showed to be more stable compared to their dissolved derivatives. Due to its high stability, dry potassium ferrate(VI) at temperature below 198 ºC can be used to prepare other ferrate(VI) salts such as silver, strontium and barium ferrate(VI) salts [77]. Despite these factors that can affect the stability of ferrate(VI), some preparation methods can conduct to an unstable product. Wet oxidation method is the one showed to be more successful and practical compared to electrochemical and dry methods, but it also showed some weaknesses of generating an unstable ferrate(VI) product as the reaction occurs in the aqueous medium. In-situ electrochemical synthesis of ferrate(VI) can be also a reliable technique for getting a more stable product. In the study conducted by Panagoulopoulos [78] at the University of Surrey to assess the performance of K2FeO4 in water and wastewater treatment, conservation conditions showed that light has no effect on the stability of ferrate(VI) solutions. APPLICATION OF FERRATE(VI) SALTS The ability of ferrate(VI) to act as a disinfectant, flocculant, oxidant, and coagulant makes it more attractive than other existing chemicals currently being applied in water and wastewater treatments such as aluminum sulphate, ferric chloride, potassium permanganate and chromium trioxide. However, using ferrate(VI) as a multipurpose chemical offers several advantages such as reduction of cost for treatment due to coagulating and oxidising properties in a single dosing and mixing unit and generating environmentally friendly by-products [58,79]. For example, De Luca et al. [80] compared the coagulating activities of ferrate(VI) to alum, and their results showed that ferrate(VI) removed the higher percentage of bromodichloromethane, 1,2-dichlorobenzene, naphthalene, and trichloroethylene when coupled with paddle or gas flocculation than alum. Two oxidation methods, viz., Fenton’s reagent and ferrate(VI), treating mature leachate containing organic material such as humic substances from landfills were also compared in another similar study conducted by Batarseh et al. [81]. Fenton’s reagent is also known as a powerful AOP, which uses hydrogen peroxide and iron(II) to generate the hydroxyl-free radical. Like ferrate(VI), Fenton’s reagent may also act as a coagulant because of the ferrous iron generated through its sequestration. However, both oxidation methods were found to remove organic materials through physical and chemical processes. Even if Fenton’s reagent reduced dissolved organic carbon (DOC) and chemical oxygen demand (COD) more than ferrate(VI) and generated more readily biodegradable by-products (BBPs), ferrate(VI) was more advantageous because it was active over a wider pH range [81]. The lower the pH, the greater removal of organic compounds revealing the strong 48


Production, Characterization and Application of Ferrate(VI) in Water and Wastewater Treatments

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capacity of ferrate(VI) to work in the acidic medium. Both processes reduced leachate organic content to acceptable release limits. However, the Fentonâ&#x20AC;&#x2122;s reagent could be utilised as a pre-treatment to biological treatment while ferrate(VI) should be used where BBPs are not required [81]. Ferrate(VI) has also been applied to oxidise different pollutants such as sulphur- and nitrogen-containing compounds [21]. Results showed that the reaction between ferrate(VI) and sulphur or nitrogen-containing pollutants followed the first-order reaction kinetics with the reaction rate increasing with a decrease in pH values. At stoichiometric values, ferrate(VI) was able to oxidise hydrogen thiocyanate, thioacetamide, sulphide, thiourea, and cyanide to non-hazardous by-products. Ferrate(VI) also sequestrates into ferric ions in an aqueous medium, another harmless by-product which can further be used in the coagulation processes [24,50,79,82]. During coagulation, the floc size is larger when applying ferrate(VI) as opposed to alum, suggesting that a ferrate(VI) is a better coagulant because of reduced turbidity observed in highly organic waters [22,41]. When used as a disinfectant, studies have shown that ferrate(VI) salt is more effective than chlorine in reducing different types of bacteria and viruses [37,78]. Furthermore, ferrate(VI) has been used to control odour, to remove pharmaceutical pollutants such as amoxicillin, ciprofloxacin, 2,4-dichlorophenoxyacetic acid, and flurbiprofen from wastewater [74], to stabilise and dewater primary sludge [83], and to remove freshwater humic substances from water [84]. Interest has also been focused on the reaction of ferrate(VI) salts with several organic contaminants. For example, Waite and Gilbert [85] studied the impact of ferrate(VI) on benzene, toluene, xylene, chlorobenzene, nitrobenzene, aniline, allylbenzene, and phenol. Phenol and naphthalene were also 100% degraded during a study performed by De Luca et al. [86]. Trichloroethylene was also significantly degraded at 96.2%. Graham et al. [87] found the decomposition of phenol by ferrate(VI) ion at a molar ratio of 5:1 [ferrate(VI): phenol] to be greatest at pH 9.2. The degradation greatly decreased to a pH of 11 due to the low reactivity of ferrate(VI). Very different outcomes were obtained for the reaction between ferrate(VI) and 2,4- trichlorophenol (TCP). The pH range for the highest decay was 5.8-7.0. Above 7, the degradation of TCP decreased progressively. The molar ratio of 5:1 again gave the highest percentage degradation around 87%. Recently, Sun et al. [88] also produced ferrate(VI) solution using the electrochemical method and this has been used to decompose phenol in water at two concentration levels (2 and 5 ppm). The maximum degradation efficiency was approximately 70% and the optimum pH for phenol treatment was 9.0 [88]. Experimental studies conducted by treating phenol using other predictable coagulants such as polyaluminum chloride (PAC) and ferric chloride revealed that the elimination of phenol by ferrate(VI) occurred mostly by oxidative conversion [88]. In another study, the removal of fulvic acids (FA) and humic substances (HS) with ferrate(VI) has also created attention because of its coagulating and oxidising properties. The proper dose of ferrate(VI) and the pH of the reaction between ferrate(VI) and HS or FA were optimised [24]. The ferrate(VI) dosages ranged from 0 to 20 ppm and the pH values tested were 4, 5, 6 and 8. The effectiveness of ferrate (VI) was tested against the performance of ferric sulphate (FS) to reduce the compounds listed above [89]. Ferrate(VI) performed better than FS at removing DOC at pH 6 and 8, and a dosing range of 2-12 ppm as Fe. Over a dosing range of 2-14 ppm as Fe with the same values of pH, ferrate(VI) also removed more UV 254-absorbing compounds. Ferrate(VI) was successful at removing colour at all pH ranges and at dosages of 6 ppm or greater [89]. At low dosages, ferrate(VI) was superior to FS for preventing THM formation. Although, at higher dosages of ferrate(VI), THM formation increased, while for FS, the THM formation remained constant [89]. The above results showed that ferrate(VI) was superior to FS in eliminating natural organic matter, which can produce DBPs when reacting with chlorine. The study of Cooley [89] also compared the capacity of ferrate(VI), chlorine, aluminum sulphate (AS), and FS in inactivation of E. coli, removal of total COD and dissolved COD. Ferrate(VI) required a much lower dosage requirement of 6 ppm as Fe to inactivate 100% E. coli, while FS with chlorine required either 4 or 8 ppm as Fe, and 10 or 8 ppm as chlorine, respectively. Lastly, less sludge was produced, while more pollutants were removed, when ferrate(VI) was used as a coagulant. The same concentrations of AS and FS were used as ferrate(VI), in millimoles as aluminum or iron, respectively. At lower dosages, 49


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ferrate(VI) still generated less sludge and removed more pollutants [89]. These experimental studies further confirmed that ferrate(VI) can be applied as a disinfectant, oxidant and coagulant of wastewater and water treatment. Decomposition of benzothiophene (BT) in an aqueous medium by K2FeO4 was also investigated [90,91]. The decomposition efficiency of BT has been recorded at several values of pH and ferrate(VI) dosages at a fixed initial concentration of BT. This BT was removed promptly within 30 seconds by K2FeO4 while the highest decomposition efficiency was reached at pH 5 and the lowest one at pH 9. Similarly, the initial rate constant of BT increased with the decreasing of the initial concentration of BT [92]. Lee and Tiwari [92] used ferrate(VI) to remove Ni, Cu and Cu-Ni cyanide complexes in an effort to deal with metal-complexed cyanide wastes. On one hand, for Ni and Cu cyanide system, a fast and productive oxidation of cyanide ion happened at pH 10 in these complexes; almost a complete Cu removal was relatively reached at pH 13. On the other hand, Ni concentration was only attenuated at pH 10 through precipitation process and then decreased when pH increased to 13 [92]. Comparable results were also detected in Cu-Ni cyanide complex, where a complete removal of Cu and CN was attained treating with ferrate(VI) while Ni was partially eliminated. Li, Wang, Liu and Zhang [5] and Lee, Um and Yoon [10] investigated the oxidising ability of the K2FeO4, ferrate(VI)– hypochlorite liquid mixture and KMnO4 by decolourising the azo dye Orange II. However, K2FeO4 showed to be more effective than KMnO4 while the ferrate(VI)–hypochlorite liquid mixture containing a residual hypochlorite was even more effective whether the low dosage of ferrate(VI) solution or high concentration of dye was used. The initial pH of the solution had little influence on the colour elimination by the ferrate(VI)–hypochlorite liquid mixture. KMnO4 was also applied to degrade an Active Brillant Red X-3B (9% of TOC and 42% of COD and 99% of colour removal) [93] and for wastewater treatment comprising anthraquinone and azo dyes (colour removal of 87%) [13]. Additionally, the oxidation ability of ferrate(VI) to remove various pollutants in water and wastewater has been established [44]. These pollutants include thiocyanates, sulphides, ammonia, metal cyanide complexes, iodides, heavy metals, carbohydrates, cycloalkanes, toluene, alcohols, ketones, phenols, aminobenzene, emerging micropollutants such as pharmaceutical and personal care products (PPCPs) and endocrine disrupting chemicals (EDCs), triclosan and benzotriazoles. Among these environmental pollutants, ferrate(VI) showed to be very effective in the removal of arsenic species from water at a comparatively low concentration level (2 ppm) [44,92,94-96]. Moreover, the combined application of low concentration of ferrate(VI) (below 0.5 ppm) and Fe(III) as the main coagulant agent was found to be an effective process for the arsenic removal. Pharmaceuticals in water and wastewater treatment processes, including photo-catalytic degradation, ozonation and other AOPs have been explored by several researchers [74]. Lately, ferrate(VI) has been studied widely, as it could be an effective alternative to conventional AOPs for the degradation of pharmaceutical pollutants. Ferrate(VI) has many benefits due to its oxidising and coagulating properties. Thus, ferrate(VI) is likely to be one of the most useful and multifunction chemicals in water and wastewater treatments. Ferrate(VI) has been applied in the breakdown of N-nitrosodimethylamine (NDMA) from aqueous media under the simulated batch reactor (SBR) operations [29]. The degradation of NDMA was followed by the second-order rate constant at a wide pH range of 6–12 [97]. A β- blocker propranolol was also treated with ferrate(VI) in the SBR system [98]. A preliminary but useful study was conducted for the detection and treatment of ciprofloxacin from wastewaters. It was found that ferrate(VI) enabled to remove more than 60% of ciprofloxacin and this was even increased at higher concentrations of ferrate(VI), that is, at 1 ppm [96]. The 5-chloro-2-[2,4dichlorophenoxy]-phenol with commercial name of Triclosan, which is an antimicrobial agent and extensively used as PCPs, seemingly enters into the aquatic environment was treated with ferrate(VI) at pH ranging between 7 and 10. The overall apparent rate constant was found to be 746 M−1 s−1 at pH 7.0 and a complete decomposition was reached at the ferrate(VI) to pollutant ratio of 10:1 [94]. Bisphenol-A (BPA) was degraded slightly at acidic conditions pH range of 5-6 and showed that about 50% of BPA was apparently mineralised at the ferrate(VI)/BPA molar ratio 4:1. It was also confirmed that the oxidation of BPA was suppressed in the presence of metasilicate, humic acid and tert-butanol, 50


Production, Characterization and Application of Ferrate(VI) in Water and Wastewater Treatments

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whereas the oxidation of BPA was further increased in the presence of hydrogen carbonate ions [99]. A more descriptive study was also conducted in the oxidative removal of other EDCs, namely: 17ι-ethynylestradiol (EE2), estriol (E3), β-estradiol (E2), and estrone (E1) at a pH range 8 to 12 [44,95]. The results indicated that ferrate(VI) was more reactive at lower pH conditions and also followed secondorder rate kinetics in the degradation of these pollutants [100]. These studies confirmed that ferrate(VI) is a strong oxidant for efficient degradation of water emerging micropollutants such as PCPs and EDCs as well as pharmaceuticals. Other studies also demonstrated that ferrate(VI) is a useful oxidant in the degradation of several metal-complexed species, organic and inorganic pollutants and the sequestrated ferrate(VI) into iron(III) enabled to remove significantly the free metallic impurities by coagulation process [92,101,102]. Also, all advantages and disadvantages of using ferrate(VI) as oxidant and disinfectant are shown in Table I. Table I. Advantages and disadvantages of using different current oxidants and disinfectants Oxidant and disinfectant

Advantages

Disadvantages

Chlorine

-Low cost

-The possibility of producing dangerous byproducts such as three halomethanes

-High removal efficiency -Availability -The possibility of long-term storage of chlorine in cylinders Ozone

-Toxicity for water and sewage treatment plant staffs -The need to dechlorinate treated wastewater before releasing into environment

-High capacity and high speed of oxidation and disinfection

-Possibility of remaining few cysts and viruses after disinfection process

-Converting of ozone to oxygen after disinfection process

-Oxidation by ozone requires complex equipment

-Non-toxic by-products

-The high price of ozone production

-Ability of odour and taste removal

-Producing of solid by-products -Corrosion in the equipment of water and wastewater treatment

Ferrate(VI)

-Excessive capacity of oxidation and disinfection -Non-toxic by-products

-Low ferrate(VI) production rate -Lack of stability for long-term storage

-Ability of colloidal particles coagulation -Ability of coagulation, oxidation and disinfection simultaneously -Needing smaller wastewater treatment plant -Low application cost -Ability of heavy metal and inorganic removal

CONCLUSION This review found that ferrate(VI) salts are currently applied in water and wastewater treatment processes at piloting levels due to their strong oxidising, disinfecting, flocculating and coagulating tendencies. The reviewed studies also indicated that ferrate(VI) can remove bacteria, partially or totally 51


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oxidise or degrade inorganic and organic pollutants, emerging micropollutants such as EDCs, PPCPs, illicit drugs, reduce or completely precipitate suspended particulate materials, metals, and metalcomplexed species in a single mixing and dosing unit. Other studies also demonstrated that ferrate(VI) is a useful coagulating agent as the sequestrated ferrate(VI) into iron(III) (environmentally-friendly ferricbased compounds) enabled to remove significantly free metallic impurities through coagulation and sedimentation processes. Under acidic conditions, the oxidation potential of the ferrate(VI) salts is higher than any other oxidant that can be applied in water and wastewater treatment processes. Regardless of several valuable properties in environmental studies, ferrate(VI) continued to be unavailable on the market due to the high cost of production and chemical instability. Three promising methods for manufacturing liquid of solid ferrate(VI) were also identified in this review, namely: wet chemical oxidation method, dry method and electrochemical method. For this reason, several studies have been conducted to explore its effective application in full-scale water and wastewater treatments. Stability of ferrate(VI) solution depends on many factors such as coexisting ions in the solution, temperature, pH and concentration. For temperature of the solution, research showed that ferrate(VI) salts are more stable at low temperature approximately at 0.5 ยบC. Phosphate buffer solution and high concentration of potassium hydroxide (more than 10 M) were found to retard or decline the ferrate(VI) degradation. Nitrate ions and diatomite can also be used for the conservation of ferrate(VI) salts. In another study, sodium ferrate(VI) in 50% of sodium hydroxide degrades gradually at ambient temperature and can be preserved with slight degradation for a period of one month at 0 ยบC. Solid ferrate(VI) salts showed to be more stable compared to their dissolved derivatives. Wet oxidation method is the one showed to be more successful and practical compare to electrochemical and dry methods, but it also showed some weaknesses of generating an unstable ferrate(VI) product as the reaction occurs in the aqueous medium. To avoid this, washing and drying of the final product can direct to the stable ferrate(VI). Insitu electrochemical preparation of ferrate(VI) can also be a reliable technique for getting a more stable product. Lastly, conservation conditions showed that light has no effect on the stability of ferrate(VI) solutions. Recommendations Much work has been done on water and wastewater treatment by removing, degrading, disinfecting, and oxidising different inorganic and organic pollutants as well as emerging micropollutants, but a few works have been done on removing metals from wastewater as well as for acid mine drainage (AMD) using ferrate(VI) salts. The authors recommend also to apply these ferrate(VI) salts in AMD treatment as they can work as a powerful disinfectant, coagulant and oxidant in order to reduce the energy consumption during aeration and pumping, and prevent generation of toxic by-products currently encountered during the AMD treatment. Self-decomposition of ferrate(VI) salts provides ferric ions in the solution and latter can be used to remove sulphates and other metal ions through co-precipitation and coagulation processes. Acknowledgement This work has been financially supported by the Faculty of Science, University of Johannesburg, South Africa. The authors would like also to thank the group members from the LAB 3404 and Prof. Philiswa N. Nomngongo, Doornfontein Campus, University of Johannesburg, South Africa. Manuscript received: June 4, 2019; revised manuscript received: August 26, 2019; manuscript accepted: October 3, 2019; published online: October 18, 2019.

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Production, Characterization and Application of Ferrate(VI) in Water and Wastewater Treatments

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Technical Note

Br. J. Anal. Chem., 2019, 6 (25) pp 58-66 DOI: 10.30744/brjac.2179-3425.TN-25-2019

Point-of-use Determination of Fluoride and Phosphorus in Water through a Smartphone using the PhotoMetrix® App Cristiane Pappis Oliveira Santos

Marcia Librelotto Luiza Baumann Alessandra Betina Parckert Roberta Iberê Damé Teixeira Gilson Augusto Helfer Eduardo Alexis Lobo Adilson Ben da Costa*

Universidade de Santa Cruz do Sul, 96815-900, Santa Cruz do Sul, RS, Brazil

Graphical Abstract

The PhotoMetrix® application was used as a colorimetric analysis tool to determinate the fluoride and phosphorus ion concentration in treated and natural waters.

This research aimed to demonstrate the use of a colorimetric analysis tool using a smartphone application called PhotoMetrix® to determinate the fluoride and phosphorus ion concentration in treated and natural waters. The determinations were made using the conventional spectrophotometric approach [2-(4-sulfophenylazo)-1,8-dihydroxy-3,6-naphthalene disulfonate (SPADNS) reagent for fluoride measurements and the molybdenum blue reaction for phosphorus measurements], and then a smartphone equipped with the PhotoMetrix® application was used to compare the results obtained by the two procedures. An analytical curve was developed, and three triplicate samples were analyzed. The coefficient of determination (R2) for phosphorus and fluoride for the conventional method and for the method using the PhotoMetrix® application were 0.990 and 0.998, and 0.999 and 0.999, respectively. The average results obtained using the application showed satisfactory correspondence values of 99.2% (phosphorus) and 100% (fluoride) compared to the reference method. No significant differences between the two methods of quantification were identified (p>0.05, paired t-test). In conclusion, the results demonstrated the efficiency of this new analytical tool, which allows for quick and accurate analysis of fluoride and phosphorus ion concentrations in the field, as well as on an industrial scale. Keywords: smartphone, water analysis, fluoride, phosphorus, point-of-use INTRODUCTION Safe drinking water, whether treated or from a natural source, as defined by the World Health Organization (WHO), should not represent any significant risk to health throughout life, regardless of the 58


Point-of-use Determination of Fluoride and Phosphorus in Water through a Smartphone using the PhotoMetrix® App

Technical Note

consumer’s level of sensitivity [1]. Consequently, the microbiological, physical, and chemical parameters of drinking water must meet certain standards [2,3]. Globally, due to violations of the recommended standards of potable water, around 1.1 billion people lack access to safe drinking water [1,4–6]. The analysis of water quality is extremely important because it enables the detection of various substances, such as fluoride and phosphorus ions [7,8]. The determination of these parameters is usually performed by colorimetric methods commonly applied in the investigation of chemicals in treated waters. Such procedures replace the subjective color responses with an objective numerical system, which allows for the quantification of substances present in the analyzed samples [9]. As established by the regulatory bodies for drinking water, a maximum concentration of 1.5 mg L-1 of fluoride is permitted [1]. The presence of this ion in drinking water at controlled levels is important for human health because it prevents cavities. However, excessive ingestion of this substance may cause dental fluorosis, increase the incidence of bone fractures, and impair thyroid function [1,10]. Fluoride can be determined using several methods, such as ion chromatography, gas chromatography, electrochemical procedures, spectrometric measurements, and fluorescence [11–16]. One of the most widely used methods for the determination of fluoride is the 2-(4-sulfophenylazo)-1,8-dihydroxy-3,6naphthalene disulfonate (SPADNS) spectrophotometric method. However, a spectrophotometer is required for the absorbance measurements, and the analysis is not yet suitable for in situ monitoring [17]. In addition to fluoride, phosphorus analysis is also of extreme relevance because, at elevated levels, phosphorous leads to eutrophication and the occurrence of harmful algal blooms [18]. One example is the occurrence of toxic cyanobacterial blooms in surface water supplies [19]. According to Brazilian legislation, a maximum concentration of 0.15 mg L-1 of phosphorus is allowed in a lotic environment and in tributaries of intermediate environments [20]. In natural waters, phosphorus can be found in various “dissolved” forms, mostly as inorganic orthophosphates, condensed or polyphosphates, and organic phosphates. Among the most widely used methods for the determination of phosphorus in natural waters is the molybdenum blue reaction. In this reaction, detection is based on the measurement of molybdenum orthophosphate (PO43-), using either a batch or flow-based approach. Although, inductively coupled plasma (ICP)-based methods (ICP-atomic emission spectrometry and ICP-mass spectrometry) can also be used if the concentration of phosphorous is sufficiently high [21,22]. However, this equipment is relatively expensive, has limited portability, and requires trained operators. Thus, it is worthwhile to develop new techniques for water quality determination that provide rapid, low-cost, and portable analytics. Point-of-use technologies have affordable testing systems that bypass the necessity for specialized personnel. Furthermore, such devices can perform analytical measurements in resource-limited environments (e.g., emergency situations), which is a key advantage compared to conventional benchtop approaches [23]. Some smartphone-based colorimetric assays already exist. For example, in the determination of ochratoxin A and microorganisms, viscosity analysis and measurement of fat in cured meat products [24–31]. Moreover, there are currently free applications (apps) available that can be used to make simple and quick calibration curves. Among these methods is the app called PhotoMetrix®, which allows for image acquisition, processing, and presentation of results. This app uses the device’s main camera to acquire images, which are analyzed and decomposed by punctuations and uploads [24,32]. The smartphone´s camera functions as a portable colorimeter, allowing for accurate tests to be performed economically in the field (in situ) measurements [25]. The app is able to conduct univariate linear regression calibration with variables separated from the red, green, and blue (RGB); hue, saturation, and value (HSV); hue, saturation, and intensity (HSI); and hue, saturation, and lightness (HSL) color systems. The camera of the smartphone responds to red, green, and blue lights, and it can also perform multivariate calibration [32]. The objective of this study was to develop an analytical methodology for the determination of fluoride and phosphorus ions present in natural waters by monitoring the colorimetric reactions involved in conventional methods through a smartphone based PhotoMetrix® app. 59


Technical Note

Pappis, C.; Librelotto, M.; Baumann, L.; Parckert, A. B.; Santos, R. O.; Teixeira, I. D.; Helfer, G. A.; Lobo, E. A.; da Costa, A. B.

MATERIALS AND METHODS Samples, reagents, and standards The samples were collected from March to July 2017 at the University of Santa Cruz do Sul, RS, Brazil. Three different samples were monitored, one subterranean water (artesian well) sample and two samples of water treated with a bone charcoal filter. For the determination of fluoride using the SPADNS technique [33], SPADNS reagent (Synth, Diadema, SP, Brazil), zirconium octahydrate (ZrOCl2.8H2O) (Vetec, Duque de Caxias, RJ, Brazil), HCl (Synth, Diadema, SP, Brazil), and NaF (Synth, Diadema, SP, Brazil) were used. The SPADNS solution was prepared by dissolving 958 mg of the reagent in 500 mL of deionized water. For the preparation of the zirconium oxychloride solution, 133 mg of the reagent was diluted to 500 mL in a volumetric flask containing 25 mL of distilled water and 350 mL of concentrated HCl. Finally, the colorimetric solution was prepared by mixing equal volumes of SPADNS and zirconium oxychloride solutions. The determination of aqueous phosphate through the reduction of phosphomolybdic acid using ascorbic acid was conducted, using sulfuric acid (18.4 M, H2SO4, Synth, Diadema, SP, Brazil), antimony and potassium tartrate solution [40 g L-1, K(SbO)C4H4O6⋅1/2H2O, Vetec, Duque de Caxias, RJ, Brazil], ammonium molybdate [(NH4)6Mo7O24⋅4H2O, Vetec, Duque de Caxias, RJ, Brazil], ascorbic acid (0.1 M, C6H8O6, Nuclear, Diadema, SP, Brazil), and trisodium phosphate (Na3PO4, Synth, Diadema, SP, Brazil). A combined reagent was made by mixing 50 mL of sulfuric acid, 5 mL of the antimony and potassium tartrate solution, 15 mL of the ammonium molybdate solution, and 30 mL of the ascorbic acid solution. Dilutions and reagent preparation were done using distilled and deionized water (>19 MΩ cm-1). Instrumentation The conventional colorimetric reactions were performed using a spectrophotometer [33] (Femto, 600 Plus, São Paulo, Brazil). A Samsung Nexus 5 mobile device, with an Android 6.0.1 operating system, and the PhotoMetrix® app were used. The Photometrix® univariate analysis module was used to perform the calibration and sampling, according to work by Helfer (2017) [24]. The apparatus constructed to analyze the amount of fluoride and phosphorus in the samples through the mobile platform is shown in Figure 1. It consisted of a black, high-density polyethylene box, 42 × 19 × 9 cm in size, with a cover containing an opening for engaging the mobile device. A piece of polytetrafluoroethylene (PTFE, 10 cm in height) was placed in the interior of the box. The piece of PTFE had a central diameter of 1 cm for the addition of the solution and a 0.5 cm diameter in the lateral region for the introduction of a 6 W light emitting diode (LED) lamp. The LED was connected to a device that modulated the power intensity supplied from the battery (9 V) in order to control the intensity of light emitted. The smartphone was positioned on top of the box, and the images were acquired by the main camera (8 megapixel) through the hole in the cover. The luminosity inside the box was maintained with the LED lamp to keep the luminosity variation constant, avoiding the influence of external light.

Figure 1. Apparatus used for the analysis with PhotoMetrix®. 60


Point-of-use Determination of Fluoride and Phosphorus in Water through a Smartphone using the PhotoMetrix® App

Technical Note

Determination of fluoride and phosphorus The determination of fluoride and phosphorus was performed according to the procedures described in the standard methods for the examination of water and wastewater [33]. A calibration curve was constructed from reference solutions of fluoride in the concentration range 0–1.4 mg L-1. After the addition of the SPADNS reagent and zirconium oxychloride (1 mL) in the samples and in the reference solution (5 mL), the color generated in the reaction was measured after 5 min of equilibration time (but no more than 20 min). For the determination of phosphorus, a calibration curve was prepared from a phosphate reference standard at concentrations of 0 to 0.25 mg L-1. After the addition of the combined reagent (8 mL) in the samples and in the reference solution (50 mL), the color generated in the reaction was measured after 10 min (but no more than 30 min). The calibration curves and the samples were analyzed by the conventional method (spectrophotometry at a wavelength of 570 and 580 nm for phosphorus and fluoride, respectively) and by the proposed method. The region of interest (ROI) in the images acquired by the smartphone camera were 64 × 64 pixels (4096 points of color). The univariate analysis module was used (Figure 2) because the procedures adopted in both analyses were related only to one coloration at different intensities with RGB color system variables. All samples were analyzed in triplicate. Before the determination of the analytes by the new method, preliminary tests were done to define the optimal distance between the camera and the solution (i.e., the best LED intensity). Fluoride and phosphorus values were expressed in mg L-1. The figures of merit, such as the accuracy, limit of detection (LOD), and limit of quantification (LOQ), were calculated according to the EURACHEM manual (2014). Estimation of the LOD (3s) and LOQ (10s) was done by considering the analysis of 10 blank samples [34].

Figure 2. PhotoMetrix® application interface, with univariate analysis options shown.

RESULTS AND DISCUSSION Determination of fluoride in water For the determination of aqueous fluoride using the conventional SPADNS method with spectrophotometric absorbance measurements, the calibration curve (y = -0.159x + 0.672) presented a coefficient of determination (R2) of 0.990. In comparison, the smartphone-based colorimetric analysis using the PhotoMetrix® app generated a calibration curve (y = 35.813x - 1.585) with R2=0.998 (Figure 3). Since the PhotoMetrix® app uses the RGB norm vector standard as the analytical answer, the 61


Pappis, C.; Librelotto, M.; Baumann, L.; Parckert, A. B.; Santos, R. O.; Teixeira, I. D.; Helfer, G. A.; Lobo, E. A.; da Costa, A. B.

Technical Note

calibration model always has a positive slope, unlike the spectrophotometer, which uses absorbance values [32,35].

Figure 3. Standard solutions used to create the calibration curve (left) and the calibration plot (right) for fluoride determination with the PhotoMetrix® application [amount of shade × fluorine concentration (mg L-1)].

For the spectrophotometric analysis of fluoride, the LOD and LOQ were estimated to be 0.08 and 0.10 mg L-1, respectively. In the PhotoMetrix® app, the corresponding LOD and LOQ values were estimated to be 0.05 and 0.10 mg L-1. These values show the equivalence of fluoride determination acquired through a smartphone-based colorimetric analysis using the PhotoMetrix® app relative to the conventional method. After establishing the calibration curves and the LOD and LOQ values, the natural and treated water samples were analyzed. Table I provides the fluoride results obtained by the conventional and PhotoMetrix® methods. No significant differences (p=0.6349, paired t-test) were identified between the two results. Table I. Results obtained for the determination of fluoride (mg L-1) (n=3) Sample

Spectrophotometer

PhotoMetrix®

Raw water

1.06 ± 0.004

1.06 ± 0.005

Treated water 1

0.13 ± 0.004

0.13 ± 0.008

Treated water 2

0.42 ± 0.003

0.42 ± 0.005

As indicated in Table I, the raw water sample, which originated from an underground subterranean station, had a higher concentration of fluoride ions than the other samples. Nonetheless, the analyzed natural fountain water was still within the recommended standards for drinking water (1.5 mg L-1). In comparison, the remaining samples presented lower fluoride concentrations because they had undergone treatment in the university itself, which aims to control the amount of fluoride in drinking water. The samples analyzed by the SPADNS method and the colorimetric determinations made by different devices showed highly concordant values. For the raw water, the accuracy of the fluoride reading by the 62


Point-of-use Determination of Fluoride and Phosphorus in Water through a Smartphone using the PhotoMetrix® App

Technical Note

PhotoMetrix® app relative to the spectrophotometric approach was 100.09%, and for the treated waters the accuracy was 98% and 100% for samples 1 and 2, respectively. In previous work [25], fluoride determinations were performed using three different smartphones with the colorimetric analysis app, and the results were compared to the traditional ion-selective electrode technique. The accuracy values (87.6–105%) demonstrated good agreement among the procedure [25]. There are very few studies in the literature that describe the determination of analytes using mobile apps. However, due to several advantages, considerable growth in this research field is anticipated. Furthermore, our study, together with the results documented in similar work, leads us to believe that fluoride determination can be easily combined with the conventional spectrophotometric method (SPADNS) in an easy, fast, and reliable way using mobile devices. Determination of phosphorus in water Through the spectrophotometric determination of phosphorus in natural and treated waters, a calibration curve (y = 0.646x + 0.002) with an R2 equal to 0.999 was obtained. With the PhotoMetrix® app, the calibration curve obtained (y = 414.602x + 1.638) had an R2 value of 0.999 (Figure 4). The LOD and LOQ were 0.012 and 0.018 mg L-1, respectively, for the spectrophotometric determination of phosphorus and 0.010 and 0.019 mg L-1, respectively, for the PhotoMetrix® approach. The LOD and LOQ for the analysis of phosphorus in both methods were similar and very low, being appropriate even for the determination of low concentrations of phosphorus.

Figure 4. Standard solutions used to create the calibration curve (left) and the calibration plot (right) for phosphorus determination using the PhotoMetrix® application [amount of hue × phosphorus concentration (mg L-1)].

The results obtained for the detection of phosphorus in water samples using the respective reference and PhotoMetrix® methods are presented in Table II. No significant differences (p=0.4226, paired t-test) were identified between the two results.

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Pappis, C.; Librelotto, M.; Baumann, L.; Parckert, A. B.; Santos, R. O.; Teixeira, I. D.; Helfer, G. A.; Lobo, E. A.; da Costa, A. B.

Table II. Results obtained for the determination of phosphorus (mg L-1) (n=3) Sample

Spectrophotometer

PhotoMetrix®

Raw water

0.249 ± 0.0009

0.250 ± 0.0010

Treated water 1

0.044 ± 0.0005

0.044 ± 0.0030

Treated water 2

0.051 ± 0.0008

0.051 ± 0.0023

The concentrations of phosphorus found in the treated water samples were within the limits established by Brazilian legislation (maximum phosphorus concentration of 0.15 mg L-1 in non-polluted waters). Moreover, it is possible to verify the agreement between the new method of colorimetric analysis and the spectrophotometric approach, considering an accuracy of 100.4% for the natural water and 100% for the treated waters. A comparative analysis was conducted between the fluorine and phosphorus concentrations obtained by the reference method and those presented by the app for the three water samples. No significant differences between the two methods of quantification were identified (p>0.05, paired t-test). The proposed method uses the same analytical procedure as the reference method; therefore, the use of PhotoMetrix® does not result in a reduction in reagents and materials. However, there is a substantial gain in the time of analysis, the mobility, and the obtaining of results. These benefits arise because the app generates the analytical curve and superimposes the values of the samples directly on the calibration curve, while simultaneously providing the results of the analysis. CONCLUSIONS The study allowed for the development of a new analytical method for the analysis of fluorine and phosphorus using a mobile device app. The assay was applied to natural and treated waters; however, it can be expanded to a wide variety of samples. The analyses carried out by the conventional method and with the PhotoMetrix® app presented concordant values. Also, the new technique exhibited satisfactory figures of merit. The efficiency of this new analysis tool for the determination of fluoride and phosphorus ions present in treated and natural waters highlights its potential for rapid and accessible analysis. Moreover, it represents a valuable method for field analysis and for use on an industrial scale and in a school environment. The developed method also presented advantages when compared to the conventional method because it reduces the analysis time, it enables greater mobility, and it offers a significant increase in the analytical frequency. In addition, the PhotoMetrix® app allows for results to be sent by e-mail in real time to various registered consumers or authorities responsible for the water supply system. Acknowledgments The authors thank the National Council for Scientific and Technological Development (CNPq), the Coordination for the Improvement of Higher Education Personnel (CAPES), and the State of Rio Grande do Sul Research Foundation (FAPERGS). Manuscript received: August 7, 2019; revised manuscript received: November 25, 2019; manuscript accepted: December 9, 2019; published online: December 23, 2019. REFERENCES 1. World Health Organization. Guidelines for drinking-water quality. 2017, p 631 (https://apps.who. int/iris/bitstream/handle/10665/254637/9789241549950-eng.pdf?sequence=1). 64


Point-of-use Determination of Fluoride and Phosphorus in Water through a Smartphone using the PhotoMetrix® App

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2. Ministério da Saúde, Portaria nº 2.914, de 12 de dezembro de 2011. Brasília, Brazil, (http://www. saude.mg.gov.br/index.php?option=com_gmg&controller=document&id=8014). 3. Gwenzi, W.; Dunjana, N.; Pisa, C.; Tauro, T.; Nyamadzawo, G. Sustainability of Water Quality and Ecology, 2015, 6 (Supplement C), pp 107-118 (https://doi.org/10.1016/j.swaqe.2015.01.006). 4. Colvara, J. G.; de Lima, A. S.; da Silva, W. P. Braz. J. Food Technol., 2009, 2, pp 11-14 (http://bjft. ital.sp.gov.br/especiais/especial_2009/v11_edesp_03.pdf). 5. Lia-Beng, T.; Shen-Liang, W.; Kow-Tong, C. J. Chronic Dis., 1997, 50 (Supplement 1), p S7 (https://doi.org/10.1016/S0895-4356(97)87181-8). 6. Katsanou, K.; Karapanagioti, H. K. Encyclopedia of Food and Health, 2016, pp 463-469 (https:// doi.org/10.1016/B978-0-12-384947-2.00742-X). 7. Guissouma, W.; Hakami, O.; Al-Rajab, A. J.; Tarhouni, J. Chemosphere, 2017, 177 (Supplement C), pp 102-108 (https://doi.org/10.1016/j.chemosphere.2017.03.011). 8. Mohammadi, A. A.; Yousefi, M.; Mahvi, A. H. Journal Data in Brief, 2017, 13 (Supplement C), pp 312-315 (https://doi.org/10.1016/j.dib.2017.05.045). 9. Gilchrist, A.; Nobbs, J. Colorimetry, Theory. In: Lindon, J. C.; Tranter, G. E.; Koppenaal, D. W. (Eds.). Encyclopedia of Spectroscopy and Spectrometry (Third Edition), Academic Press: Oxford, 2017; pp 328-333, eBook ISBN: 9780128032251 (https://www.elsevier.com/books/encyclopediaof-spectroscopy-and-spectrometry/lindon/978-0-12-803224-4) 10. Ozsvath, D. L. Rev. Environ. Sci. Bio/Technol., 2009, 8 (1), pp 59-79 (https://doi.org/10.1007/ s11157-008-9136-9). 11. Lou, C.; Guo, D.; Wang, N.; Wu, S.; Zhang, P.; Zhu, Y. J. Chromatogr. A, 2017, 1500, pp 145-152 (https://doi.org/10.1016/j.chroma.2017.04.029). 12. Kwon, S. M.; Shin, H. S. J. Chromatogr A, 2015, 1407 (Supplement C), pp 216-221 (https://doi. org/10.1016/j.chroma.2015.06.066). 13. Tao, J.; Zhao, P.; Li, Y.; Zhao, W.; Xiao, Y.; Yang, R. Anal. Chim. Acta, 2016, 918 (Supplement C), pp 97-102 (https://doi.org/10.1016/j.aca.2016.03.025). 14. Balarama, V.; Mullapudi, V. B. K.; Dheram, K. J. Food Drug Anal., 2018, 26 (1), pp 385-392 (https://doi.org/10.1016/j.jfda.2016.09.001). 15. Zhao, Y. H.; Li, Y.; Long, Y.; Zhou, Z.; Tang, Z.; Deng, K.; Zhang, S. Tetrahedron Lett., 2017, 58 (13), pp 1351-1355 (https://doi.org/10.1016/j.tetlet.2017.02.066). 16. Marques, T. L.; Coelho, N. M. M. Talanta, 2013, 105 (Supplement C), pp 69-74 (https://doi. org/10.1016/j.talanta.2012.11.071). 17. Xiong, Y.; Wu, J.; Wang, Q.; Xu, J.; Fang, S.; Chen, J.; Duan, M. Talanta, 2017, 174 (Supplement C), pp 372-379 (https://doi.org/10.1016/j.talanta.2017.06.024). 18. Lobo, E. A.; Schuch, M.; Heinrich, C. G.; da Costa, A. B.; Düpont, A.; Wetzel, C. E.; Ector, L. Environ. Monit. Assess., 2015, 187 (6), p 354 (https://doi.org/10.1007/s10661-015-4586-3). 19. He, X.; Liu, Y. L.; Conklin, A.; Westrick, J.; Weavers, L. K.; Dionysiou, D. D.; Lenhart, J. J.; Mouser, P. J.; Szlag, D.; Walker, H. W. Harmful algae, 2016, 54, pp 174-193 (https://doi.org/10.1016/j. hal.2016.01.001). 20. Conselho Nacional do Meio Ambiente — CONAMA, Resolução Nº 357/2005, 2005. Available from: http://www2.mma.gov.br/port/conama/legiabre.cfm?codlegi=459 [Accessed 31 August 2019]. 21. Worsfold, P.; McKelvie, I.; Monbet, P. Anal. Chim. Acta, 2016, 918 (Supplement C), pp 8-20 (https://doi.org/10.1016/j.aca.2016.02.047). 22. Chaves, E. S.; dos Santos, E. J.; Araujo, R. G. O.; Oliveira, J. V.; Frescura, V. L. A.; Curtius, A. J. Microchem. J., 2010, 96 (1), pp 71-76 (https://doi.org/10.1016/j.microc.2010.01.021). 23. Giordano, G. F.; Vicentini, M. B. R.; Murer, R. C.; Augusto, F.; Ferrão, M. F.; Helfer, G. A.; da Costa, A. B.; Gobbi, A. L.; Hantao, L. W.; Lima, R. S. Electrochim. Acta, 2016, 219, pp 170-177 (https://doi.org/10.1016/j.electacta.2016.09.157).

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24. Helfer, G. A.; Magnus, V. S.; Böck, F. C.; Teichmann, A.; Ferrão, M. F.; Costa, A. B. d. J. Braz. Chem. Soc., 2017, 28 (2), pp 328-335 (http://dx.doi.org/10.5935/0103-5053.20160182). 25. Levin, S.; Krishnan, S.; Rajkumar, S.; Halery, N.; Balkunde, P. Sci. Total Environ., 2016, 551, pp 101-107 (https://doi.org/10.1016/j.scitotenv.2016.01.156). 26. Peleki, A.; da Silva, A. EJVES Short Reports, 2016, 32, pp 1-3 (https://doi.org/10.1016/j. ejvssr.2016.04.004). 27. Xu, W.; Lu, S.; Chen, Y.; Zhao, T.; Jiang, Y.; Wang, Y.; Chen, X. Sensors and Actuators B: Chemical, 2015, 220, pp 326-330 (https://doi.org/10.1016/j.snb.2015.05.088). 28. Cruz-Fernández, M.; Luque-Cobija, M. J.; Cervera, M. L.; Morales-Rubio, A.; de la Guardia, M. Microchem. J., 2017, 132, pp 8-14 (https://doi.org/10.1016/j.microc.2016.12.020). 29. Roda, A.; Calabretta, M. M.; Calabria, D.; Caliceti, C.; Cevenini, L.; Lopreside, A.; Zangheri, M. Compr. Anal. Chem., 2017, 77, pp 237-286 (https://doi.org/10.1016/bs.coac.2017.05.007). 30. Rateni, G.; Dario, P.; Cavallo, F. Sensors, 2017, 17 (6), p 1453 (https://doi.org/10.3390/ s17061453). 31. Han, P.; Dong, D.; Zhao, X.; Jiao, L.; Lang, Y. Computers and Electronics in Agriculture, 2016, 123, pp 232-241 (https://doi.org/10.1016/j.compag.2016.02.024). 32. http://www.photometrix.com.br/#proj [Accessed 31 August 2019]. 33. American Public Health Association. Standard Methods for the Examination of Water and Wastewater. Washington DC, 2005, 21st ed., ISBN 0-87553-047-8. 34. Eurachem, The fitness for purpose of analytical methods: A laboratory guide to method validation and related topics, 2014, p 75, ISBN 978-91-87461-59-0. 35. Lyra, W. S.; Santos, V. B.; Dionízio, A. G. G.; Martins, V. L.; Almeida, L. F.; Gaião, E. N.; Diniz, P. H. G. D.; Silva, E. C.; Araujo, M. C. U. Talanta, 2009, 77, pp 1584-1589 (https://doi.org/10.1016/j. talanta.2008.09.057).

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Br. J. Anal. Chem., 2019, 6 (25) pp 67-73

6th Analitica Latin America Conference Addressed Topics that are Directly Connected to Industry Demands The 6th Analitica Latin America Conference took place on September 24–26, 2019, at the Convention Center São Paulo Expo, São Paulo, SP, Brazil. More than 35 hours of lectures and debates were offered to 200 participants from universities, research centers and industries, with the objective of disseminating knowledge and increasing interactions between academia and the productive sector.

Attendees at one of the 6th Analitica Latin America Conference lectures. Photo: Analitica Latin America.

The opening lecture, entitled “Applications of Nanotechnology in the Global Cannabis Industry”, was presented by Dr. Sergey Mokin from Purileaf Brands Corporation, Niagara Falls, Ontario, CA. On each day of the Analitica Latin America Conference two topics of great interest were addressed. On the first day the topics covered were “Innovation in Analytical Chemistry” and “Processes and Automation”. The first theme was developed through lectures given by: Guilherme Dal Lago, Head of Innovation from Raízen; Rosele Botelho Coelho and Marcio Luís de Sousa Borges, both from Braskem’s Quality Control Laboratory; William Reis de Araujo and Ronei Poppi, both PhD professors at the Institute of Chemistry, University of Campinas; and Felipe Lugão, mass spectrometry specialist at Nova Analytica. The second theme, “Processes and Automation”, was addressed by: Mario Gilberto Kool Monteiro, from Globaltek, Brazil; Eduardo Postay, from Asea Brown Boveri, Brazil; Aerenton Ferreira Bueno, technical advisor at Petrobras; and Thimo Post, from InProcess Instruments. On the second day of the event, the topics covered were “Nanotechnology” and “Forensics”. The keynote speaker on nanotechnology was Dr. Henrique Eisi Toma, professor at the Institute of Chemistry of the University of São Paulo (IQ-USP) and Coordinator of “Núcleo de Apoio à Pesquisa em Nanotecnologia e Nanociências (NAP-NN)”, a support center for nanotechnology and nanoscience research at the University of São Paulo. Dr. Toma gave a lecture entitled ‘Nanotechnology – Investing in Efficiency and Sustainability”. Next, nanotechnology continued to be discussed through lectures by: Fernando Tentoni Dias, from Metal-Chek Brazil; Dr. Delmárcio Gomes Silva, professor at Mackenzie Presbyterian University, São Paulo; Dr. Koiti Araki, professor at IQ-USP and Coordinator of SisNANOUSP, one of the associated laboratories of the “Sistema Nacional de Laboratórios em Nanotecnologia (SisNANO)”, a Brazilian nanotechnology laboratory system; Helton Pereira Nogueira, PhD student at IQ-USP Supramolecular Chemistry and Nanotechnology Laboratory; and Daniel Minozzi, member of 67


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the board of directors at Nanox Tecnologia. The theme “Forensics” was addressed with lectures given by: Dr. Henrique Marcelo Gualberto Pereira, professor at the Institute of Chemistry of the Federal University of Rio de Janeiro (IQ-UFRJ) and coordinator of the Brazilian Doping Control Laboratory (LBCD-LADETEC/IQ-UFRJ), accredited by the World Antidoping Agency; Dr. Virginia Martins Carvalho, professor at the Faculty of Pharmacy of UFRJ; Dr. Aline Thais Bruni, professor at the Faculty of Philosophy, Sciences and Languages of Ribeirão Preto, USP; and Dr. Wendell Karlos Tomazelli Coltro, professor at the Institute of Chemistry of the Federal University of Goiás. At the end of the first two days of the conference, the attendees participated in brief oral presentations of works selected from the submitted abstracts, a poster discussion session and also visited the Analitica Latin America Expo.

Poster session of the 6th Analitica Latin America Conference. Photo: Analitica Latin America.

The third and final day of the event opened with a lecture entitled “An Overview of the Global Cannabis Market – Challenges Associated with Cannabis Testing for Marijuana and Hemp”, by Dr. Charlie Schmidt, PerkinElmer Product Line Leader for the Americas. Then, the themes “Analytical Chemistry and Foods” and “Startup Lab” were developed. On analytical chemistry and food, lectures were presented by: Fernando Vitorino da Silva, from the Nestlé Quality Assurance Center in São Paulo; Michael Murgu, mass spectrometry applications specialist at Waters Corporation; Dr. Ana Rita de Araujo Nogueira, researcher at Embrapa Southeast Livestock, São Carlos, SP; Dr. Juliana Naozuka, professor at the Federal University of São Paulo (UNIFESP); and Dr. Paula Regina Fortes, researcher at Alba Sensors and Diagnostics. The “Startup Lab” lectures were presented by: Dr. Lúcio Agnes, professor at IQ-USP and Innovation Coordinator of the State of São Paulo Research Foundation (FAPESP); Dr. Emanuel Carrilho, professor at the Institute of Chemistry of São Carlos, USP; Eduardo Albuquerque and Rafael Fernandes of Conquer School; and Armando Parducci of SpecLab. The last day of the conference was special for the Brazilian Journal of Analytical Chemistry (BrJAC), because it was marked by the delivery of the first “Young Talent in Analytical Chemistry” award. BrJAC created this award to recognize outstanding researchers in Analytical Chemistry who are younger than 35 years old at the award date. The researcher selected to receive this award was Prof. Dr. Leandro Wang Hantao, an assistant professor in the Department of Analytical Chemistry at the Institute of 68


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Chemistry, University of Campinas (IQ-Unicamp). “First, I would like to thank BrJAC for nominating me for this award. Receiving this recognition was very rewarding and important to build trust in our independent research. The team is also a valuable and indispensable element in this achievement. I am very grateful to the current members of our team, Amilton Oliveira, André Paiva, Beatriz Vizioli, Julian Ballén, Juliana Crucello, Nathália Porto, Roselaine Facanali and Victor Ferreira” thanked Hantao.

From left to right: Prof. Dr. Thiago R. L. C. Paixão (University of São Paulo and President of the Analitica LA Conference), Prof. Dr. Leandro Hantao (University of Campinas and Young Talent in Analytical Chemistry award winner) and Luciene Campos (BrJAC advertiser). Photo: Analitica Latin America.

Prof. Dr. Leandro Hantao gave a brief interview to BrJAC, describing what his early career was like and also giving advice to those who start out as chemistry professionals, as given below: BrJAC: How did you start your career? Hantao: I started my career right after my doctorate defense. In 2015, I met Angelo Gobbi of the National Center for Research in Energy and Materials (CNPEM) and was hired to work in his group. The following two years were very productive, which enabled the approval of research grants, as well training of human resources. I am very proud of the three trainees, Augusto Guilhen, Rodrigo Passini and Vanessa Mucédola, who faced the research with determination and resilience. In 2017, I was hired by Unicamp to work at the Institute of Chemistry. Two professionals marked this beginning of my career, Danilo Pierone from Nova Analitica and Rogério Carvalho from Petrobras. Both colleagues trusted our work and we started our partnerships, which are essential to our laboratory. Since then, we have been working closely with the private sector, especially Rhodia Solvay Group, thanks to the continuous support of Jonatas Rodrigues. The first generation of students have also been essential for our group to grow positively. Fortunately, we share the same qualities and goals. BrJAC: What advice would you offer to early career people? Hantao: Face all challenges as your best partners. Strive for excellence in your work and in everything you participate. Help build one single culture by making the most of the university’s diversity. Ensure integrity and ethics in everything. 69


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BrJAC: What are your plans for the future? Hantao: Train excellent professionals in chemistry. I had excellent examples of mentors during my graduate studies, such as Prof. Dr. Fabio Augusto and Prof. Dr. Ronei Poppi, both from IQ-Unicamp, and Prof. Dr. Jared Anderson from Iowa State University (IA, USA). BrJAC: What are you currently working on? Hantao: Our research uses separation techniques to solve petrochemical and environmental challenges. Examples include comprehensive two-dimensional gas chromatography (GC × GC), liquid chromatography (LC) and mass spectrometry (MS). In the petrochemical area, we are developing sample extraction and characterization methods related to the flow assurance and oil recovery. Environmental applications are developed in collaboration with Prof. Dr. Cassiana Montagner (IQ-Unicamp) for the study of water quality and by-products from water treatment. We have conducted the study of food processing in cooperation with Prof. Dr. Juliana Hashimoto and Prof. Dr. Priscila Efraim of the School of Food Engineering (FEA-Unicamp). Finally, we have studied native plant essential oils in collaboration with Dr. Marcia Ortiz Mayo Marques of the Campinas Agronomic Institute (IAC).

Prof. Dr. Leandro Hantao along with his research group. From left to right: Bruna Regina Ribeiro, Nathália Porto, André Paiva, Leandro Hantao, Amilton Oliveira, Juliana Crucello, Breno Pollo and Julian Ballén. Photo: Leandro Hantao.

BrJAC will offer the “Young Talent in Analytical Chemistry” award annually at events related to analytical chemistry, such as the Brazilian Meeting on Analytical Chemistry (ENQA) and the Analitica Latin America Congress, which take place in alternate years. The award will consist of a merit recognition diploma and a registration voucher for the national event on analytical chemistry (ENQA or Analitica Latin America Congress) subsequent to the award. The choice of the researcher to be awarded will be made by a committee designated by the Editor-in-Chief of BrJAC. In addition to the award offered by BrJAC, the Scientific Committee of the 6th Analitica Latin America Conference awarded the best scientific work submitted. The winner of this award was Carla Pereira de Morais, doctoral student at the Institute of Chemistry of São Carlos, USP, with the work entitled “Development of a Libs System and Optimization of Parameters that Influence River Sediment Analysis”. Co-authors of this work are: Milene Corso Mitsuyuki (Embrapa Instrumentation), Gustavo Nicolodelli (Institute of Physics of the Federal University of Mato Grosso do Sul), Stéphane Mounier (Université 70


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de Toulon, France), and Débora Marcondes Bastos Pereira Milori (Embrapa Instrumentation). Carla Pereira de Morais received a registration to participate in the PITTCON Conference & Expo 2020, including accommodation and airfare expenses. PITTCON will take place on March 1–5, 2020, in Chicago, IL, USA. 15th Analitica Latin America Expo In parallel with the 6th Analitica Latin America Conference, the 15th Analitica Latin America Expo was attended by 7592 visitors who were able to learn about the main innovations of more than 400 brands in the analytical chemistry sector that were present at the exhibition. This Analitica Latin America Expo had 52 new exhibitors and occupied an area of 14,000 m², 16% larger than the previous one. On the first day of the event there was the launching ceremony of the Brazilian Nanotechnology Association (Brasil Nano), which arrived to further contribute to the development of science and technology in the country. “It is an honor to be here being prestigious with the support of NürnbergMesse Brasil. We will continue to build partnerships, working together to advance this segment in Brazil”, said Leandro Antunes Berti, Institutional President of Brasil Nano. A modern and innovative session in the Expo called “Talk SCIENCE” merged the main themes in Life & Science. Debates were highlighted on advances in medical cannabis, forensic science, doping in sport, academic innovations at FAPESP, food safety management, etc. Talk SCIENCE is also an online content platform for researchers to update on Life & Science. To learn more about Talk SCIENCE, visit the website.

Talk SCIENCE Session. Photo: Analitica Latin America.

A parallel event called the “Nano Trade Show” had the participation of Embrapa — one of Brazil’s leading state-owned agricultural research companies — who presented innovations ranging from nanopigments to food solutions. Also present was “Doctor Nano Future Technologies”, a nanotechnology company geared to food who presented products that may be increasingly present in the daily lives of Brazilians. Also new at the Expo was the Business Roundtable, which was a success for the participants. During the two-hour roundtable there were 190 meetings, 65 buyers, 18 exhibitors and BRL 11.5 million in new business. Some exhibiting companies present at the Expo Agilent Technologies, a leader in the life sciences, diagnostics and applied chemistry markets, providing instruments, services, consumables and applications to laboratories around the world, presented gas and liquid chromatographs, both stand-alone and coupled to mass spectrometers, 71


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molecular and atomic absorption spectrometers, consumables and software. Allcrom, a company that has been operating in the Brazilian market for approximately 30 years, representing companies from different countries, has exhibited launches such as ChroZen UHPLC, HPLC YL9100+, GC YL6500 with PAL Injector, and GC and MS from Young In Chromass. In addition, as Phenomenex’s exclusive representative in Brazil, Allcrom launched new chiral columns for HPLC model LUX, the Kinetex PS C18 column, Security Link, which is a hand-tight connection system for HPLC/UHPLC, and the ZB-624 PLUS column for GC.

Aerial view of Analitica Latin America Expo. Photo: Analitica Latin America.

Anton Paar, a company that develops, manufactures and distributes worldwide highly accurate laboratory instruments and process measurement systems, as well as customized automation and robotics solutions, presented the Multiwave 7000 microwave-assisted digestion system, the ViscoQC 300 rotational viscometer, the Diana 700 atmospheric distillation analyzer, the RapidOxy 100 oxidation stability meter, the Raman Cora 100 portable spectrometer and the Tosca Series atomic force microscope. Nova Analitica, due to the quality of the products it distributes in the market and its technical support team, has become one of the best scientific product suppliers in the Brazilian market and presented Miele glassware washers, Rainin pipettes, Lauda thermostatic baths, Suez TOC analyzers, Milestone microwaves and consumables for chromatography and spectrometry. DataMed highlighted Thermo Scientific’s TSX line of freezers and refrigerators, which provide better temperature uniformity and energy savings without compromising sample integrity. A demonstration of this product and a promotion of CO2 incubators were made at the exhibition. Metrohm has introduced novelties in potentiometric titrators that are now also available to the pharmaceutical industry, such as high-precision OMNIS Karl Fischer titrators and portable analyzers that allow quick analysis on the palm. Another highlight was B&W Tek’s Raman spectroscopy line. SCIEX presented: the SCIEX Triple Quad 5500+ LC-MS/MS System (QTRAP Ready); Echo MS, the first mass spectrometry system based on acoustic droplet ejection sampling technology; hyphenated systems with a Phytronix LDTD ion source; and systems for capillary electrophoresis. The instruments perform every test from routine testing to more complex and challenging analysis. Thermo Fisher Scientific launched several innovations, including instruments for sample preparation, chromatography, mass spectrometry, elemental analysis, and software for analysis and data management. Inside its booth, Thermo Fisher gave live demonstrations of the sample preparation process and its integration with analysis up to the final report generation through software. Veolia exhibited the following lines: PURELAB® Chorus, the first modular water purification system; 72


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PURELAB® Flex, which provides ultrapure and purified water with constant monitoring of water quality to the point of distribution, in the amount required for any application; and CENTRA, a system capable of producing over 200 liters of water per hour and storing up to 350 liters. Waters exposed seven instruments from its product portfolio, as well as demonstrating the use of these instruments in real time. Among the instruments presented were liquid chromatographs, mass spectrometers, rheometers and thermal analysis systems. For all companies present at Analitica Latin America Expo 2019, visit: https://www.analiticanet.com. br/en.

Analitica Latin America Expo provided close exchanges between exhibitors and visitors. Photo: Analitica Latin America.

The next Analitica Latin America Expo will take place on September 28–30, 2021, in parallel with an exhibition by the Brazilian Association of Paint Manufacturers (Abrafati), the main paint industry event. The synergy of the two events will contribute to the strengthening of both sectors. “With each Analitica Latin America Expo, we try to offer a comprehensive and dynamic event that contributes to the analytical chemistry market in our country. We understand the importance and complexity of this event and market segment for national development. For this reason, we have made every effort to deliver once again a trade show that matches our visitors’ and exhibitors’ expectations. The idea is to keep growing,” concluded Diego de Carvalho, portfolio director at NürnbergMesse Brazil. Source: With information from NürnbergMesse Brazil/Analitica Latin America Conference & Expo

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Br. J. Anal. Chem., 2019, 6 (25) pp 74-76

6th EspeQBrasil Brought Together Leading Researchers to Reflect on Chemical Speciation The 6th Brazilian Meeting on Chemical Speciation (EspeQBrasil) was held at the Ondina Campus of the Federal University of Bahia, September 3–5, 2019. It was attended by experts from Brazil and abroad, who articulated discussions on the progress and challenges of chemical speciation. The event’s program included plenary conferences and mini conferences given by leading scientists in the national and international scientific landscape, a round table, oral presentation and poster discussion sessions, and an exhibition of instruments, products and services for analytical laboratories. The opening conference was held by Prof. Dr. Manuel Miró Lladó from the University of the Balearic Islands (Spain), who spoke about “Automatic flow-through bioaccessibility and bioavailability methods for trace elements in environmental solids and foodstuff”. Two of the plenary conferences presented were: “Speciomics: Integrating bioanalytical information”, by Prof. Dr. Marco Aurélio Zezzi Arruda from the University of Campinas (Brazil); and “Antimony means no money: The controversy about the chemical behavior of antimony species”, by Prof. Dr. Waldo Emerzon Quiroz Venegas from the Pontifical Catholic University of Valparaíso (Chile). Among the mini conferences, topics such as “Biogeochemical behavior of iron in estuarine environment” by Prof. Dr. Marco Tadeu Grassi (Federal University of Paraná, Brazil), “Challenges in halogen speciation and food fractionation studies” by Prof. Dr. Marcia Foster Mesko (Federal University of Pelotas, Brazil), and “Effects of food processing on bioaccessibility of essential and potentially toxic elements” by Prof. Dr. Wagna Piler Carvalho dos Santos (Federal Institute of Education, Science and Technology of Bahia, Brazil) were addressed. Check out the full program here.

Prof. Dr. Manuel Miró presenting the opening conference of the 6th EspeQBrasil.

The topic “Sample preparation for chemical speciation analysis” was discussed at a round table coordinated by Prof. Dr. Maria Goreti Rodrigues Vale (Federal University of Rio Grande do Sul). Prof. Dr. Pedro Vitoriano Oliveira (University of São Paulo, Brazil) spoke about “Chemical speciation in the agrochemical sector: Needs and challenges” and Prof. Dr. Marcos de Almeida Bezerra (State University of Southwest Bahia, Brazil) spoke about “Speciation of metallic species using cloud point extraction”.

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Speakers at the round table on “Sample preparation for chemical speciation analysis”. From left to right: Dr. Pedro V. Oliveira, Dr. Maria Goreti R. Vale, Dr. Marcos de Almeida Bezerra, and Dr. Maria das Graças Andrade Korn, from the Federal University of Bahia and Coordinator of the 6th EspQBrasil.

Technical lectures were also given by some companies present at the event. Bruno Menezes Siqueira, from Nova Analitica, presented “New aspects and technologies in elemental chemical speciation”; Rodolfo Lorençatto of Agilent Technologies Brasil talked about “Separate, ionize, determine! Recent technological advances in HPLC-ICP-MS/MS“; and Robson Nunes of Anton Paar Brasil Ltda spoke about “Using microwave systems for sample preparation for chemical speciation”.

Exhibition and coffee break area.

EspeQBrasil was created in 2006, from the “Workshop on Chemical Analysis of Speciation” held at the 29th Annual Meeting of the Brazilian Chemical Society. EspeQBrasil is an important event for the progress of scientific research in the country, because through discussions and information exchange it is possible to create new research groups and leverage the development of scientific and technological research of national and international interest. EspeQBrasil 2019 aimed to bring together the main research groups in the country involved in 75


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chemical speciation. During the meeting, it was possible to reflect and discuss speciation as an interdisciplinary tool, and bring together renowned researchers, recent PhDs, doctoral, master and undergraduate students, as well as private sector professionals.

Poster discussion session

EspeQBrasil 2019 was supported by the: National Institute of Science and Technology (INCT) – Energy & Environment; Bahia Center for Analytical Chemistry Research (NQA); Coordination for the Improvement of Higher Education Personnel (CAPES); National Council for Scientific and Technological Development (CNPq); and State of Bahia Research Foundation (FAPESB). The Brazilian Journal of Analytical Chemistry was also present at the event and, to show appreciation to its readers and event attendees, raffled off print editions of the journal and its mascot “Fokka”. Source: With information from EspeQBrasil 2019. Photos: EspeqQ2019.

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Br. J. Anal. Chem., 2019, 6 (25) pp 77-85 PDF

This section is dedicated for sponsor responsibility articles.

Analysis of Elemental Impurities in Drug Products using the Thermo Scientific iCAP 7400 ICP-OES Duo Sanja Asendorf Thermo Fisher Scientific, Bremen, Germany

Trace elemental impurities in pharmaceutical products are potentially harmful and thus their determination is of great importance. The work described here demonstrates compliance with 21 Code of Federal Regulation (CFR) Part 11 and analysis according to latest implementation of United States Pharmacopeia (USP) General Chapters <232> and <233>. Keywords: Drug products, Elemental impurities, ICH Q3D, Metals, Pharmaceutical, USP 232, USP 233 INTRODUCTION Impurities in pharmaceutical products are of great concern not only due to the inherent toxicity of certain contaminants, but also due to the adverse effects that contaminants may have on drug stability and shelf-life. This necessitates the monitoring of organic and inorganic impurities throughout the pharmaceutical manufacturing process, from raw ingredients to final products. Recently, USP announced measures to modernize (and replace) the USP General Chapter for Heavy Metals <231> by proposing two new General Chapters: <232> Elemental Impurities – Limits (1) and <233> Elemental Impurities – Procedures (2). The rationale behind introducing the new chapters was to provide a modern equivalent to USP General Chapter <231>, which is based on a more than one hundred-year-old colorimetric test (‘heavy metals test’) involving the precipitation of ten sulfide-forming elements and visually comparing the color of the resulting precipitate to that of a 10 mg·kg-1 lead standard. There are several known deficiencies with the method including: the inability to differentiate between the levels of individual contaminants, use of potentially hazardous solvents such as thioacetamide and the use of a furnace during the preparation of certain samples, which results in significant loss of volatile contaminants such as tin and mercury. USP General Chapter <232> sets out the permissible levels of twenty-four elements in final drug products according to limits established in ICH guideline Q3D (3). The guideline uses toxicological data to set the limits, which are then expressed in terms of a permissible daily exposure (PDE) limit. The route of administration (oral, parenteral, or inhalation) is taken into account when setting the PDE, with orally administered drugs having a higher permissible limit than drugs that are delivered parenterally or by inhalation. Elements included in the chapter have been placed into three classes, based on their toxicity and likelihood of occurrence in the drug product. The classification scheme is intended to focus the risk assessment on those elements that are the most toxic but also have a reasonable probability of inclusion in the drug product. For element PDEs and classification, see Table I. Table I. PDE limits for elemental impurities in drug products Element

Class

Oral PDE (μg day-1)

Parenteral PDE (μg day-1)

Inhalation PDE (μg day-1)

Cadmium

1

5

2

2

Lead

1

5

5

5

Arsenic

1

15

15

2

Mercury

1

30

3

1 77


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Table I. PDE limits for elemental impurities in drug products (Cont.) Element

Class

Oral PDE (μg day-1)

Parenteral PDE (μg day-1)

Inhalation PDE (μg day-1)

Cobalt

2A

50

5

3

Vanadium

2A

100

10

1

Nickel

2A

200

20

5

Thallium

2B

8

8

8

Gold

2B

100

100

1

Palladium

2B

100

10

1

Iridium

2B

100

10

1

Osmium

2B

100

10

1

Rhodium

2B

100

10

1

Ruthenium

2B

100

10

1

Selenium

2B

150

80

130

Silver

2B

150

10

7

Platinum

2B

100

10

1

Lithium

3

550

250

25

Antimony

3

1200

90

20

Barium

3

1400

700

300

Molybdenum

3

3000

1500

10

Copper

3

3000

300

30

Tin

3

6000

600

60

Chromium

3

11000

1100

3

USP General Chapter <233> deals with sample preparation strategies and analytical detection techniques to measure the elements defined in chapter <232>. This includes the choice between two ICP-based technologies (ICP-OES and ICP-MS), as well as a protocol to establish alternative test procedures. The official date for implementation of the new chapters was January 1, 2018 and marks the date on which <232> and <233> are applicable to drug product producers. A further consequence of the implementation process for General Chapters <232> and <233> is the complete removal of USP General Chapter <231> Heavy Metals from the compendia on January 1, 2018. Past January 1, 2018 chapter <231> will no longer be valid and testing must instead conform to the limits set out in chapter <232>, using the procedures set out in chapter <233> (analysis by ICP-OES, ICP-MS or an acceptable alternative procedure). In future all drug products produced and sold in the U.S. must comply with the limits set by USP General Chapter <232>. Drug substances and excipients will be tested and reported for elemental impurities. Similarly, nutraceutical products must comply with the limits set by USP General Chapter <2232> (4), which extends only to arsenic, mercury, cadmium and lead. Speciation of organic and inorganic elemental forms is critical for the analysis of Dietary Supplements.

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MATERIALS AND METHODS Instrumentation For the sample analysis, the Thermo Scientific™ iCAP™ 7400 ICP-OES Duo was used together with an aqueous sample introduction kit and an internal standard kit for online addition of the internal standard. A Teledyne CETAC Technologies ASX-560 Autosampler was used to transfer the sample to the introduction system of the ICP-OES. The iCAP 7400 ICP-OES Duo is well suited to this type of application due to its low detection capabilities for the elements of interest, as well as for its ability to resolve complex spectra. Both of these points are critical in relation to the low limits stipulated for elements such as arsenic and mercury. In addition, elements such as palladium, platinum, osmium and iridium produce many emission lines when excited in the plasma, which need to be resolved effectively to avoid spectral interferences. The Thermo Scientific™ iCAP™ 7000 Series Qualification Kit and Thermo Scientific™ Qtegra™ Intelligent Scientific Data Solution™ (ISDS) Software were used to ensure that the analysis can meet the requirements of the FDA 21 CFR Part 11 regulations relating to the use and control of electronic records (5). Standard and sample preparation Standards and spikes Two standard stock solutions with different element compositions were prepared from single element solutions (1000 mg·kg-1 and 10000 mg·kg-1, SPEX CertiPrep Group, Metuchen, USA). Stock solution A contained Ag, As, Ba, Cd, Co, Cu, Cr, Hg, Li, Mo, Ni, Pb, Sb, Se, Sn, Tl and V whereas stock solution B contained Au, Ir, Os, Pd, Pt, Rh and Ru. The individual solutions were made up with ultrapure water (18 MΩ) and hydrochloric acid (TraceMetal™ Grade, Fisher Chemical, Loughborough, UK) to a final concentration of 5% HCl. All spike solutions and an internal standard solution of yttrium (5 mg·kg-1) were prepared in the same way. To stabilize mercury in stock solution A, 10 mg·kg-1 gold was added to it. As a calibration blank 5% HCl was used. Two sets of standardization solutions and sample spike solutions were prepared, one for elements contained in stock solution A and one for those in stock solution B. Samples To validate the developed method for use in compliance with USP General Chapter <233> a cough medicine from a local pharmacy (acetylcysteine, ACC 600) in the form of an effervescent tablet was analyzed. One gram of the tablet was diluted in a few mL of ultrapure water (18 MΩ) and the developing CO2 was allowed to degas. After the reaction had subsided, the aliquot was acidified to a final concentration of 5% HCl, spiked accordingly for the various tests of the validation procedure and filled up with ultrapure water to a final volume of 50 mL. Target Elements and calculation of the J value Elements with the potential of being present in the material under test are called Target Elements within USP General Chapters <232> and <233>. In any case, arsenic, cadmium, lead, and mercury have to be included in the Target Element evaluation when testing is done to demonstrate compliance. Target Elements should also include any elements that may be added through material processing or storage. The accepted concentration value for the elemental impurity being evaluated is called the Target Limit. Exceeding the Target Limit indicates that a material under test exceeds the acceptable value. To calculate the Target Limit, the permissible daily exposure (PDE) limit is divided by the maximum daily serving size or maximum daily dose (MDD). Due to sample preparation techniques and different working ranges of the specified instrumentation, the concentration of the elements of interest at the Target Limit has to be calculated including the dilution factor. This concentration is known as the J value: J Value = PDE / MDD x Dilution factor

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With an MDD of 2 gram per day and a dilution factor of 50, the J value concentrations were calculated for the cough medicine according to Table II. Table II. J value for ACC effervescent tablets with MDD of 2 gram per day and a dilution of 50x Target Element

Concentration (mg·kg-1)

Target Element

Concentration (mg·kg-1)

Cd

0.05

Rh

1

Pb

0.05

Ru

1

As

0.15

Se

1.5

Hg

0.3

Ag

1.5

Co

0.5

Pt

1

V

1

Li

5.5

Ni

2

Sb

12

Tl

0.08

Ba

14

Au

1

Mo

30

Pd

1

Cu

30

Ir

1

Sn

60

Os

1

Cr

110

Method development The parameters used for the method can be found in Table III. The plasma was ignited and the instrument allowed to warm up for a period of 15 minutes. A spectrometer optimization was performed directly before each analysis. Table III. Instrument parameters Parameter

Setting

Pump Tubing (Standard Pump)

Sample Tygon® orange/white Drain Tygon® white/white Internal Standard Tygon® orange/blue

Analysis Pump Speed

50 rpm

Spray Chamber

Glass Cyclonic

Nebulizer

Burgener Mira Mist

Nebulizer Gas Flow

0.5 L min-1

Coolant Gas Flow

12 L min-1

Auxiliary Gas Flow

0.5 L min-1

Center Tube

2 mm

RF Power

1150 W

Plasma View

Axial

Radial

Exposure Time

UV 15 s, Vis 5 s

Vis 5 s

A method was created in Qtegra ISDS Software. The wavelengths used for the analysis are shown in Table IV. These were selected as they were mostly free from interferences and provided the sensitivity to 80


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quantify the elements of interest in the expected concentration range. The observed interferences were corrected for by inter-element corrections (IEC) which were set up in the software. The wavelengths of the internal standard yttrium were applied according to the plasma view and wavelength range (UV or Vis). Table IV. Analyte, internal standard wavelengths and view as well as interfering elements and correlation coefficient of the calibration curve (R2) Element and wavelength (nm)

View

Internal standard wavelength (nm)

Interfering elements

Cd 226.502

Axial

Y 224.306

1.0000

Pb 182.205

Axial

Y 224.306

0.9992

As 189.042

Axial

Y 224.306

1.0000

Hg 184.950

Axial

Y 224.306

0.9999

Co 228.616

Axial

Y 224.306

1.0000

V 309.311

Axial

Y 324.228

1.0000

Ni 221.647

Axial

Y 224.306

1.0000

Tl 190.856

Axial

Y 224.306

1.0000

Au 267.595

Axial

Y 324.228

0.9994

Pd 324.270

Axial

Y 324.228

0.9995

Ir 215.268

Axial

Y 224.306

0.9996

Os 228.226

Axial

Y 224.306

Rh 343.489

Axial

Y 360.073

Ru 266.161

Axial

Y 324.228

Se 206.279

Axial

Y 224.306

1.0000

Ag 328.068

Axial

Y 324.228

1.0000

Pt 203.646

Axial

Y 224.306

0.9995

Li 610.362

Radial

Y 371.030

Sb 217.581

Axial

Y 224.306

1.0000

Ba 455.403

Radial

Y 371.030

0.9997

Mo 284.823

Radial

Y 324.228

0.9989

Cu 224.700

Radial

Y 360.073

1.0000

Sn 226.891

Axial

Y 224.306

1.0000

Cr 357.869

Radial

Y 360.073

0.9991

Mo

R2

0.9995 0.9989

Cr

Na

0.9994

0.9994

Validation procedure In order to validate the used method, the tests defined in USP General Chapter <233> under “Alternate Procedure Validation” – “Quantitative Procedures” were conducted. Accuracy For the accuracy test, the instrument was calibrated with standard solutions containing 0.5 J and 1.5 J of the Target Elements. Six samples were spiked with three times each, 0.5 J and 1.5 J of all Target Elements. According to the acceptance criteria, the mean recovery of the three replicates has to be 81


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within 70-150% at each concentration. As the recoveries were within 86-109% (Table V) the acceptance criterion for accuracy of the method is fulfilled. Moreover, limit of quantification, range and linearity are demonstrated to be suitable by meeting the accuracy requirements. Table V. Average recoveries (in percentages) of 3 replicate sample spikes at each 0.5 J and 1.5 J demonstrating accuracy of the method Average spike recovery 0.5 J (n=3)

Average spike recovery 1.5 J (n=3)

Cd

96

97

Pb

94

94

As

97

103

Hg

93

97

Co

96

98

V

100

99

Ni

95

97

Tl

86

94

Au

100

100

Pd

98

99

Ir

98

99

Os

100

101

Rh

101

102

Ru

94

96

Se

106

106

Ag

94

100

Pt

98

98

Li

102

98

Sb

97

100

Ba

101

98

Mo

100

100

Cu

109

94

Sn

94

97

Cr

101

98

Element

Precision Precision was tested by means of repeatability and ruggedness of the method. For the repeatability test, six independent samples of material under test were spiked at a concentration of 1 J for each Target Element. The acceptance criterion in USP General Chapter <233> states a relative standard deviation (RSD) of not more than (NMT) 20% between the repeats for each Target Element. The calculated RSDs are clearly in the required range, varying between 0.7-2.5% (Table VI). Ruggedness of the method was determined by performing the repeatability experiment on two different days. The total RSD of the repeated analysis (n=12) was 1.5-6.0% (Table VI) and is therefore clearly below the acceptance criterion of NMT 25% RSD for each Target Element. 82


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Table VI. RSDs of 6 as well as 12 replicate sample spikes at 1 J demonstrating repeatability and ruggedness of the method Element

RSD (n=6) NMT 20%

RSD (n=12) NMT 25%

Cd

1.7

1.6

Pb

2.2

6.0

As

2.5

2.1

Hg

2.2

2.2

Co

1.7

1.7

V

1.2

1.8

Ni

1.7

1.7

Tl

2.1

2.5

Au

1.0

1.7

Pd

1.2

1.9

Ir

0.9

1.7

Os

0.7

1.6

Rh

0.9

1.7

Ru

1.3

1.7

Se

1.6

1.9

Ag

1.4

2.1

Pt

0.8

1.8

Li

2.5

5.2

Sb

2.0

1.7

Ba

2.4

2.5

Mo

1.8

1.5

Cu

2.1

2.6

Sn

1.8

1.7

Cr

2.1

1.7

Specificity According to USP General Chapter <233>, specificity is the ability to assess the analyte unequivocally in the presence of components that may be expected to be present, including other Target Elements and matrix components. To ensure the identity of the analyte, two wavelengths for each element were analyzed and the subarrays examined carefully for any interferences. As the accuracy and precision tests show appropriate results within the defined ranges, specificity of the method is verified (see Table VII). Table VII. Accuracy (shown as average spike recovery) and precision (RSD) results for the analysis of six replicate sample spikes at 1 J (all results are in percentages) Element and wavelength (nm)

Accuracy (Recovery, n=6)

Precision (RSD, n=6)

Element and wavelength (nm)

Accuracy (Recovery, n=6)

Precision (RSD, n=6)

Cd 226.502

95.7

1.7

Rh 343.489

102.0

0.9

Cd 214.438

96.1

1.6

Rh 339.682

102.7

0.9

Pb 220.353

92.5

4.7

Ru 267.876

95.6

1.5

Pb 182.205

99.0

2.2

Ru 266.161

95.1

1.3

As 189.042

100.3

2.5

Se 196.090

105.9

2.0 83


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Table VII. Accuracy (shown as average spike recovery) and precision (RSD) results for the analysis of six replicate sample spikes at 1 J (all results are in percentages) (Cont.) Element and wavelength (nm)

Accuracy (Recovery, n=6)

Precision (RSD, n=6)

Element and wavelength (nm)

Accuracy (Recovery, n=6)

Precision (RSD, n=6)

As 228.812

100.9

2.8

Se 206.279

105.0

1.6

Hg 184.950

93.6

2.2

Ag 328.068

97.6

1.4

Hg 194.227

93.2

1.9

Ag 338.289

92.8

1.8

Co 228.616

95.8

1.7

Pt 203.646

97.8

0.8

Co 238.892

94.0

0.8

Pt 214.423

97.1

0.8

V 310.230

98.1

1.1

Li 610.362

93.7

2.5

V 309.311

98.6

1.2

Li 670.784

108.7

2.4

Ni 231.604

95.6

1.7

Sb 206.833

97.0

2.1

Ni 221.647

95.2

1.7

Sb 217.581

96.8

2.0

Tl 190.856

92.1

2.1

Ba 455.403

98.1

2.4

Au 242.795

98.9

1.0

Ba 493.409

94.7

3.1

Au 267.595

99.7

1.0

Mo 281.615

97.3

1.9

Pd 324.270

99.4

1.2

Mo 284.823

98.1

1.8

Pd 340.458

101.3

1.0

Cu 219.958

98.4

2.2

Ir 212.681

99.5

0.9

Cu 224.700

98.7

2.1

Ir 215.268

99.3

0.9

Sn 226.891

94.2

1.8

Os 228.226

100.1

0.7

Sn 283.999

94.7

1.9

Os 225.585

99.5

0.6

Cr 284.325

96.1

1.9

Cr 357.869

97.2

2.1

RESULTS All requirements for method validation were met by analyzing a series of unspiked and spiked samples at different multiples of the J value. To show system suitability of the indicated Procedure 1: ICP-OES, the instrument was calibrated with a blank and two standardization solutions: • Blank – Matched matrix: 5% HCl • Standardization solution 1 - 1.5 J in 5% HCl • Standardization solution 2 - 0.5 J in 5% HCl The results obtained from standardization solution 1 before and after the analysis of the sample solutions were compared. The suitability criterion of NMT 20% drift between analyses was met according to Table VIII. Table VIII. Analysis results for the determination of system suitability (drift)

84

Element

Before (mg·kg-1)

After (mg·kg-1)

RSD (%)

Cd

0.075

0.077

1.5

Pb

0.075

0.078

2.7

As

0.225

0.238

3.9

Hg

0.453

0.464

1.7


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Table VIII. Analysis results for the determination of system suitability (drift) (Cont.) Element

Before (mg·kg-1)

After (mg·kg-1)

RSD (%)

Co

0.753

0.773

1.9

V

1.50

1.52

0.7

Ni

3.01

3.08

1.5

Tl

0.120

0.124

2.3

Au

1.48

1.48

0.2

Pd

1.48

1.47

0.7

Ir

1.48

1.49

0.2

Os

1.48

1.48

0.1

Rh

1.47

1.46

0.3

Ru

1.48

1.48

0.0

Se

2.25

2.31

2.0

Ag

2.25

2.24

0.3

Pt

1.48

1.48

0.1

Li

8.37

8.09

2.5

Sb

18.1

18.4

1.4

Ba

21.1

21.0

0.5

Mo

45.9

45.6

0.5

Cu

45.0

44.3

1.1

Sn

90.2

92.3

1.6

Cr

168

163

1.9

CONCLUSION The analysis shows that the Thermo Scientific iCAP 7000 Plus Series ICP-OES delivers excellent accuracy and sensitivity for analyses of trace elements and major components in drug products in conformity with the present USP General Chapters <232> Elemental Impurities – Limits and <233> Elemental Impurities - Procedures. The results obtained prove the excellent ability of the instrument to resolve complex sample spectra, and the achieved detection limits demonstrate the suitability of the instrument to analyze toxic trace elements like arsenic and mercury for which the stipulated limits are very low. REFERENCES 1. United States Pharmacopeia (USP) General Chapter <232> Elemental Impurities—Limits, USP 40-NF 35, First Supplement. 2. United States Pharmacopeia (USP) General Chapter <233> Elemental Impurities—Procedures, USP 38-NF 33, Second Supplement. 3. United States Pharmacopeia (USP) General Chapter <2232> Elemental Contaminants in Dietary Supplements <2232>, USP 38-NF 33, Second Supplement. 4. European Medicines Agency. ICH Q3D Impurities: Guideline for Elemental Impurities, Current Step 4 Version, 2014. 5. U. S. Food & Drug Administration — FDA. 21 C.F.R. 11 Revised as of April 1, 2017. This sponsor report is the responsibility of Thermo Fisher Scientifc.

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Br. J. Anal. Chem., 2019, 6 (25) pp 86-94 PDF

This section is dedicated for sponsor responsibility articles.

Tomorrowâ&#x20AC;&#x2122;s Quantitation with the TSQ Fortis Mass Spectrometer: Robust, Reproducible Quantitation Workflows of Haloacetic Acids, Bromate, and Dalapon in Water according to EPA Method 557 Neloni Wijeratne1, Jonathan Beck1, Claudia Martins1, Mary Blackburn1, Debadeep Bhattacharyya2, Beau Sullivan3, Andrey Khorst3 1

Thermo Fisher Scientific, San Jose, CA. 2Thermo Fisher Scientific, Boston, MA. 3Santa Clara Valley Water District, San Jose, CA, USA

The goal of this work was the development and easy implementation of a robust, reliable, and reproducible workflow solution for the analysis and quantitation of nine haloacetic acids, bromate, and dalapon in water using a triple quadrupole (QqQ) mass spectrometer (MS). Keywords: Haloacetic acids, bromate, dalapon, triple quadrupole MS, TSQ Fortis MS, quantitation workflow solution, disinfection byproducts, TraceFinder software, EPA Method 557 INTRODUCTION Clean drinking water is becoming more scarce in todayâ&#x20AC;&#x2122;s world and contamination can result in long-lasting damage to human health. Along with purifying water by means of mechanical measures, disinfection also plays an essential role in ensuring the supply of clean drinking water. Drinking water goes through an extensive disinfection process to ensure high quality; however, by-products from the disinfection process can result in health risks. As an example, haloacetic acids (HAAs) form as a result of the disinfection of by-products when water is chlorinated to kill disease-causing microbes [1]. Bromate is formed when disinfecting ozone reacts with naturally occuring bromide. Regardless of how these by-products form, excessive consumption can result in serious health issues, such as cancer [2]. As described above, HAAs are formed as a result of chlorination of water where chlorine reacts with naturally occurring organic and inorganic matter in the water, such as decaying vegetation, to produce disinfection by-products (DBPs), including HAAs. Of the nine species of HAAs, five are currently regulated by the EPA (HAA5): monochloroacetic acid (MCAA), dichloroacetic acid (DCAA), trichloroacetic acid (TCAA), monobromoacetic acid (MBAA), and dibromoacetic acid (DBAA). The remaining four HAAs are currently unregulated: bromochloroacetic acid (BCAA), bromodichloroacetic acid (BDCAA), dibromochloroacetic acid (DBCAA), and tribromoacetic acid (TBAA). Bromate can arise as a byproduct of the ozonation of bromide-containing water depending on the conditions (pH, temperature, etc.) prevalent at the treatment site [3]. According to regulations, drinking water plants must determine the concentration of disinfection by-products in drinking water prior to release. EPA Method 557 has been validated for the determination of haloacetic acids, bromate, and dalapon. The analysis of contaminants, especially polar molecules in drinking water, can be effected using one of several techniques. Analysis of polar molecules utilizing LC is challenging, as LC typically works best for non-polar molecules, and suffers from high matrix resulting from groundwaters that are often evaluated prior to entry into drinking water utilities. This calls for derivatization of samples, which can be time consuming and adds challenges towards achieving the result, faster and with confidence. Fortunately, ion chromatography (IC) offers some significant benefits owing to its capability to analyze polar molecules, especially in higher matrix waters. In this study, a robust, reliable, reproducible quantitation assay for determination of HAAs, bromate, and dalapon in drinking water with IC-MS/ 86


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MS using a Thermo Scientific™ Dionex™ ICS-5000+ Hybrid HPIC™ system, a Thermo Scientific™ TSQ Fortis™ triple quadrupole mass spectrometer, and Thermo Scientific™ TraceFinder™ version 4.1 software is reported. EXPERIMENTAL Sample preparation Drinking water samples were collected from municipal tap water sources. NH4Cl was added as a preservative at 100 mg/L to all water samples. No further sample preparation was performed prior to injection. Ion chromatography IC analysis was performed on the Dionex ICS-5000+ Hybrid HPIC system. Samples were directly injected; no sample pre-treatment was required. The IC KOH gradient conditions are indicated in Table I. A 100 μL sample was injected onto a 2 × 250 mm Thermo Scientific™ Dionex™ IonPac™ AS24A column, which is specifically designed to separate method analytes from the following common anions (matrix components) in drinking water: chloride, carbonate, sulfate, and nitrate. A guard column (Thermo Scientific™ Dionex™ IonPac™ AG24A, 2 × 50 mm column) and a Thermo Scientific™ Dionex™ ASRS-500 electrolytically regenerated suppressor were used. The mobile phase was 300 μL/min KOH, which was automatically prepared by the eluent generator of the ICS-5000+. The concentration of the KOH was changed during the method run to achieve a gradient elution profile. Isopropyl alcohol was added to the eluent post column via a T at a rate of 200 μL/min to assist in nebulization of the eluent in the MS ion source. The Thermo Scientific™ Dionex™ AXP auxiliary pump water for suppressor regeneration was maintained at 600 μL/min. The column temperature was maintained at 15 °C. Table I. IC gradient information Time (min)

KOH Concentration (mM)

0.00

7.00

15.10

7.00

30.80

18.00

31.00

60.00

46.00

60.00

47.00

7.00

58.00

7.00

Hydroxide eluent was generated using an electrolytic eluent generation, which provides smoother and more reproducible gradients than conventional pump proportioning valves, and a continuously regenerated trap column removed contaminants to provide pure eluent throughout the run. A matrix diversion valve was placed in line prior to the mass spectrometer (MS) to divert the high sample matrix anions from the mass spectrometer source that normally cause signal suppression in the mass spectrometer. Thus, the use of hydroxide eluent and suppression in the reagent-free IC system is more powerful for the separation and detection of organic acids than reversed-phase separations that require acidic addition (to protonate the compounds to acetic acids) or addition of stabilizing salts, both of which undermine analysis. Isopropyl alcohol (0.2 mL/min) was added into the eluent stream via a mixing tee immediately after the matrix diversion valve. The isopropyl alcohol enabled desolvation of the mobile phase and acted as a makeup flow when the IC eluent was diverted to waste. Mass spectrometry The TSQ Fortis triple quadrupole mass spectrometer was used for this analysis. All compounds for 87


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this study were analyzed in negative ion heated electrospray (HESI) mode. The experimental conditions were optimized with a static spray voltage, a cycle time of 2.3 s, and both Q1 and Q3 resolution were maintained at 0.7 Da FWHM. The SRM table along with other critical MS features for all the target analytes are listed in Table II. Individual standards were infused into the mass spectrometer to determine optimum tube lens settings and collision energies for the product ions. Software Data acquisition and processing were conducted using TraceFinder software version 4.1 Table II. Optimized mass spectrometer transitions for each compound analyzed in this experiment. Following EPA Method 557 [4] only one product ion was monitored for each precursor ion. Precursor (m/z)

Product (m/z)

Collision Energy (V)

Tube Lens (V)

Source Fragmentation (V)

MCAA

92.85

35.1

10.23

92

22.9

MCAA_IS

93.99

35.1

10.23

92

22.9

DCAA

127.00

83.0

10.23

57

0

Bromate

127.00

110.8

21.56

68

13.1

MBAA

136.85

78.9

11.82

45

0

MBAA_IS

137.94

78.9

10.23

52

0

DCAA_IS

128.00

84.0

10.23

50

0

Dalapon

141.00

97.0

10.23

53

0

TCAA_161

160.81

116.9

10.23

55

0

TCAA_IS

161.91

117.8

10.23

42

0

BDCAA

163.00

81.0

10.23

63

21.2

TCAA_163

163.00

119.0

10.23

56

27.7

BCAA

172.77

128.8

10.23

73

0

DBCAA

207.00

79.0

14.55

82

18

DBAA

216.78

172.7

10.23

58

0

TBAA

251.00

79.0

18.64

84

21.2

Compound

RESULTS AND DISCUSSION The data obtained were from the laboratory synthetic sample matrix (LSSM). The LSSM is a prepared matrix of 250 mg/L each of chloride and sulfate, 150 mg/L of bicarbonate, 20 mg/L of nitrate, and 100 mg/L ammonium chloride preservative, for a total chloride concentration of 316 mg/L. Chromatograms of all eleven compounds are shown in Figure 1. The selectivity offered by the Dionex IonPac AS24A column enabled good separation of the HAAs from the typical inorganic matrix ions. Such selectivity and ability to resolve and identify every analyte signal allows matrix signals of chloride, sulfate, nitrate, and bicarbonate to be diverted to waste during the analytical run and avoids contamination of the ESI-MS/MS instrument source. This capability is not possible with LC-based separations. An internal 88


Sponsor Report

standard mixture of 13C-labeled MCAA, MBAA, DCAA, and TCAA was spiked into each sample at 4 ppb. The chromatograms of each of the 13C-labeled analytes at 4 μg/L are shown in Figure 2. All calibration standards were prepared in deionized water containing 100 mg/L NH4Cl as a preservative. The calibration curves were generated using internal standard calibrations for all the HAAs in water.

Figure 1. Ion chromatograms of HAAs: (A) MCAA, (B) MBAA, (C) Bromate, (D) Dalapon, (E) DCAA, (F) BCAA, (G) DBAA, (H) TCAA, (I) BDCAA, (J) DBCAA and (K) TBAA at 1 μg/L.

Figure 2. Ion chromatograms of the internal standards of the four mentioned analytes at 4 μg/L.

Linearity greater than 0.99 was achieved for all 11 components observed, and each of the analytes were run over the entire concentration range in a six-point calibration curve. HAAs were calibrated between the range of 0.25 μg/L to 20 μg/L, exhibiting two orders of linear dynamic range (Figure 3).

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Figure 3-1. Calibration curve with the chromatogram at the lowest concentration calibrator (0.25 μg/L) for each HAA: (A) MCAA, (B) MBAA, (C) DCAA.

All the HAAs were detected at all concentration levels (Figure 3 and Table III). Some of the analytes, such as MCAA, TBAA, DBCAA, and BDCAA, had responses that approached their limits of detection at 0.25 μg/L. However, the workflow solution utilizing the Dionex ICS-5000+ Hybrid HPIC system and TSQ Fortis MS allows enough sensitivity, selectivity, and robustness to detect each of the HAAs at all concentration ranges. In addition, it should be noted that TCAA sensitivity is very strongly correlated with the source temperature of the mass spectrometer as well as the column temperature of the IC column. For this reason, the column temperature was maintained at 15 ºC as specified in the EPA method. Additionally, to improve the TCAA detection, the effect of temperature of the MS source on the response of TCAA was tested. Temperatures of 200 °C for both the ion transfer tube and vaporizer were found to be optimal for TCAA detection without impacting the detection of the other eight analytes. This phenomenon of TCAA temperature sensitivity has been reported in studies with other MS instrumentation 90


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configurations and also has an effect on brominated HAAs [4].

Figure 3-2. Calibration curve with the chromatogram at the lowest concentration calibrator (0.25 Îźg/L) for each HAA: (D) DBAA, (E) TCAA, (F) TBAA, (G) BCAA. 91


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Figure 3-3. Calibration curve with the chromatogram at the lowest concentration calibrator (0.25 Îźg/L) for each HAA: (H) DBCAA, (I) BDCAA, (J) Bromate, and (K) Dalpon.

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Tap water sample analysis Tap water samples from different cities in the Bay Area, were analyzed for the presence of all analytes contained in the method. Tap water samples were collected in accordance with the EPA Method 557 procedure [5], with NH4Cl added as a preservative as it reacts with residual chlorine preventing further production of haloacetic acids after sampling. Internal standards were added and the samples were quantified. The levels of each compound detected in the samples are shown in Table IV. The amount of HAA5 (MCAA, DCAA, TCAA, MBAA, and MCAA) is less than the maximum contaminant level, 60 μg/L. Table III. Peak area for each HAA over the concentration range (0.25–20 μg/L) Conc. (μg/L)

MCAA

MBAA

DCAA

DBAA

TCAA

TBAA

BCAA

0.25

1427

3209

17596

19525

2905

608

11483

853

0.5

2879

5691

33336

37950

5024

1412

23423

1

6641

10458

66049

73734

14692

3285

2

13815

20473

132264

147128

31505

5

29513

42485

273500

307224

10

57913

91405

555573

20

109508

167859

1099224

DBCAA BDCAA

Bromate

Dalapon

1380

7967

8472

1742

2671

15759

17263

51086

3487

5255

31539

35453

6245

102765

6999

9581

61106

72283

67865

13724

213529

14369

19763

126251

148971

628113

132877

28156

436224

30277

41249

260205

303844

1257242

265959

56145

865828

60456

83566

525701

599003

Table IV. Detected concentrations of the compounds LSSM (μg/L)

MRL (μg/L)

QCS (μg/L)

City A (μg/L)

City A LFM* (μg/L)

City A LFMD* (μg/L)

MCAA

9.04

0.42

4.0

0.83

2.80

2.76

MBAA

10.16

0.51

5.2

0.54

2.60

2.51

Bromate

9.95

0.47

5.3

0.00

2.23

2.14

DCAA

10.29

0.51

7.6

5.78

7.77

7.69

Dalapon

10.35

0.58

0.21

2.36

2.24

BCAA

10.45

0.55

9.7

5.10

6.72

6.72

DBAA

10.23

0.55

5.5

2.63

4.38

4.28

TCAA

9.81

0.27

1.2

4.31

6.07

6.21

TBAA

9.96

0.55

0.63

2.48

2.60

BDCAA

9.82

0.59

6.03

7.98

7.90

CDBAA

9.87

0.58

3.83

5.34

5.84

Compound

*LFM = Laboratory Fortified Matrix / *LFMD = Laboratory Fortified Matrix Duplicate

CONCLUSION The presence of disinfectants ensures increased safety for drinking water; however, the by-products of disinfectants also give rise to HAAs, bromates, and dalapon, excessive consumption of which can result in severe health issues. Analysis and quantitation of these contaminants in water can pose several challenges, especially with the increasing complexity of contaminants. Reagent-free IC systems coupled with the TSQ Fortis MS is a powerful platform solution that offers several advantages towards developing robust, reproducible, fast, and sensitive quantitation of polar molecules, as shown in this report. A robust, reproducible workflow solution for the analysis and quantitation of HAAs, bromates, 93


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and dalapon was developed. This method offers significant advantages over GC-ECD methods such as EPA Method 552 that require up to 4 hrs of sample preparation per sample. This IC-MS/MS method is direct injection and requires no sample preparation, thus offering significant advantages and cost savings. All the analytes in this assay were detected to the lowest calibration level and the accuracy is within the criteria. All 22 samples that were tested against a previously provided calibration curve achieved higher sensitivity with better robustness. The resolution between the matrix peaks and HAAs is excellent, which allows for minimum interference in detection, as well as ensuring a cleaner ion source of the mass spectrometer. Last but not the least, the optimal performance of the Dionex ICS-5000+ Hybrid HPIC system and TSQ Fortis MS platform solution exhibited excellent reproducibility and quantitation of the HAAs in water samples. REFERENCES 1. Beck, J. R., et al. “EPA Method 557 Quantitation of Haloacetic Acids, Bromate, and Dalapon in Drinking Water Using Ion Chromatography and Tandem Mass Spectrometry.” Thermo Fisher Scientific Poster Note 64430, 2016. 2. http://water.epa.gov/drink/contaminants/basicinformation/dalapon.cfm 3. Pisarenko, A. N.; Stanford, B. D.; Quiñones O.; Pacey G. E.; Gordon G.; Snyder S. A. Anal. Chim. Acta, 2010, 659 (1-2), pp 216-223 (https://doi.org/10.1016/j.aca.2009.11.061). 4. Slignsby, R.; Saini, C.; Pohl, C.; Jack, R. The Measurement of Haloacetic Acids in Drinking Water Using IC-MS/MS–Method Performance, Presented at the Pittsburgh Conference, New Orleans, LA, March 2008. 5. U.S. EPA Method 557: Determination of Haloacetic Acids Bromate and Dalapon in Drinking Water by Ion Chromatography Electrospray Ionization Tandem Mass Spectrometry (IC-ESI-MS/MS), 2009. This sponsor report is the responsibility of Thermo Fisher Scientifc.

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Sponsor Report

Br. J. Anal. Chem., 2019, 6 (25) pp 95-98 PDF

This section is dedicated for sponsor responsibility articles.

Sample Preparation of Polymers for Trace Metal Analysis Ensuring high-quality and productivity in elemental analysis of polymer samples using the Milestone ETHOS UP INTRODUCTION Polymers represent a broad class of compounds with a tremendous range of physical properties. While some of these compounds are relatively easy to prepare for trace metals analysis, most polymeric and plastic materials are very stable matrices and require extremely high temperatures and pressures to achieve complete digestion, which can be difficult to reach. Since polymers are principally organic, they generate a lot of pressure during the digestion processes. There are many challenges using traditional methods such as hot plates and Parr bombs to digest these highly stable matrices. These challenges include acid requirements, contamination, acid handling, lengthy digestions cycles and exposure of chemists to acid fumes. Closed vessel microwave technology is a proven alternative to these methods which speeds up the sample preparation process, improves the recovery of all the elements (including volatiles) and reduces possible sources of contamination. Two certified reference materials were used in this study to evaluate the efficacy of the ETHOS UP in the digestion of polymer samples: ECR680 polyethylene (High level) and ECR680K low denisity polyethylene (Low level). The analysis was performed on Mercury, Arsenic, Cadmium, Chromium, Lead and Zinc elements, as mentioned in the “Restriction of Hazardous Substances Directive,” also known with the acronym “RoHS.” MATERIALS AND METHODS In this industry report, a recovery study on certified reference polymer materials has been performed in order to prove the efficacy of ETHOS UP in the sample preparation for metal analysis. Instrument The ETHOS UP meets the requirements of modern analytical labs. It offers several unique benefits including: • Increased ease of use and productivity • Enhanced control in all vessels • Fast, accurate and traceable • Superior safety and digestion quality The ETHOS UP is a flexible and high performing platform used for elemental analysis and routine determinations in many applications. Its construction of stainless steel coated with five PTFE layers and accommodates both high-pressure and high-throughput rotors.

Figure 1. Milestone’s ETHOS UP.

easyTEMP Milestone’s easyTEMP contactless sensor directly controls the temperature of all samples and solutions, providing accurate temperature feedback to ensure complete digestion in all vessels and high safety. The superior temperature measurement of easyTEMP allows the processing of different samples of similar reactivity, thus reducing labor time and increasing overall throughput. Figure 2. easyTEMP contactless direct temperature sensor. 95


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This technology combines the fast and accurate reading of an in-situ temperature sensor with the flexibility of an infrared sensor. The ETHOS UP software provides digestion history traceability and temperature measurement for every sample. The temperature diagram and profiles are displayed realtime, and can be subsequently saved on the ETHOS UP terminal. SK-15 High Pressure Rotor The SK-15 rotor perfectly matches the needs of a modern analytical lab to determine trace elements, thanks to its ability to digest large sample amounts at high temperature (up to 300 °C) and pressure (up to 100 bar). The 15-position rotor is controlled by a contactless direct temperature sensor that controls the internal temperature of all vessels throughout the digestion cycle. This ensures complete and reproducible digestions of even the most difficult and reactive samples. The SK-15 also features Milestone’s patented “vent-and-reseal” technology for controlling the internal pressure of each vessel. Figure 3. SK15 easyTEMP High Pressure Rotor.

User Interface The ETHOS UP comes with a dedicated touch screen terminal and easyCONTROL software which incorporates our expertise and know-how in microwave sample preparation. The ETHOS UP userinterface provides full control all digestion parameters, provides complete documentation and expedites the overall digestion procedure. The terminal is equipped with multiple USB and ethernet ports for interfacing the instrument to external devices and the laboratory network. The ETHOS UP controller is user-friendly, icon-driven, multi-language and 21 CFR Part 11 compliant. To find the method which best suits your application, simply select from the vast library of pre-stored methods. Included with the ETHOS UP is a unique web-based application: Milestone Connect. This app allows you to become a part of the Milestone community and gain exclusive access to a robust library of information: lists of parts, technical notes, user manuals, video tutorials, continuously updated application notes and all relevant scientific articles.

Figure 4. easyCONTROL built-in library.

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Analytical Procedure Table I. Sample amount and acid mixture used for the microwave digestion run ETHOS UP — SK 15 easyTEMP Sample

Sample amount

Acid misxture

Polyethylene (ERM EC680)

0.5 g

5 mL of HNO3 65%

Low density polyethylene (ERM EC680K)

0.5 g

5 mL of HNO3 65%

Table II. Microwave program used for digestion of samples Step

Time

T2

Power

1

00:20:00

210 ºC

1800 W

2

00:10:00

210 ºC

1800 W

- Final dilution: 50 mL with deionized water

Figure 5. Microwave Run Report and multiple temperature traceability.

Quantification ICP-OES Instrumental Parameters: RF power (W): 1300; Plasma flow (L/min): 15.0; Auxiliary Flow (L/min): 1.5; Nebulizer Flow (L/min): 0.75; Replicate read time (s): 10; Instrument stabilization delay (s): 15; Sample Uptake Delay (s): 30; Pump Rate (rpm): 15; Rinse Time (s): 10; Replicates: 3. RESULTS AND DISCUSSION The performance of the Milestone ETHOS UP equipped with SK-15 rotor and easyTEMP was evaluated through a recovery study on polyethylene and low density polyethylene (ERM EC680 and ERM EC680K respectively). The samples were digested with Milestone’s ETHOS UP and subsequently analyzed via ICP-OES.

97


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Table III. Data of the recovery study on ERM EC 680 Certified value (mg Kg-1)

Recovery % (n=3)

RSD (%)

As

30.9 ± 0.7

102.3

1.3

Cd

140.8 ± 2.5

98.6

2.6

Cr

114.6 ± 2.6

101.8

1.1

Hg

25.3 ± 1.0

93.5

0.8

Pb

107.6 ± 2.8

96.7

1.4

Table IV. Data of the recovery study on ERM EC 680K

a b

Certified value (mg Kg-1)

Recovery % (n=3)

RSD (%)

As

4.1 ± 0.5

101.4

1.4

Cd

19.6 ± 1.4

94.9

1.6

Cr

20.2 ± 1.1

-a

-a

Hgb

4.64 ± 0.2

96.7

1.0

Pb

13.6 ± 0.5

97.3

2.7

Znc

137.0 ± 20.0

98

1.6

Average of 5.2 mg/Kg (RSD 2.6%) (to be compared with the Acid digestable Cr: 2.9- 16.2 mg/Kg). Analyzed with ICP cold vapor generator module. cIndicative values as reported in the certificate.

The analytical results are shown in tables III and IV with good recoveries of all elements and RSDs below 3%. This demonstrates the robustness and reproducibility of digestion microwave digestion using the ETHOS UP equipped with SK-15 easyTEMP technology. CONCLUSION The data shown in this industry report demonstrates full recovery of the element reported in the certificates of the reference material. Highly reactive samples such as polymers can be completely digested, even in large sample amounts along with samples of similar reactivities. The digestion process was accurately controlled by the easyTEMP sensor, ensuring superior digestion quality and reliable results. In addition to full analyte recovery, microwave digestion using the Milestone ETHOS UP provides the highest level of reproducibility, great ease of use and high productivity. This sponsor report is the responsibility of Milestone.

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BrJAC Editor-in-Chief Prof. Dr. Marco Aurélio Zezzi Arruda was recently honored as Fellow of the Royal Society of Chemistry The Royal Society of Chemistry (RSC) acknowledges significant achievement by chemists, and being elected Fellow by this society is one of the highest honors bestowed to chemists. To be eligible to become a Fellow of the Royal Society of Chemistry (FRSC), chemists need to have held a senior position for more than five years and their efforts recognized to have made an impact in any field of the chemical sciences. BrJAC congratulates its Editor-in-Chief for this achievement. Marco Aurélio Zezzi Arruda is currently director of the Institute of Chemistry at the University of Campinas (IQ-Unicamp), Campinas, Brazil, and also Full Professor Marco Aurélio Zezzi Arruda at the Department of Analytical Chemistry in the same institute. He also coordinates the Sample Preparation, Spectrometry and Mechanization Group (GEPAM) and is a member of the advisory board of the Brazilian Institute of Science and Technology (INCT) for Bioanalytics. He was a visiting guest professor at the Centre National de la Recherche Scientifique (CNRS), Pau, France and at the Universitat de Les Illes Balears, UIB, Spain. Additionally, he acted as advisor in more than 50 master dissertations or PhD theses. In addition to being Editor-in-Chief of the Brazilian Journal of Analytical Chemistry, he is a member of the editorial team or advisory board of the Journal of Analytical Atomic Spectrometry, Metallomics and the Journal of Integrated Omics. He is also a member of the Brazilian Chemistry Association (ABQ) and was coordinator of the inorganic mass spectrometry branch of the Brazilian Society for Mass Spectrometry (BrMASS) from 2010 to 2019. Marco Aurélio Zezzi Arruda is the author or co-author of over 210 research articles, six book chapters, five patents, over 50 invited lectures at national/international meetings and the editor of two books (Trends in Sample Preparation and Metallomics: The Science of Biometals). Additionally, he has over 5100 citations in the literature and an h-index of 38. He has received various awards in recognition of his work, namely: in 2015, the award for a career in pioneering science from the Proteomass Scientific Society, Portugal; in 2016, the academic recognition award “Zeferino Vaz” from the University of Campinas, Brazil; in 2017, the IV Prize of the Brazilian Society for the Progress of Science and the Unicamp Inventors Award of the Innovation Agency (INOVA); in 2018, the Adilson Curtius medal in recognition of developments in atomic and mass spectrometry; and in 2019 he was admitted as Fellow of the Royal Society of Chemistry. The RSC, founded in 1841, is the United Kingdom’s professional body for chemical scientists and the largest organization in Europe for advancing the chemical sciences. The society partners with industry and academia, promotes collaboration and innovation, advises governments on policy and promotes the talent, information and ideas that lead to advances in science. The RSC carries out research, publishes journals, books and databases, as well as hosting conferences, seminars and workshops. The designation FRSC is given to a group of elected Fellows of the RSC who have made major contributions to chemistry and other interface disciplines, such as biological chemistry.

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Thermo Scientific iCAP 7000 Plus Series ICP-OES Powerful, Easy-to-Use, Solution for Multi-Element Analysis The iCAP 7000 Plus Series ICP-OES provides low cost multi-element analysis for measuring trace elements in a diverse sample range. The instrument combines advanced performance with high productivity and ease of use, resulting in consistently reliable data, whilst ensuring compliance with global regulations and standards. The user-friendly sample introduction system with push-fit connections ensures rapid assembly and disassembly for cleaning and maintenance. Additional sample introduction components can be added to increase the speed of analysis or for the analysis of special sample types. The high resolution optics enable effective interference separation. At 200 nm, the resolution is 7 pm enabling the simple analysis of complex line-rich samples without excessively elaborate deconvolution. The low number of optical surfaces reduces reflective losses and maximizes light transmission from plasma to detector for superior detection limits. The echelle polychromator is thermostatically controlled to 0.1˚C to achieve long-term stability with recalibration typically only required every 24 hours. The iCAP 7000 Plus Series ICP-OES features superior signal detection and large working dynamic range due to the unique CID. The CID enables complete access to the full spectrum between 166 and 847 nm in both radial and axial views, with the additional functionality to perform post-run integration of previously unquantified elements. Analyze challenging samples with a self optimizing robust plasma delivered by the swing frequency RF generator. The innovative design of the iCAP 7000 Plus Series ICP-OES delivers powerful analytical performance and stability. The innovative ICP-OES technology is driven by the Thermo Scientific™ Qtegra™ Intelligent Scientific Data Solution™ (ISDS) software and the Element Finder plug-in. The plug-in reduces method development time and removes the need for wavelength selection by the user. This delivers powerful, high performance and low-cost analysis for both high throughput routine and research laboratories. The Thermo Scientific iCAP 7200 ICP-OES is a simple alternative to the Atomic Absorption technique and Microwave Plasma technology, providing a multi-element analysis solution for laboratories with increasing demands for sample throughput and lower detection limit capability. The Thermo Scientific iCAP 7400 ICP-OES is ideal for QA/QC and contract laboratories requiring highest sensitivity from full wavelength coverage. The instrument achieves an advanced level of performance for a range of liquid applications with the minimum of user set-up and maintenance. The instrument offers laboratories broad analytical capabilities with stability, sensitivity and regulatory compliance. The Thermo Scientific iCAP 7600 ICP-OES is the ideal solution for the most demanding analytical challenges. The instrument has the highest throughput, sensitivity and detection limits. Productivity is increased by the integrated sample loop which efficiently delivers the sample to the plasma. The iCAP 7600 ICP-OES maximizes scalability and advanced accessory connectivity to support expanding laboratory requirements.

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iCAP 7000 Series: Powerful, easy-to-use, solution for multi-element analysis The Thermo Scientific™ iCAP™ 7000 Plus Series ICP-OES provides low cost multi-element analysis for measuring trace elements in a diverse sample range. The innovative ICP-OES technology is driven by the Thermo Scientific™ Qtegra™ Intelligent Scientific Data Solution™ (ISDS) software and the Element Finder plug-in. The plug-in reduces method development time and removes the need for wavelength selection by the user. Thermo Scientific iCAP 7000 Series

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Thermo Scientific TSQ Fortis Triple Quadrupole Mass Spectrometer Fast and Robust Quantitation for every Environmental and Food Safety workflow With evolving challenges in environmental and food safety applications, it’s important to have the right platform for performing confident quantitation of multiple analytes in a complex mixture. The Thermo Scientific™ TSQ Fortis™ triple quadrupole mass spectrometer provides superior robustness — enabling round-the-clock operation and the ability to report reliable results, rapidly. Designed for ease, the TSQ Fortis MS platform enables confident quantitation of hundreds of samples in complex matrices, every day. • • • • • • •

Increased robustness — Active Ion Management Plus (AIM+) includes the Matrix Separator Ion Guide (MSIG)—ensures extended system uptime by keeping the ion path clean Maximum productivity — fast turnaround times while ensuring excellent quantitative results for extended lists of contaminants Designed for more ease — comprehensive workflows enabled by software that ensure confident analysis Quantitation at regulatory levels — of contaminants in environmental samples and pesticides in food samples Usability — simplified user maintenance and intuitive software experience Consistent performance under challenging conditions Precision, accuracy and sensitivity for demanding applications

Robust, innovative design The reliable instrument design, intuitive software, and comprehensive workflow solutions developed with the TSQ Fortis triple quadrupole mass spectrometer help ensure superior productivity for quantifying hundreds of compounds of all types — in any matrix, by any user. • Enhanced dual-mode discrete-dynode electron multiplier detector • QR4 Segmented Quadrupole mass filter with hyperbolic surfaces • Ion beam guide with neutral blocker • OptaMax NG ion source APCI ready • Ion transfer tube and sweep cone The TSQ Fortis MS provides a new level of confidence.

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Ethos UP and Milestone Connect

High Performance Microwave Digestion Systems Open the door to a new Milestone! The new ETHOS UP is the most advanced microwave digestion systems Milestone has ever manufactured. The new Milestone ETHOS microwave cavity has a volume in excess of 70 litres, by far the largest currently available; up to 44 samples can be accommodated, improving productivity and sample preparation throughput. The new Milestone ETHOS UP is equipped with the most advanced yet easy to use reaction sensors for complete quality control of the digestion conditions. In combination with our ‘vent-and-reseal’ vessel technology, the sensors ensure complete and safe digestions without any loss of volatile compounds Included with the brand-new ETHOS UP microwave digestion system is a unique web based application – Milestone Connect. The app provides up to date information and extended instrument control from outside the laboratory. By adding the IP address of your network, operators will be able to control the ETHOS UP from outside the laboratory with remote monitoring of every sample in the digestion run and other information related to the system on any wifi-enabled mobile device. That ultimately helps to provide high quality sample preparation. The app works on various external devices such as PC, tablets or smartphones connected to the ETHOS UP. Users will be part of Milestone scientific community and will gain an exclusive access to Milestone contents: application notes, digestion tips and techniques, Milestone library, scientific articles, video tutorials, special offers, news and a helpon-line section. Milestone know-how and 26-year experience in sample preparation are now available for chemists to provide instant support available 24 hours a day, 7 days a week.

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Pittcon Conference & Expo Be Amongst the best in PITTCON 2020... The Future of Laboratory Sciences

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SelectScience® Pioneers online Communication and Promotes Scientific Success since 1998

SelectScience® promotes scientists and their work, accelerating the communication of successful science. SelectScience® informs scientists about the best products and applications through online peer-to-peer information and product reviews. Scientists can make better decisions using independent, expert information and gain easy access to manufacturers. SelectScience® informs the global community through Editorial, Q&A and Application Articles, Featured Topics, Event Coverage, Video and Webinar programs.

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Editorial Article: Analytical chemistry round-up for 2019 — Take a look back through 2019 at the best content from the analytical community In the past 12 months the SelectScience editors have had the opportunity to speak with leading scientists, host fascinating and informative webinars and travel to international conferences, all with a view to bringing the latest techniques and technology trends from across the field. In this end-of-year round-up, they look again at the most compelling news and content of 2019 and reflect on the new technologies which have made the greatest impact in the field. Read this editorial article here Video: Identifying True Unknowns in Water Using High-Resolution Mass Spectrometry Potentially harmful by-products from hydraulic fracturing, including bromide, iodide and fracking chemicals, can contaminate drinking water. Dr. Susan Richardson, Professor of Chemistry at the University of South Carolina and ASMS President for 2020, shares her team’s research on the impact of fracking on the safety of drinking water. She explains how, by using high-resolution mass spectrometry, GC-MS and LC-MS, they are able to capture and assess all unknown chemicals to ensure drinking water is as safe as possible. Watch this video here Webinar: Future challenges in the food industry: How to increase throughput in sample preparation and qPCR the right way Quality criteria often have to meet national and international standards and the rising number of daily examinations on food composition or possible contamination pose new challenges to molecular biology investigations. In this webinar, experts in the area of life sciences, sample preparation and qPCR will provide methods and solutions for the most common challenges associated with high-throughput realtime PCR, with a special focus on analysis in the food industry. Attend the webinar here

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CHROMacademy helps Increase your Knowledge, Efficiency and Productivity in the Lab

CHROMacademy is the world’s largest eLearning website for analytical scientists. With a vast library of high-quality animated and interactive eLearning topics, webcasts, tutorials, practical information and troubleshooting tools CHROMacademy helps you refresh your chromatography skills or learn something completely new. A subscription to CHROMacademy provides you with complete access to all content including: • Thousands of eLearning topics covering HPLC / GC / Sample Prep / Mass Spec / Infrared / Basic Lab Skills / Biochromatography Each channel contains e-Learning modules, webcasts, tutorials, tech tips, quick guides and interactive tools and certified assessments. With over 3,000 pages of content, CHROMacademy has something for everyone. • Video Training Courses Each course contains 4 x 1.5-hour video training sessions, released over 4 weeks, with full tutor support and certification. • Ask the Expert – 24-hour Chromatography Support A team of analytical experts are on hand to help fix your instrument and chromatographic problems, offer advice on method development & validation, column choice, data analysis and much more. • Assessments Test your knowledge, certificates awarded upon completion. • Full archive of Essential Guide Webcasts and Tutorials Over 70 training topics covered by industry experts. • Application Notes and LCGC Articles The latest application notes & LCGC articles. • Troubleshooting and Virtual Lab Tools Become the lab expert with our HPLC and GC Troubleshooters. • User Forum Communicate with others interested in analytical science. Lite members have access to less than 5% of CHROMacademy content. Premier members get so much more! For more information, please visit www.chromacademy.com/subscription.html 110


Notices of Books

Br. J. Anal. Chem., 2019, 6 (25)

Electroanalytical Chemistry: Principles, Best Practices, and Case Studies Gary A. Mabbott, Author February, 2020. Publisher: John Wiley & Sons Written for undergraduate majors in chemistry and chemical engineering, this book provides a strong foundation in electrochemical principles and best practices. Teaches the basic principles of electroanalytical chemistry and illustrates best practices through the use of case studies of organic reactions and catalysis using voltammetric methods and of the measurement of clinical and environmental analytes by potentiometric techniques. Read more … GC-MS of Biologically and Environmentally Significant Organic Compounds: TMS Derivatives Valery A. Isidorov, Author April, 2020. Publisher: John Wiley & Sons This book provides a library of mass spectra of 1,725 biologically and environmentally important organic compounds, in the form of their trimethylsilyl derivatives, as well as their linear temperature programmed chromatographic retention indices, whose values are in the range of 700-4700 index units. Read more … Multidimensional Analytical Techniques in Environmental Research Regina Duarte, Armando Duarte, Editors June 2020. Publisher: Elsevier This book is a comprehensive resource on the many multidimensional analytical strategies to qualitatively and quantitatively assess and map the organic and inorganic pollutants in complex atmospheric, water and soil matrices. Sections cover the wide variety of multidimensional analytical techniques assisted by multiway data analysis tools, and the use of synchrotron-radiation-based techniques combined with other spectroscopic approaches to explore and map the speciation of elements. Read more … Espectrometria de massas: fundamentos, instrumentação e aplicações Fernando Mauro Lanças, Author May 2019. Publisher: Atomo This book provides a current view of mass spectrometry, both isolated and coupled with separation techniques such as chromatography. The fundamentals of each, current instrumentation and its main application niches are discussed, as well as the projection of its advance in the near future, especially by miniaturization and total automation. Read more … Chemistry of Environmental Systems: Fundamental Principles and Analytical Methods Jeffrey S. Gaffney, Nancy A. Marley, Authors September 2019. Publisher: John Wiley & Sons This book offers a comprehensive review of modern environmental chemistry, discussing the chemistry and interconnections between the atmosphere, hydrosphere, geosphere and biosphere. Explores the chemistries of the natural environmental systems and demonstrates how these chemical processes change when anthropogenic emissions are introduced into the whole earth system. A range of environmental analytical methodologies is described. Read more … 112


Periodicals & Websites

Br. J. Anal. Chem., 2019, 6 (25)

American Laboratory The American Laboratory® publication is a platform that provides comprehensive technology coverage for lab professionals at all stages of their careers. Unlike singlechannel publications, American Laboratory® is a multidisciplinary resource that engages scientists through print, digital, mobile, multimedia, and social channels to provide practical information and solutions for cutting-edge results. Addressing basic research, clinical diagnostics, drug discovery, environmental, food and beverage, forensics, and other markets, American Laboratory combines in-depth articles, news, and video to deliver the latest advances in their fields. Read more LCGC Chromatographyonline.com is the premier global resource for unbiased, peerreviewed technical information on the field of chromatography and the separation sciences. Combining all of the resources from the regional editions (LCGC North America, LCGC Europe, and LCGC Asia-Pacific) of award winning magazines, Chromatographyonline delivers practical, nuts-and-bolts information to help scientists and lab managers become more proficient in the use of chromatographic techniques and instrumentation, thereby making laboratories more productive and businesses around the world more successful. Read more Scientia Chromatographica Scientia Chromatographica is the first and to date the only Latin American scientific journal dedicated exclusively to Chromatographic and Related Techniques (Mass Spectrometry, Sample Preparation, Electrophoresis, etc.). With a highly qualified and internationally recognized Editorial Board, it covers all chromatography topics (HPLC, GC, SFC) in all their formats, in addition to discussing related topics such as “The Pillars of Chromatography”, Quality Management, Troubleshooting, Hyphenation (GC-MS, LC-MS, SPE-LC-MS/MS) and others. It also provides columns containing general information, such as: calendar, meeting report, bookstore, etc. Read more Select Science SelectScience® promotes scientists and their work, accelerating the communication of successful science. SelectScience® informs scientists about the best products and applications through online peer-to-peer information and product reviews. Scientists can make better decisions using independent, expert information and gain easy access to manufacturers. SelectScience® informs the global community through Editorial, Features, Video and Webinar programs. Read more Spectroscopy Spectroscopy’s mission is to enhance productivity, efficiency, and the overall value of spectroscopic instruments and methods as a practical analytical technology across a variety of fields. Scientists, technicians, and laboratory managers gain proficiency and competitive advantage for the real-world issues they face through unbiased, peer-reviewed technical articles, trusted troubleshooting advice, and best-practice application solutions. Read more

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Events

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2020 March 1 – 5 PITTCON Conference and Expo 2020 McCormick Place, Chicago, IL, USA https://pittcon.org/pittcon-2020/ May 18 – 21 27th Topical Meeting of the International Society of Electrochemistry “Electroanalytical Chemistry and Bioelectroanalysis” Salt Lake City, Utah, USA https://topical27.ise-online.org/ May 24 – 29 44nd International Symposium on Capillary Chromatography & 17th GCxGC Syposium Congress Centre, Riva del Garda, TN, Italy http://iscc44.chromaleont.it/slider.html May 26 – 29 43rd Annual Meeting of the Brazilian Chemical Society (43rd RASBQ) Centro de Convenções, Maceió, AL, Brazil http://www.sbq.org.br/reunioes-anuais June 2 – 4 Fine Chemical Engineering — FCE Pharma, International Exhibition of Technology for the Pharmaceutical Industry São Paulo Expo, São Paulo, SP, Brazil https://www.fcepharma.com.br/ June 14 – 18 18th European Conference on Electroanalysis (ESEAC 2020) Vilnius, Lithuania http://www.eseac2020.com/ June 21 – 26 18th Chemometrics in Analytical Chemistry (CAC2020) Courmayeur, Italy and Chamonix, France https://cac2020.sciencesconf.org/ August 10 – 13 Brazilian Meeting on Forensic Chemistry (7th EnqFor) & 4th Meeting of the Brazilian Society of Forensic Sciences (SBCF) Ribeirão Preto, SP, Brazil August 29 – September 4 XXIII International Mass Spectrometry Conference (IMSC 2020) Windsor Oceânico Hotel, Rio de Janeiro, RJ, Brazil https://www.imsc2020.com/

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2020 August 30 – September 4 71st Annual Meeting of the International Society of Electrochemistry — “Electrochemistry towards Excellence” Belgrade, Serbia https://annual71.ise-online.org/ September 14 – 17 20th Brazilian Meeting on Analytical Chemistry (20th ENQA) & 8th Ibero-American Congress of Analytical Chemistry (8th CIAQA) Wish Serrano Resort and Convention, Gramado, RS, Brazil enqa2020@ufsm.br www.enqa2020.com.br September 15 – 17 Advanced Mathematical and Computational Tools in Metrology and Testing XII (AMCTM 2020) Sarajevo, Bosnia and Herzegovina http://www.amctm2020.ba/ September 21 – 24 Rio Oil & Gas 2020 Riocentro, Rio de Janeiro, RJ, Brazil https://www.riooilgas.com.br/ October 20 – 21 18th Congress on Quality in Metrology (ENQUALAB 2020) São Paulo, SP https://www.enqualab.net/ October 26 – 30 49th Annual Meeting of the Brazilian Society of Biochemistry and molecular Biology (SBBq) & Meeting of the International Union of Biochemistry and Molecular Biology (IUBMB) Foz do Iguaçu, PR, Brazil November 8 – 11 XVI Latin American Congress on Organic Geochemistry (ALAGO) Niterói, RJ, Brazil https://alago2020.com/ December 10 – 11 International Conference on Metrology, Measurement and Inspection (ICMMI 2020) New York City, USA https://waset.org/metrology-measurement-and-inspection-conference-in-december-2020-in-new-york

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Acknowledgments BrJAC editors are grateful to all those who have reviewed papers in 2019 using significant time and effort to provide constructive inputs. Aline Lima Hermes Müller – Universidade Federal de Santa Maria Amauri Antonio Menegário – Universidade Estadual Paulista Júlio de Mesquita Filho Ana Cristi Basile Dias – Universidade de Brasília Ana Rita de Araújo Nogueira – Embrapa Pecuária Sudeste Anne-Helene Fostier – Universidade Estadual de Campinas Boaventura Freire dos Reis – Universidade de São Paulo Bruno Campos Janegitz – Universidade Federal de São Carlos Carin von Mühlen – Universidade do Estado do Rio de Janeiro Cassiana Carolina Montagner Raimundo – Universidade Estadual de Campinas Cassiana Seimi Nomura – Universidade de São Paulo Claudia Blindauer – University of Warwick, UK Claudio Francisco Tormena – Universidade Estadual de Campinas Dirk Schaumlöffel – University of Pau, FR Edenir Rodrigues Pereira Filho – Universidade Federal de São Carlos Edmar Isaías de Melo – Universidade Federal de Uberlândia Eduardo Costa de Figueiredo – Universidade Federal de Alfenas Eduardo Richter – Universidade Federal de Uberlândia Elaine Moreschi – Nestlé Brasil Elias Zagatto – Universidade de São Paulo Fabio Augusto – Universidade Estadual de Campinas Fábio Ferreira Gonçalves – Universidade Federal do Rio Grande Felipe Moura Araújo da Silva – Universidade Federal do Amazonas Gabriel Gustinelli Arantes de Carvalho – Universidade de São Paulo Geisamanda Pedrini Brandão Athayde – Universidade Federal do Espírito Santo Gisele Lopes – Universidade Federal do Ceará Gustavo de Souza Pessôa – EMS Indústria Farmacêutica Hector Henrique Ferreira Koolen – Universidade do Estado do Amazonas Italo Odone Mazali – Universidade Estadual de Campinas Jemmyson Romario de Jesus – Universidade Estadual de Campinas Joaquim de Araújo Nóbrega – Universidade Federal de São Carlos Juliana Naozuka – Universidade Federal de São Paulo Juliano Smanioto Barin – Universidade Federal de Santa Maria Leandro Machado de Carvalho – Universidade Federal de Santa Maria Leandro Wang Hantao – Universidade Estadual de Campinas Liziara da Costa Cabrera – Universidade Federal da Fronteira Sul Madson de Godoi Pereira – Universidade do Estado da Bahia Manoel Martins – Universidade Federal do Rio Grande Márcia Andreia Mesquita Silva da Veiga – Universidade de São Paulo Marcio Vidotti – Universidade Federal do Paraná Marco Flores Ferrão – Universidade Federal do Rio Grande do Sul Marcos de Almeida Bezerra – Universidade Estadual do Sudoeste da Bahia Maria Del Pilar Sotomayor – Universidade Estadual Paulista Júlio de Mesquita Filho Maria Eugenia Queiroz Nassur – Universidade de São Paulo Mariela Piston – Universidad de la Republica, UY Monise Cristina Ribeiro Casanova Coltro – Instituto Federal de Goiás Senador Canedo Noemi Nagata – Universidade Federal do Paraná 116


Acknowledgments

Paula Fernandes de Aguiar – Universidade Federal do Rio de Janeiro Paulo Clairmont Feitosa de Lima Gomes – Universidade Estadual Paulista Júlio de Mesquita Filho Rafael Rodrigues Cunha – Universidade Federal de Uberlândia Renata Stábile Amais – Universidade Estadual de Campinas Renato Zanella – Universidade Federal de Santa Maria Ricardo Erthal Santelli – Universidade Federal do Rio de Janeiro Roberta Oliveira Santos – Universidade de Santa Cruz do Sul Rodinei Augusti – Universidade Federal de Minas Gerais Rodrigo Barcellos Hoff – Ministério da Agricultura, Pecuária e Abastecimento Rodrigo Moretto Galazzi – Universidade Estadual de Campinas Rodrigo Mendes Pereira – Universidade Federal do ABC Ronei Poppi – Universidade Estadual de Campinas Sergiane Caldas Barbosa – Universidade Federal da Fronteira Sul Solange Cadore – Universidade Estadual de Campinas Tatiana Dillenburg Saint’Pierre – Pontifícia Universidade Católica do Rio de Janeiro Tiele Medianeira Rizzetti – Universidade de Santa Cruz do Sul Valderi Luiz Dressler – Universidade Federal de Santa Maria Valeriano Antonio Corbellini – Universidade de Santa Cruz do Sul Vanize Caldeira da Costa – Universidade Federal de Pelotas Verônica Maria de Araújo Calado – Universidade Federal do Rio de Janeiro

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Guidelines for Authors

PDF

Scope The Brazilian Journal of Analytical Chemistry (BrJAC) is dedicated to the diffusion of significant and original knowledge in all branches of Analytical Chemistry. BrJAC is addressed to professionals involved in science, technology and innovation projects in Analytical Chemistry, at universities, research centers and in industry. Professional Ethics Manuscripts submitted for publication in BrJAC cannot have been previously published or be currently submitted for publication in another journal. BrJAC publishes original, unpublished scientific articles and technical notes that are peer reviewed in the double-blind way. Review process BrJAC’s review process begins with an initial screening of the manuscripts by the editor-in-chief, who evaluates the adequacy of the study to the journal scope. Manuscripts accepted in this screening are then forwarded to at least two reviewers who are experts in the related field. As evaluation criteria, the reviewers employ originality, scientific quality, contribution to knowledge in the field of Analytical Chemistry, the theoretical foundation and bibliography, the presentation of relevant and consistent results, compliance to the BrJAC’s guidelines, and the clarity of writing and presentation. BrJAC is a quarterly journal that, in addition to scientific articles and technical notes, also publishes reviews, interviews, points of view, letters, sponsor reports, and features related to analytical chemistry. Brief description of the documents that can be submitted by the authors • Articles: Full descriptions of an original research finding in Analytical Chemistry. Articles undergo double-blind full peer review. • Reviews: Articles on well-established subjects, including a critical analysis of the bibliographic references and conclusions. Manuscripts submitted for publication as reviews must be original and unpublished. Reviews undergo double-blind full peer review. • Technical Notes: Concise descriptions of a development in analytical method, new technique, procedure or equipment falling within the scope of BrJAC. Technical notes also undergo doubleblind full peer review. The title of the manuscript submitted for technical note must be preceded by the words “Technical note”. • Letters: Discussions, comments, suggestions on issues related to Analytical Chemistry, and consultations to authors. Letters are welcome and will be published at the discretion of the BrJAC editor-in-chief. • Points of view: The expression of a personal opinion on some relevant subject in Analytical Chemistry. Points of View are welcome and will be published at the discretion of the BrJAC editor-in-chief. • Releases: Articles providing new and relevant information for the community involved in Analytical Chemistry. Download a template here Path: Log In / Manuscript Submission / Online Submission

Manuscript (MS) preparation • Language: English is the language adopted by BrJAC. • Required items: the MS must include a title, a graphical abstract, an abstract, keywords, and the following sections: Introduction, Materials and Methods, Results and Discussion, Conclusion, and References. • Identification of authors: the MS must NOT contain the authors’ names nor affiliations. This information must be in the cover letter to the editor-in-chief. This rule is necessary because the MS is subjected to double-blind review. • Layout: the lines in the MS must be numbered consecutively and double-spaced throughout the text. 118


Guidelines

• Graphics and Tables: must appear close to the discussion about them in the text. For figures use Arabic numbers, and for tables use Roman numbers. • Permission to use content already published: for figures, graphs, diagrams, tables, etc. identical to others previously published in the literature, the author must ask for publication permission from the company or scientific society holding the copyrights, and send this permission to the BrJAC editor-in-chief with the final version of the manuscript. • Chemical nomenclature: should conform to the rules of the International Union of Pure and Applied Chemistry (IUPAC) and Chemical Abstracts Service. It is recommended that, whenever possible, authors follow the International System of Units, the International Vocabulary of Metrology (VIM) and the NIST General Table of Units of Measurement. Abbreviations are not recommended except those recognized by the International Bureau of Weights and Measures or those recorded and established in scientific publications. • References: must be cited by numbers in square brackets. It is recommended that references older than 5 (five) years be avoided, except in relevant cases. Include references that are accessible to readers. References should be thoroughly checked for errors by the authors before submission. See how to format the references in the following item. Examples of reference formatting Journals 1. Orlando, R. M.; Nascentes, C. C.; Botelho, B. G.; Moreira, J. S.; Costa, K. A.; Boratto, V. H. M. Anal. Chem. 2019, 91 (10), pp 6471-6478 (https://doi.org/10.1021/acs.analchem.8b04943).

• Publications with more than 10 authors, list the first 10 authors followed by a semicolon and et al. • Titles of journals must be abbreviated as defined by the Chemical Abstracts Service Source Index (http:// cassi.cas.org/search.jsp).

Electronic journals 2. Sapozhnikova, Y.; Hoh, E. LCGC North Am. 2019, 37 (1), pp 52-65. Available from: http:// www.chromatographyonline.com/suspect-screening-chemicals-food-packaging-plastic-filmcomprehensive-two-dimensional-gas-chromatogr [Accessed 20 January 2019]. Books 3. Burgot, J.-L. Ionic Equilibria in Analytical Chemistry. Springer Science & Business Media, New York, 2012, Chapter 11, p 181. 4. Griffiths, W. J.; Ogundare, M.; Meljon, A.; Wang, Y. Mass Spectrometry for Steroid Analysis. In: Mike, S. L. (Ed.). Mass Spectrometry Handbook, v. 7 of Wiley Series on Pharmaceutical Science and Biotechnology: Practices, Applications and Methods. John Wiley & Sons, Hoboken, N.J., 2012, pp 297-338. Standard methods 5. International Organization for Standardization. ISO 26603. Plastics — Aromatic isocyanates for use in the production of polyurethanes — Determination of total chlorine. Geneva, CH: ISO, 2017. Master’s and doctoral theses or other academic literature 6. Dantas, W. F. C. Application of multivariate curve resolution methods and optical spectroscopy in forensic and photochemical analysis. Doctoral thesis, 2019, Institute of Chemistry, University of Campinas, Campinas, SP, Brazil. Patents 7. Trygve, R.; Perelman, G. US 9053915 B2, June 9, 2015, Agilent Technologies Inc., Santa Clara, CA, US. 119


Guidelines

Web pages 8. http://www.chromedia.org/chromedia [Accessed 10 January 2019]. Unpublished source 9. Viner, R.; Horn, D. M.; Damoc, E.; Konijnenberg, A. Integrative Structural Proteomics Analysis of the 20S Proteasome Complex (WP-25). Poster presented at the XXII International Mass Spectrometry Conference (IMSC 2018) / August 26-31, 2018, Florence, IT. 10. Author, A. A. J. Braz. Chem. Soc., in press. 11. Author, B. B., 2017, submitted for publication. 12. Author, C. C., 2018, unpublished manuscript. Note: Unpublished results may be mentioned only with express authorization of the author(s). Personal communications can be accepted exceptionally.

Download templates here Path: Log In / Manuscript Submission / Online Submission Manuscript submission Three different files, as described below, must be sent online through the website www.brjac.com.br 1. A Cover Letter (PDF file): addressed to the editor-in-chief, with the manuscript title, the full names of the authors and their affiliations, and the complete contact information of the corresponding author, including the ORCID iD. This letter should also inform to which section of the BrJAC the manuscript is being submitted (e.g. Article, Review, Technical Note, Point of View or Letter). The cover letter should also contain a statement that the article has not been previously published and is not under consideration for publication elsewhere. 2. The manuscript PDF file that must NOT mention the names of the authors nor their affiliations. 3. A similarities analysis report on the manuscript obtained through an anti-plagiarism software. (BrJAC indicates CopySpiderŠ freeware to support similarities checking analyzes. Download the CopySpider freeware at: www.copyspider.com.br

Revised manuscript submission Based on the comments and suggestions of the reviewers and editors a revision of the manuscript may be requested to the authors. A revised manuscript should be submitted by the authors, containing the changes made in the manuscript clearly highlighted. Letters to the reviewers, one to each reviewer, must also be submitted answering in detail to the questions made by them, and describing the changes made in the manuscript. Copyright When submitting their manuscript for publication, the authors agree that the copyright will become the property of the Brazilian Journal of Analytical Chemistry, if and when accepted for publication. The copyright comprises exclusive rights of reproduction and distribution of the articles, including reprints, photographic reproductions, microfilms or any other reproductions similar in nature, including translations. Final Considerations Whatever the nature of the submitted manuscript, it must be original in terms of methodology, information, interpretation or criticism. As to the contents of published articles, the sole responsibility belongs to the authors, and Br. J. Anal. Chem. and its editors, editorial board, employees and collaborators are fully exempt from any responsibility for the data, opinions or unfounded statements. BrJAC reserves the right to make, whenever necessary, small alterations to the manuscripts in order to adapt them to the journal rules or make them clearer in style, while respecting the original contents. The article will be sent to the authors for approval prior to publication.

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