Bioremediation and Bioeconomy
Edited by M.N.V. Prasad
Department of Plant Sciences
University of Hyderabad, Telangana, India
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ISBN: 978-0-12-802830-8
Edward Gatliff
Applied Natural Sciences, Inc., Hamilton, Ohio, USA
M.A. Glazyrina
Ural Federal University named after First President of Russia B.N. Yeltsin, Ekaterinburg, Russia
S. Gopalakrishnan
International Crops Research Institute for the Semi-Arid Tropics (ICRISAT), Patancheru, Telangana, India
C. Grison
FRE 3673 – Bioinspired Chemistry and Ecological Innovations – CNRS, University of Montpellier 2, Stratoz – Cap Alpha, Avenue de l’Europe, 34830 Clapiers, France
U. Jena
Desert Research Institute, Reno, NV, USA
V. Kanaganahalli
International Crops Research Institute for the Semi-Arid Tropics (ICRISAT), Patancheru, Telangana, India
Srujana Kathi
Pondicherry University, Kalapet, Puducherry, India
J. Koelmel
University of Hyderabad, Hyderabad, Telangana, India
A. Kumar
Indian School of Mines, Dhanbad, Jharkhand, India
G. Labuto
Universidade Federal de São Paulo, São Paulo, SP, Brazil
G. Lemoine
Établissement Public Foncier Nord-Pas de Calais, Euralille, France
P. James Linton
Geosyntec, Clearwater, Florida, USA
N.V. Lukina
Ural Federal University named after First President of Russia B.N. Yeltsin, Ekaterinburg, Russia
S.K. Maiti
Indian School of Mines, Dhanbad, Jharkhand, India
M.G. Maleva
Ural Federal University named after First President of Russia B.N. Yeltsin, Ekaterinburg, Russia
O. Meesungnoen
Mahasarakham University, Maha Sarakham, Thailand
G. Mohanakrishna
VITO—Flemish Institute for Technological Research, Mol, Belgium
R. Naidu
University of Newcastle, Newcastle, NSW, Australia
W. Nakbanpote
Mahasarakham University, Maha Sarakham, Thailand
T.K. Olszewski
Organic Chemistry, Wroclaw University of Technology, Wroclaw
D. Pant
VITO—Flemish Institute for Technological Research, Mol, Belgium
E.G. Papazoglou
Agricultural University of Athens, Athens, Greece
M.S. Paul
St. John’s College, Agra, India
C. Phadermrod
Padaeng Industry Public Co. Ltd. (Mae Sot Office), Tak, Thailand
M.N.V. Prasad
University of Hyderabad, Hyderabad, Telangana, India, and Ural Federal University named after First President of Russia B.N. Yeltsin, Ekaterinburg, Russia
J. Pratas
University of Coimbra, Coimbra, Portugal
M. Rajkumar
Central University of Tamil Nadu, Thiruvarur, Tamil Nadu, India
E.A. Rakov
Ural Federal University named after First President of Russia B.N. Yeltsin, Ekaterinburg, Russia
P. Srinivas Rao
International Crops Research Institute for the Semi-Arid Tropics (ICRISAT), Patancheru, Telangana, India
G.A. Ravishankar
Dayananda Sagar Institutions, Bengaluru, Karnataka, India
Douglas J. Riddle
RELLC, Mountain Center, California, USA
D. Rose
University of Hyderabad, Hyderabad, Telangana, India
H. Sarma
N N Saikia College, Titabar, Assam, India
A. Sathya
International Crops Research Institute for the Semi-Arid Tropics (ICRISAT), Patancheru, Telangana, India
Preface
Environmental decontamination is an integral part of bioeconomy and sustainable development. Biodiversity is being used as raw material for environmental decontamination, and this field has grown phenomenally in recent years, having emerged less than 3 decades ago. On the other hand, the volume of contaminated substrates (water, soil, and air) is increasing due to anthropogenic and technogenic sources of organic and inorganic contaminants. Metals are the most prevalent inorganic pollutants/ contaminants and are widely used for a wide variety of needs from building materials to information technology. Metal contamination is a global problem.
Today with a growing economy extensive industrialization and extraction of natural resources have resulted in environmental contamination and pollution. Large amounts of toxic waste have been dispersed in thousands of contaminated sites spread all over the globe. These pollutants belong to two main classes: inorganic and organic. The challenge is to develop innovative and cost-effective solutions to decontaminate polluted environments. In this direction, bioremediation is emerging as an invaluable tool for environmental cleanup.
Various strategies are being applied to reduce the levels of contamination. Cultivation of industrial and environmental crops in contaminated soils is one such option. If the contaminant concentration exceeds the permissible level in edible parts, it poses serious health concerns. Therefore, in such cases non-edible crop production and valorization to value chain and value additions is a feasible proposition.
The advancement in this field is toward production of diverse biofuels (solid, liquid, and gaseous). Essentially, bioremediation is centered on bioenergy and use of bioresources harvested from environmentally perturbed/stressed agro-ecosystems. Although bioremediation contractors must profit from the activity, the primary driver is regulatory compliance rather than manufacturing profit. It is an attractive technology in the context of bioeconomy. This book will address the bottlenecks and solutions to the existing limitations in field scale and the relevant techniques. Crucial aspects of biorefinery are also covered.
Globally, land and water resources are under immense pressure due to land degradation, pollution, population explosion, urbanization, and global economic development. Large amounts of toxic waste have been dispersed in thousands of contaminated sites, and bioremediation is emerging as an invaluable tool for environmental cleanup. Bioremediation and Bioeconomy addresses this challenge by presenting innovative and cost-effective solutions to decontaminate polluted environments, including usage of contaminated land and wastewater for bioproducts such as natural fibers, biocomposites, and fuels to boost the economy.
Bioremediation and Bioeconomy provides a common platform for scientists from various backgrounds to find sustainable solutions to these environmental issues. This book will also address all the topical issues crucial for understanding the ecosystem approaches for a sustainable development. It provides an overview of ecosystem approaches, conservation of natural resources, pollution abatement, and mitigation.
This book is a collective effort of 65 contributors from 14 countries: Australia, Belgium, Brazil, China, France, Greece, India, Nigeria, Poland, Portugal, Russia, Thailand, Ukraine and USA.
The book includes 26 chapters grouped in 8 sections:
1. Bioproducts from Contaminated Substrates (Soil and Water) (Chapters 1–4)
2. Biomass Energy, Biodiesel and Biofuel from Contaminated Substrates (Chapters 5–8)
3. Ornamentals and Crops for Contaminated Substrates (Chapters 9–12)
4. Brownfield Development for Smart Bioeconomy (Chapters 13–16)
5. Algal Bioproducts, Biofuels, Biorefinery for Business Opportunities (Chapters 17 and 18)
6. Bioprocesses, Bioengineering for Boosting Bio-Based Economy (Chapters 19–21)
7. Case Studies (Chapters 22 and 24)
8. New Biology (Chapters 25 and 26)
The book provides a comprehensive review of new information on bio-phyto-rhizoremediation. Moreover, I feel that this is the first attempt to link bio-phyto-rhizoremediation to bio-based economy citing several examples. The unique features of this books include (a) numerous color figures, flow diagrams, tables, and updated literature; (b) strategies to utilize contaminated susbtrates for producing bioresources and cogeneration of value chain and value addition products boosting bioeconomy; and (c) several success stories.
M.N.V. Prasad
Department of Plant Sciences
University of Hyderabad Telangana, India
5 May 2015
a = Brassica napus (rape-seed)
b = Helianthus annuus (sunflower)
c = Glycine max (soybean)
Primary feed-stock for production of biodiesel in Ukraine. Brassica and Helianthus are acknowledged for their phytoremediation potential to polish contaminated soils. The harvested produce is ideal for bioenergy.
FIGURE 1
Primary feed-stock for production of biodiesel in Ukraine.
This review chapter presents the nowadays situation of heavy metals pollution on Ukraine territory and the possibility of using oilseed crops (rapeseed, soybean, and sunflower) for 50% cleanup of the areas polluted by heavy metals.
2 MONITORING OF HEAVY METALS POLLUTION IN UKRAINE
The report of EEA-UNEP (2000) regarding the status of soil contamination in Europe (Figure 2) has shown that in Eastern Europe problems of diffuse soil contamination is greatest compared to other European countries. The high contamination of heavy metals is shown in Ukraine, especially in the Chernobyl area. Unfortunately, the international literature is still missing detailed analysis of heavy metals contamination in Ukraine.
The Ministry of Nature Protection of Ukraine reported that lead concentrations in the capital city of Kyiv were 4.6 times higher than the permissible limit. It was reported that the main source of lead in the air and soil is from automobile activities. Major sources of lead include gasoline combustion, also nonferrous smelting, and mining (Chiras, 2009).
About 90% of toxic metals accumulate from atmosphere to soil, where they migrate in groundwater, become absorbed by plants, and get into the trophic chains (Lozanovskaya et al., 1998; Anonymous, 1998; Trahtenberg, 1998; Alekseeva, 1987). According to coefficient of load factor, it has been established that in some regions of Ukraine the level of metal pollution of soil, including mobile forms, exceeds the permissible level by 2-14 times (Gaevsky and Pelypets, 1999; Nikolaychuk and Hrabovsky, 2000). In particular, the content of lead in soils of northern agricultural regions (Zhytomyr, Sumy, Rivne, Chernihiv, and Kyiv) exceeds the permissible level by 3 to 9 times (Shestapalov et al., 1996).
A similar tendency is observed for soil in the region of Kyiv Polesye, where concentration of metal exceeds the natural level by 3 times (Brooks, 1982; Shestapalov et al., 1996) (Figure 3).
2
Probable problem areas of diffuse contamination in Europe (EEA-UNEP, 2000) * - agricultural areas which can use chemical during plant cultivation.
Second place among heavy metals highly contaminating Ukraine soil is nickel. It’s known that the main anthropogenic source of nickel emission is combustion of fossil fuels and traffic ( Krsti ć et al., 2007 ). Nickel is widely used in silver refineries, alloy, pigments electroplating, zinc-based casting, and storage batteries too, which also can have the effect of increasing nickel pollution.
FIGURE
Content of lead on territory of Ukraine
High level (more than 20 mg/kg)
Average level (more than 10 mg/kg)
Low level (4-10 mg/kg)
The map of lead pollution in Ukraine
FIGURE 3
The map of lead pollution on territory of Ukraine.
Volyn
Lviv
Ternopil
Ivano-Frankivsk
Zakarpattia Chernivtsi Khmelnytskyi
Vinnytsia
Odessa
Rivne
Zhytomyr Kyiv
Sumy
Poltava
Cherkasy
Mykolaiv
Kherson
SEA OF AZOV
BLACK SEA
Autonomous Republic of Crimea
Sevastopol
Donetsk Zaporizhia
Kirovohrad Dnipropetrovsk
Kharkiv
Luhansk
Chemihiv
Area polluted by copper (65-250 mg/kg)
Area polluted by chromium (25-80 mg/kg)
The map of copper pollution in Ukraine
5
The map of copper and chromium pollution on territory of Ukraine.
Rivne
Volyn
Zakarpatiya
Zhytomyr
Kyiv
Chernihiv
Ivano-Frankivsk
Ternopil Khmelnytskyl
Vinnytsia
Cherkasy
Kirovohrad
Mykolaiv
Sevastopol
Autonomous Republic of Crimea
Odesa
Kherson
Dnipropetrovsk
Poltava
Kharkiv
Donetsk
Zaporizhia
SEA OF AZOV
BLACK SEA
Chernivtsi
FIGURE
7
oil production in Ukraine (Myrna van Leeuwen et al., 2012).
8
Sunflower oil production in Ukraine (Myrna van Leeuwen et al., 2012).
engagement and investment continue to be stronger for production feedstock than for fuels. For instance, in Ukraine there is no direct support for the production of fuels through the European Bank for Reconstruction and Development (EBRD); the bank is, however, an important credit grantor in the agricultural sector (EBRD, 2013). Moreover, Germany in particular has supported crop production in Ukraine in the past, for example through a GIZ project on sustainable biofuel
FIGURE
Soybean
FIGURE
production (IER, 2010) as well as through seminars and conferences on (sustainable) biofuel production embedded in the activities of the German-Ukrainian Agricultural Policy Dialogue (APD, 2013). This is due to the fact that according to the Renewable Energy Directive (European Parliament and Council, 2009) liquid biofuels have to follow certain sustainability criteria (e.g., sustainable crops must not be grown on areas with high biodiversity or with high existing carbon stock). The economic and social benefits that Ukraine can gain from its agricultural sector depend very strongly not just on the development of that sector itself but also on the benefits gained from the further use of this output. As a producer of rapeseed (and other crops) for the global market and thus as a producer of biofuel feedstock for other economies, Ukraine can follow the trajectory of other economies dependent on primary commodity exports (Schaffartzik et al., 2014).
4 BIODIESEL PRODUCED FROM OILSEED CROPS
Plant triacylglycerols are energy-rich compounds of reduced carbon available from nature. Most plant oils are derived from triacylglycerols stored in seeds (Srivastava and Prasad, 2000; Demirbas, 2006). During seed development, photosynthate from the mother plant is imported in the form of sugars, and the seed converts these into precursors of fatty acid biosynthesis. Given their chemical similarities, plant oils represent a logical substitute for conventional diesel, a nonrenewable energy source. However, as plant oils are too viscous for use in modern diesel engines, they are converted to fatty acid esters. Most plant labels have a viscosity range that is much higher than that of conventional diesel: 17.3-32.9 mm2/s compared to 1.9-4.1 mm2/s, respectively (Knothe and Steidley, 2005). The fatty acid methyl esters (FAMEs) found in biodiesel have a high energy density as reflected by their high heat of combustion, which is similar, if not greater, than that of conventional diesel (Knothe, 2005). Similarly, the cetane number (a measure of diesel ignition quality) of the FAMEs found in biodiesel exceeds that of conventional diesel (Knothe, 2005).
The higher oxygenated state compared to conventional diesel leads to lower carbon monoxide (CO) production and reduced emission of particulate matter (Graboski and McCormick, 1998). This latter air pollutant is especially problematic in European cities, motivating temporary curfews for diesel-powered vehicles. Biodiesel also contains little or no sulfur or aromatic compounds; in conventional diesel, the former contributes to the formation of sulfur oxide and sulfuric acid, while the aromatic compounds also increase particulate emissions and are considered carcinogens. In addition to the reduced CO and particulate emissions, the use of biodiesel confers additional advantages, including a higher flashpoint, faster biodegradation, and greater lubricity (EBB, 2004; Demirbas, 2007). Therefore, plant oil production needs to be greatly increased for biodiesel to replace a major proportion of the current and future fuel needs of the world.
The source of biodiesel usually depends on the crops amenable to the regional climate. Biodiesel is the monoalkyl esters of long-chain fatty acids derived from renewable feedstocks, such as vegetable oil or animal fats, for use in engine. Biodiesel is composed of FAMEs that can be prepared from triglycerides in vegetable oils by transesterification with methanol. The biodiesel is quite similar to conventional diesel fuel in its main characteristics (Meher et al., 2006). In the United States, soybean oil is the most commonly grown biodiesel feedstock, whereas the rapeseed (canola) oil and palm oil are the most common source for biodiesel in Europe and in tropical countries, respectively (Knothe, 2002). However, any vegetable oil—corn, cottonseed, peanut, sunflower, safflower, coconut, or palm—could be used to produce biodiesel (Demirbas, 2006). From a chemical point of view, oils from different
sources have different fatty acid compositions. The fatty acids vary in their carbon chain length and in the number of unsaturated bonds they contain (Table 1). Fats and oils are primarily water-insoluble, hydrophobic substances in the plant and animal kingdom that are made up of one mole of glycerol and three moles of fatty acids and are commonly referred as triglycerides.
Twenty-one fatty acids are screened in all the samples. The fatty acids commonly found in vegetable oil and fat are stearic, palmitic, oleic, linoleic. Other fatty acids that are also present in many of the oils and fats are myristic (tetradecanoic), palmitoleic, acachidic, linolenic, and octadecatetraenoic. Many other fatty acids are also found in oils with the above-mentioned common fatty acids. Erucle fatty acid is found only in three oils: crambe, camellia oil, and Brassica carinata. In the oil of sunflower and soybean, the content of the fatty acid is different in the same plant species, which may be due to either the varietal or instrumental difference or in the different parts of plants.
Chemically the oil/fats consist of 90-98% triglycerides and small amount of mono- and diglycerides. Triglycerides are esters of three fatty acids and one glycerol. These contain a substantial amount of oxygen in their structures. When three fatty acids are identical, the product is simple triglycerides; when they are dissimilar, the product is mixed triglycerides, fatty acids which are fully saturated with hydrogen have no double bonds. Fatty acids with one missing hydrogen molecule have one double bond between carbon atoms and are called monosaturated. The fatty acids that have more than one missing hydrogen molecule or have more than one double bond are called polyunsaturated. Fully saturated triglycerides lead to excessive carbon deposits in engines. The fatty acids are different in relation to the chain length, degree of unsaturation, or presence of other chemical functions. Chemically, biodiesel is referred to as the mono alkyl esters of long-chain fatty acids derived from renewable lipid sources. Biodiesel is the name for a variety of ester-based oxygenated fuel from renewable biological sources. It can be used in compression ignition engines with little or no modification (Demirbas, 2002).
Biodiesel is made in a chemical process called transesterification, in which organically derived oils (vegetable oils, animal fats, and recycled restaurant greases) are combined with alcohol (usually methanol) and chemically altered to form fatty esters such as methyl ester. Biodiesel consists of alkyl (usually methyl) esters instead of the alkanes and aromatic hydrocarbons of petroleum-derived diesel. Diesel has no oxygen compound. It is a good quality of fuel (Singh and Singh, 2010).
Oil, ester, and diesel have different numbers of carbon and hydrogen compounds. On the other hand, in the case of vegetable oils oxidation resistance is markedly affected by the fatty acid composition. The large size of vegetable oil molecules (typically three or more times larger than hydrocarbon fuel molecules) and the presence of oxygen in the molecules suggest that some fuel properties of vegetable oil would differ markedly from those of hydrocarbon fuels (Goering et al., 1982).
Since biodiesel is produced in quite differently scaled plants from vegetable oils of varying origin and quality, it was necessary to create standards for fuel quality to guarantee engine performance without any difficulties. Austria was the first country in the world to define and approve the standards for rapeseed oil methyl esters as diesel fuel. As standardization is a prerequisite for successful market introduction and penetration of biodiesel, standards or guidelines for the quality of biodiesel has also been defined in other countries such as Germany, Italy, France, the Czech Republic, and the United States (Meher et al., 2006).
The parameters that define the quality of biodiesel can be divided into two groups. One group contains general parameters, which are also used for mineral oil-based fuel, and the other group describes the chemical composition and purity of fatty acid alkyl esters ( Mittelbach,
Table 1 Fatty Acid Composition of Rapeseed, Sunflower, and Soybean Oil from Different Sources (%)
Demirbas (2002, 2003) and Balat and Balat (2008)
Goering et al. (1982)
Demirbas (2003) and Balat and Balat (2008)
Goering et al. (1982)
Goering et al. (1982)
S. No. Vegetable Oil
3. Sunflower
Demirbas (2003) 6. Soybean
Demirbas (2003)
7. Soybean
