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Characterization of organic pollutants present in Canal Suarez, San Juan Bay Estuary, Puerto Rico X. Perez¹, L. Roberson¹, M. Miller³ , and L. Diaz² ¹Department of Environmental Science, UPR-Río Piedras, ²Department of Chemistry, UPR-Río Piedras,³Institute of Neurobiology, UPR-Medical Sciences

INTRODUCTION

RESULTS – Quantified Data

MATERIALS & METHODS The water samples were collected in cleaned glass bottles, filtered through 15 mm qualitative filter paper Grade 1 (Whatman, UK) , bringing its pH to 6 and kept at 4oC until analysis. The sediment were collected in cleaned glass jars, dried and ground. Each samples was analyzed tripled. Two different extraction methods were used in order to achieve a more complete characterization of all pollutants present in the samples: 1.

2.

Solid phase micro extraction (SPME) : The analysis was performed with a 30-mm Polydimethylsiloxane (PDMS) fiber from Supelco and following the methodology of Cortazar, et al. 2002. Solid phase extraction (SPE): Discovery DSC-18 tubes from Supelco were used as stationary phase and 10 mL of methyl acetate as elution solvent . The water samples were prepared with 25 ml/L of methanol. After elution the samples were concentrated using and inert flow of nitrogen.

Fig. 3 Concentrations (ppt) and distribution of Phthalate esters quantized in the Canal Suarez

Ph1 Dibutyl phthalate

Bottom water (ppt) Anthracene, 2-methyl42.640 3,4'-Diisopropyl-1,1'-biphenyl 37.643 9-Methylene-fluorene 38.771 Fluoranthene 75.967 3-Isopropylgona-1,3,5(10),6,8,11,13-heptaene 77.042 Naphthalene 80.767 Naphthalene, 2-(phenylmethyl) 89.133 3,6-Dimethylphenanthrene 96.531

RESULTS

CS

Piñones Lagoon (PL), Condado Lagoon (CL), and Puerto Nuevo River (PNR).

We found 42 contaminants from a variety of chemical compounds including PAHs, phthalate esters, pesticides, herbicides and pharmaceutical compounds. Only a portion of these pollutants have been quantified to date due to availability of standards.

The PAHs only were found in bottom water, the Table 2 contains their concentrations in parts per trillion. Fig. 4 Concentration and distribution of Pesticide, Drugs and Explosive quantized in the Canal Suarez

Table 1. Partial list of organic pollutants identified in the different samples of Canal Suarez.

SPECIFIC AIMS -Characterize and quantify organic pollutants present in sediment, surface water, and bottom water from monitoring stations in Canal Suarez, Piñones Lagoon and Condado Lagoon. -Analyze tissue and hemolymph of the blue crab, Callinectes sapidus (Fig 2), for the presence of organic pollutants - Test the actions of the most abundant organic pollutants on the Callinectes sapidus heart circuit.

Fig. 2. Callinectes sapidus

Di-n-octyl phthalate Phthalic acid, butyl 8-methylnonyl ester Naphthalene, 6-ethyl-1,2,3,4-tetrahydro-1,1 Azacyclohexan-2-carboxylic acid amide

Sample Surface Bottom Sediment water water X X X X

1,3,5-Cycloheptatriene, 2,4-di-t-butyl-7,7-dimethyl3-(1,5-Dimethyl-hexyl)-3a,10,10,12b-tetramethyl1,2,3 7,8-Epoxylanostan-11-ol, 3-acetoxy1,1-Difluoro-2-methyl-3-ethyl cyclopropane

X

X

Pesticide, herbicide

Hexobarbital p-Trifluoromethoxybenzamide

X X

X X

Drug Drug Drug Drug

2C-D 2,6-Dimethyl-4-ethylpyridine

X X

Drug Drug

2-Amino-3-benzoylmethyl-5-benzylthio-1,3,4thiadiazole Cinchophen Octadecane, 3-ethyl-5-(2-ethylbutyl)

X

Drug

X X

PHAs-Drug Petroleum products

Heptadecane, 9-hexylHexadecane

X

X X

X

Petroleum products Petroleum products

Vinylsulfonamide

X

antimicrobial agent

Trimethylamine

X

antimicrobial agent

X

explosive explosive

X

alcohol

X

2-metil-1-nitropropano à-Nitroguanidine

X

1-Penten-4-ol

X

Additional studies must be done to determine sources and sinks as well as impact on the ecosystem flora and fauna.

FUTURE DIRECTIONS •Add more sampling stations in the water bodies connected to Canal Suarez, as well as add additional sampling in other seasons to examine the distribution of contaminants throughout the watershed. •With GIS tools, analyze the land use around the estuary to determine possible sources of contamination. •In collaboration with CariCOOS.org, understand the movement of contaminants using a flow model between water bodies. •Measure the impact of different concentrations of pollutants in the semi-intact working heart preparation of our crab model (Callinectes sapidus).

LITERATURE CITED

Pesticide, herbicide Pesticide, herbicide

X

Pes2 Benzene, 1,4dichloroPes3 Clorophene

Phthalate (Plasticizer ) Phthalate (Plasticizer ) Pesticide, herbicide Pesticide, herbicide

X

Phenyl phosphorodichloridite tert-Hexadecanethio

Pes1 Benzyl Benzoate

Common Uses

Table 1 contains the distribution of as yet unquantified organic pollutants in Canal Suarez grouped by common use.

Concentration (ppt)

Contaminant chemical name

Here we show the presence of a wide variety of pollutants, including PAHs, phthalate esters, pesticides, herbicides and pharmaceutical compounds in both water and sediment samples from a single site within the San Juan Bay Estuary. This is the first time a study of this kind has been made. Alondra et al. (2010) and Otero et al. (2011) analyzed pollutants in water, sediment and tissue in water bodies of Puerto Rico, and Dissanayake (2010) studied the physiological effects in crustaceans. However, a single comprehensive analysis of total semi volatile and volatile organic pollutants at a field site has never been done. Our results show a wide variety of organic pollutants in all phases (water and sediment) with significant concentrations. For example, dibutyl phthalate concentrations in bottom water were 12.8 ppt, over twice the OSHA recommended Exposure limit (REL) of 5.0 ppt. In addition, each pollutant may be below the REL or have unknown impacts singly, but together can have a large synergistic impact on the ecosystem.

Contaminant chemical name

PL

Fig. 1. Monitoring Stations in the San Juan Bay Estuary: Canal Suarez (CS),

Ph5 Phthalic acid

Table 2. Concentration of PHAs quantized in bottom water in the Canal Suarez

CL

PNR

Ph4 Dimethyl 2,6naphthalene dicarboxylate

Compound

Both analyses were coupled to GC-MS (Agilent 6890NAgilent 5973) and compound identification was made using AMDIS/NIST computer program.

San Juan Bay Estuary

Ph2 Benzyl butyl phthalate Ph3 Mehp

Concentration (ppt)

The Canal Suarez (CS) is one of three channels that connect the bodies of water that form the San Juan Bay Estuary (SJBE) and crossing one of the main roads within the San Juan Metropolitan area (Fig 1). The Estuary is surrounded by eight densely populated municipalities (approximately 1.2 million people total). These urban surroundings can cause substantial damage to the SJBE as a result of land use, wastewater discharges, solid waste disposal, and other anthropogenic impacts. These factors have been and are affecting water quality and the deterioration of the life of organisms in both terrestrial and aquatic systems. The estuary is inhabited by a large number of species including birds, amphibians, crustaceans (blue crab), reptiles, fish and wetland plants, many of which are important ecologically or commercially (Laureano, E. et. al. 2009). Our project chose three sampling sites within the estuary. We have analyzed the CS sediment, surface water, and bottom water to determined the organic pollutant present in this point. The effects of the found pollutants on the crab heart circuit will be studied to provide a better understanding of the sublethal effects of these contaminants on the estuary ecosystem.

CONCLUSIONS

Dr1

3,5-di-tert-Butyl-4hydroxy acetophenone

Dr2

Phenol, 2,6-bis(1,1dimethylethyl) 4ethyl

Ex1

Benzenamine, 4octyl-N-(4octylphenyl)-

Compound

The figures 3 and 4 shows the concentration and distribution of the Phthalates, PHAs, Pesticides, Drugs and Explosives quantized. These contaminants are used in a wide variety of readily available products including detergents, cosmetics, gasoline, chemical solvents, plasticizers, adhesives, drugs and others.

1. Laureano, E. et al. 2010. Programa del Estuario de la Bahia de San Juan. Segundo Informe de la condicion ambiental del Estuario de la Bahia de San Juan. 2. Cortazar, E. et al. 2002. MultiSimplex optimization of the solid-phase microextraction–gas chromatographic–mass spectrometric determination of polycyclic aromatic hydrocarbons, polychlorinated biphenyls and phthalates from water samples. Jo Chromatography A, 978 :165– 175 3. Aldarondra J. 2010 Trace metals, PAHs, and PCBs in sediments from the Jobos Bay area in PR. Marine Pollution Bulletin 60: 1350–1358 4. Otero, E. et al. 2011. Report: Estuarine Environmental Indicators for the San Juan Bay Estuary: Assessment of Sediment and Fish Tissue Contaminants. The SJBE Program, and the USEPA Reg. 2 5. Dissanayake, A. Bamber S. 2010. Monitoring PAH contamination in the field (Southwest Iberian Peninsula): Biomonitoring using fluorescence spectrophotometry and physiological assessments in the shore crab Carcinus maenas (L.) (Crustacea:Decapoda). Marine Environmental Research 70:65-72

ACKNOWLEDGEMENTS AND CONTACT INFORMATION Dr. Gonzalez-Illan; undergraduate students Gabriela Sosa., Keishla Valentin., Andrea Mercedes. and Paola Lebron. This project has been supported by a grant from the NSF CREST program and the Department of Environmental Science, UPRRP

Contacts: -Xochitl Perez, 787-367-3604, xochitl.perez@upr.edu -Loretta Roberson, loretta.roberson@gmail.com -Liz Diaz, lizvazquez8@gmail.com -Mark Miller, mark.miller@upr.edu


Characterization of organic pollutants present in Canal Suarez,San Juan Bay Estuary, Puerto Rico