Trace metals, PAHs, and PCBs in sediments from the Jobos Bay area in Puerto Rico

Marine Pollution Bulletin 60 (2010) 1350–1358

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Baseline

Edited by Bruce J. Richardson

The objective of BASELINE is to publish short communications on different aspects of pollution of the marine environment. Only those papers which clearly identify the quality of the data will be considered for publication. Contributors to Baseline should refer to ‘Baseline—The New Format and Content’ (Mar. Pollut. Bull. 60, 1–2).

Trace metals, PAHs, and PCBs in sediments from the Jobos Bay area in Puerto Rico Jessica X. Aldarondo-Torres a, Fatin Samara b, Imar Mansilla-Rivera a, Diana S. Aga b, Carlos J. Rodríguez-Sierra a,* a b

Department of Environmental Health, Graduate School of Public Health, Medical Sciences Campus, University of Puerto Rico, P.O. Box 365067, San Juan 00936-5067, Puerto Rico Department of Chemistry, 611 Natural Science Complex, University at Buffalo, The State University of New York, Buffalo, NY, USA

a r t i c l e Keywords: Puerto Rico Metals Organic pollutants Estuary Sediments Caribbean

i n f o

a b s t r a c t This study provides baseline information on the extent of contamination in sediments of the Jobos Bay estuary and surrounding areas in Puerto Rico. Sediments from Jobos Bay area (n = 14) had higher overall average concentrations than those from La Parguera area (n = 5, used as reference site), in lg/g dw, for As (17 vs 9), Cu (29 vs 14), Pb (11 vs 4), and Zn (64 vs 28); and in %, for Fe (2.6 vs 0.6). Sediments (n = 8) screened for PAHs and PCBs exhibited total concentrations (ng/g dw) that ranged from 40.4 to 1912, and from not detected to 11.21, respectively. The quality of sediments of Jobos Bay could be classified as low to moderate pollution. The proximity to anthropogenic sources of contamination warrants a monitoring program for inorganic and organic pollutants in Jobos Bay area for an effective coastal management program of this tropical ecosystem. Ó 2010 Elsevier Ltd. All rights reserved.

Coastal waters of tropical and sub-tropical environments have highly productive ecosystems such as estuaries and coral reefs. These two ecosystems play an important role in the life history and development of many aquatic organisms serving as migration routes, feeding, and nursery grounds (Peters et al., 1997; Chapman and Wang, 2001). Anthropogenic activities are known to have a wide-range of potential effects on these ecosystems, particularly from point and non-point sources of pollution. The release of pollutants into coastal environments is a major human concern worldwide. Among the pollutants of concern are the trace metals: arsenic, cadmium, mercury and lead; and organic chemicals such as polycyclic aromatic hydrocarbons (PAHs) and polychlorinated biphenyls (PCBs). These contaminants are known to readily accumulate in bottom sediments which serve as a repository of pollutants. Sediment contaminants could be released to the overlying water from natural (e.g., bioturbation) and anthropogenic pro* Corresponding author. Tel.: +1 787 758 2525x1451; fax: +1 787 296 2572. E-mail address: [email protected] (C.J. Rodríguez-Sierra). 0025-326X/$ - see front matter Ó 2010 Elsevier Ltd. All rights reserved. doi:10.1016/j.marpolbul.2010.06.006

cesses (e.g., dredging), resulting in potential adverse health effects to aquatic organisms, including coral reefs (Daskalakis and O’Connor, 1995; Long et al., 1995; Argese et al., 1997; Ross and DeLorenzo, 1997). Among the adverse health effects associated with these contaminants are toxicity to the kidney, nervous and reproductive systems, as well as endocrine disruption and mutations (Collier et al., 1998; Steinert et al., 1998; Nirmala et al., 1999; Ketata et al., 2007; Brar et al., 2009; Liu et al., 2008). In addition, trace metals, PAHs, and PCBs are known to bioaccumulate in edible aquatic organisms (e.g., fish), thus, representing a health risk to top predators, including humans (Fox et al., 1991; Renzoni et al., 1998; Huang et al., 2006; Díez et al., 2009). Sediment contamination by trace metals, PAHs, and PCBs has not been extensively studied in the tropics. Therefore, it is important that sediment contamination by these pollutants be assessed for better management and protection of these valuable coastal ecosystems. Jobos Bay National Estuarine Research Reserve (JBNERR), a nature reserve comprising an area of 2800 acres, is located in the south coast of Puerto Rico within the Guayama and Salinas munic-

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Fig. 1. Location of the Jobos Bay and La Parguera areas in Puerto Rico, and sampling sites in the Jobos Bay area.

ipalities. JBNERR was established in 1981, and it is part of the National Research Reserve System which is a partnership program between the United States National Oceanography Atmospheric Administration (NOAA) and the Puerto Rico Department of Natural and Environmental Resources (DNER, 2000; USEPA, 2000). JBNERR is the only reserve within the 27 National Reserves in the USA that is located in the Caribbean region (DNER, 2000). JBNERR has the second largest and most important estuary system in Puerto Rico known as Jobos Bay (Fig. 1). Jobos Bay, with a surface area of 11 km2, is a semi-closed aquatic environment, receiving an annual submerged freshwater flow input of approximately 13,000 acresfeet (1.6  107 m3) which also comes from streams, rain, and irrigation (DNER, 2000). Some important habitats in the Jobos Bay and surrounding areas (referred in this study as the Jobos Bay area) include coral reefs, seagrass beds, and mangrove forests (DNER, 2000). The fishery resources in the Jobos Bay area provide food and a livelihood for local fishermen and their families. This typical tropical Caribbean estuarine system serves as a model for coastal management practices for other Caribbean countries. However, areas around JBNERR have undergone significant agricultural, urban and industrial development that could release toxic chemical pollutants into the Bay (DNER, 2000). Examples of industrial facilities located in the vicinity of JBNERR include: an oil refinery, a coal-fire plant, pharmaceutical plants, a solid waste landfill, and a thermoelectric power plant, among others. Due to a lack of a sewage treatment plant, raw sewage is discharged directly into Jobos Bay (Sastre, 2005). There is an increasing concern that the proximity of anthropogenic activities taking place near the Jobos Bay area could result in undue pressure on this coastal ecosystem.

For example, on March 2000, thousands of used tires burned from a nearby tire recycling center, causing the release of potentially toxic chemicals into Jobos Bay. Therefore, the main objective of this study was to provide background information on the extent of contamination in sediments of the Jobos Bay area by the metals arsenic (As), cadmium (Cd), copper (Cu), iron (Fe), lead (Pb), mercury (Hg) and zinc (Zn); and the organic chemicals PAHs and PCBs. Superficial sediment samples were collected on December 2003 from 14 different stations in the Jobos Bay area (Fig. 1). Sampling sites were chosen based on proximity to potential pollution sources and in consultation with management personnel from JBNERR. For comparison purposes, and used as a reference site, sediment samples were collected on January 2004 from five stations in La Parguera area (figure not shown). La Parguera, located in the municipality of Lajas, is a popular fishing and tourist area located in the southwest coast of Puerto Rico, far from agricultural and industrial development in comparison to Jobos Bay area (Fig. 1). Surface sediment samples (one replicate per station) were collected utilizing a 15  15 cm, 11 kg Ponar stainless steel dredge (Forestry Suppliers, Inc., Jackson, Mississippi) with a sample volume of 2.4 L. Samples were placed in a glass tray and homogenized with a spatula. Any foreign object such as leaves and shells were removed. Powder-free rubber gloves were used and replaced when handling different sediment samples. Sediment samples from 14 stations were transferred from the glass tray to plastic bags for metal analyses, while 8 pre-selected sediment samples (seven from the Jobos Bay area and one from La Parguera) were transferred to pre-cleaned I-Chem Type III 500-mL wide-mouth amber jars with Teflon-lined screw caps (Fisher Scientific Corp., USA) for PCBs

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and PAHs analyses. To avoid contamination, the dredge, spatula, and glass tray were cleaned after sampling at each station in the following order: brushed with soapy water, rinsed 3–4 times with distilled deionized water (ddw), rinsed with 1% hydrochloric acid (except the dredge), several rinses with ddw, rinsed with 95% ethanol, and final rinses with ddw. Sediment samples, placed in a cooler with ice in the field, were transported to the laboratory. In the laboratory, samples in plastic bags for metal analyses were stored in a freezer at 20 °C, while samples in glass jars were refrigerated at 4 °C before being shipped to the University at Buffalo (The State University of New York, Buffalo, NY) for organic chemical analyses. The digestion methodology for sediments to analyze As, Cd, Cu, Fe, Pb, and Zn was based on the USEPA Method 3051 (USEPA, 1992; CEM Corporation, 1994). With the exception of sample 5 from Jobos Bay which was digested only once, and two other samples that were digested in triplicates (stations 10 and 25), the rest of the sediment samples were digested in duplicates for the extraction of metals. Portions of approximately 0.5 g dry weight (dw) equivalent of sediment sample was digested in a Microwave Sample Preparation microwave oven-model 1000 (CEM Corp, Matthews, NC) with 10 mL of Trace Metal Grade concentrated HNO3 (Fisher Scientific Corp., USA). After digestion, samples were filtered through a Whatman 41 paper-filter, diluted to 50 mL with distilled deionized water (ddw), and transferred to 50-mL polypropylene graduated centrifuge tubes (Corning Incorporated, Corning, NY). The extraction of Hg from sediments used a different digestion method, USEPA 7471A, which does not use microwave technology (USEPA, 1992). Briefly, 0.5 g dw equivalent of sediment samples were placed in a 125-mL glass bottle. An acid solution of 5 mL of both Trace Metal Grade concentrated H2SO4 and HNO3 was added to each glass bottle and heated for 2 min at 95 °C in a water bath.

The sample was allowed to cool. Then, 30 mL of ddw and 5% KMnO4 (volume added until there was no further change in color) was added to each sample. Potassium persulfate (8 mL) was added to each bottle and heated in a water bath at 95 °C for 1 h. The sample was diluted with ddw and a sodium chloride hydroxylamine sulfate solution was added to each digested sample right before the metal analysis to discolor the solution. For quality control and assurance, each digestion batch contained a spiked blank solution, which consisted in adding a mixture of metals of known concentrations with HNO3 to a Teflon vessel or a mixture of H2SO4 and HNO3 (for Hg analysis) in a 125-mL glass bottle, and processing it as a sample. A standard reference material for trace elements, SRM 1646a-Estuarine Sediments (U.S. Department of Commerce National Institute of Standards and Technology Gaithersburg, MD) was also used to determine the accuracy of the metal analyses. The analyses of As, Cd, Cu, Pb, Zn, and Fe in digested sediment samples were conducted with a Perkin Elmer (PE) Atomic Absorption Spectrophotometer (AAS), Model AAnalyst 800, using modified methods of USEPA (1992) for graphite furnace and direct aspiration flame modes. Hg was analyzed using a PE–FIAS 400 flow injection mercury/hydride system. As part of the quality control and assurance protocol, calibration verification standards were regularly used to evaluate the calibration curve. Blank verification samples were run during the analysis to ensure no carry over from sample to sample. Sensitivity checks were performed for every element. The minimum correlation coefficient of the calibration curve accepted was 0.995. Matrix bench spikes were also included to check for interferences in the sediment extract during the AAS analysis. Comparisons of average metal concentrations between sampling sites (Jobos Bay vs La Parguera) were determined using the non-parametric Mann– Whitney test (StatView v 5.0, SAS Institute Inc., Cary, NC).

Table 1 Average metal concentrations ± standard error (dry weight basis) in surface sediments from Jobos Bay and La Parguera areas. Station

As (lg/g)

Cd (lg/g)

Cu (lg/g)

Pb (lg/g)

Zn (lg/g)

Fe (%)

Jobos Bay 1 2 3 4 5 6 7 8 9 10 11 12 13 14 Overall average

19 ± 0.1 14 ± 2 21.2 ± 0.7 11.2 ± 0.2 10.4 15.9 ± 0.6 24 ± 2 15.2 ± 0.7 22.2 ± 0.2 26.6 ± 0.8 13.5 ± 0.4 9.6 ± 0.3 18.6 ± 0.4 8.3 ± 0.1 17 ± 1*

0.04 ± 0.00 0.06 ± 0.01 0.07 ± 0.00 0.06 ± 0.00 0.02 0.03 ± 0.00 0.05 ± 0.01 0.21 ± 0.01 0.12 ± 0.00 0.02 ± 0.00 0.02 ± 0.00 0.09 ± 0.00 0.04 ± 0.00 0.09 ± 0.01 0.06 ± 0.01

32 ± 18 45.0 ± 0.8 53 ± 1 15.0 ± 0.3 10.6 26.0 ± 0.3 15 ± 9 42 ± 4 29.9 ± 0.4 10.2 ± 0.2 1.6 ± 0.2 45 ± 2 43.3 ± 0.5 36 ± 2 29 ± 3*

15 ± 1 10 ± 1 18 ± 1 15.0 ± 0.3 2.7 7.5 ± 0.1 6.6 ± 0.0 13.1 ± 0.3 7.6 ± 0.3 2.8 ± 0.3 1.5 ± 0.2 22 ± 1 14.2 ± 0.1 15.7 ± 0.9 11 ± 1*

97.2 ± 0.4 88 ± 2 88 ± 3 61 ± 1 27.0 58.1 ± 0.6 55 ± 2 78 ± 5 51.7 ± 0.3 29.1 ± 0.6 10.8 ± 0.2 32.1 ± 0.4 86 ± 1 129 ± 8 64 ± 6*

4.1 ± 0.09 4.0 ± 0.05 3.5 ± 0.2 1.9 ± 0.04 1.1 2.5 ± 0.02 3.0 ± 0.1 2.4 ± 0.3 2.3 ± 0.02 1.6 ± 0.1 0.4 ± 0.0 3.1 ± 0.03 3.6 ± 0.02 2.6 ± 0.1 2.6 ± 0.2*

La Parguera 21 22 23 24 25 Overall average Shale valuesa TELb PELb ERMc mrl

0.71 ± 0.03 0.92 ± 0.01 1.06 ± 0.05 30 ± 1 11 ± 2 9±3 13 7.24 41.6 70 0.2

0.008** 0.01 ± 0.00 0.01 ± 0.00 0.22 ± 0.02 0.09 ± 0.01 0.07 ± 0.02 0.3 0.676 4.21 9.6 0.01

0.88 ± 0.01 0.49 ± 0.01 0.60 ± 0.00 21.1 ± 0.8 36 ± 6 14 ± 5 45 18.7 108 270 0.2

0.5 ± 0.2 0.5 ± 0.1 0.4 ± 0.1 5.3 ± 0.1 9±2 4±1 20 30.2 112 218 0.1

9±1 8±1 10 ± 2 36 ± 6 60 ± 9 28 ± 7 95 124 271 410 2

0.08 ± 0.00 0.04 ± 0.00 0.06 ± 0.00 1.2 ± 0.1 1.2 ± 0.2 0.6 ± 0.2 4.72 na na na 0.001

mrl = minimum reporting limit estimated based on a 0.5 g dw of sediment sample. * Statistical differences (p < 0.05) in the overall average metal concentrations between Jobos Bay and La Parguera. ** Below minimum reporting limit of the AAS instrument; TEL = threshold effect level; PEL = probable effect level; effects range-median (ERM); na = not available. a Krauskopf and Bird, 1995. b FDEP, 1994. c Long et al., 1995.

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Enrichment Factors (EFs) and geochemical normalization were calculated to differentiate anthropogenic from natural contribution of metals in sediments from the Jobos Bay and La Parguera areas by using the following equation

EFs ¼ ðMe=FeÞsample =ðMe=FeÞaverage shale value where (Me/Fe)sample is the metal concentration (lg/g) in relation to Fe levels (%) in sediment samples, and (Me/Fe)average shale value is the ratio of average shale values of the metal (lg/g) to Fe (%) levels, as reported by Krauskopf and Bird (1995) (Table 1). The world average shale (or crustal) value of trace metals represents the background concentration of metals in sedimentary rocks formed by clay or argillaceous material worldwide (Windom et al., 1989; Krauskopf and Bird, 1995). The average shale metal values have been used in the calculation of EFs to determine the anthropogenic contributions of metals in sediments (Conrad and Chisholm-Brause, 2004; Olivares-Rieumont et al., 2005; Acevedo et al., 2006). To correct for differences in sediments grain size, a normalization method is applied in which the trace metal level is divided by a reference element (e.g., Al, Fe) (Din, 1992; Daskalakis and O’Connor, 1995; Balls et al., 1997). In this study, Fe was used as a geochemical normalizer for the following reasons: (1) Fe is associated with fine-grained materials; (2) its geochemistry is similar to that of many trace metals; and (3) its natural sediment concentration tend to be uniform (Daskalakis and O’Connor, 1995). For the organic chemical extraction and analysis, a standard mixture of 16 PAHs was obtained from Restek (Bellefonte, PA). PAH surrogate (pyrene-d10 solution) and internal PAH standard mixture (acenaphthene-d10, phenanthrene-d10, and chrysened12) were obtained from Chemservice (West Chester, PA). PCB standards (congeners 28, 52, 101, 138, 153, 180, 209) were purchased from Accustandard Inc. (New Haven, CT) and from Chemservice (West Chester, PA) for PCBs 1, 5, 29, 47, 98, 154, 171, and 201. Dried sediments (20 g) were combined with 10 mL of HydromatrixTM, and spiked with 50 lL of pyrene-d10 solution in isooctane (5 lg/mL). Organic chemicals were extracted using a Dionex accelerated solvent extraction (ASE) system, Model 200 (Dionex Corp. Sunnyvale, CA). Sediment samples were placed into a 33-mL ASE cell fitted with two Whatman circular (1.983-cm diameter) glass microfiber filter and 6-g alumina (activated at 120 °C for 12 h). A filter was initially placed in the cell followed by 6 g of alumina, and capped with another filter with the sediment mixture atop. The extraction of sediment samples was accomplished with a mixture of dichloromethane:hexane (1:1 v/ v) with two cycles at a pressure of 1500 psi and temperature of 100 °C. The static time was 5 min, flushed volume was 60%, and purge time was 90 s. The final extract volume (30–40 mL) was evaporated to dryness under a gentle stream of N2, and the dried extract re-dissolved in 500-lL with isooctane. Sediment extracts, dissolved in isooctane, were analyzed using an Agilent 6890 GC with a MSD 5973 MS detector. The GC was equipped with an HP5MS capillary column, 0.25 mm i.d., 0.25-lm film thickness, and 30 m length (Hewlett Packard; Houston, TX). The MS was operated under selected ion monitoring (SIM) mode, monitoring the molecular mass plus two additional confirming ions for each analyte. The temperature program in the GC was as follows: starting temperature of 110 °C for 5 min, 110–200 °C at 40 °C min1 for 10 min, 200–280 °C at 7 °C min1, and 280 °C for 12 min. Detailed description of the analytical method and figures of merit (e.g., limits of detection, reproducibility, and extraction recoveries) have been reported in a previous publication (Samara et al., 2006). For the quality control and assurance of the organic chemical analysis, the extraction recoveries were obtained using the surrogate standard (pyrene-d10) solution in isooctane that was added to the sediment samples prior to extraction, and it was used to cor-

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rect for PAHs concentrations. Deuterated PAHs (acenaphthene d10, phenanthrene d-10 and chrysene d-12) and PCB 209 were used as internal standards for PAHs and PCBs, respectively. The deuterated PAH with the retention time closest to a target analyte was used in constructing a calibration curve for that particular compound. Procedural blanks were run with each batch of samples (10 samples per batch) and were taken through all phases of the analytical procedure. To determine the overall limits of detections (LOD) for the target analytes, 5 sediment samples were spiked with PCB and PAH standards at two levels (0.5 and 50 ppb) and were subjected to the same extraction and clean-up steps used for the samples. Quantification was based on the base peak, and positive identification was confirmed using the presence of two confirming ions (in the case of PCB) at the area ratios within ±10% variation. For PAHs, no fragmentation is observed in the mass spectrum, so only the molecular ion was monitored. Retention time shifts in the chromatogram were accounted for using the internal standards, and positive confirmation of the analyte was based in an agreement within ±0.2 min of the expected retention time. The overall method recovery and reproducibility based on the spiked surrogate using C-13 labelled (L) PCBs were 34 ± 8% for PCB 52L and 27 ± 13% for PCB 138L. The PCB values reported for each sample were corrected using the average recoveries of PCB 52L and PCB 138L in each sample. PCBs and PAHs are expressed on a dry weight (dw) basis. The detection limits for PCBs were in the range of 0.1–0.30 ng/g, depending on the congener. For PAHs, the detection limits ranged from 0.01 to 0.05 ng/g, with average recoveries of 75 ± 10%. The percent recovery of metals from spiked blanks varied from 83% for Hg to 96–108% for the rest of the metals, showing that the laboratory process of sediment samples did not result in significant analyte loss for most metals. On the contrary, low recoveries from the SRM 1646a estuarine sediment were obtained for Pb (61 ± 5%, n = 15), Hg (74 ± 4%, n = 2), Zn (73 ± 6%, n = 15), and Fe (75 ± 4%, n = 15); while better recoveries were observed for As (95 ± 10%, n = 15), Cd (84 ± 5%, n = 15), and Cu (84 ± 6%, n = 15). These recoveries indicate that the digestion method was not efficient in extracting all metals from the SRM sediment. However, the reproducibility of the metal concentrations measured in the SRM was generally good for this digestion method, with standard deviations of 610%. Reported metal concentrations were not corrected for the obtained percent recoveries. Concentrations of metals are reported on a dw basis. None of the stations in the Jobos Bay and La Parguera areas exhibited preferential accumulation for all metals. Overall average metal concentrations in Jobos Bay and La Parguera areas were below shale values with the exception of As in Jobos Bay (Table 1). However, some metals were present at concentrations above shale values at specific stations such as Cu (station 3), Pb (station 12), and Zn (stations 1 and 14). In the case of As, ten stations from a total of fourteen in the Jobos Bay area and one station (station 24) in La Parguera, were above the shale value of 13 lg/g. Metal with elevated concentrations above shale values may implicate anthropogenic sources. For instance, station 14 from Jobos Bay obtained the highest Zn concentration (129 lg/g), probably coming from the fire event that occurred in the year 2000 involving burned vehicle tires residues. Tire-tread materials are known to contain considerably amounts of Zn (about 1 weight percent) (Councell et al., 2004). Station 24 in La Parguera area exhibited the highest As sediment concentration (30 lg/g). Concentrations of Cd and Hg were found below shale values in all stations of Jobos Bay and La Parguera areas. The highest concentration of Cd for both sites was about 0.2 lg/g. Mercury concentrations in sediment samples from Jobos Bay and La Parguera areas are not included in Table 1 because levels were below the minimum reporting limit (1 lg/L) of the AAS instrument. Only three stations of Jobos Bay and two in

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La Parguera showed detectable levels of Hg in sediments. The highest Hg concentrations in Jobos Bay and La Parguera areas were 0.12 lg/g in station 1, and 0.16 lg/g in station 25, respectively. Overall average metal concentrations in sediments of the Jobos Bay area were statistically higher than in sediments from La Parguera area for As (17 vs. 9 lg/g), Pb (11 vs. 4 lg/g), Cu (29 vs. 14 lg/ g), Zn (64 vs. 28 lg/g), and Fe (2.6 vs. 0.6%). These marked differences in metal concentrations in sediment samples between these two sites were probably due to the fine-grained materials observed in most stations of the Jobos Bay area (13 out of 14). Fine-grained materials predominated in sediment samples from Jobos Bay area in comparison to the more sandy texture sediment from La Parguera area, based on field observations and assessing sediment texture by hand. Sandy texture was only observed in sediments from station 11 of the Jobos Bay area, showing the lowest metal concentrations of this site. In La Parguera area, only two stations had sediments of fine-grained materials (stations 24 and 25), thus, exhibiting higher metal concentrations than stations 21, 22, and 23, which have sandy texture. As expected, fine-grained sediments tended to have higher metal concentrations than sandy texture sediments. In order to determine potential ecological toxic effects, metal levels were compared to sediment quality guidelines such as threshold effect level (TEL), probable effect level (PEL), and the effects range-median (ERM). None of the sediment metal levels surpassed the ERM value, the level of metal above which toxic effects frequently occur in aquatic organisms (Long et al., 1995). However, As, Cu, and Zn (only for station 14) were between TEL and PEL values (Table 1), indicating that adverse biological effects could occur to aquatic organisms (FDEP, 1994). Enrichment factors were calculated to determine the anthropogenic contribution to metal levels in sediments from Jobos Bay and La Parguera areas. EFs were interpreted with the following scale (Birch, 2003): EFs <1 indicates no enrichment, <3 indicates minor anthropogenic contribution, 3–5 is moderate, 5–10 is moderately severe, 10–25 is severe, 25–50 is very severe, and >50 is extremely severe. Although most metal concentrations in sediments of Jobos Bay and La Parguera areas were considered low (e.g., close to or below shale values), the anthropogenic contribution was significant in some stations (Table 2). For example, the anthropogenic input of As into sediments of the Jobos Bay area was observed in all stations ranging from severe (station 11) to moderately severe (station 10), to moderate (stations 5 and 9), and to minor in the rest Table 2 Metal enrichment factors for sediments from Jobos Bay and La Parguera areas. Stations

As

Cd

Cu

Pb

Zn

Jobos Bay 1 2 3 4 5 6 7 8 9 10 11 12 13 14

1.7 1.3 2.2 2.2 3.4 2.3 2.9 2.3 3.5 6.0 12.2 1.1 1.9 1.2

0.2 0.2 0.3 0.5 0.2 0.2 0.3 1.4 0.8 0.2 0.6 0.4 0.2 0.5

0.8 1.2 1.6 0.8 1.0 1.1 0.5 1.9 1.4 0.7 0.4 1.5 1.3 1.5

0.9 0.6 1.2 1.9 0.6 0.7 0.5 1.3 0.8 0.4 0.9 1.7 0.9 1.4

1.2 1.1 1.3 1.6 1.2 1.2 0.9 1.6 1.1 0.9 1.3 0.5 1.2 2.5

3.2 7.8 6.9 9.0 3.2

1.6 5.1 3.0 2.8 1.1

1.1 1.2 1.1 1.8 3.2

1.3 2.8 1.5 1.0 1.8

5.4 9.1 8.4 1.5 2.5

La Parguera 21 22 23 24 25

of the stations (Table 2). Enrichment for the rest of the metals in the Jobos Bay area was not observed or was minor (especially for Zn). In La Parguera area, As was the metal with the highest EF, ranging from a moderate level (stations 21 and 25) to moderately severe (stations 22, 23, and 24). Moderately severe enrichment was also observed in La Parguera for Cd (station 22) and for Zn (stations 21, 22, and 23). Station 25 in La Parguera obtained the highest enrichment for Cu (3.2-moderate) in comparison to other stations of the same site and from the Jobos Bay area. Generally, sediments from La Parguera exhibited higher metal EFs than sediments from the Jobos Bay area, even though average metal concentrations in sediments of La Parguera area were significantly lower than sediments from the Jobos Bay area. In La Parguera, stations 21, 22, and 23 were located in the open sea, south from the coast where sandy texture bottom sediments predominates; while stations 24 and 25 were located within a mangrove forest, closer to the coast. Station 24 was the farthest station, located about 8 km west from the tourist township of La Parguera, in the Boquerón State Park. It is interesting to find station 24 far from potential pollution sources and to have significant metal concentrations caused by anthropogenic sources (e.g., As). A previous study (Rodríguez-Sierra and Jiménez, 2002) revealed that mojarra fish collected near station 24 in La Parguera area obtained higher As, Cd and Cu levels than mojarra fish collected from San José Lagoon (a lagoon with high sediment-metal concentrations). Hertler et al. (2009) showed a tendency for metal concentrations to increase along the coast of La Parguera area from east to west, probably due to the direction of the long shore current that takes a westerly direction. Station 24 in La Parguera area from our study was located about 5 km east from their last sampling site located west of La Parguera township (Hertler et al., 2009). Therefore, these results suggest that station 24 may serve as a repository of contaminants originating in the township of La Parguera and brought by the sea current. Further studies should be conducted in the area of station 24 to determine the extent of contamination in this nature reserve, as it is reflected in sediments and fish tissue samples. Station 25 was located adjacent to a boat docking facility. Table 3 compares the concentrations of metals observed in this study with other studies conducted in Puerto Rico and other countries in the Caribbean. Average levels of metals in sediments of Jobos Bay and La Parguera were similar to concentrations found in Joyuda Lagoon (a nature reserve in Puerto Rico) (Acevedo et al., 2006), and to recently reported average concentrations found along the coast of La Parguera (Hertler et al., 2009). However, these levels were higher than those obtained by Pait et al. (2008a) in Puerto Rico. Pait et al. (2008a) focused their study in sediment samples collected closed to coral reefs areas in southwest Puerto Rico that included La Parguera area, but with sampling sites mostly away from the coast (approximately >1 km), thus reflecting their lower average levels of metals. In contrast, metal levels in our study were generally lower than average metal concentrations found in sediments of San Jose Lagoon, a known metal-contaminated estuarine system (Acevedo et al., 2006). When compared to other countries in the Caribbean, average levels of metals in sediments of Jobos Bay and La Parguera compared to other stations in coastal areas off Havana City-Cuba regarded as ‘‘not contaminated” by González and Brügmann (1991). Also, metal levels were similar to those reported by Jaffé et al. (2003) in Montego Bay, Jamaica, except for the higher end of the concentrations range for Pb an Cd (Tables 1 and 3). However, metal levels found in our study were generally lower than metal concentrations in sediments of Havana Bay and Almedares River in Cuba (González and Brügmann, 1991; Olivares-Rieumont et al., 2005), and in parts of Montego Bay considered as highly contaminated with metals. These results show that contamination of metals in sediments of Jobos Bay and La Parguera areas were low relative to other metal-polluted aquatic systems.

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J.X. Aldarondo-Torres et al. / Marine Pollution Bulletin 60 (2010) 1350–1358 Table 3 Average or range of metal concentrations (lg/g dw*) found in sediments from other Caribbean studies. Reference

Location

This study

Puerto Rico Jobos Bay La Parguera Puerto Rico Joyuda Lagoon San José Lagoon Cuba Havana Bay Other stations (range)a Puerto Rico La Parguera (range)b Jamaica Montego Bay (range)a Cuba Havana Almedares River (range)a Puerto Rico southwest

Acevedo et al. (2006)

González and Brügmann (1991) Hertler et al. (2009) Jaffé et al. (2003) Olivares-Rieumont et al. (2005) Pait et al. (2008a) * a b

As

Cd

Cu

Fe

Hg

Pb

Zn

17 9

0.06 0.07

29 14

2.6 0.6


11 4

64 28

18 13 na na na 1.4–7.03 na 1.73

0.10 1.8 1.2 0.86–1.9 nd nd-10.0 1.0–4.3 0.01

22 105 297 4–29 8.01–63.89 3.5–73.8 71.6–420.8 5.21

4.9 3.9 0.83 0.09–1.3 0.61–2.18 na na 0.52

0.17 1.9 7.2 0.01–0.17 na nd-0.30 na <0.01

7.6 219 340 8–24 2.76–13.59 6.4–185 39.3–189.0 1.93

52 531 234 8–75 39.04–96.93 7.9–147 86.1–708.8 7.99

Fe is expressed in %; nd = not detected; na = not analyzed; mrl = minimum reporting limit of AAS (1 lg/L). Individual. Average sample metal concentration range.

Table 4 Concentrations of PAHs and PCBs (ng/g dw), and PAHs ratios in sediments of the Jobos Bay (JB) and La Parguera (LP) areas. Analyte

JB-6

JB-7

JB-9

JB-10

JB-12

JB-13

JB-14

LP-25

LMWPAHs Naphthalene Acenaphthylene Acenaphthene Fluorene Phenanthrene Anthracene

21.8 ± 0.2 5.2 ± 0.3 1.9 ± 6 3.07 ± 0.06 29.0 ± 0.7 4.1 ± 0.2

78 ± 94 11 ± 12 4±4 6±6 93 ± 112 11 ± 13

109 ± 5 8.9 ± 0.4 3.8 ± 0.2 6.5 ± 0.4 187 ± 20 13 ± 1

5.0 ± 0.3 2.54 ± 0.03 0.881 ± 0.002 2.150 ± 0.008 5.53 ± 0.05 1.8 ± 0.1

4±3 2±1 0.8 ± 0.5 1.8 ± 0.6 8±6 2±1

28 ± 1 6.40 ± 0.07 19 ± 2 10 ± 1 159 ± 24 24 ± 4

25 ± 6 8±3 15 ± 3 13 ± 4 465 ± 79 34 ± 6

8±1 4.3 ± 0.6 1.1 ± 0.2 2.77 ± 0.05 12.3 ± 1 4.6 ± 0.2

HMWPAHs Fluoranthene Pyrene Benzo[a]anthracene Chrysene Benzo[b]fluoranthene Benzo[k]fluoranthene Benzo[a]pyrene Indeno[123-cd] py Dibenzo [ah]anthracene Benzo [ghi] perylene P PAHs LMWPAHS/HMWPAHs Phen/Anthr Fluo/Py P PCBs

24 ± 1 24.2 ± 0.7 5.5 ± 0.6 5.0 ± 0.1 8±3 nd 5.5 ± 0.2 5.5 ± 0.5 2.09 ± 0.05 4.1 ± 0.2 149 0.78 7.07 0.99 3.3

75 ± 88 74 ± 87 6±6 6±6 13 ± 12 nd 7±6 4±4 2±1 4±4 394 1.06 8.45 1.01 1.78

137 ± 17 120 ± 13 10.2 ± 0.3 14.3 ± 0.3 19 ± 9 nd 7.5 ± 0.2 6.0 ± 0.4 2.1 ± 0.3 4.3 ± 0.3 648.6 1.02 14.38 1.14 3.74

5.3 ± 0.2 4.6 ± 0.3 1.54 ± 0.09 1.16 ± 0.09 2.08 ± 0.04 0.5 ± 0.7 1.645 ± 0.001 2.7 ± 0.5 1.479 ± 0.007 1.47 ± 0.04 40.4 0.80 3.07 1.15 nd

12 ± 8 10 ± 7 4±3 5±5 9±7 nd 4±3 3±2 1.5 ± 0.8 0.8 ± 0.1 67.9 0.38 4.00 1.20 1.6

183 ± 22 157 ± 18 64 ± 9 55 ± 7 66 ± 2 46 ± 10 66 ± 10 32 ± 3 4.6 ± 0.4 20 ± 1 940 0.36 6.63 1.17 2.88

416 ± 75 306 ± 55 118 ± 15 132 ± 1 136 ± 7 76 ± 15 89 ± 4 42 ± 9 10 ± 2 27 ± 6 1912 0.41 13.68 1.36 3.3

23 ± 2 20.2 ± 0.9 8.9 ± 0.5 10.0 ± 0.9 35 ± 3 nd 9±1 6±1 2.0 ± 0.4 4.2 ± 0.6 151.4 0.28 2.67 1.14 11.21

LMWPAHs and HMWPAHs = low and high molecular weight PAHs; Py = pyrene; Fluo = fluoranthene; Phen = phenanthrene; Anthr = anthracene; nd = not detected.

Sediments from seven stations of Jobos Bay area (stations 6, 7, 9, 10, 12, 13, and 14) and station 25 of La Parguera area were screened for the presence of sixteen PAHs and fourteen PCB congeners. The sixteen PAHs are those included in the EPA Method 610. The PCB congeners were selected on the basis of their predominance in commercial PCBs mixtures in both biotic and abiotic matrices, and therefore are often found in environmental samples (Ezemonye, 2005). In fact, PCB 28, 52, 101, 138, 153, and 180 are often used as indicator PCBs in many environmental monitoring studies. Total PAHs in Jobos Bay and La Parguera areas ranged from 40.4 (station 10) to 1912 (station 14) ng/g (Table 4). With the exception of benzo[k]fluoroanthene, the rest of individual PAH compounds were detected in all sediment samples (Table 4). Benzo[k]fluoroanthene was detected at higher concentrations only in stations 13 (46 ng/g) and 14 (76 ng/g) from Jobos Bay. Station 14, with the highest sediment total PAHs concentration of 1912 ng/g, is the only station considered to have high pollution level by PAHs, as classified by Gaspare et al. (2009). Station 13 had the second highest PAHs level (940 ng/g), followed by station 9 with 649 ng/g. These three stations with total PAHs higher than the NOAA National Status and Trends Program median of 415 ng/ g (Pait et al., 2008b), were located near potential sources of contamination. Station 14 was located close to a former tire recycling

center that caught fire on the year 2000. Station 13 was near the Pozuelo marina, while station 9 was adjacent to a thermoelectric plant that generates oil-based energy (Fig. 1). In general, sediments from the inner stations in the Jobos Bay (stations 6, 7, 9, 13, and 14) were more impacted by PAHs than farther away stations from the bay (stations 10 and 12), based on differences on average concentrations of total PAHs (higher in the inner stations) (Table 4, Fig. 1). The presence of high molecular weight (HMW, four- to sixrings) and low molecular weight (LMW, two- to three-rings) PAHs have been associated to sources of PAHs related to fuel-combustion (pyrolytic) and crude oil (petrogenic) contamination, respectively (Tam et al., 2001; Lee et al., 2005; Yan et al., 2009). Therefore, a ratio of LMW/HMW >1 suggests a petrogenic origin of pollution; while for a value <1, the PAHs origin is pyrolytic (Yan et al., 2009). Stations 6, 10, 12, 13 and 14 from Jobos Bay, and station 25 from La Parguera obtained LMW/HMW ratios <1, indicating pyrolytic origin of PAHs (Table 4). In contrast, stations 7 and 9 had ratios slightly above 1, suggesting a petrogenic source of PAHs (Table 4). Two additional methods used to distinguish pyrolytic and petrogenic sources of PAHs in sediments are the ratios of phenanthrene to anthracene (Phen/Anthr) and fluoranthene to pyrene

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(Fluo/Py). A Phen/Anthr ratio <10 and a Fluo/Py ratio >1 are characteristics of pyrolytic pollution, while a Phen/Anthr ratio >10 and a Fluo/Py ratio <1 are representative of petroleum-derived PAHs (Tam et al., 2001; Palma-Fleming et al., 2004; Cardellicchio et al., 2007). Except for stations 9 and 14, the rest of the stations have Phen/Anthr ratio <10 (Table 4). A Fluo/Py ratio close to or greater than 1 was obtained in all stations, suggesting that PAHs in sediment came from pyrolytic contamination (Table 4). Based on the three methods used to distinguish pyrolytic and petrogenic sources of PAHs in sediments, PAHs in stations 6, 10, 12, 13, and 25 came from combustion processes (pyrolitic). In stations 7, 9 and 14, the sources were both from pyrolytic and petrogenic pollution. For instance, station 14 had a LMW/HMW ratio <1 and a Fluo/Py ratio >1, suggesting a pyrolytic source, while a Phen/ Anthr ratio >10, indicative of a petrogenic origin (Table 4). However, sediments from station 14 appeared to be more impacted by pyrolytic-derived PAHs than petrogenic, based on the higher concentration of benzo[k]fluoroanthene, a high molecular weight 5-ring PAH, found with the highest concentration in this station (Table 4). PCBs were detected in sediments of seven stations from a total of eight stations analyzed (Table 4). However, PCBs concentrations were considered low, and most of the 14 PCB congeners analyzed were not detected. For instance, PCBs 138 and 153 were the only commonly detected congeners in sediments in most stations with concentrations (ng/g) ranging from 0.7 to 2, and from 0.5 to 1.6, respectively (data not shown in Table 4). The common detection of these two congeners is congruent with other environmental studies (Samara et al., 2006). Other PCBs detected were congeners 98 (station 9), and 101 (stations 9 and 13) ranging from 0.8 to 1.3 ng/g. Therefore, only total PCBs concentrations are presented (Table 4). Total PCB concentrations fluctuated in the Jobos Bay area from not detected in station 10, to 3.7 ng/g in station 9 (Table 4). Sediments from station 25 of La Parguera contained the highest total PCBs concentration, with 11.2 ng/g. In this station, 57% of the fourteen PCB congeners analyzed were detected, and included congeners 1, 52, 47, 98, 101, 153, 138, and 180 with concentrations fluctuating from 0.6 to 2.3 ng/g (not shown in Table 4). We did not expect to obtain higher concentrations of PCBs in an area that is recognized mainly as a fishing and tourist area. The distribution and possible sources of PCBs in sediments from La Parguera could not be determined in this study because only one sample was analyzed. However, a recent study corroborated the presence of PCBs Table 5 Sediment quality guidelines for PAHs and PCBs (ng/g dw).

Naphthalene Acenaphthylene Acenaphthene Fluorene Phenanthrene Anthracene Fluoranthene Pyrene Benzo[a]anthracene Chrysene Benzo[b]fluoranthene Benzo[k]fluoranthene Benzo[a]pyrene Indeno[123-cd]pyrene Dibenzo[ah]anthracene Benzo[ghi]perylene P PAHs P PCBs

TEL

PEL

ERL

ERM

34.6 5.87 6.71 21.2 86.7 46.9 113 153 74.8 108 na na 88.8 na 6.22 na 1684 21.6

391 128 88.9 144 544 245 1494 1398 693 846 na na 763 na 135 na 16,770 189

160 44 16 19 240 85.3 600 665 261 384 na na 430 na 63.4 430 4022 22.7

2100 640 500 540 1500 1100 5100 2600 1600 2800 na na 1600 na 260 1600 44,792 180

TEL = threshold effect level and PEL = probable effect level (FDEP, 1994). ERL = effects range-low and ERM = effects range-median (Long et al., 1995). na = not available.

in sediments adjacent to the town of La Parguera, some of which were above 22.7 ng/g (Pait et al., 2008b). When comparing concentrations of organic chemicals in sediments of the Jobos Bay and La Parguera areas with sediment quality guidelines (SQGs), it was shown that some individual PAH compounds and their sum represent a toxicological health concern to aquatic organisms. Table 5 is a summary of published SQGs for individuals PAHs, the sum of PAHs, and the sum of PCBs. Station 14 has PAH concentrations in sediments with the most ecological health concern. For instance, concentrations for nine individual PAHs and for total PAHs in this station were between TEL and PEL values, which could result in possible toxic effects to aquatic organisms (FDEP, 1994). In addition, the concentration of phenanthrene in station 14 was twice higher than the ERL value where adverse biological effects would be observed (Long et al., 1995). Although total PAH concentrations were below the TEL values for the rest of the stations, various stations such as 7, 9, and 13 exhibited individual PAHs like phenanthrene and acenaphthylene with concentrations that were between the TEL and PEL values (Tables 4 and 5), representing possible toxic effects to aquatic organisms. Total PCBs concentrations in sediments did not exceed the SQGs values, thus, biological toxic effects to aquatic organisms are not expected (Table 5). However, due to the biomagnification characteristics of PCBs through the food chain (Takeuchi et al., 2009), chronic exposure to PCBs may result in elevated concentrations in aquatic organisms (e.g., fish), and other toxic effects such as endocrine disruption (Brar et al., 2009). A comparison of total PAH and PCB concentrations is sediments of Jobos Bay and La Parguera with other studies is depicted in Table 6. PAHs in some sediment samples of Jobos Bay had concentrations that surpassed the levels found in other urbanized coastal bays such as in Daya (Yan et al., 2009) and Laizhou Bays (Liu et al., 2009) in China, Montego Bay in Jamaica (Jaffé et al., 2003), Corral Bay in Chile (Palma-Fleming et al., 2004), and the coast of Kaohsiung in Taiwan (Lee et al., 2005). The highest levels of PAHs in Jobos Bay area were similar to those obtained in sediments of Sai Keng and Tolo in Hong Kong (Tam et al., 2001), and the inner harbour of Kaohsiung in Taiwan (Lee et al., 2005). These values of PAHs in sediments of Jobos Bay and La Parguera are considered low to moderately polluted, when compared to highly contaminated sites like Ho Chung in Hong Kong (Tam et al., 2001), and to the higher end of the concentration ranges in the Mai Po in Hong Kong (Tam et al., 2001), the Dae es Salaam in Tanzania (Gaspare et al., 2009), the Mar Piccolo in Italy (Cardellicchio et al., 2007), and the Clyde Estuary in UK (Vane et al., 2007). Total PCBs in sediments of Jobos Bay and La Parguera fell in the low end concentration range of total PCBs in sediments from other regions of the world. Therefore, the pollution of sediments by PCBs is considered low. Based on results, the quality of sediments of the Jobos Bay area is generally good in comparison to La Parguera area, other aquatic systems in Puerto Rico, and elsewhere. However, some stations in the Jobos Bay area are clearly impacted by anthropogenic activities, particularly by As and PAHs (arising mainly from pyrolitic processes). Arsenic levels were observed above shale values in 71% of the samples in Jobos Bay, exhibiting minor to severe anthropogenic enrichment. Although with low concentrations, the presence of PCBs in sediments of Jobos Bay, as well as in La Parguera area, are indicative of anthropogenic inputs, as opposed to metals and PAHs that also have natural origins. Due to the lipophilic and biomagnification characteristics of PCBs through the food web, these compounds need to be studied in more detail in Jobos Bay, La Parguera, and in other aquatic systems in Puerto Rico, particularly in edible fish species. Comparison with effects-based sediment quality guidelines showed that concentrations of pollutants in some stations of Jobos Bay may result in possible toxic effects to aquatic

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J.X. Aldarondo-Torres et al. / Marine Pollution Bulletin 60 (2010) 1350–1358 Table 6 Range of concentrations of total PAHs and PCBs (ng/g dw) found in sediments reported in other studies. P Reference Location PAHs This study

Cardellicchio et al. (2007) Gaspare et al. (2009) Jaffé et al. (2003) Lee et al. (2005)

Liu et al. (2009) Palma-Fleming et al. (2004)

Samara et al. (2006) Tam et al. (2001)

Vane et al. (2007) Yan et al. (2009)

Puerto Rico Jobos Bay and La Parguera Taranto, Italy Mar Piccolo Tanzania, Africa Dae es Salaam coast Jamaica Montego Bay Kaohsiung, Taiwan Coast Inner Harbour China Laizhou Bay Corral Bay, Chile Carboneros Puerto Claro New York, USA Niagara River Hong Kong Sai Keng Tolo Ho Chung Mai Po United Kingdom Clyde estuary South China Daya Bay

P PCBs

40.4–1912

nd-11.21

380–12,750 77.9–24,600 0.97–358

2–1684 na 0.76–73

88–729 533–1750

na

23.3–292.65

na

33.26–202.87 54.70–291.59 na

na 1.70–124.6

356–1811 649–1485 1273–11,098 685–4680 630–23,711 42.5–158.2

na na na na 5.2–129.9 na

nd = not detected; na = not analyzed.

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