Trace metals in sediments of two estuarine lagoons from Puerto Rico

Environmental Pollution 141 (2006) 336e342 www.elsevier.com/locate/envpol

Trace metals in sediments of two estuarine lagoons from Puerto Rico D. Acevedo-Figueroa a,c, B.D. Jime´nez b,c, C.J. Rodrı´guez-Sierra a,* a

Department of Environmental Health, Graduate School of Public Health, Medical Sciences Campus, University of Puerto Rico, PO Box 365067, San Juan 00936-5067, Puerto Rico b Department of Biochemistry, School of Medicine, Medical Sciences Campus, University of Puerto Rico, P.O. Box 365067, San Juan 00936-5067, Puerto Rico c Center for Environmental and Toxicological Research, Medical Sciences Campus, University of Puerto Rico, P.O. Box 365067, San Juan 00936-5067, Puerto Rico Received 30 March 2005; accepted 8 August 2005

Abstract Concentrations of As, Cd, Cu, Fe, Hg, Pb and Zn were evaluated in surface sediments of two estuaries from Puerto Rico, known as San Jose´ Lagoon (SJL) and Joyuda Lagoon. Significantly higher concentrations in mg/g dw of Cd (1.8 vs. 0.1), Cu (105 vs. 22), Hg (1.9 vs. 0.17), Pb (219 vs. 8), and Zn (531 vs. 52) were found in sediment samples from SJL when compared to Joyuda Lagoon. Average concentrations of Hg, Pb, and Zn in some sediment samples from SJL were above the effect range median (ERM) that predict toxic effects to aquatic organisms. Enrichments factors using Fe as a normalizer, and correlation matrices showed that metal pollution in SJL was the product of anthropogenic sources, while the metal content in Joyuda Lagoon was of natural origins. Sediment metal concentrations found in SJL were comparable to aquatic systems classified as contaminated from other regions of the world. Ó 2005 Elsevier Ltd. All rights reserved. Keywords: Puerto Rico; Metals; Estuary; Sediments; Caribbean; Pollution

1. Introduction Natural trace metal concentrations in estuarine sediments are found at different concentrations depending on the geology of the area (Windom et al., 1989). However, estuarine sediments also receive significant anthropogenic loads of metals from both point and non-point sources increasing their natural background concentrations. The sediment compartment represents the most concentrated physical pool of metals in aquatic environments (Daskalakis and O’Connor, 1995). More than 90% of the heavy metal load in aquatic systems is bound to suspended particulate matter and sediments (Calmano et al., 1993). Therefore, sediments serve as a pool of metals that could be released to the overlying water from natural and anthropogenic processes such as bioturbation and dredging, * Corresponding author. Tel.: C1 787 758 2525x1451; fax: C1 787 759 6719. E-mail address: [email protected] (C.J. Rodrı´guez-Sierra). 0269-7491/$ - see front matter Ó 2005 Elsevier Ltd. All rights reserved. doi:10.1016/j.envpol.2005.08.037

resulting in potential adverse health effects (Daskalakis and O’Connor, 1995; Long et al., 1995; Argese et al., 1997). Because estuaries are among the most productive marine ecosystems in the world, serving as feeding, migration routes, and nursery grounds of many organisms, it is important that sediment contamination by trace metals be evaluated, and that natural versus anthropogenic contribution be distinguished for effective remedial actions against metal pollution (Din, 1992; Balls et al., 1997; Chapman and Wang, 2001). San Jose´ (SJL) is part of the San Juan Bay Estuary System (SJBES), a United States Environmental Protection Agency (USEPA)-designated estuary system of National Importance, established in 1992 with the objective of protecting and restoring the health of estuaries while supporting economic and recreational activities (USEPA, 2000). SJL is the largest body of water of the SJBES, containing a surface area of 5.5 km2 and a perimeter of 13.5 km (Negro´n-Gonza´lez, 1986; Conde-Costa, 1987). This estuary has a length and width of 4.5 km and 2.2 km, respectively, with maximum and average depths of

D. Acevedo-Figueroa et al. / Environmental Pollution 141 (2006) 336e342

11 m and 1.8 m, respectively (Negro´n-Gonza´lez, 1986; Conde-Costa, 1987). Average granulometric compositions of sediments are 32% sand, 48% silt, and 20% clay (Negro´nGonza´lez, 1986). The land around SJL is dedicated almost entirely to urban uses. Therefore, it receives large quantities of storm water run-off, sanitary discharges and solid residues that contribute to limited tidal exchange and reduced flushing resulting in elevated concentrations of chemicals and anoxic conditions from eutrophication. Despite the long history of pollution in SJL, few studies have been conducted that deal with sediment-metal contamination (Conde-Costa, 1987; Webb and Go´mez-Go´mez, 1998). Knowing the extent of sediment contamination by metals in SJL is important because government agencies are planning to dredge bottom sediments (Bailey et al., 2004). Dredging activities are known to release metals associated with sediments into the water column resulting in increase bioavailability and toxicity to aquatic organisms (Vale et al., 1998; Bonnet et al., 2000). Joyuda Lagoon, located in southwestern Puerto Rico, was established in 1980 as a Nature Reserve possessing a drainage basin of 5.8 km2 that is mostly covered by vegetation (Negro´nGonza´lez, 1986). In contrast to SJL, Joyuda Lagoon contains a smaller surface area of 1.4 km2 with a perimeter of 7.1 km (Negro´n-Gonza´lez, 1986; Santiago-Rivera and Quin˜o´nezAponte, 1995). The length and width are 2.4 km and 1.0 km, respectively (Negro´n-Gonza´lez, 1986), with an average depth of 1.1 m and a maximum depth of 2.6 m (Santiago-Rivera and Quin˜o´nez-Aponte, 1995). Sediments in Joyuda Lagoon are mainly formed by clay or argillaceous material (59e72%), with organic material fluctuating from 13% to 15% (Negro´nGonza´lez, 1986). Although Joyuda Lagoon is currently being protected, it is not immune to future environmental degradation that may result from increasing population density since this region of Puerto Rico is considered as a major tourist attraction. Information on sediment-metal concentrations in Joyuda Lagoon is lacking. To determine the extent of metal pollution in sediments from SJL and Joyuda Lagoon, it is important to subtract existing metal concentrations from natural background levels in order to derive the total enrichment caused by anthropogenic influences (Din, 1992; Balls et al., 1997; Aloupi and Angelidis, 2001; Conrad et al., 2004; Feng et al., 2004). For most estuarine systems, trace metal concentrations from natural sources could be significant affecting data interpretation regarding man-made inputs (Windom et al., 1989). For example, Windom et al. (1989) reported that natural estuarine and near shore sediments in coastal regions of the southeastern USA are comprised of mixtures of trace metals in poor (e.g., carbonates and quartz sands) and rich (e.g., clay minerals) solid phases, depending on local natural sources. The geochemical normalization has been used extensively to assess anthropogenic contributions of metals in sediments, where the ratio of natural concentrations has been defined by a normalizing factor (i.e., a metal whose concentration is unaffected by human activities) (Windom et al., 1989; Din, 1992; Daskalakis and O’Connor, 1995; Aloupi and Angelidis, 2001; Conrad et al., 2004; Feng et al., 2004). There has been

337

no agreement on the sediment elemental constituents to be used for normalization. Nevertheless, metal concentrations have been normalized against some element such as aluminum, iron or lithium that is both geochemically inactive and abundant in the fine grain material (Balls et al., 1997; Leivuori, 1998; Aloupi and Angelidis, 2001; Conrad et al., 2004; Feng et al., 2004). The use of geochemical normalization to obtain enrichment factors (EF) allows to calculate the relative importance of anthropogenic contributions to the sediments being studied (Windom et al., 1989; Balls et al., 1997; Aloupi and Angelidis, 2001; Conrad et al., 2004; Feng et al., 2004). EF factors represent the actual contamination level in the sediment (Groengroeft et al., 1998). The present study was designed to determine levels of arsenic (As), cadmium (Cd), copper (Cu), iron (Fe), mercury (Hg), lead (Pb) and zinc (Zn) in sediments of two estuaries from Puerto Rico. The objective was to perform a sediment-quality assessment in order to differentiate anthropogenic versus natural metal contributions in these two aquatic systems, using Fe as the geochemical normalizer. 2. Methods 2.1. Sample collection Superficial sediment samples were collected at 11 stations in SJL, while four stations were sampled at Joyuda Lagoon (Fig. 1). Sampling periods were in April of 1999 for SJL, and in June of 1999 for Joyuda Lagoon. Sediment samples were obtained using a Ponar stainless steel dredge. Samples were placed on a glass tray and homogenized with a stainless steel spatula. Any foreign objects such as leaves, snails or shells were discarded. Samples were transferred to plastic bags and placed in a cooler at 4
C, transported to the laboratory and stored at 20
C, until further analysis.

2.2. Sediment digestion The digestion methodology to analyze As, Cd, Cu, Fe, Pb, Zn was based on the USEPA Method 3051 (USEPA, 1992; CEM, 1994). On average, 0.5-g dry weight (dw) equivalent of duplicate sediment samples were digested with 10 mL of HNO3 in a Microwave Sample Preparation System (Model 1000, CEM Corp, Matthews, NC). Acidified sediment extracts were filtered through a Whatman 41 filter paper, diluted to 50 mL with distilled deionized water (ddw), and stored in 60-mL polypropylene Nalgene bottles. Digestion for Hg determination was based on the USEPA Method 7471 A (USEPA, 1992). Briefly, about 1-g dw equivalent of each sample was digested with 5 mL H2SO4 and 2.5 mL HNO3. Samples were placed in a water bath at a temperature of 95
C for 2 min. When samples achieved room temperature, 25 mL of ddw and 40 mL of 5% w/v KMnO4 were added. Samples were placed back in the water bath for 1 h. Digested samples were diluted to 100 mL with ddw and discolored with 10 mL of a sodium chloride-hydroxylamine sulfate solution.

2.3. Metal analyses Metal concentrations were determined using a Perkin-Elmer Atomic Absorption Spectrophotometer, Model 1100B with deuterium background correction, and analyzed using modified methods of Perkin Elmer and USEPA (Perkin Elmer, 1981; USEPA, 1992). The graphite furnace technique was used for As, Cd and Pb (EPA Methods 7060A, 7131A and 7421, respectively). The direct aspiration flame mode was used for Fe, Cu, Pb and Zn (EPA Methods 7380, 7210, 7420 and 7950, respectively), and the MHS-10 technique for Hg analysis (EPA Method 7471A).

D. Acevedo-Figueroa et al. / Environmental Pollution 141 (2006) 336e342

338

Puerto Rico San Juan Joyuda

San José Lagoon

Joyuda Lagoon N

4

3 5

W

E

S

10 11

6 2

1

9 8

7

Fig. 1. Sampling sites in San Jose´ and Joyuda lagoons.

2.4. Geochemical normalization and enrichment factors (EF)

3. Results and discussion

The geochemical normalization was obtained using Fe as the reference element for the following reasons (Daskalakis and O’Connor, 1995): (1) Fe is associated with fine solid surfaces; (2) its geochemistry is similar to that of many trace metals; and (3) its natural sediment concentration tends to be uniform. The following equation was used to estimate the EF of metals from each sediment station using Fe as a normalizer to correct for differences in sediments grain size and mineralogy:

3.1. Metal concentrations

EFZ

ðMe=FeÞsample ðMe=FeÞaverage shale value

where (Me/Fe)sample and (Me/Fe)average shale value are, respectively, the metal concentration (mg/g dw) in relation to Fe levels (% dw) in sediment samples, and average shale values taken from Krauskopf and Bird (1995) (Table 1).

2.5. Statistical analyses To determine significant differences between average metal concentrations in SJL versus Joyuda Lagoon, the ManneWhitney test was performed using the computer program StatView (SAS Institute Inc., Cary, NC). Correlation matrices were determined using the computer software ‘‘Statistical Program for Social Sciences’’ (SPSS Inc, Chicago, IL).

2.6. Quality control Powder-free rubber gloves were used and replaced after handling sediment samples from each station to avoid cross contamination. In addition, field and laboratory blanks were analyzed. Each digestion batch contained a spiked blank solution, which consisted in adding a mixture of metals of known concentrations to an empty vessel and processing it as a sample. A standard reference material of estuarine sediment, SRM 1646a (US Department of Commerce National Institute of Standards and Technology Gaithersburg, MD) was also used to determine the accuracy of the analysis. During metal analyses, 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.

Metal concentrations (mg/L) in field and laboratory blanks were below the minimum reporting limit for As (0.5), Cd (0.2), Cu (2), Hg (0.4), Pb (1), and Zn (20). Average recoveries for spiked blanks of the above metals fluctuated from 90% to 111%, while for the SRM 1646a average percent recoveries G standard deviation (n Z 5, except for Hg where n Z 2) were 94 G 6% for As, 89 G 8% for Cd, 85 G 5% for Cu, 72.0 G 0.9% for Fe, 82 G 2% for Hg, 72 G 5% for Pb, and 72 G 4% Zn. Sediments from SJL and Joyuda Lagoon showed spatial differences in metal levels (Table 1). In Joyuda Lagoon, stations N (north) and E (east) always showed the highest metal concentrations when compared to stations S (south) and W (west) probably due to different grain-size distributions. Stations N and E may have larger accumulation of fine-grained terrigenous materials as reflected by their higher concentrations of Fe (6.9% and 7.2%). In sediments of SJL, levels of Fe were similar (4%) for most stations, except for station 8 (1.6%). In SJL, station 4 consistently exhibited higher concentrations for Cd, Cu, Hg, Pb and Zn, while station 8 contained sediments with the lowest metal concentrations (Table 1). Sediments from station 8, located near the river mouth of San Anto´n Creek, had the lowest metal content in sediments of SJL due to the characteristic sandy texture of this station. Sediments with coarse particles like sand are known poor trace metal accumulators resulting in dilution of metal-contaminated fine-grained sediments (Mudroch and Azcue, 1995). Except for As and Fe, there is a general pattern of higher average metal concentrations in sediments of SJL when compared to Joyuda Lagoon. Some sediment samples of SJL have average concentrations of Hg, Pb, and Zn that were above the effect rangemedian (ERM) sediment quality guidelines (Table 1) that

D. Acevedo-Figueroa et al. / Environmental Pollution 141 (2006) 336e342

339

Table 1 Average metal concentrations G standard deviations in sediments of San Jose´ Lagoon and Joyuda Lagoon, metal sediment quality guidelines (ERM), and average shale metal values Site

As (mg/g)

SJL 1 2 3 4 5 6 7 8 9 10 11 Overall average

24.0 G 0.1 14.1 G 0.6 14.0 G 2 11.1 G 5 18.7 G 1 10.8 G 0.3 16.8 G 0.9 4.5 G 0.8 8.9 G 1 11.3 G 0.9 12.6 G 0.8 13.3 G 5

Joyuda Lagoon N S E W Overall average ERM Shale valuesa

19.4 G 2 13.3 G 0.3 29.5 G 0.8 11.3 G 0.8 18.4 G 8 70 13

a b

Cd (mg/g)

Cu (mg/g)

Fe (%)

0.9 G 0.1 1.3 G 0.01 3.6 G 0.4 4.7 G 0.2 2.3 G 0.1 1.2 G 0.02 1.1 G 0.1 0.2 G 0.0 0.9 G 0.1 1.6 G 0.1 2.1 G 0.1 1.8 G 1

77 G 3 86 G 1 152 G 7 211 G 5 79 G 2 86 G 0.5 145 G 7 29 G 2 85 G 3 105 G 2 98 G 0.3 105 G 47

3.9 G 0.3 4.3 G 0.1 4.2 G 0.2 4.0 G 0.1 4.25 G 0.2 3.6 G 0.1 4.2 G 0.3 1.6 G 0.1 4.0 G 0.1 4.4 G 0.1 4.6 G 0.1 3.9 G 0.8

0.13 G 0.03 0.07 G 0.01 0.17 G 0.01 0.03 G 0.00 0.1 G 0.06 9.6 0.3

33 G 2 15 G 0.7 28 G 1 12 G 0.3 22 G 9 270 45

7.2 G 0.3 2.9 G 0.2 6.9 G 0.2 2.5 G 0.01 4.9 G 2 nrb 4.72

Hg (mg/g)

Pb (mg/g)

Zn (mg/g)

0.7 G 0.02 0.7 G 0.04 2.6 G 0.03 4.9 G 0.6 1.2 G 0.1 1.0 G 0.0 0.6 G 0.0 0.1 G 0.0 1.1 G 0.1 1.1 G 0.04 1.4 G 0.2 1.9 G 2

92 G 5 131 G 4 488 G 18 548 G 19 168 G 15 128 G 3 216 G 15 16 G 3 101 G 4 309 G 5 217 G 32 219 G 163

266 G 18 319 G 0.4 901 G 9 1530 G 38 563 G 8 455 G 9 300 G 25 48 G 3 293 G 14 631 G 5 533 G 20 531 G 392

0.2 G 0.01 0.1 G 0.00 0.3 G 0.01 0.1 G 0.01 0.17 G 0.08 0.71 0.4

10.4 G 0.6 7.3 G 0.5 9.3 G 0.3 3.3 G 0.1 7.6 G 3 218 20

65 G 9 45 G 4 71 G 1 25 G 1 52 G 20 410 95

From Krauskopf and Bird (1995). nr is not reported.

represents the chemical level above which effects frequently occur to aquatic organisms (Long et al., 1995). The average concentration of Hg in sediments of SJL was about three times higher the ERM value of 0.71 mg/g, with station 4 achieving a Hg concentration seven times higher than the ERM. Station 4 also had Pb and Zn concentrations three and four times higher than their corresponding ERM values of 218 and 410 mg/g, respectively (Table 1). Using the ManneWhitney analysis, it was found that overall average concentrations in mg/g dw were significantly higher ( p ! 0.05) in sediments of SJL when compared to Joyuda Lagoon for Cd (1.8 vs. 0.1), Cu (105 vs. 22), Hg (1.9 vs. 0.17), Pb (219 vs. 8), and Zn (531 vs. 52), but not for As (13 vs. 18) and Fe (3.9% vs. 4.9%). The overall average metal concentration is the combination of the individual metal concentrations in sediments from each station of SJL or from Joyuda Lagoon. The concentration of some of these metals are expected to be influenced by man-made activities (Fo¨rstner, 1983). For instance, average levels of Cd, Cu, Hg, Pb and Zn in sediments of SJL were frequently higher than the world average shale values (Table 1). Conversely, their concentrations were below the average shale values in sediments of Joyuda Lagoon (Table 1). The world average shale value represents the background concentration of metals in sedimentary rocks formed by clay or argillaceous material worldwide. 3.2. Enrichment factors (EF) EF were calculated to determine if levels of metals in sediments of SJL and Joyuda Lagoon were of anthropogenic origins (e.g., contamination). EF values were interpreted as

suggested by Birch (2003) where EF ! 1 indicates no enrichment, !3 is minor; 3e5 is moderate; 5e10 is moderately severe; 10e25 is severe; 25e50 is very severe; and O50 is extremely severe. Except for As, higher enrichments were found in sediments of SJL when compared to Joyuda Lagoon (Fig. 2). Station 4 of SJL has the highest EF values for Pb (32.1), Zn (18.9), Cd (18.5), Hg (14.3), and Cu (5.5) followed by station 3 (Fig. 2). The higher EF values observed for stations 3 and 4 indicate that these two stations had the highest anthropogenic inputs when compared to the other stations (Fig. 2). These two stations receive water from a water pump station that collects the surface run-off waters during rain events coming from an urbanized area. This source of pollution to stations 3 and 4 of SJL appears to be the main contributor for Pb, Cd, Hg and Zn (Table 1). Previous studies had demonstrated that municipal and/or industrial wastewater discharges into coastal zones are the most important sources for contamination of water and sediment with heavy metals (Gonza´lez and Bru¨gmann, 1991). Station 8 in SJL showed minor anthropogenic enrichment (1 ! EF ! 3) for Cd, Cu, Pb, and Zn even though it had sediment metal concentrations comparable to Joyuda Lagoon (Table 1 and Fig. 2). In contrast, the anthropogenic contribution of metals was not significant in sediments of Joyuda Lagoon (Fig. 2). The dominant geologic formation in the Joyuda Lagoon area is of Serpentinite Formation that includes clay soils (Va´zquez-In˜igo, 1983). Soil erosion of clay particles originating from the Serpentinite Formation reach the Joyuda Lagoon by the Palma and Indio Creeks located northeast of the lagoon contributing to the backgrounds levels of metals in sediments of this lagoon (Va´zquez-In˜igo, 1983;

D. Acevedo-Figueroa et al. / Environmental Pollution 141 (2006) 336e342

340 2.5

As

2

15

Hg

12

1.5

9

1

6

0.5

3

0

0 1 2 3 4 5 6 7 8 9 10 11 N S E W

1 2 3 4 5 6 7 8 9 10 11 N S E W 40

20

Cd

Pb

15

30

10

20

5

10 0

0

1 2 3 4 5 6 7 8 9 10 11 N S E W

1 2 3 4 5 6 7 8 9 10 11 N S E W 6

20

Cu

5

Zn 15

4 3

10

2 5

1

0

0 1 2 3 4 5 6 7 8 9 10 11 N S E W

1 2 3 4 5 6 7 8 9 10 11 N S E W

Fig. 2. Metal enrichment factors in sediments of San Jose´ (represented by numbers) and Joyuda lagoons (represented by letters) sampling sites.

Acevedo-Figueroa, 2001). EF values for As in sediments of SJL and Joyuda Lagoon were similar showing minor (EF ! 3) or lacking enrichment (EF ! 1) (Fig. 2). Therefore, the anthropogenic input of As in sediment of SJL was not significant. 3.3. Correlation matrix The correlation matrix showed that Cd, Cu, Hg, Pb and Zn in SJL were highly correlated with each other showing a strong positive association (r O 0.7), but not with As and Fe (Table 2). For Joyuda Lagoon, all metals analyzed, including Fe, were highly correlated (r O 0.7) with each other (Table 2). A highly significant correlation between elements indicates their common origin. Better correlations of As, Cd, Cd, Hg, Pb, and Zn with Fe, a major component of clay minerals, indicates a natural origin of the metals as shown with sediments of Joyuda Lagoon, a nature reserve. In contrast, a weak or lack of correlation with Fe, as observed in sediments of SJL, reflects an anthropogenic contribution due to urban development occurring along the periphery of this lagoon. The high correlation obtained between Cd, Cu, Hg, Pb and Zn in sediments of SJL suggests a common pollution source. 3.4. Comparison with other studies Metal concentrations in sediments of SJL and Joyuda Lagoon were compared to other studies performed in other

areas of the world (Table 3). Generally, concentrations of Cd, Cu, Hg, Pb, and Zn in sediments of SJL were similar to levels detected in sediments classified as contaminated from other regions of the world, while metal concentrations in sediments from Joyuda Lagoon were comparable with uncontaminated sediments (Table 3). Therefore, SJL serves as a

Table 2 Correlation matrices of metal levels in San Jose´ and Joyuda lagoons Correlation between vectors values

San Jose´ As Fe Cd Cu Hg Pb Zn Joyuda As Fe Cd Cu Hg Pb Zn

As

Fe

Cd

Cu

Hg

Pb

Zn

1.000 0.536 0.064 0.115 0.055 0.012 0.014

1.000 0.435 0.495 0.303 0.437 0.388

1.000 0.840 0.943 0.931 0.966

1.000 0.858 0.909 0.863

1.000 0.881 0.973

1.000 0.928

1.000

1.000 0.835 0.955 0.720 0.968 0.701 0.881

1.000 0.928 0.979 0.946 0.877 0.925

1.000 0.869 0.987 0.880 0.981

1.000 0.870 0.918 0.903

1.000 0.818 0.944

1.000 0.954

1.000

D. Acevedo-Figueroa et al. / Environmental Pollution 141 (2006) 336e342

341

Table 3 Average metal concentrations found in sediments from different regions of the world Reference

Location

Puerto Rico San Jose´ Lagoon Joyuda Lagoon Absil and van Scheppingen (1996) Belgium Westerschelde Oosterschelde Bahena-Manjarrez et al. (2002) Mexico Coatzacoalcos River (range) Bothner et al. (1998) Farallon Islands Hawaii New Jersey US East Coast Bradley-Moran and Woods (1997) Russia Ob-Irtysh Rivers Bryan and Langston (1992) UK estuaries (range) Gonza´lez and Bru¨gmann (1991) Cuba Havana Bay Other stations (range) Leivuori (1998) Scandinavia Bothnian Bay Bothnian Sea Gulf of Finland Mora et al. (2004) Azerbaijan Iran Kazakhstan Russia

As

Cd

Cu

Fe

Hg

Pb

Zn

Classified

13 18

1.8 0.10

105 22

3.9 4.9

1.9 0.17

219 7.6

531 52

cont. uncont.

nd nd

2.85 0.22

51 2.2

nd nd

nd nd

132 5.8

134 24

cont. uncont.

nd

0.97e2.83 22.2e42.2 nd

nd

11.3e57.7 87.7e109.2 cont.

2.2 1.8 nd 5.7 nd 4.8e1740

0.51 nd 0.20 0.13 0.11 0.08e2.17

17.2 9 23 12 8.8 7e2398

nd nd nd nd nd 1.4e4.9

0.11 0.03 nd 0.04 nd 0.03e3.01

54.9 2.3 19 22 6.0 20e2753

nd nd

1.2 0.9e1.9

297 4e29

239 63 16 14.7 12.5 4.13 2.97

0.94 0.37 1.06 0.14 0.16 0.05 0.06

52 36 43 31.9 34.7 6.4 8.3

This study

4.2 25 86 58 nd 46e2821

uncont. uncont. uncont. uncont. uncont. uncont.-cont.

0.83 7.2 340 0.1e1.3 0.01e0.17 8e24

234 8e75

cont. uncont.

6.2 6.0 4.5 3.71 3.55 0.67 0.55

212 190 175 83.2 85.3 11.1 17.1

cont. cont. cont. cont. cont. uncont. uncont.

0.27 0.09 0.13 0.15 0.05 0.01 0.02

79 42 50 19.6 18.0 5.75 4.19

Concentrations are in mg/g, except Fe which is in %. nd, not determined; cont., contaminated; uncont., uncontaminated.

repository for trace metal accumulation from adjacent urban and industrialized areas.

field and laboratory assistance; and to the UPR-RCMIG12RR03051 for the laboratory support. We also thank Dr. Imar Mansilla-Rivera for reviewing this manuscript.

4. Conclusion The presence of Cd, Cu, Hg, Pb and Zn in sediments of SJL was mostly due to anthropogenic sources, while metals found in sediments of Joyuda Lagoon were of natural origins. Storm water runoff and sanitary waste derived from urban and industrial developments are among the contamination sources that directly impact sediments of SJL. Particularly, stations 3 and 4 of SJL had moderately severe to very severe enrichment of Cd, Hg, Pb, and Zn attributed to a water pump station that discharges water runoff directly into SJL. Some stations in SJL had sediment metal concentrations that have been associated with toxic effects to aquatic organisms. The negative impact of future dredging operations in SJL resulting in the release of significant levels of metals from the sediment into the water column needs to be evaluated in terms of bioaccumulation and toxicity, particularly with native species of this lagoon.

Acknowledgments This study was financially supported by NOAA-Puerto Rico Sea Grant Program (R91198) and the Puerto Rico Department of Natural and Environmental Resources. The authors are grateful to Ms. Lourdes Pe´rez for the metal analysis by AAS; to Ulda J. Pe´rez and Weldin Ortiz for their

References Absil, M., van Scheppingen, Y., 1996. Concentrations of selected heavy metals in benthic diatoms and sediment in the Westershelde estuary. Bulletin of Environmental Contamination and Toxicology 56, 1008e1015. Acevedo-Figueroa, D., 2001. Comparative analyses of heavy metals in sediment and water from two coastal lagoons in Puerto Rico. MS thesis, University of Puerto Rico, 160 pp. Aloupi, M., Angelidis, M.O., 2001. Geochemistry of natural and anthropogenic metals in the coastal sediments of the island of Lesvos, Aegean Sea. Environmental Pollution 113, 211e219. Argese, E., Ramieri, E., Bettiol, C., Pavoni, B., Chiozzotto, E., Sfriso, A., 1997. Pollutant exchange at the water/sediment interface in the Venice canals. Water Air and Soil Pollution 99, 255e263. Bahena-Manjarrez, J.L., Rosales-Hoz, L., Carranza-Edwards, A., 2002. Spatial and temporal variation of heavy metals in a tropical estuary. Environmental Geology 42, 575e582. Bailey, S.E, Schroeder, P.R., Ruiz, C.E., 2004. Design of CAD pits in San Jose´ Lagoon, San Juan, Puerto Rico. Second LACCEI International Latin American and Caribbean Conference for Engineering and Technology (LACCEI’2004), Challenges and Opportunities for Engineering Education, Research and Development, 2e4 June, Miami, Florida, USA. Balls, P.W., Hull, S., Miller, B.S., Pirie, J.M., Proctor, W., 1997. Trace metal in Scottish estuarine and coastal sediments. Marine Pollution Bulletin 34, 42e50. Birch, G. 2003. A scheme for assessing human impacts on coastal aquatic environments using sediments. In: Woodcoffe, C.D., Furness, R.A. (Eds.), Coastal GIS 2003. Wollongong University Papers in Center for

342

D. Acevedo-Figueroa et al. / Environmental Pollution 141 (2006) 336e342

Maritime Policy, 14, Australia. !http://www.ozestuaries.org/indicators/DEF_ sediment_scheme.htmlO. Bonnet, C., Babut, M., Fe´rard, J.F., Martel, L., Garric, J., 2000. Assessing the potential toxicity of resuspended sediment. Environmental Toxicology and Chemistry 19, 1290e1296. Bothner, M.H., Gill, P.W., Boothman, W.S., Taylor, B.B., Karl, H.A., 1998. Chemical gradients in sediments cores from EPA reference site off the Farallon Islands e assessing chemical indicators of dredged material disposal in the deep sea. Marine Pollution Bulletin 36, 443e457. Bradley-Moran, S., Woods, W.L., 1997. Cd, Cr, Cu, Ni and Pb in the water column and sediments of the Ob-Irtysh rivers, Russia. Marine Pollution Bulletin 35, 270e279. Bryan, G.W., Langston, W.J., 1992. Bioavailability, accumulation and effects of heavy metals in sediments with special reference to United Kingdom estuaries: a review. Environmental Pollution 76, 89e134. Calmano, W., Hong, J., Fo¨rstner, U., 1993. Binding and mobilization of heavy metals in contaminated sediments affected by pH and redox potential. Water Science and Technology 28, 223e235. CEM Corporation, 1994. Microwave Digestion Application Manual. Matthews, North Carolina. Chapman, P.M., Wang, F., 2001. Assessing sediment contamination in estuaries. Environmental Toxicology and Chemistry 20, 3e22. Conde-Costa, C., 1987. Laguna San Jose´ bathymetric and water quality survey, Puerto Rico. US Geological Survey Water Resources Division, Caribbean District, San Juan, Puerto Rico. Conrad, C.F., Chisholm-Brause, C.J., 2004. Spatial survey of trace metal contaminants in the sediments of Elizabeth River, Virginia. Marine Pollution Bulletin 49, 319e324. Daskalakis, K.D., O’Connor, T.P., 1995. Normalization and elemental sediment contamination in the Coastal United States. Environmental Science and Technology 29, 470e477. Din, Z.B., 1992. Use of aluminum to normalize heavy-metal data from estuarine and coastal sediments of Straits of Melaka. Marine Pollution Bulletin 245, 484e491. Feng, H., Han, X., Zhang, W., Yu, L., 2004. A preliminary study of heavy metal contamination in Yantze River intertidal zone due to urbanization. Marine Pollution Bulletin 49, 910e915. Fo¨rstner, U., 1983. Assessment of metal pollution in rivers and estuaries. In: Thorton, I. (Ed.), Applied Environmental Geochemistry. Academic Press, London, pp. 395e423. Gonza´lez, H., Bru¨gmann, L., 1991. Heavy metals in littoral deposits off Havana City, Cuba. Chemistry and Ecology 5, 171e179. Groengroeft, A., Jaehnig, U., Miehlich, G., Lueschow, R., Maass, V., Stachel, B., 1998. Distribution of metals in sediments of the Elbe Estuary in 1994. Water Science and Technology 37, 109e116.

Krauskopf, K.B., Bird, D.K., 1995. Introduction to Geochemistry, third ed. McGraw-Hill, New York, 589e591. Leivuori, M., 1998. Heavy metal contamination in surface sediments in the Gulf of Finland and comparison with the Gulf of Bothnia. Chemosphere 36, 43e59. Long, E.R., MacDonald, D.D., Smith, S.L., Calder, F.D., 1995. Incidence of adverse biological effects within ranges of chemical concentrations in marine and estuarine sediments. Environmental Management 19, 18e97. Mora, S., Reza-Sheikholeslami, M., Wyse, E., Azemard, S., Cassi, R., 2004. An assessment of metal contamination in coastal sediments of the Caspian Sea. Marine Pollution Bulletin 48, 61e77. Mudroch, A., Azcue, J.M., 1995. Manual of Aquatic Sediment Sampling. CRC Press, Inc., Boca Raton, FL. Negro´n-Gonza´lez, L., 1986. Lagunas de Puerto Rico, Compendio Enciclope´dico de los Recursos Naturales de Puerto Rico 3 Vol. IX. Programa de Manejo de la Zona Costanera de Puerto Rico, Departamento de Recursos Naturales y Ambientales, Estado Libre Asociado de Puerto Rico. Perkin Elmer, 1981. Analytical Methods for Atomic Absorption Spectroscopy Using the Mercury/Hydride System. Instrument Division, Perkin ElmerCorporation, Norwalk, CT. Santiago-Rivera, L., Quin˜o´nez-Aponte, V., 1995. Hydrology of Laguna Joyuda, Puerto Rico. Water Resources Investigation Report 93-4135. US Geological Survey, Water Resources Division Caribbean District, San Juan, Puerto Rico. USEPA, 1992. Test Methods for Evaluating Solid Waste, Physical/Chemical Methods. USEPA, SW-846, third ed. United States Environmental Protection Agency. USEPA, 2000. National Estuary Program. United States Environmental Protection Agency, Office of Water. !http://www.epa.gov/OWOW/estuaries/ sjb.htm#summaryO. Vale, C., Ferreira, A.M., Micaelo, C., Caetano, M., Pereira, E., Madureira, M.J., Ramalhosa, E., 1998. Mobility of contaminants in relation to dredging operations in a mesotidal estuary (Tagus estuary, Portugal). Water Science and Technology 37, 25e31. Vazque´z-In˜igo, L., 1983. Geologı´a General de Puerto Rico, sus Rocas y Minerales. Departamento de Recursos Naturales y Ambientales, Estado Libre Asociado de Puerto Rico. Webb, R., Go´mez-Go´mez, F., 1998. Synoptic Survey of Water Quality and Bottom Sediments, San Juan Bay Estuary System, Puerto Rico, December 1994eJuly 1995. US Geological Survey Report 97-4144, San Juan, Puerto Rico, 69 pp. Windom, H.L., Schropp, S.J., Calder, F.D., Ryan, J.D., Smith, R.G., Burney, L.C., Lewis, F.G., Rawlinson, C.H., 1989. Natural trace metal concentrations in estuarine and coastal marine sediments of the Southeastern United States. Environmental Science and Technology 23, 314e320.