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Stormwater impact in Guanabara Bay (Rio de Janeiro): Evidences of seasonal variability in the dynamic of the sediment heavy metals
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Estuarine, Coastal and Shelf Science xxx (2013) 1e8
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Stormwater impact in Guanabara Bay (Rio de Janeiro): Evidences of seasonal variability in the dynamic of the sediment heavy metals Q3
E.M. Fonseca a, *, J.A. Baptista Neto a, C.G. Silva a, J.J. McAlister b, B.J. Smith b, M.A. Fernandez c Departamento de Geologia/LAGEMAR, Universidade Federal Fluminense e Brazil, Av. General Milton Tavares de Souza, s/n, 4 andar, Campus da Praia Vermelha, Gragoatá, 24210-346 Niterói, RJ, Brazil b School of Geography, Queen’s University, Belfast, Northern Ireland BT7 1N, United Kingdom c Departamento de Oceanografia, Universidade do Estado do Rio de Janeiro, Brazil a
a r t i c l e i n f o
a b s t r a c t
Article history: Received 30 October 2012 Accepted 30 April 2013 Available online xxx
Guanabara Bay is one of the most prominent coastal bays in Brazil. This environment is an estuary of 91 rivers and channels, surrounded by the metropolis of Rio de Janeiro. The bay receives considerable amounts of contaminants introduced from sewage effluents, industrial discharge, urban and agricultural runoff, atmospheric fallout, and the combined inputs from the rivers, making Guanabara Bay one of the most polluted coastal environments on the Brazilian coastline. The aim of this work is to study the concentration and fractionation of the heavy metals within the sediments of the bay. In order to understand the possible seasonal influence on the heavy metal fractionation, two campaigns were carried out in two different seasons of the year (rainy and dry). Twelve stations, in four different areas, with different oceanographic characteristics, where chosen. To assess the bioavailability of the metals a selective extraction procedure was used to study the geochemical fractionation and bioavailability of Zn, Cu, Cr, Ni and Pb. The rainy season was very important with respect to variation in the total concentrations of Cr, Ni and Pb and their fractionation within different “operational” phases present in Guanabara Bay sediments. The water-soluble phase showed little importance, with respect to metal adsorption and this would suggest very low mobility of metals in the water column. Nevertheless, the potentially available metals within these sediments showed a high probability for their release and therefore cause contamination of the water column, since different parts of the bay are constantly subjected to dredging projects promoted by the harbor authorities. Ó 2013 Elsevier Ltd. All rights reserved.
Keywords: heavy metal speciation Guanabara Bay seasonal variability
1. Introduction Considered as a semi-enclosed coastal body of water which has a free connection with the open sea and within which sea water is measurably diluted with fresh water derived from land drainage (Pritchard, 1967), estuaries have been subject of considerable scientific interest over the last decades because of their environmental significance as contaminant traps (Chakraborty et al., 2009), and as such they require careful and constant monitoring and management. Especially in the estuarine-coastal environment, one of the unfortunate side effects of industrialization is the discharge of heavy metals into the environment (Alagarsamy, 2006). Concentration of trace metals in these coastal environments can be elevated due to high inputs from natural, as well as anthropogenic * Corresponding author. E-mail addresses: [email protected] (E.M. Fonseca), [email protected] (J.A. Baptista Neto), [email protected] (C.G. Silva).
sources. Thus, understanding the transport and distribution of trace metals in estuaries is an important goal for environmental chemists (Unnikrishnan and Nair, 2004). Today it is generally recognized that the particular behavior of trace metals in the environment is determined by their specific physicochemical forms (e.g. metal carbonates, oxides, sulfides, organometallic compounds, etc.) rather than by their total concentration (Stecko and Bendell-Young, 2000; Bendell-Young et al., 2002). Since only part of the metal concentrations are easily remobilized, their chemical form within the sediment is of great significance in determining their remobilization potential (Rauret et al., 1988; López-Gonzáles et al., 2006). Selective extraction is a very important tool with respect to verification of the chemical form heavy metals take in the environment, their mobility and consequently their bioavailability. Fractionation procedures provide identification and quantification of the elements present in various solid phases within a sample and are commonly used in the analysis of soils, sediments, palaeosols
0272-7714/$ e see front matter Ó 2013 Elsevier Ltd. All rights reserved. http://dx.doi.org/10.1016/j.ecss.2013.04.022
Please cite this article in press as: Fonseca, E.M., et al., Stormwater impact in Guanabara Bay (Rio de Janeiro): Evidences of seasonal variability in the dynamic of the sediment heavy metals, Estuarine, Coastal and Shelf Science (2013), http://dx.doi.org/10.1016/j.ecss.2013.04.022
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and to examine the catalytic effects of building dust on stone weathering (Chao, 1972; Agemian and Chau, 1977; Skei and Paus, 1979; Tessier et al., 1979; Ure et al., 1993; McAlister and Smith, 1999; McAlister et al., 2003, 2005, 2006, 2008). Some operational problems exist with these techniques and since selectivity of elements for a specific phase is thermodynamic, it cannot be fully achieved by these techniques due to the differences in specificity between the methods employed. However, no analytical technique will ever reflect a native situation and in spite of these problems, selective extraction constitutes a differential approach between “operationally” defined phases and identifies the phase(s) responsible for element adsorption. The most suitable extraction protocol depends on the type of sample and the information required (Tessier et al., 1979; Howard and Vandenbrink, 1999; Du Laing et al., 2002). Previous studies have generally shown that (1) labile metals (such as those extracted easily by MgCl2, acetate and diluted HCl are more bioavailable to benthic biota (Du Laing et al., 2002); (2) metals associated with the amorphous Fe-Mn oxides are unavailable for benthic organisms; (3) acid volatile sulfur concentration strongly influences the bioavailability of metals with respect to benthic animals (Ankley et al., 1991; Di Toro et al., 1992); and (4) the influence of organic coating on metal assimilation from sediment is inconsistent (Schlekat et al., 1999; Griscom et al., 2000; Lee et al., 2000). Despite the fact that metal sulfides are very insoluble in anaerobic environments, once exposed to enough oxygen some metal sulfides like CdS will be transformed into soluble CdSO4 (Di Toro et al., 1996). Gallon et al. (2004) also suggested that reductive dissolution of hydrous FeeMn oxides could release Pb from sediments to interstitial water. Therefore, the distribution, mobility and bioavailability of heavy metals are highly variable in different aquatic environments. The aim of this work is to analyze the heavy metal concentrations with respect to their chemical form, distribution and seasonal variability in surficial sediments collected from 12 stations in Guanabara Bay and to examine the extent of pollution in this area. 2. Study site Guanabara Bay in Rio de Janeiro state is one of the largest bays on the Brazilian coastline (Fig. 1). It has an area of approximately 384 km2, which includes several islands and has a coastline of 131 km long and a mean water volume of 1.87 109 m3. Over the past century the catchment area around Guanabara Bay has been strongly modified by human activities which involved deforestation and uncontrolled urban settlement. These activities have increased river flow velocities and transport of sediment load has increased by 1e2 cm year 1 (Godoy et al., 1998). Approximately 11 million inhabitants live in the greater Rio de Janeiro metropolitan area and as a result of rapid urbanization and population growth; untreated sewage is discharged directly into the bay. This area is the second largest industrial region in Brazil and has over 12,000 industries operating along Guanabara Bay drainage basin and these account for 25% of the organic pollution released to the Bay (FEEMA, 1990). Two oil refineries process 7% of the national oil and approximately 2,000 commercial ships dock in the port of Rio de Janeiro every year, making it the second largest harbor in Brazil. The bay is also the homeport to two naval bases, a shipyard, and a large number of ferries, fishing boats and yachts (Kjerfve et al., 1997). High nutrient concentrations are found in the internal areas, such as the northwestern margin (Paranhos et al., 1998; Ribeiro and Kjerfve, 2002). Severe eutrophication has made the water unsuitable for recreational use and has led to a decline of up to 90% in the fisheries industry (Carreira et al., 2004; Marques-Junior et al., 2006). Despite the intense urbanization around most of this estuarine environment, the northeastern area
of the Bay is still surrounded by mangroves that are legally protected by the Guapimirim Environmental Protection Area. As previously mentioned, large amounts of metals and organic pollutants are discharged into the bay, and most of them accumulate in the sediment. The highest metal concentrations were found in the northwest region close to the mouth of a polluted river and a large oil refinery (REDUC) (Baptista-Neto et al., 2006). A second “hot spot” is the Rio de Janeiro Port (Vilela et al., 2004; Baptista-Neto et al., 2006), situated on the western side. Jurujuba Sound, at the southeastern end of the bay may be considered a third “hot spot” (Marques-Junior et al., 2006). Furthermore, the high lead (Pb) concentration in the middle of Guanabara Bay may be related to the presence of an oil terminal (Baptista-Neto et al., 2006). Large oil spills that occurred between 1998 and 2002 have aggravated pollution problems by affecting, for example, the resident biota and its environmental quality (Meniconi et al., 2002; Kfouri et al., 2003). 3. Sampling methods and analysis Twelve sampling stations were set up at four areas with peculiar characteristics (Fig. 1). Two campaigns were carried out and these involved collecting 12 samples during the rainy and dry seasons using a small stainless Van Veen sampler. Sampling points were geo-located using geographical positioning system (GPS) to ensure consistency. After removing plants and other macro-remains, sediment from the surface was conserved in acid washed plastic bottles, preserved and transferred to laboratory for analysis. During the dry season campaign, the sample 1D was contaminated, that’s why it’s result was not used in this paper. Organic matter was calculated using a loss-on-ignition technique whereby a weighed portion of air-dried material was heated in a muffle furnace at 520 C for two hours. A selective extraction procedure was used to examine the fractionation of heavy metals (Cu, Cr, Ni, Pb and Cu) between operationally defined phases that include, water-soluble, exchangeable/ carbonate, amorphous Mn, amorphous Fe/Mn, crystalline Fe/Mn and residual phases within the samples. Mobile (labile) elements are found in the more soluble phases of the sample matrix, such as water and ion exchange sites, whereas the less mobile (non-labile) are held in the acid soluble and residual (lithogenic) phases. Selective extraction exposes these phases to a sequence of solutions of increasing concentrations using a stepwise procedure under specific conditions. Selective extraction analysis used both shaking and heating techniques (McAlister et al., 2003). Samples were air dried and the <63 mm fractions separated using a nylon mesh sieve. 0.500 g of prepared sample was weighed into acid washed polypropylene tubes and blanks were prepared by taking each extractant, without the sample through all the preparation procedures prior to analysis to keep a check on analytical accuracy and make sure no background carryover occurred from each extraction procedure. Water-soluble ions were extracted using a modified version of the Buurman et al. (1996) technique, where a smaller sample weight (0.5 g) was extracted with a lower volume of deionized water (2.5 ml), diluted to 10 ml and membrane filtered (0.2 mm), prior to analysis. This extraction protocol was modified to include the organic/sulfide phase, which was extracted using a 3:1 mixture of HNO3/HCl (Lefort aqua regia) to ensure better oxidation of organic matter. Digestion of the residual phase was carried out using a HCl/ HNO3/HF/boric acid mixture and complete dissolution of the samples was carried out using a Perkin Elmer microwave digestion system operated at 1000 W power and 75 bar pressure for 20 min. Excess fluoride was complexed with the boric acid. Analytical accuracy was monitored using a Certified Reference Material (I.G.G.E. stream sediment, China). Certified reference materials were added
Please cite this article in press as: Fonseca, E.M., et al., Stormwater impact in Guanabara Bay (Rio de Janeiro): Evidences of seasonal variability in the dynamic of the sediment heavy metals, Estuarine, Coastal and Shelf Science (2013), http://dx.doi.org/10.1016/j.ecss.2013.04.022
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3
Fig. 1. Sampling stations locations.
in Table 2. Analytical grade chemicals were used and all solutions were prepared using Grade A glassware and deionized water. Elemental analysis was carried out using a Perkin Elmer Model 3100 atomic absorption spectrometer. The limits of detection for the trace elements Cu, Pb, Zn, Cr and Ni were: 0.05, 0.15, 0.02, 0.05, 0.05 mg/ kg, respectively. In order to verify the significance of the seasonal heavy metal concentrations variability, it was applied the Kruskale Wallis test. The values of “p” below 0.05 were considered significant. 4. Results The levels of organic matter recorded were relatively high for the stations located in the interior region of the bay (Stations 1e7)
(Table 1), compared to those collected from the entrance (stations 8e10). These results highlight the significant influence that the bay circulation has on organic matter deposition. However, this parameter didn’t show variability between the dry and wet seasons. The results for total heavy metal concentrations and sequential extraction of the sediment samples in the dry season and rainy season are represented graphically in Figs. 2 and 3. The concentrations of heavy metals recorded in this study show a correlation with those available in the literature relating to Guanabara Bay (Table 2). Total Cr concentrations increased during the wet season in all the sampling stations, suggesting continental origin as a potential source for this metal (Fig. 2; Table 2). Despite this being an
Please cite this article in press as: Fonseca, E.M., et al., Stormwater impact in Guanabara Bay (Rio de Janeiro): Evidences of seasonal variability in the dynamic of the sediment heavy metals, Estuarine, Coastal and Shelf Science (2013), http://dx.doi.org/10.1016/j.ecss.2013.04.022
306 307 308 309 310 311 312 313 314 315 316 317 318 319 320 321 322 323 324 325 326 327 328 329 330 331 332 333 334 335 336 337 338 339 340 341 342 343 344 345 346 347 348 349 350 351 352 353 354 355 356 357 358 359 360 361 362 363 364 365 366 367 368 369 370
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371 Q1 372 373 374 375 376 377 378 379 380 381 382 383 384 385 386 387 388 389 390 391 392 393 394 395 396 397 398 399 400 401 402 403 404 405 406 407 408 409 410 411 412 413 414 415 416 417 418 419 420 421 422 423 424 425 426 427 428 429 430 431 432 433 434 435
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Table 1 Total organic matter concentration. Sample
Dry season (%)
Wet season (%)
1 2 3 4 5 6 7 8 9 10 11 12
e 17.7 19.0 17.6 19.8 19.0 18.2 10.2 2.7 5.7 11.1 0.8
16.0 17.8 14.3 15.2 21.3 21.0 19.3 18.4 4.5 1.8 13.9 7.5
environmental protected area, the stations located in the Guapimirin area (stations 5, 6 and 7) showed high levels of Cr when compared to the other stations around the bay. Faria et al. (1995) reported an increase in the level of heavy metals found in bottom sediments of the northeast region of Guanabara Bay. They also suggested others areas around the bay as being potential sources for heavy metals in this location. According to Pekey (2006) due to hydrodynamics, biogeochemical processes and environmental conditions (redox, pH, salinity and temperature) of estuaries, sediments are recognized as being important sinks for heavy metals in aquatic systems as well as a potential non-point source which may directly affect overlying waters. In fact, there is a need to control both point and non-point discharges, especially by controlling at source, discharges of heavy metals from all polluting industries (Bakan and Ozkoc, 2007). Concentrations of Cr in the soluble phase of these sediments for both campaigns were lower than the detection limit for this element. However, in the work carried out by Lima (1997), the concentration of Cr in mussels collected from the bay showed relatively low concentrations compared to others regions. These results would agree with other research that suggested that even if high concentrations of heavy metals were present in the sediments, their availability for biological incorporation is low, due to the dominant environmental conditions (Carvalho et al., 1991). Following an increase in the total concentration of Cr during the wet season, the residual fraction also showed an increase and this
could indicate a geological source with a predominance of continental runoff. The Cr bound in the organic/sulfide phase also showed high concentrations and Comber et al. (1995) reported similar behavior, where they highlighted the affinity of the organic and residual phases for this element. Total Ni concentrations showed a similar pattern of enrichment highlighting the influence of rainfall as an important parameter for Guanabara Bay water quality (Fig. 2). The total concentrations, however, did not show variability between the sampling stations and could be indicative of a diffuse source for this metal in the bay. Fractionation of this metal confirms this theory, since high concentrations of Ni were found in the residual phase during the wet season indicating a potential natural origin. Metals with anthropogenic origin are mainly extracted during the first steps of the sequential extraction procedure, while lithogenic metals are found in the final step of the process corresponding to the residual fraction (Ramirez et al., 2005). Ni concentrations were present in the soluble phase during the rainy season only, with the exception of samples from station 12. This pattern, during both seasons would indicated that besides a predominantly natural source, a more labile fraction is incorporated into the sediments of Guanabara Bay and this may represent an increase in its availability during the rainy season. According to the present study, Maranho et al., 2009, suggest that sediment toxicity is at its highest during the rainy season. The total concentration of Zn was very high, however, a difference between the two seasons was not obvious and this pattern was similar for the other trace metals (Fig. 2). Comparison between all the sampling stations showed homogeneity, suggesting that the Zn concentration is not only linked with the continental sources but also with the scavenging agents or naval activities present in certain locations of Guanabara Bay (stations 8, 9 and 10). Low concentrations of Zn were recorded in the soluble phase of the sediments during both seasons. On the other hand, at station 6 the carbonate phase adsorbs higher concentrations of Zn during the dry season when compared to the other metals and at station 1 during the rainy season. This trend in results agrees with the study carried out by Mortimer and Rae (2000), however, Li et al. (2001) showed Zn to be adsorbed mainly by the residual phase. The organic/sulfide phase did not adsorb high concentrations of Zn during both seasons (Fig. 3), whereas the amorphous Mn phase showed a high affinity for Zn when compared to the other metals.
Table 2 Heavy metal concentrations (mg/kg) in the study area (average)(minimum value e maximum value), compared with values from literature. Location
Pb (mg/kg)
Zn (mg/kg)
Cu (mg/kg)
Cr (mg/kg)
Ni (mg/kg)
Present study (dry season) Present study (wet season) CRM e certified value (Present study) Anal. CRM e Anal. CRM is value obtained in lab) (Present study) Guanabara Baya Sediments from the NE region of the Guanabara Bayb Jurujuba Sound, Niteróic São João de Meriti and estuary Guanabara Bayd Average shalee Average sandstonee
61.30 (22.50e89.60) 96.48 (62.70e116.80) 40.00
241.20 (16.60e115.30) 373.60 (218.70e1178.80) 52.00
58.75 (28.00e156.40) 77.64 (28.00e156.40) 177.00
59.80 (1.80e299.30) 171.60 (87.50e328.50) 87.00
38.8 (8.90e55.20) 90.60 (75.00e114.90) 25.60
44.00
57.00
179.00
91.00
26.00
100.50 (18.20e556.00) 69
237.50 (8,60e940.00) 290
60.80 (n.d. e 242.00) 119
64.80 (0.20e322.00) e
e 1
61.00 (5.00e123.00) 132.00 (11.60e212.00)
158.00 (15.00e337.00) 560.00 (169.00e1059.00)
51.00 (5.00e213.00)
89.00 (10.00e23.00)
48.00 (15.00e79.00)
20.00 7.00
95.00 16.00
45.00 10.00
90.00 35.00
68.00 2.00
a b c d e
Perin et al. (1997). Faria and Sanchez (2001). Baptista Neto et al. (1999). Barrocas et al. (1995). Turekian and Wedepohl (1961).
Please cite this article in press as: Fonseca, E.M., et al., Stormwater impact in Guanabara Bay (Rio de Janeiro): Evidences of seasonal variability in the dynamic of the sediment heavy metals, Estuarine, Coastal and Shelf Science (2013), http://dx.doi.org/10.1016/j.ecss.2013.04.022
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501 502 503 504 505 506 507 508 509 510 511 512 513 514 515 516 517 518 519 520 521 522 523 524 525 526 527 528 529 530 531 532 533 534 535 536 537 538 539 540 541 542 543 544 545 546 547 548 549 550 551 552 553 554 555 556 557 558 559 560 561 562 563 564 565
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Fig. 2. Total heavy metal concentration variation during the campaigns.
The total concentration of Pb clearly showed a difference when compared during both seasons, confirming the results discussed by Pereira et al. (2007), that the downtown area of Niterói is an important source of heavy metals for Guanabara Bay during the rainy season (Fig. 2). Automobiles are very important sources of heavy metal contamination in urban environments (Ellis, 1988; Baptista Neto et al., 1999), with Pb being one of the most significant pollutants. Results would suggest that the source of this metal at the entrance of the bay is even more significant, surpassing the inner bay concentration values. The amorphous Fe/Mn phase was shown to be very important for the adsorption of Pb (Fig. 3) and Baruah et al. (1996); Mortimer and Rae (2000) and Li et al. (2001) showed similar results where they highlighted the affinity of the reducible phase, and to a lesser but significant extent the organic/sulfide phase for this metal. Álvarez-Iglesias et al. (2003), compared samples from two distinct highly impacted areas of São Simón Bay (Spain) and showed the amorphous Fe/Mn and organic phases to have a high affinity for this metal. It is important to highlight that the soluble phase only showed concentrations of Pb during the rainy season. This would make this metal more available and may be a direct result of its super saturation in the sediment. However, in order to confirm this further research would need to be carried out by sampling the source areas
in more detail. The residual phase also showed adsorption of this metal during the rainy season. Like Zn, total Cu concentrations do not alter between the two seasons at all the stations (Fig. 2). The only exceptions were stations 9 and 10, where antifouling paints that contain high levels of Cu and are present in Niterói harbor could possibly be washed by rain and transported to the bay, thus increasing the concentration of this metal in the sediments collected from this area. It is also important to highlight how Dockyards and harbors can be important locations since sediment-associated pollutants accumulate in these areas, especially in the inner part of Guanabara Bay (Vilela et al., 2004). The soluble phase showed concentrations of Cu during the dry season (Fig. 3). The organic matter data (Table 1) suggested that the addition of organic substances during the rainy season may be responsible, at least in part, for the reduction of Cu and allowing adsorption by the soluble phase. Concentrations of Cu were bound by the organic/sulfide phase in the majority of the samples analyzed during both seasons. The reducible and oxidizable phases were shown to be important sinks for Cu. In contrast, the residual phase was shown to be much less important than the others and this behavior was also observed in several works, suggesting a great affinity of these two phases for this metal (Baruah et al., 1996; Mortimer and Rae, 2000; Li et al., 2001).
Please cite this article in press as: Fonseca, E.M., et al., Stormwater impact in Guanabara Bay (Rio de Janeiro): Evidences of seasonal variability in the dynamic of the sediment heavy metals, Estuarine, Coastal and Shelf Science (2013), http://dx.doi.org/10.1016/j.ecss.2013.04.022
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Fig. 3. Variation in the heavy metal fractionation patterns during both campaigns at the different sampling stations.
Please cite this article in press as: Fonseca, E.M., et al., Stormwater impact in Guanabara Bay (Rio de Janeiro): Evidences of seasonal variability in the dynamic of the sediment heavy metals, Estuarine, Coastal and Shelf Science (2013), http://dx.doi.org/10.1016/j.ecss.2013.04.022
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References
Table 3 Results of the KruskaleWallis test for seasonal variability of the data. Heavy metal
Zn
Cu
Pb
Cr
Ni
“p” (significance level)
0.2069
0.4602
0.0009
0.0007
0.0000
The sum of the metal concentrations in the exchangeable, carbonate, FeeMn oxide and organic/sulfide phase can be used to express the potential mobility of metals (Haung et al., 2007). In the present study, the recorded metal fractionation pattern would suggest that concentrations of Cr, Ni, Zn and Pb deposited during the wet season are not bioavailable, making Cu more available and toxic to the environment (Fig. 3). Under strong oxidizing conditions, due to degradation of organic matter, Cu could become very available and toxic to the environment. In order to check the seasonal variability significance, the statistics test of KruskaleWallis was applied, which confirm that the elements Pb, Cr and Ni concentrations, varied significantly between the two campaign, with “p“ values reaching 0.009, 0.007 and 0.000, respectively (Table 3). 5. Conclusions Rainfall levels are shown to be an important parameter with respect to the geochemistry of Guanabara Bay. These levels were responsible for the variability found in the total concentrations of Pb, Cr and Ni as well as their fractionation. The relative increase in the concentration of metals bound by the residual phase of these samples during the rainy season highlights the importance of the surrounding catchment areas for the input of sediment and water to Guanabara Bay. Variations in Pb, Cr and Ni indicated a positive relationship with Storm water events, where an increase in flux during the rainy season was shown to have an impact on their concentrations. High concentrations of Cu, were linked to the naval activities carried out in Niterói Harbor and could be an important source for this metal. Despite the absence of significant sources for metals in the regions surrounding the Guapimirim protected area e northeast of the bay, it’s environmental characteristics (particle size and the levels of organic matter) have turned this area into a potential sink for metals and probably other pollutants. Despite the high level of heavy metals in the bottom sediments of Guanabara Bay, very low concentrations are adsorbed by the soluble phase and therefore have a low risk of entering the water column. These metals are adsorbed and locked up by the organic/ sulfide and other scavenging phases. Even though this study has verified the affinity that certain “operational” phases have for heavy metals, many variations with respect to these characteristics have been reported in the literature. These differences in geochemical dynamics of the metals may possibly be explained by the presence of external parameters such as, the high concentrations of metals adsorbed by the different phases (scavengers) or the environmental physic-chemical conditions that are characteristic of Guanabara Bay. Uncited reference Q2
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Rauret, 1998. Acknowledgments The writers are also indebted with Dr Gilberto T. M. Dias for fieldwork assistance, the MSc students from Laboratório de Geologia Marinha e UFF, for their assistance during the fieldwork.
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Stormwater impact in Guanabara Bay (Rio de Janeiro): Evidences of seasonal variability in the dynamic of the sediment heavy metals Q3
E.M. Fonseca a, *, J.A. Baptista Neto a, C.G. Silva a, J.J. McAlister b, B.J. Smith b, M.A. Fernandez c Departamento de Geologia/LAGEMAR, Universidade Federal Fluminense e Brazil, Av. General Milton Tavares de Souza, s/n, 4 andar, Campus da Praia Vermelha, Gragoatá, 24210-346 Niterói, RJ, Brazil b School of Geography, Queen’s University, Belfast, Northern Ireland BT7 1N, United Kingdom c Departamento de Oceanografia, Universidade do Estado do Rio de Janeiro, Brazil a
a r t i c l e i n f o
a b s t r a c t
Article history: Received 30 October 2012 Accepted 30 April 2013 Available online xxx
Guanabara Bay is one of the most prominent coastal bays in Brazil. This environment is an estuary of 91 rivers and channels, surrounded by the metropolis of Rio de Janeiro. The bay receives considerable amounts of contaminants introduced from sewage effluents, industrial discharge, urban and agricultural runoff, atmospheric fallout, and the combined inputs from the rivers, making Guanabara Bay one of the most polluted coastal environments on the Brazilian coastline. The aim of this work is to study the concentration and fractionation of the heavy metals within the sediments of the bay. In order to understand the possible seasonal influence on the heavy metal fractionation, two campaigns were carried out in two different seasons of the year (rainy and dry). Twelve stations, in four different areas, with different oceanographic characteristics, where chosen. To assess the bioavailability of the metals a selective extraction procedure was used to study the geochemical fractionation and bioavailability of Zn, Cu, Cr, Ni and Pb. The rainy season was very important with respect to variation in the total concentrations of Cr, Ni and Pb and their fractionation within different “operational” phases present in Guanabara Bay sediments. The water-soluble phase showed little importance, with respect to metal adsorption and this would suggest very low mobility of metals in the water column. Nevertheless, the potentially available metals within these sediments showed a high probability for their release and therefore cause contamination of the water column, since different parts of the bay are constantly subjected to dredging projects promoted by the harbor authorities. Ó 2013 Elsevier Ltd. All rights reserved.
Keywords: heavy metal speciation Guanabara Bay seasonal variability
1. Introduction Considered as a semi-enclosed coastal body of water which has a free connection with the open sea and within which sea water is measurably diluted with fresh water derived from land drainage (Pritchard, 1967), estuaries have been subject of considerable scientific interest over the last decades because of their environmental significance as contaminant traps (Chakraborty et al., 2009), and as such they require careful and constant monitoring and management. Especially in the estuarine-coastal environment, one of the unfortunate side effects of industrialization is the discharge of heavy metals into the environment (Alagarsamy, 2006). Concentration of trace metals in these coastal environments can be elevated due to high inputs from natural, as well as anthropogenic * Corresponding author. E-mail addresses: [email protected] (E.M. Fonseca), [email protected] (J.A. Baptista Neto), [email protected] (C.G. Silva).
sources. Thus, understanding the transport and distribution of trace metals in estuaries is an important goal for environmental chemists (Unnikrishnan and Nair, 2004). Today it is generally recognized that the particular behavior of trace metals in the environment is determined by their specific physicochemical forms (e.g. metal carbonates, oxides, sulfides, organometallic compounds, etc.) rather than by their total concentration (Stecko and Bendell-Young, 2000; Bendell-Young et al., 2002). Since only part of the metal concentrations are easily remobilized, their chemical form within the sediment is of great significance in determining their remobilization potential (Rauret et al., 1988; López-Gonzáles et al., 2006). Selective extraction is a very important tool with respect to verification of the chemical form heavy metals take in the environment, their mobility and consequently their bioavailability. Fractionation procedures provide identification and quantification of the elements present in various solid phases within a sample and are commonly used in the analysis of soils, sediments, palaeosols
0272-7714/$ e see front matter Ó 2013 Elsevier Ltd. All rights reserved. http://dx.doi.org/10.1016/j.ecss.2013.04.022
Please cite this article in press as: Fonseca, E.M., et al., Stormwater impact in Guanabara Bay (Rio de Janeiro): Evidences of seasonal variability in the dynamic of the sediment heavy metals, Estuarine, Coastal and Shelf Science (2013), http://dx.doi.org/10.1016/j.ecss.2013.04.022
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and to examine the catalytic effects of building dust on stone weathering (Chao, 1972; Agemian and Chau, 1977; Skei and Paus, 1979; Tessier et al., 1979; Ure et al., 1993; McAlister and Smith, 1999; McAlister et al., 2003, 2005, 2006, 2008). Some operational problems exist with these techniques and since selectivity of elements for a specific phase is thermodynamic, it cannot be fully achieved by these techniques due to the differences in specificity between the methods employed. However, no analytical technique will ever reflect a native situation and in spite of these problems, selective extraction constitutes a differential approach between “operationally” defined phases and identifies the phase(s) responsible for element adsorption. The most suitable extraction protocol depends on the type of sample and the information required (Tessier et al., 1979; Howard and Vandenbrink, 1999; Du Laing et al., 2002). Previous studies have generally shown that (1) labile metals (such as those extracted easily by MgCl2, acetate and diluted HCl are more bioavailable to benthic biota (Du Laing et al., 2002); (2) metals associated with the amorphous Fe-Mn oxides are unavailable for benthic organisms; (3) acid volatile sulfur concentration strongly influences the bioavailability of metals with respect to benthic animals (Ankley et al., 1991; Di Toro et al., 1992); and (4) the influence of organic coating on metal assimilation from sediment is inconsistent (Schlekat et al., 1999; Griscom et al., 2000; Lee et al., 2000). Despite the fact that metal sulfides are very insoluble in anaerobic environments, once exposed to enough oxygen some metal sulfides like CdS will be transformed into soluble CdSO4 (Di Toro et al., 1996). Gallon et al. (2004) also suggested that reductive dissolution of hydrous FeeMn oxides could release Pb from sediments to interstitial water. Therefore, the distribution, mobility and bioavailability of heavy metals are highly variable in different aquatic environments. The aim of this work is to analyze the heavy metal concentrations with respect to their chemical form, distribution and seasonal variability in surficial sediments collected from 12 stations in Guanabara Bay and to examine the extent of pollution in this area. 2. Study site Guanabara Bay in Rio de Janeiro state is one of the largest bays on the Brazilian coastline (Fig. 1). It has an area of approximately 384 km2, which includes several islands and has a coastline of 131 km long and a mean water volume of 1.87 109 m3. Over the past century the catchment area around Guanabara Bay has been strongly modified by human activities which involved deforestation and uncontrolled urban settlement. These activities have increased river flow velocities and transport of sediment load has increased by 1e2 cm year 1 (Godoy et al., 1998). Approximately 11 million inhabitants live in the greater Rio de Janeiro metropolitan area and as a result of rapid urbanization and population growth; untreated sewage is discharged directly into the bay. This area is the second largest industrial region in Brazil and has over 12,000 industries operating along Guanabara Bay drainage basin and these account for 25% of the organic pollution released to the Bay (FEEMA, 1990). Two oil refineries process 7% of the national oil and approximately 2,000 commercial ships dock in the port of Rio de Janeiro every year, making it the second largest harbor in Brazil. The bay is also the homeport to two naval bases, a shipyard, and a large number of ferries, fishing boats and yachts (Kjerfve et al., 1997). High nutrient concentrations are found in the internal areas, such as the northwestern margin (Paranhos et al., 1998; Ribeiro and Kjerfve, 2002). Severe eutrophication has made the water unsuitable for recreational use and has led to a decline of up to 90% in the fisheries industry (Carreira et al., 2004; Marques-Junior et al., 2006). Despite the intense urbanization around most of this estuarine environment, the northeastern area
of the Bay is still surrounded by mangroves that are legally protected by the Guapimirim Environmental Protection Area. As previously mentioned, large amounts of metals and organic pollutants are discharged into the bay, and most of them accumulate in the sediment. The highest metal concentrations were found in the northwest region close to the mouth of a polluted river and a large oil refinery (REDUC) (Baptista-Neto et al., 2006). A second “hot spot” is the Rio de Janeiro Port (Vilela et al., 2004; Baptista-Neto et al., 2006), situated on the western side. Jurujuba Sound, at the southeastern end of the bay may be considered a third “hot spot” (Marques-Junior et al., 2006). Furthermore, the high lead (Pb) concentration in the middle of Guanabara Bay may be related to the presence of an oil terminal (Baptista-Neto et al., 2006). Large oil spills that occurred between 1998 and 2002 have aggravated pollution problems by affecting, for example, the resident biota and its environmental quality (Meniconi et al., 2002; Kfouri et al., 2003). 3. Sampling methods and analysis Twelve sampling stations were set up at four areas with peculiar characteristics (Fig. 1). Two campaigns were carried out and these involved collecting 12 samples during the rainy and dry seasons using a small stainless Van Veen sampler. Sampling points were geo-located using geographical positioning system (GPS) to ensure consistency. After removing plants and other macro-remains, sediment from the surface was conserved in acid washed plastic bottles, preserved and transferred to laboratory for analysis. During the dry season campaign, the sample 1D was contaminated, that’s why it’s result was not used in this paper. Organic matter was calculated using a loss-on-ignition technique whereby a weighed portion of air-dried material was heated in a muffle furnace at 520 C for two hours. A selective extraction procedure was used to examine the fractionation of heavy metals (Cu, Cr, Ni, Pb and Cu) between operationally defined phases that include, water-soluble, exchangeable/ carbonate, amorphous Mn, amorphous Fe/Mn, crystalline Fe/Mn and residual phases within the samples. Mobile (labile) elements are found in the more soluble phases of the sample matrix, such as water and ion exchange sites, whereas the less mobile (non-labile) are held in the acid soluble and residual (lithogenic) phases. Selective extraction exposes these phases to a sequence of solutions of increasing concentrations using a stepwise procedure under specific conditions. Selective extraction analysis used both shaking and heating techniques (McAlister et al., 2003). Samples were air dried and the <63 mm fractions separated using a nylon mesh sieve. 0.500 g of prepared sample was weighed into acid washed polypropylene tubes and blanks were prepared by taking each extractant, without the sample through all the preparation procedures prior to analysis to keep a check on analytical accuracy and make sure no background carryover occurred from each extraction procedure. Water-soluble ions were extracted using a modified version of the Buurman et al. (1996) technique, where a smaller sample weight (0.5 g) was extracted with a lower volume of deionized water (2.5 ml), diluted to 10 ml and membrane filtered (0.2 mm), prior to analysis. This extraction protocol was modified to include the organic/sulfide phase, which was extracted using a 3:1 mixture of HNO3/HCl (Lefort aqua regia) to ensure better oxidation of organic matter. Digestion of the residual phase was carried out using a HCl/ HNO3/HF/boric acid mixture and complete dissolution of the samples was carried out using a Perkin Elmer microwave digestion system operated at 1000 W power and 75 bar pressure for 20 min. Excess fluoride was complexed with the boric acid. Analytical accuracy was monitored using a Certified Reference Material (I.G.G.E. stream sediment, China). Certified reference materials were added
Please cite this article in press as: Fonseca, E.M., et al., Stormwater impact in Guanabara Bay (Rio de Janeiro): Evidences of seasonal variability in the dynamic of the sediment heavy metals, Estuarine, Coastal and Shelf Science (2013), http://dx.doi.org/10.1016/j.ecss.2013.04.022
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Fig. 1. Sampling stations locations.
in Table 2. Analytical grade chemicals were used and all solutions were prepared using Grade A glassware and deionized water. Elemental analysis was carried out using a Perkin Elmer Model 3100 atomic absorption spectrometer. The limits of detection for the trace elements Cu, Pb, Zn, Cr and Ni were: 0.05, 0.15, 0.02, 0.05, 0.05 mg/ kg, respectively. In order to verify the significance of the seasonal heavy metal concentrations variability, it was applied the Kruskale Wallis test. The values of “p” below 0.05 were considered significant. 4. Results The levels of organic matter recorded were relatively high for the stations located in the interior region of the bay (Stations 1e7)
(Table 1), compared to those collected from the entrance (stations 8e10). These results highlight the significant influence that the bay circulation has on organic matter deposition. However, this parameter didn’t show variability between the dry and wet seasons. The results for total heavy metal concentrations and sequential extraction of the sediment samples in the dry season and rainy season are represented graphically in Figs. 2 and 3. The concentrations of heavy metals recorded in this study show a correlation with those available in the literature relating to Guanabara Bay (Table 2). Total Cr concentrations increased during the wet season in all the sampling stations, suggesting continental origin as a potential source for this metal (Fig. 2; Table 2). Despite this being an
Please cite this article in press as: Fonseca, E.M., et al., Stormwater impact in Guanabara Bay (Rio de Janeiro): Evidences of seasonal variability in the dynamic of the sediment heavy metals, Estuarine, Coastal and Shelf Science (2013), http://dx.doi.org/10.1016/j.ecss.2013.04.022
306 307 308 309 310 311 312 313 314 315 316 317 318 319 320 321 322 323 324 325 326 327 328 329 330 331 332 333 334 335 336 337 338 339 340 341 342 343 344 345 346 347 348 349 350 351 352 353 354 355 356 357 358 359 360 361 362 363 364 365 366 367 368 369 370
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371 Q1 372 373 374 375 376 377 378 379 380 381 382 383 384 385 386 387 388 389 390 391 392 393 394 395 396 397 398 399 400 401 402 403 404 405 406 407 408 409 410 411 412 413 414 415 416 417 418 419 420 421 422 423 424 425 426 427 428 429 430 431 432 433 434 435
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Table 1 Total organic matter concentration. Sample
Dry season (%)
Wet season (%)
1 2 3 4 5 6 7 8 9 10 11 12
e 17.7 19.0 17.6 19.8 19.0 18.2 10.2 2.7 5.7 11.1 0.8
16.0 17.8 14.3 15.2 21.3 21.0 19.3 18.4 4.5 1.8 13.9 7.5
environmental protected area, the stations located in the Guapimirin area (stations 5, 6 and 7) showed high levels of Cr when compared to the other stations around the bay. Faria et al. (1995) reported an increase in the level of heavy metals found in bottom sediments of the northeast region of Guanabara Bay. They also suggested others areas around the bay as being potential sources for heavy metals in this location. According to Pekey (2006) due to hydrodynamics, biogeochemical processes and environmental conditions (redox, pH, salinity and temperature) of estuaries, sediments are recognized as being important sinks for heavy metals in aquatic systems as well as a potential non-point source which may directly affect overlying waters. In fact, there is a need to control both point and non-point discharges, especially by controlling at source, discharges of heavy metals from all polluting industries (Bakan and Ozkoc, 2007). Concentrations of Cr in the soluble phase of these sediments for both campaigns were lower than the detection limit for this element. However, in the work carried out by Lima (1997), the concentration of Cr in mussels collected from the bay showed relatively low concentrations compared to others regions. These results would agree with other research that suggested that even if high concentrations of heavy metals were present in the sediments, their availability for biological incorporation is low, due to the dominant environmental conditions (Carvalho et al., 1991). Following an increase in the total concentration of Cr during the wet season, the residual fraction also showed an increase and this
could indicate a geological source with a predominance of continental runoff. The Cr bound in the organic/sulfide phase also showed high concentrations and Comber et al. (1995) reported similar behavior, where they highlighted the affinity of the organic and residual phases for this element. Total Ni concentrations showed a similar pattern of enrichment highlighting the influence of rainfall as an important parameter for Guanabara Bay water quality (Fig. 2). The total concentrations, however, did not show variability between the sampling stations and could be indicative of a diffuse source for this metal in the bay. Fractionation of this metal confirms this theory, since high concentrations of Ni were found in the residual phase during the wet season indicating a potential natural origin. Metals with anthropogenic origin are mainly extracted during the first steps of the sequential extraction procedure, while lithogenic metals are found in the final step of the process corresponding to the residual fraction (Ramirez et al., 2005). Ni concentrations were present in the soluble phase during the rainy season only, with the exception of samples from station 12. This pattern, during both seasons would indicated that besides a predominantly natural source, a more labile fraction is incorporated into the sediments of Guanabara Bay and this may represent an increase in its availability during the rainy season. According to the present study, Maranho et al., 2009, suggest that sediment toxicity is at its highest during the rainy season. The total concentration of Zn was very high, however, a difference between the two seasons was not obvious and this pattern was similar for the other trace metals (Fig. 2). Comparison between all the sampling stations showed homogeneity, suggesting that the Zn concentration is not only linked with the continental sources but also with the scavenging agents or naval activities present in certain locations of Guanabara Bay (stations 8, 9 and 10). Low concentrations of Zn were recorded in the soluble phase of the sediments during both seasons. On the other hand, at station 6 the carbonate phase adsorbs higher concentrations of Zn during the dry season when compared to the other metals and at station 1 during the rainy season. This trend in results agrees with the study carried out by Mortimer and Rae (2000), however, Li et al. (2001) showed Zn to be adsorbed mainly by the residual phase. The organic/sulfide phase did not adsorb high concentrations of Zn during both seasons (Fig. 3), whereas the amorphous Mn phase showed a high affinity for Zn when compared to the other metals.
Table 2 Heavy metal concentrations (mg/kg) in the study area (average)(minimum value e maximum value), compared with values from literature. Location
Pb (mg/kg)
Zn (mg/kg)
Cu (mg/kg)
Cr (mg/kg)
Ni (mg/kg)
Present study (dry season) Present study (wet season) CRM e certified value (Present study) Anal. CRM e Anal. CRM is value obtained in lab) (Present study) Guanabara Baya Sediments from the NE region of the Guanabara Bayb Jurujuba Sound, Niteróic São João de Meriti and estuary Guanabara Bayd Average shalee Average sandstonee
61.30 (22.50e89.60) 96.48 (62.70e116.80) 40.00
241.20 (16.60e115.30) 373.60 (218.70e1178.80) 52.00
58.75 (28.00e156.40) 77.64 (28.00e156.40) 177.00
59.80 (1.80e299.30) 171.60 (87.50e328.50) 87.00
38.8 (8.90e55.20) 90.60 (75.00e114.90) 25.60
44.00
57.00
179.00
91.00
26.00
100.50 (18.20e556.00) 69
237.50 (8,60e940.00) 290
60.80 (n.d. e 242.00) 119
64.80 (0.20e322.00) e
e 1
61.00 (5.00e123.00) 132.00 (11.60e212.00)
158.00 (15.00e337.00) 560.00 (169.00e1059.00)
51.00 (5.00e213.00)
89.00 (10.00e23.00)
48.00 (15.00e79.00)
20.00 7.00
95.00 16.00
45.00 10.00
90.00 35.00
68.00 2.00
a b c d e
Perin et al. (1997). Faria and Sanchez (2001). Baptista Neto et al. (1999). Barrocas et al. (1995). Turekian and Wedepohl (1961).
Please cite this article in press as: Fonseca, E.M., et al., Stormwater impact in Guanabara Bay (Rio de Janeiro): Evidences of seasonal variability in the dynamic of the sediment heavy metals, Estuarine, Coastal and Shelf Science (2013), http://dx.doi.org/10.1016/j.ecss.2013.04.022
436 437 438 439 440 441 442 443 444 445 446 447 448 449 450 451 452 453 454 455 456 457 458 459 460 461 462 463 464 465 466 467 468 469 470 471 472 473 474 475 476 477 478 479 480 481 482 483 484 485 486 487 488 489 490 491 492 493 494 495 496 497 498 499 500
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501 502 503 504 505 506 507 508 509 510 511 512 513 514 515 516 517 518 519 520 521 522 523 524 525 526 527 528 529 530 531 532 533 534 535 536 537 538 539 540 541 542 543 544 545 546 547 548 549 550 551 552 553 554 555 556 557 558 559 560 561 562 563 564 565
5
Fig. 2. Total heavy metal concentration variation during the campaigns.
The total concentration of Pb clearly showed a difference when compared during both seasons, confirming the results discussed by Pereira et al. (2007), that the downtown area of Niterói is an important source of heavy metals for Guanabara Bay during the rainy season (Fig. 2). Automobiles are very important sources of heavy metal contamination in urban environments (Ellis, 1988; Baptista Neto et al., 1999), with Pb being one of the most significant pollutants. Results would suggest that the source of this metal at the entrance of the bay is even more significant, surpassing the inner bay concentration values. The amorphous Fe/Mn phase was shown to be very important for the adsorption of Pb (Fig. 3) and Baruah et al. (1996); Mortimer and Rae (2000) and Li et al. (2001) showed similar results where they highlighted the affinity of the reducible phase, and to a lesser but significant extent the organic/sulfide phase for this metal. Álvarez-Iglesias et al. (2003), compared samples from two distinct highly impacted areas of São Simón Bay (Spain) and showed the amorphous Fe/Mn and organic phases to have a high affinity for this metal. It is important to highlight that the soluble phase only showed concentrations of Pb during the rainy season. This would make this metal more available and may be a direct result of its super saturation in the sediment. However, in order to confirm this further research would need to be carried out by sampling the source areas
in more detail. The residual phase also showed adsorption of this metal during the rainy season. Like Zn, total Cu concentrations do not alter between the two seasons at all the stations (Fig. 2). The only exceptions were stations 9 and 10, where antifouling paints that contain high levels of Cu and are present in Niterói harbor could possibly be washed by rain and transported to the bay, thus increasing the concentration of this metal in the sediments collected from this area. It is also important to highlight how Dockyards and harbors can be important locations since sediment-associated pollutants accumulate in these areas, especially in the inner part of Guanabara Bay (Vilela et al., 2004). The soluble phase showed concentrations of Cu during the dry season (Fig. 3). The organic matter data (Table 1) suggested that the addition of organic substances during the rainy season may be responsible, at least in part, for the reduction of Cu and allowing adsorption by the soluble phase. Concentrations of Cu were bound by the organic/sulfide phase in the majority of the samples analyzed during both seasons. The reducible and oxidizable phases were shown to be important sinks for Cu. In contrast, the residual phase was shown to be much less important than the others and this behavior was also observed in several works, suggesting a great affinity of these two phases for this metal (Baruah et al., 1996; Mortimer and Rae, 2000; Li et al., 2001).
Please cite this article in press as: Fonseca, E.M., et al., Stormwater impact in Guanabara Bay (Rio de Janeiro): Evidences of seasonal variability in the dynamic of the sediment heavy metals, Estuarine, Coastal and Shelf Science (2013), http://dx.doi.org/10.1016/j.ecss.2013.04.022
566 567 568 569 570 571 572 573 574 575 576 577 578 579 580 581 582 583 584 585 586 587 588 589 590 591 592 593 594 595 596 597 598 599 600 601 602 603 604 605 606 607 608 609 610 611 612 613 614 615 616 617 618 619 620 621 622 623 624 625 626 627 628 629 630
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631 632 633 634 635 636 637 638 639 640 641 642 643 644 645 646 647 648 649 650 651 652 653 654 655 656 657 658 659 660 661 662 663 664 665 666 667 668 669 670 671 672 673 674 675 676 677 678 679 680 681 682 683 684 685 686 687 688 689 690 691 692 693 694 695
E.M. Fonseca et al. / Estuarine, Coastal and Shelf Science xxx (2013) 1e8
Fig. 3. Variation in the heavy metal fractionation patterns during both campaigns at the different sampling stations.
Please cite this article in press as: Fonseca, E.M., et al., Stormwater impact in Guanabara Bay (Rio de Janeiro): Evidences of seasonal variability in the dynamic of the sediment heavy metals, Estuarine, Coastal and Shelf Science (2013), http://dx.doi.org/10.1016/j.ecss.2013.04.022
696 697 698 699 700 701 702 703 704 705 706 707 708 709 710 711 712 713 714 715 716 717 718 719 720 721 722 723 724 725 726 727 728 729 730 731 732 733 734 735 736 737 738 739 740 741 742 743 744 745 746 747 748 749 750 751 752 753 754 755 756 757 758 759 760
761 762 763 764 765 766 767 768 769 770 771 772 773 774 775 776 777 778 779 780 781 782 783 784 785 786 787 788 789 790 791 792 793 794 795 796 797 798 799 800 801 802 803 804 805 806 807 808 809 810 811 812 813 814 815 816 817 818 819 820 821 822 823 824 825
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References
Table 3 Results of the KruskaleWallis test for seasonal variability of the data. Heavy metal
Zn
Cu
Pb
Cr
Ni
“p” (significance level)
0.2069
0.4602
0.0009
0.0007
0.0000
The sum of the metal concentrations in the exchangeable, carbonate, FeeMn oxide and organic/sulfide phase can be used to express the potential mobility of metals (Haung et al., 2007). In the present study, the recorded metal fractionation pattern would suggest that concentrations of Cr, Ni, Zn and Pb deposited during the wet season are not bioavailable, making Cu more available and toxic to the environment (Fig. 3). Under strong oxidizing conditions, due to degradation of organic matter, Cu could become very available and toxic to the environment. In order to check the seasonal variability significance, the statistics test of KruskaleWallis was applied, which confirm that the elements Pb, Cr and Ni concentrations, varied significantly between the two campaign, with “p“ values reaching 0.009, 0.007 and 0.000, respectively (Table 3). 5. Conclusions Rainfall levels are shown to be an important parameter with respect to the geochemistry of Guanabara Bay. These levels were responsible for the variability found in the total concentrations of Pb, Cr and Ni as well as their fractionation. The relative increase in the concentration of metals bound by the residual phase of these samples during the rainy season highlights the importance of the surrounding catchment areas for the input of sediment and water to Guanabara Bay. Variations in Pb, Cr and Ni indicated a positive relationship with Storm water events, where an increase in flux during the rainy season was shown to have an impact on their concentrations. High concentrations of Cu, were linked to the naval activities carried out in Niterói Harbor and could be an important source for this metal. Despite the absence of significant sources for metals in the regions surrounding the Guapimirim protected area e northeast of the bay, it’s environmental characteristics (particle size and the levels of organic matter) have turned this area into a potential sink for metals and probably other pollutants. Despite the high level of heavy metals in the bottom sediments of Guanabara Bay, very low concentrations are adsorbed by the soluble phase and therefore have a low risk of entering the water column. These metals are adsorbed and locked up by the organic/ sulfide and other scavenging phases. Even though this study has verified the affinity that certain “operational” phases have for heavy metals, many variations with respect to these characteristics have been reported in the literature. These differences in geochemical dynamics of the metals may possibly be explained by the presence of external parameters such as, the high concentrations of metals adsorbed by the different phases (scavengers) or the environmental physic-chemical conditions that are characteristic of Guanabara Bay. Uncited reference Q2
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Rauret, 1998. Acknowledgments The writers are also indebted with Dr Gilberto T. M. Dias for fieldwork assistance, the MSc students from Laboratório de Geologia Marinha e UFF, for their assistance during the fieldwork.
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Please cite this article in press as: Fonseca, E.M., et al., Stormwater impact in Guanabara Bay (Rio de Janeiro): Evidences of seasonal variability in the dynamic of the sediment heavy metals, Estuarine, Coastal and Shelf Science (2013), http://dx.doi.org/10.1016/j.ecss.2013.04.022
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