Chemical contamination assessment of Gulf of Mexico oysters in response to hurricanes Katrina and Rita

Hurricane Katrina made landfall on August 29, 2005 and caused widespread devastation along the central Gulf Coast states. Less than a month later Hurricane Rita followed a similar track slightly west of Katrina’s. A coordinated multi-agency response followed to collect water, sediment and tissue samples for a variety of chemical, biological and toxicological indicators. The National Oceanic and Atmospheric Administration’s National Status and Trends Program (NS&T) participated in this effort by measuring chemical contamination in sediment and oyster tissue as part of the Mussel Watch Program, a long-term monitoring program to assess spatial and temporal trends in a wide range of coastal pollutants. This paper describes results for contaminants measured in oyster tissue collected between September 29 and October 10, 2005 and discusses the results in the context of Mussel Watch and its 20-year record of chemical contamination in the region and the nation. In general, levels of metals in oyster tissue were higher then pre- hurricane levels while organic contaminants were at or near record lows. No contaminant reported here exceeded the FDA action level for food safety.     

The Effects of Small Dam Removal on the Distribution of Sedimentary Contaminants

With increasing concern over degradation of aquatic resources, issues of liability, and maintenance costs, removal of small dams has become increasing popular. Although the benefits of removal seem to outweigh the drawbacks, there is a relative paucity of studies documenting the extent and magnitude of biological and chemical changes associated with dam removal, especially those evaluating potential changes in contaminant inventories. In August and November of 2000, a run-of-the-river dam on Manatawny Creek (southeast Pennsylvania) was removed in a two-stage process. To assess the effects of dam removal on the contaminant redistribution within the creek, sedimentary concentrations of polychlorinated biphenyls (PCBs), polycyclic aromatic hydrocarbons (PAHs), and trace metals (Cd, Cr, Cu, Ni, Pb, Zn) were evaluated prior to and several months after removal. Pre- and post-removal analyses revealed elevated and spatially variable concentrations of total PAHs (ranging from approximately 200 to 81,000 ng(g dry weight) and low to moderate concentrations of trace metals and PCBs. The concentrations of these sedimentary contaminants pre- versus post-removal were not significantly different. Additionally, though the impoundment received storm water run-off and associated contaminants from the adjacent city of Pottstown, the total inventory of fine-grain sediments in the impoundment prior to removal was very low. The removal of the low-level Manatawny Creek dam did not significantly redistribute contaminants downstream. However, each dam removal should be assessed on a case by case basis where the potential of sedimentary contaminant redistribution upon dam removal exists.     

Pre- and post-fire pollutant loads in an urban fringe watershed in Southern California

Post-fire runoff has the potential to be a large source of contaminants to downstream areas. However, the magnitude of this effect in urban fringe watersheds adjacent to large sources of airborne contaminants is not well documented. The current study investigates the impacts of wildfire on stormwater contaminant loading from the upper Arroyo Seco watershed, burned in 2009. This watershed is adjacent to the Greater Los Angeles, CA, USA area and has not burned in over 60 years. Consequently, it acts as a sink for regional urban pollutants and presents an opportunity to study the impacts of wildfire. Pre- and post-fire storm samples were collected and analyzed for basic cations, trace metals, and total suspended solids. The loss of vegetation and changes in soil properties from the fire greatly increased the magnitude of storm runoff, resulting in sediment-laden floods carrying high concentrations of particulate-bound constituents. Post-fire concentrations and loads were up to three orders of magnitude greater than pre-fire values for many trace metals, including lead and cadmium. A shift was also observed in the timing of chemical delivery, where maximum suspended sediment, trace metal, and cation concentrations coincided with, rather than preceded, peak discharge in the post-fire runoff, amplifying the fire’s impacts on mass loading. The results emphasize the importance of sediment delivery as a primary mechanism for post-fire contaminant transport and suggest that traditional management practices that focus on treating only the early portion of storm runoff may be less effective following wildfire. We also advocate that watersheds impacted by regional urban pollutants have the potential to pose significant risk for downstream communities and ecosystems after fire.     

A biomonitor as a measure of an ecologically-significant fraction of metals in an industrialized harbour

Biomonitors are commonly used to assess levels of bioavailable contaminants in the environment, however the relationships between biomonitor tissue concentrations and ecological effects are rarely assessed. The present study investigated metal contamination within a highly industrialised harbour and ecological effects on sessile invertebrates. The native oyster Saccostrea glomerata was deployed as a biomonitor across twenty-six sites to test for correlations between metal levels in their tissues and the recruitment of hard-substrate invertebrates. Concentrations of lead and copper in oyster tissues were negatively correlated with densities of the dominant barnacle, Amphibalanus variegatus, and positively correlated with densities of the dominant polychaete, Hydroides elegans, and the two native encrusting bryozoans Celloporaria nodulosa and Arachnopusia unicornis. Results suggest that highly localised events drive contaminant availability and that these events pose a significant risk to fauna. Biomonitoring studies may be enhanced by running concurrent ecological surveys.     

Estimating aquatic toxicity as determined through laboratory tests of great lakes sediments containing complex mixtures of environmental contaminants

We developed and evaluated a total toxic units modeling approach for predicting mean toxicity as measured in laboratory tests for Great Lakes sediments containing complex mixtures of environmental contaminants (e.g., polychlorinated biphenyls, polycyclic aromatic hydrocarbons, pesticides, chlorinated dioxins, and metals). The approach incorporates equilibrium partitioning and organic carbon control of bioavailability for organic contaminants and acid volatile sulfide (AVS) control for metals, and includes toxic equivalency for planar organic chemicals. A toxic unit is defined as the ratio of the estimated pore-water concentration of a contaminant to the chronic toxicity of that contaminant, as estimated by U.S. Environmental Protection Agency Ambient Water Quality Criteria (AWQC). The toxic unit models we developed assume complete additivity of contaminant effects, are completely mechanistic in form, and were evaluated without any a posteriori modification of either the models or the data from which the models were developed and against which they were tested. A linear relationship between total toxic units, which included toxicity attributable to both iron and un-ionized ammonia, accounted for about 88% of observed variability in mean toxicity; a quadratic relationship accounted for almost 94%. Exclusion of either bioavailability components (i.e., equilibrium partitioning control of organic contaminants and AVS control of metals) or iron from the model substantially decreased its ability to predict mean toxicity. A model based solely on un-ionized ammonia accounted for about 47% of the variability in mean toxicity. We found the toxic unit approach to be a viable method for assessing and ranking the relative potential toxicity of contaminated sediments.The U.S. Government right to retain a non-exclusive royalty free licence in and to any copyright is acknowledged.     

Inorganic and organic contaminants in Alaskan shorebird eggs

Many shorebird populations throughout North America are thought to be declining, with potential causes attributed to habitat loss and fragmentation, reduced prey availability, increased predation, human disturbance, and increased exposure to environmental pollutants. Shorebirds may be particularly vulnerable to contaminant exposure throughout their life cycle, as they forage primarily on invertebrates in wetlands, where many contaminants accumulate disproportionately in the sediments. Therefore, it is important to document and monitor shorebird populations thought to be at risk and assess the role that environmental contaminants may have on population declines. To investigate potential threats and provide baseline data on shorebird contaminant levels in Alaskan shorebirds, contaminant concentrations were evaluated in shorebird eggs from 16 species residing in seven geographic distinct regions of Alaska. Similar to previous studies, low levels of most inorganic and organic contaminants were found, although concentrations of several inorganic and organic contaminants were higher than those of previous studies. For example, elevated strontium levels were observed in several species, especially black oystercatcher (Haematopus bachmani) sampled in Prince William Sound, Alaska. Additionally, contaminant concentrations varied among species, with significantly higher concentrations of inorganic contaminants found in eggs of pectoral sandpiper (Calidris melanotos), semipalmated sandpiper (Calidris pusilla), black oystercatcher, and bar-tailed godwit (Limosa lapponica). Similarly, significantly higher concentrations of some organic contaminants were found in the eggs of American golden plover (Pluvialis dominica), black-bellied plover (Pluvialis squatarola), pacific golden plover (Pluvialis fulva), bar-tailed godwit, and semipalmated sandpiper. Despite these elevated levels, current concentrations of contaminants in shorebird eggs suggest that breeding environments are relatively free of most contaminants and that contaminant concentrations are below levels (except potentially strontium) that would likely affect the survival of individuals and consequently regulate the species at the population level.     

Contaminant concentrations in whole-body fish and shellfish from US estuaries

Persistent bioaccumulative and toxic (PBT) pollutants are chemical contaminants that pose risks to ecosystems and human health. For these reasons, available tissue contaminant data from the US EPA Environmental Monitoring and Assessment Program’s National Coastal Assessment were examined to estimate to what areal extent PBTs are found in US estuarine resources. The data document composite, whole-body tissue chemical concentrations for 736 sampling sites across Northeast, Southeast, Gulf of Mexico, and West Coast estuaries. Tissue chemical concentrations were compared to US EPA non-cancer risk guidelines for recreational fishers, because of a lack of ecological guidelines for these chemical concentrations. Samples were analyzed for 23 PAH compounds, 21 PCB congeners, 6 DDT derivatives and metabolites, 14 chlorinated pesticides (other than DDT) and 13 metals, including mercury. Total PCBs were found to exceed recreational fisher guidelines most frequently (31% of samples evaluated), followed by mercury (29%), total PAHs (21%), and DDT and its metabolites, DDD and DDE (11%). Toxaphene, cadmium and dieldrin were found but in fewer than 1% of the samples.     

Characterization of organic chemical contaminants in sediments from Jobos Bay, Puerto Rico

Jobos Bay, located on the southeastern coast of Puerto Rico, contains a variety of habitats including mangroves, seagrass meadows, and coral reefs. The watershed surrounding the bay includes a number of towns, agricultural areas, and the Jobos Bay National Estuarine Research Reserve (NERR). Jobos Bay and the surrounding watershed are part of a Conservation Effects Assessment Project (CEAP), involving the Jobos Bay NERR, the US Department of Agriculture, and the National Oceanic and Atmospheric Administration (NOAA) to assess the benefits of agricultural best management practices (BMPs) on the terrestrial and marine environments. As part of the Jobos Bay CEAP, NOAA collected sediment samples in May 2008 to characterize over 130 organic chemical contaminants. This paper presents the results of the organic contaminant analysis. The organic contaminants detected in the sediments included polycyclic aromatic hydrocarbons (PAHs), polychlorinated biphenyls, and the pesticide DDT. PAHs at one site in the inner bay near a boat yard were significantly elevated; however, all organic contaminant classes measured were below NOAA sediment quality guidelines that would have indicated that impacts were likely. The results of this work provide an important baseline assessment of the marine environment that will assist in understanding the benefits of implementing BMPs on water quality in Jobos Bay.     

Global climate change and contaminants--an overview of opportunities and priorities for modelling the potential implications for long-term human exposure to organic compounds in the Arctic

This overview seeks to provide context and insight into the relative importance of different aspects related to global climate change for the exposure of Northern residents to organic contaminants. A key objective is to identify, from the perspective of researchers engaged in contaminant fate, transport and bioaccumulation modelling, the most useful research questions with respect to projecting the long-term trends in human exposure. Monitoring studies, modelling results, the magnitude of projected changes and simplified quantitative approaches are used to inform the discussion. Besides the influence of temperature on contaminant amplification and distribution, accumulation of organic contaminants in the Arctic is expected to be particularly sensitive to the reduction/elimination of sea-ice cover and also changes to the frequency and intensity of precipitation events (most notably for substances that are highly susceptible to precipitation scavenging). Changes to key food-web interactions, in particular the introduction of additional trophic levels, have the potential to exert a relatively high influence on contaminant exposure but the likelihood of such changes is difficult to assess. Similarly, changes in primary productivity and dynamics of organic matter in aquatic systems could be influential for very hydrophobic contaminants, but the magnitude of change that may occur is uncertain. Shifts in the amount and location of chemical use and emissions are key considerations, in particular if substances with relatively low long range transport potential are used in closer proximity to, or even within, the Arctic in the future. Temperature-dependent increases in emissions via (re)volatilization from primary and secondary sources outside the Arctic are also important in this regard. An increased frequency of boreal forest fires has relevance for compounds emitted via biomass burning and revolatilization from soil during/after burns but compound-specific analyses are limited by the availability of reliable emission factors. However, potentially more influential for human exposure than changes to the physical environment are changes in human behaviour. This includes the gradual displacement of traditional food items by imported foods from other regions, driven by prey availability and/or consumer preference, but also the possibility of increased exposure to chemicals used in packaging materials and other consumer products, driven by dietary and lifestyle choices.     

The use of leeches and logit log-linear contingency models to assess and monitor aquatic PCB contamination originating from mid-Canada radar line site 050

Abandoned military sites in northern North America are relics of the Cold War and sources of polychlorinated biphenyls (PCBs). In the late 1990s, the Canadian federal and provincial governments began the cleanup of the mid-Canada radar line in Ontario, Canada. The first site to be remediated was Site 050 (Fort Albany First Nation) in 2001; however, the community remains concerned that contaminants may have moved prior to, during, and after remediation into the Albany River directly adjacent to Site 050. Thus, the Albany River was monitored (1999, 2001, 2002) during the remediation process to determine if the cleanup itself further contaminated the aquatic compartment, using leeches (Haemopis spp.) as bioindicators. Few organochlorines were found in leeches at levels higher than the detection limit, aside from PCBs. Leech data from the present study indicated that PCB levels were significantly higher near Site 050 than the control site upstream, indicating point source contamination from Site 050. The temporal trend in leech contaminant data indicated an increase in PCB contaminant load from 1999 (pre-remediation) to 2001 (immediately post-remediation), but this difference was not statistically significant due to high variances. Nevertheless, logit log-linear contingency modeling did reveal that immediately after cleanup (2001), contaminants (CBs 99, 118, 128, 156, 170, 183) in leeches were detected significantly more frequent than expected. When taken together, leech body burden and frequency of detection data suggest that the remediation process itself further contaminated the aquatic environment, if only temporarily. Lastly, the removal of the terrestrial source of PCBs during remediation did remove the source of aquatic contaminants in that body burden of contaminants in leeches were significantly lower a year after cleanup.     

Comparison of PoraPak Rxn RP and XAD-2 adsorbents for monitoring dissolved hydrophobic organic contaminants

Accurate determination of the levels of dissolved hydrophobic organic contaminants (HOCs) is an important step in estimating the dynamics of their inputs and losses in aqueous systems. This study explores an alternative method for efficiently sampling dissolved HOCs while mitigating a number of sampling artifacts associated with traditional methods. The adsorption characteristics of a new polymeric resin, PoraPak Rxn RP (PPR), were assessed using sorption isotherm experiments and fixed bed adsorption studies. The adsorption capacities and breakthrough times for four model contaminants (phenol, p-nitrophenol, naphthalene, and 2,4,6-tribromophenol) were proportional to the contaminant’s hydrophobicity. The ability of PPR to isolate dissolved polychlorinated biphenyls (PCBs) in real samples was compared with that of XAD-2, a well-known macroporous polymer that suffers from high background contamination. The results indicated that the PPR resin can be effectively used for monitoring HOCs, with low ∑PCB levels in blanks, decreasing solvent use, and reducing extraction times.     

Estimation of pollutant partition in sandy soils with different water contents

The objectives of this work were: (1) to identify an isotherm model to relate the contaminant contents in the gas phase with those in the solid and non-aqueous liquid phases; (2) to develop a methodology for the estimation of the contaminant distribution in the different phases of the soil; and (3) to evaluate the influence of soil water content on the contaminant distribution in soil. For sandy soils with negligible contents of clay and natural organic matter, contaminated with benzene, toluene, ethylbenzene, xylene, trichloroethylene (TCE), and perchloroethylene (PCE), it was concluded that: (1) Freundlich’s model showed to be adequate to relate the contaminant contents in the gas phase with those in the solid and non-aqueous liquid phases; (2) the distribution of the contaminants in the different phases present in the soil could be estimated with differences lower than 10% for 83% of the cases; and (3) an increase of the soil water content led to a decrease of the amount of contaminant in the solid and non-aqueous liquid phases, increasing the amount in the other phases.     

Pollution and Genetic Structure of North American Populations of the Common Dandelion (Taraxacum Officinale)

Assessing the genetic structure of natural populations differentially impacted by anthropogenic contaminants can be a useful tool for evaluating the population genetic consequences of exposure to pollution. In this study, measures of genetic diversity at variable-number-tandem-repeat loci in six dandelion populations (3 urban and 3 rural) showed patterns that may have been influenced by exposure to environmental contaminants. Mean genetic similarity among individuals within a population was significantly and positively correlated with increasing levels of airborne particulate matter ( 10 m, PM₁₀) and soil concentrations of four metals (Cd, Fe, Ni and Pb). In addition, mean genetic similarity was always significantly higher at the urban sites compared to rural sites. There was a significant negative correlation between the number of genotypes at a site and increasing amounts of PM₁₀, concentrations of five soil metals (Cd, Cu, Fe, Ni and Pb), leaf tissue levels of Fe and a significant positive correlation between the extent of clonality at a site and levels of PM₁₀ and soil concentrations of five metals (Cd, Cu, Fe, Ni and Pb). Although, this study does not directly establish a causal link between the specific contaminants detected at the study sites and differences in genetic diversity, our data are consistent with the hypothesis that pollution-induced selection has contributed in some fashion to the lower genetic diversity found at the urban sites.     

Geographic differences in organic contaminants and stable isotopes (δ¹³C, δ¹⁵N) in thick-billed murre (Uria lomvia) eggs from Alaska

The contents from thick-billed murre (Uria lomvia) eggs collected at four Alaskan colonies in 2002 were analyzed for organic contaminants and carbon δ13C) and nitrogen (δ1?N) stable isotopes. Contaminant concentrations in the eggs varied from below detection limits to 230 ng g?1 wet mass for 4,4'-DDE in one egg from St Lazaria Island in the Gulf of Alaska. Eggs from this colony generally contained higher levels of contaminants and exhibited significantly different patterns compared to eggs from the Bering and Chukchi seas. Stable isotope values also varied geographically; however, these differences appeared to be related to differences in C and N baselines in the food webs instead of differences in prey. Contaminant and stable isotope correlations were inconclusive, suggesting that better information on regional food web differences and differential offloading of contaminants and stable isotopes to the eggs must be obtained before these kinds of data can be fully incorporated into seabird egg contaminant monitoring programs.     

WATER AND WASTEWATER QUALITY MONITORING, MCMURDO STATION, ANTARCTICA

McMurdo Station is the largest research station in Antarctica and has a population that ranges from 250 to 1200 people. Wastewater from the Station is macerated, was sometimes mixed with waste brine from the desalinization plant and is discharged to McMurdo Sound. Effluent water quality has been routinely monitored since 1989, and a special ambient water quality study was conducted by Idaho National Engineering Laboratory (INEL) personnel in 1992. Results of the effluent monitoring efforts show that low concentrations of a few organic contaminants have been detected, while concentrations of metals, particularly copper, are considerably higher. Ambient water quality and sea ice monitoring detected very few contaminants, all at very low levels. Only minor and variable dissolved oxygen depression was detected near the outfall. Diatom communities near the outfall differ in relative abundance, cell counts, and chlorophyll a content compared to control sites. For the purpose of evaluating the impact of McMurdo`s effluent on ambient water quality, improved effluent monitoring and sediment quality monitoring are recommended instead of frequent monitoring of ambient water quality.     

Metal concentrations in American oyster <Emphasis Type="Italic">Crassotrea virginica</Emphasis> and adjacent sediments from harvestable and non-harvestable sites in the Southeastern USA

Human population growth in coastal areas continues to threaten estuarine ecosystems and resources. Populations of Crassostrea virginica have declined across the USA due to water quality degradation, disease pressure, alteration of habitat, and other changes related to anthropogenic impacts. Metals that may be present in estuarine habitats can bioaccumulate in oysters, with potential consequences to the health of oysters and humans consumers. This study (1) evaluated the occurrence and relationships of metal concentrations in oyster tissue versus estuarine sediments, (2) examined oyster tissue concentrations in relation to state water quality designations, and (3) evaluated the potential risk for humans from oyster consumption related to metal concentrations from harvestable waters. Results indicated metal concentrations in sediments and oysters along coastal South Carolina remain low compared to other areas and that concentrations in oyster tissue and adjacent sediments were not highly correlated with each other. However, high concentrations of some metals occurred in oysters sampled from areas designated as Approved for Harvesting. This is important because most harvest area designation systems rely on regular bacterial monitoring when evaluating the safety of consumption. Others safety measurements may be necessary as part of routine monitoring.     

Kinetic of Biomarker Responses in Juveniles of the Fish Sparus aurata Exposed to Contaminated Sediments

Sediments in the National Park of the Atlantic Islands (Galicia, Spain) were affected by the spill of the tanker Prestige (November, 2002) and still present high levels of Polycyclic aromatic hydrocarbons. The adverse effects associated with the contaminants in sediments were tested using a chronic bioassay, exposing juveniles of the fish Sparus aurata (seabream). A toxicokinetic approach is proposed to evaluate sediment quality by linking chemical and ecotoxicological data along the time. Sediment samples were physicochemically characterized and the concentration of contaminants (Polycyclic aromatic hydrocarbons – PAHs – and metals) was measured. Fishes were exposed to contaminated sediments, and samples from different tissues were collected every 15 days throughout the 60 days that lasted the experiment. A biomarker of exposure (ethoxyresorufin O-deethylase activity – EROD activity) and a biomarker of effect (histopathology) were analyzed during the exposure period. Results show a relationship between the biomarkers and the concentrations in sediments of polycyclic aromatic hydrocarbons—PAHs. Besides, the toxicokinetic approach links biomarkers response providing information about the relationship between the detoxification process and the damages observed in the different tissues. The frequency of the histological damage is highest when the EROD activity slightly decreases in accordance with the mechanism of detoxification of this enzymatic system against PAHs and other organic contaminants.     

Comparative evaluation of a bioluminescent bacterial assay in terrestrial ecotoxicity testing

Despite the widespread and successful use of luminescence-based bioassays in water testing, their applications to soils and sediments is less proven. In part this is because such bioassays have mainly been carried out in an aqueous-based medium and, as such, favour contaminants that are readily water-soluble. In this study, aqueous solutions and soils contaminated with heavy metals (HM), polar organic contaminants and hydrophobic organic contaminants (HOCs) were tested using a range of luminescence-based bioassays (Vibrio fischeri, Escherichia coli HB101 pUCD607 and Pseudomonas fluorescens 10586r pUCD607). For the first two chemical groups, the assays were highly reproducible when optimised extraction procedures were employed but for HOCs the bioassay response was poor. Quantitative structure-activity relationships (QSARs) obtained from aqueous solutions had a linear response although correlation for the chemicals tested using bacterial bioassays was significantly less sensitive than that of sublethal tests for Tetrahymena pyriformis. Bacterial and Dendrobaena veneta bioassay responses to extracts from HM amended soils showed that a clear relationship between trophic levels could be obtained. There is no doubt that the wide range of bioluminescent-based bioassays offers complementary applications to traditional testing techniques but there is a significant need to justify and optimise the extraction protocol prior to application.     

Mass balance in the monitoring of pollutants in tidal rivers of the Guanabara Bay, Rio de Janeiro, Brazil

This study addressed the identification and monitoring of pollution sources of terrestrial origin in rivers (domestic sewage and industrial effluents) and critical fluvial segments in highly polluted environments under tidal influence (mixing marine and continental sources) from Guanabara Bay Basin, Rio de Janeiro, Brazil. The mass balance of contaminants was determined in conditions of continuous flow (low tide) during dry season (lower dilution capability). The results allowed the evaluation of the potential of contaminant mass generation by the different river segments and the estimation of their natural and anthropogenic components. The water quality of Igua?ú and Sarapuí Rivers were evaluated for metals and biochemical oxygen demand. The method gave an excellent response, including the possibility of sources identification and contaminated river segments ranking. The approach also offers fast execution and data interpretation, being highly efficient.     

Determination of metal partitioning in porewater extracted from the Seine River Estuary sediment (France)

Total dissolved trace and major metals and their partitioning in porewater sediment have been investigated at two sites in the Seine River estuary (France). For this purpose, solid phase extraction (SPE) has been employed using specific chelating resins for the separation and preconcentration of organic and inorganic forms of studied metals under controlled (N2) inert atmosphere. In fact, the study is focused on the development of a method for sample collection and handling under inert atmosphere in order to avoid some potential artefacts of the extracted porewater, to preserve the samples from possible chemical oxidation changes and to determine metals partitioning between organic and inorganic forms. For this point, a separation and preconcentration method using two columns in series (chelamine and C18 columns) was used. The trace and major metals fixed on the two resins for all determinations were stripped by nitric acid (2 M) and analyzed by Inductively Coupled Plasma Atomic Emission Spectroscopy (ICP-AES) and Zeeman Graphite Furnace Atomic Absorption Spectroscopy (ZGF-AAS). The relationship between the distribution of metals and physico-chemical parameters such as pH and Eh (redox potential) as a function of depth was discussed. Some tendency in the distributions and seasonal variability of these traces and major metals are improved. The concentrations for all studied metals decreased as a function of depth where iron and manganese were found at mg L(-1) levels and other metals were found at [micro sign]g L(-1) levels, as well as there were significant fractions of all metals (except of manganese) which were complexed by organic matter. The comparison of data for the major elements (Fe and Mn), obtained by direct determination (without preconcentration) and preconcentration, show a very good recovery.