Sub-lethal effects of copper to benthic invertebrates explained by sediment properties and dietary exposure

The next generation of sediment quality guidelines (SQGs) requires better established causal links between the chronic exposure and effects of metals from both dissolved and dietary sources. The potential for dietary exposure from sediment metals to cause toxic effects to benthic invertebrates is strongly influenced by the metal-binding properties of the sediments. For relatively oxidized sediments, sublethal effects of copper to the epibenthic deposit-feeding amphipod, Melita plumulosa, and the benthic harpacticoid copepod, Nitocra spinipes, were investigated. Effects on reproduction were strongly influenced by the properties of the sediments and sediment-bound copper was found to be the major contribution to the toxicity. For sediments with the same total copper concentrations, effects were less for sediments with greater concentrations of fine particles (<63 μm sediment) or particulate organic carbon (OC). The OC-normalized copper concentration in the <63 μm sediment fraction provided a single effects threshold for all sediment types. For M. plumulosa and N. spinipes, the 10% effect concentrations (EC10s) were 5.2 and 4.8 mg <63 μm Cu g(-1) OC. These chronic EC10s indicate that a SQG of 3.5 mg <63 μm Cu g(-1) OC, that was previously proposed based on a species sensitivity distribution of acute no effects thresholds data for 12 benthic organisms, will be protective for these species. The study confirms the appropriateness of using SQGs that vary with sediment properties and that SQGs of this form provide adequate protection for metal exposure via both dissolved and dietary exposure pathways.     

Calculation and uses of mean sediment quality guideline quotients: a critical review

Fine-grained sediments contaminated with complex mixtures of organic and inorganic chemical contaminants can be toxic in laboratory tests and/or cause adverse impacts to resident benthic communities. Effects-based, sediment quality guidelines (SQGs) have been developed over the past 20 years to aid in the interpretation of the relationships between chemical contamination and measures of adverse biological effects. Mean sediment quality guideline quotients (mSQGQ) can be calculated by dividing the concentrations of chemicals in sediments by their respective SQGs and calculating the mean of the quotients for the individual chemicals. The resulting index provides a method of accounting for both the presence and the concentrations of multiple chemicals in sediments relative to their effects-based guidelines. Analyses of considerable amounts of data demonstrated that both the incidence and magnitude of toxicity in laboratory tests and the incidence of impairment to benthic communities increases incrementally with increasing mSQGQs. Such concentration/response relationships provide a basis for estimating toxicological risks to sediment-dwelling organisms associated with exposure to contaminated sediments with a known degree of accuracy. This sediment quality assessment tool has been used in numerous surveys and studies since 1994. Nevertheless, mean SQGQs have some important limitations and underlying assumptions that should be understood by sediment quality assessors. This paper provides an overview of the derivation methods and some of the principal advantages, assumptions, and limitations in the use of this sediment assessmenttool. Ideally, mean SQGQs should be included with other measures including results of toxicity tests and benthic community surveys to provide a weight of evidence when assessing the relative quality of contaminated sediments.     

Predicting pore water EPA-34 PAH concentrations and toxicity in pyrogenic-impacted sediments using pyrene content

Sediment and freely dissolved pore water concentrations of the U.S. Environmental Protection Agency's list of 34 alkyl and parent PAHs (EPA-34) were measured in 335 sediment samples from 19 different sites impacted by manufactured gas plants, aluminum smelters and other pyrogenic sources. The total EPA-34 freely dissolved pore water concentration, C(pw,EPA-34), expressed as toxic units (TU) is currently considered one of the most accurate measures to assess risk at such sites; however, it is very seldom measured. With this data set, we address how accurately C(pw,EPA-34) can be estimated using limited 16 parent PAH data (EPA-16) commonly available for such sites. An exhaustive statistical analysis of the obtained data validated earlier observations that PAHs with more than 3 rings are present in similar relative abundances and their partitioning behavior typically follows Raoult's law and models developed for coal tar. As a result, sediment and freely dissolved pore water concentrations of pyrene and other 3- and 4-ring PAHs exhibit good log-log correlations (r2 > 0.8) to most individual EPA-34 PAHs and also to C(pw,EPA-34). Correlations improve further by including the ratio of high to low molecular weight PAHs, as 2-ring PAHs exhibit the most variability in terms of their relative abundance. The most practical result of the current work is that log C(pw,EPA-34) estimated by the recommended pyrene-based estimation techniques was similarly well correlated to % survival of the benthic amphipods Hyalella azteca and Leptocheirus plumulosus as directly measured log C(pw,EPA-34) values (n = 211). Incorporation of the presented C(pw,EPA-34) estimation techniques could substantially improve risk assessments and guidelines for sediments impacted by pyrogenic residues, especially when limited data are available, without requiring any extra data or measurement costs.     

Modeling trade-off between PAH toxicity reduction and negative effects of sorbent amendments to contaminated sediments

Adding activated carbon (AC) to contaminated sediment has been suggested as an effective method for sediment remediation. AC binds chemicals such as polycyclic aromatic hydrocarbons (PAHs), thus reducing the toxicity of the sediment. Negative effects of AC on benthic organisms have also been reported. Here, we present a conceptual model to quantify the trade-off, in terms of biomass changes, between the advantageous PAH toxicity reduction and the negative effects of AC on populations of benthic species. The model describes population growth, incorporates concentration-effect relationships for PAHs in the pore water and for AC, and uses an equilibrium sorption model to estimate PAH pore water concentrations as a function of AC dosage. We calibrated the model using bioassay data and analyzed it by calculating isoclines of zero population growth for two species. For the sediment evaluated here, the results show that AC may safely protect the benthic habitat against considerable sediment PAH concentrations as long as the AC dosage remains below 4%.     

Exposure-effect model for calculating copper effect concentrations in sediments with varying copper binding properties: a synthesis

An exposure-effects model is described for calculating copper effect concentrations for benthic organisms in sediments with varying copper-binding properties. It is based on a bioenergetic-based kinetic model that describes the rate of assimilation of copper by benthic organisms from dissolved and particulate phases. During acute exposures, the total copper assimilated by the organisms was used as a measure of the organisms' exposure to bioavailable copper, and toxicity occurs when the copper exposure exceeds a threshold value. Exposure-effects models were developed for nine benthic organisms and were used to predict the effect of sediment-water partitioning (Kd) and copper assimilation from ingested solids on toxic effects and how these factors will influence derived sediment quality guideline (SQG) concentrations. Species sensitivity distributions were used to calculate SQG concentrations for copper for sediments of varying copper binding properties. The modeling indicated that "single value" SQG concentrations would be ineffective for predicting the toxicity of metals in sediment. It is proposed that, for all contaminants (not just metals), a better approach would be to have SQG concentrations, or ranges, that are applied to different sediment types. SQGs should account for contaminant exposure from both water-filtration and particulate-ingestion exposure routes, as can be achieved by models of sediment-water contaminant partitioning (Kd) and the contaminant assimilation efficiency (AE) of ingested particles. The study indicates that improved mechanistic models of contaminant exposure, as influenced by both organism physiology and sediment properties, are needed to predict toxic effects in sediments.     

Including transformation products into the risk assessment for chemicals: the case of nonylphenol ethoxylate usage in Switzerland

A method for applying the risk assessment approach using ratios of predicted environmental concentrations (PECs) and predicted no-effect concentrations (PNECs) to mixtures of parent compounds and their environmental transformation products is presented. Nonylphenol ethoxylates (NPnEOs) and a selection of their most relevant transformation products are investigated as a case study illustrating the method. The PEC values of NPnEO and its transformation products are calculated with a regional multimedia fate model including the transformation kinetics of the NPnEO degradation cascade. PNEC values are derived from a selection of toxicity data on NPnEO and its transformation products. The toxicity of the emerging mixture of NPnEO and its transformation products is then estimated under the assumption of concentration addition (similar mode of action). On this basis, PEC-to-PNEC ratios for the aquatic environment and the sediment are calculated for the individual components of the mixture and the mixture itself. For this purpose, average release rates of NPnEO and its transformation products from Swiss sewage treatment plants were used. While the PEC values of the individual components do not exceed the corresponding PNEC values, the risk quotient of the mixture in water is greater than 1. In sediment, the mixture does not exceed a risk quotient of 1. A combination of sensitivity and scenario analyses is employed to identify the upper and lower bounds of the results.     

Bioaccumulation and toxic potencies of polychlorinated biphenyls and polycyclic aromatic hydrocarbons in tidal flat and coastal ecosystems of the Ariake Sea,Japan

Sediment and marine biota comprising several species of tidal flat and coastal organisms were analyzed for polychlorinated biphenyls (PCBs) including non- and mono-ortho coplanar congeners and polycyclic aromatic hydrocarbons (PAHs) to examine bioaccumulation profiles and toxic potencies of these contaminants. Concentrations of PCBs in tidal flat organisms ranged from 3.6 ng/g (wet wt) in clams to 68 ng/g (wet wt) in omnivore tidal flatfishes, a discernible trend reflecting concentrations and trophic levels. In contrast, PAHs concentrations were the highest in lower trophic organisms, such as crabs and lugworms from tidal flat, whereas those in coastal fishes, squid, and finless porpoises were less than detection limit. Greater bioaccumulation of PAHs was found in lugworms and crabs, which might be due to their direct ingestion of sediment particulates absorbed with PAHs. TCDD toxic equivalents (TEQs) were calculated for PCBs and PAHs in sediments and biota. PCBs accounted for a greater proportion of total TEQs (sum(TEQs): sum of TEQ(PCB) and TEQ(PAH)) in coastal and tidal flatfishes (>95%), while PAHs occupied a considerable portion of sum(TEQs) in sediment (>97%). Interestingly, TEQ(PAH) accounted for 37% and 81% of the sum(TEQs) in crabs and clams, respectively. Benzo[b]fluoranthene was the dominant contributor to TEQ(PAH) in both the species. Considering these observations, the environmental risks of PAHs may not be ignored in benthic tidal flat organisms due to their greater bioaccumulation through sediments.     

Phototoxicity of pyrene affects benthic algae and bacteria from the Arctic

Phototoxicity of polycyclic aromatic hydrocarbons (PAHs) in the Arctic is important to study since the future PAH load is likely to increase. In combination with the increased UV-light penetration due to ozone layer thinning, phototoxicity may be a potential problem for arctic areas. The aim of this study was to evaluate effects of pyrene and phototoxicity of pyrene on natural algae and bacteria from arctic sediments. Sediments from a shallow-water marine baywere spiked with different pyrene concentrations. Microcosms containing the sediment were incubated under three light regimes, natural sunlight with UV-light, natural sunlight without UV-light, and dark. Significant effects were evident at low pyrene concentrations, particularly in presence of UV-light, indicating phototoxicity. The microalgae were especially sensitive to the phototoxicity of pyrene. Already atthe lowest pyrene concentration (Cfree: 4 nM) algal 14C-incorporation and chlorophyll a content were reduced. The toxic effects of pyrene on the microalgae probably led to the release of organic matter. In agreement with this, bacterial activity increased at high pyrene concentrations indicated by increased oxygen consumption and increased release of inorganic N and P from the sediment. This study indicates that phototoxicity of PAHs may be relevant for sediment communities from shallow marine arctic areas at environmentally relevant pyrene concentrations.     

Use of passive samplers to mimic uptake of polycyclic aromatic hydrocarbons by benthic polychaetes

Experiments were conducted to test whether passive samplers made of low-density polyethylene (polyethylene devices, or PEDs) can estimate the extent of uptake of polycyclic aromatic hydrocarbons (PAHs) by benthic polychaetes (Nereis virens) in contaminated marine sediments. For a variety of PAHs, PEDs reached 90% equilibrium with sediment PAHs in 60 days or less. Using 60-day sediment bioaccumulation tests, we have demonstrated a significant relationship between PAH concentrations in the polychaetes and the PEDs (R2 = 0.67, p = 0.002), with the PEDs taking up less PAHs than the polychaetes. Because of this relationship, PEDs can potentially be used in a regulatory context to simulate uptake of bioavailable PAHs in contaminated marine sediments. The PED PAH concentrations were also used to calculate porewater PAH concentrations that allowed for the estimation of a linear free-energy relationship between the lipid-water distribution coefficient (Klip) and the octanol-water distribution coefficient (KOW) for PAH uptake in marine polychaetes (R2 = 0.94, p < 0.0001).     

Bioavailability of PAHs in aluminum smelter affected sediments: evaluation through assessment of pore water concentrations and in vivo bioaccumulation

Bioaccumulation of polycyclic aromatic hydrocarbons (PAHs) from coal tar pitch polluted sediments was predicted by (1) a generic approach based on organic carbon-water partitioning and Gibbs linear free energy relationship (between K(OW) and K(OC)), and (2) measurements of freely dissolved concentrations of PAHs in the sediment pore water, using passive samplers and solid phase extraction. Results from these predictions were compared with those from in vivo bioaccumulation experiments using Nereis diversicolor (Polychaeta), Hinia reticulata (Gastropoda), and Nuculoma tenuis (Bivalvia). Measured sediment/water partition coefficients were higher than predicted by the generic approach. Furthermore, predicted biota-to-sediment accumulation factors (BSAFs) derived from measured pore water concentrations were more in agreement with the bioaccumulation observed for two of the three species. Discrepancies associated with the third species (N. tenuis) were likely a result of particles remaining in the intestine (as shown by microscopic evaluation). These results indicate the importance of conducting site-specific evaluations of pore water concentrations and/or bioaccumulation studies by direct measurements to accurately provide a basis for risk assessment and remediation plans. The importance of knowledge regarding specific characteristics of model organisms is emphasized.     

Importance of unburned coal carbon, black carbon, and amorphous organic carbon to phenanthrene sorption in sediments

The aim of this paper was to estimate the contribution to total phenanthrene sorption from unburned coal and black carbon (BC; soot and charcoal) in sediment. We determined sorption isotherms for five Argonne Premium Coal standards over a wide concentration interval (0.01-10 000 ng/L). The coals showed strong and nonlinear sorption (carbon-normalized K(F) = 5.41-5.96; nF = 0.68-0.82). Coal sorption appeared to become more nonlinear with increasing coal maturity. The coal's specific surface area appeared to influence K(F). On the basis of the current coal sorption observations combined with earlier petrographic analyses and BC sorption experiments, we calculated for one particular sediment that coal, BC, and "other" OC were all important to PHE sorption in the environmentally relevant nanogram per liter range. This indicates that it is important to consider strong sorption to coal in the risk assessment of coal-impacted geosorbents (e.g., river beds) where coal is mined/shipped and manufactured gas plant sites.     

Two years after the Hebei Spirit oil spill: residual crude-derived hydrocarbons and potential AhR-mediated activities in coastal sediments

The Hebei Spirit oil spill occurred in December 2007 approximately 10 km off the coast of Taean, South Korea, on the Yellow Sea. However, the exposure and potential effects remain largely unknown. A total of 50 surface and subsurface sediment samples were collected from 22 sampling locations at the spill site in order to determine the concentration, distribution, composition of residual crudes, and to evaluate the potential ecological risk after two years of oil exposure. Samples were extracted and analyzed for 16 polycyclic aromatic hydrocarbons (PAHs), 20 alkyl-PAHs, 15 aliphatic hydrocarbons, and total petroleum hydrocarbons using GC-MSD. AhR-mediated activity associated with organic sediment extracts was screened using the H4IIE-luc cell bioassay. The response of the benthic invertebrate community was assessed by mapping the macrobenthic fauna. Elevated concentrations of residual crudes from the oil spill were primarily found in muddy bottoms, particularly in subsurface layers. In general, the bioassay results were consistent with the chemistry data in a dose-dependent manner, although the mass-balance was incomplete. More weathered samples containing greater fractions of alkylated PAHs exhibited greater AhR activity, due to the occurrence of recalcitrant AhR agonists present in residual oils. The macrobenthic population distribution exhibits signs of species-specific tolerances and/or recolonization of certain species such as Batillaria during weathering periods. Although the Hebei Spirit oil spill was a severe oil exposure, it appears the site is recovering two years later.     

Distributed sequestration and release of PAHs in weathered sediment: the role of sediment structure and organic carbon properties

Polycyclic aromatic hydrocarbon (PAH) contaminated sediments from Piles Creek (PC) and Newtown Creek (NC) in the NY/NJ Harbor estuary were separated into size fractions and further separated into low (<1.7 g cm(-3)) and high (>1.7 g cm(-3)) density fractions. The fractionated sediments were characterized for carbon content pore structure, surface area, and PAH concentration. Most PAHs (50-80%) in both sediments were associated with the low-density fraction, which represents only 3-15% of total sediment mass, at levels greater than expected based on equilibrium partitioning. PC low-density sediment had 10 times greater organic carbon-normalized equilibrium partitioning coefficients (Koc) than the other size fractions and whole sediment. Characterization of the sediment organic matter suggested that the preferential sequestration observed in PC sediment was not correlated with soot carbon but was likely due to the presence of detrital plant debris, an important food source for benthic animals. Fractional PAH desorption from whole PC sediment was significantly higher than from NC sediment after 3 months. For both sediments, a smaller percentage of the total PAHs was desorbed from the low-density fraction. However, because PAH concentrations were greatly elevated in these fractions, more PAH mass was desorbed than from the corresponding bulk and high-density fractions. These results demonstrate that PAHs are preferentially sequestered in a separable, low-density fraction at levels not predictable by equilibrium partitioning theory. Further, the low-density fraction apparently controls whole-sediment PAH release. Although plant debris appears to be an important sorbent for PAHs, this material may readily release PAHs into the aqueous phase.     

Predicting bioavailability of sediment-associated organic contaminants for Diporeia spp. and oligochaetes

Biota-sediment accumulation factors (BSAF) were calculated for Diporeia spp. and oligochaete worms exposed to polychlorinated biphenyls (PCBs) and polycyclic aromatic hydrocarbons (PAHs) from field-collected sediment. These data were compared to the contaminant fraction extracted from sediment with Tenax resin using a 24 h extraction. A previous laboratory study suggested a linear relationship between log BSAF and the contaminant fraction rapidly desorbed from sediment. However, the BSAF data in our study did not fit this relationship. Better predictive regressions for both PCBs and PAHs were found when the log of the lipid-normalized organism contaminant concentrations were plotted against the log of the Tenax-extracted organic carbon-normalized sediment contaminant concentration. Regression lines for the two species had the same slope, but the Diporeia intercept was 2.3 times larger. When adjusted for a 6 h Tenax extraction, based on a regression between 6 and 24 h Tenax extractions, data from this study and two other studies that included multiple oligochaete species fit a single predictive regression. The exception included some PAHs that fell below the regression line. Thus, a single relationship generally predicted bioaccumulation across sediments, compound classes, oligochaete species, and among laboratories.     

In-situ burning of oil in coastal marshes. 2. Oil spill cleanup efficiency as a function of oil type, marsh type, and water depth

In-situ burning of spilled oil, which receives considerable attention in marine conditions, could be an effective way to cleanup wetland oil spills. An experimental in-situ burn was conducted to study the effects of oil type, marsh type, and water depth on oil chemistry and oil removal efficiency from the water surface and sediment. In-situ burning decreased the totaltargeted alkanes and total targeted polycyclic aromatic hydrocarbons (PAHs) in the burn residues as compared to the pre-burn diesel and crude oils. Removal was even more effective for short-chain alkanes and low ring-number PAHs. Removal efficiencies for alkanes and PAHs were >98% in terms of mass balance although concentrations of some long-chain alkanes and high ring-number PAHs increased in the burn residue as compared to the pre-burn oils. Thus, in-situ burning potentially prevents floating oil from drifting into and contaminating adjacent habitats and penetrating the sediment. In addition, in-situ burning significantly removed diesel oil that had penetrated the sediment for all water depths. Furthermore, in-situ burning at a water depth 2 cm below the soil surface significantly removed crude oil that had penetrated the sediment. As a result, in-situ burning may reduce the long-term impacts of oil on benthic organisms.     

Black carbon and ecological factors affect in situ biota to sediment accumulation factors for hydrophobic organic compounds in flood plain lakes

Ecological factors may play an important role in the bioaccumulation of polychlorobiphenyls (PCBs) and polyaromatic hydrocarbons (PAHs). Geochemical and bioaccumulation behavior of these chemicals also appears to be related to the presence of black carbon (BC) in sediment. In situ PCB and PAH biota to sediment accumulation factors (BSAF) for benthic invertebrates, as well as 6h Tenax-extractable (fast-desorbing) concentrations and lake characteristics (including BC in sediment), were determined for different seasons in chemically similar but ecologically different lakes (fish-dominated turbid, algae-dominated turbid, and macrophyte-dominated). BSAFs could be explained with a model including a term for Freundlich sorption to BC and a term for uptake from fast-desorbing concentrations in ingested sediments. Freundlich coefficients for in situ sorption to BC (KF) were calculated from slow desorbing fractions and BC contents and agreed well with literature values for KF. Furthermore, in contrast to BSAFs based on total extracted concentrations, Tenax-based BSAF showed a strong positive correlation with log Kow. We therefore argue that BC caused slow desorption and limited BSAFs in these lakes. Seasonal and lake effects on BSAFs were detected, while the differences between oligochaetes and other invertebrates were small for PCBs and within a factor of 10 for PAHs. BSAFs for pyrogenic PAHs were much lower than for PCBs, which was explained by stronger sorption to BC and lesser uptake from ingested sediment.     

Solid-phase microextraction measurement of parent and alkyl polycyclic aromatic hydrocarbons in milliliter sediment pore water samples and determination of K(DOC) values

The U.S. Environmental Protection Agency (EPA) narcosis model for benthic organisms in polycyclic aromatic hydrocarbon (PAH) contaminated sediments requires the measurement of 18 parent PAHs and 16 groups of alkyl PAHs ("34" PAHs) in pore water with desired detection limits as low as nanograms per liter. Solid-phase microextraction (SPME) with gas chromatographic/mass spectrometric (GC/ MS) analysis can achieve such detection limits in small water samples, which greatly reduces the quantity of sediment pore water that has to be collected, shipped, stored, and prepared for analysis. Four sediments that ranged from urban background levels (50 mg/kg total "34" PAHs) to highly contaminated (10 000 mg/kg total PAHs) were used to develop SPME methodology for the "34" PAH determinations with only 1.5 mL of pore water per analysis. Pore water was obtained by centrifuging the wet sediment, and alum flocculation was used to remove colloids. Quantitative calibration was simplified by adding 15 two- to six-ring perdeuterated PAHs as internal standards to the water calibration standards and the pore water samples. Response factors for SPME followed by GC/MS were measured for 22 alkyl PAHs compared to their parent PAHs and used to calibrate for the 18 groups of alkyl PAHs. Dissolved organic carbon (DOC) ranging from 4 to 27 mg/L had no measurable effect on the freely dissolved concentrations of two- and three-ring PAHs. In contrast, 5-80% of the total dissolved four- to six-ring PAHs were associated with the DOC rather than being freely dissolved, corresponding to DOC/water partitioning coefficients (K(DOC)) with log K(DOC) values ranging from 4.1 (for fluoranthene) to 5.6 (for benzo[ghi]perylene). However, DOC-associated versus freely dissolved PAHs had no significant effect on the total "34" PAH concentrations or the sum of the "toxic units" (calculated bythe EPA protocol), since virtually all (86-99%) of the dissolved PAH concentrations and toxic units were contributed by two- and three-ring PAHs.     

New technique for estimating thresholds of toxicity in ecological risk assessment

The use and utility of the no observed effect concentration (NOEC) in ecological risk assessment is a contentious issue. One concern is that the NOEC is not representative of a concentration at which no biologically significant effect is occurring. A new method has been developed to estimate the threshold of toxicity, or a true NOEC, for aquatic plants. The method involves determining the effective concentration (ECx) of a number of endpoints from one species. These ECx values are plotted on a log-probability scale. The x-intercept, or a low centile, of the distribution can be interpreted as the threshold of toxicity for that plant at that response level. This threshold is the concentration at which no effects should be observed for any endpoint above that response level. It is based on the assumptions that multiple effect measures from a single species will be log-normally distributed and thatthe distribution contains all possible endpoints for that species. The thresholds and the distributions can then be used as a substitute for the NOEC or ECx in risk assessment techniques, such as hazard quotients and probabilistic ecological risk assessment. This new method of estimating toxicitythresholds is more realistic than the use of arbitrary uncertainty factors, is more conservative than current probabilistic risk assessment methods, allows for simple comparison between species and exposure duration to a toxicant, and may be useful for assessing mixture toxicity. This technique was applied to field derived data with Lemna gibba, Myriophyllum spicatum, and M. sibiricumto assess potential risks from monochloroacetic acid (MCA). Using this new risk assessment method, we conclude that MCA does not appear to pose a risk to aquatic macrophytes under field conditions at current environmental concentrations.     

Proximity of field distribution of polycyclic aromatic hydrocarbons to chemical equilibria among air, water, soil, and sediment and its implications to the coherence criteria of environmental quality objectives

The proximity of PAHs distribution to the equilibrium states among air, soil, water, and bottom sediment was assessed for future risk management and coherence test among environmental quality objectives (EQOs) in these media. Concurrently measured concentration data in the four media were used. In the study areas (Seoul, Shihwa/Banwol, and Taegu), nonequilibrium states prevailed among air, soil, and water except for some light PAHs between air and water. Elevated concentration in soil particularly caused significant deviation from equilibrium between soil and other media. Coherence criteria among these media should be determined based on steady state (not equilibrium) conditions. Sediment was in or near equilibrium with soil for all PAHs, indicating that sediment quality is closely related to soil quality and that the coherence between the EQOs of the two media is required in the study areas. As the concentration ratio of individual PAHs for a given medium pair was found to vary up to 4 orders of magnitude across the study areas, a factor of 10 as a threshold criterion for incoherence is apparently too strict to apply to the national scale of Korea.     

Distribution and mass inventories of polycyclic aromatic hydrocarbons and organochlorine pesticides in sediments of the Pearl River Estuary and the northern South China Sea

Surface sediment (0-5 cm) samples were collected from the Pearl River Estuary (PRE) and the adjacent northern South China Sea (SCS) in July 2002 and analyzed for 25 polycyclic aromatic hydrocarbons (PAHs) and 8 organochlorine pesticides (OCPs) including dichlorodiphenyltrichloroethanes (DDTs), hexachlorocyclohexanes (HCHs), and heptachlor. The total PAHs and OCPs concentrations were 138-1100 and 0.18-3.57 ng/g dry weight, respectively. Compositional pattern analysis suggested that PAHs in the PRE were derived from both pyrogenic and petrogenic sources, whereas most PAHs in the northern SCS were pyrogenically originated. The concentrations of both PAHs and OCPs were higher in the PRE than in the northern SCS, and a decreasing trend with the distance from the estuary to the open sea was observed. In addition, perylene was a predominant component in all samples and clustered with PAH compounds with high log Kow values (from phenanthrene). These findings indicated that river outflows were the major source of contamination in the offshore sediments. A preliminary assessment suggested that atmospheric deposition contributed only a minor portion of PAHs or OCPs in the sediments of the northern SCS. The sediment (0-5 cm) mass inventories were 126 and 423 metric tons for PAHs and were 0.4 and 1.4 metric tons for OCPs in the PRE and the northern SCS, respectively. Clearly, contaminated sediments of the northern SCS may be a potential source of PAHs and OCPs to the global oceans.