Biota--sediment accumulation factors for polychlorinated biphenyls, dibenzo-p-dioxins, and dibenzofurans in southern Lake Michigan lake trout (Salvelinus namaycush)

A set of high-quality, age-specific biota-sediment accumulation factors (BSAFs) for polychlorinated biphenyls (PCBs), dibenzo-p-dioxins (PCDDs), and dibenzofurans (PCDFs) have been determined from concentrations measured with high-resolution gas chromatography/high-resolution mass spectrometry, by use of the 13C isotopic dilution technique, in lake trout and surficial (0-2 cm) sediment samples from southern Lake Michigan. BSAFs ranged from <0.1 to 18 for PCBs and from <0.001 to 0.32 for PCDDs and PCDFs detected in the fish. PCBs with zero or one chlorine in an ortho position had smaller BSAFs than other PCBs. PCDDs and PCDFs with chlorines at the 2,3,7,8-positions had larger BSAFs than most other PCDDs and PCDFs. The fidelity of the relative bioaccumulation potential data between independent lake trout samples, within and among age classes, suggests that differences in slight rates of net metabolism in the food chain are important and contribute to the apparent differences in BSAFs, not only for PCDDs and PCDFs but also possibly for some PCBs. A complicating factor for non-ortho- and mono-ortho-PCBs is the uncertain contribution of enhanced affinity for black carbon (and possibly volatility) acting in concert with metabolism to reduce measured BSAFs for lake trout. On the basis of the association between chemicals with apparent slight rates of metabolism and measured dioxin-like toxicity, several PCDFs with similar measured BSAFs but unknown toxicity may be candidates for toxicity testing.     

Biomimetic extraction of PAHs and PCBs from soil with octadecyl-modified silica disks to predict their availability to earthworms

We developed a model to predict the availability of PAHs and PCBs to earthworms (Lumbricus terrestris L.) in soils. We related the uptake of PAHs and PCBs by earthworms to the extraction with octadecyl-modified silica disks (C18 disks). Eleven soils (data set A) were used to develop the model, and 14 additional soils (data set B) were used to validate it independently. The biota-to-soil accumulation factors (BSAFs) of higher molecular weight PAHs (> or =202 g mol(-1)) and PCBs were higher than the corresponding Cl8 disk-soil partition coefficients (Kdisk) in the soils of data set A. This suggested that PAHs and PCBs were not only partitioned between soil and earthworms but also selectively ingested or metabolized. Nevertheless, we could predict the BSAFs of individual PAHs and PCBs for data set A by regression equations of log BSAF on log Kdisk (r=0.47-0.87). To predict the BSAFs of all PAHs and PCBs, respectively, we derived a model for each compound class that uses Kdisk and K(ow) values. Both the compound and the compound-class specific model were suitable to predict the BSAFs of PAHs and PCBs in data set B within a factor of 10-15.     

Evaluation of two methods for prediction of bioaccumulation factors

Two methods for deriving bioaccumulation factors (BAFs) used by the U.S. Environmental Protection Agency in development of water quality criteria were evaluated using polychlorinated biphenyl (PCB) data from the Hudson River and Green Bay ecosystems. One method predicts BAF(L)fd values (BAFs based upon concentrations of freely dissolved chemical in ambient water and in the lipid fraction of tissue) using field-measured biota-sediment accumulation factors (BSAFs): greater than 90% of the predicted BAF(L)fd values were within a factor of 5 of their measured values for both ecosystems. The second method predicts BAF(L)fd values as the chemical's 1-octanol/water partition coefficient (Kow) times a food chain multiplier: greater than 90% of the predicted BAF(L)fd values were within a factor of 5 of their measured values for the Green Bay ecosystem and for three of the six sampling locations on the Hudson River. Poorer predictive ability with the Kow method for the other three sampling locations was believed to be due to the existence of environmental conditions not representative of the longer term ecosystem conditions assumed for the method. BAF(L)fd and BAF(T)t values (BAFs based upon concentrations of total chemical in ambient water and in wet tissue) were compared. The within ecosystem and across ecosystems comparisons demonstrated a 2-5-fold decrease in variability (expressed as ratios of coefficients of variation, percentile ranges, and confidence ranges) for predicted BAF(L)fd values in comparison to BAF(T)t values.     

Including sorption to black carbon in modeling bioaccumulation of polycyclic aromatic hydrocarbons: uncertainty analysis and comparison to field data

Model estimations of bioaccumulation of polycyclic aromatic hydrocarbons (PAHs) have been higher than field or laboratory data. This has been explained by strong sorption to black carbon (BC). In this paper, eight previously published bioaccumulation datasets were reinterpreted in terms of additional BC sorption. Biota--Solids Accumulation Factors (BSAFs) of PAHs typically decreased by 1-2 orders of magnitude and were better in line with field data in marine, fresh water, and terrestrial ecosystems. Probabilistic BC-inclusive modeling showed that if BC content is not accurately known, uncertainty in BSAFs is 2-3 orders of magnitude (90 percentile confidence interval) due to uncertainty in the BC sorption term. When BC contents are measured, the deviation between model estimations and field measurements reduces to about a factor of 3. This implies that including routine measurements of BC contents is crucial in improving risk estimations of PAHs.     

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.     

Connecting the dots: responses of coastal ecosystems to changing nutrient concentrations

Empirical relationships between phytoplankton biomass and nutrient concentrations established across a wide range of different ecosystems constitute fundamental quantitative tools for predicting effects of nutrient management plans. Nutrient management plans based on such relationships, mostly established over trends of increasing rather than decreasing nutrient concentrations, assume full reversibility of coastal eutrophication. Monitoring data from 28 ecosystems located in four well-studied regions were analyzed to study the generality of chlorophyll a versus nutrient relationships and their applicability for ecosystem management. We demonstrate significant differences across regions as well as between specific coastal ecosystems within regions in the response of chlorophyll a to changing nitrogen concentrations. We also show that the chlorophyll a versus nitrogen relationships over time constitute convoluted trajectories rather than simple unique relationships. The ratio of chlorophyll a to total nitrogen almost doubled over the last 30-40 years across all regions. The uniformity of these trends, or shifting baselines, suggest they may result from large-scale changes, possibly associated with global climate change and increasing human stress on coastal ecosystems. Ecosystem management must, therefore, develop adaptation strategies to face shifting baselines and maintain ecosystem services at a sustainable level rather than striving to restore an ecosystem state of the past.     

Effects of aryl hydrocarbon receptor-mediated early life stage toxicity on lake trout populations in Lake Ontario during the 20th century

Lake trout embryos and sac fry are very sensitive to toxicity associated with maternal exposures to 2,3,7,8-tetrachlorodibenzo-p-dioxin (TCDD) and structurally related chemicals that act through a common aryl hydrocarbon receptor (AHR)-mediated mechanism of action. The loading of large amounts of these chemicals into Lake Ontario during the middle of the 20th century coincided with a population decline that culminated in extirpation of this species around 1960. Prediction of past TCDD toxicity equivalence concentrations in lake trout eggs (TEC(egg)s) relative to recent conditions required fine resolution of radionuclide-dated contaminant profiles in two sediment cores; reference core specific biota--sediment accumulation factors (BSAFs) for TCDD-like chemicals in lake trout eggs; adjustment of the BSAFs for the effect of temporal changes in the chemical distributions between water and sediments; and toxicity equivalence factors based on trout early life stage mortality. When compared to the dose-response relationship for overt early life stage toxicity of TCDD to lake trout, the resulting TEC(egg)s predict an extended period during which lake trout sac fry survival was negligible. By 1940, following more than a decade of population decline attributable to reduced fry stocking and loss of adult lake trout to commercial fishing, the predicted sac fry mortality due to AHR-mediated toxicity alone explains the subsequent loss of the species. Reduced fry survival, associated with lethal and sublethal adverse effects and possibly complicated by other environmental factors, occurred after 1980 and contributed to a lack of reproductive success of stocked trout despite gradually declining TEC(egg)s. Present exposures are close to the most probable no observable adverse effect level (NOAEL TECegg = 5 pg TCDD toxicity equivalence/g egg). The toxicity predictions are very consistent with the available historical data for lake trout population levels in Lake Ontario, stocking programs, and evidence for recent improvement in natural reproduction concomitant with declining levels of persistent bioaccumulative chemicals in sediments and biota.     

Predictive environmental risk assessment of chemical mixtures: a conceptual framework

Environmental risks of chemicals are still often assessed substance-by-substance, neglecting mixture effects. This may result in risk underestimations, as the typical exposure is toward multicomponent chemical "cocktails". We use the two well established mixture toxicity concepts (Concentration Addition (CA) and Independent Action (IA)) for providing a tiered outline for environmental hazard and risk assessments of mixtures, focusing on general industrial chemicals and assuming that the "base set" of data (EC50s for algae, crustaceans, fish) is available. As mixture toxicities higher than predicted by CA are rare findings, we suggest applying CA as a precautious first tier, irrespective of the modes/mechanisms of action of the mixture components. In particular, we prove that summing up PEC/PNEC ratios might serve as a justifiable CA-approximation, in order to estimate in a first tier assessment whether there is a potential risk for an exposed ecosystem if only base-set data are available. This makes optimum use of existing single substance assessments as more demanding mixture investigations are requested only if there are first indications of an environmental risk. Finally we suggest to call for mode-of-action driven analyses only if error estimations indicate the possibility for substantial differences between CA- and IA-based assessments.     

Effects of historic PCB exposures on the reproductive success of the Hudson River striped bass population

Scientists and regulatory agencies have expressed concern that exposures to polychlorinated biphenyls (PCBs) might be contributing to reductions in the abundance of fish populations exposed to these chemicals. The specific effects of concern involve impairment of fish reproduction, including both reduced egg production and decreased viability of eggs and larvae. We tested hypotheses concerning the effects of PCBs on fish populations using long-term data sets available for the striped bass population of the Hudson River, NY, a population that has long been a subject of regulatory concern because of potential effects of PCB exposures. The data sets examined include both measurements of PCB concentrations in adult female striped bass over the period from 1976 through 1997 and estimates of the numbers of striped bass eggs, larvae, and juveniles produced annually during this same period. We found strong correlations between estimates of the abundance of spawners and the number of eggs and larvae produced by those spawners and also between independent estimates of year-class strength derived from different sampling programs. However, we found no relationships between PCB exposure and any measure of striped bass abundance or reproduction. Although inconsistent with the expected effects of PCB exposures, trends in all measures of striped bass abundance and reproductive success were consistent with the expected effects of striped bass harvest restrictions that were imposed during the 1980s. Our results demonstrate a need for caution in inferring risks to populations in nature from effects observed in laboratory studies.     

Mercury in southeastern U.S. riverine fish populations linked to water body type

We compared Hg concentrations in fishes from the regulated Black Warrior River and the unregulated Sipsey River in west Alabama whose neighboring watersheds receive equivalent atmospheric Hg deposition. Average fish fillet Hg concentrations were 3-fold higher in the unregulated river compared to the regulated river. Between river differences in Hg fish concentrations likely originate from structural (e.g., species composition) and functional (e.g., energy flow pathways) differences between the two ecosystems. We tested the generality of these findings by comparing largemouth bass Hg concentrations among unregulated rivers (n=6) and reservoirs (n=11) throughout the southern Coastal Plain geologic region. ANCOVA revealed that at a given bass length, Hg concentrations were approximately 1.75 times higher in unregulated rivers compared to regulated rivers. Aerial deposition of Hg was not correlated to largemouth bass Hg concentrations. We suggest that the link between atmospheric Hg deposition and fish Hg concentrations is significantly modulated by the structure and function of aquatic ecosystems and this accounts for much of the variation in fish Hg concentrations among systems. Unregulated floodplain-rivers in the south have some of the highest fish Hg concentrations on record and should be intensely monitored to establish human consumption risks.     

A terrestrial food-chain bioaccumulation model for POPs

Mechanistic bioaccumulation models for fish and piscivorous food-webs are widely used to assess the environmental hazard and risk of commercial chemicals, develop water quality criteria and remediation objectives, and conduct exposure assessment of pesticides in aquatic systems. Similar models for mammals and terrestrial food-webs are largely absent. As a result, the hazards and risks of bioaccumulative substances in mammals, birds, and humans remain unrecognized by regulators, and current globally used criteria for identifying bioaccumulative substances only apply to water-breathing organisms and are inadequate for protecting air-breathing organisms including mammals, birds, and human beings. In this paper, we develop and test a modeling framework that can be used to estimate the biomagnification potential and the organism-soil bioaccumulation factor of organic commercial chemicals in terrestrial food-chains. We test the model for the soil-earthworm-shrew food-chain and apply the model to illustrate that (i) chemicals with an octanol-air partition coefficient (K(OA)) < 10(5.25) do not biomagnify even if the K(ow) is high and optimal for biomagnification in fish; (ii) chemicals with a K(OA) > or = 105.25 and a K(ow) between 10(1.75) and 10(12) have a biomagnification potential unless they are metabolized at a sufficiently rapid rate (e.g., in excess of 0.3 d(-1) or a half-life time of 2.5 d for shrews).     

Variation in peak growing season net ecosystem production across the canadian arctic

Tundra ecosystems store vast amounts of soil organic carbon, which may be sensitive to climatic change. Net ecosystem production, NEP, is the net exchange of carbon dioxide (CO(2)) between landscapes and the atmosphere, and represents the balance between CO(2) uptake by photosynthesis and release by decomposition and autotrophic respiration. Here we examine CO(2) exchange across seven sites in the Canadian low and high Arctic during the peak growing season (July) in summer 2008. All sites were net sinks for atmospheric CO(2) (NEP ranged from 5 to 67 g C m(-2)), with low Arctic sites being substantially larger CO(2) sinks. The spatial difference in NEP between low and high Arctic sites was determined more by CO(2) uptake via gross ecosystem production than by CO(2) release via ecosystem respiration. Maximum gross ecosystem production at the low Arctic sites (average 8.6 μmol m(-2) s(-1)) was about 4 times larger than for high Arctic sites (average 2.4 μmol m(-2) s(-1)). NEP decreased with increasing temperature at all low Arctic sites, driven largely by the ecosystem respiration response. No consistent temperature response was found for the high Arctic sites. The results of this study clearly indicate there are large differences in tundra CO(2) exchange between high and low Arctic environments and this difference should be a central consideration in studies of Arctic carbon balance and climate change.     

Partition of environmental chemicals between maternal and fetal blood and tissues

Passage of environmental chemicals across the placenta has important toxicological consequences, as well as for choosing samples for analysis and for interpreting the results. To obtain systematic data, we collected in 2000 maternal and cord blood, cord tissue, placenta, and milk in connection with births in the Faroe Islands, where exposures to marine contaminants is increased. In 15 sample sets, we measured a total of 87 environmental chemicals, almost all of which were detected both in maternal and fetal tissues. The maternal serum lipid-based concentrations of organohalogen compounds averaged 1.7 times those of cord serum, 2.8 times those of cord tissue and placenta, and 0.7 those of milk. For organohalogen compounds detectable in all matrices, a high degree of correlation between concentrations in maternal serum and the other tissues investigated was generally observed (r(2) > 0.5). Greater degree of chlorination resulted in lower transfer from maternal serum into milk. Concentrations of pentachlorbenzene, γ-hexachlorocyclohexane, and several polychlorinated biphenyl congeners with low chlorination were higher in fetal samples and showed poor correlation with maternal levels. Perfluorinated compounds occurred in lower concentrations in cord serum than in maternal serum. Cadmium, lead, mercury, and selenium were all detected in fetal samples, but only mercury showed close correlations among concentrations in different matrices. Although the environmental chemicals examined pass through the placenta and are excreted into milk, partitions between maternal and fetal samples are not uniform.     

Use of transplanted Zebra mussels (Dreissena polymorpha) to assess the bioavailability of microcontaminants in Flemish surface waters

Zebra mussels (Dreissena polymorpha) were translocated in cages to 56 water bodies in Flanders (Belgium) during summer 2001. After six weeks, concentrations of polychlorinated biphenyls (PCBs), hexachlorobenzene (HCB), p,p'-DDE, and trace metals were measured in the transplanted mussels. It was investigated whether total dissolved water and sediment pollutant levels or bioaccumulation factors (BAFs) and biota-sediment accumulation factors (BSAFs) were predictive for mussel tissue levels. The sample sites covered a broad range both in terms of the type and concentration of the pollutants, and this was reflected in large differences in tissue concentrations of all pollutants among the sites. The highest pollutant levels in mussels were among the highest reported in the literature. For Cd and Zn levels up to 33 and 1994 microg/g dry wt. respectively were found. The lowest levels were comparable to those from uncontaminated sites in Europe and the U.S. For Cd and Zn respectively 51 and 75% of the variation in tissue levels was described. For both metals, dissolved and particulate metal contributed to the variation in accumulation. For other pollutants, relationships between tissue concentration and water or sediment concentration were weak or nonsignificant. Then the measured environmental factors (dissolved calcium, pH, oxygen, organic carbon and clay content in the sediment) were taken into account applying multiple regression analysis, and no increase in the described variation of pollutant accumulation was observed. The BAF and BSAF for all pollutants varied up to 1000-fold even after TOC-normalization. Clear negative relationships were found between BAFs/ BSAFs and environmental levels. However, even at constant environmental concentrations a 10- to 100-fold variation in BAFs/BSAFs was observed. This study illustrated the need for biological monitoring since neither environmental     

海绵及其共生微生物的生态多样性与重要性

海绵是底栖生物群落中的重要成员,广泛分布于温带、热带及极地地区,其丰度、多样性及分布规律在不同地区有明显差异。海绵可能影响其它底栖生物及生态系统特征,因而在海洋生态系统中有多种功能作用。海绵不仅在海洋生态系统中起重要作用,而且能提供大量新颖的生物活性产物。大量研究显示多种微生物能寄生在海绵体内,在微生物与其寄主海绵之间可能存在互惠共生关系。文中对海绵的重要生态作用、生物多样性、与微生物的共生关系和作为新天然产物的资源进行了讨论。     

Accumulation and depuration of polychlorinated biphenyls from field-collected sediment in three freshwater organisms

As laboratory-based bioaccumulation methods are standardized and expanded to include other test species, kinetic studies assessing the major classes of contaminants with these species are needed to adequately select the standard duration for bioaccumulation tests. In the present study we measured the uptake (28-d exposure) of polychlorinated biphenyls (PCBs; total and selected congeners) from field-contaminated sediment in the oligochaete Lumbriculus variegatus, mayfly nymph Hexagenia spp., and fathead minnow Pimephales promelas. Depuration (25 d) of PCBs was measured in organisms that had been transferred to clean sediment after the 28-d exposure. Uptake and elimination of PCBs was rapid in L. variegatus and Hexagenia spp. Tissue residues reached steady-state concentrations within 28 d; elimination rates and biota-sediment accumulation factors (BSAFs) of the PCB congeners were not correlated with K(OW). Uptake and elimination rates of PCBs were slower in P. promelas, and it is not clear whether steady-state was reached in fish tissues. Elimination rates of the PCB congeners significantly decreased with increasing K(OW) in fish. The appropriateness of a 28-d exposure for measuring steady-state concentrations in tissue of the invertebrates was confirmed, but further study is required for fish.     

Screening for PBT chemicals among the "existing" and "new" chemicals of the EU

Under the European chemicals legislation, REACH, industrial chemicals that are imported or manufactured at more than 10 t/yr need to be evaluated with respect to their persistence (P), bioaccumulation potential (B), and toxicity (T). This assessment has to be conducted for several 10,000 of chemicals but, at the same time, empirical data on degradability, bioaccumulation potential and toxicity of industrial chemicals are still scarce. Therefore, the identification of PBT chemicals among all chemicals on the market remains a challenge. We present a PBT screening of approximately 95,000 chemicals based on a comparison of estimated P, B, and T properties of each chemical with the P, B, and T thresholds defined under REACH. We also apply this screening procedure to a set of 2576 high production volume chemicals and a set of 2781 chemicals from the EU's former list of "new chemicals" (ELINCS). In the set of 95,000 chemicals, the fraction of potential PBT chemicals is around 3%, but in the ELINCS chemicals it reaches 5%. We identify the most common structural elements among the potential PBT chemicals. Analysis of the P, B, and T data for all chemicals considered here shows that the uncertainty in persistence data contributes most to the uncertainty in the number of potential PBT chemicals.     

Development of an ecosystem sensitivity model regarding mercury levels in fish using a preference modeling methodology: application to the Canadian boreal system

The objective of this study is to use a preference modeling methodology as a predictive tool to roughly assess the sensitivity of the ecosystems regarding mercury (Hg) concentrations in fish. We apply a preference modeling methodology to rank lakes within the boreal forest from highest to lowest Hg concentrations in fish using simple environmental factors. Among the numerous variables influencing Hg fate in the environment, we only retain simple key indicators that are expected to influence Hg concentrations in fish tissue such as watershed characteristics of the lake (percentage of the catchment area of the lake, ratio of drainage area versus lake area, percentage of the drainage area of the lake as wetlands, land use, and clear-cutting), lake characteristics (chlorophyll, dissolved organic carbon, pH, and fishing intensity), and atmospheric Hg inputs. Preliminary results of modeling that we carried out using a set of Canadian lakes of boreal forest data are promising. With only a minimum set of criteria, we are able to reproduce the trends of Hg contamination in fish caught in six regions of the Canadian boreal forest and classify the sensitivity of the ecosystems to Hg loadings in three categories: high, medium, and low.