Occurrence and biomagnification of organohalogen pollutants in two terrestrial predatory food chains

Organohalogen pollutants (OHPs), including dichlorodiphenyl trichloroethane and its metabolites (DDTs), polychlorinated biphenyls (PCBs), polybrominated diphenyl ethers (PBDEs), hexabromocyclododecanes (HBCDs), and dechlorane plus (DP), were determined in three raptor species, namely, the common kestrel (Falco tinnunculus), eagle owl (Bubo bubo), and little owl (Athene noctua), as well as in their primary prey items: Eurasian tree sparrow (Passer montanus) and brown rat (Rattus norvegicus). DDTs were the predominant pollutants in avian species followed by PBDEs and PCBs, then minimally contribution of HBCDs and DP. Inter-species differences in the PBDE congener profiles were observed between the owls and the common kestrels, with relatively high contributions of lower brominated congeners in the owls but highly brominated congeners in the kestrels. This result may partly be attributed to a possible greater in vivo biotransformation of highly brominated BDE congeners in owls than in kestrels. α-HBCD was the predominant diastereoisomer with a preferential enrichment of (−)-enantiomer in all the samples. No stereoselective bioaccumulation was found for DP isomers in the investigated species. Biomagnification factor (BMF) values were generally higher in the rat−owl food chain than in the sparrow−kestrel food chain. Despite this food chain-specific biomagnification, the relationships between the log BMF and log K_OW of PCBs and PBDEs followed a similar function in the two food chains, except for BDE-47, -99, and -100 in the sparrow−kestrel feeding relationship.     

Floodplain methylmercury biomagnification factor higher than that of the contiguous river (South River, Virginia USA)

Mercury biomagnification on the South River floodplain (Virginia, USA) was modeled at two locations along a river reach previously modeled for methylmercury movement through the aquatic trophic web. This provided an opportunity to compare biomagnification in adjoining trophic webs. Like the aquatic modeling results, methylmercury-based models provided better prediction than those for total mercury. Total mercury Food Web Magnification Factors (FWMF, fold per trophic level) for the two locations were 4.9 and 9.5. Methylmercury FWMF for the floodplain locations were higher (9.3 and 25.1) than that of the adjacent river (4.6). Previous speculation was not resolved regarding whether the high mercury concentrations observed in floodplain birds was materially influenced by river prey consumption by riparian spiders and subsequent spider movement into the trophic web of the adjacent floodplains. Results were consistent with a gradual methylmercury concentration increase from contaminated floodplain soil, to arthropod prey, and finally, to avian predators.     

Occurrence and seasonal variation of alkylphenols in marine organisms from the coast of Taiwan

The occurrence and distribution of alkylphenols (APs, i.e., 4-tert-octylphenol (4-t-OP) and 4-nonlyphenol isomers (4-NP)) in oysters (Crassostrea gigas), snails (Thais clavigera), coastal water and coastal sediments of the western coast of southern Taiwan are investigated. Alkylphenols were present in all matrices of interest: in water, ranging from 61 to 370 ng/l, in sediments, ranging from 27 to 190 ng/g, and in biota samples (i.e., oyster and snail), ranging from 20 to 5190 ng/g. Statistical analysis indicated that the probability distribution of most determined concentrations in oyster and snail samples was log-normal distribution. The bioaccumulation of APs resulted in a seasonal variation with respect to their compositions and concentrations in oyster and snail samples. For oysters, concentrations of APs in winter exceeded those in summer. In contrast, those in snails in summer exceeded those in winter. Estimated biomagnification factors of APs from snails to oysters ranged from 1.4 to 4.3 in summer, and 0.5 to 0.8 in winter on the dry weight basis. The results suggested that seasonally mediated physiological changes, such as dilution caused by growth, biotransformation and metabolism, may affect the bioaccumulation of APs in according to season and organism.     

Heterogeneous uptake of octamethylcyclotetrasiloxane (D4) and decamethylcyclopentasiloxane (D5) onto mineral dust aerosol under variable RH conditions

We have carried out kinetic studies to characterize the heterogeneous decay of octamethylcyclotetrasiloxane (D₄) and decamethylcyclopentasiloxane (D₅) in the presence of representative mineral dust aerosol in order to obtain a better understanding of the atmospheric fate of these siloxanes. The heterogeneous chemistry of D₄ and D₅ with various mineral dusts was studied in an environmental aerosol reaction chamber using FTIR absorption spectroscopy to monitor the reaction. The apparent heterogeneous uptake coefficient, γ_app, for D₄ and D₅ with various mineral dusts was measured under dry conditions and as a function of relative humidity (RH). In addition, the effect of initial D₄ and D₅ concentration on the rate and yield of the reaction was examined. The uptake coefficient, γ_app, for D₄ and D₅ was similar for the most reactive aerosols tested, with kaolinite ≈hematite > silica. Limited uptake onto carbon black and calcite surfaces was observed for either siloxane. Reaction with hematite and kaolinite resulted in multilayer coverages, suggesting extensive polymerization of D₄ and D₅ on the aerosol surface.     

Fathead minnow (Pimephales promelas) embryo to adult exposure to decamethylcyclopentasiloxane (D5)

The cyclic siloxane decamethylcyclopentasiloxane (D5) is a high production volume chemical which has recently been assessed under the Canadian Chemicals Management Plan (CMP). Cyclic volatile methyl siloxanes (cVMS) are one of the challenge substances in the CMP batches. To provide toxicity and growth information on a species of relevance to the Canadian environment, we assessed D5 in a fathead minnow (Pimephales promelas) embryo to young adult assay. The test was 65 d in length, and exposed fathead minnow eggs to juveniles until near maturity (60 d post-hatch). The D5 concentrations in flow-through fish exposure aquaria were about one-third of nominal D5 concentrations. Fathead minnows were exposed to 0.25, 0.82, 1.7, 3.6, and 8.7 μg L⁻¹ D5. During the exposure of fathead minnows to D5 there were few effects seen. Egg hatching and larval fish survival and growth were normal. Juvenile fish survival and growth were good in all environmentally-relevant concentrations of D5, and were similar to control fish. The two highest D5 concentrations (8.7 μg L⁻¹ and 3.6 μg L⁻¹, mean measured D5) increased the condition factors of fathead minnows compared to water control and DMSO control fish. Although there were few effects of D5 in our fathead minnow study, the compound was taken up and stored in fish bodies over the 65-d exposure. The bioconcentration factor for D5 in fathead minnows was 4450, for the lowest environmentally-relevant D5 exposure water concentrations, and 4920 for all D5 exposure concentrations tested.     

Effects of mercury on behavior and performance of northern two-lined salamanders (Eurycea bislineata)

Mercury (Hg) causes a range of deleterious effects in wildlife, but little is known about its effects on amphibians. Our objective was to determine whether Hg affects performance and behavior in two-lined salamanders (Eurycea bislineata). We collected salamanders from Hg-contaminated and reference sites and assessed speed, responsiveness, and prey capture ability. Mercury concentrations were >17× higher in salamanders from the contaminated sites and were among the highest documented in amphibians. In the first, but not in the second, locomotion trial, we found a significant effect of Hg on speed and responsiveness. In the prey capture experiment, reference salamanders ate approximately twice as many prey items as the contaminated salamanders. Together, our results suggest that sublethal Hg concentrations may negatively affect salamanders by reducing their ability to successfully execute tasks critical to survival. Future work is warranted to determine whether Hg has other sublethal effects on salamanders and whether other amphibians are similarly affected.     

Heavy metal distribution and bioaccumulation in Chihuahuan Desert Rough Harvester ant (Pogonomyrmex rugosus) populations

Heavy metal contamination can negatively impact arid ecosystems; however a thorough examination of bioaccumulation patterns has not been completed. We analyzed the distribution of As, Cd, Cu, Pb and Zn in soils, seeds and ant (Pogonomyrmex rugosus) populations of the Chihuahuan Desert near El Paso, TX, USA. Concentrations of As, Cd, Cu, and Pb in soils, seeds and ants declined as a function of distance from a now inactive Cu and Pb smelter and all five metals bioaccumulated in the granivorous ants. The average bioaccumulation factors for the metals from seeds to ants ranged from 1.04× (As) to 8.12× (Cd). The findings show bioaccumulation trends in linked trophic levels in an arid ecosystem and further investigation should focus on the impacts of heavy metal contamination at the community level.     

Dissolved oxygen and dietary phosphorus modulate utilization and effluent partitioning of phosphorus in rainbow trout (Oncorhynchus mykiss) aquaculture

Phosphorus (P) is the limiting nutrient in freshwater primary production, and excessive levels cause premature eutrophication. P levels in aquaculture effluents are now tightly regulated. Increasing our understanding of waste P partitioning into soluble, particulate, and settleable fractions is important in the management of effluent P. When water supply is limited, dissolved oxygen concentration (DO) decreases below the optimum levels. Therefore, we studied effects of DO (6 and 10mg/L) and dietary P (0.7 and 1.0% P) on rainbow trout growth, P utilization, and effluent P partitioning. Biomass increased by 40% after 3 weeks. DO at 10mg/L significantly increased fish growth and feed efficiency, and increased the amount of P in the soluble fraction of the effluent. Soluble effluent P was greater in fish fed 1.0% P. DO increases fish growth and modulates P partitioning in aquaculture effluent.     

Relationship between heavy metals pollution and genetic diversity in Mediterranean populations of the sandhopper Talitrus saltator (Montagu) (Crustacea, Amphipoda)

Trace metals are one of the groups of pollutants that reduce genetic variability in natural populations, causing the phenomenon known as “genetic erosion”. In this study we evaluate the relationship between trace metals contamination (Hg, Cd and Cu) and genetic variability, assessed using fluorescent Inter-Simple Sequence Repeats (fISSRs). We used eight populations of a well-established biomonitor of trace metals on sandy beaches: the amphipod Talitrus saltator. The trace metals analysis confirmed the ability of sandhoppers to accumulate Hg, Cd and Cu. Moreover, populations from sites with high Hg availability had the lowest values of genetic diversity. Our results validate the use of fISSR markers in genetic studies in sandhoppers and support the “genetic erosion” hypothesis by showing the negative influence of Hg contamination on sandhopper genetic diversity. Therefore, genetic variability assessed with fISSR markers could be successfully employed as a biomarker of Hg exposure.     

Factors affecting the concentration in seven-spotted ladybirds (Coccinella septempunctata L.) of Cd and Zn transferred through the food chain

The transfer of Cd and Zn from soils amended with sewage sludge was followed through a food chain consisting of wheat, aphids and the predator Coccinella septempunctata. Multiple regression models were generated to predict the concentrations of Cd and Zn in C. septempunctata. No significant model could be generated for Cd, indicting that the concentration of this metal was maintained within relatively narrow limits. A model predicting 64% of the variability in the Zn concentration of C. septempunctata was generated from of the concentration of Zn in the diet, time and rate of Zn consumption. The results suggest that decreasing the rate of food consumption is an effective mechanism to prevent the accumulation of Zn and that the availability of Zn in the aphid prey increased with the concentration in the aphids. The results emphasise the importance of using ecologically relevant food chains and exposure pathways during ecotoxicological studies.     

Dietary exposure of rainbow trout to 8:2 and 10:2 fluorotelomer alcohols and perfluorooctanesulfonamide: Uptake, transformation and elimination

The bioaccumulation of perfluorooctanesulfonamide (PFOSA) and two fluorotelomer alcohols (8:2 FTOH, 10:2 FTOH) by rainbow trout (Oncorhynchus mykiss) through dietary exposure, including depuration rates and metabolism was investigated. Concentrations in the spiked feed ranged from 10.9 μg g⁻¹ wet weight (wet wt) for PFOSA and 6.7 μg g⁻¹ wet wt for 8:2 FTOH to 5.0 μg g⁻¹ wet wt for 10:2 FTOH. Trout was fed at 1.5% body weight per day for 30 d and depuration was followed for up to 30 d following previously published dietary exposure protocols. Perfluorooctanesulfonate (PFOS) was the major perfluoroalkylsulfonate (PFSA) detected in fish following dietary exposure to PFOSA. Half-lives of PFOS and PFOSA were 16.9 ± 2.5 and 6.0 ± 0.4 d, respectively. A biomagnification factor (BMF) of 0.023 was calculated for PFOSA which indicates that dietary exposure to PFOSA does not result in biomagnification in the rainbow trout. PFOS had a BMF of 0.08. The fluorotelomer saturated acids (8:2 FTCA, 10:2 FTCA) and fluorotelomer unsaturated acids (8:2 FTUCA, 10:2 FTUCA) were the major products detected in rainbow trout following dietary exposure to 8:2 FTOH and 10:2 FTOH, respectively. Half-lives were 3.7 ± 0.4, 2.1 ± 0.5, 3.3, and 1.3 d for 10:2 FTCA, 10:2 FTUCA, 8:2 FTCA, and 8:2 FTUCA, respectively. Small amounts of perfluorooctanoate (PFOA) and perfluorodecanoate (PFDA) were also detected in the FTOH exposed fish.     

Effects of amendments on the uptake and distribution of DDT in Cucurbita pepo ssp pepo plants

The effects of soil amendments on the phytoextraction of ∑DDT (DDT + DDD + DDE) from soil ([∑DDT] ∼ 1500 ng/g) by a pumpkin variety of Cucurbita pepo ssp pepo were tested and the patterns of ∑DDT storage throughout the plant shoot were examined. The soil amendments did not increase the total amount of ∑DDT extracted into plant shoots, but new information about ∑DDT distribution in the plants was obtained. As observed previously, the ∑DDT concentration in plant leaves (mean 290 ng/g) was significantly lower than in plant stems (mean 2600 ng/g). Further analysis revealed that ∑DDT composition was consistent throughout the plant shoot and that ∑DDT concentration in leaves and stems decreased exponentially as distance from the root increased, which was previously unknown. This new information about the patterns of ∑DDT uptake and translocation within pumpkin plants highlights the need for appropriate plant sampling strategies in future POPs phytoextraction research.     

Antimony toxicity in the lichen Xanthoria parietina (L.) Th. Fr.

In this paper we tested if treating the lichen Xanthoria parietina with Sb-containing solutions causes Sb bioaccumulation as well as physiological and ultrastructural changes. Total and intracellular antimony content in Sb-treated samples increased progressively with increasing concentration in the treatment solutions. Incubation of X. parietina thalli with Sb at concentrations as low as 0.1 mM caused a decrease in sample viability, measured as intensity of respiratory activity, and damage to cell membranes, expressed in terms of membrane lipid peroxidation, as well as ultrastructural changes such as plasmolysis, impairment of the thylakoid system of the alga and cytoplasmic lipid droplets. The photosynthetic system hardly responded, at least under the tested experimental conditions.     

Bioaccumulation and depuration of metals in blue crabs (Callinectes sapidus Rathbun) from a contaminated and clean estuary

Blue crabs from a contaminated estuary (Hackensack Meadowlands-HM) and a cleaner reference site (Tuckerton-TK) were analyzed for Cr, Cu, Hg, Pb, and Zn in muscle and hepatopancreas. Crabs from each site were taken into the laboratory and fed food from the other site, or in another experiment, transplanted to the other site for eight weeks. All crabs were analyzed for metals. Overall, tissue concentrations reflected environmental conditions. Tissue differences were found for Cu, Pb and Zn (all higher in hepatopancreas), and Hg (higher in muscle). HM muscle had more Hg than TK muscle, but did not decrease after transplanting or consuming clean food. HM crabs lost Cu, Pb and Zn in hepatopancreas after being fed clean food or transplanted. TK crabs increased Hg in muscle and Cr and Zn in hepatopancreas after transplantation or being fed contaminated (HM) food. Concentrations were variable, suggesting that blue crabs may not be fully reliable bioindicators of polluted systems.     

Dietary exposure of juvenile common sole (Solea solea L.) to polybrominated diphenyl ethers (PBDEs): Part 2. Formation, bioaccumulation and elimination of hydroxylated metabolites

The uptake, elimination and transformation of six PBDE congeners (BDE-28, -47, -99, -100, -153, -209) were studied in juvenile common sole (Solea solea L.) exposed to spiked contaminated food over a three-month period, and then depurated over a five-month period. Methoxylated (MeO-) and hydroxylated (OH-) PBDEs were determined in fish plasma exposed to PBDEs and compared to those obtained in control fish. While all MeO- and some OH- congeners identified in fish plasma were found to originate from non-metabolic sources, several OH- congeners, i.e., OH-tetraBDEs and OH-pentaBDEs, were found to originate from fish metabolism. Among these, 4′-OH-BDE-49 was identified as a BDE-47 metabolite. Congener 4′-OH-BDE-101, identified here for the first time, may be the result of BDE-99 metabolic transformation. Our results unequivocally showed that PBDEs are metabolised in juvenile sole via the formation of OH- metabolites. However, this was not a major biotransformation route compared to biotransformation through debromination.     

Bioconcentration of nonylphenol in fathead minnows (Pimephales promelas)

Bioconcentration of p-nonylphenol (NP) by fathead minnows was determined under laboratory conditions. Fish were exposed continuously for 42 days to 0.33, 0.93 and 2.36 μgNP/l in a flow-through system. NP was Soxhlet extracted from whole fish homogenates with dichloromethane (DCM). The resulting extract was concentrated and bulk lipids removed by gel permeation and silica-gel chromatography. Compounds were identified and quantified by reverse-phase high-pressure liquid chromatography (RP-HPLC) with fluorescence detection. Mass spectrometry was used for verification of peak assignments. Bioconcentration factors (BCFs) ranged from 245 to 380.     

Selective accumulation of chlorinated paraffins (C12 and C16) in the olfactory organ of rainbow trout

Three ¹⁴C-labelled polychloroalkanes (C₁₂ and C₁₆), representing low (23% Cl by weight), medium (51%), and highly (68%) chlorinated paraffin (CP) mixtures, were presented to rainbow trout via the water. The uptake in fat-rich tissues was positively correlated to the degree of chlorination of the preparations. Notably, all preparations gave rise to a high and selective uptake of radioactivity in the olfactory organ and gills. This selective radiolabelling may reflect a general ability of these organs to enrich xenobiotics from the surrounding water. The olfactory organ may be a hitherto unforseen target for toxic environmental pollutants in fish.     

Bioaccumulation in Porcellio scaber (Crustacea, Isopoda) as a measure of the EDTA remediation efficiency of metal-polluted soil

Leaching using EDTA applied to a Pb, Zn and Cd polluted soil significantly reduced soil metal concentrations and the pool of metals in labile soil fractions. Metal mobility (Toxicity Characteristic Leaching Procedure), phytoavailability (diethylenetriaminepentaacetic acid extraction) and human oral-bioavailability (Physiologically Based Extraction Test) were reduced by 85-92%, 68-91% and 88-95%, respectively. The metal accumulation capacity of the terrestrial isopod Porcellio scaber (Crustacea) was used as in vivo assay of metal bioavailability, before and after soil remediation. After feeding on metal contaminated soil for two weeks, P. scaber accumulated Pb, Zn and Cd in a concentration dependent manner. The amounts of accumulated metals were, however, higher than expected on the basis of extraction (in vitro) tests. The combined results of chemical extractions and the in vivo test with P. scaber provide a more relevant picture of the availability stripping of metals after soil remediation.     

Identification of phase II in vivo metabolites of alkyl-anthracenes in rainbow trout (Oncorhynchus mykiss)

Metabolism of xenobiotics is a two-step process that increases the polarity of compounds to facilitate their excretion. In previous work, the major in vitro phase I metabolites of alkyl-anthracenes by rainbow trout (Oncorhynchus mykiss) CYP enzymes were shown to be predominantly ring hydroxylated metabolites. Here, we present the first report on the identification of in vivo phase II metabolites of alkyl-anthracenes in juvenile rainbow trout. Bile was collected from trout injected with individual alkyl-anthracenes with, in some cases, a co-injection of β-naphthoflavone (BNF). Some samples were digested with the β-glucuronidase enzyme to confirm the presence of glucuronide conjugates. The metabolites were separated using a water-acetonitrile gradient on a HPLC system equipped with a C₁₈ column and a UV-diode array detector. Trout with endogenous and BNF-induced enzymes produced the same metabolites, but higher concentrations of metabolites were detected after enzyme induction. Alkyl-anthracenes were metabolized predominantly on the rings as evidenced by the UV spectral analysis. Likewise, mass spectrometry and UV spectral analysis confirmed a predominance of glucuronide conjugates for all systems investigated.     

Compartmentation of metals in foliage of Populus tremula grown on soils with mixed contamination. I. From the tree crown to leaf cell level

In order to achieve efficient phytoextraction of heavy metals using trees, the metal allocation to aboveground tissues needs to be characterised. In his study, the distribution of heavy metals, macro- and micronutrients and the metal micro-localisation as a function of the leaf position and heavy metal treatment were analysed in poplars grown on soil with mixed metal contamination. Zinc was the most abundant contaminant in both soil and foliage and, together with cadmium, was preferentially accumulated in older foliage whereas excess copper and lead were not translocated. Changes in other element concentrations indicated an acceleration in aging as a consequence of the metal treatment. Excess zinc was irregularly accumulated inside leaf tissues, tended to saturate the veins and was more frequently stored in cell symplast than apoplast. Storage compartments including metabolically safe and sensitive subcellular sites resulted in sizable metal accumulation as well as stress reactions.