Effect of new soil metal immobilizing agents on metal toxicity to terrestrial invertebrates

Application of 5% (w:w) novel metal immobilizing agent reduced the water soluble, the calcium chloride extracted as well as the pore water concentration of zinc in soils from Maatheide, a metal contaminated site in the northeast of Belgium. Addition of the metal immobilizing agents also eliminated acute toxicity to the potworm Enchytraeus albidus and the earthworm Eisenia fetida and chronic toxicity to the springtail Folsomia candida. Cocoon production by E. fetida, however, was still adversely affected. These differences may be explained by the species dependent routes of metal uptake: F. candida is probably mainly exposed via pore water while in E. fetida dietary exposure is probably also important. From these results it is clear that organisms with different exposure routes should be used simultaneously to assess the environmental risk of metal contaminated soils.     

How contamination sources and soil properties can influence the Cd and Pb bioavailability to snails

To better understand the fate of metals in the environment, numerous parameters must be studied, such as the soil properties and the different sources of contamination for the organisms. Among bioindicators of soil quality, the garden snail (Cantareus aspersus) integrates multiple sources (e.g. soil, plant) and routes (e.g. digestive, cutaneous) of contamination. However, the contribution of each source on metal bioavailability and how soil properties influence these contributions have never been studied when considering the dynamic process of bioavailability. Using accumulation kinetics, this study showed that the main assimilation source of Cd was lettuce (68 %), whereas the main source of Pb was the soil (90 %). The plant contribution increased in response to a 2-unit soil pH decrease. Unexpectedly, an increase in the soil contribution to metal assimilation accompanied an increase in the organic matter (OM) content of the soil. For both metals, no significant excretion and influence of source on excretion have been modelled either during exposure or depuration. This study highlights how the contribution of different sources to metal bioavailability changes based on changes in soil parameters, such as pH and OM, and the complexity of the processes that modulate metal bioavailability.     

Pyrene bioavailability; effect of sediment-chemical contact time on routes of uptake in an oligochaete worm

Bioavailability of sediment-sorbed compounds may vary with increasing contact time. This may result in the dietary uptake route becoming more significant as conditions in the gut flora aid the extraction of contaminants, which have migrated into sites within the sediment particle. Such mechanisms may have important implications on risk assessments performed on substances released into the environment. A series of experiments were carried out using sediment spiked with 14C-labelled pyrene, a polycyclic aromatic hydrocarbon. The sediment was left at room temperature over a period of 220 days. Periodically (at 0, 1, 14, 28, 70, 220 days) the sediment was used to perform a bioaccumulation study using the freshwater oligochaete Lumbriculus variegatus. A novel methodology using feeding and (decapitated) non-feeding worms, allowed differentiation between uptake via ingestion and simple sorption. Results showed that there was a decline in bioavailability with time and that this was a 3 stage process. A rapid initial decline was observed over the first day when a 40% decrease was measured, an intermediate period were levels remained stable (day 14 to day 70) and an ultimate decrease in pyrene activity in worm tissue of 70% after 220 days. Over this period the chemical extractability of pyrene also decreased by 50%, as the chemical migrated deeper into unavailable sites within the sediment matrix. Normalising bioavailability to the chemically extractable fraction of pyrene within the sediment provided an overall decrease in bioavailability of 58%. The importance of the dietary route of uptake for pyrene varied during the sediment aging process, reflecting the changes in the physico-chemical interactions between the pyrene, sediment and pore water.     

Chemical assays of availability to earthworms of polycyclic aromatic hydrocarbons in soil

The bioavailable concentration of an organic pollutant is less than the concentration determined by vigorous extraction of soil. Because bioavailability varies with the particular compound, soil, and aging time, an assay for bioavailability is needed. Three methods were tested: extraction with a 25% aqueous solution of tetrahydrofuran (THF), 95% ethanol, and C18 membranes. Evaluations were conducted with a mixture of four polycyclic aromatic hydrocarbons (PAHs) added to five dissimilar soils and with pyrene as sole PAH added to six soils, and the availability of aged and freshly added compounds was determined. Assimilation by earthworms (Eisenia fetida) was used to assess bioavailability. For extraction with THF and earthworm uptake, the correlation coefficients of determination (R2) for anthracene, chrysene, pyrene, and benzo(a)pyrene added as a mixture exceeded 0.85. The R2 values for assays with the C18 membrane were 0.77 or higher. The values for pyrene added alone were 0.710 and 0.823, respectively. R2 values for assays with ethanol often exceeded 0.87, but lower values were sometimes obtained. We suggest that such solvent or solid-phase extractions may be useful in assessing PAH bioavailability.     

Factors controlling the bioaccumulation of mercury and methylmercury by the estuarine amphipod Leptocheirus plumulosus

The bioaccumulation of inorganic mercury (HgI) and monomethylmercury (MMHg) by benthic organisms and subsequent trophic transfer couples the benthic and pelagic realms of aquatic systems and provides a mechanism for transfer of sedimentary contaminants to aquatic food chains. Experiments were performed to investigate the bioavailability and bioaccumulation of particle-associated HgI and MMHg by the estuarine amphipod Leptocheirus plumulosus to further understand the controls on bioaccumulation by benthic organisms. HgI and MMHg are particle reactive and have a strong affinity for organic matter, a potential food source for amphipods. Microcosm laboratory experiments were performed to determine the effects of organic matter on Hg bioaccumulation and to determine the major route of Hg uptake (i.e. sediment ingestion, uptake from water/porewater, or uptake from 'food'). Amphipods living in organic-rich sediment spiked with Hg accumulated less Hg than those living in sediments with a lower organic matter content. Feeding had a significant impact on the amount of HgI and MMHg accumulated. Similarly, amphipods living in water with little organic matter accumulated more Hg than those living in water with a greater percentage of organic matter. MMHg was more readily available for uptake than HgI. Experimental results, coupled with results from a bioaccumulation model, suggest that accumulation of HgI and MMHg from sediment cannot be accurately predicted based solely on the total Hg, or even the MMHg, concentration of the sediment, and sediment-based bioaccumulation factors. All routes of exposure need to be considered in determining the accumulation of HgI and MMHg from sediment to benthic invertebrates.     

A laboratory study of sediment and contaminant release during gas ebullition

Significant quantities of gas are generated from labile organic matter in contaminated sediments. The implications for the gas generation and subsequent release of contaminants from sediments are unknown but may include enhanced direct transport such as pore water advection and diffusion. The behavior of gas in sediments and the resulting migration of a polyaromatic hydrocarbon, viz phenanthrene, were investigated in an experimental system with methane injection at the base of a sediment column. Hexane above the overlying water layer was used to trap any phenanthrene migrating out of the sediment layer. The rate of suspension of solid particulate matter from the sediment bed into the overlying water layer was also monitored. The experiments indicated that significant amounts of both solid particulate matter and contaminant can be released from a sediment bed by gas movement with the amount of release related to the volume of gas released. The effective mass transfer coefficient of gas bubble-facilitated contaminant release was estimated under field conditions, being around three orders of magnitude smaller than that of bioturbation. A thin sand-capping layer (2 cm) was found to dramatically reduce the amount of contaminant or particles released with the gas because it could prevent or at least reduce sediment suspension. Based on the experimental observations, gas bubble-facilitated contaminant transport pathways for both uncapped and capped systems were proposed. Sediment cores were sliced to obtain phenanthrene concentration. X-ray computed tomography (CT) was used to investigate the void space distribution in the sediment penetrated by gas bubbles. The results showed that gas bubble migration could redistribute the sediment void spaces and may facilitate pore water circulation in the sediment.     

The origin of speciation: trace metal kinetics over natural water/sediment interfaces and the consequences for bioaccumulation

The speciation of heavy metals was measured over a variety of natural and undisturbed water/sediment interfaces. Simultaneously, two benthic species (oligochaete Limnodrilus spp. and the midge Chironomus riparius) were exposed to these sediments. Under occurring redox conditions, free ion activities of trace metals Cd, Cu, Ni, Pb, and Zn were measured with a chelating exchange technique, while geochemical conditions (i.e., redox) remained in tact. Free ion activities were compared with total dissolved concentrations in pore waters and surface waters in order to relate speciation to bioaccumulation. Limnodrilus spp. and C. riparius have accumulation patterns that could be linked to time-dependent exposure concentrations, expressed as chemical speciation, in the surface water and the sediment's pore water. Concentrations of free metal ions in the overlying surface water, rather than in sediment pore water, proved to be the best predictor for uptake. For the first time, measurements are obtained from sediments without disturbing physical-chemical conditions and thus bioavailability, a major restriction of other studies so far.     

Multi-species interactions impact the accumulation of weathered 2,2-bis (p-chlorophenyl)-1,1-dichloroethylene (p,p'-DDE) from soil

The impact of interactions between the earthworms Eisenia foetida and Lumbricus terrestris and the plants Cucurbita pepo and Cucurbita maxima on the uptake of weathered p,p'-DDE from soil was determined. Although some combinations of earthworm and plant species caused significant changes in the p,p'-DDE burden in both organisms, the effects were species specific. Contaminant bioconcentration in C. pepo was increased slightly by E. foetida and by 3-fold when the plant was grown with L. terrestris. E. foetida had no effect on the contaminant BCF by C. maxima, but L. terrestris caused a 2-fold reduction in p,p'-DDE uptake by the plant. Contaminant levels in E. foetida and L. terrestris were unaffected by C. pepo. When grown with C. maxima, the concentration of p,p'-DDE decreased by approximately 4-fold and 7-fold in E. foetida and L. terrestris, respectively. The data suggest that the prediction of contaminant bioavailability should consider interactions among species.     

Equilibrium partitioning theory to predict the sediment toxicity of the anionic surfactant C(12)-2-LAS to Corophium volutator

The study of the effect of the sorption of linear alkylbenzene sulfonates (LAS) on the bioavailability to marine benthic organisms is essential to refine the environmental risk assessment of these compounds. According to the equilibrium partitioning theory (EqP), the effect concentration in water-only exposure will be similar to the effect concentration in the sediment pore water. In this work, sorption and desorption experiments with two marine sediments were carried out using the compound C₁₂-2-LAS. The effect of the sediment sorption on the toxicity of benthic organisms was studied in water-only and in sediment bioassays with the marine mud shrimp Corophium volutator. In addition, three common spiking methods were tested for its application in the toxicity tests, as well as the stability of the surfactant during the water-only and sediment-water test duration. LC50 values obtained from water-only exposure showed a good correspondence with the pore water concentrations calculated from the sorption and desorption isotherms in the spiked sediments.     

Bioaccumulation and toxicity of a cationic surfactant (DODMAC) in sediment dwelling freshwater invertebrates

Dimethyldioctadecylammonium chloride (DODMAC, CAS No. 107-64-2) is the principal active component of Di(hydrogenated tallow alkyl) dimethylammonium chloride (DHTDMAC, CAS No. 61789-80-8), a cationic surfactant formerly used principally in laundry fabric softeners. After discharge to water, DODMAC partitions strongly to sediment, therefore the assessment of the effects of DODMAC to benthic organisms is essential in any risk assessment. Chronic toxicity studies were conducted with Lumbriculus variegatus (Oligochaete), Tubifex tubifex (Oligochaete) and Caenorhabditis elegans (Nematode). NOECs were greater than 5738, 1515 and 1351 mg/kg dw, respectively, even for sub-lethal effects. Measurement of the route of uptake of DODMAC by L. variegatus demonstrated the relative importance of uptake via ingestion (86%) compared with direct contact with the sediment and via pore water (14%). The overall tendency of DODMAC to bioaccumulate, however, was low with measured accumulation factors of 0.22 and 0.78 for L. variegatus and T. tubifex, respectively.     

Role of organic acids in enhancing the desorption and uptake of weathered p,p'-DDE by Cucurbita pepo

Experiments were conducted to assess the effect of seven organic acids [succinic, tartaric, malic, malonic, oxalic, citric, ethylene-diaminetetraacetic (EDTA)] over a concentration range of two orders of magnitude (0.001-0.10 M) on the abiotic desorption of weathered p,p'-DDE and the extraction of polyvalent inorganic ions from soil. At 0.05 M all organic acids significantly increased contaminant desorption by 19-80%. Organic acids also increased the aqueous concentration of eight inorganic constituents extracted from soil, with at least a six-fold increase in the release of Al, Fe, Mn, and P at 0.001 M. Zucchini seedlings grown for 28 d in soil containing weathered p,p'-DDE (300 ng/g, dry weight) were periodically amended with distilled water, citric or oxalic acids (0.01 M). Plants receiving water removed 1.7% of the p,p'-DDE from the soil. Seedlings amended with citric or oxalic acids removed 2.1 and 1.9% of the contaminant, respectively, and contained up to 66% more contaminant in the shoot system than unamended vegetation. A second crop of untreated (distilled water) zucchini in the same soil removed more contaminant than the first crop (2.5%), although the addition of organic acids did not further enhance contaminant uptake. The data indicate that the addition of low molecular weight organic acids causes the partial dissolution of the soil structure through the chelation of inorganic structural ions, potentially enhancing bioavailability and having implications for the phytoremediation of persistent organic pollutants in soil.     

Comparative toxicity of a zinc salt, zinc powder and zinc oxide to Eisenia fetida, Enchytraeus albidus and Folsomia candida

The pore water zinc concentration and the calcium chloride extracted zinc fraction are higher in the soils spiked with a zinc salt (ZnCl2) compared to soils spiked with zinc oxide or zinc powder. Based on total zinc concentrations in the soil, the acute toxicity of zinc salt to the compost worm Eisenia fetida, the potworm Enchytraeus albidus and the springtail Folsomia candida was lower compared to zinc oxide and zinc powder. However, when expressed on the basis of pore water concentrations or calcium chloride extracted fractions, acute toxicity was higher for zinc salt, which indicated that dermal uptake via the pore water is not the only route of uptake. Chronic toxicity of zinc salt, zinc oxide and zinc powder was similar when based on total concentrations in the soil which again indicates that the pore water route of uptake is not the only route of exposure but that oral uptake is also important.     

Comparison of the method of diffusive gels in thin films with conventional extraction techniques for evaluating zinc accumulation in plants and isopods

The measurement of diffusive gels in thin films (DGT) has recently been developed to assess metal bioavailability in soils. The DGT-method is based on diffusion in a porous matrix. To test the predictive capabilities of the method with regard to metal bioavailability, a study was set up with 28 soils having a variety of textures and amounts of zinc salts added. Correlation and regression analyses were performed to compare DGT-extracted zinc levels to zinc concentrations obtained by extraction with 0.01 M CaCl(2) and 0.43 M HNO(3), digestion with aqua regia and the zinc concentration in pore water. The amount of zinc extracted with CaCl(2) correlated well with DGT-extracted zinc levels in all soils spiked with different amounts of ZnCl(2). A similar correlation was not found for zinc concentrations in soil samples collected in the field. Experiments were performed to compare zinc content in organisms and in soils. The organisms tested were plants (grass, lettuce and lupine) and the hard bodied soil dwelling isopod Oniscus asellus. Good correlations were found between zinc accumulation in grass and lettuce and the C(E) (effective concentration) measured by a DGT-device, CaCl(2) extracted zinc and the zinc content in the pore water of all soils. The correlation with C(E) was not significant for lupine, neither for spiked soils, nor for field soils (p< or =0.001). Zinc levels in the isopods were not significantly related to any set of zinc measurements. From a synthesis of all results obtained it is concluded that the DGT-methodology does not have an additional value in predicting bioavailability of zinc in terrestrial ecosystems as compared to conventional extraction methods.     

Challenges in understanding the sources of bioaccumulated metals in biota inhabiting turbid river systems

Bioaccumulation of As, Cd, Cu, Pb and Zn by Macrobrachium prawns was observed to occur in the Strickland River downstream of a gold mine at Porgera, Papua New Guinea. This was despite the total metal concentrations of waters and sediments indicating no difference from reference sites within tributaries. To provide information on potential sources and bioavailability of metals to prawns, an extensive range of analyses were made on waters, suspended solids, deposited sediments and plant materials within the river system. Dissolved metal concentrations were mostly sub-micrograms per liter and no major differences existed in concentrations or speciation between sites within the Strickland River or its tributaries. Similarly, no differences were detected between sites for total or dilute acid-extractable metal concentrations in bed sediments and plant materials, which may be ingested by the prawns. However, the rivers in this region are highly turbid and the dilute acid-extractable cadmium and zinc concentrations in suspended solids were greater at sites in the Strickland River than at sites in tributaries. The results indicated that mine-derived inputs increased the proportion of these forms of metals or metalloids in the Strickland River. These less strongly bound metals and metalloids would be more bioavailable to the prawns via the dietary pathway. The results highlighted many of the difficulties in using routine monitoring data without information on metal speciation to describe metal uptake and predict potential effects when concentrations are low and similar to background. The study indicated that the monitoring of contaminant concentrations in organisms that integrate the exposure from multiple exposure routes and durations may often be more effective for detecting impacts than intermittent monitoring of contaminants in waters and sediments.     

Grinding and sieving soil affects the availability of organic contaminants: a kinetic analysis

Field contaminated soils are often homogenized before application in bioassays and chemical assays that estimate the (bio)availability of their contaminants. The homogenization of the soil might affect the availability, and thereby the outcome of a bioassay might not reflect field situations. In this study, uptake kinetics of polycyclic aromatic hydrocarbons (PAH) by a negligible depletive passive sampler exposed to a ground and non-ground field contaminated soil were tested. The measurements illustrate how freely dissolved pore water concentrations of contaminants can be affected by soil treatment. It took more than a month, and over a year to reach steady state in the passive sampler exposed to the ground and non-ground soil, respectively. The uptake rate seemed to be limited by desorption from the soil, even though the fiber only extracted 0.2% of the soil-sorbed PAH at maximum. If these observations are translated to the field situation, where contaminants are not homogeneously distributed and disappear by (bio)degradation or physical transport processes, it is unlikely that pore water concentrations are solely determined by a thermodynamic equilibrium. Hence, exposure of organisms in these soils cannot always be estimated by sorption studies and an equilibrium partitioning approach.     

Bioavailability of polychlorinated dibenzo-p-dioxins and dibenzofurans from contaminated Wisconsin River sediment to carp

The bioavailability of 2,3,7,8-TCDD from sediment to freshwater fish was studied in laboratory exposures. Carp (10g) exposed to Wisconsin River sediment (39 pg/g) for 55 days accumulated 7.5 pg/g. Maintaining exposured fish in clean water for an additional 205 days resulted in depuration of 32–34% TCDD. These values compare to field data where sediments ranged from 30–200 pg/g and 1.5 kg carp (70 pg/g) depurated 55% in 325 days. Analysis of sediment, laboratory exposed fish, and Wisconsin River fish for other PCDDs and PCDFs showed residues of 2,3,7 and 8 substituted congeners selectively enriched.     

Plant aided bioremediation in the vadose zone: model development and applications

Phytoremediation has the potential to enhance clean up of land contaminated by various pollutants. A mathematical model that includes a two-fluid phase flow model of water flow as well as a two-region soil model of contaminant reactions was developed and applied to various bioremediation scenarios in the unsaturated zone, especially to plant-aided bioremediation. To investigate model behavior and determine the main parameters and mechanisms that affect bioremediation in unplanted and planted soils, numerical simulations of theoretical scenarios were conducted before applying the model to field data. It is observed from the results that parameters affecting the contaminant concentration in the water phase, such as aqueous solubility, the octanol-water partition coefficient, and organic carbon content of the soil controlled the contaminant fate in the vadose zone. Simulation using the developed model also characterized the fate and transport of the contaminants both in planted and unplanted soils satisfactorily for field applications. Although phytoremediation has the potential for remediation of contaminated soils, results from both modeling and field studies suggested that plants may not always enhance the remediation efficiency when the soil already has a high microbial concentration, when the contaminant bioavailability is low, or when the overall reaction is mass transfer-limited. Therefore, other steps to increase contaminant bioavailability are needed in phytoremediation applications; natural purification mechanisms such as aging, volatilization, and natural bioremediation should be considered to maximize the plant effect and minimize the cost.     

Measurement of dynamic mobilization of trace metals in sediments using DGT and comparison with bioaccumulation in Chironomus riparius: first results of an experimental study

Sediments in aquatic ecosystems are often contaminated as a result of anthropogenic activities. Sediments and benthic organisms have been used to monitor trace metals contamination. However, due to the high variability of contaminant bioavailability, the attempt to link metal concentration in sediments and contamination of the organisms or ecotoxicological effect often lead to disappointing results. The technique of diffusive gradients in thin films (DGT) has been proposed as a relevant tool to study metal bioavailability, for example for accumulation in plants. In the present study, laboratory microcosm experiments were conducted with six contaminated sediments to compare metal accumulation in DGT and bioaccumulation in a chironomid (Chironomus riparius) for Cu, Cd and Pb . Metal accumulation in DGT was measured over time then modelled to determine two parameters of the dynamic response of the metals to DGT deployment: the size of the particulate labile pool and the kinetic of the solid-dissolved phase exchange. The mobility of metals was found metal and sediment dependent. A significant relationship between metal accumulated in DGT and bioaccumulated in chironomids was found for Cu and Pb. However, total metals in sediments were the best predictors of bioaccumulation. Nevertheless, the knowledge of the metals dynamic enhanced our ability to explain the different biological uptake observed in sediments of similar total metal concentrations.     

Contamination by polycyclic aromatic hydrocarbons in the Jiulong River Estuary and Western Xiamen Sea, China

The distribution of 16 polycyclic aromatic hydrocarbons (PAHs) was determined in water, sediment and pore water of the Jiulong River Estuary and Western Xiamen Sea, China. Total PAH concentrations varied from 6.96 to 26.9 microg/l in water, 59-1177 ng/ g dry weight in surficial sediments, and 158-949 microg/l in pore water. The PAHs were present in higher levels in pore water than in surface water, due possibly to higher concentrations of dissolved organic carbon or colloids with which the hydrophobic pollutants were strongly associated. Such a concentration gradient implies a potential flux of pollutants from sediment pore water to overlying water. The levels of PAHs in water and pore water were significantly higher than those found in 1998, suggesting recent inputs of these compounds into the area and re-working of sediment phase. The composition pattern of PAHs in the three phases was dominated by high molecular weight PAHs, in particular 5-ring PAHs. The salinity profile of dissolved PAHs suggested that they all behaved non-conservatively due to deviation from the theoretical dilution line. No correlation was found between PAH concentrations in sediment and those in pore water, and the correlation between the partition coefficients of PAHs and sediment organic carbon content was not significant, suggesting the complexity of the partition behaviour of PAHs. As a result of high PAH concentrations in water and pore water, it is likely that they may have caused mortality to certain exposed organisms.     

Bioconcentration of polycyclic aromatic hydrocarbons by the freshwater oligochaete Lumbriculus variegatus

Tissue residues of the PAHs, anthracene, fluorene, fluoranthene and pyrene were determined in Lumbriculus variegatus at four time intervals during both a 96-h exposure period to monitor uptake, and a 96-h clean water period to assess depuration. Mean BCFs were 2390, 1210, 452 and 1920 for fluoranthene, anthracene, fluorene and pyrene, respectively. BCFs were positively correlated with the octanol/water partition coefficient values of the four PAHs. Depuration occurred most rapidly for fluorene, followed by anthracene and fluoranthene. No apparent depuration of pyrene was observed during the 96-h depuration period. Because of rapid depuration of some PAHs, it appears that the 24 h clean water gut clearance period recommended in conjunction with sediment bioaccumulation tests with L. variegatus has potential to result in an under-estimation of bioaccumulation of some chemicals.