Organic Contaminants In Sediments Research Articles

Meta-Analysis and Machine Learning Models for Anaerobic Biodegradation Rates of Organic Contaminants in Sediments and Sludge.

Anaerobic biodegradation rates (half-lives) of organic chemicals are pivotal for environmental risk assessment and remediation. Traditional experimental evaluation, constrained by prolonged, oxygen-free conditions, struggles to keep pace with emerging contaminants. Data-driven machine learning (ML) models serve as promising complements. However, reported quantitative structure-biodegradation relationships or ML models on anaerobic biodegradation are mostly based on small data sets (<100 records) and neglect experimental conditions, usually achieving compromised predictions. This work aimed to develop ML models for predicting the biodegradation half-lives of organic pollutants in anaerobic environments (i.e., sediment/soil and sludge). Focusing on important features of both chemicals and experimental conditions, we first curated two data sets, one for sediment/soil (SED) and the other for sludge (SLD), covering 978 records for 206 chemicals from the literature, and then conducted a meta-analysis. Next, we built a binary classification (half-life of 30 days as the cutoff) model with an accuracy of 81% and a regression model with R2 of 0.56 for SED based on LightGBM (80% and 0.31 for SLD based on Extra tree, respectively). The model interpretations underscored the significance of experimental conditions (e.g., temperature and inoculum dosage), as evidenced by their high feature importance, and the models were found to correctly capture the effects of chemical substructures, for example, branched structures and aromatic rings prolonged half-lives while methyl group and ortho-substitution on rings shortened half-lives. The applicability domains of the models were also defined, resulting in reasonable prediction for the half-lives of 41% (SED) or 67% (SLD) of over 4000 persistent, bioaccumulative, and toxic chemicals. Overall, this study pioneers ML models for predicting the anaerobic degradation half-lives, offering valuable support for future evaluation and implementation of chemical anaerobic biodegradation.

Selected legacy and emerging organic contaminants in sediments of China's Yangtze – the world's third longest river: Response to anthropogenic activities

To explore contaminant concerns as a result of anthropogenic disturbance of the river system, this study provided the first extensive investigation of the contamination profiles, possible driving factors, and ecological risks of 40 target compounds including pharmaceuticals and personal care products (PPCPs), neonicotinoid pesticides (NNIs), polybrominated diphenyl ethers (PBDEs), and polychlorinated biphenyls (PCBs) in sediments of the whole Yangtze River (the world's third longest river). Among these target compounds, PPCPs were the dominant contaminants with a total concentration (∑15PPCPs) of 2.13–14.99 ng/g, followed by ∑7PCBs (<LOD-1.97 ng/g), ∑11NNIs (<LOD-1.18 ng/g), and ∑7PBDEs (<LOD-0.78 ng/g). The results suggested that contamination levels of these chemicals were largely due to the amount used, low affinity with sediments, and effective management practices. Microplastics and anthropogenic factors (i.e., GDP per capita, population density, and urbanization rate) contributed significantly to PPCPs contamination based on correlation analysis (p < 0.05). The risk assessment suggested that PBDE 99, PBDE 183, E3, PCB 153, and PCB 118 posed relatively high risks when compared with other compounds. Therefore, it is not only necessary to take effective measures to reduce the contamination of legacy POPs, but also to improve the management and treatment of emerging organic chemicals to deal with the threat of them in the Yangtze River Basin.

Limited Effectiveness of Carbonaceous Sorbents in Sequestering Aged Organic Contaminants in Sediments.

Carbonaceous materials are often proposed for use in restoring soils or sediments contaminated with hydrophobic organic contaminants (HOCs). However, the contamination of most sites is a result of historical events, where HOCs have resided in the solid compartment for many years or decades. The prolonged contact time, or aging, leads to reduced contaminant availability and likely diminished effectiveness of using sorbents. In this study, three different carbonaceous sorbents, i.e., biochars, powdered activated carbon, and granular activated carbon, were amended to a Superfund site marine sediment contaminated with DDT residues from decades ago. The amended sediments were incubated in seawater for up to 1 year, and the freely dissolved concentration (Cfree) and the biota-sediment accumulation factors (BSAFs) for a native polychaete (Neanthes arenaceodentata) were measured. Even though the bulk sediment concentrations were very high (6.4-154.9 μg/g OC), both Cfree and BSAFs were very small, ranging from nd to 1.34 ng/L and from nd to 0.024, respectively. The addition of carbonaceous sorbents, even at 2% (w/w), did not consistently lead to reduced DDT bioaccumulation. The limited effectiveness of carbonaceous sorbents was attributed to the low DDT availability due to prolonged aging, highlighting the need for considering contaminant aging when using sorbents for remediation.

Ultra-high-performance supercritical fluid chromatography-mass spectrometry for the analysis of organic contaminants in sediments.

A nontarget screening method was developed based on D-optimal designs for ultra-high performance supercritical fluid chromatography with positive and negative electrospray ionization mode mass spectrometry. A mixture of organic contaminants such as pesticides, steroids, surfactants, phenolic and fatty acids, and polycyclic aromatic hydrocarbon derivatives, was used for the optimization. An aprotic mixture of dichloromethane and acetone [3:1] performed overall best as the injection solvent. The highest peak capacities (n) were accomplished at the shallowest gradient (1%B/min), ammonium formate (n = 378 in negative ionization mode), or ammonium acetate (n = 327in positive ionization mode) in methanol as the modifier. Capillary voltage, make-up solvent flow rate, water, and additive concentration were the most significant factors for improving peak intensity: higher peak intensities were obtained at lower additive concentrations (5mM ammonium formate), and with 5% water in positive ionization mode. Conversely, water had detrimental effects in negative ionization mode. The optimized method was used to quantify organic contaminants in 17 freshwater sediment samples from Copenhagen, Denmark. Out of 50 monitored contaminants, 35 were detected in at least one sample. Further, the method has a potential for target and nontarget screening analysis of organic contaminants in solid matrices.

Determining the reusability of Tenax beads (60–80 mesh) in estimates of bioaccessibility using single-point extractions

Single-point Tenax extractions are a viable means of estimating bioaccessibility of hydrophobic organic contaminants in sediment, soil, and intestinal fluids. One advantage of this extraction technique is that after thorough cleaning and drying, Tenax beads can be reused in subsequent extractions with the assumption that no changes in bioaccessibility estimates will occur. This assumption of reusability, however, has not been tested. Therefore, the objective of the current study was to evaluate the reusability of Tenax beads by comparing bioaccessible polychlorinated biphenyl (PCB) concentrations measured by differently aged Tenax beads. New Tenax beads (60–80 mesh) were aged through 24 h single-point Tenax extractions of clean sand 0, 1, 5, 10, 15, 20, and 25 times. The aged Tenax was then used to extract 27 PCB congeners from laboratory spiked sediment and the bioaccessible PCB concentrations were compared. Despite significant effects of PCB congener (F26, 567 = 97.291, p = 2.00 × 10−16), Tenax age (F6, 567 = 14.735, p = 1.12 × 10−15), and the interaction of these two terms (F156, 567 = 1.711, p = 4.79 × 10−6) on bioaccessible concentrations measured by Tenax, the significance was due to two PCB congeners that showed large variation during analytical quantification. For the remaining 25 congeners, no differences in bioaccessible PCB concentrations were found between differently aged Tenax, suggesting repeated use did not impact bioaccessible estimates provided by Tenax. Scanning electron microscope imaging revealed no significant changes in the visible surface area of the Tenax beads after aging (F6, 203 = 1.434, p = 0.203), suggesting no significant changes in the Tenax phase volume resulting in consistent estimates of bioaccessibility through repeated use. Given the strong correlations between single-point Tenax extractable and tissue concentrations, providing data to detail the reusability of Tenax in repeated extractions further demonstrates the applicability of this extraction technique in risk assessment.

Desorption kinetics of antipsychotic drugs from sandy sediments by diffusive gradients in thin-films technique

Dynamic processes of organic contaminants in sediments can have important toxicological implications in aquatic systems. The current study used diffusive gradients in thin-films (DGT) devices in sandy sediments spiked with nine antipsychotics and in field sandy sediments. Samplers were deployed for 1 to 30 days to determine the flux of these compounds to DGT devices and the exchange rates between the porewater and sediment solid phase. The results showed a continuous removal of antipsychotics to a binding gel and induced a mobile flux from the DGT device to the adjacent sediment solution. A dynamic model, DGT-induced fluxes in soils and sediments, was used to derive rate constants of resupply of antipsychotics from solid phase to aqueous phase (response time, Tc) and distribution coefficients for labile antipsychotics. The largest labile pool was found for lamotrigine and carbamazepine in spiked sediments. Carbamazepine, clozapine, citalopram, and lamotrigine were resupplied rapidly by sediments with Tc (25–30 min). Tc values of bupropion and amitriptyline were the longest (≈5 h), which exhibited slow desorption rates in sediments. In field sediments, high resupply was found for carbamazepine and lamotrigine, which did not show higher labile pool. The Tc values were obviously higher in the filed sediments (52–171 h). Although the adsorption process is dominant for most studied antipsychotics in both spiked sediments and field sediments, the kinetic resupply of antipsychotic compounds may not be accurately estimated by laboratory-controlled incubation experiments. More studies are needed to explore the mechanisms of desorption kinetics by using in situ DGT technique in the field.

Comparing total and accessible concentrations of hydrophobic organic contaminants in sediments and suspended particulate matter in the Danube River.

Contamination of aquatic ecosystems by hydrophobic organic contaminants (HOCs) is often assessed based on their concentrations in riverbed sediment and suspended particulate matter (SPM). However, total HOC concentration (CTOT) in sediment or SPM is of limited value for evaluating the exposure of benthic or pelagic organisms. The accessible HOC concentration (CAS) presents a useful parameter quantifying the overall pool of HOC in sediment or SPM available for fast partitioning to the water phase or biota. We applied a novel approach of ex situ sequential equilibrium partitioning with silicone elastomer sampler at a high sampler/SPM phase ratio to measure CAS of HOC in SPM from the Danube River. We compared CTOT and CAS in SPM and surface layer sediment collected at the same sites to evaluate whether HOC monitoring in the two matrices provides equivalent information on environmental quality. At most sites, there was a good agreement and correlation of organic carbon (OC)-normalised CTOT in SPM and sediment for polychlorinated biphenyls (PCBs) and the majority of organochlorine pesticides (OCPs). In contrast, CTOT of polycyclic aromatic hydrocarbons (PAHs) in SPM were up to a factor 10 lower in SPM than in sediment. Site-specific differences of OC-normalised CAS concentrations in SPM and sediments were observed for PCBs and OCPs, with accessibility mostly lower in SPM than in sediment. The highest accessibility in SPM was observed for PCBs, ranging between 15 and 30%. The accessibility of OCPs varied from 0 to 23%. SPM and riverbed sediment samples provide complementary but not mutually interchangeable information on HOC contamination.

Use of the Dynamic Technique DGT to Determine the Labile Pool Size and Kinetic Resupply of Pesticides in Soils and Sediments.

The diffusive gradients in thin films (DGT) technique has been successfully and widely applied to investigate the labile fractions of inorganic contaminants in soils and sediments, but there have been almost no applications to organic contaminants. Here we developed and tested the approach for the pesticide Atrazine (ATR) in a controlled soil experiment and in situ in an intact lake sediment core. The soil study explored the relationships between soil solution, DGT measured labile ATR and solvent extractable ATR in dosed soils of different organic matter, pH status and incubation times. The results are further interpreted using the DIFS (DGT-induced fluxes in soils and sediments) model. Resupply of ATR to the soil solution was partially sustained by the solid phase in all the soils. This was due to small labile pool size and slow kinetics, with soil pH being an important controlling factor. The in situ sediment study successfully used a DGT probe to examine labile ATR distribution through the core on the subcm scale. It demonstrated-for the first time-an easy to use in situ technique to investigate the effects of redox on resupply kinetics and biogeochemical processes of trace organic contaminants in sediments.

Concentrations and source identification of PAHs, alkyl-PAHs and other organic contaminants in sediments from a contaminated harbor in the Laurentian Great Lakes

As a result of historical industrial activity, the sediments in the inner harbor of Owen Sound Bay in the northeastern part of Lake Huron in Ontario, Canada are contaminated with organic compounds. The present study showed that the concentrations of Ʃ PAH16-EPA in all sediments in the inner harbor were above the sediment quality guidelines for the province of Ontario, Canada, with mean Ʃ PAH16-EPA concentrations at the most contaminated site of 46,000μg/kg dry weight. The concentrations of polychlorinated biphenyls, brominated diphenyl ethers, and organochlorine compounds were all below sediment quality guidelines. The patterns of PAH and alkyl-PAH compounds in sediment cores indicated that contamination is from mixed sources, with a strong indication of pyrogenic contamination from industries that used to operate in the area, including a coal gasification plant. Other areas of the bay are impacted by petrogenic contamination, potentially from spills of fuel. The even distribution of PAH and alkyl-PAH compounds throughout core profiles at depths up to 25cm indicates that this is a dynamic system and contaminated sediments are not being covered by deposition of less contaminated sediments. This study illustrates the value of determining the patterns of both PAH and alkyl-PAH compounds in sediments for regulatory purposes and also for forensic source tracking.

Stabilization of hydrophobic organic contaminants in sediments by natural zeolites: bioavailability-based assessment of efficacy using equilibrium passive sampling

As natural zeolites have been widely used as cost-effective adsorbents for plant nutrients and heavy metals in sediments, it is worthwhile to verify the potential of natural zeolites for mixed-contaminant stabilization including hydrophobic organic contaminants (HOCs). The effectiveness of natural zeolite amendment in sediment on reducing the bioaccumulation of sediment-associated HOCs in V. philippinaram (Cb) was assessed. Then, the role of sediment pore water freely dissolved HOCs (Cfree) in Cb prediction was further identified and modeled. In this study, a bioavailability-based assessment of the HOC-stabilization efficacy of natural zeolites in maricultural sediments was performed using equilibrium passive sampling. V. philippinaram was adopted as a biological indicator for HOC bioaccumulation. Polydimethylsiloxane (PDMS) was used as a passive sampler for monitoring the concentration of the Cfree. The assumption that Cfree is a central mediator driving the bioaccumulation process of HOCs from the bulk sediment to the exposed organisms was validated by correlating the reductions in Cb and Cfree of the sediments amended with natural zeolites. Subsequently, a model based on this assumption was built and verified for the bioavailability-based assessment of the stabilization efficacy of natural zeolite amendment on sediment-associated HOCs. The results showed the bioaccumulations of four kinds of HOCs (including polycyclic aromatic hydrocarbons, polybrominated diphenyl ethers, pyrethroids, and organochlorine pesticides) in V. philippinaram were reduced by 7.3–38% after the natural zeolite amendment (10% dry weight in sediments), and the Cfree values measured with PDMS were reduced proportionally. It supported the assumption that Cfree is a central mediator driving the bioaccumulation process of HOCs. Kow of HOCs and two properties of sediment were found to be significantly correlated with the reductions of the Cfree values. Based on these findings, a model to predict the Cb values of PAHs and PBDEs in V. philippinaram was built. The model was then verified by a significant correlation between the predicted and measured values of Cb. The potential of natural zeolites for the stabilization of mixed-contaminants in sediments, including HOCs, was proved as notable reductions of Cb and Cfree of HOCs in the sediments amended by natural zeolite were observed. The results also suggested PDMS is a promising tool for predicting the bioaccumulation of sediment-associated HOCs in V. philippinaram and further for assessing the stabilization efficacy of natural zeolites in maricultural sediments. Modifying natural zeolites to further improve the effectiveness of HOC stabilization is warranted.

Toxicity assessment of sediments from the Liaohe River Protected Area (China) under the influence of ammonia nitrogen, heavy metals and organic contaminants

The aim of this study was to evaluate the toxicity of ammonia nitrogen, metals and organic contaminants in sediment collected from the Liaohe River Protected Areas. The TIE was applied to 16 samples. The zeolite, resin, and coconut charcoal were used to mask toxicity of the three kinds of pollutants, respectively. Then quantitative analyses together with a battery of bioassays were performed to evaluate toxic effects. At last, the spiking tests were used to confirm the major contributors to toxicity. The results of toxicity identification showed the ammonia nitrogen, γ-HCHs, As and Cd may cause toxic hazards to benthic organisms. The significant correlation between the survival and volume ratio of the sediment and overlying water confirmed ammonia nitrogen and Cd were the major toxic pollutants that cause the biological toxicity. We confirmed bioassays combined with masking agent, spiking tests and quantitative analyses were suitable tools for detecting toxicity.

Impact of Polymer Colonization on the Fate of Organic Contaminants in Sediment.

Plastic pellets and microbes are important constitutes in sediment, but the significance of microbes colonizing on plastic pellets to the environmental fate and transport of organic contaminants has not been adequately recognized and assessed. To address this issue, low-density polyethylene (LDPE), polyoxymethylene (POM) and polypropylene (PP) slices were preloaded with dichlorodiphenyltrichloroethanes (DDTs), polycyclic aromatic hydrocarbons (PAHs) and polychlorinated biphenyls (PCBs) and incubated in abiotic and biotic sediment microcosms. Images from scanning electron microscope, Lysogeny Broth agar plates and confocal laser scanning microscope indicated that all polymer slices incubated in biotic sediments were colonized by microorganisms, particularly the LDPE slices. The occurrence of biofilms induced higher dissipation rates of DDTs and PAHs from the LDPE slice surfaces incubated in the biotic sediments than in the abiotic sediments. Plastic colonization on LDPE slice surfaces enhanced the biotransformation of DDT and some PAHs in both marine and river sediments, but had little impact on PCBs. By comparison, PP and POM with unique properties were shown to exert different impacts on the physical and microbial activities as compared to LDPE. These results clearly demonstrated that the significance of polymer surface affiliated microbes to the environmental fate and behavior of organic contaminants should be recognized.

Measuring freely dissolved DDT and metabolites in seawater using solid-phase microextraction with performance reference compounds

The coupling of disposable solid-phase microextraction (SPME) with performance reference compounds (PRCs) has been recently introduced to measure time-averaged freely dissolved concentrations (Cfree) of hydrophobic organic contaminants in sediments under laboratory conditions. To explore the use of PRC-SPME for in situ sampling in seawater, disposable PDMS fibers (35-μm and 100-μm coating) preloaded with stable isotope labeled analogues as PRCs were deployed at six stations (each with three depths) in the open ocean of the Palos Verdes Shelf (CA, USA) Superfund site for 33d to measure Cfree of DDT and its degradates. The observed values of fractional equilibration (feq) of PRCs were mostly <0.85, suggesting nonequilibrium conditions at the end of deployment. The observed feqs for the samplers varied with compound, sampling station and depth, validating the need for calibration to derive accurate Cfree. The Cfree values of DDE and DDD determined with PRC-SPME were in good agreement with those previously measured by in situ large-volume water sampling or polyethylene devices. The highest Cfree in seawater 5m off the ocean floor was 750pgL−1 for o,p′-DDE, 2170pgL−1 for p,p′-DDE, 24pgL−1 for o,p′-DDD, and 75pgL−1 for p,p′-DDD. Results of this study demonstrated the feasibility and advantages of using disposable PDMS fiber coupled with PRCs for in situ sampling.

Distributions of persistent organic contaminants in sediments and their potential impact on macrobenthic faunal community of the Geum River Estuary and Saemangeum Coast, Korea

Over the last 30 years, the Geum River Estuary and Saemangeum Coast have been subject to major environmental changes, including dike construction, reclamation, and development of industrial complexes. This study aimed to: 1) investigate the occurrence of polycyclic aromatic hydrocarbons (PAHs), alkylphenols (APs), and styrene oligomers (SOs), 2) identify the sources of sedimentary organic matter, and 3) determine key environmental factors controlling the macrozoobenthos community structure. A total of 58 surface sediments were collected from the estuary and coastal area in 2014. Specific persistent organic contaminants (POCs), including 24 PAHs, 6 APs, and 10 SOs were measured. PAHs, APs, and SOs were detected in the sediments at all sites, with concentrations varying among sites. Although POCs concentrations were generally below the Canadian sediment quality guidelines, relatively greater concentrations of POCs were found at some sites adjacent to industrial complexes and the estuarine area. Sediment organic carbon, total nitrogen, and the stable carbon isotope ratio (δ13C) were determined. Some sites near watergate had about 2–3‰ lighter δ13C values compared to other areas, indicating that these sites are affected by terrestrial organic matter. The number of species in the macrofaunal community was significantly correlated with δ13C values (p < 0.001), positively, suggesting that the origin of sedimentary organic matter is important for controlling the macrozoobenthos distribution. Overall, this research provides information about the level and sources of sediment pollution, the origins of organic matter, and the relationships with the macrofaunal community.

Detecting and quantifying organic contaminants in sediments with nuclear magnetic resonance

We have conducted proton nuclear magnetic resonance (NMR) measurements of relaxation times [Formula: see text] and [Formula: see text] as well as the diffusion coefficient [Formula: see text] to detect and quantify gasoline, diesel, crude oil, and trichloroethylene (TCE) in sediment samples containing water. The sediment samples were coarse sand, fine sand, and a sand-clay mixture. We found that water, gasoline, diesel, and crude oil all exhibited similar signal amplitudes per unit volume, whereas TCE exhibited one-tenth the signal. The ability to use [Formula: see text] measurements to distinguish the contaminant signal from the water signal depended on the bulk-fluid properties as well as the sediment texture and grain size. In the [Formula: see text] distributions for samples containing equal volumes of contaminant and water, the contaminant signal could be resolved for crude oil in sand and for gasoline and TCE in the sand-clay mixture. Adding the diffusion measurement, using either pulsed or static gradients, made it possible to distinguish diesel and crude oil in all of the samples due to the large differences between the [Formula: see text] of the contaminants and water. From the diffusion measurements, we were able to accurately quantify diesel and crude oil volumes ranging from 1% to 17% of the total sample volume. These methods could be applied in the field using NMR logging tools to quantify and monitor subsurface contamination.

Bioanalytical effect-balance model to determine the bioavailability of organic contaminants in sediments affected by black and natural carbon

In sediments several binding phases dictate the fate and bioavailability of organic contaminants. Black carbon (BC) has a high sorptive capacity for organic contaminants and can limit their bioavailability, while the fraction bound to organic carbon (OC) is considered to be readily desorbable and bioavailable. We investigated the bioavailability and mixture toxicity of sediment-associated contaminants by combining different extraction techniques with in vitro bioanalytical tools. Sediments from a harbour with high fraction of BC, and sediments from remote, agricultural and urban areas with lower BC were treated with exhaustive solvent extraction, Tenax extraction and passive sampling to estimate total, bioaccessible and bioavailable fractions, respectively. The extracts were characterized with cell-based bioassays that measure dioxin-like activity (AhR-CAFLUX) and the adaptive stress response to oxidative stress (AREc32). Resulting bioanalytical equivalents, which are effect-scaled concentrations, were applied in an effect-balance model, consistent with a mass balance-partitioning model for single chemicals. Sediments containing BC had most of the bioactivity associated to the BC fraction, while the OC fraction played a role for sediments with lower BC. As effect-based sediment-water distribution ratios demonstrated, most of the bioactivity in the AhR-CAFLUX was attributable to hydrophobic chemicals while more hydrophilic chemicals activated AREc32, even though bioanalytical equivalents in the aqueous phase remained negligible. This approach can be used to understand the fate and effects of mixtures of diverse organic contaminants in sediments that would not be possible if single chemicals were targeted by chemical analysis; and make informed risk-based decisions concerning the management of contaminated sediments.

Accumulation patterns of lipophilic organic contaminants in surface sediments and in economic important mussel and fish species from Jakarta Bay, Indonesia

Non-target screening analyses were conducted in order to identify a wide range of organic contaminants in sediment and animal tissue samples from Jakarta Bay. High concentrations of di-iso-propylnaphthalenes (DIPNs), linear alkylbenzenes (LABs) and polycyclic aromatic hydrocarbons (PAHs) were detected in all samples, whereas phenylmethoxynaphthalene (PMN), DDT and DDT metabolites (DDX) were detected at lower concentrations. In order to evaluate the uptake and accumulation by economic important mussel (Perna viridis) and fish species, contaminant patterns of DIPNs, LABs and PAHs in different compartments were compared. Different patterns of these contaminant groups were found in sediment and animal tissue samples, suggesting compound-specific accumulation and metabolism processes. Significantly higher concentrations of these three contaminant groups in mussel tissue as compared to fish tissue from Jakarta Bay were found. Because P. viridis is an important aquaculture species in Asia, this result is relevant for food safety.

Persistent organic contaminants in sediments and biota of Great Slave Lake, Canada: Slave River and long-range atmospheric source influences

Abstract Over 1993–1996, we conducted a series of studies to investigate the distributions of legacy persistent organic pollutants (POPs) in the West Basin and East Arm of Great Slave Lake with a focus on sediments and fish species common in traditional diets; lesser attention was paid to polynuclear aromatic hydrocarbons (PAHs) and chemicals associated with pulp and paper mill activity. The Slave River, formed by the confluence of the Peace and Athabasca Rivers, profoundly affects the limnology of the West Basin by transporting large quantities of water and suspended sediments into the lake. Most POPs occurred in substantially higher concentrations in sediments offshore of the Slave River inflow than in the remote East Arm where long-range atmospheric transport was inferred to be the primary source. POP concentrations tended to be higher in East Arm than the West Basin fish possibly because the low productivity of the East Arm provides less opportunity for contaminant dilution through fish growth and the adsorption onto organic particulates in the water column. Overall, POP concentrations were relatively low in plankton, lake trout fillet and burbot liver from both regions of the lake and generally comparable to other lakes located at similar latitudes. Since 1998, we have been monitoring POPs, mercury and other contaminants in lake trout and burbot under the Northern Contaminants Program in which we are contributing to national and international reporting and to the global understanding of contaminants and climate change on northern and other environments.

Embryotoxicity and genotoxicity evaluation of sediments from Yangtze River estuary using zebrafish (Danio rerio) embryos.

Sediments function both as a sink and a source of pollutants in aquatic ecosystems and may impose serious effects on benthic organisms and human health. As one of the largest estuaries in the world, the Yangtze River estuary suffers from abundant wastewater from the coastal cities. In this study, the zebrafish (Danio rerio) embryos were employed in the fish embryo test and a comet assay to evaluate the embryotoxicity and genotoxicity of the sediments from the Yangtze River estuary, respectively. Results showed that the sediments from the Yangtze River estuary significantly increased mortality, induced development abnormalities, and reduced hatching rate and heart rate of zebrafish embryos after 96 h of exposure. Significant genotoxicity was observed in the samples relative to the controls. Relatively low-level embryotoxicity and genotoxicity of sediments were found in the Yangtze River compared with other river systems. Toxic responses were also discussed in relation to the analyzed organic contaminants in sediments. More attention should be paid to non-priority pollutant monitoring in the Yangtze River estuary.

Reduction of nitroaromatics sorbed to black carbon by direct reaction with sorbed sulfides.

Sorption to black carbons is an important sink for organic contaminants in sediments. Previous research has suggested that black carbons (graphite, activated carbon, and biochar) mediate the degradation of nitrated compounds by sulfides by at least two different pathways: reduction involving electron transfer from sulfides through conductive carbon regions to the target contaminant (nitroglycerin) and degradation by sulfur-based intermediates formed by sulfide oxidation (RDX). In this study, we evaluated the applicability of black carbon-mediated reactions to a wider variety of contaminant structures, including nitrated and halogenated aromatic compounds, halogenated heterocyclic aromatic compounds, and halogenated alkanes. Among these compounds, black carbon-mediated transformation by sulfides over a 3-day time scale was limited to nitroaromatic compounds. The reaction for a series of substituted nitroaromatics proceeded by reduction, as indicated by formation of 3-bromoaniline from 3-bromonitrobenzene, and inverse correlation of log kobs with energy of the lowest unoccupied molecular orbital (ELUMO). The log kobs was correlated with sorbed sulfide concentration, but no reduction of 3-bromonitrobenzene was observed in the presence of graphite and sulfite, thiosulfate, or polysulfides. Whereas nitroglycerin reduction occurred in an electrochemical cell containing sheet graphite electrodes in which the reagents were placed in separate compartments, nitroaromatic reduction only occurred when sulfides were present in the same compartment. The results suggest that black carbon-mediated reduction of sorbed nitroaromatics by sulfides involves electron transfer directly from sorbed sulfides rather than transfer of electrons through conductive carbon regions. The existence of three different reaction pathways suggests a complexity to the sulfide-carbon system compared to the iron-carbon system, where contaminants are reduced by electron transfer through conductive carbon regions.