Concentrations Of Hydrophobic Organic Contaminants Research Articles

Determining buffering capacity of polydimethylsiloxane-based passive dosing for hydrophobic organic compounds in large-volume bioassays

Polydimethylsiloxane (PDMS) is the most widely used material for passive dosing. However, the ability of PDMS to maintain constant water concentrations of chemicals in large-volume bioassays was insufficiently investigated. In this study, we proposed a kinetic-based method to determine the buffering capacity of PDMS for maintaining constant water concentrations of hydrophobic organic contaminants (HOCs) in large-volume bioassays. A good correlation between log Kow and PDMS-water partitioning coefficients (log KPW) was observed for HOCs with log Kow values ranging from 3.30 to 7.42. For low-molecular-weight HOCs, volatile loss was identified as the primary cause of unstable water concentrations in passive dosing systems. Slow desorption from PDMS resulted in a reduction of water concentrations for high-molecular-weight HOCs. The volume ratio of PDMS to water (RV) was the key factor controlling buffering capacity. As such, buffering capacity was defined as the minimum RV required to maintain 90% of the initial water concentration and was determined to be 0.0076–0.032 for six representative HOCs. Finally, passive dosing with an RV of 0.014 was validated to effectively maintain water concentrations of phenanthrene in 2-L and 96-h toxicity tests with adult mosquitofish. By determining buffering capacity of PDMS, this study recommended specific RV values for cost-efficient implementation of passive dosing approaches in aquatic toxicology, particularly in large-volume bioassays.

Hydrophobic organic contaminants affiliated with polymer-specific microplastics in urban river tributaries and estuaries

Exposure to microplastics (MPs) and hydrophobic organic contaminants (HOCs) combined at high concentrations may induce adverse effects to aquatic organisms in laboratory-scale studies. To determine environmentally relevant concentrations of HOCs in MPs, it is essential to understand the occurrence of MP-affiliated HOCs in the aquatic environment. Here we report the occurrences of HOCs affiliated with polymer-specific floating MPs from 12 tributaries and three estuaries in the Pearl River Delta, South China. Target HOCs include nine synthetic musks (SMs), 14 ultraviolet adsorbents (UVAs), 15 polycyclic aromatic hydrocarbons (PAHs), eight polybrominated diphenyl ethers (PBDEs), and 14 polychlorinated biphenyls (PCBs). Average concentrations of MP-affiliated ∑9SM, ∑14UVA, ∑15PAH, ∑8PBDE, and ∑14PCB were 1790, 5550, 1090, 412, and 107 ng g−1, respectively. The average concentrations of HOCs affiliated with MPs of different polymer types were 9790, 7220, 72,500, and 55,800 ng g−1 for polyethylene (PE), polypropylene, polystyrene, and other MPs, respectively. As the concentration of PE was the highest among all MPs at the average concentration of 0.77 mg m−3, the monthly outflow of PE-affiliated HOCs accounted for the largest proportion (46 %) in the outflow of MP-affiliated HOCs (2.8 g) to the coastal ocean via three estuaries. These results suggest that HOCs were highly concentrated in MPs and varied among different chemicals and polymer types. Due to the differences of polymer characteristics and half-life of affiliated chemicals, future toxicology studies concerning exposure to these combined pollutants may need to specify polymer types and their affiliated chemicals.

The effect of microplastics on the depuration of hydrophobic organic contaminants in Daphnia magna: A quantitative model analysis

Microplastics are emerging pollutants that can absorb large amounts of hydrophobic organic contaminants (HOCs). However, no biodynamic model has yet been proposed to estimate their effects on HOC depuration in aquatic organisms, where the HOC concentrations are time-varying. In this work, a microplastic-inclusive biodynamic model was developed to estimate the depuration of HOCs via ingestion of microplastics. Several key parameters of the model were redefined to determine the dynamic HOC concentrations. Through the parameterized model, the relative contributions of dermal and intestinal pathways can be distinguished. Moreover, the model was verified and the vector effect of microplastics was confirmed by studying the depuration of polychlorinated biphenyl (PCB) in Daphnia magna (D. magna) with different sizes of polystyrene (PS) microplastics. The results showed that microplastics contributed to the elimination kinetics of PCBs because of the fugacity gradient between the ingested microplastics and the biota lipids, especially for the less hydrophobic PCBs. The intestinal elimination pathway via microplastics would promote overall PCB elimination, contributing 37–41 % and 29–35 % to the total flux in the 100 nm and 2 μm polystyrene (PS) microplastic suspensions, respectively. Furthermore, the contribution of microplastic uptake to total HOC elimination increased with decreasing microplastic size in water, suggesting that microplastics may protect organisms from HOC risks. In conclusion, this work demonstrated that the proposed biodynamic model is capable of estimating the dynamic depuration of HOCs for aquatic organisms. The results can shed light on a better understanding of the vector effects of microplastics.

Ethylene vinyl acetate copolymer is an efficient and alternative passive sampler of hydrophobic organic contaminants. A comparison with silicone rubber

There is a growing demand for assessing the concentrations of Hydrophobic Organic Contaminants (HOCs) in aquatic environments, including Persistent Organic Pollutants (POPs). The hydrophobicity of POPs challenges their quantification in waters due to the sub-trace concentrations, especially when using conventional spot sampling. The results from the conventional samples are only a “snapshot” of the concentrations (if detected) at the specific sampling moment. Contrary, passive sampling provides average concentration levels over weeks or months from the quantification of accumulated pollutants during the deployment period. The present work compared ethylene vinyl acetate (EVA) and silicon rubber (SR) as monophasic passive samplers to measure dissolved concentrations of HOCs. Four classes of POPs were studied: (i) polychlorinated dibenzo-p-dioxins (PCDDs), (ii) polychlorinated dibenzofurans (PCDFs), (iii) polychlorinated biphenyls (PCBs), including the dioxin-like congeners, and (iv) the polybrominated diphenyl ethers (PBDEs). The polymer-water partition coefficients (Kpw), determined by the cosolvent and crossed calibrations, were, on average, one logarithmic unit larger in EVA than in the SR. The diffusion coefficients (Dp) estimated by the “film-stacking” method were, on average, two orders of magnitude smaller in the EVA than in the SR. For both polymers, the theoretical model of mass transfer resistance confirmed that the water boundary layer controlled the absorption, thus allowing the use of Performance Reference Compounds (PRCs) to estimate the in-situ sampling rates.Larger Kpw's in EVA may be an advantage because they imply longer time scales to reach equilibrium, higher absorption capacities and hence a higher absorbed contaminant mass, especially for compounds that reach equilibrium relatively faster (log Kow < 5). In addition, the longer times to attain equilibrium for EVA maintain this sampler longer in the linear phase of absorption, and the time-weighted average concentration may only be assessed in this phase when the compounds have not yet reached equilibrium.

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.

Microplastic-water partitioning of two states halogenated PAHs: Solute and sol

The complex interactions of contaminants with microplastics significantly affect ecological risk assessments. Studies of the sorption behavior of freely dissolved hydrophobic organic contaminants (HOCs) on microplastics are common. However, concentrations of HOCs in the actual aquatic environment sometimes exceed their water solubility. A possible explanation is that a microplastic-sol-water three-phase medium (TPM) is formed in the actual water environment. Both states HOCs (in solute and sol) have the potential to migrate to particles suspended in water. To confirm this view, four kinds of microplastics and eight halogenated polycyclic aromatic hydrocarbons (HPAHs) were selected to examine the partitioning of HPAHs between microplastics and water (sol and solute). Both monolayer and multilayer coverage of HPAHs onto microplastics occurred, and chemical sorption dominated the pseudo−sorption mechanism. The microplastic−water partition ratios of HPAHs (0.12–0.74) were approximately four to five orders of magnitude lower than their corresponding KOW values, suggesting that mechanisms other than sorption were involved. Apparently, the sol HPAHs contributed almost identically large increments to both microplastics and water, and closed the gap. For microplastic−supported HPAHs, the contribution of the sol fraction was more than triple that of the dissolved fraction; the key influencing factor was the water solubility of HPAHs.

The biological pump effects of phytoplankton on the occurrence and benthic bioaccumulation of hydrophobic organic contaminants (HOCs) in a hypereutrophic lake

The distribution of hydrophobic organic contaminants (HOCs) in eutrophic ecosystems has been widely studied, but how phytoplankton blooms affect their occurrence and benthic bioaccumulation is poorly understood. To fill this knowledge gap, the biological pump effects of phytoplankton on the fate of organochlorine pesticides (OCPs) and polycyclic aromatic hydrocarbons (PAHs) in sediments and benthos (Corbicula fluminea) from Lake Taihu, a hypereutrophic lake in China, were identified. The spatial-temporal distribution of HOCs suggests that higher phytoplankton biomass, coupled with sediment organic matter (SOM) content, greatly increased the concentration of HOCs in sediments in both winter and summer seasons. This could be attributed to the biological pump effects sequestering more HOCs from water to sediments with settling phytoplankton, especially during the summer. The biological pump effects further promoted the uptake of sediment-bound HOCs by benthos. The significant positive relationships between concentrations of HOCs in sediments and benthos were observed during the winter dormancy phase of benthos. Furthermore, the benthic bioaccumulation of HOCs could be strengthened by phytoplankton, due to their contribution to SOM and the following increased bioavailability of HOCs in sediments. Further research is needed to elucidate the phytoplankton biological pump effects on the fate of HOCs in benthic food chain, especially for hypereutrophic waters.

Application of equilibrium passive sampling to profile pore water and accessible concentrations of hydrophobic organic contaminants in Danube sediments

Total concentrations of hydrophobic organic contaminants (HOCs) in sediment present a poor quality assessment parameter for aquatic organism exposure and environmental risk because they do not reflect contaminant bioavailability. The bioavailability issue of HOCs in sediments can be addressed by application of multi-ratio equilibrium passive sampling (EPS). In this study, riverbed sediment samples were collected during the Joint Danube Survey at 9 locations along the Danube River in 2013. Samples were ex-situ equilibrated with silicone passive samplers. Desorption isotherms were constructed, yielding two endpoints: pore water (CW:0) and accessible (CAS:0) concentration of polychlorinated biphenyls (PCBs), organochlorine pesticides (OCPs), polycyclic aromatic hydrocarbons (PAHs) and polybrominated diphenyl ethers in sediment. CW:0 concentrations of DDT and its breakdown products exhibited elevated levels in the low Danube, with the maximum in the river delta. Other investigated HOCs did not show any clear spatial trends along the river, and only a moderate CW:0 variability. CAS:0 in sediment ranged from 10 to 90% of the total concentration in sediment. CW:0 was compared with freely dissolved concentration in the overlaying surface water, measured likewise by passive sampling. The comparison indicated potential compound release from sediment to the water phase for PAHs with less than four aromatic rings, and for remaining HOCs either equilibrium between sediment and water, or potential compound deposition in sediment. Sorption partition coefficients of HOC to organic carbon correlated well with octanol-water partition coefficients (KOW), showing stronger sorption of PAHs to sediment than that of PCBs and OCPs having equal logKOW. Comparison of CW:0 values with European environmental quality standards indicated potential exceedance for hexachlorobenzene, fluoranthene and benzo[a]pyrene at several sites. The study demonstrates the utility of passive sampling as an innovative approach for risk-oriented monitoring of HOCs in river catchments.

Unraveling the Relationship between the Concentrations of Hydrophobic Organic Contaminants in Freshwater Fish of Different Trophic Levels and Water Using Passive Sampling.

The concentrations of hydrophobic organic compounds (HOCs) in aquatic biota are used for compliance, as well as time and spatial trend monitoring in the aqueous environment (European Union water framework directive, OSPAR). Because of trophic magnification in the food chain, the thermodynamic levels of HOCs, for example, polychlorinated biphenyl congeners, dichlorodiphenyltrichloroethane, and brominated diphenyl ether congeners, in higher trophic level (TL) organisms are expected to be strongly elevated above those in water. This work compares lipid-based concentrations at equilibrium with the water phase derived from aqueous passive sampling (CL⇌water) with the lipid-based concentrations in fillet and liver of fish (CL) at different TLs for three water bodies in the Czech Republic and Slovakia. The CL values of HOCs in fish were near CL⇌water, only after trophic magnification up to TL = 4. For fish at lower TL, CL progressively decreased relative to CL⇌water as KOW of HOCs increased above 106. The CL value decreasing toward the bottom of the food chain suggests nonequilibrium for primary producers (algae), which is in agreement with modeling passive HOC uptake by algae. Because trophic magnification and the resulting CL in fish exhibit large natural variability, CL⇌water is a viable alternative for monitoring HOCs using fish, showing a twofold lower confidence range and requiring less samples.

Assessing Benthic Bioaccumulation of Polychlorinated Dioxins/Furans and Polychlorinated Biphenyls in the Lower Passaic River (NJ, USA) Based on In Situ Passive Sampling.

Passive sampling has emerged as a promising tool to assess the presence of hydrophobic organic contaminants (HOC) in water, sediment, and biota, such as polychlorinated dibenzo-p-dioxins/furans (PCDD/Fs) or polychlorinated biphenyls (PCBs). Previous work evaluated the ability of passive samplers to predict the bioavailability of sedimentary HOCs mostly in the laboratory, often for marine organisms. The present study assessed the use of low-density polyethylene (LDPE) to derive freely dissolved concentrations of PCDD/Fs and PCBs in porewater in situ versus ex situ and in river water. An LDPE-based multisampler system was deployed at 4 locations along the lower Passaic River (NJ, USA) in sediment and the water column, where sediment and benthic species samples were also collected. Good agreement was generally observed for PCDD/F and PCB concentrations comparing in situ and ex situ approaches (within 0.30-39%). Significant linear relationships were derived between log LDPE-based and log lipid-based concentrations of PCDD/Fs and PCBs. The in situ multisampler system showed promise to derive HOC concentrations in porewater and river water and to predict the bioaccumulation potential of HOCs in benthic biota. Environ Toxicol Chem 2020;39:1174-1185. © 2020 SETAC.

Microplastic Intake, Its Biotic Drivers, and Hydrophobic Organic Contaminant Levels in the Baltic Herring

It is commonly accepted that microplastic (MP) ingestion can lead to lower food intake and bioaccumulation of hydrophobic organic contaminants (HOCs) in aquatic organisms. However, causal links between MP and contaminant levels in biota are poorly understood and in situ data are very limited. Here, we investigated whether HOC concentrations in herring muscle tissue (Clupea harengus membras) are related to MP ingestion using fish caught along the West coast of the Baltic Sea. The MP occurrence exhibited a large geographic variability, with MP found in 22.3% of the fish examined, and the population average being 0.9 MP ind-1. However, when only individuals containing MP were considered, the average MP burden was 3.9 MP ind-1. We also found that MP burden decreased with reproductive stage of the fish but increased with its body size. To predict MP abundance in fish guts, we constructed a mass-balance model using literature data on MP in the water column and physiological rates on ingestion and gut evacuation for clupeids of a similar size. The model output was in agreement with the observed values, thus supporting the validity of the results. Contaminant concentrations in the muscle tissue varied substantially across the study area but were unrelated to the MP levels in fish, suggesting a lack of direct links between the levels of HOCs and MP ingestion. Thus, despite their ubiquity, MP are unlikely to have a measurable impact on food intake or the total body burden of hydrophobic contaminants in Baltic herring.

Using the HPTLC-bioluminescence bacteria assay for the determination of acute toxicities in marine sediments and its eligibility as a monitoring assessment tool

For an integrated ecological risk assessment of marine sediment contamination, the determination of target-compound concentrations by e.g. mass spectrometric methods is not sufficient to explain sediment toxicity. Due to the presence of a multitude of environmental contaminants in this complex matrix causing a mixed toxicity, the identification and assessment of main toxicants is a challenge. One approach in identifying main toxicants is the application of effect-directed analysis (EDA). In this study, an EDA approach was developed using high performance thin layer chromatography (HPTLC) coupled to bioluminescence bacteria detection with Aliivibrio fischeri for the determination of marine sediments acute toxicity. In a first attempt, the HPTLC separation was optimized with a fast, two-step gradient to separate main hydrophobic organic contaminant (HOC) classes found in marine sediments. An easy-to-use evaluation script for the resulting bioluminescence inhibition images was programed using R. The developed method was applied to sediment extracts of two different sample sets: (i) Fourteen marine sediment samples from the German Bight representing a wide range of contaminant loads and sediment properties and (ii) sediment samples from a core representing temporal trends of contamination. Results from the HPTLC-bioluminescence bacteria assay were compared to HOC concentrations determined by GC-MS/MS. A correlation of the determined inhibition Γ-values for the PAH inhibition zone to PAH concentrations showed a very good agreement (R2 = 0.91). The results of this study were used to evaluate the suitability of the EDA approach to be used as an assessment tool for marine sediments.

PAHs, pesticides, personal care products and plastic additives in plastic debris from Spanish Mediterranean beaches

In this study the role of plastic debris as a pollution vector has been evaluated by determining the concentrations of hydrophobic organic contaminants in polymers from three Western Mediterranean coastal areas as well as their potential transfer to seawater. Plastic debris was sampled at three Iberian Peninsula Southeastern beaches, each affected by different predominant anthropogenic activities (tourism, agriculture, urban activities, transport and industry). Plastic debris was characterized by attenuated total reflection Fourier-transform infrared spectrometry. The organic contaminants were extracted from plastics by ultrasonic extraction with methanol and quantified by stir bar sorptive extraction coupled to gas chromatography–mass spectrometry (GC–MS). In two areas, the desorption of these contaminants from plastic debris to seawater during 24 h was also evaluated. The contaminant groups considered in this study (polycyclic aromatic hydrocarbons (PAHs), personal care products (PCPs), current use pesticides (CUPs), organochlorinated compounds (OCPs, including polychlorinated biphenyls and organochlorinated pesticides) and plastic additives were found in polymers from the three areas. The most abundant contaminants were plastic additives and PCPs, underlining the relevance of the leaching of plastic components, and urban and tourism activities as typical pollution sources in the coastal areas. In general, large piece-to-piece variability was found for all polymers and areas mainly as a consequence of their different origin, exposition time, use and surface-to-volume ratio. This fact difficulted the visualization of significant differences between polymers or areas, but for CUPs, whose concentrations were significantly higher in Cape Cope than in the other areas due to the influence of close agricultural activities. PCPs and CUPs were desorbed partially in seawater for 24 h, particularly the most hydrophilic compounds such as triazines and other CUPs. However, a significant fraction of other contaminants (mainly PAHs) was retained, which suggests they can be transported far away from their origin.

Evaluation of passive sampling polymers and nonequilibrium adjustment methods in a multiyear surveillance of sediment porewater PCBs.

Polymeric passive sampling devices are increasingly used to measure low-level, freely dissolved concentrations of hydrophobic organic contaminants in environmental waters. A range of polymers have been used for this purpose, and several different methods of accounting for nonequilibrium using performance reference compounds (PRCs) have been proposed. The present study explores the practical impacts of these decisions in an applied context using results from a multiyear passive sampling surveillance of polychlorinated biphenyl concentrations in sediment porewater at a contaminated marsh amended with activated carbon (AC) sorbent materials. In a series of 5 sampling events spanning almost 2 yr, we deployed polyoxymethylene and polyethylene samplers and calculated porewater concentrations with 5 different PRC adjustment methods. The results provide a basis for evaluating amendment performance by showing reductions of 34 to 97% in amended sediment porewater concentrations. They also provide a quantitative underpinning for discussions of the differences between sampling polymers, selection of PRCs, generation of high-resolution vertical profiles of porewater concentrations, and a comparison of PRC adjustment methods. For unamended sediment, older methods based on first-order kinetics agreed well with a recently developed method based on diffusion into and out of sediment beds. However, the sediment diffusion method did not work well for the sediments amended with AC. Environ Toxicol Chem 2018;37:2487-2495. © 2018 SETAC.

Role of biochar in biodegradation of nonylphenol in sediment: Increasing microbial activity versus decreasing bioavailability

The observed strong sorption of hydrophobic organic contaminants (HOCs) to biochar presents potential implications for HOCs bioavailability and bioaccessibility in sediments, while biochar could impact sediment microbial ecology. However, the comprehensive study on the effects of biochar on HOC biodegradation coupled with bioavailability and microbial ecology are rarely documented. In this paper, the effects of biochar on the biodegradation of nonylphenol (NP) were investigated using 3 different NP concentrations (20, 50 and 500 mg/Kg) in sediments amended with different percentage of rice straw biochar (RC). Results showed that the influence of RC on NP biodegradation varied with different NP concentrations. At low NP concentrations, RC suppressed NP biodegradation by reducing NP bioavailability, while at high NP concentrations, moderate RC addition promoted biodegradation by reducing toxicity of NP to microbes. The effects of NP on microbial community structures were significant (P < 0.01), but those of RC were not significant (P > 0.05). The RC affected microorganisms through altering NP toxicity, microbial quantity and activity, but not microbial community structures. This study indicated that there could be an optimal biochar percentage in biochar-sediment systems at different HOC concentrations, which strengthened HOC biodegradation process and accelerated biodegradation rate, forming adsorption-biodegradation coupled bioremediation.

Assessing the influence of confounding biological factors when estimating bioaccumulation of PCBs with passive samplers in aquatic ecosystems

Passive samplers are promising surrogates for organisms, mimicking bioaccumulation. However, several biological characteristics disturb the passive partitioning process in organisms by accelerating or restraining bioaccumulation, resulting in species-specific body residues of hydrophobic organic contaminants (HOCs). In addition to site-specific characteristics and HOC concentrations, age, sex, diet, biotransformation capability and habitat-specific characteristics may affect body residues.Two passive sampler types, polyethylene (PE) and polydimethylsiloxane (PDMS) were deployed in a PCB-contaminated freshwater lake water and sediment, respectively, to assess their bioaccumulation prediction capacity. In order to understand the importance of biological characteristics in the bioaccumulation process, we explored bioaccumulation in biota from plants and plankton to mussels and fish. The PCB concentrations in the PE sheet reflected the bioavailable concentration of PCBs slightly better than those in the PDMS samplers. Passive samplers were good predictors of PCB concentrations in fish, whereas concentrations in algae and invertebrates were overestimated. When comparing the measured concentrations in biota to the estimated concentrations using the PE samplers, the average regression slope was 0.87 for all biota and 1.22 for fish, and average modeling efficiency (EF) was 3.02 for all biota and 0.6 for fish. The best model performance was achieved for fish in trophic levels 3–4. Bioaccumulation was species-specific and dependent on the trophic level and diet. Closer examination revealed that metabolic capability changes during the life span, and source of nutrition determined the biomagnification of HOCs, which differed between the fish species. Thus, species composition and available prey selection compose a unique bioaccumulation scenario and the resulting body residues. Due to the existing variation in body residues derived from passive samplers, extrapolating the results from one to another ecosystem must be done with caution. Passive samplers, however, offer a very powerful tool for risk assessment on the ecosystem level.

Predicted effectiveness of in-situ activated carbon amendment for field sediment sites with variable site- and compound-specific characteristics

A growing body of evidence shows that the effectiveness of in-situ activated carbon (AC) amendment to treat hydrophobic organic contaminants (HOCs) in sediments can be reliably predicted using a mass transfer modeling approach. This study analyzes available field data for characterizing AC-sediment distribution after mechanical mixing of AC into sediment. Those distributions are used to develop an HOC mass transfer model that accounts for plausible heterogeneities resulting from mixing of AC into sediment. The model is applied to ten field sites in the U.S. and Europe with 2–3 representative HOCs from each site using site- and HOC-specific model parameters collected from the literature. The model predicts that the AC amendment reduces the pore-water HOC concentrations by more than 95% fifteen years after AC deployment for 18 of the 25 total simulated cases when the AC is applied at doses of 1.5 times sediment total organic carbon content with an upper limit of 5 dry wt%. The predicted effectiveness shows negative correlation with the HOC octanol–water partitioning coefficients and the sediment-water distribution coefficients, and positive correlation with the effectiveness calculated based on equilibrium coefficients of sediment and AC, suggesting the possibility for use of the values for screening-level assessments.

Review of polyoxymethylene passive sampling methods for quantifying freely dissolved porewater concentrations of hydrophobic organic contaminants.

Meth ods involving polyoxymethylene (POM) as a passive sampler are increasing in popularity to assess contaminant freely dissolved porewater concentrations in soils and sediments. These methods require contaminant-specific POM-water partition coefficients, KPOM . Certain methods for determining KPOM perform reproducibly (within 0.2 log units). However, other methods can give highly varying KPOM values (up to 2 log units), especially for polycyclic aromatic hydrocarbons (PAHs). To account for this variation, the authors tested the influence of key methodological components in KPOM determinations, including POM thickness, extraction procedures, and environmental temperature and salinity, as well as uptake kinetics in mixed and static systems. All inconsistencies in the peer-reviewed literature can be accounted for by the likelihood that thick POM materials (500 μm or thicker) do not achieve equilibrium (causing negative biases up to 1 log unit), or that certain POM extraction procedures do not ensure quantitative extraction (causing negative biases up to 2 log units). Temperature can also influence KPOM , although all previous literature studies were carried out at room temperature. The present study found that KPOM values at room temperature are independent (within 0.2 log units) of POM manufacture method, of thickness between 17 μm and 80 μm, and of salinity between 0% and 10%. Regarding kinetics, monochloro- to hexachloro-polychlorinated biphenyls (PCBs) were within 0.2 log units of equilibrium after 28 d in the mixed system, but only dichloro-PCBs achieved near equilibrium after 126 d in the static system. Based on these insights, recommended methods and KPOM values to facilitate interlaboratory reproducibility are presented.

Using performance reference compound-corrected polyethylene passive samplers and caged bivalves to measure hydrophobic contaminants of concern in urban coastal seawaters

Low-density polyethylene (PE) passive samplers containing performance reference compounds (PRCs) were deployed at multiple depths in two urban coastal marine locations to estimate dissolved concentrations of hydrophobic organic contaminants (HOCs), including dichlorodiphenyltrichloroethane (DDT) and its metabolites, polychlorinated biphenyl (PCB) congeners, and polybrominated flame retardants. PE samplers pre-loaded with PRCs were deployed at the surface, mid-column, and near bottom at sites representing the nearshore continental shelf off southern California (Santa Monica Bay, USA) and a mega commercial port (Los Angeles Harbor). After correcting for fractional equilibration using PRCs, concentrations ranged up to 100pgL−1 for PCBs and polybrominated diphenyl ethers (PBDEs), 500pgL−1 for DDMU and 300pgL−1 for DDNU, and to 1000pgL−1 for p,p′-DDE. Seawater concentrations of DDTs and PCBs increased with depth, suggesting that bed sediments serve as the source of water column HOCs in Santa Monica Bay. In contrast, no discernable pattern between surface and near-bottom concentrations in Los Angeles Harbor was observed, which were also several-fold lower (DDTs: 45–300pgL−1, PCBs: 5–50pgL−1) than those in Santa Monica Bay (DDTs: 2–1100pgL−1, PCBs: 2–250pgL−1). Accumulation by mussels co-deployed with the PE samplers at select sites was strongly correlated with PE-estimated seawater concentrations, providing further evidence that these samplers are a viable alternative for monitoring of HOC exposure. Fractional equilibration observed with the PRCs increased with decreasing PRC molar volume indicating the importance of target compound physicochemical properties when estimating water column concentrations using passive samplers in situ.

Equilibrium and kinetic modeling of contaminant immobilization by activated carbon amended to sediments in the field

Addition of activated carbons (AC) to polluted sediments and soils is an attractive remediation technique aiming at reducing pore water concentrations of hydrophobic organic contaminants (HOCs). In this study, we present (pseudo-)equilibrium as well as kinetic parameters for sorption of a series of PAHs and PCBs to powdered and granular activated carbons (AC) after three different sediment treatments: sediment mixed with powdered AC (PAC), sediment mixed with granular AC (GAC), and addition of GAC followed by 2 d mixing and subsequent removal (‘sediment stripping’). Remediation efficiency was assessed by quantifying fluxes of PAHs towards SPME passive samplers inserted in the sediment top layer, which showed that the efficiency decreased in the order of PAC > GAC stripping > GAC addition. Sorption was very strong to PAC, with Log KAC (L/kg) values up to 10.5. Log KAC values for GAC ranged from 6.3–7.1 and 4.8–6.2 for PAHs and PCBs, respectively. Log KAC values for GAC in the stripped sediment were 7.4–8.6 and 5.8–7.7 for PAH and PCB. Apparent first order adsorption rate constants for GAC (kGAC) in the stripping scenario were calculated with a first-order kinetic model and ranged from 1.6 × 10−2 (PHE) to 1.7 × 10−5 d−1 (InP). Sorption affinity parameters did not change within 9 months post treatment, confirming the longer term effectiveness of AC in field applications for PAC and GAC.