Water Significantly Changes the Ring-Cleavage Process During Aqueous Photooxidation of Toluene.

As a major constituent of aromatic compounds, toluene exists widely in environmental aqueous phases. This research investigated the aqueous-phase OH oxidation of toluene to determine how liquid water changes the radical chemistry of ring-cleavage pathways. Results show that ring-cleavage pathways through the C7 bicyclic peroxy radical (BPR) account for about 70% of total aqueous-phase oxidation pathways, which is similar to that in the gas-phase oxidation. However, detailed ring-cleavage pathways in the aqueous phase change significantly compared with those in the gas phase as shown by the decreased production of glyoxal and methylglyoxal and the enhanced production of formic acid and acetic acid as primary products, which can be attributed to the presence of liquid water. Water facilitates the formation of the BPR whose structure is different from that in the gas-phase oxidation and results in different ring-cleavage pathways through hydrogen-shift reactions. Furthermore, water helps the hydration of acyl radicals formed by the BPR to produce organic acids. With the suggested ring-cleavage mechanisms, a box model can simulate aqueous-phase product distributions better than that with the classical ring-cleavage mechanisms. Given the influence of water on reaction mechanisms, aqueous-phase oxidation of hydrophobic organic compounds may be more important than previously assumed.

Evaluation of dimethyl sulfoxide (DMSO) as a co-solvent for toxicity testing of hydrophobic organic compounds.

Toxicity testing of hydrophobic compounds with low aqueous solubility remains challenging. Dimethyl sulfoxide (DMSO) is widely used as a co-solvent for toxicity testing of hydrophobic chemicals, but it may modulate chemical toxicity patterns. In this study, we critically evaluated the suitability of DMSO as a co-solvent for toxicity testing of hydrophobic organic compounds in aqueous solutions. As the toxicity measure, we used growth inhibition of a natural bacterial community, and the test toxicants included phenol, BTEX (benzene, toluene, ethylbenzene and xylene) and transformation products of polycyclic aromatic hydrocarbons (PAHs). We found that dose-response curves for phenol were unaffected by DMSO concentrations up to 10% (v/v) and that DMSO (5% v/v) did not affect the degree of bacterial growth inhibition for any of the other test compounds in short-term experiments (3.5 h). By contrast, marked co-solvent effects of DMSO were observed in the long-term assay (25 and 27 h). We therefore conclude that DMSO has excellent co-solvent properties for short-term (≤3.5 h) toxicity testing of sparingly water-soluble compounds and its application provides a simple, inexpensive approach for screening of various environmentally relevant hydrophobic chemicals. Importantly, the use of DMSO allows for generation of full dose-responses that may otherwise not be attained.

Development and evaluation of MTLSER and QSAR models for predicting polyethylene-water partition coefficients.

Current study was aimed to make further improvements in measuring low density polyethylene (LDPE) -water partition coefficient (KPE-w) for organic chemicals. Modified theoretical linear solvation energy relationship (MTLSER) model and quantitative structure activity relationship (QSAR) model were developed for predicting KPE-w values from chemical descriptors. With the MTLSER model, α (average molecular polarizability), µ (dipole moment) and q- (net charge of the most negative atoms) as significant variables were screened. With the QSAR model, main control factors of KPE-w values, such as CrippenLogP (Crippen octanol-water partition coefficient), CIC0 (neighborhood symmetry of 0-order) and GATS2p (Geary autocorrelation-lag2/weighted by polarizabilities) were studied. As per our best knowledge, this is the first attempt to predict polymer-water partition coefficient using the MTLSER model. Statistical parameters, correlation coefficient (R2) and cross-validation coefficients (Q2) were ranging from 0.811 to 0.951 and 0.761 to 0.949, respectively, which indicated that the models appropriately fit the results, and also showed robustness and predictive capacity. Mechanism interpretation suggested that the main factors governing the partition process between LDPE and water were the molecular polarizability and hydrophobicity. The results of this study provide an excellent tool for predicting log KPE-w values of most common hydrophobic organic compounds, within the applicability domains to reduce experimental cost and time for innovation.

Ecological Risk Assessment of HCH and DDT Residues in a Sediment Core from the Küçükçekmece Lagoon, Turkey.

The residues of organochlorine pesticides (HCHs and DDTs) in a dated (137Cs and 210Pb) sediment core from the Küçükçekmece Lagoon, an urban lake at the southern entrance of the future Canal Istanbul Project, an artificial watercourse, were analyzed with the gas chromatograph equipped with electron capture detector (GC 63Ni-ECD). Concentrations of ∑HCH and ∑DDT along the core varied between 0.4 and 469.4 (average 51.4) ng g-1 dw, and between 0.5 and 72.0 (average 7.4) ng g-1 dw, respectively. α-HCH was the predominant isomer (98%) and followed by γ-isomer (2%). The highest concentrations of technical HCH were found in the sediments dated 1963-1972, whilst the DDT concentrations had their maximum around 1945. The highest concentrations of γ-HCH and p,p'-DDT exceeded probable-effect level values which can lead to frequently cause adverse effects on aquatic biota.

Relationship between metabolic enzyme activities and bioaccumulation kinetics of PAHs in zebrafish (Danio rerio).

Many studies have investigated bioaccumulation and metabolism of polycyclic aromatic hydrocarbons (PAHs) in aquatic organisms. However, lack of studies investigated both processes simultaneously, and the interaction between these two processes is less understood so far. This study investigated the bioaccumulation kinetics of PAHs and metabolic enzyme activities, including total cytochrome P450 (CYPs) and total superoxide dismutase (T-SOD), in zebrafish. Mature zebrafish were exposed to the mixture of phenanthrene and anthracene under constant concentration maintained by passive dosing systems for 16days. The results showed that PAH concentrations in zebrafish experienced a peak value after exposure for 1.5days, and then decreased gradually. The bioaccumulation equilibrium was achieved after exposure for 12days. Both of the uptake rate constants (ku) and the elimination rate constants (ke) decreased after the peak value. The variation of PAH concentrations and metabolic enzyme activities in zebrafish had an interactive relationship. The activities of CYPs and T-SOD increased initially with the increase of PAH concentrations, but decreased to the lowest state when PAH concentrations reached the peak value. When the bioaccumulation equilibrium of PAHs was achieved, CYPs and T-SOD activities also reached the steady state. In general, CYPs and T-SOD activities were activated after exposure to PAHs. The decrease of PAH concentrations in zebrafish after the peak value may be attributed to the great drop of ku and the variation of CYPs activities. This study suggests that an interactive relationship exists between bioaccumulation kinetics of PAHs and metabolic enzyme activities in aquatic organisms.

Two-phase system model to predict hydrophobic organic compound partition to heterogeneous soil dissolved organic matter across China.

Soil dissolved organic matter (SDOM) is an important part of the DOM pool in terrestrial systems, influencing the transport and fate of many pollutants. In this study, SDOMs from different regions across China were compared by a series of spectroscopic methods, including UV-vis spectroscopy, fluorescence spectroscopy, and Fourier transform infrared (FTIR) spectroscopy, and the hydrophobicity was quantified by partition coefficients of SDOM in the aqueous two-phase system (KATPS). The molecular weight, aromaticity, and hydrophobicity of SDOM from different regions exhibited strong heterogeneity, KATPS combined with UV-vis and fluorescence indices can be readily used for differentiating heterogeneous SDOM, and SDOMs were compositionally and structurally different from DOMs in aquatic systems based on spectral characterization. Importantly, the two-phase system (TPS) model has only been validated by DOMs in freshwater systems, and good organic carbon‒water partition coefficient (KOC) predictive power (RMSE = 0.11) could be provided by the TPS model when applied to heterogeneous SDOM without calibration, showing its broad applicability. Our results demonstrate the applicability of the TPS model for predicting the sorption behavior of terrestrial DOM, broadening the application scope of the TPS model and indicating its potential as a routine model for the risk assessment of hydrophobic organic compounds (HOCs) in organic contaminated sites.

Predicting apparent adsorption capacity of sediment-amended activated carbon for hydrophobic organic contaminants using machine learning.

In-situ stabilization of hydrophobic organic compounds (HOCs) using activated carbon (AC) is a promising sediment remediation approach. However, predicting HOC adsorption capacity of sediment-amended AC remains a challenge because a prediction model is currently unavailable. Thus, the objective of this study was to develop machine learning models that could predict the apparent adsorption capacity of sediment-amended AC (KAC,apparent) for HOCs. These models were trained using 186 sets of experimental data obtained from the literature. The best-performing model among those employing various model frameworks, machine learning algorithms, and combination of candidate input features excellently predicted logKAC,apparent with a coefficient of determination of 0.94 on the test dataset. Its prediction results and experimental data for KAC,apparent agreed within 0.5 log units with few exceptions. Analysis of feature importance for the machine learning model revealed that KAC,apparent was strongly correlated with the hydrophobicity of HOCs and the particle size of AC, which agreed well with the current knowledge obtained from experimental and mechanistic assessments. On the other hand, correlation of KAC,apparent to sediment characteristics, duration of AC-sediment contact, and AC dose identified in the model disagreed with relevant arguments made in the literature, calling for further assessment in this subject. This study highlights the promising capability of machine learning in predicting adsorption capacity of AC in complex systems. It offers unique insights into the influence of model parameters on KAC,apparent.

Evaluation of the use of biochar to stabilize polycyclic aromatic hydrocarbons and phthalates in sediment.

Three types of biochar (BC) (mulberry biochar (MB), wheat straw biochar, and pine tree sawdust biochar) were prepared and used to stabilize hydrophobic organic compounds (HOCs) in contaminated sediment. The kinetics of HOC adsorption to the BCs had two distinct stages. The second stage adsorption process was longer for MB than the other BCs, presumably because MB contained large pores, mesopores, and micropores. The adsorption isotherms for the three BCs were described well by the Freundlich model. The adsorption capacities of MB, WS and PT for HOCs ranged between 106.7 and 1202 µg/g, 135.1 and 1002 µg/g, and 255.6 and 909 µg/g, respectively. The apparent HOC adsorption coefficients (KBC-w) for the three BCs were determined from the isotherm data and were similar. The HOC logKOW values correlated well with the logKBC-w values. In sediment slurry experiments, HOCs were much more effectively stabilized by MB than wheat straw and pine tree sawdust biochar. This was probably because of the MB pore characteristics that favored adsorption of HOCs of various molecular sizes. The Fourier-transform infrared and Raman spectra indicated that the main binding mechanisms were hydrogen boding, hydrophobic interactions, and π-π interactions. MB was found to be a possible agent for stabilizing HOCs in contaminated sediment. HOCs in sediment slurry continued to become adsorbed to MB for a long time, indicating that relatively long reaction times should be allowed for in situ remediation using MB.

Filtration of biopolymer PHB particles loaded with synthetic musks does not cause significant bioaccumulation in marine mussels.

The role of the biopolymer polyhydroxybutyrate (PHB, <250 µm) as a vehicle of a synthetic musks mixture (celestolide, galaxolide, tonalide, musk xylene, musk moskene and musk ketone) to Mytilus galloprovincialis was investigated. For 30 days, virgin PHB, virgin PHB+musks (6.82 µg g-1) and weathered PHB+musks, were daily spiked into tanks containing mussels, followed by a 10-day depuration period. Water and tissues samples were collected to measure exposure concentrations and accumulation in tissues. Mussels were able to actively filter microplastics in suspension but the concentration of the musks found in tissues (celestolide, galaxolide, tonalide) were markedly lower than the spiked concentration. Estimated Trophic Transfer Factors suggest that PHB will only play a minor role on musks accumulation in marine mussels, even if our results suggest a slightly extended persistence in tissues of musks loaded to weathered PHB.

Microplastics and associated organic pollutants in beach sediments from the Gulf of Guinea (SE Atlantic) coastal ecosystems.

Microplastics (MPs) are emerging pollutants of global concern due to their pervasiveness, sorptive capacity for organic and inorganic pollutants, and direct and indirect toxicity to organisms and ecosystems. This study aimed to assess the concentration and the statistical difference in the concentration of microplastic-sorbed organic pollutants from two ecosystems, the marine and estuarine lagoon. Surface sediment from the estuarine lagoon and marine ecosystems were sampled for microplastics (1-5 mm). A total of 3680 MP particles were collected. The plastics were analyzed for polycyclic aromatic hydrocarbons (PAHs), polychlorinated biphenyls (PCBs) and organochlorine pesticides (OCPs). ∑PAHs, ∑PCBs and ∑OCPs were between 0.00 and 0.32 mg/kg, 0.00-0.53 mg/kg and 0.04-2.02 mg/kg, respectively. The results showed a correlation of -0.2, 0.8 and 0.2 between the number of MPs and the concentration of PAHs, PCBs and OCPs, respectively, suggesting that the potential risk of accumulation of plastic-sorbed PCBs is higher than those of OCPs and PAHs. Mann Whitney U test (at 95% confidence level) indicated no statistical difference in the concentration of organic pollutants in lagoon and beach MPs. In addition, we found no significant difference in the accumulation of organic pollutants in MPs from beach drift and high waterlines. The result suggests that the concentration of microplastics-sorbed organic pollutants in both ecosystems is comparable and likely to pose similar potential risks. We recommend that plastic pollution in all ecosystems require attention.

Basic principles and problems in decontamination of natural disperse systems. The electrokinetic treatment of soils.

The main chemical, biological and physical methods of deactivation of such natural disperse systems as soils and bottom sediments from charged and uncharged pollutants are analyzed. The impact of properties of natural disperse systems and the substances causing their contamination on the expediency of using some specific detoxication method is considered. The peculiarities of ex-situ and in-situ treatment are indicated. It is shown that in many cases the use of such well-known methods as washing, flushing, solidification/stabilization, thermal processing, steam extraction, and others is effective and rational. Advantages and disadvantages of considered methods are presented. Much attention is devoted to the fine disperse systems with low aerodynamic and hydrodynamic permeations, which are most complicated from the viewpoint of decontamination and best suited for the use of the electrokinetic decontamination method. Electrokinetic treatment demonstrates an optimal compromise between the degree of decontamination and energy consumption in comparison with other methods, for example, thermal processing. The performance efficiency by using this method is studied depending on such characteristics of dispersions subjected to decontamination as the initial soil pH value, its exchange capacity and buffer capacity. It has been shown that one of the ecologically acceptable ways to accelerate and enhance electrokinetic remediation is the electrohydrodynamic pH control by selecting the pumping rate of neutral electrolytes in electrode chambers. Examples of applying this method for remediation of different types of soil from heavy metals and hydrophobic organic compounds are presented.

Promotion of the biodegradation of phenanthrene adsorbed on microplastics by the functional bacterial consortium QY1 in the presence of humic acid: Bioavailability and toxicity evaluation.

The adsorption of hydrophobic organic compounds (HOCs) by microplastics (MPs) has attracted great attention in recent years. However, the ultimate environmental fate of the HOCs sorbed on MPs (HOCs-MPs) is poorly understood. In this work, we investigated the potential influence of the biotransformation process on the environmental fate of phenanthrene (PHE, a model HOC) sorbed on MPs (PHE-MPs) under the existence of humic acid (HA, the main ingredient of dissolved organic matter (DOM)) in the aquatic environment. The results indicated that the adsorption behavior of PHE on MPs decreased its bioavailability and thus inhibited its biotransformation efficiency. However, HA significantly promoted the biodegradation rate and percentage of PHE-MPs. This was probably because HA improved the desorption of PHE from MPs, which promoted the acquisition of PHE by bacteria from the aqueous phase. Further, HA dramatically increased the bacterial community diversity and richness and altered the community composition. The richness of some PHE-degrading bacteria, such as Methylobacillus and Sphingomonas, significantly increased, which may also be an important factor for promoting PHE biodegradation. Molecular ecological network analysis implied that HA enhanced the modularity and complexity of bacterial interaction networks, which was beneficial to maintaining the functional stability of the consortium QY1. Besides, HA decreased the cytotoxicity of functional microbes induced by HOCs-MPs. This work broadens our knowledge of the environmental fate of HOCs-MPs and interactions of MPs, HOCs, DOMs and functional microbial consortiums in aqueous environments.

Performance comparison of silicone and low-density polyethylene as passive samplers in a global monitoring network for aquatic organic contaminants.

Contamination with hydrophobic organic compounds (HOCs) such as persistent organic pollutants negatively affects global water quality. Accurate and globally comparable monitoring data are required to understand better the HOCs distribution and environmental fate. We present the first results of a proof-of-concept global monitoring campaign, the Aquatic Global Passive Sampling initiative (AQUA-GAPS), performed between 2016 and 2020, for assessing trends of freely dissolved HOC concentrations in global surface waters. One of the pilot campaign aims was to compare performance characteristics of silicone (SSP) and low-density polyethylene (PE) sheets co-deployed in parallel under identical conditions, i.e. at the same site, using the same deployment design, and for an equal period. Individual exposures lasted between 36 and 400 days, and samples were collected from 22 freshwater and 40 marine locations. The sampler inter-comparability is based on a rationale of common underlying principles, i.e. HOC diffusion through a water boundary layer (WBL) and absorption by the polymer. In the integrative uptake phase, equal surface-specific uptake in both samplers was observed for HOCs with a molecular volume less than 300 Å3. For those HOCs, transport in the WBL controls the uptake as mass transfer in the polymer is over 20-times faster. In such a case, sampled HOC mass can be converted into aqueous concentrations using available models derived for WBL-controlled sampling using performance reference compounds. In contrast, for larger molecules, surface-specific uptake to PE was lower than to SSP. Diffusion in PE is slower than in SSP, and it is likely that for large molecules, diffusion in PE limits the transport from water to the sampler, complicating the interpretation. Although both samplers provided mostly well comparable results, we recommend, based on simpler practical handling, simpler data interpretation, and better availability of reliable polymer-water partition coefficients, silicone-based samplers for future operation in the worldwide monitoring programme.

Exploring the partitioning of hydrophobic organic compounds between water, suspended particulate matter and diverse fish species in a German river ecosystem.

Background: Bioaccumulation of hydrophobic organic compounds (HOCs) along freshwater food chains is a major environmental concern as top predators in food webs are relevant for human consumption. To characterize and manage the associated risks, considerable numbers of organisms are sampled regularly for monitoring purposes. However, ethical and financial issues call for an alternative, more generic and more robust approach for assessing the internal exposure of fish that circumvents large variability in biota sampling due to interindividual differences. Passive sampling devices (PSDs) offer a fugacity-based approach for pollutant enrichment from different abiotic environmental compartments with a subsequent estimation of bioaccumulation in fish which we explored and compared to HOC concentrations in fish as determined using traditional approaches. Results: In this study, concentrations in silicone-based PSDs applied to the water phase and suspended particulate matter (SPM) of a river polluted with HOCs were used to estimate the concentration in model lipids at thermodynamic equilibrium with either environmental compartment. For comparison, muscle tissue of seven fish species (trophic level 1.8 to 2.8) was extracted using traditional exhaustive solvent extraction, and the lipid-normalized concentrations of HOCs were determined. The PSD-based data from SPM proved to be a more conservative estimator for HOCs accumulated in fish than those from water. Body length of the fish was found to be more suitable to describe increasing accumulation of HOCs than their trophic level as derived from stable isotope analysis and might offer a suitable alternative for future studies. Conclusions: By combining fugacity-based sampling in the abiotic environment, translation into corresponding concentrations in model lipids and body length as an indicator for increasing bioaccumulation in fish, we present a suggestion for a robust approach that may be a meaningful addition to conventional monitoring methods. This approach potentially increases the efficiency of existing monitoring programs without the need to regularly sacrifice vertebrate species. Supplementary Information: The online version contains supplementary material available at 10.1186/s12302-022-00644-w.

Prediction of hydrophobic organic compound partition to algal organic matter through the growth cycle of Microcystis aeruginosa.

Algal organic matter (AOM) is an important source for the dissolved organic matter (DOM) pool in aquatic systems, particularly in eutrophic waters. In this study, we reported the dynamic pattern of AOM hydrophobicity during the growth cycle of Microcystis aeruginosa using the partition coefficients of AOM in the aqueous two-phase system (KATPS) as a simple quantitative measure. AOM hydrophobicity had significant and non-monotonic changes during the growth cycle. It increased in the lag and early exponential phases, then decreased in the late exponential and stationary phases, and rebounded in the decline phase. AOM hydrophobicity determined using the resin fractionation, SUVA254, and nuclear magnetic resonance methods shared similar non-monotonic pattern. Nevertheless, the correlations among these indicators were poor. The partition behavior of polycyclic aromatic hydrocarbons and chlorobenzenes to AOM was assessed based the KATPS dataset and the two-phase system (TPS) model. The TPS model showed good prediction power for the partition behavior of AOM with an RMSE of 0.23, suggesting that it was applicable to AOM from Microcystis aeruginosa. Our results indicate that algae activity will influence the overall hydrophobicity of the DOM pool depending on the growth phase, resulting in changes in the bioavailability of hydrophobic organic compounds in aquatic systems.

Can the hydrophobic organic contaminants in the filtrate passing through 0.45 µm filter membranes reflect the water quality?

In the traditional water quality assessment, the concentration of total dissolved hydrophobic organic compounds (HOCs) passing through 0.45 µm filter membranes is usually used to evaluate the influence of HOCs on water quality. However, the bioavailability of dissolved organic matter (DOM)-associated and particle-associated HOCs is not considered. In the present work, pyrene, fulvic acid, and natural suspended particles (SPS) were used to simulate natural water (raw water). The immobilization and pyrene content in the tissues of D. magna caused by total pyrene in the raw water and those caused by freely dissolved pyrene with the concentration equal to the total dissolved pyrene in the filtrate of raw water were compared to determine whether the total dissolved pyrene concentration can reflect the water quality. The results indicated that when the DOM concentration was 5 mg C L-1 and the SPS concentration was higher than 0.2-0.4 g L-1, the bioavailability of pyrene was underestimated by the traditional water quality assessment because of the SPS-associated pyrene, and it was underestimated by 23.6-63.9% when SPS concentration was higher than 0.6 g L-1 due to the neglection of SPS-associated pyrene. Furthermore, the threshold value of SPS concentration was related to the SPS size and composition, and the effects of SPS and DOM on water quality were influenced by the concentration, size, and composition of SPS as well as the molecular weight of DOM. This study suggests that the traditional water quality assessment should be improved by comprehensively considering concentrations and characteristics of SPS and DOM.

Toxicokinetics of hydrophobic organic compounds in oligochaeta: A critical review.

Toxicokinetic studies appertain to the fundamental research of soil bioavailability. However, the research outcomes of aspects influencing uptake and elimination of hydrophobic organic compounds have not been summarized so far. In our review, a recapitulation of available toxicokinetic data (i.e. experimental conditions, if the steady state was reached, uptake and elimination rate constants, and bioaccumulation factors) is presented in well-arranged tables. Further, toxicokinetic models are overviewed in the schematic form. In the review, the required information could be quickly found and/or the experimental gaps easily identified. Generally a little is known about the effects of soil properties other than soil organic matter. Limited or no data are available about soil treatment, food supply during laboratory exposure, and metabolization in oligochaeta. The impact of these factors might be important especially for arable soils with typically low organic matter content but high consequences on humans. Besides these circumstances, other uncertainties between published studies have been found. Firstly, the scientific results are provided in heterogenous units: bioaccumulation factors as well as the rate constants are reported in dry or wet weight of soil and earthworms. The steady state is another critical factor because the time to reach the equilibrium is influenced not only by soil and compound characteristics but for example also by aging. Nevertheless, toxicokinetic studies bring irreplaceable information about the real situation in soil and our review help to define missing knowledge and estimate the scientific priorities.

Effect of suspended particles with different grain sizes on the bioaccumulation of PAHs by zebrafish (Danio rerio).

The physicochemical characteristics are different for suspended particles (SPS) with different sizes in rivers. Here, we studied the effect of SPS (1 g L-1) with three different sizes (63-106 µm, 20-63 µm, and <20 µm) on the bioaccumulation of deuterated polycyclic aromatic hydrocarbons (phenanthrene-d10, anthracene-d10, fluoranthene-d10 and pyrene-d10) in zebrafish using passive dosing devices to maintain the freely dissolved concentrations of PAHs-d10 constant in water. The results showed that all the three grain size SPS could be ingested by zebrafish, and there was no significant difference in the amount of ingested SPS among the three grain sizes. The concentrations (lipid-normalized or not) of PAHs-d10 in zebrafish were promoted in the presence of the three different size SPS, and the PAH-d10 concentrations in zebrafish increased with decreasing particle size. Compared with the systems without SPS, the lipid-normalized concentrations of PAHs-d10 increased by 12%-72%, 34%-130%, and 60%-196%, respectively in zebrafish in systems with 63-106 µm, 20-63 µm, and <20 µm of SPS after exposure for 20 h. The stronger effect of SPS with smaller grain sizes was probably due to their lower organic carbon content, lower ratio of black carbon to organic carbon content, smaller particle size, and higher dissolved organic matter contents, which could promote the desorption of PAHs-d10 from ingested SPS and bioaccessibility of PAHs-d10 to zebrafish. This study suggests that in addition to SPS concentration, the suspended particle size should be considered in ecological risk assessment for hydrophobic organic compounds in aquatic environment.

Impact of passive sampler protection apparatus on sediment porewater profiles of hydrophobic organic compounds.

Passive sampling techniques have been widely used to determine the dissolved concentration profiles of hydrophobic organic compounds (HOCs) in sediment porewater. However, the effects of having a protection for the passive sampler on profiling HOCs concentrations in sediment porewater, especially in deep sediment, have remained unclear. To address this issue, low density polyethylene passive samplers with and without protectors, which consisted of glass fiber filter and porous stainless steel shield, were simultaneously deployed in sediment of the Dongjiang River, South China. The results showed that the protectors retarded the dissipation of performance reference compounds (PRCs) from the sampler by a factor of 2-9. The protectors seemed to exert a negligible effect on the measured concentrations of PAHs, BDE-47, and BDE-99 in surficial sediment porewater (0-14 cm depth) from both samplers. However, the sediment porewater concentration profiles of PAHs and BDE-47 from the sampler with protectors were in agreement with those normalized by dry weight in deep sediment (16-34 cm depth), indicating that a diffusion layer established by the protectors may minimize the probability of local depletion of the target analytes in deep sediment. In addition, the log Koc values of PAHs, BDE-47, and BDE-99 exhibited a slight increasing trend with sediment depth. This finding suggested that in situ passive sampling techniques could be a feasible tool in determining the site-specific log Koc values of HOCs at different sediment depths.

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.