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.

Elevated temperature enhances the bioavailability of pyrene to Daphnia magna in the presence of dissolved organic matter: Implications for the effect of climate warming.

Dissolved organic matter (DOM) is an essential factor in natural waters to affect the bioavailability of hydrophobic organic compounds (HOCs). Climate warming may influence the partition of HOCs between DOM and water as well as the physiology of organisms. Thus, we hypothesized that elevated temperature might affect the bioavailability of HOCs in the presence of DOM. To test this hypothesis, the effect of temperature on the bioavailability of pyrene to Daphnia magna (D. magna) in water-DOM (fulvic acid) system was investigated. The results showed that, although the concentration of freely dissolved pyrene increased slightly with temperature in the presence of DOM when the level of total dissolved pyrene was kept constant, D. magna immobilization (increased by 50.0-167%) and internal body burden of pyrene (increased by 18.4-41.5%) increased significantly with every 4 °C increase in temperature (16, 20, 24 °C). The main reasonable explanation for this result is that elevated temperature promoted pyrene uptake by D. magna. It was found that the increase percentage of 1-hydroxypyrene (main metabolite of pyrene) concentrations with temperature was higher than that of pyrene concentrations in the body except gut of D. magna. This result indicated that increased temperature might enhance the metabolic rates of D. magna, thus leading to increased uptake rate of freely dissolved and DOM-associated pyrene. This study suggests that elevated temperature might enhance the bioavailability of HOCs in natural waters through influencing both the bioavailable fraction of HOCs and their uptake rates in aquatic organisms, and this should be considered for evaluating their eco-environmental risks under the context of climate warming.

Fate of particle-bound polycyclic aromatic hydrocarbons in the river-influenced continental margin of the northern Gulf of Mexico.

This study utilizes suspended particles and seafloor sediments collected from the northern Gulf of Mexico (GOM) continental margin to study the fate, transport, residence times and accumulation rates of particle-bound polycyclic aromatic hydrocarbons (PAHs). Total particulate-PAHs and particulate organic carbon (POC) varied between 0.9 and 7.0 ng/L, and 4-131 µg/L, respectively. Particulate-PAHs were positively correlated with POC, while both particulate-PAHs and POC were negatively correlated with salinity (P-value < 0.05). These results show that the river-derived particle influx and associated POC are important vectors for transport and fate of particulate-PAHs in the river-dominated northern GOM continental ecosystems. The composition of underlying seafloor sediment-PAHs were not correlated to the water column particulate-PAHs, which is attributed to re-mineralization, sediment resuspension/redistribution and different timescales of comparison. The 210Pb-derived residence time of particles and associated particulate-PAHs in water column varied between 2 and 39 days. Residence times of particulate-PAHs were significantly correlated with seafloor sediment-PAHs accumulation rates, shorter water column residence times leading to higher PAHs accumulation rates.

An exponential model based new approach for correcting aqueous concentrations of hydrophobic organic chemicals measured by polyethylene passive samplers.

Although low density polyethylene (PE) passive samplers show promise for the measurement of aqueous phase hydrophobic organic chemicals (HOCs), the lack of a practical and unsophisticated approach to account for non-equilibrium exposure conditions has impeded widespread acceptance and thus application in situ. The goal of this study was to develop a streamlined approach based on an exponential model and a convection mass transfer principle for correcting aqueous concentrations for HOCs deduced by PE samplers under non-equilibrium conditions. First, uptake rate constants (k1), elimination rate constants (k2), and seawater-PE equilibrium partition coefficients (KPEWs) were determined in laboratory experiments for a diverse suite of HOCs with logKow range of 3.4-8.3. Linear relationships between log k2 and logKow, and between log KPEW and logKow were established. Second, PE samplers pre-loaded with 13C-labeled performance reference compounds (PRCs) were deployed in the ocean to determine their k2in situ. By applying boundary layer and convection mass transfer theories, ratio (C) of k2 values in field and laboratory exposures was estimated. This C value was demonstrated a constant that was only determined by water velocities and widths of PE strips. A generic equation with C and logKow as parameters was eventually established for extrapolation of non-equilibrium correction factors for the water boundary layer-controlled HOCs. Characterizing the hydrodynamic conditions indicated the sampler configuration and mooring mode should aim at sustaining laminar flow on the PE surface for optimal mass transfer. The PE estimates corrected using this novel approach possessed high accuracy and acceptable precision, and can be suited for a broad spectrum of HOCs. The presented method should facilitate routine utilization of the PE samplers.

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.

Dissolved organic matter affects both bioconcentration kinetics and steady-state concentrations of polycyclic aromatic hydrocarbons in zebrafish (Danio rerio).

Dissolved organic matter (DOM) is ubiquitous in natural aquatic ecosystems. The association of hydrophobic organic compounds (HOCs), such as polycyclic aromatic hydrocarbons (PAHs), with DOM may have a large impact on HOC fractions in water and their bioconcentration in fish. However, the effects of DOM on HOC bioconcentration in fish are not well understood, especially whether DOM will affect the bioconcentration steady-state concentrations of HOCs in fish is still confusing. Thus, this study investigated the effects of three DOM including gallic acid (GA), tannic acid (TA), and humic acid (HA) with molecular weights ranging from 170 Da to about 10 kDa at different concentrations (1, 5, and 15 mgOC L-1) on the bioconcentration of PAHs including phenanthrene, anthracene, fluoranthene, and pyrene in zebrafish (Danio rerio), with the PAH freely dissolved concentrations maintained constant by passive dosing systems. The results revealed that the presence of DOM generally increased the bioconcentration steady-state concentrations of the PAHs in zebrafish (Cb-ss), with the increase ranging from 28.1% to 204.0%, and the increase of Cb-ss promoted by TA with middle molecular weight (1700 Da) was the highest among the studied DOM. Moreover, the Cb-ss increased with the concentrations of GA with low molecular weight and TA with middle molecular weight in water, whereas decreased with increasing concentrations of HA with high molecular weight. The uptake rate constants of the PAHs in zebrafish with DOM were higher than that without DOM. Ingestion of DOM and direct accumulation of PAHs associated with DOM might be primary influencing mechanisms of DOM on the Cb-ss, and whether the facilitated diffusive mass transfer by DOM will affect the Cb-ss needs to be further studied. This study suggested that DOM-associated HOCs should be considered in future HOC risk assessment in addition to the freely dissolved HOCs.

Effect of dissolved organic matter on pre-equilibrium passive sampling: A predictive QSAR modeling study.

Pre-equilibrium passive sampling is a simple and promising technique for studying sampling kinetics, which is crucial to determine the distribution, transfer and fate of hydrophobic organic compounds (HOCs) in environmental water and organisms. Environmental water samples contain complex matrices that complicate the traditional calibration process for obtaining the accurate rate constants. This study proposed a QSAR model to predict the sampling rate constants of HOCs (polycyclic aromatic hydrocarbons (PAHs), polychlorinated biphenyls (PCBs) and pesticides) in aqueous systems containing complex matrices. A homemade flow-through system was established to simulate an actual aqueous environment containing dissolved organic matter (DOM) i.e. humic acid (HA) and (2-Hydroxypropyl)-ß-cyclodextrin (ß-HPCD)), and to obtain the experimental rate constants. Then, a quantitative structure-activity relationship (QSAR) model using Genetic Algorithm-Multiple Linear Regression (GA-MLR) was found to correlate the experimental rate constants to the system state including physicochemical parameters of the HOCs and DOM which were calculated and selected as descriptors by Density Functional Theory (DFT) and Chem 3D. The experimental results showed that the rate constants significantly increased as the concentration of DOM increased, and the enhancement factors of 70-fold and 34-fold were observed for the HOCs in HA and ß-HPCD, respectively. The established QSAR model was validated as credible (RAdj.2=0.862) and predictable (Q2=0.835) in estimating the rate constants of HOCs for complex aqueous sampling, and a probable mechanism was developed by comparison to the reported theoretical study. MAIN FINDING OF THE WORK: The present study established a QSAR model of passive sampling rate constants and calibrated the effect of DOM on the sampling kinetics.

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.

Development of TLSER model and QSAR model for predicting partition coefficients of hydrophobic organic chemicals between low density polyethylene film and water.

Partition coefficients are vital parameters for measuring accurately the chemicals concentrations by passive sampling devices. Given the wide use of low density polyethylene (LDPE) film in passive sampling, we developed a theoretical linear solvation energy relationship (TLSER) model and a quantitative structure-activity relationship (QSAR) model for the prediction of the partition coefficient of chemicals between LDPE and water (Kpew). For chemicals with the octanol-water partition coefficient (log Kow) <8, a TLSER model with Vx (McGowan volume) and qA- (the most negative charge on O, N, S, X atoms) as descriptors was developed, but the model had relatively low determination coefficient (R2) and cross-validated coefficient (Q2). In order to further explore the theoretical mechanisms involved in the partition process, a QSAR model with four descriptors (MLOGP (Moriguchi octanol-water partition coeff.), P_VSA_s_3 (P_VSA-like on I-state, bin 3), Hy (hydrophilic factor) and NssO (number of atoms of type ssO)) was established, and statistical analysis indicated that the model had satisfactory goodness-of-fit, robustness and predictive ability. For chemicals with log KOW>8, a TLSER model with Vx and a QSAR model with MLOGP as descriptor were developed. This is the first paper to explore the models for highly hydrophobic chemicals. The applicability domain of the models, characterized by the Euclidean distance-based method and Williams plot, covered a large number of structurally diverse chemicals, which included nearly all the common hydrophobic organic compounds. Additionally, through mechanism interpretation, we explored the structural features those governing the partition behavior of chemicals between LDPE and water.