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In this study, a functionalized Co3O4-Bi2O3-Ti catalytic membrane (CBO-Ti-M) was prepared and applied for removing organic pollutants via activating peroxymonosulfate (PMS) in the dead-end filtration mode. Characterizations including scanning electron microcopy (SEM), X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS) showed that the Co3O4-Bi2O3 catalyst was successfully supported on the Ti membrane. The CBO-Ti-M /PMS system could efficiently remove various organic pollutants such as sulfamethoxazole, methyl orange, bisphenol A and methylene blue, achieving removal efficiencies of 98.0%-99.5%. The effects of PMS concentration, flow rate and solution environment on degradation efficiency were investigated in detail. Furthermore, quenching experiments, electron spin resonance (ESR) and in-situ open circuit potential (OCP) tests collectively demonstrated that singlet oxygen as well as the non-radical electron transfer pathway mainly contributed in the reaction mechanism. The synergistic effect of Co and Bi was illustrated according to XPS results, and the possible degradation pathway of MB was proposed based on LC-MS analysis. Reusability test showed that pollutant removal efficiency with the CBO-Ti-M /PMS system remained stable in four runs and limited metal leaching was observed.

In the present study, five magnetic multi-walled carbon nanotubes (MMWCNTs) with different diameters were prepared and their performance on the sorptive removal of methylene blue (MB) from water was investigated. Transmission electron microscope, scanning electron microscope, Fourier transform infrared spectrometer, X-ray diffraction, and vibrating sample magnetometer confirm that the surface of these MMWCNTs has been decorated by Fe3O4 nanoparticles, which renders the MMWCNTs superparamagnetic. Thus, these MMWCNTs can be easily separated from water after the adsorption. During the adsorption process, pH slightly affected the removal efficiency of MB and the adsorption performed better under weak alkaline conditions. Adsorption kinetics followed the pseudo-second-order kinetic model well, and the Dubinin-Radushkevich model fitted the isotherms best. The maximum adsorption capacity for MB reached 204.2 mg/g, and the values decreased with increasing diameters of MMWCNTs due to decreasing specific surface areas. The thermodynamics parameters indicated the spontaneous and exothermic nature of the adsorption. The reusability test showed that MMWCNTs could be used for 6 cycles without significant loss of the adsorption capacity. And common ions (K+, Na+, Ca2+ and Al3+) and SDS in water did not show greatly effects on the removal efficiency of MB. Hence, MMWCNTs prepared in this study could be promising adsorbents for dyes removal from wastewater.

Once released into natural water, the environmental behavior and fate of C60 could inevitably been affected by humic acid (HA), sunlight, and hydrodynamic conditions. However, the combined effects of these factors are not so clear. Therefore, in the present study, effects of HA, sunlight, and agitation intensity on generation and properties of aqu/nC60 were investigated. The results indicated that HA could increase the concentration of aqu/nC60 mainly through the steric hindrance effect. The higher agitation intensity led to higher concentrations of aqu/nC60 and more efficient steric stabilization was formed by HA. Sunlight irradiation promoted the surface oxidization and consequently enhanced the dispersion of C60. The relative order of the influence on the UV/vis concentration was sunlight > agitation intensity > HA. In addition, HA might not always enhance the dispersion of aqu/nC60 due to light screening/ROS scavenging, over-coating, or chain-like bridging mechanism. Therefore, evaluating the environmental behavior and fate of C60 should take these factors into account together.

This study aims to evaluate the subacute toxic effects of oil under different treatments on marine organism by simulating natural contaminative processes. In this study, 120# (RMD15) fuel oil was selected as the pollutant and marine medaka (Oryzias melastigma) embryos as the experimental organism. The developmental toxicity of different volume concentrations (0.05%, 0.2%, 1% and 5%) of water-accommodated fractions, biologicallyenhanced water-accommodated fractions, and chemically-enhanced water-accommodated fractions on the embryos in different exposure time (8, 15 and 22 d) were compared and the content of relevant polycyclic aromatic hydrocarbons (PAHs) was studied (in dispersion and in vivo). The subacute toxic effects were assessed in terms of antioxidant activities of enzymes (superoxide dismutase, catalase and glutathione S-transferase) and the blue sac disease (BSD) indexes.The results showed that the BSD indexes of the treatment groups were significantly higher than the respective control groups and showed positive correlations with both concentration and exposure time. The experiments with three antioxidant enzymes indicated that enzymatic activities of the embryos changed dramatically under the oxidation stress of petroleum hydrocarbons, especially after adding the dispersants. With the increase of petroleum hydrocarbon concentration and exposure time, the three enzymes showed different degrees of induction and inhibition effects.

In the present study, the thermodynamic relationship between log KOW and the solvation free energy from water to octanol (ΔGOW) was employed to estimate log KOW of PCBs. HF/MIDI!6D was identified to be the optimal calculation level for both the geometry optimization and energy calculation. Based on the optimal calculation level, ΔGOW values were calculated and used to estimate the log KOW values of PCBs. It was found that the intermolecular interactions of PCBs in the aqueous phase and octanol phase were similar, resulting in different effects of the dimer on the estimation of log KOW of PCBs from that on log KOA of PCBs. Compared with other reported models, the ΔGOW model had comparable goodness-of-fit and predictive ability, and a more universal application domain. Therefore, the solvation free energy method could be a promising method for the prediction of KOW.

Microplastics are a ubiquitous contaminant of marine ecosystems that have received considerable global attention. The effects of microplastic ingestion on some marine biota have been evaluated, but the uptake, elimination, and histopathological impacts of microplastics remain under-investigated especially for zooplankton larvae. Here, we show that 10 μm polystyrene microspheres can be ingested and egested by Artemia parthenogenetica larvae, which impact their health. The results indicate that A. parthenogenetica larvae have a varying capacity to consume 10 μm polystyrene microspheres that is dependent on microplastic exposure concentrations, exposure times, and the availability of food. The lowest level of microplastics that was ingested by A. parthenogenetica was 0.15 particles/individual when exposed to 10 particles/mL and 0.05 particles/individual when exposed to 1 particle/mL over 24 h and 14 d, respectively. A. parthenogenetica larvae were able to egest feces with microplastics within 3 h of ingestion. However, ingested microplastics persisted in individuals for up to 14 days. Furthermore, microalgal feeding was significantly reduced by 27.2% in the presence of 102 particles/mL microplastics over 24 h. Histological analyses indicated that a greater abundance of lipid droplets was present among epithelia after 24 h of exposure at a concentration of 10 particles/mL. Moreover, intestinal epithelia were deformed and disorderedly arranged after 14 d of exposure. Overall, these results indicate that marine microplastic pollution could pose a threat to A. parthenogenetica health, especially that of larvae. Consequently, further research is required to evaluate the potential physiological and histopathological effects of microplastics for other marine invertebrate species.

To further understand the underlying mechanisms involved in the developmental toxicity of crude oil and chemically dispersed crude oil on fish early-life stages (ELS), zebrafish (Danio rerio) embryos were exposed to GM-2 chemical dispersant (DISP), low-energy water-accommodated fractions (LEWAF), and chemically enhanced WAF (CEWAF) of Merey crude oil at sublethal concentrations for 120 h. We employed the General Morphology Score (GMS) and General Teratogenic Score (GTS) systems in conjunction with high-throughput RNA-Seq analysis to evaluate the phenotypic and transcriptomic responses in zebrafish ELS. Results showed that ΣPAHs concentrations in LEWAF and CEWAF solutions were 507.63 ± 80.95 ng·L−1 and 4039.51 ± 241.26 ng·L−1, respectively. The GMS and GTS values indicated that CEWAF exposure caused more severe developmental delay and higher frequencies of teratogenic effects than LEWAF exposure. Moreover, no significant change in heart rate was observed in LEWAF treatment, while CEWAF exposure caused a significant reduction in heart rate. LEWAF and CEWAF exposure exhibited an overt change in eye area, with a reduction of 4.0% and 25.3% (relative to the control), respectively. Additionally, no obvious impact on phenotypic development was observed in zebrafish embryo-larvae following DISP exposure. Significant changes in gene expression were detected in LEWAF and CEWAF treatments, with a total of 957 and 2062 differentially expressed genes (DEGs), respectively, while DISP exposure altered only 91 DEGs. Functional enrichment analysis revealed that LEWAF and CEWAF exposure caused significant perturbations in the pathways associated with phototransduction, retinol metabolism, metabolism of xenobiotics by cytochrome P450, and immune response-related pathways. Our results provide more valid evidence to corroborate the previous suggestion that ocular impairment is an equal or possibly more sensitive biomarker than cardiotoxicity in fish ELS exposed to oil-derived PAHs. All these findings could gain further mechanistic insights into the effects of crude oil and chemical dispersant on fish ELS.

In this work, three different processes including ultrafiltration (UF), separated magnetic ion exchange resin (MIEX)-UF and integrated MIEX/UF were employed to investigate the introduction of MIEX on biological membrane fouling control in synthetic bacteria solutions. Independent UF was firstly performed using extracellular polymeric substances (EPS)- free live bacteria, live bacteria, or dead bacteria as feed, and the operation time when TMP reached 35 kPa was 105, 75 or 55 min respectively. The most severe fouling with dead bacteria was attributed to EPS and some endocellular components which favored the adhesion of bacteria on membrane surface. The introduction of MIEX helped to alleviate membrane fouling, and the alleviation effect for EPS-free live bacteria feed was the least significant. It was inferred that the organic substances could be firstly adsorbed by the anion-exchange resin and then promote the adhesion of bacteria. This was supported by direct adsorption tests with MIEX where the removal efficiencies followed the order of dead bacteria > live bacteria > EPS-free live bacteria. The integrated process worked better than the separated one in both single cycle and multi cycle filtration tests, and this was mainly attributed to the dynamic resin layer, which worked in several manners, including acting as a physical barrier, enhancing adsorption/adhesion of foulants and suppressing reproduction of the bacteria. Regeneration of MIEX was also conducted with aqueous NaCl or NaHCO3. The removal efficiency was much more stable in the latter case, which could still reach 33% after five cycles (~83% of the initial capacity).

Polyoxometalate, K6TiW11O39Sn·7H2O (TiW11Sn), was synthesized and characterized. TiW11Sn and K6ZrW11O39Sn·12H2O (ZrW11Sn) were evaluated for their photocatalytic degradation of triarylmethane (brilliant green and acid blue 9), bisazo (C.I. reactive black 5), and monoazo dyestuffs (C.I. reactive red 24, C.I. reactive red 194, and C.I. reactive orange 5) with natural sunlight in homogeneous aqueous solutions. TiW11Sn and ZrW11Sn effectively and photocatalytically decolorized the dyestuffs. The TiW11Sn- and ZrW11Sn-mediated photocatalytic degradation of the dyestuffs involved a pseudo-first-order reaction and was modeled by Langmuir–Hinshelwood-type kinetics. The observed pseudo-first-order rate constants (K/) of triarylmethane dyestuffs were generally bigger than that of the azo dyestuffs. Quantitative structure–property relationship models of the K/ of the dyestuffs were developed using partial least-square regression. The cumulative variance of the dependent variable explained by the partial least...

Aggregation of C60, as an important process governing its mobility and toxicity, has been quantitatively investigated. However, effects of sunlight and agitation intensity on the aggregation behavior of aqu/nC60 produced via extended mixing, have not been clarified. Therefore, in the present study, the aggregation behavior of aqu/nC60 produced at 500 and 800 rpm in the absence and presence of sunlight was investigated. Aggregation with increasing concentrations could be accelerated, while changes of Zave and zeta potential were not obvious. Critical coagulation concentrations (CCCs) of aqu/nC60 obtained at 800 rpm in the absence/presence of sunlight and that at 500 rpm under sunlight were 330, 205 and 170 mM NaCl, and 10.0, 2.6 and 3.1 mM CaCl2, respectively. These CCCs indicated that the aqu/nC60 prepared by the extended mixing were more stable than those produced by other methods. Salt-induced aggregation occurred more easily for aqu/nC60 formed under sunlight than that formed in the dark. Extra surface oxidation induced by high agitation intensity remarkably increased the stability of aqu/nC60 in NaCl solutions. In contrast, in CaCl2 solutions, aqu/nC60 formed at high agitation intensity had similar stability or even inadequate stability to that obtained at low agitation intensity due to the charge neutralization and cross-link bridging.

Temperature-dependent octanol-air partition coefficients (KOA) are of great importance in assessing the environmental behavior and fate of persistent organic pollutants including polychlorinated biphenyls (PCBs). Due to the tremendous amounts of time, effort and cost needed for the experimental determination of KOA, it is desirable to develop a rapid and precise predictive method to estimate KOA just based on molecular structure. In the present study, a predictive model for log KOA of PCBs at ambient temperatures was developed based on the thermodynamic relationship between KOA and the solvation free energy from air to octanol (ΔGOA). For the calculation of ΔGOA of PCBs, the optimal combination of theoretical method and basis-set was identified to be HF/MIDI!6D for both geometry optimization and energy calculation. Dimer formation could affect the partition behavior and promote the apparent KOA values of PCBs. After taking the effect of dimer formation into account, the goodness-of-fit, predictive ability, and robustness of the predictive model were significantly improved. Apparent log KOA values of PCBs at different ambient temperatures ranging from 283.15 to 303.15 K were predicted. Compared with other reported models, the model developed in the present study had not only comparable goodness-of-fit and predictive ability, but also a universal application domain and the relative independency of experimental data. Therefore, the solvation free energy method could be a promising method for the prediction of KOA.

Microplastics are a contaminant of emerging concern which enter the marine environment from a variety of sources. The ingestion and toxic effects of microplastics on marine life, especially for filter feeders, are a cause of concern in view of their ubiquitous nature and their similar size as food sources. To assess the toxic effects of microspheres ingested by brine shrimp larvae, we exposed Artemia parthenogenetica to 10 μm polystyrene microspheres at different concentrations. These concentrations were approximate to the extrapolated marine aquatic environmentally relevant concentrations. The lowest polystyrene concentrations at which ingestion was visualized in A. parthenogenetica were 12 ± 0.57 particles/mL (6.7 ± 0.32 μg/L) and 1.1 ± 0.16 particles/mL (0.61 ± 0.088 μg/L), respectively. There were no significant impacts on the survival, growth or development in A. parthenogenetica occurring over the 14-d exposure across a range of polystyrene nominal concentrations (1–1000 particles/mL or 0.55–550 μg/L). However, abnormal ultrastructures of intestinal epithelial cells were observed upon exposure to polystyrene microspheres, including fewer and disordered microvilli, an increased number of mitochondrion and the appearance of autophagosome. These phenomena could affect nutrition absorption and energy metabolism. Although no major acute or chronic toxicity effects on A. parthenogenetica were observed over 24-h or 14-d exposures, this study provides evidence that the ingestion of polystyrene microplastics at extrapolated environmentally relevant concentrations can be visualized through a microscope to be causing a series of responses in intestinal epithelial cells.

Stranding of oil onto a coastline after an oil spill threatens the health of marine benthic organisms. Here, the transgenerational effects of exposure to stranded heavy fuel oil (HFO) on the sea urchin Strongylocentrotus intermedius were assessed. The column containing gravel coated with HFO was prepared in the laboratory to simulate HFO-contaminated gravel shorelines. Adult sea urchins were exposed for 21 days to either a HFO-oiled gravel column at the oil loading of 3000 μg oil/g gravel or a non-HFO-oiled gravel column (as the control treatment) and then offspring were either exposed to HFO or ambient seawater conditions. The sublethal exposure to HFO for 21 days induced polycyclic aromatic hydrocarbons (PAHs) accumulation in gonads, accompanied by increased levels of oxidative lipid, protein and DNA damage and a reduction in total antioxidant capacity. Analysis of gametes indicated that both maternal and paternal exposure could result in the transfer of PAHs and DNA damage to their offspring. Parental (maternal, paternal or both) exposure to HFO caused increases in malformation rates of offspring compared to those from control parents under ambient seawater condition. Continued HFO exposure in the offspring resulted in further increased malformation rates compared with those reared in ambient seawater, as well as oxidative lipid, protein and DNA damage. Furthermore, mother exposure history reduced the total antioxidant capacity of larvae to response to continued HFO exposure. Overall, the results suggest an increased sensitivity to toxic effects of HFO in larvae from exposed both parents compared with those from control parents in S. intermedius, which may consequently affect the recruitment and population maintenance.

Mariculture activities and river inputs lead to coastal seawaters with DOM levels that are comparable to or even higher than those in terrestrial water bodies. However, effects of seawater DOM, and especially of DOM occurring in areas impacted by mariculture, on photodegradation of organic micropollutants, are largely unknown. In this study, simulated sunlight irradiation experiments were performed to probe the effects of DOM extracted from mariculture impacted seawaters and from offshore areas, on photodegradation of three sulfonamide antibiotics (SAs). Results show that the SAs are transformed mainly by indirect photodegradation induced by triplet excited DOM (3DOM*). Compared with DOM from the more pristine coastal waters, the DOM from mariculture impacted areas undergoes less photobleaching, contains higher percentage of humic-like materials and higher proportions of aromatic and carbonyl structures. Thus, the DOM from mariculture areas exhibits higher rates of light absorption, higher formation quantum yields of 3DOM*, higher 3DOM* steady-state concentrations and higher reactivity on photodegradation of the SAs. Photochemistry of the seawater DOM is different from that reported for freshwater lake DOM. This study highlights the importance of probing the effects of DOM from coastal seawaters on photodegradation of organic micropollutants since coastal seawaters are sinks of many aquatic pollutants.

In the present study, the contamination level and spatial distribution of PFASs in the water dissolved phase and suspended particulate matter (SPM) phase of the Dalian Bay, and the SPM-water partition behavior were investigated. The total concentrations of PFASs (∑PFASs) in the water dissolved phase ranged from 6.9 to 17.1 ng L−1, with perfluorooctanoic acid (PFOA), perfluorobutanoic acid, and perfluorobutane sulfonate (PFBS) as the predominant PFASs, while ∑PFASs in SPM ranged from 1.7 to 27.5 ng g−1 dw with higher contributions from PFBS, perfluorooctane sulfonic acid and PFOA. As for the pollution distribution, the concentrations of PFASs inside the Dalian Bay were higher than those outside the bay. For perfluoroalkyl carboxylic acid (PFCAs) and perfluoroalkane sulfonic acids (PFSAs), the suspended particulate matter-water partition coefficient (log Kd) values ranged from 2.62 to 3.76, and from 3.39 to 3.56, respectively. The log Kd values of PFASs generally increased with the increasing perfluorinated carbon chain length. Short-chain PFCAs were mostly detected in the water dissolved phase, while long-chain PFCAs and PFSAs appeared to bind more strongly to SPM phase. The contamination level of long-chain PFCAs and PFSAs could be underestimated if only the water dissolved phase were measured. Therefore, further investigations should consider the role of SPM on the environmental behavior and fate of PFASs in the aquatic environment.

In the present study, magnetic multi-walled carbon nanotubes (MMWCNTs), magnetic single-walled carbon nanotubes (MSWCNT) and magnetic graphene nanosheets (MGNS) were prepared and the sorptive removal of phenanthrene from water by them was investigated. TEM analysis showed that carbon nanomaterials (CNMs) were coated with iron oxide nanoparticles, which were proved by Fourier transform infrared spectrometer. Magnetism determination also confirmed the formation of strong magnetic nanoparticles with saturation magnetization >31 emu/g. pH slightly affected the removal rate of phenanthrene and the adsorption performed better under weak acid conditions. Pseudo-second-order kinetic model was more suitable to describe the kinetic process, while Polanyi theory-based Dubinin−Astakhov model fitted the isothermal data best. MSWCNT exhibited the highest adsorption capacity, followed by MGNS and MMWCNTs. Adsorption thermodynamic parameters, including Gibbs free energy changes, enthalpy changes and entropy changes, were all negative, suggesting that the adsorption was a spontaneous, exothermic and entropy reduction process. The MCNMs prepared could be easily regenerated and reused, providing a promising alternative for the sorptive removal of phenanthrene from contaminated water.

Poly- and perfluorinated compounds (PFCs) are a class of global environmental pollutants that are of concern regarding their environmental fate and adverse effects. However, data on the basic physicochemical property of PFCs are still limited. To fill part of the data gaps, temperature-dependent predictive models for vapor pressure of PFCs were developed based on previously reported experimental data. The applicability domain of the models was analyzed using the Williams plot and the influential points and the response outliers were identified. The statistical performance of the models was significantly improved by removing these influential points and response outliers. This procedure confirmed the importance of properly defining the applicability domain of the predictive models. It is shown that the main factors governing the vapor pressure of PFCs, are intermolecular dispersive interactions, hydrogen bonding, temperature, intermolecular dipole-induced dipole interactions and dipole–dipole interactions. Although the model obtained could be used to reliably predict the vapor pressures of certain PFCs at different temperatures, it is essential that the prediction must fall within the applicability domain of the model and the temperature range for reliable predictions.

Perfluorooctane sulfonate (PFOS) and perfluorooctanoic acid (PFOA) are two kinds of emerging contaminants most studied in recent years. However, there is limited information about their combined toxicity to aquatic organisms. In the present study, the single and combined toxicity of PFOA and PFOS to zebrafish (Danio rerio) embryos were investigated. PFOS was more toxic than PFOA for the single toxicity. In four mixtures, PFOS and PFOA showed complex interactive effects that changed from additive to synergistic effect, then to antagonistic effect, and at last turnover to synergic effect again, with increased molar ratios of PFOS. Neither the concentration-addition model nor the independent-action model could predict the combined effects when strong interactive effects existed. Although the interactive effects of PFOS and PFOA affected their combined toxicity, the trend of mixture toxicity still showed an increase with increasing molar ratios of PFOS in the mixture.

The organochlorine pesticides (OCP) in Eastern-Barvaria at Haidel 1160 m a.s.l. were monitored with a low volume active air sampler and semi-permeable membrane devices (SPMD). The air sampling rates (R air ) of SPMD for OCP were calculated. Quantitative structure-property relationship (QSPR) models of R air of SPMD were developed for OCP with partial least square (PLS) regression. Quantum chemical descriptors computed by semi-empirical PM6 method were used as predictor variables. The cumulative variance of the dependent variable explained by the PLS components and determined by cross-validation (Q 2 cum ), for the optimal models, is 0.637, indicating that the model has good predictive ability and robustness, and could be used to estimate R air values of OCP. The main factors governing R air of OCP are intermolecular interactions and the energy required for cave-forming in dissolution of OCP into triolein of SPMD.

Perfluoroalkyl substances (PFASs) have been recognized as emerging environmental pollutants. However, there is limited information on the contamination level and spatial distribution of PFASs in the Shuangtaizi Estuary, where the Shuangtaizi Hekou Nature Reserve is located. In the present study, the contamination level and spatial distribution of PFASs in surface water (approximately 0.5 m below the surface) and bottom water (about 0.5 m above the bottom) of the Shuangtaizi Estuary were investigated. The data indicated that the Shuangtaizi Estuary was commonly contaminated by PFASs. The total concentration of PFASs in surface and bottom water of the Shuangtaizi Estuary ranged from 66.2 to 185 ng L(-1) and from 44.8 to 209 ng L(-1), respectively. The predominant PFASs were perfluorobutanoic acid (PFBA), perfluoropentanoic acid, perfluorooctanoic acid, perfluorohexanoic acid and perfluorobutane sulfonate (PFBS). In general, PFAS concentrations in surface water samples were lower than those in bottom water samples. The spatial distribution of PFASs in the Shuangtaizi Estuary was mainly affected by particular landform, tide and residual currents in Liaodong Bay. The total mass flux of 15 PFASs from the Shuangtaizi River to Liaodong Bay was estimated to be 352 kg year(-1), which was lower than the total flux from the Daling River and the Daliao River. As short-chain PFASs, such as PFBS and PFBA, have been the prevalent compounds in some places and are continuously produced and used, long-term monitoring and effective pollution controls are suggested.

Perfluorooctane sulfonate (PFOS) is an ubiquitous persistent organic pollutant, which can be bioaccumulated and cause adverse effects on organisms. However, there is very limited information about the toxic effects of PFOS to marine organisms and its mechanisms. Therefore, in the present study, adult sea urchins Glyptocidaris crenularis were exposed to PFOS for 21 d, followed by a 7-d depuration period, in order to investigate the toxicity of PFOS to sea urchin and its potential epigenetic mechanisms. Sea urchins dropped spines, and lowered down the motor ability and feeding ability after the PFOS exposure. Superoxide dismutase activities in supernatant of coelomic fluid of sea urchin increased firstly and then dropped down, while the change of the catalase activity took an opposite trend during the exposure period. They both approached to the corresponding activity of the control after the depuration period. The DNA methylation polymorphism, methylation rate and demethylation rate in sea urchin gonad all increased following the prolonged exposure time, and then decreased after the depuration period. The demethylation rates were lower than the corresponding methylation rates, therefore methylation events were dominant during the whole experimental period. This might suggest that sea urchin have strong self-protection mechanisms and can survive from the PFOS exposure presented in this study. Further efforts are needed to more precisely investigate the DNA methylation effects of PFOS and the self-protection mechanism of sea urchin.

Based on quantum chemical descriptors and topological descriptors, temperature-dependent predictive models for vapor pressures (P) of oxygen-containing polycyclic aromatic hydrocarbons (OPAHs) were developed following a variable selection procedure. The cross-validated Q cum 4 of the final model, 0.930, shows that the model has good predictive ability and robustness. In view of difficulties to measurements of P of OPAHs, the model could be used to estimate P values at different temperatures. The main factors influencing logP values of OPAHs, from important to less important, are hydrogen bond force, intermolecular dispersive interactions, electrostatic interactions, temperature and entropic factor.

Four quantitative structure-activity relationships were developed for toxicity of selected photosynthesis (PHS) inhibitors and acetolactate synthase (ALS) inhibitors to Chlorella Vulgaris and Raphidocelis subcapitata using a mechanism-based approach. These models have good fitness and predictive ability. The potential of electron transfer, intermolecular interactions with weak electron-transfer, and intermolecular dispersive interactions between PHS inhibitors and the active site of action are key factors influencing the toxicity of these PHS inhibitors. Intermolecular weak electron-transfer interactions and intermolecular dispersive interactions mainly determine the toxicity of these ALS inhibitors. Sulfonyl is an important functional group governing the toxicity of ALS inhibitors investigated.

Subcooled liquid vapor pressures (P(L)) are of great importance for assessing the persistent behavior of organic pollutants. As P(L) cannot be determined by direct experiments, it is of interest to develop and evaluate various predictive methods. In the current study, gas chromatography retention index (GC-RI) and quantitative structure-property relationship (QSPR) methods were used to develop predictive models for P(L) of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs). The model development was based on P(L) values converted from consistent experimental solid vapor pressures (P(S)). The P(L) values predicted by the two methods are highly consistent with each other, and in-between sets of values predicted by others. Since the QSPR method can be regarded as independent of experiments, and can be used to interpret intermolecular interactions that govern the magnitude of P(L), it may be superior to the GC-RI method.

Based on quantum chemical and topological descriptors, temperature-dependent predictive models for solid vapor pressure ( P S ) of PCDD/Fs were developed. The inclusion of the two topological descriptors, Kier symmetry index (S0K) and Kier flexibility index (PHI), as predictor variables, improved the statistical significance of models. Thus the entropic factors described by the two topological descriptors play a role in influencing the P S values. The cumulative variance of the dependent variable explained by the PLS components and determined by cross-validation ( Q cum 2 ), for the final model, is 0.972, indicating that the model has good predictive ability and robustness, and could be used to estimate P S values of PCDD/Fs at different temperatures. The main factors governing log P S values of PCDD/Fs, from important to less important, are temperature, intermolecular dispersive interactions, entropic factor, and intermolecular dipole–dipole and dipole–induced dipole interactions.

Organochlorine pesticides (OCP) were monitored at the Weissfluhjoch site (Switzerland) and the top of Mt. Sonnblick (Austria) with a low volume active air sampler and semipermeable membrane devices (SPMD). The air sampling rates (Rair) of the SPMD for OCP were calculated. Statistical tests showed that there was no significant difference between Rair at the two different sampling sites. Quantitative structure-property relationship (QSPR) models of the Rair of the SPMD were developed for OCP using partial least square (PLS) regression. Quantum chemical descriptors computed by the semi-empirical PM6 method were used as predictor variables. The cumulative variance of the dependent variable explained by the PLS components and determined by cross-validation (Q2cum) was >0.818 for each optimal model. This indicates that the model has good predictive ability and robustness. The Rair of the SPMD for OCP is related to the total energy, the van der Waals area and the total dipole moment of the OCP molecules. The main factors governing Rair values of OCP are intermolecular interactions and the energy required for cavity-formation in dissolution of OCP into triolein of the SPMD. The linear correlation coefficient between predicted and experimental values were all >0.921.