Occurrence, spatial distribution, and ecological risk of benzotriazole UV stabilizers (BUVs) in sediments from Bohai sea of China.

Benzotriazoles are a class of ultraviolet absorbents which absorb UV ranging from 280 to 400 nm and are widely used in personal care products and industrial production. Their residues in environmental matrices have received great concern in recent years, but most studies have focused on pollution in water and few have examined BUVs in marine sediments. In this study, we investigated the occurrence, potential sources, and ecological risk of 15 types of BUVs in the sediments of Bohai Sea in China for the first time. The total concentrations of the 15 BUVs ranged from 0.139 to 4.125 ng/g dw with a median concentration of 0.340 ng/g. UV-327 and UV-360 were predominant among the BUV congeners, accounting for 22.6% and 17.7% of the total concentration of Σ15BUVs, respectively. The detection frequencies of the BUV congeners generally exceeded 95%, reflecting the wide use and persistence of these chemicals. The concentrations of the BUV congeners in this study were one order of magnitude lower than those in other areas. Moreover, the distributions of BUVs presented a decreasing gradient from nearshore to offshore, indicating that coastal input was the main influencing factor. Two potential primary sources, plastic manufacturing and domestic wastewater, were identified via principle component analysis. The ecological risks of BUVs to aquatic organisms in the sediments were evaluated using the risk quotient (RQ) method. Generally, the risk to aquatic organisms from exposure to BUVs in Bohai Sea could be considered low at the measured concentrations. While our study provides important new insight into the ecological risks of BUVs in the estuary, further research on the pollution levels and toxicity risks of BUVs in Bohai Sea should be conducted to better understand the ecological effect of these pollutants.

Preparation and application of a molecularly imprinted monolith for specific recognition of domoic acid.

In this work, a molecularly imprinted monolithic column was synthesized by a facile procedure and was applied for specific recognition of domoic acid, an amnesic shellfish poison. The poly(4-vinylpyridine-co-ethylene glycol dimethacrylate) molecularly imprinted monolith was synthesized in a stainless steel column by in situ polymerization. Pentane-1,3,5-tricarboxylic acid was used as a dummy imprinting template instead of the highly toxic and expensive target molecule. It is the first time that a molecularly imprinted monolith is introduced for separation and detection of domoic acid. After optimizing the preparation conditions, the prepared imprinted monolith was systematically characterized and exhibited excellent stability and permeability as a HPLC stationary phase. The results of chromatographic analysis demonstrated that the molecularly imprinted monolith exhibited specific retention and selective recognition toward domoic acid, with an imprinted factor up to 3.77. Furthermore, the molecularly imprinted monolith was successfully applied for selective enrichment of domoic acid from biological samples. Graphical abstract A molecularly imprinted monolith was prepared by using a dummy imprinted template and was successfully applied for specific recognition of domoic acid.

Applying adverse outcome pathways and species sensitivity-weighted distribution to predicted-no-effect concentration derivation and quantitative ecological risk assessment for bisphenol A and 4-nonylphenol in aquatic environments: A case study on Tianjin City, China.

Adverse outcome pathways (AOPs) are a novel concept that effectively considers the toxic modes of action and guides the ecological risk assessment of chemicals. To better use toxicity data including biochemical or molecular responses and mechanistic data, we further developed a species sensitivity-weighted distribution (SSWD) method for bisphenol A and 4-nonylphenol. Their aquatic predicted-no-effect concentrations (PNECs) were derived using the log-normal statistical extrapolation method. We calculated aquatic PNECs of bisphenol A and 4-nonylphenol with values of 4.01 and 0.721 µg/L, respectively. The ecological risk of each chemical in different aquatic environments near Tianjin, China, a coastal municipality along the Bohai Sea, was characterized by hazard quotient and probabilistic risk quotient assessment techniques. Hazard quotients of 7.02 and 5.99 at 2 municipal sewage sites using all of the endpoints were observed for 4-nonylphenol, which indicated high ecological risks posed by 4-nonylphenol to aquatic organisms, especially endocrine-disrupting effects. Moreover, a high ecological risk of 4-nonylphenol was indicated based on the probabilistic risk quotient method. The present results show that combining the SSWD method and the AOP concept could better protect aquatic organisms from adverse effects such as endocrine disruption and could decrease uncertainty in ecological risk assessment. Environ Toxicol Chem 2018;37:551-562. © 2017 SETAC.

The distribution of and biodegradation impact on spilled oil in sediments from Dalian Bay, NE China.

Three cores collected in the area of 16th July 2010 oil spill by box crab in May 2013 and July 2014 at the Dalian Bay have been geochemically characterized to investigate the fate of chemical components in sediments. The total organic carbon, extractable organic matter contents and biomarker compositions have been applied for the differentiation of alien organic matters from in situ ones and evaluation of the biodegradation impact. Multivariate statistical analysis suggests four groups of sediments. Except a few samples at deepest part of BQ050, majority samples have certain affinity with the spilled oil. The most contaminated sediments occur at site BQ050 and the spilled oil has migrated to 8-12 cm depth. The degree of contamination can be ranked by the similarity of molecular compositions with spilled oil. Variable biomarker components in sediment extracts were also altered by ongoing biodegradation.

Aquatic predicted no-effect concentrations of 16 polycyclic aromatic hydrocarbons and their ecological risks in surface seawater of Liaodong Bay, China.

Polycyclic aromatic hydrocarbons (PAHs), a class of ubiquitous pollutants in marine environments, exhibit moderate to high adverse effects on aquatic organisms and humans. However, the lack of PAH toxicity data for aquatic organism has limited evaluation of their ecological risks. In the present study, aquatic predicted no-effect concentrations (PNECs) of 16 priority PAHs were derived based on species sensitivity distribution models, and their probabilistic ecological risks in seawater of Liaodong Bay, Bohai Sea, China, were assessed. A quantitative structure-activity relationship method was adopted to achieve the predicted chronic toxicity data for the PNEC derivation. Good agreement for aquatic PNECs of 8 PAHs based on predicted and experimental chronic toxicity data was observed (R(2) = 0.746), and the calculated PNECs ranged from 0.011 µg/L to 205.3 µg/L. A significant log-linear relationship also existed between the octanol-water partition coefficient and PNECs derived from experimental toxicity data (R(2) = 0.757). A similar order of ecological risks for the 16 PAH species in seawater of Liaodong Bay was found by probabilistic risk quotient and joint probability curve methods. The individual high ecological risk of benzo[a]pyrene, benzo[b]fluoranthene, and benz[a]anthracene needs to be determined. The combined ecological risk of PAHs in seawater of Liaodong Bay calculated by the joint probability curve method was 13.9%, indicating a high risk as a result of co-exposure to PAHs. Environ Toxicol Chem 2016;35:1587-1593. © 2015 SETAC.

Characterizing the distribution of selected PBDEs in soil, moss and reindeer dung at Ny-Ålesund of the Arctic.

Distribution of 12 selected polybrominated diphenyl ethers (PBDEs) was characterized in soil, moss and reindeer dung samples collected simultaneously at Ny-Ålesund of the Arctic. The average PBDE concentrations were 42 pg/g (dry weight) in soil, 122 pg/g in moss and 72 pg/g in reindeer dung. Significant log/log-linear relationship was observed between the soil/moss quotients (QSM) and the sub-cooled liquid vapor pressures of PBDEs (r(2)=0.80). Moreover, excellent log/log-linear relationships between QSM and the octanol/air partition coefficients as well as between the moss/dung quotient (QMD) and the octanol/water partition coefficients of PBDEs were also observed, indicating that the physicochemical properties of PBDEs are appropriate parameters for characterizing the distribution of PBDEs in soil, moss and reindeer dung at Ny-Ålesund. Capsule abstract: Significant log-linear correlations were observed between physicochemical properties of PBDEs and their soil/moss (moss/dung) quotients.

Comparative effects of biological and chemical dispersants on the bioavailability and toxicity of crude oil to early life stages of marine medaka (Oryzias melastigma).

The authors assessed the bioavailability and chronic toxicity of water-accommodated fractions of crude oil (WAFs) and 2 dispersants plus dispersed crude oil (chemical dispersant + crude oil [CE-WAF] and biological dispersant + crude oil [BE-WAF]) on the early life stages of marine medaka, Oryzias melastigma. The results showed that the addition of the 2 dispersants caused a 3- and 4-fold increase in concentrations of summed priority polycyclic aromatic hydrocarbons (PAHs) and high-molecular-weight PAHs with 3 or more benzene rings. The chemical and biological dispersants increased the bioavailability (as measured by ethoxyresorufin-O-dethylase activity) of crude oil 6-fold and 3-fold, respectively. Based on nominal concentrations, chronic toxicity (as measured by deformity) in WAFs exhibited a 10-fold increase in CE-WAF and a 3-fold increase in BE-WAF, respectively. When total petroleum hydrocarbon was measured, the differences between WAF and CE-WAF treatments disappeared, and CE-WAF was approximately 10 times more toxic than BE-WAF. Compared with the chemical dispersant, the biological dispersant possibly modified the toxicity of oil hydrocarbons because of the increase in the proportion of 2- and 3-ringed PAHs in water. The chemical and biological dispersants enhanced short-term bioaccumulation and toxicity, through different mechanisms. These properties should be considered in addition to their efficacy in degrading oil when oil spill management strategies are selected.

Aquatic predicted no-effect concentration for three polycyclic aromatic hydrocarbons and probabilistic ecological risk assessment in Liaodong Bay of the Bohai Sea, China.

Predicted no-effect concentration (PNEC) is often used in ecological risk assessment to determine low-risk concentrations for chemicals. In the present study, native marine species were selected for toxicity testing. The PNECs for three polycyclic aromatic hydrocarbons (PAHs), specifically phenanthrene (Phe), pyrene (Pyr), and benzo[a]pyrene (BaP), were derived from chronic and acute toxicity data with log-normal statistical methods. The achieved PNECs for Phe, Pyr, and BaP were 2.33, 1.09, and 0.011 µg/L, respectively. In Jinzhou Bay and the Shuangtaizi River Estuary of Liaodong Bay in the Bohai Sea, China, the surface water concentrations of the three PAHs were analyzed by gas chromatography-mass spectrometry. Based on two probabilistic ecological risk assessment (PERA) methods, namely probabilistic risk quotient and joint probability curve, the potential risk of Phe, Pyr, and BaP in Jinzhou Bay and Shuangtaizi River Estuary was assessed. The same order of ecological risk (BaP > Phe > Pyr) was found by both models. Our study considered regional characteristics of marine biota during the calculation of PNECs, and the PERA methods provided probabilities of potential ecological risks of chemicals. Within the study area, further research on BaP is required due to its high potential ecological risk.

Congener specific distributions of polybrominated diphenyl ethers (PBDEs) in sediment and mussel (Mytilus edulis) of the Bo Sea, China.

Congener specific distributions of polybrominated diphenyl ethers (PBDEs) were investigated in sediment and mussel (Mytilus edulis) collected from the coast of Bo Sea, China. The median values of BDE-209 and SigmaPBDEs (including BDE-17, -28, -47, -66, -71, -85, -99, -100, -138, -153, -154, -183 and -190) were 2.29 and 0.16 ng g(-1)dry weight in sediment, and 2.43 and 0.68 ng g(-1)dry weight in mussel, respectively. BDE-209 was the predominant congener (61-99% in mussel and 75-99% in sediment except for one sample with 17%). Different congener patterns (excluding BDE-209) were observed between sediment and mussel, which were attributed to individual congener's bioaccumulation potential and/or the ability to metabolize. The four most abundant congeners were BDE-47 (40.3%), -99 (22.5%), -71 (8.9%) and -28 (5.8%) in sediment, and -47 (36.4%), -28 (14.5%), -154 (8.6%) and -71 (8.6%) in mussel, respectively. The ratios of BDE-47/BDE-99 and BDE-100/BDE-99 in sediment were lower than those in mussel, indicating higher transformation and uptake rate of BDE-99 in mussel. The biota-sediment accumulation factor (BSAF) of individual PBDE congeners declined with the increase of their logarithm of octanol-water partition coefficients (log K(OW)) except for BDE-154, indicating congeners with higher logK(OW) were more likely to retain in sediment. These can be explained with a high affinity of these compounds for carbonaceous geosorbents, and molecular steric hindrance that limits large, very hydrophobic organic compounds from penetrating the cellular membranes.

Correlations between physicochemical properties of PAHs and their distribution in soil, moss and reindeer dung at Ny-Alesund of the Arctic.

Concentrations of 16 polycyclic aromatic hydrocarbons (PAHs) in soil, moss and reindeer dung collected at Ny-Alesund of the Arctic were measured to investigate their accumulation trends and distribution in the three compartments. Compared with the other regions, the proportions of 2 + 3 ring PAHs to the total PAHs were higher, whereas the proportions of 5 + 6 ring PAHs were lower in the three compartments at Ny-Alesund. Significant log/log-linear relationship was observed between the sub-cooled liquid vapor pressure (p(L)( degrees )) and the soil/moss quotient (Q(SM)). The relation was similar to the relationship between the gas/particle partition coefficient (K(P)) and p(L)( degrees ) of PAHs, implying Q(SM) would be a "mirror image" of K(P). Excellent log/log-linear relationships were observed between Q(SM) and K(OA) as well as between the moss/dung quotient (Q(MD)) and K(OW). The results presented here indicate the physicochemical properties are suitable for characterizing the distribution of PAHs in soil, moss and reindeer dung.