The industrial chlorinated paraffins (CPs) are comprised of short-chain (SCCPs), medium chain (MCCPs), and long chain (LCCPs) CPs. Although SCCPs and MCCPs are environmentally ubiquitous, little is known about CPs in humans. This study established a method for simultaneous determination of 261 SCCP, MCCP, and LCCP congener groups in one injection by reversed ultrahigh-pressure liquid chromatography coupled with chlorine-enhanced electron spray ionization-quadrupole time-of-flight mass spectrometry. The method yielded good peak shapes, high sensitivities, and low coeluted interferences for all examined CPs. LCCPs with carbon numbers of 21 to 27 were detected in their standard technical mixtures, and MCCPs and LCCPs impurities were detected in the LCCP and MCCP standard technical mixtures, respectively, causing quantification deviations when these mixtures were used for calibration. After considering these impurities’ contribution to the total concentrations, the quantification accuracies for ∑SCCPs, ∑MCCPs, and ∑LCCPs ranged from 95.1 ± 8.4% to 105.6 ± 9.2% in the eight CP technical mixtures. The method was successfully applied to determine CPs in about 6 g human blood samples from a general population, and estimated ∑SCCP, ∑MCCP, and ∑LCCP concentrations to be 370–35 000, 130–3200, and 22–530 ng/g lipid weight (n = 50), respectively. A comparison of blood and soil/air CP profiles from the same areas suggested a relatively higher potential for the accumulation of SCCPs, compared with MCCPs, in humans.

Habitat is of great importance in determining the trophic transfer of pollutants in freshwater ecosystems; however, the major factors influencing chemical trophodynamics in pelagic and benthic food webs remain unclear. This study investigated the levels of p,p′-dichlorodiphenyldichloroethylene (p,p′-DDE), polycyclic aromatic hydrocarbons (PAHs), and substituted PAHs (s-PAHs) in 2 plankton species, 6 invertebrate species, and 10 fish species collected from Lake Dianchi in southern China. Relatively high concentrations of PAHs and s-PAHs were detected with total concentrations of 11.4–1400 ng/g wet weight (ww) and 5.3–115 ng/g ww, respectively. Stable isotope analysis and stomach content analysis were applied to quantitatively determine the trophic level of individual organisms and discriminate between pelagic and benthic pathways, and the trophodynamics of the detected compounds in the two food webs were assessed. P,p′-DDE was found to exhibit relatively higher trophic magnification rate in the pelagic food web than in the benthic food web. In contrast, PAHs and s-PAHs exhibited greater dilution rates along the trophic levels in the pelagic food web. The lower species differences of pollutants accumulated in benthic organisms compared to pelagic organisms is attributable to extra uptake via ingested sediment in benthos. The average uptake proportions of PAHs and s-PAHs via ingested sediment in benthic biotas were estimated to be 31–77%, and that of p,p′-DDE was 46%. The uptake routes are of importance for assessing the trophic magnification potentials of organic pollutants, especially in eutrophic freshwater ecosystems.

The present study applied nontargeted screening techniques as a novel approach to evaluate the tap water samples collected during the “4.11” tap water pollution incident occurred on April 11, 2014 in Lanzhou in west China. Multivariate analysis (PCA and OPLS-DA) of about 3000 chemical features obtained in extracts of tap water samples by ultrahigh-pressure liquid chromatography quadrupole time-of-flight mass spectrometry (UPLC-QTOF-MS) analysis showed significantly different chemical profiles in tap water from pollution regions versus reference regions during the event. These different chemical profiles in samples from different regions were not observed in samples collected during the nonpollution period. The compounds responsible for the differences in profiles between regions were identified as naphthenic acids (NAs) and oxidized NAs (oxy-NAs) after the sample extracts underwent bromination to explore saturations, dansylation to identify hydroxylations and corresponding MS/MS mode analysis. A consistent finding was further observed in the targeted analysis of NA mixtures, demonstrating that the Lanzhou “4.11” tap water pollution incident could be attributed to oil spill pollution, and NA mixtures would be a marker for oil contamination. Such evaluations can help to rapidly discriminate pollution sources in accidental pollution events and contribute to regular water monitoring management of water safety issues.

The use of trophic magnification factors (TMFs) to characterize the bioaccumulation potentials of chemicals was encouraged; however, the method for the assessment of trophic magnification potentials is still lacking. We optimized the in vitro assays used for the measurement of intrinsic clearance in liver microsomes by incorporating benzo[a]pyrene (B(a)P) as a benchmark compound. The intrinsic clearance of 40 compounds was then measured in microsomes from fish (weevers) and birds (quail); the characteristics of the trophic transfer of these 40 compounds were previously investigated in an aquatic food web in Bohai in northern China. Chemicals that are biotransformed at a rate similar to or higher than that of B[a]P in the microsomes of both weevers and quail (in vitro intrinsic clearance values, CL; CL/CLB[a]P: 0.1 to 2.4) generally exhibited no significant trophic magnification or dilution in the food web (TMF ≈ 1 or < 1), whereas chemicals that are biotransformed at extremely slow rates compared with B[a]P (CL/CLB[a]P: 0 to 0.2) showed significant trophic magnification in the food web (TMF > 1). The in vitro intrinsic clearance values of the target chemicals were found to be consistent with their respective trophic transfer behavior in the aquatic food web. Significant negative correlations were also found between the TMFs and the intrinsic clearance values of all target chemicals obtained in microsomes from both weevers and quail. Multiple linear regression analysis showed that biotransformation rates (CL/CLB[a]P) are a more important factor compared with the lipophilicity of the chemicals (log Kow) in the assessment of the trophic magnification of chemicals in the aquatic food web.

Naphthenic acids (NAs) are one class of compounds in wastewaters from petroleum industries that are known to cause toxic effects, and their removal from oilfield wastewater is an important challenge for remediation of large volumes of petrochemical effluents. The present study investigated occurrences and behaviors of total NAs and aromatic NAs in a refinery wastewater treatment plant, located in north China, which combined physicochemical and biological processes. Concentrations of total NAs were semiquantified to be 113–392 μg/L in wastewater from all the treatment units, and the percentages of aromatic NAs in total NAs was estimated to be 2.1–8.8%. The mass reduction for total NAs and aromatic NAs was 15 ± 16% and 7.5 ± 24% after the physicochemical treatment, respectively. Great mass reduction (total NAs: 65 ± 11%, aromatic NAs: 86 ± 5%) was observed in the biological treatment units, and antiestrogenic activities observed in wastewater from physicochemical treatment units disappeared in the effluent of the activated sludge system. The distributions of mass fractions of NAs demonstrated that biodegradation via activated sludge was the major mechanism for removing alicyclic NAs, aromatic NAs, and related toxicities in the plant, and the polycyclic NA congener classes were relatively recalcitrant to biodegradation, which is a complete contrast to the preferential adsorption of NAs with higher cyclicity (low Z value). Removal efficiencies of total NAs were 73 ± 17% in summer, which were higher than those in winter (53 ± 15%), and the seasonal variation was possibly due to the relatively high microbial biotransformation activities in the activated sludge system in summer (indexed by O3–NAs/NAs). The results of the investigations indicated that biotransformation of NA mixtures by the activated sludge system were largely affected by temperature, and employing an efficient adsorbent together with biodegradation processes would help cost-effectively remove NAs in petroleum effluents.

Oxy-naphthenic acids (oxy-NAs) are one of the major components of NA mixtures in wastewaters from petroleum industries. The limited available data indicated that oxy-NAs were considered as a potential marker for the degradation of NAs, and some oxy-NAs exhibited endocrine disrupting activities. However, the lack of information on the structures and occurrences of oxy-NAs in oilfield wastewaters limited the interpretations of the biotransformation pathways of NAs and structure-specific toxicity. A sensitive method for simultaneous determination of oxy-NAs together with NAs was developed by combining MAX extraction column and UPLC-ESI–-QTOF-MS. The 2000-fold SPE preconcentration step was highly specific for acids and the prewash solvent greatly reduced matrix effects in the UPLC-ESI–-QTOF-MS analysis, resulting in an increase in sensitivity down to detection limits in the ng/L range. To provide structural information within each oxy-NA isomer class, a new method was developed by derivatizing oxy-NAs with dansyl chloride by UPLC-ESI+-QTOF-MS. The molecular ion dansyl derivatives from the corresponding oxy-NAs and characteristic fragmentation ions, not detected before derivatization, were observed in the extracts of oilfield wastewater, providing evidence that O3–NAs and O4–NAs were mainly composed of OH–NAs and (OH)2–NAs, respectively. Semiquantification of oxy-NAs and NAs in various oilfield wastewaters revealed NAs, O3–NAs, and O4–NAs present at concentrations of 187–397, 44–146, and 40–108 μg/L, respectively. Significantly different profiles of NA mixtures were observed in petroleum refinery wastewater and oil sands extraction water, but the profile of oxy-NAs was similar to NAs in different wastewaters suggesting the existence of biotransformation between NAs and oxy-NAs in the environment, and hydroxylation could be one of the major biotransformation pathways of NAs.

While occurrences and origins of hydroxylated (OH-) polybrominated diphenyl ethers (PBDEs) in organisms have been reported, the fates of these compounds in abiotic matrixes and related trophodynamics are unclear. The present study measured concentrations of nine OH-PBDEs, twelve methoxylated (MeO-) PBDEs, and eleven PBDEs in marine sediments and explored the trophodynamics of OH-PBDEs in five invertebrates, eight fish, and two species of birds from Liaodong Bay, north China. While concentrations of PBDEs were less than the limit of quantification in sediments, concentrations of ΣOH-PBDEs and ΣMeO-PBDEs were 3.2–116 pg/g dry weight (dw) and 3.8–56 pg/g dw, respectively. When the detected compounds were incubated in native marine sediments the interconversion between 6-OH-BDE47 and 6-MeO-BDE47 was observed. This result is consistent with the similar spatial distributions and significant correlation between the concentrations of these naturally occurring compounds. 6-OH-BDE47 and 2′-OH-BDE68 were detected as the two major congeners in organisms collected from Liaodong Bay, and concentrations were 0.24 ± 0.005 ng/g lw (lipid weight) and 0.088 ± 0.006 ng/g lw, respectively. Biota-sediment accumulation factors (BSAFs) for invertebrates of 6-OH-BDE47 and 2′-OH-BDE68 were 0.017–0.96 and 0.19–1.5 (except for short-necked clam: 6.3), respectively. Lipid-normalized concentrations of 6-OH-BDE47 and 2′-OH-BDE68 decreased significantly with trophic level with TMFs of 0.21 and 0.15, respectively. The fates of OH-PBDEs in sediment together with their trophodynamics in marine food webs suggested that OH-PBDEs are partitioned into sediment and undergo biodilution in the marine food web.

•Vegetable and cereal ingestion were the main contributors to exposure of Pb/Cr and Mn/Cd, respectively.•Concentrations of Pb/Cr in vegetables grown near MSWI were significantly higher.•Blood concentrations of Pb/Cr in populations near MSWI were significantly higher.•MSWI-local food-human is an important exposure pathway for residents living near MSWI.The potential health effects of toxic chemicals (e.g. heavy metals) emitted by municipal solid waste incinerators (MSWIs) are of great concern to local residents, however there have been few studies on the contributions of different exposure pathways and their subsequent effects on the body burden of residents living near MSWIs. In this study, multiple exposure routes of heavy metals including Pb, Cr, Cd and Mn were assessed by investigating the metals in foods (such as vegetables, crops, meats and fruits etc.), drinking water, ambient air and soil collected surrounding an MSWI in Shenzhen, south China. Vegetable ingestion played the most important role in the total average daily dose of Pb and Cr, and cereals were the key exposure routes for Mn and Cd. Compound-specific contaminations were observed in the investigated areas, with Pb and Cr present in the surrounding environment, having accumulated to relatively high levels in the local vegetables, and the intake of contaminated vegetable foods greatly influencing the body burden of Pb and Cr. Consistently, significantly high blood concentrations of Pb and Cr were detected in the local residents compared to a referenced population, and a lack of significant differences was found for Cd and Mn. The results possibly suggested that emission of MSWI influenced the external exposure doses of the major pathways of Pb and Cr in this study, and resulted in the different body burden of metals in humans living near a MSWI. MSWI-local food-humans is an important exposure pathway for residents living near MSWI, and thus should not be neglected in developing future strategies and policies to prevent the high risks suffered by residents living near MSWIs.Download high-res image (295KB)Download full-size image