Impacts of Seasonal Variation on Organochlorine Pesticides in the East China Sea and Northern South China Sea.

To investigate the characteristics of historic-use organochlorine pesticides (OCPs) in the marginal seawater of China, we examined the seasonal and spatial distributions of hexachlorobenzene (HCB), hexachlorocyclohexanes (HCHs), and dichlorodiphenyltrichloroethane (DDTs) in the northern South China Sea (NSCS, 18-23° N) and East China Sea (ECS, 26-32° N). Seasonally, in the NSCS, the significantly higher concentrations (p < 0.05) of HCB, HCHs, and DDTs were found in summer, autumn, and summer through autumn, respectively. In the ECS, the higher concentrations were found in summer through winter, autumn, and summer. Spatially, HCB concentrations were significantly higher in the NSCS than in the ECS during all seasons except winter. During all four seasons, concentrations of HCHs were significantly higher in the NSCS than in the ECS. In summer and autumn, concentrations of DDTs were significantly higher in the NSCS than in the ECS, while no significant differences were found in spring and winter. Generally, regional usage, river-influenced coastal plumes, phytoplankton abundances, and ocean currents played crucial roles in the input, transport, degradation, and dilution of OCPs. These dynamic factors along with the seasonally alternating monsoon directly influenced the seasonal and spatial characteristics of OCPs. Furthermore, the profiles and diagnostic ratios of HCHs and DDTs revealed highly weathered OCP residues, attributed to eroded soils carried by surface runoff and long-range oceanic and atmospheric transport.

Fossil Fuel-Derived Polycyclic Aromatic Hydrocarbons in the Taiwan Strait, China, and Fluxes across the Air-Water Interface.

On the basis of the application of compound-specific radiocarbon analysis (CSRA) and air-water exchange models, the contributions of fossil fuel and biomass burning derived polycyclic aromatic hydrocarbons (PAHs) as well as their air-water transport were elucidated. The results showed that fossil fuel-derived PAHs (an average contribution of 89%) presented the net volatilization process at the air-water interface of the Taiwan Strait in summer. Net volatile fluxes of the dominant fluorene and phenanthrene (>58% of the total PAHs) were 27 ± 2.8 µg m-2 day-1, significantly higher than the dry deposition fluxes (average 0.43 µg m-2 day-1). The Δ14C contents of selected PAHs (fluorene, phenanthrene plus anthracene, fluoranthene, and pyrene) determined by CSRA in the dissolved seawater ranged from -997 ± 4‰ to -873 ± 6‰, indicating that 89-100% (95 ± 4%) of PAHs were supplied by fossil fuels. The South China Sea warm current originating from the southwest China in summer (98%) and the Min-Zhe coastal current originating from the north China in winter (97%) input more fossil fuel PAHs than the Jiulong River estuary (90%) and Xiamen harbor water (93%). The more radioactive decayed 14C of fluoranthene (a 4-ring PAH) than that of phenanthrene and anthracene (3-ring PAHs) represented a greater fossil fuel contribution to the former in dissolved seawater.

Seasonal Variation of Terrigenous Polycyclic Aromatic Hydrocarbons along the Marginal Seas of China: Input, Phase Partitioning, and Ocean-Current Transport.

To study the spatial distributions and seasonal differences of concentrations, source identification, and phase partitioning of polycyclic aromatic hydrocarbons (PAHs) in surface water, intensive sampling was carried out along the marginal seas of China in four seasons. In the northern South China Sea (SCS), the highest PAH levels occurred in the summer (July to August) and autumn (October to November). In the East China Sea (ECS) and the Yellow Sea, the highest occurred in the summer (August) and winter (December). In all areas, the lowest PAH levels were found in the spring (May to June). The estimated mass inventory of PAHs in the surface water (0-5 m) of the northern SCS and ECS accounted for less than 8% of PAHs outflow into the offshore environment. That showed the consistent seasonal variation with PAHs levels. Land- and ocean-based emissions, surface runoff, and the open seawater dilution were the most important environmental factors influencing the seasonal heterogeneity and the spatial distributions of PAH in the surface water. The decline of observed organic carbon normalized partition coefficients in the four seasons was probably affected by the presence of submicrometer-sized soot particles accompanying the PAH outflow from China.

A methodological review of compound-specific radiocarbon analysis for polycyclic aromatic hydrocarbons in environmental matrices.

Identifying the sources of polycyclic aromatic hydrocarbons (PAHs) in complex environmental matrices is essential for understanding the impact of combustion-related human activities on the environment. Since the turn of the century, advances in analytical capability and accuracy of accelerator mass spectrometry (AMS) have made it possible to accurately determine the source apportionment of PAHs based on their radiocarbon (14C) mass conservation. This also allows us to trace the environmental transport processes of PAHs from the perspective of molecular 14C. However, natural environmental matrices have very low concentrations of PAHs (ppb to ppm level). To meet the requirements of carbon weight for 14C measurement by AMS, trace PAHs in complex environmental matrices must be enriched thousands of times, and then higher purity individual PAH molecules should be obtained through a series of complex purification procedures. Therefore, the technical difficulty is the main challenge in expanding the application of compound-specific 14C analysis in environmental science. This article reviews the detailed pretreatment procedures for 14C measurement of specific PAHs, including sample enrichment, extraction and purification of aromatic components, preparation of compound-specific PAHs by preparative capillary gas chromatography, graphitization of samples with ultra-small carbon content, and relevant quality control and assurance procedures. This study aims to help environmental geoscientists understand the technical process of 14C analysis of PAHs and inspire new scientific questions related to environmental science. To our knowledge, this is the first comprehensive review of the technical method of compound-specific 14C analysis for PAHs.

Fine particles and pyrogenic carbon fractions regulate PAH partitioning and burial in a eutrophic shallow lake.

Aquatic particles and organic carbon (OC) regulate the occurrence and transport of hydrophobic organic contaminants such as polycyclic aromatic hydrocarbons (PAHs) in water-suspended particle-sediment interfaces. Conventional studies on the mechanisms regulating the relationships between PAHs and total particles/OC have ignored micro-scale regulatory factors such as particle size and OC composition. Field research in the eutrophic shallow Lake Taihu, China, revealed that the fine particle fractions 2.7-10 µm in diameter had stronger PAH adsorption capacity and significantly regulated PAH particle size distribution and water-particle partitioning. Selective PAH biodegradation by planktonic microorganisms probably significantly weakened the capacity of the coarse fractions to regulate PAHs. OC fragments at different temperature gradients had markedly different influences on the particle size distribution of PAHs. High-temperature pyrogenic OC fractions (part of black carbon) were the principal OC regulatory factors for medium-to high-molecular-weight PAHs. However, the OC fragments did not directly affect the particle distribution of low-molecular-weight PAHs. During particle deposition and burial, microbial PAH utilization and efficiency probably regulated the burial potential of various hydrophobic PAH species. Biodegradation of relatively less hydrophobic PAHs with octanol-water partition coefficients (log Kow) < 5.8 showed an increasing trend with decreasing PAH hydrophobicity. Biological pump action of the relatively higher hydrophobic PAH species (log Kow > 5.8) showed a decreasing trend with increasing PAH hydrophobicity. The discoveries of the present work further clarified the mechanisms of PAH partitioning and burial in a eutrophic shallow lake and collectively provides a valuable reference for modeling the transport and dispersal mechanisms of hydrophobic, particle-bound organic contaminants in other aquatic ecosystems.

Legacy and emerging persistent organic pollutants in the marginal seas of China: Occurrence and phase partitioning.

Emerging per-and polyfluoroalkyl substances (PFASs) and traditional organochlorine pesticides (OCPs), polycyclic aromatic hydrocarbons (PAHs) in the marginal seas of China were analyzed to study the occurrence, transport and phase partitioning. The influence of organic carbon (OC) and element carbon (EC) on particulate emerging pollutants in seawater was studied for the first time. The concentrations of PFASs, OCPs and PAHs in the seawater (dissolved phase plus particulate phase) ranged from 1.4 to 8.6, 0.76 to 4.3 and 8.4 to 130 ng L-1, respectively. Pollutants in the northern East China Sea were generally higher than that in the southern East China Sea and South China Sea, which may be attribute to river discharges and land sources in the Yangtze River Delta. The Yellow Sea Coastal Current and Yangtze River Dilute Water drove the transport of contaminants from north to south marginal seas. Positive correlations between EC and PAHs were found, which can be explained by co-emission of them during combustion. Moreover, positive correlations between OC, EC and Log Kd for BkF, BeP, HCB, 6:2 FTSA were found, which demonstrated that OC and EC promoted the partitioning of these high oleophilic compounds to suspended particle.

Compound-specific radiocarbon reveals sources and land-sea transport of polycyclic aromatic hydrocarbons in an urban estuary.

As typical chemical indicators of the Anthropocene, polycyclic aromatic hydrocarbons (PAHs) and their environmental behavior in urban estuaries can reveal the influence of anthropogenic activities on coastal zones worldwide. In contrast to conventional approaches based on concentration datasets, we provide a compound-specific radiocarbon (14C) perspective to quantitatively evaluate the sources and land‒sea transport of PAHs in an estuarine‒coastal surficial sedimentary system impacted by anthropogenic activities and coastal currents. Compound-specific 14C of PAHs and their 14C end-member mixing models showed that 67-73% of fluoranthene and pyrene and 76-80% of five- and six-ring PAHs in the Jiulong River Estuary (JRE, China) originated from fossil fuels (e.g., coal, oil spill, and petroleum-related emissions). In the adjacent Western Taiwan Strait (WTS), the contributions of fossil fuel to these PAH groups were higher at 74-79% and 84-87%, respectively. Furthermore, as a significant biomarker for source allocation of terrigenous organic matter, perylene, a typical five-ring PAH, and its land‒sea transport from the basin through the JRE and finally to the WTS was quantitatively evaluated based on the 14C transport models. In the JRE, fluvial erosions and anthropogenic emissions affected the 14C signature of perylene (Δ14Cperylene, -535 ± 5‰) with contributions of > 38% and < 62%, respectively. From the JRE to the WTS, the decreased Δ14Cperylene (-735 ± 4‰) could be attributed to the long‒range transport of "ocean current-driven" perylene (-919 ± 53‰) with a contribution of 53 ± 8%. This compound-specific 14C approach and PAH transport model help provide a valuable reference for accurately quantifying land‒sea transport and burial of organic pollutants in estuarine‒coastal sedimentary systems.

Spatial-temporal distribution and transport flux of polycyclic aromatic hydrocarbons in a large hydropower reservoir of Southeast China: Implication for impoundment impacts.

In order to investigate the impacts of dam-related water impoundment on the spatial-temporal variations and transport of anthropogenic organic pollutants, 15 priority polycyclic aromatic hydrocarbons (PAHs) were analyzed in water samples from the Shuikou Reservoir (SKR) of the Minjiang River. The SKR was formed after the construction of the Shuikou Dam, which is the largest hydropower station in Southeast China. The water samples were collected from the backwater zone of the SKR, in both the wet and dry seasons, corresponding to the drainage and impoundment periods of water flow, respectively. The concentrations of the dissolved PAHs in surface water from the wet season (average of 161 ±â€¯97 ng L-1) were significantly higher (ANOVA, p < 0.01) than those from the dry season (average of 43 ±â€¯21 ng L-1). PAH concentrations in the SKR decreased from upstream (industrialized cities) to downstream (rural towns or counties), indicating high PAH loads caused by intensive urbanization effects. The high proportions of 3-ring PAHs in the wet season were from local sources via surface runoff; while the elevated proportions of 4- to 6- ring PAHs in the dry season reflected atmospheric deposition emerged of these PAHs and/or volatilization of 3-ring PAHs enhanced. Molecular diagnostic ratios of PAH isomers in multimedium and principal component analysis indicated that PAH presence in the SKR was mainly attributed to pyrogenic origin. The isomeric ratios of fluoranthene to fluoranthene plus pyrene in the wet season were homogeneous, implying that there were continuous new inputs along the riverine runoff. However, these ratios showed spatial downward trend in the dry season, indicating continued degradation of PAHs occurred along the transport path during the impoundment period. The input and output fluxes of PAHs in the SKR were 5330 kg yr-1 and 2991 kg yr-1, revealing that the reservoir retained contaminants after impoundment of the hydropower dam.

Traditional and emerging organophosphate esters (OPEs) in indoor dust of Nanjing, eastern China: Occurrence, human exposure, and risk assessment.

Here, fifteen OPEs were investigated in n = 50 floor dust samples collected from six types of indoor spaces in Nanjing, eastern China, in the year 2018. Ten OPEs, including tris(2-chloroethyl) phosphate (TCEP), tris(2-chloroisopropyl) phosphate (TCIPP), tris(1,3-dichloro-isopropyl) phosphate (TDCIPP), tris(2-ethylhexyl) phosphate (TEHP), tris(2-butoxyethyl) phosphate (TBOEP), 2-ethylhexyl-diphenyl phosphate (EHDPP), triphenyl phosphate (TPHP), tris(methyl-phenyl) phosphate (TMPP), 4-biphenylyl diphenyl phosphate (4-BPDP) and tris(2-biphenylyl) phosphate (TBPP), were detected in at least one of the analyzed samples (>method limits of quantification). Regardless of indoor spaces, EHDPP (34% of Σ8OPEs, mean: 1.43 µg/g) and TDCIPP (19%, 0.81 µg/g) were the ascendant OPEs in indoor floor dust. 4-BPDP and TBPP were detectable in indoor floor dust samples, but at relatively low detection frequencies with 2% and 10%, respectively. Various indoor microenvironments exhibited different pollution characteristics of OPEs. Floor dust collected from electronic product maintenance centers contained the richest OPE contaminants with highest mean Σ8OPEs concentration of 7.92 µg/g. On the basis of measured Σ10OPEs concentrations in dust sample, we estimated daily intake via floor dust ingestion to be 1.37, 0.75 and 1.24 ng/kg BW/day for electronic engineers, undergraduates, and graduate students under mean-exposure scenario, respectively. Overall, our study reported the occurrence of 4-BPDP and TBPP in environmental samples for the first time, and demonstrated that indoor floor dust ingestion exposure does values were far less than reference dosage values of oral toxicity proposed by United States Environmental Protection Agency (USEPA) Integrated Risk Information System.

Dietary intake of legacy and emerging halogenated flame retardants using food market basket estimations in Nanjing, eastern China.

Food products are inevitably contaminated by flame retardants throughout their lifecycle (i.e., during production, use, and disposal). In order to evaluate the dietary intake of legacy and emerging halogenated flame retardants (HFRs) in typical market food in China, we investigate the distribution and profile of 27 legacy polybrominated diphenyl ethers (PBDEs) and 16 emerging HFRs (EHFRs) in 9 food categories (meat, poultry, aquatic food, eggs, dairy products, cereals, vegetables, nuts and fruits, and sugar). A total of 105 food samples collected from three markets in Nanjing, eastern China were included for evaluation. The highest concentrations of PBDEs and EHFRs were found in aquatic foods (means of 0.834 ng/g wet weight (ww) and 0.348 ng/g ww, respectively), and the lowest concentrations were found in sugar (means of 0.020 ng/g ww for PBDEs and 0.014 ng/g ww for EHFRs). 2,2',4-tribromodiphenyl ether (BDE-17), a legacy HFR, and hexabromobenzene (HBBz), an EHFR, were the predominant pollutants in the investigated food samples. Concentrations of HBBz and 2,3-dibromopropyl tribromophenyl ether (DPTE) were comparable to those of some PBDEs in certain food samples. The concentrations of the total EHFRs and total PBDEs found in animal-based food samples were significantly greater than those in plant-based food samples. Comparison of the estimated total dietary intake of HFRs and their corresponding non-cancer reference dose (United States Environmental Protection Agency) suggests a low overall health risk. To the best of our knowledge, the present study is the first to simultaneously determine 27 PBDEs and 16 EHFRs in representative foods from Chinese markets. BDE-17, HBBz, and DPTE were the predominant congeners among the 43 investigated HFRs and meat and aquatic foods were the primary sources of PBDEs and EHFRs to the total local dietary intake.

Seasonal variation and spatial transport of polycyclic aromatic hydrocarbons in water of the subtropical Jiulong River watershed and estuary, Southeast China.

Riverine runoff is one of the most important pathways of pollutants entering the oceans. To study the seasonal variations, spatial transports, sources and mass fluxes of polycyclic aromatic hydrocarbons (PAHs) from the subtropical Jiulong River watershed to estuary, water samples were collected in wet and dry seasons. PAH concentrations showed significant temporal-spatial variations (ANOVA, p < 0.05). In the watershed, PAH concentrations in wet season (48.6 ±â€¯18.2 ng L-1) were significantly lower than in dry season (90.3 ±â€¯18.5 ng L-1). In contrast, estuarine PAH concentrations in wet season (67.1 ±â€¯24.6 ng L-1) were significantly higher than in dry season (27.4 ±â€¯10.6 ng L-1) (p < 0.0001). The spatial variations of PAH concentrations in wet and dry seasons reflected positive and restricted transport processes occurred in the river. These findings might be subjected to seasonal changes in precipitation, water discharge, hydrodynamic conditions, and human activities. The compositional patterns of PAHs illustrated that fluorene and phenanthrene were the dominant compounds in the watershed, while phenanthrene was predominant in the estuary. Source analysis by molecular diagnostic ratios and PMF model indicated that fossil fuel and biomass combustion and petroleum both contributed to the presence of PAHs, and the high contributions of pyrogenic PAHs might be related to urban rainstorm runoff in winter and atmospheric inputs in winter. Although the estimated flux of PAHs from watershed to estuary was about 676 kg yr-1 with a low level by comparing the data obtained in the worldwide, continue concern of PAHs in the Jiulong River is recommended due to the intense human activities.

Distribution and isotopic composition of sedimentary black carbon in a subtropical estuarine-coastal region of the western Taiwan Strait: Implications for tracing anthropogenic inputs.

Estuarine and coastal margins are strongly influenced by anthropogenic inputs. To trace anthropogenic inputs to the subtropical Jiulong River Estuary (JRE) and the adjacent western Taiwan Strait (WTS), black carbon (BC) and its stable carbon isotope composition (δ13СBC) in surface sediments were investigated as an indicator of human activities. The concentrations of sedimentary BC were measured by an emerging method of thermal/optical reflectance with wet-chemical treatment (BCTOR, including char and soot), and the conventional method of chemothermal oxidation (BCCTO, related to the soot fraction) was also used to determine BCCTO concentrations and δ13СBC compositions. In the JRE and adjacent WTS, the concentrations of BCTOR (0.77 to 3.79 mg g-1) were higher than those of BCCTO (0.55 to 2.46 mg g-1), and both were similar to the moderate ranges obtained in other coastal sediments around the world. The small offsets between δ13СTOC and δ13СBC and the relatively low char/soot ratios revealed that fossil fuel combustion-derived contributions were likely more significant compared with inputs from biomass burning. The decreasing BC concentrations and increasing δ13СBC values with increasing distance from the JRE towards the adjacent WTS, indicates the decline of land-based anthropogenic inputs through fluvial transport. Furthermore, the differences in BC/TOC and char/soot values between the southern and northern WTS, indicated an effective preferential dispersal of the fluvial BC to the southern coast. The estimation for mass inventories of sedimentary BC in the coastal WTS showed that direct riverine discharge from the JRE was nearly equivalent to atmospheric deposition, and both of them contributed half of the sedimentary BC sink. To balance the sedimentary BC budget in the coastal WTS, long-range alongshore sediment transport driven by the Fujian-Zhejiang coastal current containing Yangtze River derived materials (indirect riverine discharge) could be another significant input pathway to contribute sedimentary BC.

Biomonitoring of organophosphate triesters and diesters in human blood in Jiangsu Province, eastern China: Occurrences, associations, and suspect screening of novel metabolites.

Since organophosphate (OP) triesters are ubiquitous in environmental matrices, there is an increasing concern regarding human exposure to OP triesters or their metabolites. In this study, we measured levels of 16 OP triesters and 4 OP diesters in n = 99 human blood samples of non-occupationally exposed adults (aged 18-87) from Jiangsu Province, eastern China. Based on the measured concentrations, statistical difference and correlativity were calculated to characterize the population diversity and potential sources of OP triester and diester. Di (2-ethylhexyl) phosphate (DEHP) and 2-ethylhexyl diphenyl phosphate (EHDPP) were found in many participants' blood, with median concentrations of 1.2 (range: n.d. - 44.7, detection frequency: 99%) and 0.85 (n.d. - 28.8, 68%) ng mL-1, respectively. Blood samples of older participants contained significantly lower concentrations of OP diesters or triesters than their younger counterparts (p < 0.01). Regional- and age-specific differences in the blood concentrations of OP triesters and diesters were attributed to disparities in environmental exposure intensity. EHDPP and tris (phenyl) phosphate (TPHP), the predominant OP triesters, exhibited significant positive correlation (p < 0.01, r = 0.84) suggestive of analogous transport behavior from similar exposure sources to humans. The increased correlations between diphenyl phosphate (DPHP) and TPHP as well as with EHDPP as observed from the multivariate regression suggests that DPHP could be derived from the metabolism of both TPHP (the crucial precursor) and EHDPP. When the blood samples were subsequently screened using high-resolution spectrometry, we detected five novel OP metabolites: glucuronide conjugates of hydroxylated DEHP (OH-DEHP glucuronide conjugate), 2-ethylhexyl monophenyl phosphate (EHMPP), hydroxylated EHMPP (OH-EHMPP), dihydroxylated bis(2-butoxyethyl) phosphate (di-OH-BBOEP), and dihydroxylated tris(butyl) phosphate (di-OH-TNBP). Overall, this study provides novel information regarding the occurrence of OP triesters and diesters, and further suggested several novel OP metabolites in human blood.

Evaluation of marine sediment contamination by polycyclic aromatic hydrocarbons along the Karachi coast, Pakistan, 11 years after the Tasman Spirit oil spill.

On July 27, 2003, a spill of approximately 31,000 tons of Iranian light crude oil affected the coast of Karachi, Pakistan. Approximately 11 years after the spill, we analyzed polycyclic aromatic hydrocarbons (PAHs) and their alkylated homologues (alkyl-PAHs) as the indicators to evaluate the residual effect of oil spill to the sediment along the Karachi coast. The total concentrations (dry weight) of parent PAHs and alkyl-PAHs ranged from 121.9 to 735.4 and 42.3-1149.9 ng/g, respectively. The estuary and harbor were the two regions with the highest levels of PAHs in the sediment. Conversely, sedimentary PAHs in the oil spill areas and remote coastal areas showed significantly lower levels. Although the results of the source identification indicated the up to 75.2% of the contribution from petroleum and its derivatives, this could only reflect the direct impact of the Karachi city on the presence of PAHs in the coastal sedimentary environment and did not indicated that the oil spill continues to stay 11 years later. Compared with 11 years ago, the sharply reduced PAH content, great changed composition, and the degradation driven trend of diagnostic ratios all indicated a sharp decrease in the influence of PAHs caused by the oil spill. Finally, the ecological risk caused by the PAH residual in the marine sedimentary ecosystem had disappeared along the Karachi coasts, Pakistan.

Distribution of flame retardants in smartphones and identification of current-use organic chemicals including three novel aryl organophosphate esters.

Smartphones have become an integral tool of society; in the year 2017, approximately 30% of the global population used smartphones. After their life cycle of use, most smartphones are not recycled and are instead discarded as e-waste, which increases the probability that chemicals they contain will eventually be released into the natural environment. In this study, the concentration and distribution of 52 major flame retardant (FR) chemicals were measured in eight components of seven models of largely produced smartphones. The results demonstrated that organophosphate esters (OPEs) were the principal FRs in these smartphone devices, while a suite of halogenated flame retardants (HFRs), including 25 polybrominated diphenyl ethers (PBDEs), were not detected. Triphenyl phosphate (TPHP) was the primary FR in the smartphones, followed by tris(2-butoxyethyl) phosphate (TBOEP), 2-ethylhexyl diphenyl phosphate (EHDPP), triethyl phosphate (TEP), tris(2-chloroethyl) phosphate (TCEP), and tris(2-chloroisopropyl) phosphate (TCIPP), respectively. The average smartphone contained 3.37 × 107 ng TPHP/unit, which was concentrated in the phone screen. We estimated the annual amount of ΣOPEs and TPHP in smartphones used globally to be 53.5 and 51.8 tons, respectively. Extracts of phone screens were further analyzed by use of an untargeted screening strategy, and other 10 organic chemicals were identified. Interestingly, 3 out of them shared similar backbone structure of TPHP, and these 3 chemicals were tri(2,4-di-t-butylphenyl) phosphate (TDTBPP; CAS No. 95906-11-9), 2-biphenylol diphenyl phosphate (BPDPP; 132-29-6), and tris (2-biphenyl) phosphate (TBPHP; 132-28-5). Collectively, this study provided the first information on distribution of major FRs in different components of smartphones, and also identified other 10 current-use organic chemicals including three novel aryl OPEs which should be considered in further environmental studies including in toxicological and monitoring programs.

Concentration, distribution and sources of perfluoroalkyl substances and organochlorine pesticides in surface sediments of the northern Bering Sea, Chukchi Sea and adjacent Arctic Ocean.

Perfluoroalkyl substances (PFAS) and organochlorine pesticides (OCPs) in surface sediments were investigated from the Bering Sea, the Chukchi Sea and adjacent Arctic Ocean in 2010. Total concentrations (dry weight) of Σ14PFAS in surface sediments (0.85 ±â€¯0.22 ng g-1) of the Bering Sea were lower than that in the Chukchi Sea and adjacent Arctic Ocean (1.27 ±â€¯0.53 ng g-1). Perfluoro-butanoic acid (PFBS) and perfluoro-octanoic acid (PFOA) were the dominant PFAS in these areas. The concentrations of Σ15OCPs in the sediment of the Bering Sea (13.00 ±â€¯6.17 ng g-1) was slightly higher than that in the Chukchi and Arctic Ocean (12.05 ±â€¯2.27 ng g-1). The most abundant OCPs were hexachlorocyclohexane isomers (HCHs) and dichlorodiphenyltrichloroethane (DDT) and its metabolites. The composition patterns of HCHs and DDTs indicated that they were mainly derived from the early residues via river runoff. Increasing trends of PFAS, HCHs and DDTs in surface sediments from the Bering Sea to the Arctic Ocean were found, indicating oceanic transport. In summary, the concentrations of OCPs were orders of magnitude greater than the observed PFAS concentrations, and the concentrations of PFAS and OCPs in surface sediments from the Bering Sea to the Chukchi Sea and adjacent Arctic Ocean are at the low to moderate levels by comparing with other coastal and marine sediments worldwide.

Transport of terrigenous polycyclic aromatic hydrocarbons affected by the coastal upwelling in the northwestern coast of South China Sea.

Coastal upwelling prevails in the coast of Hainan Island, the northern South China Sea (SCS) during summer. We studied the influences of the upwelling on the horizontal and vertical transport of terrigenous polycyclic aromatic hydrocarbons (PAHs). PAHs in dissolved and suspended particulate phase of water samples were determined in the upper (depth < 1 m) and water column (depth > 10 m). PAH levels decreased sharply from inshore to offshore to open sea. The results showed that terrestrial input was the main source of coastal PAHs. Perylene, an important indicator of land plant-derived PAH, showed the significant correlation with PAHs (p < 0.005). This implied that fluvial transport was the primary pathway of terrigenous PAHs into the coast of northern SCS. Variations of the concentrations, compositions and diagnostic ratios of PAHs, accompanied the partition equilibrium in the water column, could indicate the selective degradation of PAHs by the plankton affected by upwelling. Different from the "traditional" transport pathway of PAHs in the water column (surface enrichment-depth depletion distribution), the upwelling could provide the original driver to elevate the upward diffusion of sediment entrained contaminants towards the intermediate even the upper waters. It could also enhance the outward diffusion of terrigenous PAHs accompanied by the offshore transport of the upper waters. Therefore, the transport pathway of PAHs can be summarized by the coastal upwelling rising PAHs with their subsequent transport offshore and settling in the adjacent open sea.

Anthropogenic organochlorine compounds as potential tracers for regional water masses: A case study of estuarine plume, coastal eddy, wind-driven upwelling and long-range warm current.

Water masses are the crucial factor driving the terrigenous anthropogenic organochlorine compounds (OCs) migration from the coast to open sea. Therefore, organochlorine pesticides (OCPs) and polychlorinated biphenyls (PCBs) were investigated in the Northern South China Sea (NSCS), where different types of water masses are generated by the East Asian summer monsoon: Pearl River estuary plume (PREP), Guangdong offshore eddy (GDEC), South China Sea warm current (SCSWC) and wind-driven upwelling current (WDUC). No discrepant distributions of OC concentrations were found in these water masses (p > 0.05). However, compositions and diagnostic ratios of HCHs, DDTs, trans- or cis-chlordane and PCBs could reflect the discrepancies in the input, transport and transformation of OCs caused by the hydrological characteristics of water masses, therefore, this allowing them to serve as potential tracers of regional water masses. In detail, α/γ-HCH and ß-HCH percentages could indicate the weathered residue in the GDEC, long-range transport in the SCSWC, rapid photodegradation in the surface WDUC and biodegradation in the deep WDUC, respectively. The predominance of o, p'-DDT and p, p'-DDT could indicate fresh input in the PREP, GDEC and WDUC. DDT/DDTs of ratios <0.5 also reflected long-range transport in the SCSWC. Different DDD/DDE ratios indicated different oxygen environments of microbial degradation in the surface and deep water of the WDUC. Trans/cis-chlordane ratios could indicate the selective degradation of trans-chlordane in different water masses. Finally, a higher proportion of penta-PCB could reflect the strong paint additive sources carried by river erosion in the PREP.

Polybrominated diphenyl ethers, organochlorine pesticides, and polycyclic aromatic hydrocarbons in water from the Jiulong River Estuary, China: levels, distributions, influencing factors, and risk assessment.

Estuarine systems play an important role in the transportation and transformation of organic pollutants from rivers. Polybrominated diphenyl ether (PBDE), organochlorine pesticide (OCP), and polycyclic aromatic hydrocarbon (PAH) concentrations in water of the Jiulong River Estuary (JRE), China, were investigated to characterize their distribution, possible source, and potential ecological risk as well as the influencing factors. The total concentrations of PBDEs, OCPs, and PAHs varied from 5.2 to 12.3 pg L-1, from 29.1 to 96.4 ng L-1, and from 28.6 to 48.5 ng L-1, respectively. Their compositions were all consistent at different stations; even the input pathways were multifarious. A source analysis showed that PBDEs may come from the flame retardant usages of penta-BDE and deca-BDE; hexachlorocyclohexane isomers (HCHs) were from the use of technical HCHs, while DDTs were attributed to early residuals of industrial sources, and PAHs were mainly from pyrolytic sources. The spatial distributions of PBDEs and OCPs were quite similar with their concentrations, decreasing along the estuary and then increasing when passing the Xiamen Harbor. PAH concentrations were similar along the whole estuary, suggesting that local sources and hydrological conditions might be the influencing factors. The concentrations of these pollutants changed with tidal conditions and were positively correlated with SPM, DOC, and chlorophyll a but negatively correlated with salinity. The ecological risk assessment revealed that OCPs and PAHs posed slightly higher potential risks to aquatic organism in the study area.

Over 100-year sedimentary record of polycyclic aromatic hydrocarbons (PAHs) and organochlorine compounds (OCs) in the continental shelf of the East China Sea.

Historical records of polycyclic aromatic hydrocarbons (PAHs), organochlorine pesticides (OCPs) and polychlorinated biphenyls (PCBs) were analyzed in two dated sediment cores (DH05 and DH11) collected from the continental shelf of the East China Sea (ECS) to investigate the influence of anthropogenic activities on marine sediment over the past century. The concentrations and fluxes of 15 PAHs were in the range of 28.6-96.5 ng g-1 and 7.6-35.2 ng cm-2 yr-1 in DH05 (1920s-2009), 18.8-76.4 ng g-1 and 13.9-30.9 ng cm-2 yr-1 in DH11 (1860s-2009). The sedimentary records of PAHs in the two cores generally reflected the economic development and energy consumption change in China. Identification of sources suggested that PAHs in ECS were predominantly from petrogenic origin and various combustion sources. A change of source from low- and moderate-temperature combustion to high-temperature combustion process was observed. Although a production ban of technical HCH and DDT was imposed in China in 1983, their sedimentary fluxes display increasing trends or strong rebounds from 1980s to 1990s as recorded in the core profiles. High proportions of DDD + DDE and γ-HCH suggested those OCPs mainly derived from early residuals. Temporal trends of PCBs presented relative high levels from 1970s to 1980s and high proportions of PCB congeners with 3-6 chlorines atoms indicated industrial sources.