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Identifying causative toxicants in mixtures is critical, but this task is challenging when mixtures contain multiple chemical classes. Effect-based methods are used to complement chemical analyses to identify toxicants, yet conventional bioassays typically rely on an apical and/or single endpoint, providing limited diagnostic potential to guide chemical prioritization. We proposed an event-driven taxonomy framework for mixture risk assessment that relied on high-throughput screening bioassays and toxicant identification integrated by deep learning. In this work, the framework was evaluated using chemical mixtures in sediments eliciting aryl-hydrocarbon receptor activation and oxidative stress response. Mixture prediction using target analysis explained <10% of observed sediment bioactivity. To identify additional contaminants, two deep learning models were developed to predict fingerprints of a pool of bioactive substances (event driver fingerprint, EDFP) and convert these candidates to MS-readable information (event driver ion, EDION) for nontarget analysis. Two libraries with 121 and 118 fingerprints were established, and 247 bioactive compounds were identified at confidence level 2 or 3 in sediment extract using GC-qToF-MS. Among them, 12 toxicants were analytically confirmed using reference standards. Collectively, we present a "bioactivity-signature-toxicant" strategy to deconvolute mixtures and to connect patchy data sets and guide nontarget analysis for diverse chemicals that elicit the same bioactivity.

The fate of hydrophobic organic compounds in aquatic environment are largely determined by their exchange at sediment-water interface, which is highly dynamic and subject to rapidly evolving environmental conditions. In turn, environmental conditions may be governed by both physicochemical parameters and anthropogenic events. To examine the importance of various impact factors, passive sampling devices were deployed at the seafloor of Hailing Bay, an urbanized estuarine bay in Guangdong Province of South China to measure the sediment-water diffusion fluxes of several metabolites of dichlorodiphenyltrichloroethane (DDT), p,p'-DDE, p,p'-DDD and o,p'-DDD. The physicochemical properties of water (temperature, pH, salinity and dissolved oxygen) and surface sediment (sediment organic matter, physical composition, pH, water content, colony forming unit and catalase activity) were also measured. The results showed that the diffusion fluxes of o,p'-DDD, p,p'-DDD and p,p'-DDE at sites A1 and A2 near a fishing boat maintenance facility ranged from 0.42 to 4.73 ng m -2 d -1 (from sediment to overlying water), whereas those at offshore sites varied between -0.03 and -3.02 ng m -2 d -1 (from overlying water to sediment), implicating A1 and A2 as the sources of the target compounds. The distribution patterns of the diffusion fluxes of the target compounds were different from those of water and sediment parameters (water temperature, salinity, sediment texture, pH, colony forming unit and catalase activity) at six sampling sites. This finding suggested that none of these parameters were critical in dictating the sediment-water diffusion fluxes. Besides, decreases in the contents of kerogen and black carbon by 6.7% and 11% would enhance the diffusion fluxes of the target compounds by 11-14% and 12-23%, respectively, at site A1, indicating that kerogen and black carbon were the key factors in mediating the sediment-water diffusion fluxes of DDT-related compounds in field environments., (Copyright © 2016 Elsevier Ltd. All rights reserved.)

Natural organic matter and grain size are considered as important parameters dictating the transport and fate of organic compounds in sediment. However, increasing evidence suggested that manufactured debris may alter the underlying mechanisms for biogeochemical cycling of organic compounds. To examine this assumption, estuarine sediment and embedded debris were collected from a fishery base in Guangdong Province of South China and analyzed for organophosphorus flame retardants (OPFRs), phthalates (PAEs), organotin compounds (OTs) and dichlorodiphenyltrichloroethanes (DDTs). Coarse-size debris (>200μm) were heterogeneously distributed in sediment, and most abundant near the boat maintenance facilities, aquaculture zone and shipping channel. The median concentrations of OPFRs, OTs, PAEs and DDTs in debris were 11, 0.2, 11 and 3.9μgg(-1) dry sample weight(-1), respectively, 1 to 3 orders of magnitude greater than those in bulk sediment (19, 60, 240 and 570ngg(-1) dry sample weight(-1), respectively). Furthermore, OPFRs, OTs and PAEs were mostly (>99%) enriched in coarse-size (63-2000μm) sediment, and there was no significant correlation (p>0.05) between the concentrations of OPFRs, OTs and PAEs in bulk and size-fractioned sediment samples and total organic carbon or grain size, similar to the distribution pattern of DDTs reported previously. When distinct debris were removed from the light-density (<1.7gcm(-3)) fraction of coarse-size (200-2000μm) sediment, the concentration levels of OPFRs, OTs, PAEs and DDTs declined by 84%, 59%, 55% and 7%, respectively. Obviously, debris irregularly distributed in sediment can alter the sediment sorption capacity for OPFRs, OTs and PAEs, and thus may undermine the significance of organic matter and grain size to the distribution of organic chemicals in sediment. Finally, commonly used procedures for preparing sediment samples and screening of debris may disturb the grain size distribution or underestimate the abundance of heavy-density debris, resulting in flawed sediment quality assessment., (Copyright © 2016 Elsevier B.V. All rights reserved.)

An overlooked issue for field application of in situ performance reference compound (PRC) calibration methods is the validity of the assumption that both the sorption of a target compound and desorption of its corresponding PRC follow the first-order kinetics with the same rate constants under stagnant conditions. In the present study, disposable polydimethylsiloxane fibers of 2 sizes (7 and 35 µm) impregnated with 8 (13) C-labeled or deuterated PRCs were statically deployed into different marine sediments, from which the kinetics for sorption of the target compounds and desorption of the PRCs were characterized. Nonsymmetrical profiles were observed for exchange of the target analytes and their corresponding PRCs in sediment under stagnant conditions. The hysteretic desorption of PRCs in the kinetic regime may be ascribed to the low chemical potential between the fiber and sediment porewater, which reflects the inability of water molecules to rapidly diffuse through sediment to solvate the PRCs in the aqueous layer around the fiber surface. A moderate correlation (r = 0.77 and r = 0.57, p < 0.05 for both regressions) between the PRC-calibrated equilibrium concentrations of 1,1-dichloro-2,2-bis-(chlorophenyl) ethylene (p,p'-DDE) and polychlorinated biphenyl (PCB)-153 and the lipid normalized levels in worms (Neanthes arenaceodentata) was obtained in co-exposure tests under simulating field conditions, probably resulting from slightly overestimated bioavailability because of the hysteretic desorption of PRCs and toxic effects. Environ Toxicol Chem 2016;35:1978-1985. © 2015 SETAC., (© 2015 SETAC.)

Freely dissolved polycyclic aromatic hydrocarbons (PAHs) were monitored in seven inland lakes of Antarctica by a polyethylene (PE)-based passive sampling technique, with the objective of tracking human footprints. The measured concentrations of PAHs were in the range of 14-360 ng L(-1) with the highest values concentrated around the Russian Progress II Station, indicating the significance of human activities to the loading of PAHs in Antarctica. The concentrations of PAHs in the inland lakes were in the upper part of the PAHs levels in aquatic environments from remote and background regions across the globe. The composition profiles of PAHs indicated that PAHs in the inland lakes were derived mainly from local oil spills, which was corroborated by a large number of fuel spillage reports from ship and plane crash incidents in Antarctica during recent years. Clearly, local human activities, rather than long-range transport, are the dominant sources of PAH contamination to the inland lakes. Finally, the present study demonstrates the efficacy of PE-based passive samplers for investigating PAHs in the aquatic environment of Antarctica under complex field conditions., (Copyright © 2016 Elsevier Ltd. All rights reserved.)

Surface sediments collected along the entire continental shelf of China, including Yellow Sea, the East China Sea (ECS) inner shelf and the South China Sea (SCS), were analyzed for linear alkylbenzenes (LABs), from which regional anthropogenic influences on the marine environment were assessed. The occurrence of LABs (5.6-77 ng/g; mean: 25 ng/g; median: 20 ng/g) implied light sewage contamination in coast sediment off China. Specifically, the SCS had higher sedimentary LAB levels than Yellow Sea and the ECS inner shelf, which was mainly related to the intensity of domestic wastewater discharge and marine fishing activities. Values of L/S and C₁₃/C₁₂ (defined in the main text) suggested certain degradation while I/E indicated limited degradation of LABs. Also, additional input sources and congener inter-conversions may have contributed to the inconsistent results for degradation of LABs in offshore sediments. Atmospheric inputs and wastewater discharge from marine fishing vessels predominantly contributed to sedimentary LABs in Yellow Sea and the SCS, while riverine input was mainly responsible for LABs along the ECS inner shelf., (Copyright © 2014 Elsevier Ltd. All rights reserved.)

To examine the impacts of urbanization and industrialization on the coastal environment, sediment samples were collected from an urbanized coastal zone (i.e., Daya Bay and Hong Kong waters of South China) and analyzed for 20 polybrominated diphenyl ethers (PBDEs) and 10 alternative halogenated flame retardants (AHFRs). The sum concentration of PBDEs was in the range of 1.7-55 (mean: 17) ng g(-1), suggesting a moderate pollution level compared to the global range. The higher fractions of AHFRs (i.e., TBB+TBPH, BTBPE and DBDPE) than those of legacy PBDEs (i.e., penta-BDE, octa-BDE and deca-BDE) corresponded with the phasing out of PBDEs and increasing demand for AHFRs. Heavy contamination occurred at the estuary of Dan'ao River flowing through the Daya Bay Economic Zone, home to a variety of petrochemicals and electronics manufacturing facilities. The concentrations of HFRs in surface sediments of Hong Kong were the highest in Victoria Harbor, which receives around 1.4 million tons of primarily treated sewage daily, and a good relationship (r(2) = 0.80; p < 0.0001) between the HFR concentration and population density in each council district was observed, highlighting the effect of urbanization. Moreover, the AHFR concentrations were significantly correlated (r(2) > 0.73; p < 0.05) with the production volume of electronic devices, production value of electronic industries and population size, demonstrating the importance of industrializing and urbanizing processes in dictating the historical input patterns of AHFRs.

Molecular diffusion across the sediment-water interface, as one of the key geochemical processes, dictates whether a sediment is a source or sink of chemicals, providing useful data in designing remedial actions. Despite ample previous efforts in quantifying sediment-water diffusion fluxes, the resulting methods are largely unsatisfactory. Herein, we introduce a novel passive sampling device capable of measuring vertical profiles of chemical concentrations near the sediment-water interface, from which diffusion fluxes can be calculated based on a model that we developed. In laboratory testing, diffusion fluxes (0.032-310 ng m(-2) d(-1)) of dichlorodiphenyltrichloroethane and its metabolites obtained from the present sampling device were consistent with those (0.38-610 ng m(-2) d(-1)) determined by using a conventional active sampling method, solid-phase extraction/liquid-liquid extraction. Field deployment of the sampling device yielded individual diffusion fluxes of p,p'-DDD, p,p'-DDE, p,p'-DDMU, o,p'-DDMU, p,p'-DDNU, and p,p'-DBP in the range of 5.9-150 ng m(-2) d(-1), which were comparable to those (5.5-85 ng m(-2) d(-1)) obtained with a benthic chamber. Moreover, diffusion fluxes of p,p'-DDT and o,p'-DDT obtained with the sampling device were negative; i.e., the sediment is acting as a sink for these chemicals, while that could not be found using the benthic chamber. Thus, the passive sampling device can provide better information about the movement of chemicals through the sediment and overlying water for the choice of remedial strategies.

Solid-phase microextraction (SPME) has often been used to estimate the freely dissolved concentration (Cfree ) of organic contaminants in sediments. A significant limitation in the application of SPME for Cfree measurement is the requirement for attaining equilibrium partition, which is often difficult for strongly hydrophobic compounds such as DDT. A method was developed using SPME with stable isotope-labeled analogues as performance reference compounds (PRCs) to measure Cfree of DDT and metabolites (DDTs) in marine sediments. Six (13) C-labeled or deuterated PRCs were impregnated into polydimethylsiloxane (PDMS) fiber before use. Desorption of PRCs from PDMS fibers and absorption of DDTs from sediment were isotropic in a range of sediments evaluated ex situ under well-mixed conditions. When applied to a historically contaminated marine sediment from a Superfund site, the PRC-SPME method yielded Cfree values identical to those found by using a conventional equilibrium SPME approach (Eq-SPME), whereas the time for mixing was reduced from 9 d to only 9 h. The PRC-SPME method was further evaluated against bioaccumulation of DDTs by Neanthes arenaceodentata in the contaminated sediment with or without amendment of activated carbon or sand. Strong correlations were consistently found between the derived equilibrium concentrations on the fiber and lipid-normalized tissue residues for DDTs in the worms. Results from the present study clearly demonstrated the feasibility of coupling PRCs with SPME sampling to greatly shorten sampling time, thus affording much improved flexibility in the use of SPME for bioavailability evaluation., (Copyright © 2013 SETAC.)

In situ measurements of hydrophobic organic chemicals in sediment porewater, a central component in assessing the bioavailability and mobility of chemicals in sediment, have been scarce. Here, we introduce a multisection passive sampler with low-density polyethylene (LDPE) as the sorbent phase, which is appropriate for measuring vertical concentration profiles of chemicals in sediment porewater. This sampler is composed of a series of identical sampling cells insulated with seclusion rings. In each section, sorption of chemicals into LDPE is diffusion-controlled through the water layer separated from the sediment by a glass fiber filtration membrane and a porous stainless steel shield. Pilot laboratory testing indicated that the sampler can roughly determine the porewater concentrations of 1,1-dichloro-2,2-bis-(chlorophenyl)ethane (p,p'-DDD) and 1,1-dichloro-2,2-bis-(chlorophenyl)ethylene (p,p'-DDE), comparable to those yielded through centrifugation/liquid-liquid extraction, a conventional technique for sampling sediment porewater. Field deployment of the sampler was performed in an urbanized coastal region to measure the depth profiles of dichlorodiphenyltrichloroethane and its metabolites in sediment porewater. Sampling rate-calibrated and performance reference compound-calibrated concentrations were calculated, which were consistent with those obtained by the centrifugation/liquid-liquid extraction method. These results verified the utility of the sampler for measuring depth profiles of sediment porewater chemicals.

The occurrence of sterols and n-alkanes in surface sediments from rivers and canals in the Niger Delta, Nigeria, determined with a gas chromatography-mass spectrometry method, was used to assess the impacts of anthropogenic activities in the area. The concentrations of total sterols (∑₈Sterol) and n-alkanes (∑₂₈n-alkane) in the sediments ranged from 133 to 2040 ng/g and 474 to 79,200 ng/g, respectively. An evaluation of the source diagnostic indices indicated that petroleum related sources (petrogenic) were the main contributor of n-alkanes in the samples, with minor contribution from higher plants waxes (biogenic), while the sterols were mainly of biogenic origin. The ratio of α-cholestanone/(α-cholestanone+β-cholestanone), a commonly used source diagnostic index, implicated no fecal contamination in most of the sediment samples under investigation. These results have established the occurrence of anthropogenic contamination in Niger Delta sediments with significant contributions from petrogenic sources., (Copyright © 2012 Elsevier B.V. All rights reserved.)

Sediment samples from the marine systems along the coast of China, covering Yellow Sea, inner shelf of the East China Sea (ECS) and the South China Sea (SCS), were analyzed for n-alkanes and organic carbon. The concentrations of Σn-C(15-35) were 120-1680 ng g(-1) dry weight with an average of 560 ng g(-1). Short-chain n-alkanes (C(21)) were mainly derived from terrestrial higher plants. Organic carbon deposited into Yellow Sea and Southeast Hainan within the SCS was mainly of terrestrial (13-110%; mean: 58%) and marine (48-110%; mean: 86%) sources, respectively. On the other hand, organic carbon accumulated in the SCS adjacent to the Pearl River Estuary was derived from both terrestrial and marine sources., (Copyright © 2012 Elsevier Ltd. All rights reserved.)

Sediments collected from the continental shelf of China, embracing Yellow Sea, inner shelf of the East China Sea (ECS), and the South China Sea (SCS), were analyzed for polycyclic aromatic hydrocarbons (PAHs). The concentrations of anthropogenic PAHs (Σ(18)PAH) were 27-224 ng/g dry weight, with an average of 82 ng/g. Sedimentary PAHs in the continental shelf off China were mainly derived from mixed residues of biomass, coal, and petroleum combustion. Fluvial transport and atmospheric deposition mainly accounted for sediment PAHs in the ECS inner shelf and Yellow Sea (and the SCS), respectively. Furthermore, statistically higher levels of Σ(18)PAH (28-224 ng/g; mean 110 ng/g) in the Yellow Sea sediment than in the SCS sediment (28-109 ng/g; mean 58 ng/g) were probably resulted from higher PAH emissions from coke industry and domestic coal combustion in North China than in South China., (Copyright © 2012 Elsevier Ltd. All rights reserved.)

Sources, compositions, and historical records of polycyclic aromatic hydrocarbons (PAHs) in sediment cores collected from the Yellow Sea and the South China Sea were analyzed to investigate the influence of anthropogenic activities. The occurrence of PAHs was mainly derived from various combustion sources, especially the combustion of biomass and domestic coal. Uniform composition of sedimentary PAHs (52-62% of phenanthrene, benzo[b]fluoranthene, indeno[1,2,3-cd]pyrene, and benzo[g,h,i]perylene) suggested air-borne mixtures intractable to degradation. The concentrations of the sum of 15 PAHs (16 priority pollutants designed by the United States Environmental Protection Agency minus naphthalene; designed as Σ(15)PAH) in Yellow Sea sediment cores were generally higher than those in the South China Sea. The profiles of Σ(15)PAH concentrations recorded in the sediment cores closely followed historical socioeconomic development in China. In general, Σ(15)PAH concentrations started to increase from the background pollution level posed by agricultural economy at the turn of 20th century. In addition, a Σ(15)PAH concentration reduction was observed during the Chinese Civil War (1946-1949) and Great Cultural Revolution (1966-1976), suggesting them as setbacks for economic development in Chinese history. Increasing PAH emissions as a result of increasing coal combustion associated with the rapid urbanization and industrialization since the implementation of the Reform and Open Policy (since 1978) accounted for the fast growth of Σ(15)PAH concentrations in sediment cores. The decline of Σ(15)PAH concentrations from subsurface maximum until sampling time was inconsistent with current-day economic development in China, and may possibly suggest emission reductions due to decreasing proportional use of domestic coal and increasing consumption of cleaner energies (natural gas and liquefied petroleum gas).

Surface sediments collected from the coastal region off South China were analyzed for persistent organic pollutants (POPs), including polybrominated diphenyl ethers (PBDEs), polycyclic aromatic hydrocarbons (PAHs), and organochlorine pesticides (OCPs). The concentrations of BDE-209, Σ(12)PBDE, Σ(15)PAH, Σ(7)PAH, and Σ(11)OCP were 0.22 to 26.3, 0.01 to 0.77, 13.9 to 271, 6 to 133, and 0.9 to 104 ng/g, respectively. The spatial distribution patterns of PBDEs and PAHs suggested that the eastern coastal region was slightly more contaminated than the western coast. In addition, the concentrations of dichlorodiphenyltrichloroethane (DDT) and its metabolites (DDXs) were highly variable, with the highest level found at a site in Zhanjiang Bay, which might have been reflective of the impact of antifouling paints mainly used in boat maintenance in harbor areas. The predominance of BDE-209 in the study region was consistent with the usage pattern of penta-, octa-, and deca-BDEs in China, whereas sediment PAHs appeared to have been derived largely from coal or wood and petroleum combustion. Preliminary assessments indicated that terrestrial inputs, such as atmospheric transport and riverine runoff, may have been the major input pathways for PBDEs and PAHs, respectively, to accumulate in coastal sediment off South China. Conversely, residues of DDT-containing antifouling paints associated with shipping activities and boat maintenance accounted for most of the accumulated sediment DDTs., (Copyright © 2012 SETAC.)

Forty-five sediment samples collected from Dongjiang River, which drains one of the most industrialized and urbanized regions in South China, were analyzed for 19 linear alkylbenzene (LAB) components. The sample dry weight-based concentrations of total LABs (ΣLAB) ranged from 1.5 to 410 ng/g. Comparison of the relative abundances of n-dodecylbenzenes (or C(12) -LABs) and internal to external ratio (I/E) values in riverine sediment, wastewater, and sediment samples from the outfalls of paper mills, as well as three brands of domestic detergents obtained from the present and previous studies, implicated the occurrence of untreated wastewater in the sampling sites. Levels of ΣLAB were significantly linear correlated with those of total organic carbon (TOC) but not with those of polycyclic aromatic hydrocarbons. Multiple linear regression integrated principal component analysis indicated that 56% of LABs in wastewater in the study area were treated, but the extent of degradation of LABs was low. Finally, it is proposed that ineffective law enforcement and loopholes in the current regulations for wastewater discharge account for the substantial amount (44%) of untreated wastewater discharged in the study region., (Copyright © 2012 SETAC.)

The heavy metal inventory and the ecological risk of the estuarine sediments in Hailing Bay, an important maricultural zone along the southern coast of China, were investigated. Results show that the surface sediments were mainly polluted by As (2.17-20.34 mg/kg), Ni (1.37-42.50mg/kg), Cu (1.21-58.84 mg/kg) and Zn (11.69-219.22 mg/kg). Furthermore, the aquafarming zone was significantly more polluted than the non-aquafarming zone, and cluster analysis suggested additional sources of heavy metal input in the aquafarming zone. As, Cr, Cu, Ni, Pb and Zn were mainly present in the non-bioavailable residual form in the surface sediments, whereas Cd was predominantly in the highly mobile acid soluble and reducible fractions. The ecological risk of the polluted sediments stemmed mainly from Cd, and from As, Cu and Pb to less degrees. The highest potential risks occurred near the aquaculture base, indicating the need to control heavy metal inputs from aquafarming activities., (Copyright © 2012 Elsevier Ltd. All rights reserved.)

Existing evidence indicated that dichlorodiphenyltrichloroethane (DDT)-containing antifouling paints were an important source of DDT residues to mariculture zones. However, the magnitude of the impact on aquafarming environment has remained largely unknown. In the present study, the concentrations of DDT and its metabolites (designated as DDXs) were determined in harbor sediment and antifouling paint samples collected from a typical mariculture zone in South China. Compositional and concentration correlation analyses implicated the DDT-containing antifouling paints for fishing boat maintenance as an important source of DDT in the mariculture zone. The annual emission of DDXs to the study region was estimated at 0.58 tons/yr. Furthermore, a comparison of the expected DDT loadings in pelagic fish and field measurements indicated that fish feed especially trash fish was a major source of DDTs in the fish body. Nevertheless, the use of DDT-containing antifouling paints should be limited to prevent further deterioration in aquafarming environment., (Copyright © 2011 Elsevier Ltd. All rights reserved.)

In order to evaluate the effect of local anthropogenic activities on Chaohu Lake, one of the most eutrophicated lakes in China, surface sediments have been collected from the whole lake with 0.05 × 0.05 degree latitude/longitude resolution and in the estuaries of three main inflowing rivers. The concentrations of the 28 polycyclic aromatic hydrocarbons (PAHs) determined were in a range 82.4-13,000 ng g(-1) with an average value of 1670 ng g(-1) dry weight for total 28 PAHs (referred to as Σ(28)PAH). Amongst the 28 PAHs, 16 are listed as high priority PAHs by the USEPA and they were in the range of 60.8-10,200 ng g(-1) with an average value of 1230 ng g(-1) for the total of them (referred to as Σ(16)PAH); 7 are known as carcinogenic PAHs and their levels ranged from 34.2 to 6400 ng g(-1) with an average of 815 ng g(-1) in total (referred to as Σ(7)PAH). Chaohu Lake was considered significantly polluted by PAHs through the comparison with the PAH burdens in fresh-water lakes both in China and worldwide. Toxic units (TUs) evaluation showed some sampling locations possibly were over the median lethal level for benthic invertebrate. The highest PAH concentrations were found in sediments from the Nanfei River estuary, suggesting the major contributor of PAHs contamination to the lake. The PAHs with four and five rings were found to be dominant among the PAHs detected in all of the sediment samples, and perylene was the most abundant. Σ(16)PAH had a good correlation with those PAHs from pyrogenic sources, such as anthracene and phenanthrene, but a poor correlation with perylene. The results demonstrated that the environmental behavior of PAHs from pyrogenic sources is significantly different to that of perylene from diagenetic sources. The PAHs in sediments were mainly from traffic-related emission by qualitatively assessing with the diagnostic ratios of PAH isomers, and the ratios for low molecular weight PAHs were strongly altered during their transport.

Although the production and use of dichlorodiphenyltrichloroethane (DDT), a legacy component of persistent organic pollutants, have been highly restricted worldwide, the environmental fate of DDT has remained a great concern as it is not only ubiquitous and bioaccumulative but can also be degraded to a series of metabolites that may be more hazardous ecologically. The present study, taking advantage of the abundant levels of DDT and its metabolites in a subtropical coastal region of China, investigated into the degradation pathways of DDT in natural coastal sediment. Sediment profiles indicated that degradation of 1,1,1-trichloro-2,2-bis-(p-chlorophenyl)ethane (p,p'-DDT) to 1,1-dichloro-2,2-bis-(p-chlorophenyl)ethane (p,p'-DDD) mainly occurred in sediment of the top 20 cm layer. 1,1-dichloro-2,2-bis-(p-chlorophenyl)ethylene (p,p'-DDE), aerobically transformed from p,p'-DDT prior to sedimentation, was likely to degrade to 1-chloro-2,2-bis-(p-chlorophenyl)ethylene (p,p'-DDMU) which was further converted to 2,2-bis(p-chlorophenyl)ethylene (p,p'-DDNU). In addition, p,p'-DDNU could be transformed to 2,2-bis(p-chlorophenyl)ethane (p,p'-DDNS) and other high-order metabolites. On the other hand, the conversions of p,p'-DDD to p,p'-DDMU and 1-chloro-2,2-bis-(p-chlorophenyl)ethane (p,p'-DDMS) to p,p'-DDNU were deemed slow in anaerobic sediment. Therefore, the present study confirmed all the degradation pathways involving reductive dechlorination and p,p'-DDE being a more important precursor for p,p'-DDMU than p,p'-DDD in anaerobic sediment, as proposed previously. On the other hand, the present study suggested that p,p'-DDMU instead of p,p'-DDMS was more likely the precursor for formation of high-order metabolites. Based on the current assessments, use of (DDD+DDE)/DDTs to indicate whether there is fresh DDT input may lead to large uncertainties if the concentrations of high-order metabolites are not negligible. Similarly, ecological risk assessment associated with DDT should be conducted with consideration of high-order DDT metabolites.

Sediment samples collected from downstream of the Dongjiang River, a highly urbanized river network within the Pearl River Delta of South China, were analyzed for 28 polycyclic aromatic hydrocarbons (PAHs). Total concentrations of 28 PAHs, 16 priority PAHs designated by the United States Environmental Protection Agency (USEPA) and the seven carcinogenic PAHs classified by the USEPA ranged from 480 to 4600, 100 to 3400 and 10 to 1700 ng/g dry weight, respectively. Principal component analysis-based stepwise multivariate linear regression showed that sediment PAHs were predominantly derived from coal combustion, refined fossil fuel combustion and oil spills, accounting for 37%, 32% and 23%, respectively, of the total loading. The levels of sediment PAHs remained steady from 2002 to 2008, during which fossil fuel consumption had doubled, probably reflecting efforts to control PAH emissions from fossil fuel combustion. Finally, use of natural gas and liquefied petroleum gas in automobiles should be encouraged to improve environmental quality., (Copyright © 2011 Elsevier Ltd. All rights reserved.)

The distribution of polycyclic aromatic hydrocarbons (PAHs) in sediments from rivers and canals adjoining some oil exploration sites in the Niger Delta and surface soils from host communities were examined. The concentrations of 28 target PAHs ranged from 65 to 331 ng/g (average: 168 ng/g) and from 24 to 120 ng/g (average: 80 ng/g) in the sediment and soil samples, respectively. Two-ring PAHs were the dominant components accounting for approximately 45% of the total PAHs detected. Assessment of the PAH compound ratios, phenanthrene/athracene (Phe/Ant) and fluoranthene/pyrene (Flu/Pyr), suggested that the PAHs in most sediment samples were predominantly of petrogenic origin which may have resulted from incessant oil pipeline leakages in the area. On the other hand, PAHs of pyrogenic sources were present predominantly in surface soils, an indication that gas flaring associated with oil exploration work in the Delta mostly affects the surface soils. An assessment using a set of widely cited sediment quality guidelines indicated that the majority of the sediment samples collected from the rivers of the delta does not pose a serious threat to the ecosystem except for two locations, Imo river and Oginni canal where PAH-contaminated sediments were likely to be acutely toxic to certain sediment dwellers.

Sediment-quality assessment often is hindered by the lack of agreement between chemical and biological lines of evidence. One limitation is that the bulk sediment toxicant concentration, the most widely used chemical parameter, does not always represent the bioavailable concentration, particularly for hydrophobic organic compounds (HOCs) in highly contaminated sediments. In the present study, we developed and tested a pore-water sampler that uses solid-phase microextraction (SPME) to measure freely dissolved (bioavailable) HOC concentrations. A single polydimethylsiloxane (PDMS)-coated SPME fiber is secured in a compact, protective housing that allows aqueous exchange with whole sediment while eliminating direct contact with sediment particles. Fibers with three PDMS coating thicknesses were first calibrated for 12 model HOCs of current regulatory concern. Precalibrated samplers were exposed to spiked estuarine sediment in laboratory microcosms to determine the time to equilibrium and the equilibrium concentrations across a range of sediment contamination. Time to equilibrium ranged from 14 to 110 d, with 30 d being sufficient for more than half the target HOCs. Equilibrium SPME measurements, ranging from 0.009 to 2,400 ng/L, were highly correlated with but, in general, lower than HOC pore-water concentrations determined independently by liquid-liquid extraction. This concept shows promise for directly measuring the freely dissolved concentration of HOCs in sediment pore water, a previously difficult-to-measure parameter that will improve our ability to assess the impacts of contaminated sediments.

The Pearl River Delta (PRD), located in South China and adjacent to the South China Sea, is comprised of a complicated hydrological system; therefore, it was a great challenge to sample adequately to measure fluxes of organic and inorganic materials to the coastal ocean. In this study, several sampling designs, including five-point (the number of sampling points along the river cross-section and three samples collected at the upper, middle, and bottom parts at each vertical line), three-point (at the middle and two other profiles), one-point (at the middle profile), and single-point (upper, middle, or bottom sub-sampling point at the middle profile) methods, were assessed using total organic carbon (TOC) and suspended particulate matter (SPM) as the measurables. Statistical analysis showed that the three- and five-point designs were consistent with one another for TOC measurements (p > 0.05). The three- and one-point sampling methods also yielded similar TOC results (95% of the differences within 10%). Single-point sampling yielded considerably larger errors than the three- and one-point designs, relative to the results from the five-point design, but sampling at the middle sub-point from the middle profile of a river achieved a relatively smaller error than sampling at the upper or bottom sub-point. Comparison of the sampling frequencies of 12 times a year, four times a year, and twice a year indicated that the frequency of twice a year was sufficient to acquire representative TOC data, but larger sample size and higher sampling frequency were deemed necessary to characterize SPM.

To verify a theoretical mass balance and multiple compartment partitioning model developed to predict freely dissolved concentrations (FDCs) of hydrophobic organic chemicals (HOCs) using negligible depletion-solid phase microextraction (nd-SPME), a series of sediment slurry experiments were performed using disposable poly(dimethyl)siloxane (PDMS) coated-SPME fibers and (14)C-radiolabeled HOC analogs. First, pre-calibration of disposable PDMS coated fibers for four model compounds (phenanthrene, PCB 52, PCB 153 and p,p'-DDE) with good precision (PCB 52>PCB 153, and the measured and predicted C(pw) values were not substantially different from empirically determined values except for p,p'-DDE.

The average concentrations of SigmaLABs (sum of C10-C13-LABs) in runoff samples collected from the eight major riverine outlets of the Pearl River Delta (PRD) of China ranged from 1.4 to 6124 ng/L in the dissolved phase and from 0.01 to 11.4 microg/g dry weight in the particulate phase during March 2005-February 2006. The annual riverine flux of SigmaLABs from the PRD to the coastal ocean was estimated at approximately 14 tons/yr. The inventories of SigmaLABs in agricultural lands of Guangdong Province ranged from 313 to 1825 kg/yr. The early and late rice fields were the major sink of LABs, accounting for approximately 68% of total LABs inventory in agricultural lands. The social-economically estimated annual discharge of LABs from household detergents in the PRD was approximately 696 tons/yr, more than an order of magnitude higher than that estimated from field measurements (about 14 tons/yr), which was attributed to several factors.

Polycyclic aromatic hydrocarbons (PAHs) were measured in 59 surface sediments from rivers in the Pearl River Delta and the northern continental shelf of the South China Sea. Total PAH concentrations varied from 138 to 6,793 ng/g dry weight. The sources of PAH inputs to sediments in the Pearl River Delta were qualitatively and quantitatively determined by diagnostic ratios and principal components analysis with multiple linear regression. The results showed that on average coal and wood combustion, petroleum spills, vehicle emissions, and nature sources contributed 36%, 27%, 25%, and 12% of total PAHs, respectively. Coal and biomass combustion was the main source of PAHs in sediments of the South China Sea, whereas petroleum combustion was the main source of pyrolytic PAHs in riverine and estuarine sediments of the Pearl River Delta. Perylene was formed in situ in river sediments and then transported to coastal areas along with other PAHs. The relative abundance of perylene from five-ring PAHs can be used to estimate the contribution of riverine-discharged PAHs to coastal sediments.

Samples of surface water, suspended particulate matter (SPM), and surface sediment, collected from the Pear River Estuary, Guangdong Province, China in July of 2002 and April of 2003, were analyzed for hexachlorocyclohexanes (HCHs) and dichlorodiphenyltrichloroethanes (DDTs) using gas chromatography with electron capture detection. The levels of total HCHs in water varied from 213 to 3,116 pg/L, although in sediments they ranged from 181 to 1,388 pg/g dry weight. The levels of DDTs were in the range of 228 to 3,284 pg/L in water and 57 to 2,244 pg/g dry weight in sediments, respectively. The observed spatial and temporal variability of concentrations of the target compounds in water body could be attributed to the differences of SPM contents in water body and organic carbon contents in SPM between the two sampling periods. Seven of the 10 water samples collected in July of 2002 had the ratio of dichlorodiphenyltrichloroethane/(dichlorobischlorophenylethane + dichlorodiphenyldichloroethylene) (DDT/[DDD + DDE]) higher than one, indicating that there were likely fresh inputs of DDT to the Pearl River Estuary. The significant positive correlations between the organochlorine pesticide concentrations and organic carbon contents in SPM and sediments indicated that organic matter played an important role in controlling the distributions of these pollutants in the marine environment. Varied correlations between the partition coefficients of pollutants and total organic carbon, salinity, and total SPM contents have been observed, which indicated the influences of these factors on controlling the transport and fate of pollutants in the marine environment.

The present study provides information on the time trend of PBDEs in three sediment cores from the Pearl River Estuary (PRE), South China, using 210Pb dating technique. The sigmaPBDEs (except for BDE 209) concentrations in all sediment cores increased gradually from the bottom (mid-1970s) to the middle layer (later 1980s and early 1990s) followed by different temporal trends in different locations to the surface sediments, reflecting the variations in the consumption of commercial penta-BDEs mixture in different regions of the Pearl River Delta. The BDE 209 concentrations remained constant until 1990 and thereafter increased exponentially to the present, with doubling times of 2.6 +/- 0.5-6.4 +/- 1.6 years, suggesting the increasing market demands for deca-BDE mixture after 1990 in China. The inventories of sigmaPBDEs and BDE 209 in sediments of the PRE were 56.0 and 368.2 ng cm(-2), respectively, and the total burden of PBDEs in the PRE were estimated at 8.6 metric tons. The current sigmaPBDEs and BDE 209 fluxes to the PRE were 2.1 and 29.7 ng cm(-2) yr(-1), respectively. The concurrent increase of BDE 209 fluxes and the annual gross industrial output values of electronics manufacturing revealed that the rapid growth of electronics manufacturing in this region since the early 1990s was responsible for the sharp rise of BDE 209 fluxes in the past decade. The PBDE congener compositions of the cores indicated the various input pathways for PBDEs transport to different locations of the estuary.

The contents of nonhydrolyzable organic matter (NHC) and black carbon (BC) were measured in soils and sediments from the Pearl River Delta, South China. Polycyclic aromatic hydrocarbons (PAHs) were extracted respectively by Soxhlet and an accelerated solvent extraction device (ASE) using different solvents. In addition, sequential aqueous leaching at different temperatures was carried out. The PAH content extracted with the sequential three solvent ASE is two times higher than that using the Soxhlet extraction method. The relationship of the PAH content with the NHC content is very significant. The PAH concentrations measured at various temperature steps fit well to the Van't Hoff equation and the enthalpy was estimated. The investigation indicates that condensed organic matter such as kerogen carbon, aged organic matter, and BC is relevant for the extraction and distribution of native PAHs in the investigated field soils and sediments.

Polybrominated diphenyl ethers (PBDEs) were analyzed in three invertebrate species, five fish species with different living and feeding habits, and surface sediments collected from the Pearl River Estuary, South China. The concentrations of 10 PBDE congeners (BDEs 28, 47, 66, 99, 100, 85, 154, 153, 138, and 183) ranged from 34.1 to 444.5 ng/g lipid and from 9.88 to 39.0 ng/g organic carbon in biota and sediment samples, respectively. In sediments and some biota samples, BDE 209 was found as the major congener, ranging from nondetectable to 623.5 ng/g lipid in biota samples and from 792 to 4,137 ng/g organic carbon in sediment samples. Different levels of PBDEs in various biota species were attributed to the different feeding habits of the aquatic species or their ability to metabolize PBDE. Different congener profiles between the biota and sediment samples were observed and attributed to the bioaccumulation potential or the ability to metabolize individual BDE congeners. Polybrominated diphenyl ether levels in the biota from the Pearl River Estuary correlated well with lipid contents but did not correlate with the biota lengths. The distribution of biota-sediment accumulation factors for individual PBDE congeners was consistent with the general pattern predicted from a widely used bioaccumulation model.

A total of 32 surface sediments collected from the Yangtze River Estuary, Hangzhou Bay and the Qiantang River were analyzed for polybrominated diphenyl ethers (PBDEs). The concentrations of summation operatorPBDEs (sum of 12 PBDE congeners without BDE 209) and BDE 209 varied from n.d. to 0.55 and from 0.16 to 94.6 ng/g, respectively. The spatial variability of summation operatorPBDEs concentrations indicated that waste discharge from the urban areas might been the main source of PBDEs in the Yangtze River Delta. BDE 209 was the predominant congener (approximately 90-100%) detected among the 13 congeners, consistent with the fact that technical deca-BDE mixtures are presently the dominant technical PBDE mixtures used in China. Compared to published data acquired from other locales, PBDE congeners with less than four bromines were more abundant in the present study area. The hydrodynamic conditions may likely be a significant factor in dictating the observed levels and congener distribution patterns of PBDEs.

Spatial and temporal distributions of polybrominated diphenyl ethers (PBDEs) in sediments of the Pearl River Delta (PRD) and adjacent South China Sea (SCS) of southern China were examined. A total of 66 surface sediment samples were collected and analyzed to determine the concentrations of 10 PBDE congeners (BDE-28, -47, -66, -100, -99, -154, -153, -138, -183, and -209). The concentrations of BDE-209 and SigmaPBDEs (defined as the sum of all targeted PBDE congeners except for BDE-209) ranged from 0.4 to 7340 and from 0.04 to 94.7 ng/g, respectively. The SigmaPBDEs concentrations were mostly < 50 ng/g, within the range for riverine and coastal sediments around the world, whereas the BDE-209 concentrations at the most contaminated sites were at the high end of the worldwide figures. Congener compositions were dominated by BDE-209 (72.6 - 99.7%), with minor contributions from penta- and octa-BDEs. Slightly different PBDE compositions were observed among samples collected from different locations, attributable to possible decomposition of highly brominated congeners and/or redistribution between particles of various sizes during atmospheric or fluvial transportation. The PBDE patterns in the SCS and Pearl River Estuary sediments were similar to those in sediments of the Zhujiang and Dongjiang Rivers, reflecting the widespread influence from local inputs. Analyses of two short sediment cores collected from the Pearl River Estuary showed that concentrations of BDE-209 rapidly increased in the upper layers of both cores, coincident with the growth of the electronics manufacturing capacities in the PRD region. The major sources of PBDEs were probably waste discharges from the cities of Guangzhou, Dongguan, and Shenzhen, the three fastest growing urban centers in the PRD.

Despite the recent efforts to investigate the distribution and fate of persistent organic pollutants in the tropical and subtropical regions of Asia, very little was known about the temporal change of polychlorinated biphenyls (PCBs) in the environmental ecosystem of China. In this study, three dated sediment cores collected from the Pearl River Delta of southern China were analyzed for a large suite of PCB congeners, from which the temporal profiles of PCB abundances, fluxes, and homologue patterns were constructed. The sedimentary inventories of total PCBs at the sampling sites ranged from 480 to 1310 ng/cm2, at the low end of the worldwide figures. Although production and use of PCBs have been banned or highly restricted in China since the early 1980s, the fluxes of total PCBs continued to increase in the Pearl River Delta sediments. There was a concurrent increase of PCB fluxes and gross domestic product per capita in the region from 1980 to 1997, and a decline of agricultural land use was evident at the same time. Apparently, large-scale land transform since the early 1980s as well as emissions from the PCB-containing electrical equipments were responsible for the sharp rise of PCB fluxes in the recent sediments. The difference in the PCB homologue patterns from 1940 to the mid-1970s was probably indicative of the different timelines of PCB usage in Macao/Hong Kong and mainland China and the differenttypes of technical PCBs commercially used. PCBs were detectable in sediments deposited well before the time frame when production of PCBs began (before 1930) and were relatively enriched in the less chlorinated homologue groups (3Cl and 4Cl PCBs), suggesting the downward mobility of lightly chlorinated PCB congeners in the sediment column.

The coastal region off Macao is a known depositional zone for persistent organic pollutants (POPs) in the Pearl River Delta and Estuary of southern China and an important gateway for the regional contributions of contamination to the globe. This paper presents a comprehensive assessment of the input sources and transport pathways of polycyclic aromatic hydrocarbons (PAHs) found in the coastal sediments of Macao, based on measurements of 48 2-7 ring PAHs and 7 sulfur/oxygenated (S/O) PAH derivatives in 45 sediment, 13 street dust, and 68 aerosol samples. Total sediment PAHs concentrations ranged from 294 to 12741 ng/g, categorized as moderate contamination compared to other regions of Asia and the world. In addition, the PAH compounds appeared to be bound more strongly to aromatics-rich soot particles than to natural organic matter, implying a prevailing atmospheric transport route for PAHs to Macao's coast. Compositional analysis and principal component analysis (PCA) suggested that different classes of PAHs in the coastal sediments of Macao may have been derived from different input sources via various transport pathways. For example, alkylated and S/O PAHs were likely derived from fossil fuel leakage and transported to sediments by both aerosols particles and street runoff. High-molecular-weight parent PAHs were predominantly originated from automobile exhausts and distributed by direct and indirect atmospheric deposition. Low-molecular-weight parent PAHs, on the other hand, may have stemmed from lower temperature combustion and fossil fuel (such as diesel) spillage from ships and boats and were transported to sediments by river runoff or direct discharge as well as by air-water exchange.

Contaminant inputs from wastewater discharge, a major source of contamination to Santa Monica Bay (SMB), have declined drastically during the last three decades as a result of improved treatment processes and better source control. To assess the concomitant temporal changes in the SMB sediments, a study was initiated in June 1997, in which 25 box cores were collected using a stratified random sampling design. Five sediment strata corresponding to the time intervals of 1890-1920, 1932-1963, 1965-1979, 1979-1989, and 1989-1997 were identified using (210)Pb dating techniques. Samples from each stratum were analyzed for metals, 1,1,1-Trichloro-2,2-bis(p-chlorophenyl)ethane (DDT) and its metabolites (DDTs), polychlorinated biphenyls (PCBs), and total organic carbon (TOC). Samples from the 1965-1979, 1979-1989, and 1989-1997 strata were also analyzed for polycyclic aromatic hydrocarbons (PAHs) and linear alkylbenzenes (LABs). Sediment metal concentrations increased from 1890-1979 and were similar during the time intervals of 1965-1979, 1979-1989, and 1989-1997, although the mass emissions of trace metals from sewage inputs declined substantially during the same time period. Trace organic contamination in SMB was generally highest in sediments corresponding to deposition during the years of 1965-1979 or 1979-1989 and showed a decline in concentration in the 1989-1997 stratum. Temporal trends of contamination were greatest in sediments collected from areas near the Hyperion Treatment Plant (HTP) outfall system and on the slope of Redondo Canyon. The highest contaminant concentrations were present in sediments near the HTP 7-mile outfall in the 1965-1979 stratum. Elevated trace metal and organic concentrations were still present in the 1989-1997 stratum of most stations, suggesting that sediment contaminants have moved vertically in the sediment column since sludge discharges from the 7-mile outfall (a dominant source of contamination to the bay) ceased in 1987. The widespread distributions of DDTs and PCBs in SMB and highly confined distribution of LABs around the HTP outfall system were indicative of a dispersal mechanism remobilizing historically deposited contaminants to areas relatively remote from the point of discharge.

The uptake patterns and toxicity of polychlorinated biphenyl (PCB) congeners in the white sea urchin, Lytechinus pictus, on exposure to contaminated sediments were investigated. First-order modeling of uptake of the 10 most abundant PCB congeners or domains (containing more than one coeluting congener) by L. pictus indicated that a 35-d exposure was insufficient to reach steady state. Bioaccumulation of PCBs in sea urchins exhibited substantial difference between field and amended sediments, suggesting that caution must be exercised in sample preparation. Some evidence was observed of dependence of measured biota-sediment accumulation factors (BSAFs) on K(ow), indicating that equilibrium partitioning of PCBs may not always be achieved between biota lipid, sediment organic carbon, and water. Survival of L. pictus was unaffected by exposure to field and amended sediments with PCB concentrations varying more than three orders of magnitude. The growth measures (diameter, wt, and gonad wt) were significantly reduced in L. pictus exposed to San Diego Bay ([SDB]; San Diego, CA, USA) sediment, whereas they were relatively unaffected after exposure to amended sediments (with much higher PCB concentrations than SDB sediment) prepared from a New Bedford Harbor (MA, USA) sediment. The toxic effects as measured by the growth rates in L. pictus were likely attributable to polycyclic aromatic hydrocarbons (PAHs), which were elevated in SDB sediment (7.3 microg/g), rather than PCBs.

Sediments of San Diego Bay (SDB) are known to contain elevated levels of polychlorinated biphenyls (PCBs). While numerous efforts have been made to monitor the spatial or temporal trends of contamination in SDB, no studies have been directed toward measurements of water column contamination. We measured PCB concentrations in the water column of SDB with an in situ sampling system. Except for one sample collected near the bay mouth, all other samples contained higher PCB concentrations than the 30-day average discharge limit established by the California Ocean Plan. The highest concentrations of water column PCBs occurred in the Central Bay, consistent with the previous findings that sediments in the Central Bay contained higher PCB levels than those in the North and South Bays. Based on the water volume of 2.2 x 10(8) cm3 at a lower water level, it was estimated that approximately 1,000 g of PCBs is transported out of SDB via tidal exchange annually. This indicates that water column transport driven by tidal exchange is a viable mechanism reducing PCB contamination within SDB.

Spatial distribution of chlorinated hydrocarbons [chlorinated pesticides (CPs) and polychlorinated biphenyls (PCBs)] and polycyclic aromatic hydrocarbons (PAHs) was measured in riverine and estuarine sediment samples from Pearl River Delta, China, collected in 1997. Concentrations of CPs of the riverine sediment samples range from 12 to 158 ng/g, dry weight, while those of PCBs range from 11 to 486 ng/g. The CPs concentrations of the estuarine sediment samples are in the range 6-1658 ng/g, while concentrations of PCBs are in the range 10-339 ng/g. Total PAH concentration ranges from 1168 to 21,329 ng/g in the riverine sediment samples, whereas the PAH concentration ranges from 323 to 14,812 ng/g in the sediment samples of the Estuary. Sediment samples of the Zhujiang River and Macao harbor around the Estuary show the highest concentrations of CPs, PCBs, and PAHs. Possible factors affecting the distribution patterns are also discussed based on the usage history of the chemicals, hydrologic condition, and land erosion due to urbanization processes. The composition of PAHs is investigated and used to assess petrogenic, combustion and naturally derived PAHs of the sediment samples of the Pearl River Delta. In addition, the concentrations of a number of organic compounds of the Pearl River Delta samples indicate that sediments of the Zhujiang river and Macao harbor are most likely to pose biological impairment.