Anthropogenic activities have contributed moderately to increased inputs of organic materials in marginal seas off China.

Sediment has been recognized as a gigantic sink of organic materials and therefore can record temporal input trends. To examine the impact of anthropogenic activities on the marginal seas off China, sediment cores were collected from the Yellow Sea, the inner shelf of the East China Sea (ECS), and the South China Sea (SCS) to investigate the sources and spatial and temporal variations of organic materials, i.e., total organic carbon (TOC) and aliphatic hydrocarbons. The concentration ranges of TOC were 0.5-1.29, 0.63-0.83, and 0.33-0.85%, while those of Σn-C14-35 (sum of n-alkanes with carbon numbers of 14-35) were 0.08-1.5, 0.13-1.97, and 0.35-0.96 µg/g dry weight in sediment cores from the Yellow Sea, ECS inner shelf, and the SCS, respectively. Terrestrial higher plants were an important source of aliphatic hydrocarbons in marine sediments off China. The spatial distribution of Σn-C14-35 concentrations and source diagnostic ratios suggested a greater load of terrestrial organic materials in the Yellow Sea than in the ECS and SCS. Temporally, TOC and Σn-C14-35 concentrations increased with time and peaked at either the surface or immediate subsurface layers. This increase was probably reflective of elevated inputs of organic materials to marginal seas off China in recent years, and attributed partly to the impacts of intensified anthropogenic activities in mainland China. Source diagnostics also suggested that aliphatic hydrocarbons were mainly derived from biogenic sources, with a minority in surface sediment layers from petroleum sources, consistent with the above-mentioned postulation.

Sediment records of polycyclic aromatic hydrocarbons (PAHs) in the continental shelf of China: implications for evolving anthropogenic impacts.

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).

Organophosphate tri-esters and di-esters in drinking water and surface water from the Pearl River Delta, South China: Implications for human exposure.

Some organophosphate di-esters (di-OPEs) have been found to be more toxic than their respective tri-esters. The environmental occurrence of di-OPEs remains largely unclear. A total of 106 water samples, including 56 drinking water (bottled, barreled, and tap water) and 50 surface water (lake and river) samples were collected and analyzed for 10 organophosphate tri-esters (tri-OPEs) and 7 di-OPEs. The concentrations (range (median)) of ∑7di-OPE were 2.8-22 (9.7), 1.1-5.8 (2.6), 3.7-250 (120), 13-410 (220), and 92-930 (210) ng/L in bottled water, barreled water, tap water, lake water, and river water, respectively. In all types of water samples, tris(1-chloro-2-propyl) phosphate was the dominant tri-OPE compound. Diphenyl phosphate was the predominant di-OPE compound in tap water and surface water, while di-n-butyl phosphate and bis(2-ethylhexyl) phosphate was the dominant compound in bottled water and barreled water, respectively. Source analysis suggested diverse sources of di-OPEs, including industrial applications, effluents of municipal wastewater treatment plants, degradation from tri-OPEs during production/usage and under natural environmental conditions. The non-carcinogenic and carcinogenic risks of OPEs were lower than the theoretical threshold of risk, indicating the human health risks to OPEs via drinking water consumption were negligible. More studies are needed to explore environmental behaviors of di-OPEs in the aquatic environment and to investigate ecological risks.

An overview of organophosphate esters and their metabolites in humans: Analytical methods, occurrence, and biomonitoring.

With the strict regulation of brominated flame retardants, organophosphate esters (OPEs) have been extensively used as replacements. Increasing concerns on OPEs have aroused due to their extensive distribution in the environment and humans, as well as their potential toxicities. Recent studies have demonstrated that some organophosphate di-esters are even more toxic than their respective tri-esters. This review summarized the current state of knowledge on the analytical methodologies (including sample collection and preparation, instrumental analysis, and the feasibility of each potential human matrix), as well as the occurrences of OPEs and/or their metabolites (m-OPEs) in various human matrices. Organophosphate esters are readily metabolized in human thus only limited studies reported their occurrences in blood and breast milk, whereas abundant studies are available regarding the occurrences of m-OPEs rather than OPEs in urine. Since none of the matrix is suitable all the time, appropriate matrix should be selected depending on the aims of biomonitoring studies, e.g., high throughput screening or body burden estimation. Biomonitoring with non-invasive matrices such as hair and/or nail is useful to screen specific populations that might be under high exposure risks while urine is more suitable to provide valuable information on body burden. In terms of urinary monitoring, specific biomarkers have been identified for some OPE compounds, including tri(2-butoxyethyl) phosphate, tri(1,3-dichloro-2-propyl) phosphate, tri(2-chloroethyl) phosphate and tri(1-chloro-2-propyl) phosphate. Further studies are required to identify suitable urinary biomarkers for other OPE compounds, especially the emerging ones.

Temporal-spatial distribution of synthetic pyrethroids in overlying water and surface sediments in Guangzhou waterways: potential input mechanisms and ecological risk to aquatic systems.

Temporal-spatial distribution of synthetic pyrethroids (SPs) in overlying water and surface sediments and ecological risk to aquatic systems were investigated, where paired water and surface sediments were collected during dry and wet periods in Guangzhou urban waterways. Eight target SPs (i.e., tefluthrin, bifenthrin, cyhalothrin, permethrin, cyfluthrin, cypermethrin, esfenvalerate, and deltamethrin), with cypermethrin and permethrin as major components, were ubiquitously detected in both water (dissolved and particle phases, separately) and sediments. Significant increases of ΣSP (sum of eight SPs) concentrations were observed in both water and sediment from the dry period to the wet period. The spatial distribution of SPs was mostly impacted by land-use type, with the highest ΣSP concentrations in the residential areas, which indicates the massive application of pyrethroids in household mosquito control. It is demonstrated that SPs preferred to be adsorbed to the particles, and rainfall-induced runoff was suggested as an important mechanism that moved SPs to the receiving waterways. A rising trend on sediment concentrations of SPs in the Guangzhou area in the last decade implied increasing application of pyrethroid insecticides, with cypermethrin and permethrin as the dominant components, where the contamination of SPs was positively related with urbanization rate (e.g., resident population and green coverage area). A special emphasis was placed on the potential effects of both individual SPs and their mixtures in three trophic levels (i.e., algae, daphnia, and fish) using toxic units (TUs) and risk quotients (RQs) for water and sediments. In spite of no acute effects due to SPs in the sediments, the toxic units showed daphnia as the most sensitive species in water, with acute risks to daphnia exhibited in several sampling sites. The risk assessment points out that a chronic toxicity (RQ index) caused by SPs in three trophic levels (algae, daphnia, and fish) exists, especially in Daphnia magna. Graphical abstract.

Occurrence, fate and ecological risk of chlorinated paraffins in Asia: A review.

Chlorinated paraffins (CPs), complex mixtures of polychlorinated alkanes, are widely used in various industries and are thus ubiquitous in the receiving environment. The present study comprehensively reviewed the occurrence, fate and ecological risk of CPs in various environmental matrices in Asia. Releases from the production and consumption of CPs or CP-containing materials, wastewater discharge and irrigation, sewage sludge application, long-range atmospheric transport and aerial deposition have been found to be most likely sources and transport mechanisms for the dispersion of CPs in various environmental matrices, such as air, water, sediment, soil and biota. CPs can be bioaccumulated in biota and biomagnified through food webs, likely causing toxic ecological effects in organisms and posing health risks to humans. Inhalation, dust ingestion and dietary intake are strongly suggested as the major routes of human exposure. Research gaps are discussed to highlight the perspectives of future research to improve future efforts regarding the analysis of CPs, the environmental occurrence and elimination of CPs, the total environmental pressure, and the risks to organisms and populations.

Organophosphorus flame retardants and plasticizers: sources, occurrence, toxicity and human exposure.

Due to the restricted use and ban of brominated flame retardants, organophosphorus compounds (OPs), extensively used as flame retardants and plasticizers, are ubiquitous in various environmental compartments worldwide. The present study shows that the release of OPs from a wide variety of commercial products and wastewater discharge might be considered as primary emission sources and that high potential of long-range atmospheric transport and persistence of OPs would be responsible for their presence in various matrices on a global scale. The occurrence and environmental behaviors of OPs in diverse matrices (e.g., dust, air, water, sediment, soil and biota) are reviewed. Human exposures to OPs via dermal contact, dust ingestion, inhalation and dietary intake are comprehensively evaluated. Finally, this study identifies gaps in the existing issues and generates a future agenda for the emerging contaminants OPs.

Tracking anthropogenic influences on the continental shelf of China with sedimentary linear alkylbenzenes (LABs).

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.

Utility of soil linear alkylbenzenes to assess regional anthropogenic influences with special reference to atmospheric transport.

Tracing regional anthropogenic influences is important for assessing the magnitude of human interferences with the environment. In the present study, the utility of soil linear alkylbenzenes (LABs) as indicators of anthropogenic influences was examined, with the emphasis on the role of atmospheric transport in dissipating LABs from input sources to remote areas. The Pearl River Delta, South China, which has experienced rapid economic growth and urbanization, was selected as the study region. The concentrations of LABs (mean: 8.6 ng/g and median: 5.7 ng/g, with an outlier of 2,020 ng/g excluded) suggested that sewage contamination throughout the entire study region was generally light. The spatial variation of sewage pollution was significantly positively correlated with population density and per capita gross domestic product, with hot spots concentrated in the central PRD. Atmospheric deposition was hypothesized as an important input route for soil LABs in forestry and drinking water source areas with little impact of irrigation or direct wastewater discharge. This proposition could explain the opposite spatial patterns of LAB concentrations and values of a biodegradation index (5-C12+5-C13)/(5-C11+5-C10), where i-Cn defines a specific LAB congener with i and n indicating the position of the phenyl group and the number of carbon atoms on the alkyl chain, respectively. These findings somewhat validated LABs as tracers of regional anthropogenically derived contamination, with atmospheric transport of LABs as a viable dissipating mechanism.

Polycyclic aromatic hydrocarbons (PAHs) in continental shelf sediment of China: implications for anthropogenic influences on coastal marine environment.

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.