Occurrence, compositional distribution, and toxicity assessment of pyrethroid insecticides in sediments from the fluvial systems of Chaohu Lake, Eastern China.

Surface sediment-associated synthetic pyrethroid insecticides (SPs) are known to pose high risks to the benthic organisms in Chaohu Lake, a shallow lake of Eastern China. However, the pollution status of the lake's tributaries and estuaries is still unknown. The present study was conducted to investigate the occurrence, compositional distribution, and toxicity of 12 currently used SPs in the surface sediments from four important tributaries, as well as in the sediment cores at their estuaries, using GC-MS for quantification. All SPs selected were detectable, with cypermethrin, es/fenvalerate, and permethrin dominant in both surface and core sediments, suggesting that these compounds were extensively applied. Urban samples contained the highest summed concentrations of the 12 SPs analyzed (Σ12SP) in both surface and core sediments compared with rural samples, suggesting that urban areas near aquatic environments posed high risks for SPs. The mean concentration of Σ12SP in surface sediments of each river was generally higher than that found in core sediments from its corresponding estuary, perhaps implying recent increases in SP usage. Surface sediments were significantly dominated by cypermethrin and permethrin, whereas core sediments were dominated by permethrin and es/fenvalerate. The compositional distributions demonstrated a spatial variation for surface sediments because urban sediments generally contained greater percentages of permethrin and cypermethrin, but rural sediments had significant levels of es/fenvalerate and cypermethrin. In all sediment cores, the percentage of permethrin gradually increased, whereas es/fenvalerate tended to decrease, from the bottom sediments to the top, indicating that the former represented fresh input, whereas the latter represented historical residue. Most urban samples would be expected to be highly toxic to benthic organisms due to the residue of SPs based on a calculation of toxic units (TUs) using toxicity data of the amphipod Hyalella azteca. However, low TU values were found for the samples from rural areas. These results indicate that the bottom sediments were exposed to high risk largely by the residual SPs from urban areas. The summed TUs were mostly attributable to cypermethrin, followed by λ-cyhalothrin and es/fenvalerate. Despite permethrin contributing ∼28.7 % of the Σ12SP concentration, it only represented 6.34 % of the summed TUs. Therefore, our results suggest that high levels of urbanization can increase the accumulation of SPs in aquatic environments.

PAHs in the Chinese environment: levels, inventory mass, source and toxic potency assessment.

This paper presents a systematic but preliminary study on the levels, inventory mass, emission sources and risk of exposure to PAHs in China by examining 14 polycyclic aromatic hydrocarbons (from the 16 priority PAHs listed by the U.S. EPA, excluding naphthalene and acenaphthylene) in four main environmental media (air, water, soil and sediment). The concentration of individual PAHs in the air, soil, freshwater, seawater, freshwater sediment and marine sediment of China was compared with the global concentration range (GCR) of PAHs from a large number of studies. The PAH levels were found at the high end of the GCR in the air, at the upper middle of the GCR in the water body, and at the middle of the GCR in the soil and sediment. These indicate that PAHs still are emitted heavily in China. About 530 000 tons of Σ14PAH was estimated to be distributed into these four media in China. Soil possesses the highest proportion of the PAHs (60%), and the air has the lowest proportion (<0.5%). Therefore, the soil and sediment play an important role in the storage of PAHs. More than 10 thousand tons of PAHs are emitted from all kinds of sources. Firewood, straw, domestic and coking were considered as the main emissions of PAHs in the energy supply. A benzo[a]pyrene (BaP) based hazard quotient (HQ) was introduced to assess the potential toxic risk of exposure. The terrestrial water environment was found to have a high BaP exposure. The HQ value was more than 1 for 58% of freshwater and 39% of freshwater sediment samples. Urban and developed sites were considered to have high BaP exposure risk.

Halogenated organic contaminants (HOCs) in sediment from a highly eutrophicated lake, China: occurrence, distribution and mass inventories.

Halogenated organic contaminants (HOCs) including 16 polybrominated diphenyl ethers (PBDEs) and 37 polychlorinated biphenyls (PCBs) were determined in 49 surfacial sediments from Chaohu Lake, a highly eutrophicated lake, China. PBDEs were detected in almost samples with the range of the total concentration (defined as Σ(16)PBDEs) from 0.84 to 86.6 ng g(-1). Compared with the occurrence of PBDEs in Pearl River Delta and Yangtze River Delta in China, lower percentage of BDE-209 over the concentration of Σ(16)PBDEs was inferred by the high-volume application of penta-BDE mixture product for local domestic furniture purpose. The total concentration of 37 PCBs (Σ(37)PCBs) ranged from 0.05 to 3.36 ng g(-1) with the most detection of PCB-1, -4, -52 and -71. Both the concentrations of Σ(16)PBDE and Σ(37)PCB poorly correlated with total organic carbon (TOC), suggesting the significant contribution of phytoplankton organic carbons to sediment TOC. The contamination by PBDEs and PCBs in western region of the lake was significantly more serious than in eastern lake. Our findings about the higher residues of PBDEs and PCBs in sediments at the estuary of Nanfei River compared to the other estuaries also supported the conclusion that urban area (Hefei city) was the main source of PBDEs and PCBs. The comparison with the concentration of HOC in the present study with those in other lacustrine sediments around the world suggested the contamination by PBDEs in Chaohu Lake is at middle of the global concentration range, whereas PCBs is at low end of the global range which could be elucidated by local economic development and historical usage of PBDEs and PCBs. The mass inventories of HOCs in the lake were estimated at 561 and 38 kg, which corresponds to only 0.000006% and 0.0001% of these global historical produce volumes, respectively.

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).

Polycyclic aromatic hydrocarbons in upstream riverine runoff of the Pearl River Delta, China: an assessment of regional input sources.

Water samples collected from upstream tributaries of the Pearl River Delta (PRD) and from locations within the PRD (South China) were analyzed for 27 polycyclic aromatic hydrocarbons (PAHs). Average concentrations (aqueous plus particulate) of total 27 PAHs (Σ(27)PAH), 16 priority PAHs designated by the United States Environmental Protection Agency (USEPA) except naphthalene (Σ(15)PAH), and the seven carcinogenic PAHs (Σ(7)PAH) classified by the USEPA were 260 ± 410, 130 ± 310, and 15 ± 12 ng/L, respectively. Riverine PAHs were predominantly generated from coal and vegetation combustion, coke production, vehicle exhausts, and petroleum residues, accounting for 28%, 25%, 22% and 21%, respectively, on average. Upstream riverine fluxes of Σ(27)PAH and Σ(15)PAH amounted to 38.9 and 12.9 tons/year, respectively. The net contributions of Σ(27)PAH and Σ(15)PAH from sources within the PRD were estimated at 21.4 and 21.0 tons/year, respectively.

Assessment of aquatic wastewater pollution in a highly industrialized zone with sediment linear alkylbenzenes.

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.

Occurrence, source apportionment and toxicity assessment of polycyclic aromatic hydrocarbons in surface sediments of Chaohu, one of the most polluted lakes in China.

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.

Organochlorine pesticides and polychlorinated biphenyls in riverine runoff of the Pearl River Delta, China: assessment of mass loading, input source and environmental fate.

A large-scale sampling program was conducted to simultaneously collect water samples at the eight major riverine runoff outlets of the Pearl River Delta (PRD), South China to assess the importance of riverine runoff in transporting anthropogenic pollutants from terrestrial sources to the coastal ocean. The concentrations of Sigma21OCPs (sum of 21 OCP components) and Sigma20PCBs (sum of 20 PCB congeners) were 2.57-41.2 and 0.12-1.47 ng/L, respectively. Compositional distributions of DDTs suggested the possibility of new input sources in the study area, but contributions from dicofol seemed considerably low. The annual inputs of Sigma21OCPs and Sigma20PCBs were 3090 and 215 kg, with those of total HCHs and DDTs being 1110 and 1020 kg, respectively. A mass balance consideration indicated that riverine runoff is the major mode carrying OCPs from the PRD to the coastal ocean, and the majority of OCPs is further dissipated to open seas.

Assessment of sampling designs to measure riverine fluxes from the Pearl River Delta, China to the South China Sea.

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.