Development of an in vitro model to simulate migration of organic contaminants from pad products to human sweat and enhance dermal exposure risk assessment.

Dermal sorption is an important route for human exposure to organic chemicals embedded in consumer products, but the related chemical migration from consumer products to sweats was often overlooked in assessing skin exposure risk. To address this issue, the present study selected polycyclic aromatic hydrocarbons (PAHs), phthalic acid esters (PAEs), and benzothiazoles (BTs) as the target compounds and developed an in vitro simulation model with two artificial sweats (i.e., acidic and alkaline), a sorbent, and a PVC standard material. An appropriate biological inhibitor (ampicillin) and incubation time of 20 d for assessing the maximum migration efficiency of chemicals were selected. The mass balance of the target compounds during the in vitro incubation was verified. The established in vitro simulation model was used to determine the migration ratios of PAEs and BTs in three types of mouse pads. The maximum migration ratios of DBP, DIBP, DEHP, and BT from leather pad to both sweats were less than those for silicone and rubber pads. Key controlling parameters in migration ratios should be examined in subsequent investigations. Risk assessment showed that the daily exposure doses of PAEs and BTs in mouse pads were higher than the literature data. The hazard index of PAEs in leather pad exceed 1, indicating that PAEs could induce non-carcinogenic effects to human health through hand contact. Overall, the established in vitro simulation model provides a feasible alternative for assessing the potential risk for dermal exposure to consumer products.

A comprehensive risk assessment of human inhalation exposure to atmospheric halogenated flame retardants and organophosphate esters in an urban zone.

Inhalation exposure to flame retardants used as additives to minimize fire risk and plasticizers is ubiquitous in human daily activities, but has not been adequately assessed. To address this research gap, the present study conducted an assessment of human health risk for four age groups through inhalation exposure to size fractionated particle-bound and gaseous halogenated flame retardants (polybrominated diphenyl ethers (PBDEs) and alternative halogenated flame retardants (AHFRs)) and organophosphate esters (OPEs) at indoor and outdoor environments (school, office, and residence) in three districts of a megacity (Guangzhou, China). Results demonstrated that OPEs were the dominant components among all targets. Indoor daily intakes of PBDEs and OPEs were 13-16 times greater than outdoor levels for all age groups. Gaseous OPEs contributed significantly greater than particle-bound compounds to daily intakes of all target compounds. Based on the different life scenarios, hazard quotient (HQ) and incremental life cancer risk (ILCR) from adults exposure to PBDEs and OPEs in indoor and outdoor settings were the greatest, followed by adolescents, children, and seniors. The estimated HQ and ILCR for all age groups both indoors and outdoors were lower than the safe level (HQ = 1 and ILCR = 10-6), indicating that the potential health risk for local residents in Guangzhou via inhalation exposure to atmospheric halogenated flame retardants and OPEs was low.

In vitro inhalation bioaccessibility for particle-bound hydrophobic organic chemicals: Method development, effects of particle size and hydrophobicity, and risk assessment.

Bioaccessibility of particle-bound hydrophobic organic contaminants and related particle size effects are significant for assessing the potential human health risk via inhalation exposure, but have not been clearly evaluated. To fill this knowledge gap, the present study developed an in vitro method to estimate the inhalation bioaccessibility of particulate polycyclic aromatic hydrocarbons (PAHs) using simulated human lung fluids, i.e., a modified Gamble's solution (MGS) and artificial lysosomal fluid (ALF) with Tenax as the absorption media. Assay parameters, namely incubation time (10 d) and influence of filter use, were optimized for establishing the in vitro method. The results showed that the bioaccessibility of PAHs increased with increasing particle size, but other factors, such as total organic carbon and chemical hydrophobicity, also played a large role in the fate of these compounds. The results from this portion of the present study were then used to evaluate human health risk, which showed that the risk of these particle-bound PAHs by incorporating size-dependent PAHs bioaccessibility and deposition efficiency in the human respiratory tract into inhalation exposure risk calculations was reduced by >90% when compared to using total concentration. This suggested that the inhalation bioaccessibility and deposition efficiency of hydrophobic organic chemicals should be included in human health risk assessment.

[Spatial Distribution of DDTs and PCBs in Wild Fish from Hong Kong Coastal Areas and Potential Human Health Risk Assessment].

To examine the distributional patterns of persistent organic pollutants in the wild fish of Hong Kong and assess the health risks associated with consuming them, two typical kinds of persistent organic pollutants, such as dichlorodiphenyltrichloroethane (DDTs) and polychlorinated biphenyls (PCBs), were determined in 31 kinds of fishes caught from the coastal areas of Hong Kong. The results indicate that the concentrations of DDTs and PCBs in the wild fishes were in the ranges of 0.44-17 ng·g-1 and 0.028-6.3 ng·g-1, respectively, which were at the low end of the global ranges. Spatially, the lowest concentrations of DDTs and PCBs were found in the fishes occurring in the west of Lantau Island and Tolo Harbor. Furthermore, the feeding habits and living environments of the fishes could have some influence on the accumulation of DDTs and PCBs in them. Source diagnostics indicated that DDTs in these fishes mainly originated from historical residues, but the fishes which migrate for relatively longer distances may be subject to DDT contamination in the estuaries. Finally, human health risk assessments suggested that the increased potential lifetime cancer risk of local adolescences and adults exposed to DDTs and PCBs via wild fish consumption was high. Therefore, the local residents in Hong Kong should reduce their daily intake of wild fish caught from the surrounding coastal regions.

Assessment of airborne polycyclic aromatic hydrocarbons in a megacity of South China: Spatiotemporal variability, indoor-outdoor interplay and potential human health risk.

Although a number of studies have assessed the occurrence of atmospheric polycyclic aromatic hydrocarbons (PAHs) in indoor environment, few studies have systemically examined the indoor-outdoor interplay of size-dependent particulate PAHs and potential health risk based on daily lifestyles. In the present study, size-dependent particle and gaseous samples were collected both indoors and outdoors within selected schools, offices and residences located in three districts of Guangzhou, China with different urbanization levels during the dry and wet weather seasons. Results from measurements of PAHs showed that higher total PAH concentrations occurred in residential areas than in other settings and in indoor than in outdoor environments. Compositional profiles and size distribution patterns of particle-bound PAHs were similar indoors and outdoors, predominated by 4-and 5-ring PAHs and the 0.56-1.0 µm particle fraction. Statistical analyses indicated that outdoor sources may have contributed to 38-99% and 62-100% of the variations for indoor particle-bound and gaseous PAH concentrations, respectively. Incremental life cancer risk (ILCR) from human exposure to indoor and outdoor PAHs based on different lifestyles followed the order of adults > children > adolescents > seniors. All average ILCR values for four age groups were below the lower limit of the Safe Acceptable Range (10-6). In addition, the ILCR value for adults (average: 7.2 × 10-7; 95% CI: 5.4 × 10-8‒2.5 × 10-6), estimated from outdoor air PAH levels with 24-h exposure time, was significantly higher than our assessment results (average: 5.9 × 10-7; 95% CI: 6.3 × 10-8‒1.9 × 10-6), suggesting the significance of assessing human inhalation exposure risks of indoor and outdoor PAHs in urban air based on daily lifestyles.

Organophosphate Triesters and Diester Degradation Products in Municipal Sludge from Wastewater Treatment Plants in China: Spatial Patterns and Ecological Implications.

Little is known about the occurrences, distributions, sources, and potential risks of organophosphate (OP) triesters and diester degradation products in municipal sludge from wastewater treatment plants (WWTPs). In this study, we conducted the first nationwide survey to simultaneously determine a suite of 11 OP triesters and six diester degradation products in sludge from WWTPs across China. All OP triesters were detected and three diesters were identified for the first time in sludge samples. Total concentrations of OP triesters and diester degradation products were in the ranges of 43.9-2160 and 17.0-1300 ng (g of dry weight)-1, respectively, indicating relatively low pollution levels in China compared with those of several developed countries. A distinct geographical variation of higher concentrations of OP triesters and diesters in East China than in Central and West China was observed, suggesting that regional levels of organophosphate esters are associated with the magnitudes of regional economic development. Source analysis revealed nonchlorinated OP diesters are mainly derived from degradation in WWTPs, while chlorinated OP diesters were largely sourced from outside WWTPs. The estimated total emission fluxes of OP triesters and diesters via land-application sludge in China were approximately 330 and 134 kg/year, respectively. Further risk assessment based on risk quotient values in sludge-applied soils indicated low to medium risks for most OP triesters and diesters except tris(methylphenyl) phosphate. The significant accumulation of OP triesters and widespread occurrence of diester degradation products in sludge raise environmental concerns about these contaminants.

Global trends of research on emerging contaminants in the environment and humans: a literature assimilation.

Available literature data on five typical groups of emerging contaminants (EMCs), i.e., chlorinated paraffins (CPs), dechlorane plus and related compounds (DPs), hexabromocyclododecanes (HBCDs), phthalate esters, and pyrethroids, accumulated between 2003 and 2013 were assimilated. Research efforts were categorized by environmental compartments and countries, so that global trends of research on EMCs and data gaps can be identified. The number of articles on the target EMCs ranged from 126 to 1,379 between 2003 and 2013. The numbers of articles on CPs, DPs, HBCDs, and pyrethroids largely followed the sequence of biota > sediment ≥ air > water ≥ soil > human tissue, whereas the sequence for phthalate esters was water > sediment > soil > human tissue ≥ biota ≥ air. Comprehensive studies on the target EMCs in biological samples and human tissues have been conducted worldwide. However, investigations into the occurrence of the target EMCs in soil of background areas and water are still scarce. Finally, developed and moderately developed countries, such as the USA, China, Canada, Japan, and Germany, were the main contributors to the global research efforts on EMCs, suggesting that economic prosperity may be one of the main factors propelling scientific research on EMCs.

[Spatial distribution and risk assessment of insecticides in surface soil from a rapidly urbanizing region].

To examine the distribution patterns of organic contaminants in rapidly urbanizing regions, the levels and spatial distributions of 19 overlooked insecticides, i. e., phenyl-pyrazole class (fipronil), chlordane, endosulfan, nonachlor, hexachlorobenzene, heptachlor, dieldrin, aldrin, endrin, methoxychlor and their metabolites, were examined in 229 soil samples collected from the Pearl River Delta (PRD) and surrounding areas. The results indicated that higher insecticide levels distributed in the central PRD, while lower levels congested in the surrounding areas. The similar spatial patterns between the levels of insecticides and economic prosperity or population density demonstrated that social-economic factors may have dictated the spatial patterns of insecticides. In addition, the changing of land-use types during urbanization processes, e.g., historical plowlands have been converted into residential landscapes, resulted in high concentrations of banned insecticides in metropolis of the central PRD. Source diagnostics indicated that new inputs of technical chlordane products existed in the PRD and surrounding areas. Fipronil was degraded into fipronil sulfone and fipronil sulfide in most soil samples because of its low half-life in soil. Finally, a risk assessment of 19 insecticides in soil for human health suggested that six samples collected from the major administrative districts with dense population had potential cancer or non-cancer risk to human health. Therefore, these overlooked insecticides should be concerned in future environmental research.

Assessment of organochlorine pesticides residues in higher plants from oil exploration areas of Niger Delta, Nigeria.

The concentrations and distributions of organochlorine pesticides (OCPs) in some higher plant samples collected from oil exploration areas of the Niger Delta, Nigeria were examined. The concentrations of Σ(25)OCP ranged from 82 to 424, 44 to 200 , 34 to 358, 33 to 106 and 16 to 75 ng/g in Olomoro, Oginni, Uzere, Irri and Calabar plants, respectively. The compositional profiles of the analysed OCPs in most of the plants showed no fresh inputs in the area. The OCPs detected in the samples could have resulted from pesticide usage for intense farming activities cum the use of pesticides to control household pests and insects in the area. Drilling fluids and corrosion inhibitors used in petroleum explorations also have chlorinated compounds as additives thereby serving as potential sources of OCPs. Among the studied plants, elephant grass showed high bioaccumulation and phytoremediation potentials of OCPs. The ΣHCH concentrations exceeded the allowable daily intake limit thereby serving as potential threat to humans.

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.

Bioaccumulation of trace metals in farmed fish from South China and potential risk assessment.

Concentrations of trace metals were determined in water, sediment, fish feed and two species of farmed fish, pompano and snapper, collected from Daya Bay and Hailing Bay of South China in July 2007 and January 2008. Total average concentrations of Cu, Pb, Zn, Cd, Cr, Hg and As were 1.6, 2.7, 27.3, 0.025, 0.62, 0.18 and 0.59 µg/g dry wt in pompano and 1.5, 2.6, 23.6, 0.020, 0.55, 0.22 and 0.53 µg/g dry wt in snapper. In general, the concentrations of all target metals except Hg were positively correlated with lipid contents whereas negative correlations were observed between the metal concentrations and fish body weights. Model calculation indicated that dietary uptake of Zn and Cd predominate their accumulation in snapper, accounting for 99.9% and 98.2% of the total inputs. Risk assessments suggested that potential ecological and human health risk may be present due to elevated Pb concentrations in sediment and farmed fish.

Law enforcement and global collaboration are the keys to containing e-waste tsunami in China.

Various levels of regulation are needed to stem the environmental health crisis due to e-waste importation and disposal in China.

Occurrence, source diagnosis, and biological effect assessment of DDT and its metabolites in various environmental compartments of the Pearl River Delta, South China: a review.

This review summarizes and analyzes available data in the literature (mostly after 2000) on the occurrence of dichlorodiphenyltrichloroethane (DDT) and its main metabolites, dichlorodiphenyldichloroethane (DDD) and chlorodiphenyldichloroethylene (DDE), in the environment of the Pearl River Delta (PRD), South China. Generally, the concentration levels of the sum of DDT, DDD, and DDE, designated as DDTs thereafter, have not significantly declined since 1983. However, the composition of DDTs residues has changed with time. DDTs in soil, freshwater sediment and freshwater fish species were mainly residues from chronological use. There is evidence that new point sources, such as dicofol and anti-fouling paint, may have contributed DDTs to various environmental compartments. Risk assessment against existing criteria indicated that the levels of DDTs in water and some fish species may pose adverse effects to humans or wildlife, and those in sediment/soil may also cause negative impacts to the eco-environment of the PRD.

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.

Occurrence, phase distribution, and mass loadings of benzothiazoles in riverine runoff of the Pearl River Delta, China.

A set of six benzothiazoles was determined in riverine runoff samples of the Pearl River Delta (PRD) collected monthly from March 2005 to February 2006. The concentrations of total benzothiazoles ranged from 220 to 611 ng/L, with benzothiazole (BT) being the most prominent (82%), followed by 2-methylthiobenzothiazole (MBT),thianaphthene (TN), and triphenylene (TP). The annual fluxes ofTN, BT, MBT, dibenzothiophene (DBT), 2-(4-morpholinyl)benzothiazole (24MoBT), and TP from the PRD to the coastal ocean were 1.94, 65.1, 10.1,0.63, 0.18, and 0.89 tons/yr, summing to yield an annual flux of 79 tons/yr for total benzothiazoles. In the PRD, approximately 1.1 x 10(5) tons of rubber are estimated to be released into the environment each year. This corresponds to the annual fluxes of 13 tons/yr for BT and 0.4 tons/yr for 24MoBT from tire particles. The annual fluxes of BT from scrap tires from Japan, Korea, Brazil, the European Union, the United States, and China were 99, 21, 36, 270, 328, and 120 tons/yr, respectively. The fluxes of 24MoBT from the same countries were 3.0, 0.5, 1.1, 8.4, 10.3, and 3.8 tons/ yr, respectively. These results indicated that tire-wear particles and scrap tires are the dominant sources of benzothiazoles in the environment. By comparison, Asia may be the major contributor to the global input of benzothiazoles from auto tires in the coming years. Overall, the six benzothiazoles under investigation appeared to be suitable tracers of pollutant inputs to surface runoff within the PRD aquatic system. In addition, 24MoBT seemed more appropriate than BT to trace tire rubber residues and therefore can be a good indicator of economic development and urbanization in a specific region.

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.