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Halogenated polycyclic aromatic hydrocarbons (HPAHs) have been reported to occur in air, sediment, fly ash, and biota samples. This review summarized current existing data on the environmental occurrence, behavior, physicochemical properties, emission sources, and toxic equivalents of HPAHs. Firstly, the physicochemical properties of HPAHs were summarized. Then, an overview of environmental occurrence of HPAHs in ambient matrices including biological samples was reviewed. Meanwhile, the emission sources and possible formation mechanisms of HPAHs were discussed. Apart from that, the aryl hydrocarbon receptor (AhR)-mediated activities were summarized, which indicated that the position and number of halogen atoms on the parent PAHs molecule were important determinant factors affecting the AhR-mediated activity of individual HPAHs congeners. Finally, some research recommendations on HPAHs were given., (Copyright © 2012 Elsevier Ltd. All rights reserved.)

Human exposure to polycyclic aromatic hydrocarbons (PAHs) and halogenated PAHs (HPAHs) via food consumption is still not clear in south China so far. The goals of this work are to assess human exposure to parent and halogenated PAHs via food ingestion and the cancer risk for population in Shenzhen, a new urban center in south China. Sixteen PAHs and nine HPAHs were determined in vegetable, pork and rice samples collected from Shenzhen. In general, the population in Shenzhen was exposed to higher levels of PAHs via food ingestion in comparison to that reported for other countries in recent years, but lower than that estimated for two northern cities in China. The cancer risk values induced by exposure to PAHs and HPAHs for male and female on each subgroup were between the serious risk level (10(-4)) and the acceptable risk level (10(-6)). Children faced the highest cancer risk, followed by adolescents, seniors and adults., (Copyright © 2012 Elsevier B.V. All rights reserved.)

The present study measured eight PBDE congeners' (BDE-28, 47, 99, 100, 153, 154, 183, and 209) exposure via ingestion of indoor dust and soil, inhalation, and food consumption. Contributions to PBDEs exposure from different media revealed that indoor dust (dust suspended in air) was not an important exposure route for PBDE congeners for adults in Shenzhen, China. Food consumption contributed more to daily intake of Σ(8)BDE, especially for lower-brominated PBDE congeners. Based on calculated average total daily intake, hazard quotients were determined to estimate the non-cancer risks of PBDE exposure. Meanwhile, cancer risk was also estimated assuming that the oral cancer slope factors of all PBDE congeners are equipotent as BDE-209. The hazard quotients ranged from 1.2×10(-5) (BDE-209) to 2.0×10(-2) (BDE-47), suggesting a low deleterious risk with regard to PBDEs. The cancer risk value ranged from 1.1×10(-24) to 5.5×10(-21) implying that the total risks due to exposure to PBDEs via all exposure routes are extremely low for adults., (Copyright © 2012 Elsevier B.V. All rights reserved.)

Rice is the staple food for approximate two thirds of the Chinese population. However, human exposure to parent and halogenated polycyclic aromatic hydrocarbons (PAHs) via rice consumption is still not clear for Chinese people so far. The goals of this work are to assess human exposure to PAHs and halogenated PAHs (HPAHs) via rice ingestion and the cancer risk for Chinese population. 16 PAHs and eight HPAHs were determined in rice samples collected from 18 provinces in China. In general terms, the general population in China was exposed to higher levels of PAHs via rice ingestion in comparison to that via cereals for other countries. The cancer risk values induced by exposure to PAHs and HPAHs for male and female on each age group were between the priority risk level (10(-4)) and the acceptable risk level (10(-6)). Children faced the highest cancer risk, followed by adolescents and adults., (Copyright © 2012 Elsevier Ltd. All rights reserved.)

Surface sediments collected from the Maozhou River watershed in Shenzhen were analyzed for the concentration levels and spatial distribution characteristics of halogenated polycyclic aromatic hydrocarbons (HPAHs) using GC-MS. Total concentrations of three chlorinated polycyclic aromatic hydrocarbons (ClPAHs) and six brominated polycyclic aromatic hydrocarbons (BrPAHs) of concern ranged from 3.00 to 301 ng x g(-1) and 7.52 to 285 ng x g(-1), respectively. Source appointments indicated that the HPAHs in these surface sediments were mainly derived from waste incineration, fossil fuel combustion, vehicle emission, and burning of crop straw, accounting for 40%, 20.5% 11.9%, and 11.7% of the total loading, respectively. Additionally, the toxic equivalency quotients (TEQ) of total ClPAHs and BrPAHs ranged from 7.95 to 38.1 pg x g(-1) and 38.1 to 105 pg x g(-1) respectively. Finally, the relationships between the HPAHs levels and different land use types were examined. Results indicated that the levels of HPAHs in surface sediments showed a decreasing trend after the first increase to the peak with the density of industrial land, but inversely proportional to the density of agricultural land.

A maar lake is an excellent ecosystem to study the atmospheric deposition of pollutants, as its contaminants are primarily by atmospheric deposition. In this study, a sediment core from Sihailongwan Maar Lake, Northeast China, was collected and the historical atmospherically deposited polycyclic aromatic hydrocarbons (PAHs) were analyzed. The concentrations of TPAHs (the sum of the US EPA proposed 16 priority PAHs, excluding naphthalene and pyrene) ranged from 473.9 to 2289 ng g(-1) with a slow increasing stage in the deeper sediments and a sharp increasing stage in the upper sediments. The input rate of TPAHs, especially that of PAH(9) (the sum of fluoranthene, benzo(a)anthracene, chrysene, benzo(b)fluoranthene, benzo(k)fluoranthene, benzo(a)pyrene, indeno(1,2,3-cd)pyrene, dibenzo(ah)anthrathene, and benzo(ghi)perylene), correlated well to the Chinese historical socioeconomic data. This indicates that sediment PAHs were mainly derived from human activities and PAH(9) can be regarded as a better indicator of the local socioeconomic development. Source identification suggested that PAHs were originated primarily from mixed sources (e.g., coal and biomass burning and petroleum combustion), except for perylene which was mostly of diagenetic origin. In addition, the down-core PAHs profile clearly illustrated that PAHs sources in Northeast China experienced a transformation from low- and moderate temperature to high-temperature combustion processes, especially after the late 1980s. Additionally, an ecological risk assessment using two redefined biological thresholds (TEQ(ERL) and TEQ(ERM)) indicated that most of the PAHs measured in the present sediment core would not cause an immediate toxic effect; only FLU and PHEN are a potential source of concern for biological impairment.

Currently, a number of food producers use hypochlorite to bleach food and inhibit the growth of bacteria, preserving the food. Because the presence of high amounts of nitrogen could result in the formation of semicarbazide (SEM), the bleaching process could be one of the predominant sources of SEM in food. To investigate this, we selected instant bottled bird's nest as an example of a food that is bleached in its production. SEM was detected in 27 of 28 instant bottled bird's nest samples. The levels of SEM detected mostly fell in the range of 5 to 50 μg/kg, which accounted for 75% of all samples measured. The SEM detected in the instant bottled bird's nest was found to have originated neither from the use of the antimicrobial agent nitrofurazone nor from azodicarbonamide, which is used as a blowing agent in gaskets used to seal the metal lid of the bottle. Instead, it could have originated from the bleaching process used in the preparation of the nests. Additionally, human exposure to SEM via consumption of instant bottled bird's nest for five subgroups of the population was estimated. Sensitivity analysis suggested that concentration of SEM in food is the most significant parameter governing human exposure via consumption of SEM-containing food.

In the present study, 16 priority polycyclic aromatic hydrocarbons (Σ(16) PAHs), including seven carcinogenic PAHs (Σ(7) PAHs) designated by the U.S. Environmental Protection Agency, in surface sediment from an urban river (Shenzhen, south China) were measured. The concentrations of Σ(16) PAHs and Σ(7) PAHs ranged from 27.92 to 7409 ng/g and 0.53 to 2326 ng/g, respectively. Source appointments indicated that the PAHs in surface sediments were mainly derived from coal combustion (36.6%), oil spills (22.2%), vehicle emission (19.5%), and waste incineration (12.1%). The ecological risks posed by PAHs and several halogenated PAHs in these sediment samples were assessed using two redefined guidelines incorporating the toxic equivalency quotients (TEQs) of individual PAH congeners: (1) TEQs effect range-low, and (2) TEQs effect range-median. The authors' results suggested that the PAHs they measured in most of the sediments in this urban river would not cause acute biological effects. On the contrary, the ecological risk posed by some halogenated PAHs was much higher than that of their corresponding parent PAHs. Finally, the relationships between PAH levels and catchment urbanization processes were examined. The results indicated that rapid urbanization has led to an obvious increase in PAH contamination in surface sediments., (Copyright © 2012 SETAC.)

Nine chlorinated and brominated polycyclic aromatic hydrocarbons (Cl/BrPAHs) and five parent polycyclic aromatic hydrocarbons (PAHs) were measured in urban surface soil and fly ash samples collected from Shenzhen, south China in winter 2010. The concentrations of total Cl/BrPAHs and PAHs in soil ranged from below the reporting limit to 142 ng/g and from 4.34 to 158 µg/g, respectively, and in fly ash they ranged from 17.7 to 19.5 ng/g and 26.1 to 28.3 µg/g, respectively. Concentrations of Cl/BrPAHs and parent PAHs were not significantly correlated with each other in soil or in fly ash, suggesting that Cl/BrPAHs were formed mainly by mechanisms other than direct halogenation of parent PAHs. Estimated mass inventories of 2-BrFlu varied from 68.1 kg in commercial land to 669 kg in countryside land, the highest among all Cl/BrPAHs. Loss fluxes via soil erosion accounted for only small proportions of total soil mass inventories of Cl/BrPAHs. Average daily human intake via soil ingestion decreased with increasing age, with 2-BrFlu as the main contributor. Children of 0 to 8 years old were the most sensitive subgroup (13.7 pg/kg body wt/d for total Cl/BrPAHs), and females were more sensitive than males in the same age group. The mean dioxin-like toxic equivalency quotient (TEQ) concentration of total Cl/BrPAHs (0.008 ng-TEQ/g) was lower in soil than in fly ash (0.06 ng-TEQ/g). Conversely, the mean TEQ concentration of total parent PAHs (2.23 ng-TEQ/g) was higher in soil than in fly ash., (Copyright © 2012 SETAC.)

Mining effluents are the main source of metals in the surrounding aquatic environment. The mining district of Purple Mountain has a history of copper mining for more than 30 years, but there is limited investigation of metal bioaccumulation in the aquatic creatures from the Tingjiang river catchment affected by the mining activities. In this study, we collected grass carps (Ctenopharyngodon idellus) from four sites, and analyzed the accumulation of chromium (Cr), nickel (Ni), manganese (Mn), copper (Cu), zinc (Zn), arsenic (As), cadmium (Cd), mercury (Hg), and lead (Pb) in ten tissues (scale, skin, muscle, gill, liver, kidney, fish maw, heart, stomach, and intestine) of the fish samples. Among all tissue samples, the highest concentrations (micrograms per gram wet weight) of Ni (0.263), Cu (69.2), Zn (84.0), As (0.259), Cd (0.640), Hg (0.051), and Pb (0.534) were noted in the liver, gill, and kidney tissues, whereas the highest concentrations of Cr (0.356) and Mn (62.7) were detected in the skin and intestine, respectively. These results gave a better understanding of the variability of metals distribution in different fish tissues. In comparison with the sample sites, metals (especially Mn, Cu, Zn, Ni, and Pb) in liver, gill, kidney, stomach, and intestine showed more inter-site differences than other tissues. The inter-site differences also revealed that site 1 and 2 increased fish uptake of Cu, Zn, Ni, and Pb, which may indicate that the copper mine and urban effluents contributed to high levels of these metals in aquatic environments in site 1 and 2. A potential food safety issue may emerge depending on the mining activities in this region because some metals in a few tissue samples exceeded the guideline values for human consumption of fish.

One hundred and fourteen surface sediments were collected from the Maozhou River Watershed in Shenzhen, China from December 2009 to January 2010. Three individual chlorinated polycyclic aromatic hydrocarbons (ClPAHs), six individual brominated polycyclic aromatic hydrocarbons (BrPAHs), and five corresponding parent polycyclic aromatic hydrocarbons (PAHs) were determined. The concentration of 9-chlorophenanthrene was the highest ranging from 0.51-289 ng g(-1) (average, 16.5 ng g(-1)). For BrPAHs, the concentration of 2-bromofluorene was the highest ranging from 0.31-266 ng g(-1) (average, 35.3 ng g(-1)). No correlation was observed between the concentrations of ClPAHs and parent PAHs in surface sediments. In addition, there was no correlation between 1-bromopyrene, 7-bromobenz(a)anthracene and 9,10-dibromoanthracene, and corresponding parent PAHs. However, a significant correlation was found between 9-bromophenanthrene and phenanthrene (p < 0.01), between 9-bromoanthracene and anthracene (p < 0.05), and between 2-bromofluorene and fluorene (p < 0.05). Six fly ash samples collected from one of the municipal domestic waste incineration plants in Shenzhen were also analyzed for source identification. The concentration of 7-bromobenz(a)anthracene was the highest, ranging from 3.21-4.08 ng g(-1). In addition, 2-bromofluorene was not detected in all the fly ash samples. No correlation was found between the concentrations of Cl-/BrPAHs and corresponding parent PAHs in fly ashes. We also examined the relationship between the levels of Cl-/BrPAHs in surface sediments and the urbanization process. Our results suggested the levels of individual Cl-/BrPAHs congeners presented a similar increasing trend with the increasing urbanization level.

This study examined polybrominated diphenyl ethers (PBDEs) in central air conditioner filter (CACF) dust from a new office building in Shenzhen, China. Human exposure to PBDE via dust inhalation and ingestion were also estimated. PBDEs level in CACF dust was lower than those in the other countries and regions. Approximately 0.671 pg/kg bw/day PM(2.5) (Particulate Matter up to 2.5 μm in size) bounded Σ(15)PBDEs can be inhaled deep into the lungs and 4.123 pg/kg bw/day PM(10) (Particulate Matter up to 10 μm in size) bounded Σ(15)PBDEs tend to be deposited in the upper parts of the respiratory system. The average total intake of Σ(15)PBDEs via dust inhalation and ingestion for adults reached ∼ 141 pg/kg bw/day in this building. This value was far below the reference dose (RfD) recommended by United States Environmental Protection Agency. Human exposure to PBDEs via dust inhalation and ingestion in the new building is less than the old ones., (Copyright © 2010 Elsevier Ltd. All rights reserved.)

To determine the incidence of organochlorine pesticides (OCPs) in soil in a rapid urbanization region, soil samples from various land use types in Shenzhen were collected in winter, 2007. The concentration of dichlorodiphenyltrichloroethanes (DDTs) and hexachlorocyclohexanes (HCHs) ranged from non-detected to 149 ng g(-1) and 19 to 88 ng g(-1), respectively. The highest levels of OCPs were observed in soil from traffic and industry areas, reflecting that intensive human disturbance make the soil pollution accumulation more disperse. HCHs and DDTs profiles revealed that the sources were associated mainly with lindane and technical DDTs, respectively, while HCHs in the soil of Shenzhen might originate from both recent and historical sources. The loss of OCPs by soil erosion will enter surface runoff and impose impact on the water environment. Non-dietary exposure estimation indicates that children were the most sensitive group. The average daily exposure to OCPs for males was more serious than for females. Non-dietary exposure to DDTs and HCHs in residential blocks of Shenzhen were far below the acceptable daily intake recommended by the Food and Agriculture Organization/World Health Organization.

Polybrominated diphenyl ethers (PBDEs) were measured in soil and three plant species samples taken at different land use areas in Shenzhen China. The concentrations of Σ(7)BDEs (BDE-28, BDE-47, BDE-99, BDE-100, BDE-153, BDE-154, and BDE-183) and BDE-209 in the surface soils ranged from 0.23 to 271 and 8.9 to 5,956 ng/g dry weight (dw), respectively. These figures are comparable to that in the soils of electronic waste dismantling sites. BDE-209 was the predominant congener (contributes 85-99% of Σ(8)PBDEs (Σ(7)PBDEs plus BDE-209)) in soils. The regression slopes of total organic carbon and individual BDE congeners were rather gentle, indicating that factors other than soil organic matter regulated the soil concentrations. Proximity to sources of deposition processes might be the major factors. In the plant leaves, Σ(7)BDEs and BDE-209 concentrations ranged from 1.29 to 5.91 and 5.49 to 28.2 ng/g dw, respectively. BDE-209 is also the dominant component, but the contribution was much lower compared with that in soils. Bauhinia purpurea Linn. and Michelia alba DC. show some similarities on the uptake of PBDEs, while Ficus microcarpa var. pusillifolia is different from them. The correlations between plant leaf concentrations and predicted gaseous concentrations were moderate, indicating that gaseous concentration did not influence the leaf concentration significantly.

Our previous study indicated that the current level of polycyclic aromatic hydrocarbons (PAHs) in Shenzhen soil is in the low-end of world soil PAH pollution. In this study, the fate of PAHs in the soil of Shenzhen was investigated. The mass inventories of Σ(27)PAHs and Σ(15)PAHs (defined as the sum of the 27 or 15 PAH compounds sought) in topsoil of Shenzhen were ∼204 and ∼152 metric tons, respectively. Fate estimation of Σ(15)PAHs shows that air-soil gaseous exchange is the primary environmental process with ∼10,076 kg/year diffusing from soil to air. Rain washing (∼1131 kg/year from air to soil) is the most important input pathway followed by wet (∼17 kg/year) and dry deposition (∼8 kg/year) to soils in Shenzhen. The transport of Σ(15)PAHs by soil erosion is a crucial loss process for soil PAHs in Shenzhen (1918 kg/year for water runoff and 657 kg/year for solid runoff from soil). Moreover, degradation is not ignorable at present (95 kg/year). Comparison of inventory and residue (defined as Σ(15)PAHs left in topsoils after all environmental loss processes) suggested that input and loss of high molecular weight PAHs for Shenzhen's soil reached apparent equilibrium. Soil PAH pollution in Shenzhen will stay in a quasi-steady state for a long period and the natural environmental processes can not significantly reduce the pollution.

Twenty eight polycyclic aromatic hydrocarbons (PAHs) were determined for a total of 203 top soil samples collected from eight different land categories in Shenzhen, China during the winter of 2007. The concentrations, compositional profile, and the potential sources of PAHs in soil were discussed. Overall, PAH pollution in the soil of Shenzhen is still in the low-end of the world after 30 years rapid urbanization. Based on that, human exposure to soil PAHs via inhalation and soil particle intake were estimated as well. The concentrations of Sigma(28)PAHs in Shenzhen soil ranged from 2.68 to 17,767 ng g(-1) (average: 546 ng g(-1)). The highest levels of PAHs were found in the traffic land (average: 2104 ng g(-1)) and the lowest concentrations were detected in forest land (average: 144 ng g(-1)) in eight land categories. PAH isomeric ratios indicated that PAHs in Shenzhen soil were mainly derived from combustion. In the current pollution levels in Shenzhen, children aged 0 to 8 were the most sensitive sub-group of exposure to PAHs (59.2 ng (kg d)(-1)), and the exposure to PAHs for males (36.2 ng (kg d)(-1)) was more serious than for females (32.7 ng (kg d)(-1)). Inhalation was the major way of non-dietary exposure (over 96%).

Various classes of persistent halogenated compounds (PHCs) can be released into the environment due to improper handling and disposal of electronic waste (e-waste), which creates severe environmental problems and poses hazards to human health as well. In this review, polybrominated diphenyl ethers (PBDEs), polybrominated biphenyls (PBBs), tetrabromobisphenol A (TBBPA), polybrominated phenols (PBPs), polychlorinated biphenyls (PCBs), polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs), polybrominated dibenzo-p-dioxins and dibenzofurans (PBDD/Fs), and chlorinated polycyclic aromatic hydrocarbons (ClPAHs) are the main target contaminants for examination. As the world's largest importer and recycler of e-waste, China has been under tremendous pressure to deal with this huge e-waste situation. This review assesses the magnitude of the e-waste problems in China based on data obtained from the last several years, during which many significant investigations have been conducted. Comparative analyses of the concentrations of several classes of toxic compounds, in which e-waste recycling sites are compared with reference sites in China, have indicated that improper e-waste handling affects the environment of dismantling sites more than that of control sites. An assessment of the annual mass loadings of PBDEs, PBBs, TBBPA, PBPs, PCDD/Fs, and ClPAHs from e-waste in China has shown that PBDEs are the dominant components of PHCs in e-waste, followed by ClPAHs and PCDD/Fs. The annual loadings of PBDEs, ClPAHs, and PCDD/Fs emission were estimated to range from 76,200 to 182,000, 900 to 2,000 and 3 to 8 kg/year, respectively. However, PCDD/Fs and ClPAHs should not be neglected because they are also primarily released from e-waste recycling processes. Overall, the magnitude of human exposure to these toxics in e-waste sites in China is at the high end of the global range., (Copyright 2010 SETAC.)

To determine the potential input sources of polybrominated diphenyl ethers (PBDEs) to fish farming environments in South China, samples of seven various environmental matrices were collected from October 2006-September 2007. Tri- to deca-BDEs were detected in all samples analyzed, with mean concentrations (+ or - standard deviations) at 5.7 + or - 3.6 ng/L in pond water, 15 + or - 11 ng/g dry wt. in pond sediment, 12 + or - 3.8 ng/g dry wt. in bank soil, 21 + or - 20 ng/g lipid wt. in fish, and 93 + or - 62 ng/g lipid wt. in fish feeds. In addition, BDE-209 was the major constituent in all samples except fish and BDE-47 was predominant in fish samples. Relatively high abundances of BDE-49 were detected in all the samples compared to those in the penta-BDE technical products. Several bioaccumulation factors were evaluated. Finally, statistical analyses suggested that fish feed, as well as pond water at a lesser degree, may have been the major source of PBDEs in freshwater farmed fish., (Copyright 2009 Elsevier Ltd. All rights reserved.)

Domestic sewage is a potential source of contamination deteriorating water quality in rivers and coastal environments. The present study determined the concentrations of eight steroids in both filtrate and suspended particulate matter (SPM) samples collected monthly at the eight major riverine runoff outlets of the Pearl River Delta (PRD), South China, from March 2005 to February 2006. The concentration of the eight steroids (sum of which is defined as Sigma(8)steroid) in the filtrate and SPM samples ranged 16.7-1340 ng L(-1) and 0.44-240 microg g(-1), respectively. The filtrate samples contained the highest levels of cholesterol (CHOE) and stigmasterol (STIG) on average, whereas the SPM samples had the largest relative abundances of CHOE and coprostanol (COP). In general, larger proportions of the steroids were associated with SPM than with the filtrate phase. The combined (filtrate plus SPM) concentrations of COP in riverine runoff of the PRD were at the midpoint of the global range in surface water. The concentrations of Sigma(8)steroid and COP in SPM were not significantly correlated with particulate organic carbon (POC), riverine runoff, or SPM concentrations, which indicates the dominance of nonpoint input sources for the occurrence of steroids in the PRD. The annual riverine inputs of Sigma(8)steroid and COP were estimated at 360 and 31.6 tons yr(-1), respectively, and the monthly inputs of both Sigma(8)steroid and COP were positively correlated with monthly runoff discharge. Furthermore, the concentrations of Sigma(8)steroid, COP, and CHOE showed significant temporal and spatial variability. These results can be explained by a combination of climatic characteristics, socioeconomic conditions, and steroid sources. Analyses of the diagnostic indices of COP and background information suggested that riverine runoff from the PRD may have been affected by domestic wastewater, which appeared to be a major COP source to the Pearl River Estuary and South China Sea.

The mass emissions of linear alkylbenzenes (LABs), benzothiazole (BT), and 2-[4-morpholinyl]benzothiazole (24MoBT) from anthropogenic activities within one year were estimated according to the population and the number of automobiles in the Pearl River Delta (PRD), South China. Based on the estimation, the distribution of these compounds among various environmental media was simulated with a mass balance box model established in the present study. The results showed that 79% of LABs generated in the PRD was stored in sediment while only 1.3% of LABs was presumably transported to the adjacent South China Sea (SCS). On the contrary, 47% of BT and 77% of 24MoBT generated in the region were carried with riverine runoff to the coastal ocean. The results from the present study suggest that hydrophobic compounds tend to stay in the watershed of the PRD, whereas hydrophilic ones mainly outflow to the coastal ocean.

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

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.

Riverine runoff samples were collected monthly from March 2005 to February 2006 from the eight major outlets of the Pearl River Delta (PRD), South China, and analyzed to obtain the concentrations of n-alkanes in both the filtrate and particulate phases. The average concentrations of Sigma(C15-C34) (i.e., sum of C15 to C34 normal alkanes) ranged from 0.06 to 2.97 microg/L (mean, 0.64 microg/L) in filtrate samples and from 1.00 to 98.8 microg/g (average, 19.8 microg/g dry weight) in particulate samples. Compared to results from around the world, the levels of hydrocarbon compounds in the PRD were at the high end of the global range. Evaluation of compositional indices of n-alkanes indicated that petroleum-related sources are the main contributor of n-alkanes found in the PRD, with minor contributions from high plant wax. Regression analyses appeared to suggest that n-alkanes are transported into the aquatic environment of the PRD via various pathways, and the transport mechanisms also are considerably influenced by the complex hydrologic conditions in the PRD. The annual riverine input of Sigma(C15-C34) from the PRD to the coastal ocean was 360 tons/year, or the equivalent of approximately 8,800 tons/year of petroleum hydrocarbons. The emission of Sigma(C15-C34) from all sources in the PRD was estimated at 39,000 tons/year, or 2.4 g/day per capita. Overall, the PRD contributes approximately 0.2% of the annual global input of n-alkanes to the coastal oceans, similar to the contributions of polycyclic aromatic hydrocarbons, further indicating that the PRD has been a significant source of hydrocarbon contamination to the global coastal marine environment.

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.

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.

A total of 1008 samples were collected from the eight major riverine runoff outlets in the Pearl River Delta (PRD) during 2005-2006 to estimate the fluxes of total organic carbon (TOC) to the coastal ocean off South China. The average dissolved organic carbon (DOC) concentration was 1.67 mg/L with a range of 1.38-2.13 mg/L. Concentrations of particulate organic carbon (POC) ranged from 2.66-4.12% of total suspended particulate matter (SPM). The fluxes of TOC and SPM from the PRD via the eight outlets were 9.2 x 10(5) and 2.5 x 10(7)tons/yr, respectively. Temporal variations in POC and DOC were observed at all outlets due to the large variability in runoff levels because of the seasonality of rainfall, and the riverine discharge amount was an important factor controlling TOC flux. The net contribution of organic carbon from the PRD to the coastal ocean represented approximately 0.1-0.2% of total organic carbon transported by rivers worldwide.

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.

Riverine runoff is an important mode to transport anthropogenic pollutants from terrestrial sources to oceans. Polybrominated diphenyl ethers (PBDEs) were measured in riverine runoff samples from the eight major outlets within the Pearl River Delta (PRD), China, an economically fast developing region housing a vast number of electronics manufacturing and assembling plants. The sigma 17PBDEs (sum of 17 BDE congeners, i.e., BDE-28, -47, -66, -85, -99, -100, -138, -153, -154, -183, -196, -197, -203, -206, -207, -208, and -209) concentrations varied from 344 to 68,000 pg/L, with those of BDE-209, BDE-47, and BDE-99 being 335-65200, 3-143, and <1-200 pg/L, respectively. These levels were in the high end of the global PBDEs concentrations in the aquatic environments. The monthly inputs of sigma 17PBDEs ranged from 0.21 to 215 kg at individual outlets, and the annual input of sigma 17PBDEs from all the outlets was estimated at 2140 kg/year. Of the target BDE congeners, BDE-209 was the most predominant component with an annual input of 1960 kg/year, followed by BDE-47 (13.3 kg/year) and BDE-99 (11.7 kg/year). An extrapolation of the past use of PBDEs in the region concluded that 23 metric tons of sigma 17PBDEs have been discharged into the coastal ocean from the PRD in the last 20 years. The amount of PBDEs imported to China in the form of e-waste was estimated at 35000 metric tons/year, higher than the annual domestic production of brominated fire retardants (approximately 10000 metric tons/year) and the annual riverine input of total PBDEs from the PRD, suggesting that the majority of PBDEs inventory has been accumulated from importation of e-wastes. Because of the continuous importation of e-wastes and strong demand for brominated fire retardants, the impact of PBDEs on China's and the world's environments is expected to persist for many years to come.

On the basis of a monthly sampling effort from March 2005 to February 2006, the total concentrations of the sums of 27 and 15 polycyclic aromatic hydrocarbons (defined as sigma27PAHs and sigma15PAHs, respectively) in riverine runoff of the Pearl River Delta (PRD), China, and associated fluxes were determined. No clear temporal and spatial trends of PAH concentrations were found at all eight riverine runoff outlets where the samples were collected. The annual fluxes of sigma27PAHs and sigma15PAHs from the PRD to the coastal ocean were 60.2 and 33.9 metric tons, respectively. Assuming that riverine flux was positively related to the regional emission of PAHs, the annual riverine fluxes from five major rivers in China to the global oceans were estimated, which are quite significant relative to other major rivers of the world. On the basis of mass balance considerations, approximately 87% of sigma15PAHs inputting to the Pearl River Estuary and northern South China Sea was derived from riverine runoff from the PRD. In addition, approcimately 22.3 metric tons of sigma15PAHs annually outflow to open seas, which is equivalent to a concentration of 0.34 pg/L in the global oceans if the PAHs are evenly distributed in the upper 200 m of the water column. A comparison with the global background level of PAHs indicated that approximately 0.4% of PAHs in the open oceans may have been contributed by 1-year discharge from the PRD.