Microplastic-water partitioning of two states halogenated PAHs: Solute and sol.

The complex interactions of contaminants with microplastics significantly affect ecological risk assessments. Studies of the sorption behavior of freely dissolved hydrophobic organic contaminants (HOCs) on microplastics are common. However, concentrations of HOCs in the actual aquatic environment sometimes exceed their water solubility. A possible explanation is that a microplastic-sol-water three-phase medium (TPM) is formed in the actual water environment. Both states HOCs (in solute and sol) have the potential to migrate to particles suspended in water. To confirm this view, four kinds of microplastics and eight halogenated polycyclic aromatic hydrocarbons (HPAHs) were selected to examine the partitioning of HPAHs between microplastics and water (sol and solute). Both monolayer and multilayer coverage of HPAHs onto microplastics occurred, and chemical sorption dominated the pseudo-sorption mechanism. The microplastic-water partition ratios of HPAHs (0.12-0.74) were approximately four to five orders of magnitude lower than their corresponding KOW values, suggesting that mechanisms other than sorption were involved. Apparently, the sol HPAHs contributed almost identically large increments to both microplastics and water, and closed the gap. For microplastic-supported HPAHs, the contribution of the sol fraction was more than triple that of the dissolved fraction; the key influencing factor was the water solubility of HPAHs.

Investigating the spatial distribution of polychlorinated biphenyls in sediment in the Pearl River Delta, South China.

One hundred forty-three surface sediment (0-5 cm depth) samples were collected from locations representing industrialized areas, less-industrialized areas, and e-waste recycling areas in the Pearl River Delta (PRD). The spatial distribution of polychlorinated biphenyls (PCBs) and their potential adverse effects on aquatic organisms were investigated. The average PCB concentration in the less-industrialized areas (background) in the PRD was approximately 10 ng/g dry weight (dw), which was generally half that found in the industrialized areas (approximately 22 ng/g dw). Severe PCB contamination, with concentrations ranging from 1000 to 26500 ng/g dw, was found in pond sediments collected from e-waste recycling areas. It is very likely that such contamination would have had adverse effects on the aquatic biota there. PCBs in the e-waste recycling areas were dominated by penta- and hex-PCB congeners, which made them significantly different from those found in other regions, where tri- and tetra-PCB congeners were predominant. Higher abundances of less chlorinated congeners were seen in the less-industrialized areas compared to the industrialized areas. Differences in the transport abilities of different congeners, together with dechlorination of higher chlorinated congeners, is the most likely reasons for this.

Linear alkylbenzenes in riverine runoff of the Pearl River Delta (China) and their application as anthropogenic molecular markers in coastal environments.

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.

Riverine inputs of total organic carbon and suspended particulate matter from the Pearl River Delta to the coastal ocean off South China.

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.

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.