Heavy metals contamination, potential pathways and risks along the Indus Drainage System of Pakistan.

Riverine water exposed to heavy metals (HMs) pollution is a major concern in the world because of its serious effects on ecosystem and human health. This study assessed the pollution status, sources, diffusion and potential risks of Mn, Co, Cu, Zn, Cr, Ni, Cd, Hg and Pb for the first time along the entire Indus Drainage System of Pakistan. The concentrations of nine HMs in the riverine water ranged from 5.05-101.59 µg/L with a mean value of 41.51 µg/L. The overall metals quantification along the drainage was significantly high (27% of the total) in River Chenab followed by River Indus (26%) > Soan (20%) > Ravi (19%) > Kabul (5%) > Swat (3%). The potential sources of contamination were identified to be the surrounding geogenic activities, industrial/municipal wastewater discharges, agricultural and surface runoffs by using multivariate statistics including metals correlation analysis, hierarchical cluster analysis and principal component analysis. The average mass flux of ∑HMs in the entire drainage was approximately 10.24 tons/year, to which the River Indus contributed 84% of the total, Chenab 11%, Ravi 3%, Kabul 1%, and Soan 1% with more prevalence of biological essential (Zn&Mn) and non-essential (Ni&Cr) metals. In terms of ecological risk, the riverine water metals contamination (1.59 to 57.06) was within the risk threshold (ERI < 110), while the risks of ∑carcinogenic metals for exposed children and adults along the basin were significantly influenced between acceptable to high cancer risk by Cd, Co, Ni, Cr and Pb.

Assessing the contribution of atmospheric transport and tourism activities to the occurrence of perfluoroalkyl acids (PFAAs) in an Alpine Nature Reserve.

Perfluoroalkyl acids (PFAAs) are ubiquitous in the global environment, even in remote regions. With increasing production and application of PFAAs in China, their distribution patterns have been widely reported, however with less attention to inland northwestern regions. Long-range transport and direct releases from local activities have been regarded as the main reasons for PFAAs distribution in such a remote area. To identify and quantify the contributions of different sources to PFAAs occurrences, an investigation was conducted in the Tianchi lake, nature reserve. A total of 20 water samples, 8 soil, 4 sediment and 10 fresh snow samples were collected and analyzed in 2015. The mean PFAAs concentrations were 3.38 ng L-1 in surface water, 1.06 ng g-1 dw in soil, 0.53 ng g-1 dw in sediment, and 3.31 ng L-1 in fresh snow, respectively. High levels of PFAAs were observed in surface water (15.41 ng L-1) from Western Tianchi pond and surface snow (14.24 ng L-1) from the site near a ski resort around Tianchi Lake indicating potential pollution by local human activities. The correlation between individual concentrations among water, soil and snow indicated the snow deposition as an important source. Although with limited sample size, principal component analysis associated with multiple linear regression (PCA-MLR) and positive matrix factorization (PMF) analyses have identified two major sources, which are characterized as tourism activities with dominance of perfluorooctanoic acid (PFOA) and long-range transport with abundant perfluorobutanoic acid (PFBA). Their contributions to total levels were 41% and 52%, respectively. These two sources contributed differently to the PFAAs presences in Tianchi and Western Tianchi Lakes. Source analysis indicates that the western Tianchi lake with a relatively small catchment was affected mainly by local activities.

Simulating transport, flux, and ecological risk of perfluorooctanoate in a river affected by a major fluorochemical manufacturer in northern China.

Perfluoroalkyl acids (PFAAs) have been widely detected and pose potential risks to both human and ecosystem health. Since the probation of perfluorooctane sulfonate (PFOS) by the Stockholm Convention, perfluorooctanoate (PFOA) has frequently been used as a chemical intermediate and processing aid. Owing to a lack of effective treatment technologies for PFOA, surrounding environments have been highly affected. Previous studies by our group have reported elevated PFOA levels in the Xiaoqing River, which receives sewage from a major fluorochemical manufacturer in northern China. To further explore the transport, flux, and ecological risk of the perfluorooctanoate in the river, this study conducted a 2-year sampling campaign of surface water from 2014 to 2015. An extremely high PFOA concentration (mean: 62.3 µg L-1) was observed for the Xiaoqing River in comparison with other studies. The highest average concentration and flux of PFOA were recorded in the autumn and summer, respectively. With data on selected hydrological parameters and cross-sections, PFOA concentrations were modeled using DHI MIKE 11. To explore the current loads and environmental capacity of PFOA, two scenarios (i.e., emissions based on observed concentrations and on the predicted no-effects concentration, PNEC) were set. The simulation results based on observed data showed that PFOA loads in the Xiaoqing River were 11.4 t in 2014, and 12.5 t in 2015. Based on the PNEC, the environmental carrying capacity of PFOA was estimated to be 13.9 t in 2014, and 13.8 t in 2015. The current loads of PFOA were found to approach the maximum environmental carrying capacity. Relatively high risks around both the fluorine industrial park (FIP) and estuary area were identified. In comparison with other suggested guidelines, threats to the ecological status of the river would be severe, which suggests that stringent management and emission criteria are needed for this industry.

Potential effects of changes in climate and emissions on distribution and fate of perfluorooctane sulfonate in the Bohai Rim, China.

Climate change and emissions rates of contaminants are expected to affect distribution and fate of Persistent Organic Pollutants (POPs) in the environment, however, studies on these combined factors are rare. In this study, Perfluorooctane Sulfonate (PFOS) is used as an example to assess how those two factors synthetically affect fate and disposition of POPs in the Bohai Rim of China by using the Berkeley-Trent-Urban-Rural (BETR-Urban-Rural) model. We set up three climate change scenarios and four emission scenarios to conduct the simulations. The results show that climate change could have significant effects on the transport and fate of PFOS mainly including advection, inter-compartmental transfer under the "worst case" emission scenario. For most grids, a remarkable decrease in concentrations of PFOS are predicted for fresh water and urban soil in the future, with precipitation and temperature being predominant factors, whilst for coastal water and rural soil, an increasing trend is predicted. Additionally, predicted sum of sources to the Bohai Sea increases greater than removals from the Bohai Sea in the future, adding evidence that concentrations of PFOS in coastal water will increase more in the future. Under scenarios of reduced emissions and climate change, concentrations of PFOS in each compartment decreased more rapidly over time. We suggest that assessment of future climate change impacts on fate of PFOS could take emission reductions into consideration.

Identify biosorption effects of Thiobacillus towards perfluorooctanoic acid (PFOA): Pilot study from field to laboratory.

The concentration of Perfluoroalkyl acids (PFAAs) and the bacterial community composition along the Xiaoqing River were explored with HPLC-MS/MS and Illumina high-throughput sequencing in present study. The results showed that perfluorooctanoic acid (PFOA) was the predominant PFAAs in all sediment samples, and high level of PFOA could lead to an evident increase in the abundance of Thiobacillus. Thiobacillus was identified with the survival ability in high concentrations of PFOA accordingly. Therefore, Thiobacillus thioparus and Thiobacillus denitrificans were selected as receptors to design indoor biosorption experiment. The growth curves under different PFOA concentrations and residual rates of PFOA in the processes of cultivation were analyzed. The results showed that upwards concentrations of PFOA below 5000 ng/L led to an obvious increase in the growth rate of T. thioparus. Whereas PFOA promoted the growth of T. denitrificans in a relatively limited range of concentration, and the effect was not obvious. The addition of different concentrations of PFOA had no apparent effects on pH values in the media of both T. thioparus and T. denitrificans. The concentrations of PFOA in liquid media reduced after the process of bacteria culturing. The removal rates of T. thioparus and T. denitrificans to PFOA were 21.1-26.8% and 13.5-18.4%, respectively. The current findings indicated that T. thioparus could play a significant role as potential biosorbent with the ability to eliminate PFOA effectively in aquatic environment, which would provide novel information for PFOA ecological decontamination and remediation.

Using hydrodynamic model to predict PFOS and PFOA transport in the Daling River and its tributary, a heavily polluted river into the Bohai Sea, China.

Perfluorooctane sulfonate (PFOS) and perfluorooctanoic acid (PFOA) are extremely persistent in the environment, and have the potential for long-range transport. The present study focused on the Daling River and its tributary, a larger river flowing into Liaodong Bay of the Bohai Sea. Recent studies have shown the elevated levels of PFOS and PFOA in the Daling River. Hence, the objective of this study was to investigate the seasonal changes, fate and transport modeling of PFOS and PFOA concentrations using one-dimensional DHI MIKE-11 river model. We designed three scenarios to assess the risk of PFOS and PFOA in surface water: the measured concentrations, constant maximum and the magnitude of a continuous constant load. The mean absolute errors divided by the mean of measured concentrations were 41-64% for PFOS and 29-36% for PFOA. The result indicated that PFOS and PFOA in the downstream of the Daling River would not reach a harmful level with the current load. The fluorochemical parks contributed an average of 44.57% of the total PFOS and 95.44% of the total PFOA flow that reached the estuary. The mass flow was observed as 1.74 kg y-1 for PFOS and 40.57 kg y-1 for PFOA to the Bohai Sea. These modeling results may be useful for monitoring the status and trends of emerging POPs and will help the determination of the risk to both humans and wildlife, in the estuarine and coastal areas of the Bohai Sea, China.