Persistent organic pollutants control strategy in China

The development of Persistent Organic Pollutants(POPs) control policy in China in the context of international concerns on POPs was reviewed. The aspects of the Chinese POPs control strategies were analyzed, and compared with those of developed counterparts (e.g. US, EU, Japan). Currently, while the legal framework on POPs management, which complies with international guidelines has been established, it should be improved in the areas of special POPs management, risk assessment, the precautionary principle, life-cycle management and technical support capacity. The analysis of Chinese POPs policy and suggestions for strengthening the science-based decision making capacity are not only useful for Chinese decision-makers, but also a case study for developing world and make a great contribution for the global elimination of POPs to make a toxic-free future.

Distribution of persistent organic pollutants in aggregate fractions of a temperate forest and semi-rural soil

The fate of persistent organic pollutants (POPs) and their interactions with aggregates of forest soils are not completely understood. Our objectives here were to quantify the distribution of different POPs in water-stable aggregate fractions and to study their influence on soil organic carbon (Corg) content. Soil samples were taken from a forest-site, Gogerddan (G) and a semi-rural site, Hazelrigg (H) in Great Britain, from 0-2 and 2-5?cm and 0-4 and 8-12?cm soil depth, respectively. POPs analyzed were PAHs, PCBs, total DDT, PBDEs and HCB. The bulk soil analysis showed that the concentration of POPs was significantly higher (p?≤?0.05) in forest site G than in semi-rural site H, particularly at the surface soil levels compared to the subsurface soil depths in both sites. Total concentrations of PCBs and PAHs of both sites were positively correlated with Corg contents. POPs concentrations and Corg, Nt contents of forest site G were significantly higher (p?≤?0.05) in water-stable macro aggregates (>0.25, >1, >2?mm) than the micro aggregates (>0.053?mm). The POP concentrations of all aggregate fractions after normalizing to their respective Corg content were increased due higher contamination and strong sorption by Corg. These results showed a strong effect of Corg on the partitioning of organic pollutants to soil aggregate size fractions. The present study affirms the ecological significance of forest soils act as a potential sink of POPs. In summary, our results suggest that aggregate fractions may promote soil C storage and act as a potential POP sink in surface soil without increasing their concentration in the aggregate fraction of subsoil.

Sources and Trends of Persistent Organic Pollutants at Three Passive Monitoring Sites in South Africa

The Stockholm Convention on Persistent Organic Pollutants (SCPOPs) is an international treaty that operates under the patronage of the United Nations (UN) to control certain chemicals that are considered persistent organic pollutants (POPs). They are of great concern because of their adverse effects on human health and the environment. Exposure to POPs may lead to cancer, infertility, respiratory infections, and other health complications. It is therefore critical to study the degree of human and environmental exposure to these POPs. Passive air sampling was conducted in South Africa to evaluate the presence and trends of persistent organic pollutants at Barberspan (rural agricultural), Vanderbijl Park (urban industrial) and Molopo Nature Reserve (isolated nature reserve). Samples were collected in 2012. Passive air samplers using poly were used for sampling. The Buchi System B-811 automatic extractor was used to analyze for dichloro-diphenyl-trichlorethane (DDT), pentachlorobenzene (PeCB), hexechlorobenzene (HCB) polychlorinated biphenyls (PCBs) and hexachlorocyclohexane (HCH). Sampling was conducted for a period of one year. POPs concentrations were generally low at all sites, but Vanderbijl Park had the highest concentrations. Seasonal changes in concentrations were much the same at the three sites with temperatures and wind patterns being major factors. The presence of these chemicals in Molopo Nature Reserve and Barberspan is evidence of long range transportation over dry semi desert areas. Back-trajectories indicate possible sources, including areas where DDT is used for malaria control. The presence of POPs is areas they have never been in use poses health and environmental risks in these areas.

Research Progress and Challenges on Persistent Organic Pollutants in Lakes

Lakes are the main reservoirs of persistent organic pollutants(POPs)from land,atmo sphere and rivers.POPs in lakes undergo complex exchange,transformation,and degradation between water-air-sediment-biota interfaces,which are constrained and regulated by various physical,chemical and biological factors.POPs can affect ecological conditions,chemical properties of water and sedi ments,and biodiversity of the lake system.Therefore,it is important to study the sources,migration,transformation,environmental behavior and ecological impacts of POPs in lake ecosystems.This re view summarizes research progress on detection technologies,diversity and origins,historical records,migration and transformation,distribution patterns,degradation and toxic effects of POPs in lakes.Fi nally,future directions related to POPs in lakes were summarized.

A comparative QSAR study on the estrogenic activities of persistent organic pollutants by PLS and SVM

Quantitative structure-activity relationships(QSARs)were determined using partial least square(PLS)and support vector machine(SVM).The predicted values by the final QSAR models were in good agreement with the corresponding experimental values.Chemical estrogenic activities are related to atomic properties(atomic Sanderson electronegativities,van der Waals volumes and polarizabilities).Comparison of the results obtained from two models,the SVM method exhibited better overall performances.Besides,three PLS models were constructed for some specific families based on their chemical structures.These predictive models should be useful to rapidly identify potential estrogenic endocrine disrupting chemicals.

One stone two birds： Degradation of persistent organic pollutants to a valuable industrial chemical production of pentafluoropropionyl fluoride from HFPO oligomers catalyzed by cesium fluoride in tetraglyme

Hexafluoropropylene oxide（HFPO） oligomers are toxic,bioaccumulative,and persistent organic pollutants（POPs）.Consuming the harmful chemicals to prevent them from releasing to nature is of serious significance as far as both natural environments and human health are concerned.In this study,investigation on degradation of HFPO oligomers to pentafluoropropionyl fluoride（PPF）,a valuable industrial chemical,is reported.Different combinations of alkali metal fluoride in either diglyme or tetraglyme under both flask and batch autoclave conditions were examined.Under the optimal reaction conditions,HFPO oligomers（n = 2-10） were completely degraded to PPF in over 90%yield.Reactions on200 g scale were tested and no deduction of efficiency was observed,which indicates the potential for practical industrial application of this chemistry.

Addressing the environmental risk of persistent organic pollutants in China

The Stockholm Convention on persistent organic pollutants （POPs） was adopted in 2001. This year is the 10th anniversary of the adoption of the Convention. Until now, 22 chemicals or chemical categories have been listed as POPs in the Stockholm Convention. The POPs Research Center was established in Tsinghua University in the same year when the Convention was adopted. In the last ten years, much work has been done by Chinese researchers to understand the environ- mental risk of POPs in China. This article aims to review the recent research progress of our POPs Research Center and some other Chinese researchers＇ studies in addressing the environmental risk of POPs, including the priority screening and inventory study of POPs, monitoring and modeling of POPs pollution and exposure, and environ- mental risk assessment and modeling of POPs. Although great advances in addressing the environmental risk of POPs have been made in recent years, we are still facing quite a few problems, such as data scarcity and uncertainty in environmental risk assessment of POPs. The study on the effect of POPs mixtures is in its infancy and currently POPs are usually assessed from legal perspective by risk assessment of single chemicals. These problems should be well addressed by further efforts. Further studies should also be taken in future to study environment risk of POPs by considering aspects of coupled dynamics between climate processes and POPs. Such sound scientific, riskbased information can support decision-making aiming to effectively minimize the risk level of POPs.

Organochlorine compounds and polycyclic aromatic hydrocarbons in surface sediment from Baiyangdian Lake,North China:Concentrations,sources profiles and potential risk

Organochlorine pesticides （OCPs）, polychlorinated biphenyls （PCBs）, and polycyclic aromatic hydrocarbons （PAHs） were determined in nineteen surface sediment samples collected from Baiyangdian Lake and its inflowing river （Fuhe River） in North China. Total concentrations of OCPs, PCBs and PAHs in sediments ranged from 5.4 to 707.6 ng]g, 2.3 to 197.8 ng/g, and 101.3 to 6360.5 ng]g, respectively. The levels of contaminants in Fuhe River were significantly higher than those in Baiyandian Lake. For hexachlorocyclohexane （HCHs） and dichlorodiphenytrich/oroethanes （DDTs）, α-HCH and p,p＇-DDT were predominant isomers; while for PCBs, PCB 28/31, PCB 40/103, PCB 60, PCB 101, and PCB 118 were predominant congeners. Possible sources derived from historical usage for OCPs and incomplete combustion fuel, wood, and coal and exhaustion of boats or cars for PAHs. Risk assessment of sediment indicated that sediments in Fuhe River were likely to pose potential biological adverse impact.

Application of TLSER method in predicting the aqueous solubility and n-octanol/water partition coefficient of PCBs,PCDDs and PCDFs

The theoretical linear solvation energy relationship(TLSER) approach was adopted to predict the aqueous solubility and n -octanol/water partition coefficient of three groups of environmentally important chemicals-polychlorinated biphenyls(PCBs), polychlorinated dibenzodioxins and dibenzofurans(PCDDs and PCDFs). For each compound, five quantum parameters were calculated using AM1 semiempirical molecular orbital methods and used as structure descriptors: average molecular polarizability(α), energy of the lowest unoccupied molecular orbit( E _ LUMO ), energy of the highest occupied molecular orbit( E _ HOMO ), the most positive charge on a hydrogen atom( q _+), and the most negative atomic partial charge( q _-) in the solute molecule. Then standard independent variables in TLSER equation was extracted and two series of quantitative equations between these quantum parameters and aqueous solubility and n -octanol/water partition coefficient were obtained by stepwise multiple linear regression(MLR) method. The developed equations have both quite high accuracy and explicit meanings. And the cross-validation test illustrated the good predictive power and stability of the established models. The results showed that TLSER could be used as a promising approach in the estimation of partition and solubility properties of macromolecular chemicals, such as persistent organic pollutants.

Gridded inventories of historical usage for selected organochlorine pesticides in Heilongjiang River Basin, China

The use of technical HCH （1, 2, 3, 4, 5, 6-hexachlorocyclohexane）, DDT （dichlorodiphenyltrichloroethane） and lindane in Heilongjiang River Basin （HRB） of China was studied. Between 1952 and 1984 the total usage in the HRB was 108900 t for technical HCH, and 4900 t for DDT, respectively, and the use of DDT due to dicofol application in the HRB was 220 t from 1984 to 2003. The usage of lindane in HRB was 109 t from 1991 to 2000. The results show that the highest technical HCH use （41800 t） in HRB was on maize, accounting for 38.3% of the total usage on all crops, followed by the use on wheat （28000 t, 25.7%） and on soybean （26600 t, 24.4%）. The highest DDT use （2300 t） was on soybean, accounting for 46.8% of the total usage on all crops, followed by the use on maize （1500 t, 31.3%） and on sorghum （600 t, 13.2%）. The major use of lindane was mainly on wheat. Gridded usage inventories of these three OCPs （organochlorine pesticides）, in HRB with a 1/6° latitude by 1/4° longitude resolution have been created by using different gridded cropland as surrogates. Some soil samples have also been collected in HRB. Data of usage and soil concentrations of 5： HCH in HRB match quite well to those in Shanghai region, and much higher soil concentration of 5： DDT in Shanghai region could be due to much heavier dicofol use in this region.

Prediction of Aqueous Solubility for 209 Polychlorinated Diphenyl Ethers from Molecular Structural Parameters by DFT Method

Optimized calculations of 209 polychlorinated diphenyl ethers （PCDEs） and diphenyl ethers were carried out at the B3LYP/6-31G^＊ level with the Gaussian 98 program. Based on the theoretical linear solvation energy relationship （TLSER） model, the obtained structural parameters were taken as theoretical descriptors to establish the novel QSPR model for predicting aqueous solubility （-lgSw） of PCDEs. The model obtained in this work contains two variables： mean molecular polarizability （a） and the most positive partial charge on a hydrogen atom （qH^＋）, of which RE = 0.9606 and SD = 0.32. And the results of cross-validation test also show that the model exhibits optimum stability and better predictive power. Moreover, the predictive power of the new model is better than that of MCIs method.

Endocrine disrupting chemicals in mixture and obesity,diabetes and related metabolic disorders

Obesity and associated metabolic disorders represent a major societal challenge in health and quality of life with large psychological consequences in addition to physical disabilities. They are also one of the leading causes of morbidity and mortality. Although, different etiologic factors including excessive food intake and reduced physical activity have been well identified, they cannot explain the kinetics of epidemic evolution of obesity and diabetes with prevalence rates reaching pandemic proportions. Interestingly, convincing data have shown that environmental pollutants, specifically those endowed with endocrine disrupting activities, could contribute to the etiology of these multifactorial metabolic disorders. Within this review, we will recapitulate characteristics of endocrine disruption. We will demonstrate that metabolic disorders could originate from endocrine disruption with a particular focus on convincing data from the literature. Eventually, we will present how handling an original mouse model of chronic exposition to a mixture of pollutants allowed demonstrating that a mixture of pollutants each at doses beyond their active dose could induce substantial deleterious effects on several metabolic end-points. This proof-of-concept study, as well as other studies on mixtures of pollutants, stresses the needs for revisiting the current threshold model used in risk assessment which does not take into account potential effects of mixtures containing pollutants at environmental doses, e.g., the real life exposure. Certainly, more studies are necessary to better determine the nature of the chemicals to which humans are exposed and at which level, and their health impact. As well, research studies on substitute products are essential to identify harmless molecules.

Challenges of organic pollutant photocatalysis by biochar‑based catalysts

With the fast development of industrialization and urbanization,large amounts of organic pollutants are released into the natural environment.The efficient elimination of organic pollutants is thereby crucial for environmental pollution treatment and human health.In the last decades,photocatalytic degradation of persistent organic pollutants has attracted multidisciplinary interest because of its simple operation on a large scale.However,the whole processes for the photocatalytic degradation of organic pollutants are still unclear.In this perspective,the contribution of reactive species,the contribution of photocatalysts,the analysis of intermediate products,the charge transfer and fast carrier recombination are discussed on biochar-based photocatalysts.

Distribution and release of 2,4,5-trichlorobiphenyl in ice

The distribution of persistent organic pollutants（POPs） in ice and the release of POPs from ice during ice melting have an important influence on the eco-environment and water quality of a river. Through laboratory simulation experiments, the distribution and release of 2,4,5-trichlorobiphenyl（PCB29） in ice and the partition coefficients of PCB29 in ice water at different temperatures, concentrations, and p H levels were studied. The results showed that, at different temperatures and concentrations, the concentration of PCB29 in ice increased progressively with depth. The modes of release of different concentrations of PCB29 from ice were obtained. A large amount of PCB29 was released rapidly in the first melting period, and then the remaining PCB29 was released uniformly. The p H value dominated both the distribution and late release of PCB29 in ice. In ice water, at different temperatures, concentrations, and p H levels, the majority of PCB29 entered the water, and a lesser amount remained in the ice. Finally, laboratory experiment results were verified with field investigations. A theoretical framework is provided by this research of the behavior of POPs in ice under different environmental conditions, but a more quantitative understanding of the behavior of POPs in ice will need to be developed through further laboratory studies combined with field investigations.

Degradation of Acenaphthene by Ozone

To investigate the oxidation of acenaphthene （Ace）, a polycyclic aromatic hydrocarbon （PAH） with a saturated C-C bond by ozone and to characterize the intermediate products of ozonation. Methods Ozone was generated from filtered dry oxygen by an ozone generator and continually bubbled into a reactor containing lg/L Ace dissolved in an acetonitrile/water solvent mixture （90/10, v/v） at a rate of 0.5 mg/s. HPLC was used to analyze the Ace concentration. Total organic carbon （TOC） was used to measure the amount of water soluble organic compounds. GC-MS was used to identify the ozonized products. Oxygen uptake rate （OUR） of activated sludge was used to characterize the biodegradability of ozonized products. Results During the ozonation process, Ace was degraded, new organic compounds were produced and these intermediate products were difficult mineralize by ozone, with increasing TOC of soluble organics. The ozonized products were degraded by activated sludge more easily than Ace. Conclusion Ozonation decomposes the Ace and improves its biodegradability. The ozonation combined with biological treatment is probably an efficient and economical way to mineralize acenaphthene in wastewater.

Evaluating the effectiveness of using ClO_2 bleaching as substitution of traditional Cl_2 on PCDD/F reduction in a non-wood pulp and paper mill using reeds as raw materials

The effectiveness of ClO_2 bleaching as a replacement for conventional Cl_2 bleaching,which is intensively practiced in developing countries,to reduce polychlorinated dibenzo-p-dioxins and dibenzofurans(PCDD/Fs)in non-wood pulp and paper mills has not been field tested.The first field study was performed to investigate PCDD/F variations when ClO_2 bleaching was used as a substitute for conventional Cl_2 bleaching in a non-wood pulp and paper mill.It was found that the PCDD/F toxic equivalents(TEQs)in solid and effluent samples were approximately 1.3–14.9 times lower when ClO_2 bleaching was used instead of the conventional Cl_2 bleaching.2,3,7,8-Substituted tetrachlorinated dibenzofurans(2,3,7,8-TCDF)were the dominant contributors to total PCDD/F TEQs in samples from the investigated mill when using conventional Cl_2 bleaching.The formation amounts of 2,3,7,8-TCDF were reduced from 1.56–2.76 pg TEQ/g to 0.02–0.32 pg TEQ/g in solid samples when ClO_2 bleaching was used instead of the conventional Cl_2 bleaching.The replacement of Cl_2 with ClO_2 might decrease the chlorination reactions of dibenzofuran as potential precursors,and thus reduce the formation amounts of 2,3,7,8-TCDF.The results could provide important knowledge for suggesting the best available technique for PCDD/F reduction for non-wood pulp and paper mills in developing countries.

Inventory of unintentional POPs emission from anthropogenic sources in Antarctica

In spite of remote location and very limited human activities,Antarctica is affected by persistent organic pollutants(POPs).POPs investigation in Antarctica has a comparatively long history,but there are still large knowledge gaps in assessment of their emission into environment.In the paper the results of the first inventory of unintentional POPs emission from anthropogenic sources in Antarctica for modern period and preliminary estimate for the late 1980s are presented.Assessment of dioxin/furans(PCDD/Fs)emission in different media,as well as polychlorinated biphenyls(PCBs)and hexachlorobenzene(HCB)in air is based on methodology of emission factors and indicators of human activity.The following sources of POPs emission have been estimated:power generation and heating,waste incineration,mobile sources and open burning of waste(in the past).According to the data obtained,annual PCDD/Fs air emission for modern period comprises 60.74 mg toxic equivalent(TEQ),PCBs-5.09 mg TEQ,and HCB-457.6 mg.Additionally 2.5 mg TEQ of dioxin/furans is released to residues,so total PCDD/Fs emission is amounted 63.23 mg TEQ.Waste incineration makes the greatest contribution to POPs emission(96% of PCDD/Fs,98%of PCBs and 36% of HCB air emission).In late 1980s open burning of waste was the major source of POPs.Retrospective assessment shows that over a 30-year period air emissions of PCDD/Fs decreased about 13 times,PCBs-15 times and HCB-57 times,primarily due to the prohibition of open burning of waste in compliance with the Protocol on Environmental Protection to the Antarctic Treaty requirements.

Preliminary Study on Formulating Water Quality Standards for Estuaries of China

In China,the water quality standards in operation include the Environmental Quality Standard for Surface Water（GB3838-2002）and Water Quality Standards for Seawater（GB3097-1997）.However,these two standards are currently not suitable for the estuarial zones of China because of the unique properties of water environment in estuaries.We proposed preliminarily a basic idea and technical workflow in formulating water quality standards for the estuaries of China based on analyzing the water environment properties of estuaries comprehensively and comparing various parameters and their standard values mentioned in these two standards above.Issues pertinent to the formulation of the water quality standards for estuaries,e.g.nutrient,heavy metals and persistent organic pollutants（POPs）,are highly concerned.The objective of this paper is to provide technical support for the formulation of scientific water quality standards and the assessment of water quality of the estuaries of China.