Sodium p-perfluorous nonenoxybenzene sulfonate (OBS) is widely used in China as fire-fighting foam co-formulant and oil production agent, because it is an economical alternative to perfluorooctane sulfonate (PFOS), classified as persistent organic pollutant by the Stockholm Convention. Such chemical very likely possesses toxicological and bioaccumulative characteristics that are similar to PFOS and many other perfluorinated compounds. However, in this first report we demonstrate that OBS, in spite of its non-readily biodegradability, can be decomposed by UV/H2O2 or even sole UV (254 nm) system (contrary to PFOS). More than 96% OBS is degraded in aqueous solution within 20 minutes by both methods thanks to its peculiar molecular structure. Yet, after 2 h reaction UV/H2O2 gives 99% sulfate recovery, while in UV system only 61% sulfate is detected; fluoride recovery was less than 16% for both treatments. Such results, corroborated by intermediate identification, highlight that UV/H2O2 system can effectively destroy the OBS sulfonated aromatic moiety. On contrary, it remains intact in several products of the UV treatment, raising a concern on their potential toxicity. Such results demonstrate OBS better degradability and treatability, compared to other perfluorinated chemicals, and suggest that it might be biodegraded on long term. Moreover, these findings may be of help for a more environmentally friendly eco-design of other fluorinated alternatives.

The destruction of persistent organic pollutants (POPs) is a large challenge in particular in developing and emerging economies. To date, a detailed assessment of non-combustion technologies with respect to formation of dioxins is lacking. In this study, an assessment of mechanochemical (MC) destruction technology for polychlorinated biphenyls (PCBs) and polybrominated diphenyl ethers (PBDEs) in contaminated soil remediation was conducted. Actual applied conditions of pilot-scale MC POPs destruction process indicates that the temperature increase inside the ball mills has the potential to form high levels of toxic polybrominated and polychlorinated dibenzo-p-dioxins and dibenzofurans (PXDD/Fs) when dioxin precursors are present. Therefore, the MC technology was modified for treatment of the PCB and PBDE containing soil including an efficient cooling system which could prevent the formation of PXDD/F during the destruction of PCBs and PBDEs. This is likely relevant for all contaminated soils containing relevant dioxin precursor and need to be considered for treatment of soils with MC and probably other non-combustion technologies.

The fate and removal of pharmaceuticals and personal care products (PPCPs) in wastewater treatment plants (WWTPs) has received great attention during the last decade. Numerous data concerning concentrations in the water phase can be found in the literature, however corresponding data from sludge as well as associated mass balance calculations are very limited. In the present study, the adsorbed and dissolved concentrations of 9 PPCPs were investigated in each unit of a WWTP in Beijing, China. Based on the calculation of mass balance, the relative mass distribution and removal efficiency of each target compound was obtained at each process. The amount of PPCPs entering into the WWTP ranged from 12 g·d–1 to 3848 g·d–1. Five target compounds (caffeine, chloramphenicol, bezafibrate, clofibric acid, and N,N-diethyl-meta-toluamide) were effectively removed, with rates of 57%–100%. Negative removal efficiencies were obtained for sulpiride, metoprolol, nalidixic acid, and carbamazepine, ranging from -19% to -79%. PPCPs mainly existed in dissolved form (≥92%) in both the raw influent and the final effluent. The sludge cake carried a much lower amount of PPCPs (17 g·d–1) compared with the discharged effluent (402 g·d–1). In A2/O treatment tanks, the anaerobic and anoxic tanks showed good performance for PPCPs removal, and the amount of adsorbed PPCPs was increased. The results reveal that both the dissolved and the adsorbed phases should be considered when assessing the removal capacity of each A2/O tank.

Pentachloronitrobenzene (PCNB) products have been reported to contain relatively high levels of polychlorinated dibenzo-p-dioxins (PCDDs), polychlorinated dibenzofurans (PCDFs) as impurities. No data was available for Chinese PCNB products which are still produced and used in China. Therefore, we analysed Chinese PCNB products, including two raw pesticides and three formulations available on the market. In all samples, PCDDs, PCDFs, and dioxin-like polychlorinated biphenyls (DL-PCBs) were detected at levels exceeding Japanese regulation limits. The concentrations of PCDDs and PCDFs (0.16 to 0.93 ng TEQ g−1) were lower than the PCNB formulations measured from the Australian market (3.9 ng TEQ g−1). However, the Toxic Equivalent (TEQ) contribution from DL-PCBs (0.7 to 2.5 ng TEQ g−1) to total TEQ was higher compared to PCDDs and PCDFs. This discovery demonstrated that it is necessary to consider the DL-PCBs impurity in organochlorine pesticides and other organochlorine chemicals in particular chlorinated aromatic compounds for adequate risk assessment. In addition to DL-PCBs, other unintentionally POPs—hexachlorobenzene (HCB) (3.7 to 52 ng g−1) and pentachlorobenzene (PeCBz) (0.04 to 0.3 ng g−1) which are listed in the Stockholm Convention—were detected in the PCNB samples. The PCNB production steps were assessed for their unintentional POPs formation potential. Thermolysis of the aromatic compounds using iron chloride (FeCl3) as catalyst is suggested as relevant production step for (DL-)PCBs formation. Since the levels in the formulated PCNB recalculated to active ingredient were higher compared to the raw pesticide, the formulation process (e.g., milling) may also have had an influence on additional PCDD/Fs and PCBs formation.

Impurity of polychlorinated naphthalenes (PCNs) in commercial polychlorinated biphenyl (PCB) formulations has been recognized as a relevant source of PCNs in the environment. Congener-specific analysis of most main PCB formulations has been accomplished previously, excluding the Chinese product. The insulating oil in a stored Chinese electric capacitor containing the major Chinese technical formulation “PCB3” was sampled and tested by isotope dilution technology using high-resolution gas chromatography coupled to high-resolution mass spectrometry (HRGC/HRMS). The detected concentration of PCNs in the Chinese PCB oil sample was 1,307.5 μg/g and therefore significantly higher than that reported in PCB formulations from other countries, as well as that in the transformer oil (ASKAREL Nr 1740) additionally tested in the present study for comparison. Based on the measurement, the total amount of PCNs in Chinese PCB3 oil is estimated to be 7.8 t, which would mean only 0.005 % of global production of PCNs of 150,000 t. The homolog profile is similar to those of PCN in Aroclor 1262 and Clophen A40, where the contributions from hexa-CNs and hepta-CNs are predominant and accounted for similar proportions. The Toxic Equivalent Quantity (TEQ) concentration of dioxin-like PCN congeners is 0.47 μg TEQ/g, with the dominant contributors of CN-73 and CN-66/67. This TEQ content from PCN is higher than that in most other PCB formulations with the exemption of the Russian Sovol formulation. The total TEQ in the historic 6,000 t of the Chinese PCB3 formulation is estimated to be 2.8 kg TEQ.

In the present study, mechanochemical (MC) treatment of polybrominated diphenyl ethers (PBDEs), a kind of emerging persistent organic pollutant (POPs), was performed using a high energy ball mill. With Bi2O3 as co-milling reagent, deca-BDE was effectively destroyed and no hazardous intermediates or organic products were observed in the MC reaction. Meanwhile, BiOBr, a promising visible light photocatalyst, was proved to be the final product which could be utilized in further steps. Neither excessive Bi2O3 nor unreacted deca-BDE was left after the reaction as they were originally added at stoichiometric ratio for BiOBr formation. FITR and Raman analyses demonstrate the collapse of deca-BDE skeleton and the cleavage of C–Br bonds with the generation of inorganic carbon, revealing the mechanism of carbonization and debromination. The gaseous products at different reaction atmosphere were also analyzed, showing that mostly CO2 with a fraction of CO were released during the MC process. The reaction formula of deca-BDE and Bi2O3 was then proposed based on the identified final products. Besides, the photocatalytic activity of the generated BiOBr was evaluated using methyl orange as the model pollutant. A good degradation performance from BiOBr was achieved under both simulated sunlight and visible light irradiation, indicating the possibility for its further utilization.

The occurrence of 15 pharmaceuticals and personal care products in the influent and effluent from the wastewater treatment plant (WWTP) and its receiving water in Beijing, China were determined. Results from the present study confirmed that caffeine, N,N-diethyl-m-toluamide and chloramphenicol were removed at a high rate (>70 % efficiency). In contrast, removal efficiency of the other 12 compounds was quite poor (ranged from −40 % to 58 %). Some compounds in the receiving river were present at higher concentrations compared to those in the WWTP effluent, indicating that sources other than treated effluents are present. The risk to the aquatic environment was estimated by a ratio of measured environmental concentration and predicted no-effect concentration. For those compounds found in the effluent and surface water, mefenamic acid, trimethoprim and gemfibrozil may pose a medium risk to aquatic environment.

This is the first report on the environmental occurrence of a chlorinated polyfluorinated ether sulfonate (locally called F-53B, C8ClF16O4SK). It has been widely applied as a mist suppressant by the chrome plating industry in China for decades but has evaded the attention of environmental research and regulation. In this study, F-53B was found in high concentrations (43–78 and 65–112 μg/L for the effluent and influent, respectively) in wastewater from the chrome plating industry in the city of Wenzhou, China. F-53B was not successfully removed by the wastewater treatments in place. Consequently, it was detected in surface water that receives the treated wastewater at similar levels to PFOS (ca. 10–50 ng/L) and the concentration decreased with the increasing distance from the wastewater discharge point along the river. Initial data presented here suggest that F-53B is moderately toxic (Zebrafish LC50-96 h 15.5 mg/L) and is as resistant to degradation as PFOS. While current usage is limited to the chrome plating industry, the increasing demand for PFOS alternatives in other sectors may result in expanded usage. Collectively, the results of this work call for future assessments on the effects of this overlooked contaminant and its presence and fate in the environment.

Perfluorooctane sulfonate (PFOS) and perfluorooctanoic acid (PFOA) have received high concerns due to their extreme persistence, and very few technologies have been reported for their complete destruction. For sound PFCs wastes disposal, mechanochemical method was employed using a planetary ball mill. Potassium hydroxide (KOH) was identified as the best comilling reagent and nearly complete destruction of both PFOS and PFOA was realized. The measured water-soluble fluoride accounted for most of the organic fluorine. The final products of PFOS after treatment were shown to be KF and K2SO4 by XRD analysis. The mass ratio between PFOS and KOH significantly affected the fluoride recovery but not for PFOS destruction and the sulfate recovery. The gradual formation of sulfate and fluoride reveals that the degradation of PFOS is initiated with the dissociation of the sulfonate group. FTIR spectra further showed the disappearance of the −CF3 and −CF2– groups with the generation of sulfate. The cleavage of C–F bonds in PFOS and the formation of fluoride ion were also identified by XPS spectra. On the basis of these results, possible reaction pathways were proposed. The approach was also successfully applied for the destruction of PFOS and PFOA homologues with different chain lengths.

Endosulfan, a persistent organic pollutant newly listed under the Stockholm Convention, is currently widely produced and used as a pesticide in China. Concentrations of endosulfans (including α-, β-isomers, and their metabolite endosulfan sulfate) were determined in surface soil collected from Huai’an city, where the largest endosulfan producer is located. The concentrations of Σendosulfan (sum of α-endosulfan, β-endosulfan, and endosulfan sulfate) at all sites ranged from 0.28 to 44.81 ng/g dry weight (dw), following a lognormal distribution. The geometric mean was 1.09 ng/g dw, and the geometric standard deviation was 3.02. The β-endosulfan levels were consistently greater than those of α-isomer. The concentration ratios of α-endosulfan to β-endosulfan ranged from 0.03 to 0.70, which were much lower than the commercial endosulfan mixture. This is because that α-endosulfan is more volatile and degrades faster than β-endosulfan in soil. The contour map of Σendosulfan levels in soil indicates that the factory was the point pollution source with the highest endosulfan level in its surrounding area, especially the southern area. However, the non-point agricultural sources are more important. Based on Monte Carlo simulation, the Σendosulfan inventory in soil in Huai’an is estimated to be 0.8–3.0 tons. In order to understand the potential ecological risk of endosulfan, the Monte Carlo-based hazard quotient distribution was estimated and showed that Σendosulfan posed a potentially high risk to soil organisms. To our knowledge, this study is the first that reports soil pollution and risk of endosulfan around the manufacturer in China. This study will help China’s implementation of Stockholm Convention for the reduction and elimination of endosulfan in future.

Dechlorane Plus (DP) has been used as a highly chlorinated flame retardant substituting those that are now internationally regulated under the Stockholm Convention. Nevertheless DP’s environmental behavior has seldom been studied in China. There is only one DP manufacturer producing DP since 2005, which is located in Huai’an, Jiangsu Province. The DP levels in 21 soil samples that were taken from Huai’an in October 2009 and determined by gas chromatography/electron-capture negative ion–mass spectrometry (GC/ECNI–MS) method ranged from 0.83 to 1.2 × 103 ng g−1, following a lognormal distribution. The geometric mean was 5.1 ng g−1 dry weight (dw) and the geometric standard deviation was 4.6. Sampled soils had fanti[Canti-DP/(Csyn-DP + Canti-DP)] values of 0.67–0.85, with the average value of 0.79, which are close to the values in DP commercial products. This suggests that the main DP pollution source is the commercial DP product. The contour map of DP levels in soil indicated that the factory was the point pollution source with the highest DP level in its surrounding area, especially the southern area. A Monte Carlo based inventory estimation was conducted. The DP inventory in Huai’an is estimated to be 4–31 tons. To our knowledge, this study is the first that reports soil pollution by DP.