Electrogeneration of H(2) for Pd-catalytic hydrodechlorination of 2,4-dichlorophenol in groundwater

A novel electrolytic groundwater remediation process, which used the H₂ continuously generated at cathode to achieve in situ catalytic hydrodechlorination, was developed for the treatment of 2,4-dichlorophenol (2,4-DCP) in groundwater. Catalytic hydrodechlorination using Pd supported on bamboo charcoal and external H₂ showed that 2,4-DCP was completely dechlorinated to phenol within 30 min at pH ? 5.5. In a divided electrolytic system, the catalytic hydrodechlorination of 2,4-DCP in cathodic compartment by H₂ generated at the cathode under 20 and 50 mA reached 100% at 120 and 60 min, respectively. Two column experiments with influent pHs of 5.5 (unconditioned) and 2 were conducted to evaluate the feasibility of this process. The 2,4-DCP removal efficiencies were about 63% and nearly 100% at influent pHs of 5.5 and 2, respectively. Phenol was solely produced by 2,4-DCP hydrodechlorination, and was subsequently degraded at the anode. A low pH could enhance the hydrodechlorination, but was not necessarily required. This study provides the preliminary results of a novel effective electrolytic process for the remediation of groundwater contaminated by chlorinated aromatics.     

Chronic toxicity of copper on embryo development in Chinese toad, Bufo gargarizans

This study examined the effects of copper exposure on embryonic development of Chinese toad, Bufo gargarizans. Firstly, the LC₅₀ values from 24 to 96 h of exposure were 3.61 × 10⁻⁶ M, by means of a 4 d toxicity test with B. gargarizans embryos. Secondly, Chinese toad embryos were exposed to 10⁻⁹-10⁻⁶ M copper from mid gastrula stage to operculum completion stage. Measurements included mortality, tadpole weight, tadpole total length, growth retardation, duration of different embryo stages and malformation. Embryonic survival was not affected by copper. Relative to control tadpoles, significantly decreased weight and total length were found at 10^-9-10^-6 M reduced percentage of the embryos in right operculum stage after 10 d exposure to copper and reduced percentage of embryos in operculum completion stage after 12 d exposure to copper were also observed. Moreover, the duration of embryonic development increased at neural, circulation and operculum development stage in copper-treated groups. For the scanning microscope and histological observation, the abnormalities were malformation of wavy dorsal fin, flexural tail, curvature body axis, yolk sac oedema and reduced pigmentation in the yolk sac. Histopathological changes in olfactory, retinal epithelium and skin were also observed. DNA strand breaks exposed to the copper were analyzed by DNA ladder. In conclusion, copper induced toxic effects on B. gargarizans embryos. The present study indicated chronic toxicity tests may provide more accurate way in formulating the “safe levels” of heavy metals to amphibian.     

Transformation of tetrabromobisphenol A in the presence of different solvents and metals

Solvent-based separation method is presumably an efficient and environmentally beneficial approach for elimination of brominated flame retardants (BFRs) from waste electrical and electronic equipment (WEEE). The overall goal of this study was to evaluate possible effects of organic solvent on the behavior of BFRs during solvent-based processing of WEEE. We initiated a set of batch experiments for examining the rates and possible pathways of transformation of a representative BFR (tetrabromobisphenol A, TBBPA) using acetone, toluene, and methanol as the solvents. Our results showed that toluene and methanol had no effect on the transformation of TBBPA, but approximately 20% of TBBPA (100 mg L⁻¹) was transformed by acetone within 2 h at 50 °C. Analysis of the products with GC-MS showed that two high-molecular-weight products (MW = 586) were major products of the transformation reactions. The role of acetone as a reactant in the transformation of TBBPA was further validated with dueterated acetone. In addition, the effects of co-existing metals in WEEE (i.e., Zn, Cu, and Ni) on the transformation of TBBPA in the solvent systems were investigated. These metals tested were found to greatly enhance the rates of TBBPA transformation. The metal facilitated solvent reactions with TBBPA may lower the extractability of TBBPA by formation of larger and less soluble products, hence potentially increasing the cost for separating the chemical from WEEE.     

Identification of priority pharmaceuticals in the water environment of China

In recent years, increasing attention has been paid to the trace-level contamination of pharmaceuticals in the water environment all over the world. Considering a large number of pharmaceuticals used, it is crucial to establish a priority list of pharmaceuticals that should be monitored and/or treated first. In the present study, we developed a ranking system based on the pharmaceutical consumption, removal performance in the wastewater treatment plants (WWTPs) and potential ecological effects, and applied to the situation of China. 39 pharmaceuticals, which had available consumption data and also been reported previously in the WWTPs of China, were selected as candidate pharmaceuticals. Among them, seventeen pharmaceuticals were considered as priority pharmaceuticals, out of which, erythromycin, diclofenac acid and ibuprofen, had the high priority. Compared with other literatures, we found that some pharmaceuticals given concerns to globally should also be included in the priority list in China; while some pharmaceuticals, not mentioned in other literatures, such as cefalexin, ketoconazole, should be also given prior consideration in China. Among all the therapeutic classes, antibiotics, which were grossly abused in China, contributed the most to the priority pharmaceuticals. However, priority antibiotics accounted for only 32% of candidate antibiotics, while 71% and 100% of the candidate anti-inflammatory and antilipidemic respectively were identified as the priority pharmaceuticals, indicating that antibiotics might be overanxiously considered in the previous studies on their behaviors in the WWTPs of China.     

Chlorinated and brominated organic contaminants in fish from Shanghai markets: a case study of human exposure

In the present study were two favorite edible fish species for local residents, i.e., mandarin fish and crawfish, collected from the Shanghai market and analyzed for selected organochlorine pesticides (OCPs), polychlorinated biphenyls (PCBs), hexabromocyclododecane (HBCDD), polybrominated diphenyl ethers (PBDEs) and methoxylated PBDEs (MeO-PBDEs). Efforts were also made to identify the potential sources of these contaminants. Comparable concentrations of hexachlorocyclohexanes (HCHs), dichlorodiphenyltrichloroethanes (DDTs) and HBCDD were found in muscle tissue of mandarin fish from Guangdong (GDF), the Pearl River Delta and from Taihu Lake (TLF), the Yangtze River Delta. Levels of chlordanes, PCBs and PBDEs were about one magnitude lower in TLF compared to GDF. The concentrations of OCPs in the butter-like gland of the crawfish (CFB) were 2-5 times of those in the crawfish muscle (CFM) while concentrations of PCBs, PBDEs and MeO-PBDEs were comparable. The different patterns and levels of chlorinated and brominated organohalogen contaminants seen in mandarin fish from GDF and TLF indicates that different types of chemicals might be used in the two delta regions. The present study also shows a good correlation between the concentrations of hexachlorobenzene (HCB) and pentachloroanisol (PCA) in fish for the first time. Fish consumption limits based on chemical contaminants with non-carcinogenic effects were calculated. The estimated maximum daily consumption limit for GDF, TLF, CFM and CFB were 1.5, 2.6, 3.7 and 0.08 kg, respectively, indicating no significant risk regarding the persistent organic pollutants measured in the present study.     

Distribution and bioavailability of ceria nanoparticles in an aquatic ecosystem model

Along with the increasing utilization of engineered nanoparticles, there is a growing concern for the potential environmental and health effects of exposure to these newly designed materials. Understanding the behavior of nanoparticles in the environment is a basic need. The present study aims to investigate the distribution and fate of ceria nanoparticles in an aquatic system model which consists of sediments, water, hornworts, fish and snails, using a radiotracer technique. Concentrations of ceria in the samples at regular time intervals were measured. Ceria nanoparticles were readily removed from the water column and partitioned between different organisms. Both snail and fish have fast absorption and clearance abilities. Hornwort has the highest bioaccumulation factors. At the end of the experiment, sediments accumulated most of the nanoparticles with a recovery of 75.7 ± 27.3% of total ceria nanoparticles, suggesting that sediments are major sinks of ceria nanoparticles.     

Formation pathways of polychlorinated dibenzofurans (PCDFs) in sediments contaminated with PCBs during the thermal desorption process

Thermal desorption has attracted considerable interest as a remediation technology for the removal of dioxins and polychlorinated biphenyls (PCBs) from contaminated soils and sediments. Although several research groups have confirmed that polychlorinated dibenzofurans (PCDFs) are formed from PCBs during the thermal desorption of sediments contaminated with PCB, the formation pathways remain poorly understood. Herein, thermal desorption has been used to develop a greater understanding of the formation pathways of PCDFs from sediments contaminated with PCBs. PCB decomposition experiments of sediments contaminated with PCBs were performed over 5 min at 450 °C with a gas composition of 10% O(2)/90% N(2), either in the absence (Run 1) or presence (Run 2-4) of one of three different (13)C(12)-labeled PCB individual standards. The results of Run 1 showed that 99.96% of PCBs and 98.40% of polychlorinated dibenzo-p-dioxins (PCDDs) in the treated sediments had decomposed, whereas the concentration levels of PCDFs had increased by a factor of 31. The addition of different (13)C(12)-labeled PCBs to the sediment sample yielded different (13)C(12)-PCDFs isomer patterns, with formation pathways including loss of ortho-Cl(2), loss of HCl involving a 2,3-chlorine shift, loss of ortho-H(2) and dechlorination.     

Biological degradation and microbial function effect of norfloxacin in a soil under different conditions

This paper investigated the degradation kinetics of norfloxacin in a soil, and its effects on soil respiration and nitrogen transformation under different conditions. Compared to the sterile control, the degradation rates of norfloxacin in the non-sterile soil were greatly enhanced, suggesting that microorganisms played a major role in the degradation. Accelerated degradation for norfloxacin in the soil was observed with decreasing concentrations (30 mg/kg to 5 mg/kg) with its half-life decreasing from 62 days to 31 days. Amending swine manure into the soil and increasing the soil moisture level enhanced the biological degradation of norfloxacin. No obvious inhibition of norfloxacin on soil respiration was observed in the soil, while only slight effect on nitrogen transformation was found. The results suggested that norfloxacin at the reported environmental concentrations (<100 mg/kg) would have little effect on microbial activity and functions in the soils.     

Cosorption of organic chemicals with different properties: their shared and different sorption sites

Complementary sorption of different chemicals was expected and investigating the relationship between the sorption inhibition of primary sorbate (ΔQ(pri)) and sorption of secondary sorbate (Q(sec)) could provide a new angle to understand coadsorption of different chemicals. This study used bisphenol A (BPA) as the primary adsorbate, sulfamethoxazole (SMX) as the competitor, and carbon nanotubes as model adsorbents to study their complementary and competitive adsorption. At low BPA concentrations, the sorption of SMX (Q(sec)) exceeded BPA sorption inhibition (ΔQ(pri)), indicating that these two chemicals complementarily adsorbed on their respectively preferred sorption sites. At high BPA concentrations, higher ΔQ(pri) was observed in comparison to Q(sec), which may be resulted from different packing efficiencies of the adsorbed SMX and BPA. This study emphasized that both competitive and complementary sorption should be discussed in binary sorption system.     

Removal of genotoxicity in chlorinated secondary effluent of a domestic wastewater treatment plant during dechlorination

Purpose  

Dechlorination with tetravalent sulfur is widely used in wastewater treatment processes after chlorination. Dechlorination can remove certain genotoxic disinfection by-products (DBPs). However, the reactions occurring during dechlorination of chlorinated secondary effluent and their genotoxic chemicals are still very complex, and the related genotoxicity changes remain unknown. Therefore, the effects of dechlorination on genotoxicity in secondary effluent and its fractions and typical genotoxic chemical after chlorination were evaluated.