Photocatalytic degradation with immobilised TiO(2) of three selected neonicotinoid insecticides: imidacloprid, thiamethoxam and clothianidin

This research focused on photocatalytic degradation of imidacloprid, thiamethoxam and clothianidin employing a tailor-made photoreactor with six polychromatic fluorescent UVA (broad maximum at 355 nm) lamps and immobilised titanium dioxide (TiO₂) on glass slides. The disappearance was followed by high pressure liquid chromatography (HPLC-DAD) analyses, wherein the efficiency of mineralization was monitored by measurements of total organic carbon (TOC). Within 2 h of photocatalysis, all three neonicotinoids were degraded following first order kinetics with rate constants k = 0.035 ± 0.001 min⁻¹ for imidacloprid, k = 0.019 ± 0.001 min⁻¹ for thiamethoxam and k = 0.021 ± 0.000 min⁻¹ for clothianidin. However, the rate of mineralization was low, i.e. 19.1 ± 0.2% for imidacloprid, 14.4 ± 2.9% for thiamethoxam and 14.1 ± 0.4% for clothianidin. This indicates that several transformation products were formed instead. Some of them were observed within HPLC-DAD analyses and structures were proposed according to the liquid chromatography-electro spray ionization tandem mass spectrometry analyses (LC-ESI-MS/MS). The formation of clothianidin, as thiamethoxam transformation product, was reported for the first time.     

Volatile organic compounds at swine facilities: A critical review

Volatile organic compounds (VOCs) are regulated aerial pollutants that have environmental and health concerns. Swine operations produce and emit a complex mixture of VOCs with a wide range of molecular weights and a variety of physicochemical properties. Significant progress has been made in this area since the first experiment on VOCs at a swine facility in the early 1960s. A total of 47 research institutions in 15 North American, European, and Asian countries contributed to an increasing number of scientific publications. Nearly half of the research papers were published by U.S. institutions.Investigated major VOC sources included air inside swine barns, in headspaces of manure storages and composts, in open atmosphere above swine wastewater, and surrounding swine farms. They also included liquid swine manure and wastewater, and dusts inside and outside swine barns. Most of the sample analyses have been focusing on identification of VOC compounds and their relationship with odors. More than 500 VOCs have been identified. About 60% and 10% of the studies contributed to the quantification of VOC concentrations and emissions, respectively. The largest numbers of VOC compounds with reported concentrations in a single experimental study were 82 in air, 36 in manure, and 34 in dust samples.The relatively abundant VOC compounds that were quantified in at least two independent studies included acetic acid, butanoic acid (butyric acid), dimethyl disulfide, dimethyl sulfide, iso-valeric, p-cresol, propionic acid, skatole, trimethyl amine, and valeric acid in air. They included acetic acid, p-cresol, iso-butyric acid, butyric acid, indole, phenol, propionic acid, iso-valeric acid, and skatole in manure. In dust samples, they were acetic acid, propionic acid, butyric acid, valeric acid, p-cresol, hexanal, and decanal. Swine facility VOCs were preferentially bound to smaller-size dusts.Identification and quantification of VOCs were restricted by using instruments based on gas Chromatography (GC) and liquid chromatography (LC) with different detectors most of which require time-consuming procedures to obtain results. Various methodologies and technologies in sampling, sample preparation, and sample analysis have been used. Only four publications reported using GC based analyzers and PTR-MS (proton-transfer-reaction mass spectrometry) that allowed continuous VOC measurement. Because of this, the majority of experimental studies were only performed on limited numbers of air, manure, or dust samples. Many aerial VOCs had concentrations that were too low to be identified by the GC peaks.Although VOCs emitted from swine facilities have environmental concerns, only a few studies investigated VOC emission rates, which ranged from 3.0 to 176.5 mg d⁻¹ kg⁻¹ pig at swine finishing barns and from 2.3 to 45.2 g d⁻¹ m⁻² at manure storages. Similar to the other pollutants, spatial and temporal variations of aerial VOC concentrations and emissions existed and were significantly affected by manure management systems, barn structural designs, and ventilation rates.Scientific research in this area has been mainly driven by odor nuisance, instead of environment or health concerns. Compared with other aerial pollutants in animal agriculture, the current scientific knowledge about VOCs at swine facilities is still very limited and far from sufficient to develop reliable emission factors.     

Determination of flame-retardant hexabromocyclododecane diastereomers in textiles

To establish a concise and rapid procedure to analyze hexabromocyclododecane (HBCD) diastereomers in flame-retarded textiles, three different methods of extraction—Soxhlet, ultrasonic, and soaking extractions with toluene and dichloromethane (DCM)—were compared. During Soxhlet extraction using toluene, the percent contribution of α-HBCD to total HBCDs increased slightly and that of γ-HBCD decreased, indicating that γ-HBCD was isomerized to some extent at the boiling point of toluene (110.6 °C). For ultrasonic extraction, the temperature of the water bath can easily increase over time during the procedure, which might lead to undesirable effects. Therefore, we considered soaking extraction with DCM to be the most facile procedure to analyze HBCD diastereomers in textiles. Using the method established in this study, commercially available textiles in Japan (n = 10) were analyzed to understand the actual composition of HBCD contents and its diastereomer profiles. With the exception of one textile sample, HBCDs were detected in all the samples analyzed, with concentrations ranging from 22 000 to 43 000 mg kg⁻¹ (i.e. 2.2–4.3%). We found a higher proportion of the α-diastereomer in most textile products compared with that of commercial HBCD mixtures, indicating that γ-HBCD isomerized to α-diastereomer by heating processes to incorporate the commercial formulation into treated materials or that the α-diastereomer preferentially absorbed onto textile materials during the manufacturing of flame-retarded consumer products.     

Persistence of C-labeled atrazine and its residues in a field lysimeter soil after 22 years

Twenty-two years after the last application of ring-¹⁴C-labeled atrazine at customary rate (1.7 kg ha⁻¹) on an agriculturally used outdoor lysimeter, atrazine is still detectable by means of accelerated solvent extraction and LC-MS/MS analysis. Extractions of the 0-10 cm soil layer yielded 60% of the residual ¹⁴C-activity. The extracts contained atrazine (1.0 μg kg⁻¹) and 2-hydroxy-atrazine (42.5 μg kg⁻¹). Extractions of the material of the lowest layer 55-60 cm consisting of fine gravel yielded 93% of residual ¹⁴C-activity, of which 3.4 μg kg⁻¹ was detected as atrazine and 17.7 μg kg⁻¹ was 2-hydroxy-atrazine. The detection of atrazine in the lowest layer was of almost four times higher mass than in the upper soil layer. These findings highlight the fact that atrazine is unexpectedly persistent in soil. The overall persistence of atrazine in the environment might represent a potential risk for successive groundwater contamination by leaching even after 22 years of environmental exposure.     

Levels and distribution of organophosphorus flame retardants and plasticizers in fishes from Manila Bay, the Philippines

Organophosphorus compounds (OPCs) and stable isotope ratios (δ¹³C and δ¹⁵N) were determined in 58 fishes belonging to 20 species collected from Manila Bay, the Philippines. OPCs were detected in most of the samples and found up to μg/g lw (lipid weight) level, suggesting their ubiquitous presence in the coastal marine environment of the Philippines. Higher levels (>1000 ng/g lw) of total OPCs were determined in yellowstriped goatfish, silver sillago, tripletail wrasse and bumpnose trevally indicates either their active uptake from ambient water or lower metabolic capacity of these species. Levels of triphenyl phosphate (TPhP) in demersal species showed a positive correlation with δ¹⁵N, indicating that TPhP was adsorbed onto the particle, settled down to the bottom sediment and accumulated through the benthic food web rather than the pelagic. Estimated dietary intake of OPCs in Manila Bay fishes were four to five orders of magnitude lower than the proposed reference dose (RfD).     

Risk assessment for human consumption of perfluorinated compound-contaminated freshwater and marine fish from Hong Kong and Xiamen

Perfluorinated compounds (PFCs) are man-made fluoro-surfactants that are identified as global pollutants and can pose health risks to humans and wildlife. Two aspects of risk assessment were conducted in this study, including exposure and response. Exposure was estimated by using the concentrations of PFCs in fish and applying standard exposure factors. Among different PFCs, PFOS, PFOA, PFNA, PFDA, PFUdA and PFTrDA were detected. Total concentrations of PFC in fish ranged from 0.27-8.4 ng g⁻¹ to 0.37-8.7 ng g⁻¹ respectively in Hong Kong and Xiamen. The calculated hazard ratio (HR) of PFOS for all fish was less than 1.0. However, the HR for mandarin fish in Hong Kong and bighead carp, grass carp and tilapia in Xiamen, had HR values of approximately 0.5, indicating that frequent consumption of these 4 more contaminated fish species might pose an unacceptable risk to human health. Our data support the notion that the released/disposed chemical pollutants into water systems make fish a source of environmental toxicants to humans. The risks and potential effects of PFCs to health of coastal population in the Pearl River Delta are of concern.     

超声波萃取-GC/MS法测定橡胶轮胎中的多环芳烃

建立了超声波萃取-气相色谱/质谱(GC/MS)联用测定轮胎制品中多环芳(PAHs)的分析方法.优化了超声波萃取条件,采用MS的选择离子检测方式对PAHs进行定性定量分析.结果表明,16种PAHs的平均加标回收率为75.4%～88.0%,相对标准偏差(n=5)为0.66%～11.90%,方法检出限在1.0～4.0 ng/mL.     

北京大气中CFC-11的浓度观测与变化趋势

近几年大气中CFC的浓度在人类活动的影响下发生了迅速变化,考虑到CFC浓度变化对平流层臭氧和全球变暖的影响,采用两步深冷冻浓缩自动进样系统,配以气相色谱/质谱联机对北京大气中的CFC-11进行了连续观测.结果表明,1999～2003年CFC-11的浓度季节变化均呈单峰形态,峰值出现在7～8月,月平均浓度最高值为1149.5±531.9×10^-12(体积分数);谷值出现在春季的3～5月份,月平均浓度最低值为487.5±131.5×10^-12(体积分数);北京大气中CF-11年平均浓度在观测时间段内呈先上升后下降的趋势,其中1995～1998年增长较快,平均增长率为17.9%,1999年后呈缓慢下降趋势,平均下降率为10.7%,平均浓度是Mauna Loa全球基准观测站观测到大气本底CFC-11浓度的3～5倍.     

超高效液相色谱-串联质谱法测定水中拟除虫菊酯和有机磷农药残留

采用直接进样法和萃取浓缩法2种前处理方式,通过超高效液相色谱-串联质谱法对水中20种拟除虫菊酯类和有机磷类农药进行了测定,并对仪器条件的选择和前处理条件的优化进行了探讨.结果表明,20种农药的线性关系良好,相关系数均>0.999,直接进样法检出限为0.21～2.47μg/L,回收率为81.0％ ～119％,相对标准偏差...