Metabolism of 14C‐carbaryl and 14C‐1‐naphthol in moist and flooded soils

Abstract

The metabolism of ¹⁴C‐carbaryl and ¹⁴C‐1‐naphthol in moist and flooded soils was studied in a continuous flow‐through system over a period of 28 days permitting ¹⁴C‐mass balance. The percent distribution of radiocarbon in organic volatiles, carbon dioxide, extractable and non‐extractable (bound) fractions of soils were determined. Organic volatiles could not be detected in both carbaryl and 1‐naphthol treated soils. More of ¹⁴CO₂ (25.6%) was evolved from moist than flooded soil (15.1%) treated with carbaryl. However, the mineralization of ¹⁴C‐1‐naphthol was negligible. The extractable radiocarbon was more in flooded soil (28.9%) than moist soil (5.5%) from carbaryl treatment. Less than one percent was present as parent compound, whereas carbaryl was mainly metabolized to 5‐hydroxy carbaryl in moist soil and to 4‐ and 5‐hydroxy carbaryl in flooded soil. The extractable radiocarbon amounted to 18.2 and 24.3% in moist and flooded soils respectively and the parent compound was less than one percent with 1‐naphthol treatment. Most of the radiocarbon was found as soil bound residues; the formation being more with 1‐naphthol than carbaryl. Humin fraction of the soil organic matter contributed most to soil bound residues of both carbaryl and 1‐naphthol.     

Distribution and persistence of carbaryl in some terrestrial and aquatic components of a forest environment

Abstract

An oil‐based formulation of carbaryl (1‐naphthyl N‐methyl‐carbamate) (Sevin‐2‐Oil) was applied twice by a fixed‐wing aircraft at a dosage rate of 280 g of A.I./ha/application to a coniferous forest near Allardville, New Brunswick. The highest concentrations of the chemical in fir foliage, litter and forest soil 1 h after application were respectively 4.20, 1.21 and 0.59 ppm (fresh weight). The residues dissipated rapidly and the DT50 values obtained from the depletion curves were 2.3 d for foliage and 1.5 d for litter and soil samples. Very low levels (<0.1 ppm) of carbaryl persisted in foliage and litter beyond the 10 d sampling period. The maximum residue level found in stream water was 0.314 ppm and more than 50% of it had dissipated within 1 h. Low but detectable levels (0.001 ppm) of the chemical persisted in water until the end of the 10 d sampling period. Sediment samples contained a maximum level of 0.04 ppm, which dissipated below the detection limit within 5 h. Brook trout and slimy sculpins captured in the stream 1 d after the spray contained on average about 0.04 ppm of carbaryl and none of it was found in 3 d postspray samples.     

Soil bound residues of carbaryl and 1‐naphthol: Release and mineralization in soil,and uptake by plants

Abstract

¹⁴C‐carbaryl and ¹⁴C‐1‐naphthol form soil bound residues which get partially released when barley was grown. ¹⁴C‐residues could be detected in both shoot and root in the case of carbaryl treatment while only roots showed ¹⁴C‐residues in the case of 1‐naphthol. Flooding enhanced release of the bound residues while soil amendment did not. There was greater mineralization of bound residues of carbaryl than that of 1‐naphthol. Rice straw amendment enhanced mineralization.     

Tube-Immunoassay for Rapid Detection of Carbaryl Residues in Agricultural Products

An antibody-based rapid, quantitative, and qualitative tube enzyme-linked immunosorbent assay (tube-ELISA) was developed and used to determine carbaryl (1-naphthyl methylcarbamate) residues in agricultural products (apple, Chinese cabbage, rice, and barley). The tube-ELISA is a competitive immunoassay in which the antibody is coated in the polystyrene tube, with a dynamic range between 0.7 and 46.3 μg kg^?1. Carbaryl was extracted from each agricultural sample by hand-shaking with methanol and examined for application to on-site analysis. After the liquid extraction, the sample extracts diluted with buffer were analyzed by rapid tube-ELISA directly. The overall test time was around 15–30 min, including sample preparation and assay performance. The results obtained from tube-ELISA correlated well with high-performance liquid chromatography (R ² > 0.9). The study shows that tube-ELISA is useful as a quality control tool and can be used to quantitatively detect carbaryl as well.     

Persistence and biodegradation of carbaryl in soils

Abstract

The persistence of the methylcarbamate pesticide carbaryl was studied in four soils under flooded conditions. A substantial portion of the pesticide was recovered from all soils even after 15 days of its application, with the recovery ranging from 37% in an alluvial soil to 73% in an acid sulfate soil. The degradation of carbaryl was more rapid under flooded conditions than under nonflooded conditions. A bacterium, Pseudomonas cepacia, isolated from a flooded soil amended with a related methylcarbamate pesticide carbofuran, degraded carbaryl in a mineral medium supplemented with yeast extract.     

紫外线-氯联合高级氧化体系降解水中的萘普生

采用高级氧化(advanced oxidation processes, AOPs)技术去除水体中的药物及个人护理品(PPCPs)污染物,选取PPCPs中的典型物质萘普生(NPX)为研究对象,探讨了其在UV/氯体系中的降解特性。结果表明：在UV/氯体系中,NPX的降解遵循拟一级动力学模型。氯剂量越高,溶液pH越低,越有利于NPX的降解;不同水基质种类对UV/氯工艺降解NPX的效果有不同影响,HCO3-和HA的存在抑制了NPX的降解,而Cl-的存在明显促进了NPX的降解。UV/氯工艺是一种行之有效的处理PPCPs的技术,但与直接氯氧化相比,UV/氯工艺会有生成更多消毒副产物的风险,需要在实际应用中加以注意。     

Fenton 法降解抗生素磺胺间甲氧嘧啶钠

应用Fenton高级氧化技术降解水溶液中抗生素磺胺间甲氧嘧啶钠(SMMS),系统探讨了起始pH、CSMMS、CFe2+、CH2O2和温度等因素对SMMS降解效果的影响。结果表明:CSMMS=4.53 mg/L,pH=4.0,CH2O2=0.49 mmol/L,CFe2+=19.51μmol/L,T=25℃为最佳反应条件。在最佳条件下,87.4%的SMMS可以在120 min内降解。反应动力学研究表明Fenton氧化降解SMMS分为两个阶段,快速反应阶段和慢速反应阶段,并建立了两阶段动力学模型,模型拟合结果较好。研究结果为含有SMMS的污废水处理提供了基础数据和科学参考。     

Differential enhanced degradation of cis‐ and trans‐1,3‐D in soil with a history of repeated field applications of 1,3‐D

Abstract

The fumigant 1,3‐dichloropropene (1,3‐D) is considered to be a potential alternative to methyl bromide. The degradation rates of cis‐ and trans‐l,3‐D in soil from a treated site during three successive annual applications of 1,3‐D progressively increased with an increase in the number of annual applications. The enhancement was greater for trans‐l,3‐D degradation than cis‐l,3‐D. In untreated soil, the degradation rates of the two isomers were similar. The enhancement lasted slightly longer than 2 years after annual field application of 1,3‐D had ceased. A single field reapplication of 1,3‐D to the treated site that had not been treated for 2 years resulted in resumed differential enhanced degradation of cis‐ and trans‐l,3‐D. Microorganisms were responsible for the enhanced degradation.     

A sensitive monoclonal antibody-based enzyme-linked immunosorbent assay for chlorpyrifos residue determination in Chinese agricultural samples

A monoclonal antibody-based competitive antibody-coated enzyme-linked immunosorbent assay (ELISA) was developed and optimized for determining chlorpyrifos residue in agricultural products. The IC₅₀ and IC₁₀ of this ELISA were 3.3 ng/mL and 0.1 ng/mL respectively. The average recoveries in six agricultural products were between 79.5% and 118.0%, with the intra-assay coefficient of variation being less than 8 %. The limit of detection for all tested products was 30 ng/g. To the best of our knowledge, this assay has the best specificity among all the published research on ELISAs for chlorpyrifos.     

石化综合污水处理厂出水溶解性微生物产物的特性

溶解性微生物产物(soluble microbial products,SMP)是生化系统出水残留COD的主要组成部分,通过采用分子量截留超滤分离、有机物树脂分离等方法对某石化综合污水处理厂出水SMP的分子量分布、亲水特性进行了分析研究.结果表明,水样中的SMP占出水残留COD的85%左右。SMP中主要成分是蛋白质,出水中小于1 kDa的有机物是SMP中的主要物质。树脂分离实验表明,亲水性有机物和疏水酸性有机物分别约占出水SMP的50%和20%,是需要进一步处理削减的主要物质类别。     

慢速可生物降解有机物的转化特性及利用

通过对西安市城市污水处理厂碳源赋存特性和生物降解性分析,探明了西安市城市污水厂碳源的分布特性。西安市污水厂原水中颗粒态COD占总COD的65%左右,以慢速可生物降解有机物为主,是污水厂进水碳源的主要组成部分。分析评价了慢速可生物降解有机物的转化特性与利用潜力,结果表明,在好氧和厌氧2种条件下慢速可生物降解有机物会发生水解发酵作用,在8 h内转化率分别达到58%和65%。其中第1小时为慢速可生物降解有机物的限速阶段,降解缓慢。从第2~4小时降解转化速率显著提高,此后速率逐渐平缓。慢速可生物降解有机物水解产物主要有挥发性脂肪酸(VFAs)、多糖和蛋白类等易于直接被微生物利用的物质。与此同时,也会产生一些腐殖质类的难降解有机物,并在处理过程中会引发其结构改变,趋于生物可利用。     

Life Cycle Assessment as Part of Sustainability Assessment for Chemicals (5 pp)

Background LCA is the only internationally standardized environmental assessment tool (ISO 14040-43) for product systems, including services and processes. The analysis is done ‘from cradle-to-grave’, i.e. over the whole life cycle. LCA is essentially a comparative method: different systems fulfilling the same function (serving the same purpose) are compared on the basis of a ‘functional unit’ - a quantitative measure of this function or purpose. It is often believed that LCA can be used for judging the (relative) sustainability of product systems. This is only partly true, however, since LCA is restricted to the environmental part of the triad ‘environment/ecology - economy - social aspects (including intergenerational fairness)’ which constitutes sustainability. Standardized assessment tools for the second and the third part are still lacking, but Life Cycle Costing (LCC) seems to be a promising candidate for the economic part. Social Life Cycle Assessment still has to be developed on the basis of known social indicators.Method and Limitations LCA is most frequently used for the comparative assessment or optimization analysis of final products. Materials and chemicals are difficult to analyse from cradle-to-grave, since they are used in many, often innumerable product systems, which all would have to be studied in detail to give a complete LCA of a particular material or substance! This complete analysis of a material or chemical is evidently only possible in such cases where one main application exists. But even if one main application does exist, e.g. in the case of surfactants (chemicals) and detergents (final products), the latter may exist in a great abundance of compositions. Therefore, chemicals and materials are better analysed ‘from cradle-to-factory gate’, leaving the analysis of the final product(s), the use phase and the ‘end-of-life’ phases to specific, full LCAs.Conclusion A comparative assessment of production processes is possible, if the chemicals (the same is true for materials) produced by different methods have exactly the same properties. In this case, the downstream phases may be considered as a ‘black box’ and left out of the assessment. Such truncated LCAs can be used for environmental comparisons, but less so for the (environmental) optimization analysis of a specific chemical: the phases considered as ‘black box’ and left out may actually be the dominant ones. A sustainability assessment should be performed at the product level and contain the results of LCC and social assessments. Equal and consistent system boundaries will have to be used for these life cycle tools which only together can fulfil the aim of assessing the sustainability of product systems.     

Variations in expression of carbon isotope fractionation of chlorinated ethenes during biologically enhanced PCE dissolution close to a source zone

The stable carbon isotope values of tetrachloroethene (PCE) and its degradation products were monitored during studies of biologically enhanced dissolution of PCE dense nonaqueous phase liquid (DNAPL) to determine the effect of PCE dissolution on observed isotope values. The degradation of PCE was monitored in a 2-dimensional model aquifer and in a pilot test cell (PTC) at Dover Air Force Base, both with emplaced PCE DNAPL sources. Within the plume down gradient from the source, the isotopic fractionation of dissolved PCE and its degradation products were consistent with those observed in biodegradation laboratory studies. However, close to the source zone significant shifts in the isotope values of dissolved PCE were not observed in either the model aquifer or PTC due to the constant input of newly dissolved, non fractionated PCE, and the small isotopic fractionation associated with PCE reductive dechlorination by the mixed microbial culture used. Therefore the identification of reductive dechlorination in the presence of PCE DNAPL was based upon the appearance of daughter products and the isotope values of those daughter products. An isotope model was developed to simulate isotope values of PCE during the dissolution and degradation of PCE adjacent to a DNAPL source zone. With the exception of very high degradation rate constants (>1/day) stable carbon isotope values of PCE estimated by the model remained within error of the isotope value of the PCE DNAPL, consistent with measured isotope values in the model aquifer and in the PTC.     

Prioritizing research for trace pollutants and emerging contaminants in the freshwater environment

Organic chemicals have been detected at trace concentrations in the freshwater environment for decades. Though the term trace pollutant indicates low concentrations normally in the nanogram or microgram per liter range, many of these pollutants can exceed an acceptable daily intake (ADI) for humans. Trace pollutants referred to as emerging contaminants (ECs) have recently been detected in the freshwater environment and may have adverse human health effects. Analytical techniques continue to improve; therefore, the number and frequency of detections of ECs are increasing. It is difficult for regulators to restrict use of pollutants that are a human health hazard; scientists to improve treatment techniques for higher priority pollutants; and the public to modify consumption patterns due to the vast number of ECs and the breadth of literature on the occurrence, use, and toxicity. Hence, this paper examines literature containing occurrence and toxicity data for three broad classes of trace pollutants and ECs (industrials, pesticides, and pharmaceuticals and personal care products (PPCPs)), and assesses the relevance of 71 individual compounds. The evaluation indicates that widely used industrials (BPF) and PPCPs (AHTN, HHCB, ibuprofen, and estriol) occur frequently in samples from the freshwater environment but toxicity data were not available; thus, it is important to establish their ADI. Other widely used industrials (BDE-47, BDE-99) and pesticides (benomyl, carbendazim, aldrin, endrin, ethion, malathion, biphenthrin, and cypermethrin) have established ADI values but occurrence in the freshwater environment was not well documented. The highest priority pollutants for regulation and treatment should include industrials (PFOA, PFOS and DEHP), pesticides (diazinon, methoxychlor, and dieldrin), and PPCPs (EE2, carbamazepine, βE2, DEET, triclosan, acetaminophen, and E1) because they occur frequently in the freshwater environment and pose a human health hazard at environmental concentrations.     

Temporal and spatial patterns of micropollutants in urban receiving waters

Based on a monitoring program over the course of a year, we characterize the temporal and spatial distribution of selected micropollutants in an urban watershed within the city of Leipzig, Germany. Micropollutants revealed a ubiquitous presence in untreated and treated wastewater, surface water and groundwater. The loads of 4-nonylphenol in the effluents of the municipal wastewater treatment plant followed a seasonal trend, whereas the loads of all other micropollutants were highly variable and not correlated to seasons. In the surface water, load seasonality of caffeine, galaxolide and tonalide resulted from a rapid removal with increased water temperature. The loads of 4-nonylphenol and of caffeine in the colder months increased when rainfall occurred. In the groundwater, complex spatial and temporal patterns were apparent and were related to varying input, retardation and removal processes. As a consequence, an assessment of micropollutants in urban waters should consider different micropollutants' temporal and spatial variability.     

膜-生物反应器中溶解性微生物产物的研究进展

本文就膜 -生物反应器中溶解性微生物产物的生成特性及其影响的研究进展进行了总结。在膜 -生物反应器中 ,膜的高效固液分离作用在提高系统容积负荷和出水水质的同时 ,也使生物反应器成为一个相对封闭的系统。以腐殖质、多糖、蛋白质等物质为主要成分的溶解性微生物产物是生物处理出水中溶解性TOC或COD的主要组成部分 ,主要产生于微生物的基质分解过程和内源呼吸过程 ,其高分子物质的含量较多且可生物降解性较差 ,因此 ,在膜 -生物反应器中会出现积累。溶解性微生物产物的过高积累不仅有可能降低膜过滤出水的水质稳定性 ,而且有可能影响污泥活性 ,并引起膜污染。进水浓度和污泥浓度是影响溶解性微生物产物产生量的重要因素。目前有关膜 -生物反应器中溶解性微生物产物的研究还很不完善 ,有很多问题需进一步研究     

城市污水中有关新型微污染物PPCPs归趋研究的进展

药品和个人护理用品 (PPCPs) 是最近十年引起关注的新型有机微量污染物,其引起的环境安全风险受到人们越来越多的关注。一些研究发现,城市污水处理厂出水中存在着一定浓度的PPCPs,城市污水排放是PPCPs进入环境的一条重要途径。从城市污水中PPCPs的分析方法、迁移转化和减量化技术研究等三个方面综述了有关PPCPs在城市污水中归趋的研究进展,介绍了我国城市污水中PPCPs的研究现状;并对在我国进行相关研究提出了建议,以期推动相关研究的开展。     

排水管道中CH4、H2S与N2O的产生机制及其控制策略

排水管道厌氧环境会产生甲烷 (CH₄) 与硫化氢 (H₂S) ,而好氧及缺氧环境又会诱发氧化亚氮 (N₂O) 。污水中所含有机物 (COD) 、氮 (N) 和硫酸盐 (SO₄²⁻) 是产生这些气体的主要根源。系统综述了3种有害气体的产生机理,厘清污水中污染物、管道中微生物及管道环境对有害气体产生的影响。基于此,有针对性地提出了这几类气态污染物的控制策略。其中,对CH₄与H₂S的抑制手段集中在向管道中投加药剂以限制其产生源头,然而投加NO₃⁻或NO₂⁻药剂与通入氧气这两种控制手段可能会导致N₂O这种温室气体的大量产生。因此,应充分了解排水管道中各复杂因素之间的相互作用,以实现对有害污染气体的控制,并实现碳减排的目标。     

天然气全氧燃烧尾气生活垃圾气化热力学分析

基于Aspen Plus模拟平台,运用吉布斯能最小化原理,以天然气全氧燃烧尾气（后续称为烟气）作为气化剂,选取反应温度和烟气流量与生活垃圾量比（E/M）作为影响因素,气化炉温度变化范围为400~1 500℃,E/M范围0~3.0,对几种典型生活垃圾（木屑、纸屑、塑料、橡胶和厨余）气化进行模拟计算。模拟结果表明,以烟气作为生活垃圾气化剂,可制备富氢产品气,产品气为中热值燃气。温度在800℃左右时,H2的体积分数达到峰值46.75%,反应温度大于800℃时,反应温度的增加对提升产品气的热值、CO的含量有一定作用,但H2的含量和产品气产率有所下降,反应温度过高增加气化的能源投入,反应温度应控制在800~1 000℃范围。高温烟气的过量导致产品气热值和品质下降,E/M宜控制在0.4~1.0区间范围。     

中型污水处理厂中药物和个人护理品的分布与去除

为了解15种药物及个人护理用品(PPCPs)在中小型污水处理厂中的分布及其去除效果,采用液相色谱-串联质谱(LC-MS/MS)技术对3座A2/O工艺的污水处理厂水样进行分析研究。结果显示,除普萘洛尔、吉非罗平和吲哚美辛在3座中小型污水处理厂各个工艺单元中均未被检出外,其余12种目标化合物的检出频率在90%~100%之间。进水水样中PPCPs的平均检出浓度为2 285.4 ng/L,其中咖啡因(CF)的平均检出浓度最高为973.3 ng/L,酮洛芬(KP)的平均检出浓度次之为844.7 ng/L,两者之和占进水水样中PPCPs平均含量的79.5%,表明污水处理厂的主要污染物为CF和KP。3座污水处理厂对CF的去除效果最为显著,平均去除率为95.3%,对15种PPCPs总去除效率在39.3%~82.8%之间。