土壤中莠去津及其降解产物的提取及高效液相色谱-质谱分析

建立了高效液相色谱-质谱联用(HPLC-MS)选择离子检测(SIM)分析环境土样中的痕量莠去津及其降解产物脱乙基莠去津(deethylatrazine,DEA)、脱异丙基莠去津(deisopropylatrazine,DIA)、羟基化莠去津(HA)的方法。土样用双蒸水超声提取,然后用Waters Oasis MCX固相萃取小柱富集纯化土样提取液,测得莠去津及其降解物在不同加标浓度(4.5~120 ng/g)下的回收率为：莠去津40.4%~82.0%,DEA 60.6%~86.5%,DIA 69.2%~86     

Degradation of 5-Dialkylamino-Substituted Chlorsulfuron Derivatives in Alkaline Soil

Sulfonylurea herbicides are widely used as acetolactate synthase (ALS) inhibitors due to their super-efficient activity. However, some sulfonylurea herbicides show toxicity under crop rotation due to their long degradation time, for example, chlorsulfuron. Our research goal is to obtain chlorsulfuron-derived herbicides with controllable degradation time, good crop safety and high herbicidal activities. Based on our previously reported results in acidic soil, we studied the degradation behaviors of 5-dialkylamino-substituted chlorsulfuron derivatives (NL101–NL108) in alkaline soil (pH 8.39). The experimental data indicate that addition of the 5-dialkylamino groups on the benzene ring of chlorsulfuron greatly accelerated degradation in alkaline soil. These chlorsulfuron derivatives degrade 10.8 to 51.8 times faster than chlorsulfuron and exhibit excellent crop safety on wheat and corn (through pre-emergence treatment). With a comprehensive consideration of structures, bioassay activities, soil degradation and crop safety, it could be concluded that 5-dialkylamino-substituted chlorsulfuron derivatives are potential green sulfonylurea herbicides for pre-emergence treatment on both wheat and corn. The study also provides valuable information for the discovery of new sulfonylurea herbicides for crop rotation.     

光催化降解土壤中多环芳烃

多环芳烃(PAHs)是一类广泛分布于土壤中的持久性有机污染物,其化学结构稳定,具有高疏水性、难降解性和三致毒性,多产生于交通运输、工业生产、垃圾焚烧等人为活动中。近年来,日益严峻的PAHs污染给土壤生态、食品安全和民众健康带来严重威胁。因此,对土壤PAHs污染的治理具有重要意义且亟待解决。在众多PAHs处理技术中,光催化技术凭借能耗低、操作简便、环境友好等优势,受到了研究者们的广泛关注。本文概述了PAHs的光催化降解机理与途径,综述了光催化修复土壤PAHs领域的研究进展,讨论了不同环境因素对催化剂降解效果的影响,并总结了当前光催化技术应用于土壤PAHs污染修复所面临的挑战。     

Controllable Effect of Structural Modification of Sulfonylurea Herbicides on Soil Degradation

The study of soil degradation behaviors of sulfonylurea herbicides in relation to their different structural attributes is utmost important for us to comprehend the development of new eco‐friendly herbicides. It is postulated that the structural modification of the chemical structures could influence their degradation rates in soil. Nine devised structures were synthesized to study their herbicidal activity as well as their soil degradation behaviors respectively. The novel compounds I‐3 – I‐7 were characterized by UV, ¹H NMR and ¹³C NMR, MS and EA. Bioassays indicated that most of target compounds displayed superior herbicidal activities in comparison with Chlorsulfuron. Soil degradation results further confirmed our previous assumption that the introduction of electron‐donating substituents at 5^th position of the benzene ring distinctly increased their degradation rates, among which dimethylamino and diethylamino groups can adjust the degradation rate to a more favorable status.     

Study of Clethodim Degradation and By-Product Formation in Chlorinated Water by HPLC

Two of the most commonly used chlorinating agents for water disinfection, hypochlorite and chloramines, were employed to investigate the degradation of clethodim in conditions simulating tap water treatment. The main clethodim degradation products were identified by using liquid chromatography (LC) coupled with mass spectrometry (MS). The main degradation process was oxidation to sulfoxide and then to sulfone. Degradation half-life was calculated for both parent clethodim and the first degradation product, clethodim sulfoxide. Whereas some other different minor by-products were identified when the degradation occurs with either sodium hypochlorite or chloramines, no other chlorinated by-products were found under the conditions tested.     

Selective Hydrogenation of Carvone and o-Xylene (cis-trans) on Pd/Y Exchanged Zeolites

o-Xylene and carvone hydrogenation on supported Pd on exchanged Y-zeolites was done. A controlled selectivity of hydrogen stereoaddition (cis- and trans-) in o-xylene and a large control of the multiple hydrogen addition in carvone were obtained. These effects were achieved by controlling the exchanged Y zeolites acidity.     

Comparison by Life-Cycle Assessment of Alternative Processes for Carvone and Verbenone Production

Verbenone and carvone are allylic monoterpenoid ketones with many applications in the fine chemicals industry that can be obtained, respectively, from the allylic oxidation of α-pinene and limonene over a silica-supported iron hexadecachlorinated phthalocyanine (FePcCl₁₆-NH₂-SiO₂) catalyst and with t-butyl hydroperoxide (TBHP) as oxidant. As there are no reported analyses of the environmental impacts associated with catalytic transformation of terpenes into value-added products that include the steps associated with synthesis of the catalyst and several options of raw materials in the process, this contribution reports the evaluation of the environmental impacts in the conceptual process to produce verbenone and carvone considering two scenarios (SI-raw-oils and SII-purified-oils). The impact categories were evaluated using ReCiPe and IPCC methods implemented in SimaPro 9.3 software. The environmental impacts in the synthesis of the heterogeneous catalyst FePcCl₁₆-NH₂-SiO₂ showed that the highest burdens in terms of environmental impact come from the use of fossil fuel energy sources and solvents, which primarily affect human health. The most significant environmental impacts associated with carvone and verbenone production are global warming and fine particulate matter formation, with fewer environmental impacts associated with the process that starts directly from turpentine and orange oils (SI-raw-oils) instead of the previously extracted α-pinene and limonene (SII-purified-oils). As TBHP was identified as a hotspot in the production process of verbenone and carvone, it is necessary to choose a more environmentally friendly and energy-efficient oxidizing agent for the oxidation of turpentine and orange oils.     

Degradation of Isoproturon in Soil in Relation to Changes of Microbial Biomass and Activity in Small-Scale Laboratory and Outdoor Studies

Abstract

The soil degradation of isoproturon under standardized laboratory conditions was compared to that carried out in an outdoor experiment using lysimeters. After application of ¹⁴C-labelled formulated isoproturon (1.5 kg A.I./ha), radiochemical analysis, as well as microbial investigations, were performed to relate changes in soil microbial biomass to its capability of degrading isoproturon. The results showed that the microbial biomass, as well as its dehydrogenase activity, varied under field conditions due to fluctuations of temperature and soil moisture. In the laboratory experiment the microbial biomass decreased during the 100 day experimental period, this reduction being the result of the experimental conditions. Consequently, the herbicide was degraded more quickly in the outdoor experiment where leaching, formation of ¹⁴CO₂ uptake by plants, and photolysis also took place, than in the laboratory experiment. Further microbiological investigation in the laboratory experiment showed that specific populations known to be responsible for the metabolic degradation of the compound were enhanced in the isoproturon-treated soil.     

Application of Second Derivative Ultraviolet Spectrometry Part II: Determination of Cinnamic Aldehyde and Carvone in Volatile Oils

Abstract

A rapid and simple method for determining cinnamic aldehyde in cinnamon and cassia oils and carvone in caraway and dill oils is presented. These oils are diluted with ethanol and their respective constituents are directly determined by measuring peak-trough amplitudes of the generated second derivative spectra at certain wavelengths. The results obtained are reasonably reproducible with a coefficient of variation less than 2%.     

Alkaline Soil Degradation and Crop Safety of 5-Substituted Chlorsulfuron Derivatives

Sulfonylurea herbicides can lead to serious weed resistance due to their long degradation times and large-scale applications. This is especially true for chlorsulfuron, a widely used acetolactate synthase inhibitor used around the world. Its persistence in soil often affects the growth of crop seedlings in the following crop rotation, and leads to serious environmental pollution all over the world. Our research goal is to obtain chlorsulfuron-derived herbicides with high herbicidal activities, fast degradation times, as well as good crop safety. On account of the slow natural degradation of chlorsulfuron in alkaline soil, based on the previously reported results in acidic soil, the degradation behaviours of 5-substituted chlorsulfuron analogues (L101–L107) were investigated in a soil with pH 8.39. The experimental data indicated that 5-substituted chlorsulfuron compounds could accelerate degradation rates in alkaline soil, and thus, highlighted the potential for rational controllable degradation in soil. The degradation rates of these chlorsulfuron derivatives were accelerated by 1.84–77.22-fold, compared to chlorsulfuron, and exhibited excellent crop safety in wheat and corn (through pre-emergence treatment). In combination with bioassay activities, acidic and alkaline soil degradation, and crop safety, it was concluded that compounds L104 and L107, with ethyl or methyl groups, are potential green sulfonylurea herbicides for pre-emergence treatment on wheat and corn. This paper provides a reference for the further design of new sulfonylurea herbicides with high herbicidal activity, fast, controllable degradation rates, and high crop safety.     

Pyrrolic and Dipyrrolic Chlorophyll Degradation Products in Plants and Herbivores

The degradation of chlorophyll, the omnipresent green pigment, has been investigated intensively over the last 30 years resulting in many elucidated tetrapyrrolic degradation products. With a comparison to the degradation of the structurally similar heme, we hereby propose a novel additional chlorophyll degradation mechanism to mono- and dipyrrolic products. This is the first proof of the occurrence of a family of mono- and dipyrrols in leaves that are previously only known as heme degradation products. This product family is also found in spit and feces of herbivores with specific metabolomic patterns reflecting the origin of the samples. Based on chromatographic and mass spectrometric evidence as well as on mechanistic considerations we also suggest several tentative new degradation products. One of them, dihydro BOX A, was fully confirmed as a novel natural product by synthesis and comparison of its spectroscopic data.     

溶液pH值对二嗪磷紫外光降解产物及降解途径的影响

在低压汞灯(253.7 nm)光照条件下, 研究了溶液pH值对农药二嗪磷光降解产物及降解途径的影响. 结果表明: 不同溶液pH值条件下二嗪磷的光降解均符合一级反应动力学, 其在中性(pH=7.0, k=0.0234 min^-1)和碱性(pH=10.0, k=0.0236 min^-1)条件下的光降解速率基本相同, 且略高于酸性(pH=4.0, k=0.0193 min^-1)时的光降解速率. 通过UPLC-ESI-MS/MS对降解产物测定分析发现: 溶液pH值显著地影响了二嗪磷光降解产物的种类及生成量. 溶液pH=4.0、7.0和10.0的二嗪磷溶液分别UV光照60 min时分别检出了五种、八种和六种主要的光降解产物, 且同一产物在不同pH值条件下的生成量存在显著差异. 结合MS和MS/MS质谱图信息, 推导出了二嗪磷主要光降解产物的分子结构, 并根据光降解产物种类及生成量随光照时间的变化关系提出了不同溶液pH值时二嗪磷的可能降解途径.     

Degradation of Neonicotinoids and Caffeine from Surface Water by Photolysis

Along with rapid social development, the use of insecticides and caffeine-containing products increases, a trend that is also reflected in the composition of surface waters. This study is focused on the phototreatment of a surface water containing three neonicotinoids (imidacloprid, thiamethoxam, and clothianidin) and caffeine. Firstly, the radiation absorption of the target pollutants and the effect of the water matrix components were evaluated. It was observed that the maximum absorption peaks appear at wavelengths ranging from 246 to 274 nm, and that the water matrix did not affect the efficiency of the removal of the target pollutants. It was found that the insecticides were efficiently removed after a very short exposure to UV irradiation, while the addition of hydrogen peroxide was needed for an efficient caffeine depletion. The electrical energy per order was estimated, being the lowest energy required (9.5 kWh m⁻³ order⁻¹) for the depletion of thiamethoxan by indirect photolysis, and a concentration of hydrogen peroxide of 5 mg dm⁻³. Finally, a preliminary evaluation on the formation of by-products reveals that these compounds play a key role in the evolution of the ecotoxicity of the samples, and that the application of direct photolysis reduces the concentration of these intermediates.     

超声-光催化降解水中有机污染物

超声-光催化是一项近年发展起来的废水处理的新型高级氧化技术。该技术利用超声的空化效应、自由基效应以及机械效应强化光催化的催化效能,实现超声和光催化对水中有机污染物的协同降解。本文从水中有机污染物的超声-光催化降解机理、降解动力学、影响因素（光催化剂类型和投加量、超声频率和强度、溶液pH值、温度、反应物初始浓度、溶解性气体和离子强度）和反应器类型（悬浮型、固定床型）4个方面介绍了相关研究进展,提出了目前存在的主要问题,并展望了超声-光催化降解水中有机污染物的发展方向。     

地表水和饮用水中NDMA的降解方法*

NDMA（二甲基亚硝胺）是在地表水和消毒后的饮用水中新检测到的强致癌污染物,研究其去除方法对保护公众健康和发展安全的水工业具有重要的现实意义。本文综述了NDMA的去除方法,分析了挥发﹑汽提﹑吸附﹑反渗透﹑生物处理﹑金属催化还原﹑UV处理﹑自然光解和二氧化钛光催化方法的优缺点,并探讨了该领域的研究方向,旨在为解决地表水和饮用水中的亚硝胺污染问题开发高效、实用的方法和途径提供新的思路。     

Efficient and Sensitive Method for Quantitative Determination and Validation of Umbelliferone, Carvone and Myristicin in Anethum graveolens and Carum carvi Seed

An efficient HPTLC method for the analysis of umbelliferone, carvone and myristicin in Anethum graveolens and Carum carvi seed was developed. The method employed HPTLC plates precoated with silica gel 60 F₂₅₄ as the stationary phase. Methanol extracts of seeds from three different sources were used. The calibration plot for umbelliferone, carvone and myristicin were linear with the correlation coefficient of 0.997 ± 0.016, 0.999 ± 0.009 and 0.999 ± 0.013, respectively, which were indicative of good linear dependence of peak area on concentration. The method permits reliable quantification of umbelliferone, carvone and myristicin and showed good resolution and separation. The method was validated as per ICH guidelines. To study the accuracy of the method, recovery studies were performed by the method of standard addition at three different levels and the average percentage recovery was found to be 99.05% for umbelliferone, 100.28% for carvone and 99.8% for myristicin. The proposed HPTLC method for quantitative monitoring of umbelliferone, carvone and myristicin in A. graveolens and C. carvi seed can be used for routine quality testing of these extracts.     

Anaerobic Degradation of PCB in Soils

Abstract

The anaerobic degradation of PCB in loamy and clayey soils containing indigeneous microflora was studied. The anaerobic conditions were created by an argon atmosphere in the flasks containing soil flooded by a liquid medium with glucose. GC-ECD analysis of soil extracts after 40 day incubation showed, in addition to the concentration changes of the less chlorinated PCB congeners, a significant decrease in the concentration of highly chlorinated congeners in both soils. The results indicate that in both soil types reductive dehalogenation of PCB congeners was encountered.     

硫辛酸片含量与降解物的高效液相色谱测定研究

建立了硫辛酸片中硫辛酸及其降解物快速测定的高效液相色谱方法。采用Waters XBridge色谱柱(5μm,150 mm×4.6 mm),流动相为0.05 mol/L磷酸二氢钾溶液(磷酸调至pH 2.5)-乙腈-甲醇(50∶45∶5),流速为1.0 mL/min,进样量为20μL,二极管阵列检测器,检测波长为220 nm,全波长扫描范围为200～400 nm,柱温为室温。结果表明,在上述色谱条件下,硫辛酸浓度在0.4～20.0 mg/L范围内线性关系良好(r=0.999 9);其检出限为0.2 mg/L;定量下限为0.6 mg/L;精密度RSD(n=12)为3.4%;加标回收率为100.9%,RSD为2.0%。该法简便、快速、准确、选择性好、灵敏度高,可用于硫辛酸片含量与降解物的测定。     

Degradation of medium-chain-length polyhydroxyalkanoates in tropical forest and mangrove soils

Bacterial polyhydroxyalkanoates (PHAs) are perceived to be a suitable alternative to petrochemical plastics because they have similar material properties, are environmentally degradable, and are produced from renewable resources. In this study, the in situ degradation of medium-chain-length PHA (PHA_MCL) films in tropical forest and mangrove soils was assessed. The PHA_MCL was produced by Pseudomonas putida PGA1 using saponified palm kernel oil (SPKO) as the carbon source. After 112 d of burial, there was 16.7% reduction in gross weight of the films buried in acidic forest soil (FS), 3.0% in the ones buried in alkaline forest soil by the side of a stream (FSst) and 4.5% in those buried in mangrove soil (MS). There was a slight decrease in molecular weight for the films buried in FS but not for the films buried in FSst and in MS. However, no changes were observed for the melting temperature, glass transition temperature, monomer compositions, structure, and functional group analyses of the films from any of the burial sites during the test period. This means that the integral properties of the films were maintained during that period and degradation was by surface erosion. Scanning electron microscopy of the films from the three sites revealed holes on the film surfaces which could be attributed to attack by microorganisms and bigger organisms such as detritivores. For comparison purposes, films of polyhydroxybutyrate (PHB), a short-chain-length PHA, and polyethylene (PE) were buried together with the PHA_MCL films in all three sites. The PHB films disintegrated completely in MS and lost 73.5% of their initial weight in FSst, but only 4.6% in FS suggesting that water movement played a major role in breaking up the brittle PHB films. The PE films did not register any weight loss in any of the test sites.