Photodegradation of acetochlor in water and UV photoproducts identified by mass spectrometry

The sunlight photodegradation half-lives of 20 mg/L acetochlor were 151, 154 and 169 days in de-ionized water, river water and paddy water, respectively. When exposed to ultraviolet (UV) light, acetochlor in aqueous solution was rapidly degraded. The half-lives were7.1, 10.1, and 11.5 min in de-ionized water, river water and paddy water, respectively. Photopreduets of acetochlor were identified by gas chromatography/mass spectrometry(GC/MS) and found at least twelve photoproducts resulted from dechlorination with subsequent hydrtrxylation and cyclization processes. The chemical structures of ten photoproducts were presumed on the basis of mass spectrum interpretation and literature data. Photoproducts are identified as 2-ethyl-6-methylaniline; N, N-diethylaniline ; 4, 8-dimethyl-2-oxo- 1,2,3,4- tetrahydroquino-line; 2-oxo-N-(2-ethyl-6-methylphenyl)-N-(ethoxymethyl) acetamide; N-(ethoxymethyl)-2‘-ethyl-6‘-methylformanilide; 1-hydroxyaeetyl-2-ethoxyl-7-ethylind ole; 8-ethyl-l-ethoxymethyl-2-oxo-1, 2, 3, 4-tetrahydroquinoline; 4, 8-dimethyl-l-ethoxymethyl-2-oxo-1, 2, 3, 4-tetrahydroquinoline; 2-hydroxy-2‘-ethyl-6‘-methyl-N-(ethoxymethyl) acetanilide and a compound related to acetochlor. The other two photoproducts were detected by GC/MS although their chemical structure was unknown.     

Adsorption and correlation with their thermodynamic properties of triazine herbicides on soils

IntroductionAdsorptionofherbicidesonsoilfromwaterisanimportantfactoraffectingtheirfate,biologicalactivity,andpersistenceinsoil watersystem .Itisoftenaffectedbyseveralpropertiesofsoil.Betterunderstandingofadsorptionanditsaffectingfactorswillmakeitpossibletoadjusttheherbicidedosageaccordingtosoilproperties,thusreducingtheenvironmentalpollutionofherbicidesintheenvironment.Fig .1　StructuresofthreetriazineherbicidesAmongthepost emergentherbicides,triazineherbicidesaremostcommonlyusedworldwideonco…     

The rise of glyphosate and new opportunities for biosentinel early‐warning studies

Glyphosate has become the most commonly used herbicide worldwide and is reputedly environmentally benign, nontoxic, and safe for use near wildlife and humans. However, studies indicate its toxicity is underestimated and its persistence in the environment is greater than once thought. Its actions as a neurotoxin and endocrine disruptor indicate its potential to act in similar ways to persistent organic pollutants such as the organochlorines dichlorodiphenyltrichloroethane (DDT) and dioxin. Exposure to glyphosate and glyphosate‐based herbicides for both wildlife and people is likely to be chronic and at sublethal levels, with multiple and ongoing exposure events occurring in urban and agricultural landscapes. Despite this, there has been little research on the impact of glyphosate on wildlife populations, and existing studies appear in the agricultural, toxicology, and water‐chemistry literature that may have limited visibility among wildlife biologists. These studies clearly demonstrate a link between chronic exposure and neurotoxicity, endocrine disruption, cell damage, and immune suppression. There is a strong case for the recognition of glyphosate as an emerging organic contaminant and substantial potential exists for collaborative research among ecologists, toxicologists, and chemists to quantify the impact of glyphosate on wildlife and to evaluate the role of biosentinel species in a preemptive move to mitigate downstream impacts on people. There is scope to develop a decision framework to aid the choice of species to biomonitor and analysis methods based on the target contaminant, spatial and temporal extent of contamination, and perceived risk. Birds in particular offer considerable potential in this role because they span agricultural and urban environments, coastal, inland, and wetland ecosystems where glyphosate residues are known to be present.     

添加不同 N源条件下典型除草剂对土壤呼吸和 N2O排放的影响

通过室内土壤培养实验,采用间歇密闭培养-气相色谱法研究了添加不同N源条件下我国典型旱地除草剂对农田土壤呼吸和N2O排放的影响.结果表明,在添加（NH4）2SO4氮源条件下,莠去津和百草枯对土壤呼吸和N2O排放无显著影响（P〉0.05）.草甘膦显著抑制了土壤呼吸（P〈0.05）,是对照的78.5%,N2O的排放无显著影响（P〉0.05）,仅表现为均值降低了20.1%.苯磺隆显著促进了土壤呼吸（P〈0.05）,是对照的1.1倍,对N2O排放也无显著影响（P〉0.05）.乙草胺显著促进了土壤呼吸和N2O的排放（P〈0.05）,分别是对照的1.1和1.5倍.在添加尿素的条件下,莠去津和乙草胺对土壤呼吸和N2O排放无显著影响（P〉0.05）.百草枯显著促进了N2O的排放（P〈0.05）,是对照的1.4倍,却对土壤呼吸无显著影响（P〉0.05）.草甘膦显著抑制了土壤呼吸（P〈0.05）,仅为对照的82.5%,对N2O的排放却无显著影响（P〉0.05）.苯磺隆显著促进了土壤呼吸和N2O的排放（P〈0.05）,其分别是对照的1.3和1.6倍.鉴于不同除草剂对不同微生物生理代谢影响的复杂性,其对温室气体的作用和影响还需长期田间试验研究.     

Review of Pesticide Retention Processes Occurring in Buffer Strips Receiving Agricultural Runoff1

Arora, Kapil, Steven K. Mickelson, Matthew J. Helmers, and James L. Baker, 2010. Review of Pesticide Retention Processes Occurring in Buffer Strips Receiving Agricultural Runoff. Journal of the American Water Resources Association (JAWRA) 46(3):618-647. DOI: 10.1111/j.1752-1688.2010.00438.x Abstract: Review of the published results shows that the retention of the two pesticide carrier phases (runoff volume and sediment mass) influences pesticide mass transport through buffer strips. Data averaged across different studies showed that the buffer strips retained 45% of runoff volume (ranging between 0 and 100%) and 76% of sediment mass (ranging between 2 and 100%). Sorption (soil sorption coefficient, K_oc) is one key pesticide property affecting its transport with the two carrier phases through buffer strips. Data from different studies for pesticide mass retention for weakly (K_oc < 100), moderately (100 < K_oc < 1,000), and strongly sorbed pesticides (K_oc > 1,000) averaged (with ranges) 61 (0-100), 63 (0-100), and 76 (53-100) %, respectively. Because there are more data for runoff volume and sediment mass retention, the average retentions of both carrier phases were used to calculate that the buffer strips would retain 45% of weakly to moderately sorbed and 70% of strongly sorbed pesticides on an average basis. As pesticide mass retention presented is only an average across several studies with different experimental setups, the application of these results to actual field conditions should be carefully examined.     

色谱质谱联用技术在一起农药污染事故应急监测中的应用

在一起污染源应急事故中,色谱质谱联用技术在确定污染源类型,并快速做出准确定性定量分析中发挥了重要作用。通过气相色谱-质谱联用技术,首先确定可能污染物类型为三嗪类化合物;之后,通过液相色谱-串连质谱全扫描,推断可能为三嗪类除草剂——甲磺隆。正、负ESI子离子全扫描后图谱与甲磺隆标准物质图谱相对照,完全吻合。最后,通过SRM模式下对380.0→139.0的母、子离子选择反应监测,测定了农田灌溉水源和土壤中甲磺隆的含量。     

2,4-D mineralization in unsaturated and near-saturated surface soils of an undulating,cultivated Canadian prairie landscape

The herbicide 2,4-D [2,4-(dichlorophenoxy) acetic acid] is one of the most widely used pesticides in the Canadian prairies and is frequently detected as a ground and surface water contaminant. The objective of this paper was to determine the magnitude and extent of variation of 2,4-D mineralization in a cultivated undulating prairie landscape. Microcosm incubation experiments, using a 4 × 3 × 2 factorial experimental design (soil moisture, 4 levels: 60, 85, 110, 135% of field capacity; slope position, 3 levels: upper-, mid- and lower-slopes; soil depth, 2 levels: 0–5 and 5–15 cm), were used to assess 2,4-D mineralization. The first-order mineralization rate constant (k₁) varied from 0.03 to 0.22 day^{? 1}, while total 2,4-D mineralization varied from 31 to 52%. At near-saturated conditions (110 and 135% of field capacity), the onset of 2,4-D degradation was delayed in soil obtained from the upper- and mid-slopes but not in soils obtained from the lower-slope position. The k₁ and total 2,4-D mineralizationwas significantly influenced by all three factors and their interactions. The Freundlich sorption coefficient of 2,4-D ranged from 0.83 to 2.46 ug ^1–1/ng^{? 1} mL^1/n and was significantly influenced by variations in soil organic carbon content across slope positions. The infield variability of 2,4-D sorption and mineralization observed across slope positions in this undulating field was comparable in magnitude and extent to the regional variability of 2,4-D sorption and mineralization observed in surface soils across Manitoba. The large variability of 2,4-D mineralization and sorption at different slope positions in this cultivated undulating field suggests that landform segmentation models, which are used to delineate slope positions, are important considerations in pesticide fate studies.     

Combined effect of diuron and simazine on photosystem II photochemistry in a sandy soil and soil amended with solid olive-mill waste

Diuron (3-(3,4-dichlorophenyl)- = 1,1-dimethylurea) and simazine (6-chloro-N ², N ⁴-diethyl-1,3,5-triazine-2,4-diamine) are soil-applied herbicides used in olive crops. The objective of this study is to investigate the effect of these herbicides on Photosystem II photochemistry of Olea europaea L., and whether the amendment of soil with an organic waste (OW) from olive oil production industry modifies this effect. For this purpose, herbicide soil adsorption studies, with unamended and OW-amended soil, and chlorophyll fluorescence measurements in adult olive leaves, after one, two and three weeks of soil herbicide treatment and/or OW amendment, were performed. Soil application of these herbicides reduced the efficiency of Photosystem II photochemistry of olive trees due to chronic photoinhibition, and this effect is counterbalanced by the addition of OW to the soil. OW reduces herbicide uptake by the plant due to an increase in herbicide adsorption.     

Exposure Times to the Spring Atrazine Flush Along a Stream-Reservoir System1

Stoeckel, James A., Jade Morris, Elizabeth Ames, David C. Glover, Michael J. Vanni, William Renwick, and María J. González, 2012. Exposure Times to the Spring Atrazine Flush Along a Stream-Reservoir System. Journal of the American Water Resources Association (JAWRA) 48(3): 616-634. DOI: 10.1111/j.1752-1688.2011.00633.x Abstract: We used enzyme-linked immunosorbent assay to examine reservoir-mediated shifts in spring to fall exposure of aquatic organisms to the spring atrazine pulse over four years in a Midwestern stream-reservoir system. Peak atrazine concentrations in the major inflowing stream exceeded 10 μg/l in all four years. The reservoir had a beneficial effect in two of four years by diluting atrazine below the 10 μg/l threshold. However, during the other two years, exposure times above 10 μg/l were approximately doubled in the reservoir compared to the major inflowing stream. Thresholds of 3 and 5 μg/l were exceeded during all four years in the reservoir. The uplake and downlake reservoir sites were four to five times more likely to exceed these thresholds and aquatic organisms were subjected to longer exposure times above these thresholds compared to the inflowing stream. Release of elevated atrazine concentrations from the reservoir extended exposure times in the outflowing stream. This effect was most pronounced just below the dam. Aquatic organisms upstream of the reservoir were most likely to experience acute exposures whereas organisms within and immediately downstream of the reservoir were more likely to experience chronic exposures. The ubiquity of reservoirs and the annual spring herbicide flush highlight the importance of considering the presence and relative location of reservoirs when assessing risk to aquatic communities as well as locations of drinking water intakes.     

盐析分相微萃取—高效液相色谱法测定水中含氯除草剂

采用盐析分相微萃取—高效液相色谱法同时测定水中3种含氯除草剂,建立并优化了反相离子对液相色谱条件,考察了萃取剂种类、盐析剂的种类和加入量及试样pH对萃取效果的影响。对氯苯氧乙酸、2,4-二氯苯氧乙酸和2,4-滴丁酯的质量浓度在0.1~100.0mg/L内与色谱峰面积呈良好的线性关系,相关系数不低于0.9992。平均回收率分别为96.29%、79.16%和70.21%,相对标准偏差小于5.3%。该方法操作简便、绿色环保,适合于水中含氯除草剂的测定。