Modelling the dissipation kinetics of six commonly used pesticides in two contrasting soils of New Zealand

We used three non-linear bi-phasic models, bi-exponential (BEXP), first-order double exponential decay (FODED), and first-order two-compartment (FOTC), to fit the measured degradation data for six commonly used pesticides (atrazine, terbuthylazine, bromacil, diazinon, hexazinone and procymidone) in two New Zealand soils. Corresponding DT₅₀ and DT₉₀ values for each compound were numerically obtained and compared against those estimated by simple first-order kinetic (SFOK) model. All 3 non-linear models gave good fit of the measured data under both soil depths and were well supported by the values obtained for the respective statistical indices (RMSE, CRM and r ²). The FOTC model gave by far the best fit for most compounds, followed by the FODED and BEXP models. Overall, DT₅₀ values derived by non-linear models for the six compounds in soils from both sites were lower than the values obtained by the SFOK model. Differences in the SFOK and the three non-linear models derived DT₉₀were, however, an order of magnitude higher for some compounds, while for others differences were very small. Although all three non-linear models described most data by giving excellent fits, in a few instances > 5–10% asymptotes hindered the estimation of DT₉₀ values. This work shows that when degradation deviates from first-order kinetic, application of non-linear decay models to describe the kinetics of degradation becomes important in order to derive the true end-points for pesticides in soil.     

Kinetics and mechanism of the hydrolysis of thiamethoxam

The degradation of thiamethoxam [(EZ)-3-(2-chloro-1,3-thiazol-5-yl-methyl)-5-methyl-1,3,5-oxadiazinan-4-ylidene (nitro) amine] insecticide in buffers at different pH and temperature levels was investigated in laboratory studies. Acidic hydrolysis under conventional heating conditions and alkaline hydrolysis under both conventional heating and microwave conditions were carried out. Different hydrolysis products were found to form under alkaline and acidic conditions. Hydrolysis of thiamethoxam in acidic, neutral and alkaline buffers followed first-order reaction rate kinetics at pH 4, 7 and 9.2, respectively. Thiamethoxam readily hydrolyzed in alkaline buffer but was comparatively stable in neutral buffer solution. The main products formed under different conditions were characterized on the basis of infrared (IR), ¹H-NMR and Mass spectroscopy. The possible mechanisms for the formation of these hydrolysis products have also been proposed.     

Sorption and degradation of neonicotinoid insecticides in tropical soils

ABSTRACT

Neonicotinoids are the most widely applied class of insecticides in cocoa farming in Ghana. Despite the intensive application of these insecticides, knowledge of their fate in the Ghanaian and sub-Saharan African environment remains low. This study examined the behavior of neonicotinoids in soils from cocoa plantations in Ghana by estimating their sorption and degradation using established kinetic models and isotherms. Studies of sorption were conducted using the batch equilibrium method on imidacloprid, thiamethoxam, clothianidin, acetamiprid and thiacloprid, while degradation of imidacloprid, thiamethoxam and their respective deuterated counterparts was studied using models proposed by the European forum for coordination of pesticide fate and their use (FOCUS). Analytes were extracted using the quick, easy, cheap, effective, rugged and safe (QuEChERS) procedure and quantified by liquid chromatography-tandem mass spectrometry (LC–MS/MS). Average recoveries were high (≥ 85%) for all analytes. The findings from the study suggest that neonicotinoid insecticides may be persistent in the soils studied based on estimated half-lives > 150 days. The study also revealed generally low-sorption coefficients for neonicotinoids in soils, largely influenced by soil organic carbon.     

Degradation of alachlor using an enhanced sono-Fenton process with efficient Fenton's reagent dosages

In this study, an enhanced sono-Fenton process for the degradation of alachlor is presented. At high ultrasonic power, low pH, and in the presence of adequate Fenton's reagent dosages, alachlor degradation can reach nearly 100%. The toxicity of treated alachlor wastewater, which was measured by changes in cell viability, slightly decreased after the Fenton or ultrasound/H₂O₂ process and significantly decreased after the enhanced sono-Fenton process. A satisfactory relationship was observed between the total organic carbon removal and cell viability increment, indicating that alachlor mineralization is a key step in reducing the toxicity of the solution. The formation of alachlor degradation byproducts was observed during the oxidation process, in which the first step was the substitution of a chloride by a hydroxyl group. In conclusion, the enhanced sono-Fenton process was effective in the degradation and detoxification of alachlor within a short reaction time. Thus, the treated wastewater can then be passed through a biological treatment unit for further treatment.     

Kresoxim methyl dissipation kinetics and its residue effect on soil extra-cellular and intra-cellular enzymatic activity in four different soils of India

The rate of degradation of kresoxim methyl and its effect on soil extra-cellular (acid phosphatase, alkaline phosphatase and β-glucosidase) and intra-cellular (dehydrogenase) enzymes were explored in four different soils of India. In all the tested soils, the degradation rate was faster at the beginning, which slowed down with time indicating a non-linear pattern of degradation. Rate of degradation in black soil was fastest followed by saline, brown and red soils, respectively and followed 1st or 1st + 1st order kinetics with half-life ranging between 1–6 days for natural soil and 1–19 days for sterile soils. The rate of degradation in natural against sterilized soils suggests that microbial degradation might be the major pathway of residue dissipation. Although small changes in enzyme activities were observed, kresoxim methyl did not have any significant deleterious effect on the enzymatic activity of the various test soils in long run. Simple correlation studies between degradation percentage and individual enzyme activities did not establish any significant relationships. The pattern and change of enzyme activity was primarily due to the effect of the incubation period rather than the effect of kresoxim methyl itself.     

低温喹啉降解菌的筛选及降解性能

从吉林石化污水处理厂的活性污泥中驯化、筛选获得一株降解效率高且生长速率快高效耐冷菌,命名为WS-5.该菌能以喹啉作为惟一的碳源、氮源及能源.结合菌体的形态观察、生理生化特性实验及16S rDNA序列同源性对比分析,鉴定菌株WS-5为恶臭假单胞菌(Pseudomonas putida).不同降解条件下的实验结果表明,菌株WS-5的最佳降解条件是投菌量为15％,pH值范围在8～10,摇床转速为100 r/min.最佳降解环境下对200 mg/L的喹啉在132 h降解率达到了85.3％.菌株WS-5对初始喹啉浓度为50、100、200和300 mg/L的初始喹啉浓度分别在36、72、192和262 h内完全降解.这将为今后在低温条件下处理含喹啉废水提供技术指导.     

响应面法优化克浅十油田废水的混凝沉淀工艺

以克浅十污水处理站原水为研究对象,采用混凝沉淀工艺,探讨优选出的复配混凝剂投加量、助凝剂投加量及静置时间对原水中浊度和总铁去除效果的影响.应用Box-Behnken中心组合实验和响应面分析法,建立混凝剂对处理原水的二次多项式数学模型,确定了混凝沉淀去除原水浊度和总铁的优化工艺参数分别为:复配混凝剂投加量为152.15 mg/L、143.84 mg/L,助凝剂投加量为4.14 mg/L、4.32 mg/L,静置时间为11.77 min、11.22 min.在此工艺条件下回归方程得到的浊度和总铁的去除率预测值与实验值接近,且拟合性良好,误差介于3％～5％之间.通过均值内插法,对比浊度和总铁的多元二次回归方程,推导得出的2组最佳工艺条件均能满足浊度和总铁的去除要求.     

碘掺杂TiO2可见光光催化性能研究

在低于100℃温度条件下,采用溶胶-凝胶法以钛酸正丁酯为钛源,碘酸钾为碘源,制备了I掺杂纳米TiO2催化剂(I-TiO2),运用X-射线衍射(XRD)、透射电镜(TEM)及X-射线光电子能谱(XPS)等对催化剂进行表征,结果表明,TiO2及I-TiO2催化剂均为锐钛矿,I吸附并包裹在TiO2表面或以间隙进入的形式存在,并未进入TiO2晶格。通过在可见光照射下(λ>420 nm)以罗丹明B(Rhodamine B,RhB)的光催化降解为探针反应研究了在不同条件下制备催化剂的催化性能,结果表明,掺杂比为nI:nTi=0.05∶1,焙烧温度为400℃,降解介质条件pH=7时,I-TiO2光催化活性明显优于未掺杂的TiO2。光催化降解过程通过红外光谱(IR),总有机碳(TOC)跟踪测定,比较了TiO2掺杂前后降解RhB和对氯苯酚(4-CP)的光催化特性差异;同时采用苯甲酸荧光光度法跟踪测定体系中的氧化物种,表明在可见光下,I-TiO2光催化体系中产生.OH高活性氧化物种从而氧化降解目标化合物。     

降解菌ZQ5与紫茉莉对芘污染土壤的联合修复

在温室盆栽条件下,通过单独种植紫茉莉、单独接种多环芳烃(PAHs)模式化合物芘的专性降解菌ZQ5和两者的联合修复的3种处理,对芘污染土壤的修复效果进行了研究。结果表明,经90 d修复后,植物-微生物联合修复可将人工污染土壤中的芘降解81.1%,将石油污染土壤中的芘降解50.3%,其修复效率明显高于其他2种处理,是紫茉莉修复的1.98倍,是降解菌ZQ5修复的1.39倍。ZQ5的不同接菌量对于修复60 d后的降解率影响不大。外源生物修复条件下,10～20 cm土壤的修复效率要高于5 cm土壤;自然降解条件下,5 cm土层降解率略高于其他土层。     

四环素高效降解酵母菌Trichosporon mycotoxinivoransXPY-10降解特性

Trichosporon mycotoxinivorans XPY-10是一株分离自抗生素制药厂的高效四环素降解酵母菌。为了建立该菌株降解四环素的适宜条件,分别研究了碳源、有机氮源、金属离子等营养物质及初始底物浓度、接种量、pH、温度、装液量、摇床转速等理化因素对菌体生长及四环素降解效率的影响。结果表明,菌株XPY-10生长的最适碳源和氮源分别为蔗糖和蛋白胨。在含有0.05% FeSO₄的培养基中,菌株XPY-10降解四环素的适宜条件为：接种量2%,pH 8,温度34℃,装液量100 mL（250 mL 三角瓶）,摇床转速180 r/min。在此条件下,菌株XPY-10在7 d内对初始浓度为600 mg/L的四环素降解率为83.63%。本菌株对养殖废水及制药废水中四环素的污染治理有一定的应用前景。