Hydrolysis and soil sorption of insecticide pyraclofos

The hydrolysis of the insecticide pyraclofos in buffered solutions at pH 5.0, 7.0 and 9.0, and its sorption on four soils of different physicochemical properties were investigated. The results showed that the degradation of pyraclofos in buffered solutions followed pseudo-first-order kinetics. At 40 degrees C, the rate constants for the hydrolysis of pyraclofos at pH 5.0, 7.0 and 9.0 were 0.0214, 0.1293, and 2.1656 d(-1), respectively. Pyraclofos was relatively stable under both acidic and neutral conditions, while it was readily hydrolyzed under basic conditions. The sorption of pyraclofos on four soils was well described by the Freundlich equation. The sorption constant, K(f), increased with an increase in soil organic carbon content, suggesting that organic carbon content was an important factor affecting sorption. The K(oc) values for Xiaoshan clay loam soil, Hangzhou I clay loam soil, Hangzhou II soil, and Fuyang silt loam soil were 30.4, 6.7, 5.3, and 7.1, respectively. These results suggest that the sorption of pyraclofos on the tested soils was relatively weak.     

生物碳和土壤性质对乙草胺吸附行为的影响

生物碳施加到土壤中可能会影响污染物的环境归趋,而吸附作用是其关键控制因素,为此,本研究考察了400、500和600℃下制备的玉米秸秆生物碳(分别记作CS400、CS500和CS600)和土壤性质对乙草胺吸附行为的影响。结果表明,生物碳和土壤对乙草胺的吸附等温线符合Freundlich模型(R2≥0.99)。随着生物碳热解温度的升高(从CS400到CS600),生物碳吸附乙草胺的非线性指数n值减小且logKOC值增大,说明吸附非线性程度和吸附能力增强,这是因为生物碳炭化程度增强(H/C原子比减小),疏水性增强(O/C原子比减小)和比表面积增大而有利于对乙草胺的吸附,吸附机制以表面吸附为主(比如疏水作用、π-π EDA作用和孔填充作用)。然而,土壤吸附乙草胺的n值(0.95)接近1.0,说明该吸附作用几乎是线性吸附,以分配作用机制为主。3种生物碳对乙草胺的吸附能力都高于土壤,特别是CS600对乙草胺的吸附能力(logKOC)比土壤及文献报道的土壤和沉积物高一个数量及以上,说明生物碳可能会有效保留土壤中的乙草胺而降低其迁移性。     

The equilibria of bisolute sorption on soil

The goal of this study was to investigate the effects of both concentration levels and loading sequence or contamination history of each pollutant on the equilibrium sorption of mixed organic pollutants on soils. We measured binary sorption equilibria for a soil using ten concentration levels for both phenanthrene and naphthalene. Both solutes were either simultaneously loaded or sequentially loaded (i.e., the second sorbate was loaded after the sorption of the first sorbate had attained equilibrium) on soil. The results showed different competitive sorption equilibria between phenanthrene and naphthalene. In the presence of phenanthrene and regardless of loading sequence, naphthalene exhibited consistently lower sorption capacities and the ideal adsorbed solution theory (IAST) slightly underestimates the naphthalene sorption equilibria. Conversely, the sorption equilibria of phenanthrene in the presence of naphthalene depended upon the loading sequence of the two sorbates on the soil. Little competition from naphthalene on the sorption equilibria of phenanthrene was observed when phenanthrene was loaded either simultaneously with or sequentially after naphthalene, but appreciable competition from naphthalene was observed when the soil had been pre-contaminated with phenanthrene. IAST slightly underestimates the phenanthrene sorption equilibria observed in the latter system, but it cannot estimate the phenanthrene sorption equilibria in the former two systems. We proposed that adsorption on internal surfaces of ink-bottle shaped pores within relatively flexible sorbent matrix may have caused the competitive sorption phenomena observed in this study. The study suggests that contamination history may have strong influence on the equilibrium sorption of organic pollutant mixtures.     

LAS对土壤中多环芳烃吸附行为的影响

研究了阴离子表面活性剂十二烷基苯磺酸钠(LAS)对PAHs在土壤中吸附行为的影响.结果表明,LAS改变了PAHs在土水体系中的吸附/解吸平衡,吸附态LAS可提高土壤对PAHs的吸附,而溶解态LAS则增加了PAHs的表观溶解度,这2种作用的综合结果改变了PAHs在土水体系中的吸附系数.因此,文中用表观吸附系数来描述PAHs在土壤-水-LAS体系中的综合吸附行为.     

LAS对土壤中多环芳烃吸附行为的影响

研究了阴离子表面活性剂十二烷基苯磺酸钠（LAS）对PAHs在士壤中吸附行为的影响。结果表明，LAS改变了PAHs在土水体系中的吸附／解吸平衡，吸附态LAS可提高土壤对PAHs的吸附，而溶解态LAS则增加了PAHs的表观溶解度，这2种作用的综合结果改变了PAHs在土水体系中的吸附系数。凶此，文中用表观吸附系数来描述PAHs在土壤-水-LAS体系中的综合吸附行为。     

Phenylurea herbicide sorption to biochars and agricultural soil

Biochar is increasingly been used as a soil amendment to improve water-holding capacity, reduce nutrient leaching, increase soil pH, and also as a means to reduce contamination through sorption of heavy metals or organic pollutants. The sorption behavior of three phenylurea herbicides (monuron, diuron and linuron) on five biochars (Enhanced Biochar, Hog Waste, Turkey Litter, Walnut Shell and Wood Feedstock) and an agricultural soil (Yolo silt loam) was investigated using a batch equilibration method. Sorption isotherms of herbicides to biochars were well described by the Freundlich model (R² = 0.93–0.97). The adsorption K_F values ranged from 6.94 to 1306.95 mg kg^?1 and indicated the sorption of herbicides in the biochars and Yolo soil was in the sequence of linuron > diuron > monuron and walnut shell biochar > wood feedstock biochar > turkey litter biochar > enhanced biochar > hog waste biochar > Yolo soil. These data show that sorption of herbicides to biochar can have both positive (reduced off-site transport) and negative (reduced herbicide efficacy) implications and specific biochar properties, such as H/C ratio and surface area, should be considered together with soil type, agriculture chemical and climate condition in biochar application to agricultural soil to optimize the system for both agricultural and environmental benefits.     

Degradation and sorption of imidacloprid in dissimilar surface and subsurface soils

Degradation and sorption/desorption are important processes affecting the leaching of pesticides through soil. This research characterized the degradation and sorption of imidacloprid (1-[(6-chloro-3-pyridinyl)-methyl]-N-nitro-2-imidazolidinimine) in Drummer (silty clay loam) and Exeter (sandy loam) surface soils and their corresponding subsurface soils using sequential extraction methods over 400 days. By the end of the incubation, approximately 55% of imidacloprid applied at a rate of 1.0 mg kg^?1 degraded in the Exeter sandy loam surface and subsurface soils, compared to 40% of applied imidacloprid within 300 days in Drummer surface and subsurface soils. At the 0.1 mg kg^?1 application rate, dissipation was slower for all four soils. Water-extractable imidacloprid in Exeter surface soil decreased from 98% of applied at day 1 to > 70% of the imidacloprid remaining after 400 d, as compared to 55% in the Drummer surface soil at day 1 and 12% at day 400. These data suggest that imidacloprid was bioavailable to degrading soil microorganisms and sorption/desorption was not the limiting factor for biodegradation. In subsurface soils > 40% of ¹⁴C-benzoic acid was mineralized over 21 days, demonstrating an active microbial community. In contrast, cumulative ¹⁴CO₂ was less than 1.5% of applied ¹⁴C-imidacloprid in all soils over 400 d. Qualitative differences in the microbial communities appear to limit the degradation of imidacloprid in the subsurface soils.     

生物炭对土壤吸附邻苯二甲酸二乙酯的影响

选择花生壳为原材料,采用限氧升温法在450、700℃温度下分别热解2、4、6 h制备6种生物炭,在对其表面性质和元素组成进行分析的基础上,重点考察生物炭对土壤吸附邻苯二甲酸二乙酯（diethyl phthalate,DEP）的影响。结果表明：生物炭的比表面积和总孔体积随着热解温度的升高而增加,热解时间的延长也会提高比表面积和总孔体积,而4 h是较为适宜的热解时间;生物炭中元素组成主要受热解温度的影响,热解时间的作用很小,热解温度的升高使生物炭的芳香性增强,极性降低;添加生物炭能显著提高土壤对DEP的吸附能力;Langmuir模型和Freundlich模型均能较好地拟合添加生物炭土壤对DEP的吸附特征;在不同的平衡浓度条件下,生物炭对土壤吸附DEP的贡献率介于82.07%~99.49%之间,表明生物炭对土壤中DEP的吸附发挥着主导作用。相关分析发现,吸附参数ΔKoc与生物炭的比表面积和总孔体积具有显著相关性,提高比表面积和改善孔隙结构可以增强生物炭对DEP的吸附能力。     

pH和温度对2,2’,4,4’-四溴联苯醚在土壤中吸附和解吸行为的影响研究

研究了pH和温度对2,2’,4,4’-四溴联苯醚(BDE-47)在土壤中的吸附和解吸行为的影响。结果表明,pH和温度都可以影响BDE-47在受试土壤中的吸附和解吸行为。pH升高或降低均会使土壤对BDE-47的吸附能力提高,且在碱性环境中提高的程度更大;酸性或碱性条件下BDE-47在土壤中的解吸滞后性显著增强。温度降低后,土壤对BDE-47的吸附能力提高,5℃时的单点分配系数(Kd,表征土壤对BDE-47的吸附能力)是25℃时的1.03~1.67倍;温度由25℃降低到5℃后,BDE-47在土壤中的解吸滞后性增强。     

生物质炭添加量对BDE-47在土壤中吸附和解吸行为的影响

研究了添加生物质炭对2,2’,4,4’-四溴联苯醚(BDE-47)在土壤中吸附和解吸行为的影响。结果表明,在受试天然土壤中添加不同量的生物质炭,土壤对BDE-47吸附能力的变化程度也将不同,当生物质炭添加量为2.0%(质量分数,下同)以下时,随着生物质炭添加量的增加,土壤对BDE-47吸附能力的提高程度越明显,BDE-47的解吸滞后性则呈现先上升后下降的趋势。当生物质炭添加量为0.1%、0.5%时,土壤单点分配系数分别为原土壤的0.98~1.39、1.02~1.50倍;当生物质炭添加量为1.0%、2.0%时,土壤单点分配系数分别为原土壤的1.44~1.68、3.25~3.27倍;生物质炭添加量为1.0%时,BDE-47的解吸滞后性最显著。     

Modelling the biphasic sorption of simazine,imidacloprid, and boscalid in water/soil systems

The sorption kinetics of simazine (6-chloro-N,N′-diethyl-1,3,5-triazine-2,4-diamine), imidacloprid (1-(6-chloro-3-pyridylmethyl)-N-nitroimidazolidin-2-ylideneamine), and boscalid (2-chloro-N-(4′-chlorobiphenyl-2-yl)nicotinamide), three pesticides of wide use in agriculture, was determined in five different water/soil systems over a time interval from the initial few seconds to about 1 month. In all the experiments, sorption kinetics showed a biphasic pattern characterized by an initial, relatively short phase with a high sorption rate and a later phase with much a lower sorption rate. Initial sorption capacity increased with soil organic carbon content and with sorbate hydrophobicity. We postulate that the first phase of the process involves a fast second-order sorption reaction on superficial sites of soil particles, whereas the second phase depends on diffusion-controlled migration to internal binding sites. A kinetic equation based on this hybrid model accurately fitted all data sets. Less satisfactory results were obtained employing the pseudo-first order, pseudo-second order, Elovich, two site non-equilibrium, or Weber-Morris equation. The superior performance of the hybrid model for describing boscalid sorption probably reflects the high hydrophobic character and consequent low diffusion rates of this compound. The accuracy of modelling was in any case strongly dependent on the time interval considered.     

Dissipation and sorption of six commonly used pesticides in two contrasting soils of New Zealand

We investigated dissipation and sorption of atrazine, terbuthylazine, bromacil, diazinon, hexazinone and procymidone in two contrasting New Zealand soils (0–10 cm and 40–50 cm) under controlled laboratory conditions. The six pesticides showed marked differences in their degradation rates in both top- and subsoils, and the estimated DT₅₀ values for the compounds were: 19–120 (atrazine), 10–36 (terbuthylazine), 12–46 (bromacil), 7–25 (diazinon), 8–92 (hexazinone) and 13–60 days for procymidone. Diazinon had the lowest range for DT₅₀ values, while bromacil and hexazinone gave the highest DT₅₀ values under any given condition on any soil type. Batch derived effective distribution coefficient (K _d ^eff) values for the pesticides varied markedly with bromacil and hexazinone exhibiting low sorption affinity for the soils at either depth, while diazinon gave high sorption values. Comparison of pesticide degradation in sterile and non-sterile soils suggests that microbial degradation was the major dissipation pathway for all six compounds, although little influence of abiotic degradation was noticeable for diazinon and procymidone.     

复合纳米材料对土壤重金属离子吸持固化的模拟研究

土壤中过量重金属离子可通过食物链和地表水系统危害人群健康。通过土柱淋溶模拟实验,研究了SiO2-Al2O3-Fe2O3等复合纳米材料对土壤溶液中Cu2+、Cd2+、Pb2+、Zn2+和Ni2+的吸持与固化特征。分别向重金属含量4倍于土壤二级标准(GB15618-1995)的土壤中添加0%、4%、6%和10%的复合纳米材料,分析不同深度土壤渗滤液以及土柱上栽培植物不同部位中重金属的含量。结果表明,碱性壤质土壤中重金属向下的迁移量很少;在含4%复合纳米材料土柱中,其吸持固化土壤溶液中63%的Cu、79%的Cd、68%的Pb、89%的Zn和76%的Ni;在含6%复合纳米材料土柱中,其吸持固化土壤溶液中82%的Cu、92%的Cd、76%的Pb、91%的Zn和88%的Ni;再增加土柱中复合纳米材料的含量,其吸持固化效果并不再显著增加。     

Influence of sugar cane vinasse on the sorption and degradation of herbicides in soil under controlled conditions

This study reports the influence of sugar cane vinasse on the persistence, sorption and leaching potential of diuron (3-(3,4-dichlorophenyl)-1,1-dimethylurea), hexazinone (3-cyclohexyl-6-(dimethylamino)-1-methyl-1,3,5-triazine-2,4-dione) and tebuthiuron (1-(5-tert-butyl-1,3,4-thiadiazol-2-yl)-1,3-dimethylurea) in both a clay and sandy soil from a tropical area of Brazil. The experiments were conducted out under controlled laboratory conditions. The addition of sugarcane vinasse to soil influenced the persistence and sorption of the herbicides in both the studied clay and sandy soils, with a considerable decrease in the diuron DT₅₀ values in clay soil. The Ground Water Ubiquity Score (GUS) Index classifies the herbicides as leachers in both soils and treatments, with the exception of diuron, which is classified as a non-leacher in clay soil-vinasse and as a transient herbicide in sandy soil. These results suggest that special attention should be given to areas such as those where the sandy soil was collected in this study, which is a recharge area of the Guarani Aquifer and is likely to experience groundwater contamination due to the high leaching potential of the applied pesticides.     

Comparative assessment of metribuzin sorption efficiency of biochar,hydrochar and vermicompost

Abstract

In this study, we used two biochars (BC) produced from grapevine pruning residues (BCgv) and red spruce wood (BCrs), two hydrochars (HC) from urban pruning residues (HCup) and the organic fraction of municipal solid wastes (HCuw), and two vermicomposts (VC) obtained vermicomposting digestates from buffalo manure (VCbm) and mixed feedstock (VCmf). Adsorption kinetics and isotherms of metribuzin onto these materials were performed. Sorption kinetics followed preferentially a pseudo-second-order model, thus indicating the occurrence of chemical interactions between the sorbate and the adsorbents. Adsorption constants were calculated using the Freundlich and Langmuir models. Metribuzin sorption data on BCgv and both HC fitted preferentially the Freundlich equation, whereas on the other materials data fitted both isotherms well (r?>?0.95). Metribuzin sorption capacity of the materials followed the trend BC?>?HC?>?VC. Sorption constants of metribuzin normalised per organic carbon content (K_OC) on BCgv, BCrs, HCup, HCuw, VCbm and VCmf were 561, 383, 251, 214, 102 and 84?L kg^?1, respectively. A significant positive correlation (P?=?0.016) was calculated between distribution coefficients (K_d) of all materials and the corresponding organic carbon contents, thus indicating a prominent role of the organic fraction of these materials in the adsorption of metribuzin.     

Priorities for forestry insecticide application technology research

Abstract

A survey was conducted to determine research priorities for forest insecticide application technology research. The target audience was persons with an interest in the topic (users, applicators, researchers, regulators). One quarter of the forestry users of insecticides felt that ground application technology research should have higher priority whereas three quarters felt that aerial application technology research should have higher priority. Five problems which ranked high for most respondent groups, were: 1) Increase the residual efficacy of Bt and viruses; 2) Determine how to develop public support for aerial application of insecticides in forestry; 3) Determine appropriate, scientifically‐based buffer zone widths required to prevent significant environmental impact in sensitive areas; 4) Develop techniques for rapid and accurate determination of Bt and virus tank mix potency; 5) Develop a practical deposit assessment technique for operational Bt and virus applications.     

Maize,switchgrass, and ponderosa pine biochar added to soil increased herbicide sorption and decreased herbicide efficacy

Biochar, a by-product of pyrolysis made from a wide array of plant biomass when producing biofuels, is a proposed soil amendment to improve soil health. This study measured herbicide sorption and efficacy when soils were treated with low (1% w/w) or high (10% w/w) amounts of biochar manufactured from different feedstocks [maize (Zea mays) stover, switchgrass (Panicum vigatum), and ponderosa pine (Pinus ponderosa)], and treated with different post-processing techniques. Twenty-four hour batch equilibration measured sorption of ¹⁴C-labelled atrazine or 2,4-D to two soil types with and without biochar amendments. Herbicide efficacy was measured with and without biochar using speed of seed germination tests of sensitive species. Biochar amended soils sorbed more herbicide than untreated soils, with major differences due to biochar application rate but minor differences due to biochar type or post-process handling technique. Biochar presence increased the speed of seed germination compared with herbicide alone addition. These data indicate that biochar addition to soil can increase herbicide sorption and reduce efficacy. Evaluation for site-specific biochar applications may be warranted to obtain maximal benefits without compromising other agronomic practices.     

Time dependent sorption behavior of dinotefuran,imidacloprid and thiamethoxam

Dinetofuran (DNT), imidacloprid (IMD) and thiamethoxam (THM) are among the neonicotinoid insecticides widely used for managing insect pests of agricultural and veterinary importance. Environmental occurrence of neonicotinoid in post-application scenario poses unknown issues to human health and ecology. A sorption kinetic study provides much needed information on physico-chemical interaction of neonicotinoid with soil material. In this research study, time-dependent sorption behavior of DNT, IMD and THM in vineyard soil was studied. Sorption kinetics studies were conducted over a period of 96 hours with sampling duration varying from 0, 2, 4, 8, 12, 24, 60 and 96 hours. All three neonicotinoids exhibited very low sorption potential for the soil investigated. Overall percent sorption for all three neonicotinoids was below 20.04 ± 2.03% with highest percent sorption being observed for IMD followed by DNT and THM. All three neonicotinoids are highly soluble with solubility increasing with IMD < THM < DNT. Although, DNT has the highest solubility among all three neonicotinoids investigated, it exhibited higher percent sorption compared to THM, indicating factors other than solubility influenced the sorption kinetics. Low sorption potential of neonicotinoids indicates greater leaching potential with regard to groundwater and surface water contamination.     

Observations on the influence of water and soil pH on the persistence of insecticides

Abstract

The pH‐disappearance rate profiles were determined at ca. 25°C for 24 insecticides at 4 or 5 pH values over the range 4.5 to 8.0 in sterile phosphate buffers prepared in water‐ethanol (99: 1 v/v). Half‐lives measured at pH 8 were generally smaller than at lower pH values. Changes in half lives between pH 8.0 and 4.5 were largest (>1000x) for the aryl carbamates, carbofuran and carbaryl, the oxime carbamate, oxamyl, and the organophosphorus insecticide, trichlorfon. In contrast, half lives of phorate, terbufos, heptachlor, fensulfothion and aldicarb were affected only slightly by pH changes. Under the experimental conditions described half lives at pH8 varied from 1–2 days for trichlorfon and oxamyl to >1 year for fensulfothion and cyper‐methrin. Insecticide persistence on alumina (acid, neutral and basic), mineral soils amended with aluminum sulfate or calcium hydroxide to different pH values and four natural soils of different pH was examined. No correlation was observed between the measured pH of these solids and the rate of disappearance of selected insecticides applied to them. These observations demonstrate the difficulty of extrapolating the pH dependent disappearance behaviour observed in homogeneous solution to partially solid heterogeneous systems such as soil.