Determination of glyphosate residue in maize and rice using a fast and easy method involving liquid chromatography–mass spectrometry (LC/MS/MS)

A fast and easy method was developed for the determination of glyphosate in maize and rice by using liquid chromatography triple quadrupole mass spectrometry with a Dionex Ion Pack column and phosphate buffer mobile phase. Samples were extracted with an acidified methanol solution. An isotope-labeled internal standard was added to the sample before extraction to ensure accurate tracking and quantification. The method’s performance was evaluated through a series of assessments to determine the accuracy, precision, linearity, matrix effect, limit of detection (LOD), and limit of quantification (LOQ). The mean recoveries for both matrices were within 70–105% at three fortification levels, including the LOQ. The precision for replicates was <20% (RSD%) for both matrices. Good linearity (R²=0.9982) was obtained over the concentration range of 0.01–1.5?mg kg^?1. The LOD was determined to be 0.002?mg kg^?1 for rice and 0.004?mg kg^?1 for maize. The LOQ was 0.01?mg kg^?1 for both maize and rice. Due to its versatility, the proposed method could be considered useful for the determination of glyphosate in cereals in routine analysis.     

Rice and wheat straw ashes: Characterization and modeling of pretilachlor sorption kinetics and adsorption isotherm

The rice straw ash (RSA) and wheat straw ash (WSA) were explored as low cost adsorbent for pretilachlor removal from water. The ashes were characterized and sorption behavior of pretilachlor was evaluated. Kinetics study suggested that the modified Elovich model best explained the pretilachlor sorption on both the ashes. The adsorption data were analyzed using 2-, 3- and 4-parameter models and nine error functions were used to compute the best fit isotherm by nonlinear regression analysis. The pretilachlor was more sorbed onto the RSA (22.0–92.2%) than the WSA (11.4–61.4%) and percent adsorption decreased with increase in the herbicide concentration in solution. Isotherm model optimization analysis suggested that the Freundlich and the Temkin isotherms were the best models to predict the pretilachlor adsorption onto the RSA and the WSA. The error analysis suggested that the reciprocal of the observed squared (ROS) and the reciprocal of the predicted squared (RPS) error functions provided the best determination of the adsorption constants for the Freundlich and the Temkin isotherms, respectively. The RSA, which exhibited higher pretilachlor sorption potential, can be utilized as low cost adsorbent for pesticide removal from contaminated water.     

Vegetative Buffer Strips for Reducing Herbicide Transport in Runoff: Effects of Buffer Width,Vegetation, and Season

The effectiveness of vegetative buffer strips (VBS) for reducing herbicide transport has not been well documented for runoff prone soils. A multi‐year plot‐scale study was conducted on an eroded claypan soil with the following objectives: (1) assess the effects of buffer width, vegetation, and season on runoff transport of atrazine (ATR), metolachlor (MET), and glyphosate; (2) develop VBS design criteria for herbicides; and (3) compare differences in soil quality among vegetation treatments. Rainfall simulation was used to create uniform antecedent soil water content and to generate runoff. Vegetation treatment and buffer width impacted herbicide loads much more than season. Grass treatments reduced herbicide loads by 19‐28% and sediment loads by 67% compared to the control. Grass treatments increased retention of dissolved‐phase herbicides by both infiltration and adsorption, but adsorption accounted for the greatest proportion of retained herbicide load. This latter finding indicated VBS can be effective on poorly drained soils or when the source to buffer area ratio is high. Grass treatments modestly improved surface soil quality 8‐13 years after establishment, with significant increases in organic C, total N, and ATR and MET sorption compared to continuously tilled control. Herbicide loads as a function of buffer width were well described by first‐order decay models which indicated VBS can provide significant load reductions under anticipated field conditions.     

除草剂异丙莠诱发蚕豆根尖细胞遗传损伤的研究

以蚕豆根尖为材料,研究除草剂异丙莠对蚕豆根尖细胞的遗传毒性效应。采用蚕豆根尖微核技术,以不同浓度的异丙莠为诱变剂,测定蚕豆根尖细胞的有丝分裂指数、微核率和染色体畸变率。结果表明,异丙莠能诱发较高频率的微核率,即在一定浓度范围内,其微核率随异丙莠处理浓度的升高而增加,但随着异丙莠浓度进一步升高而呈下降趋势;异丙莠能降低蚕豆根尖细胞有丝分裂指数并诱导染色体产生多种类型的畸变。一定剂量的除草剂异丙莠对蚕豆根尖细胞具有明显的遗传毒性。     

Histochemical and histopathological study of the intestine of the earthworm (Pheretima elongata) exposed to a field dose of the herbicide glyphosate

Histopathological and histochemical variations in non-specific esterases of the intestinal epithelial lining of the earthworm (Pheretima elongata), exposed to a single field dose of the herbicide glyphosate, were studied on the first, second, third, and fourth week of exposure. A severe cell death was observed in the intestine during the first and second weeks of exposure and mortality exceeded 50 percent. In the third week of exposure, the cells of the intestinal lining of the worms which had survived started regenerating and in the fourth week of exposure the epithelial lining regained its original characteristics and architecture, suggesting the high regenerative power of earthworms. Non-specific esterases showed an intense activity in the first week of the exposure and then decreased in the second week to nearly a minimum, where the entire cell structure was lost. However, the activity of the enzyme remained low until the third week where there was a small rise in the activity, and was confined to certain places in the cytoplasm. In the fourth week, almost a complete regeneration of the epithelial lining as well as the non-specific esterases activity was observed and became quite similar to that of the control worms. These results suggest that glyphosate, even at the recommended field dose, could cause cell death and interfere with non-specific esterases activity of the epithelial lining of the intestine of P. elongata causing at least 50 percent mortality in the population of the worms.     

除草剂2，4-D在土壤中吸附常数的测定

介绍除草剂２,４－Ｄ在４种不同有机碳含量、不同ｐＨ值的土壤中吸附常数的测定．结果表明,４种土壤对２,４－Ｄ的吸附等温线均符合非线形的Ｆｒｅｕｎｄｌｉｃｈ吸附等温式,其有机碳吸附常数的平均值为２３９．６．２,４－Ｄ的吸附常数与土壤有机碳含量呈正相关,土壤的ｐＨ值对２,４－Ｄ的吸附也有一定的影响．     

Fate of metolachlor under subirrigation in a sandy soil: A lysimeter study

Abstract

A three‐year field lysimeter study was conducted to investigate the role of subirrigation systems in reducing the risk of water pollution from metolachlor (2‐chloro‐N‐(2‐ethyl‐6‐methlphenyl)‐N‐(2‐methoxy‐l‐methylethyl)acetamide). Nine large PVC lysimeters, 1 m long x 0.45 m diameter, were packed with a sandy soil. Three water table management treatments, i.e. two subirrigation treatments with constant water table depths of 0.4 and 0.8 m, respectively, and a free drainage treatment in a completely randomized design with three replicates were used. Corn (Zea mays L.) was grown in each lysimeter, and at the beginning of summer of each year metolachlor was applied, at the locally recommended rate of 2.75 kg a.i./ha. Soil and water samples were collected at different time intervals after each natural or simulated rainfall event. Metolachlor was extracted from these samples and analyzed using Gas Chromatography.

Results obtained in this three year study, (1993–1995), lead to the conclusion that metolachlor is quite mobile since it leached to a depth of 0.85 m below the soil surface quite early in the growing season. Metolachlor concentrations decreased with depth as well as with time. The shallower water table in the 0.4 m subirrigation treatment showed less residues in the soil solution than that of other treatments. However, a mass balance study, supported by an independent laboratory investigation, shows that water table management, statistically, has no significant effect on the reduction of metolachlor residues in sandy soils.     

Laboratory study on leachability of five herbicides in South Australian soils

Abstract

Norflurazon, oxadiazon, oxyfluorfen, trifluralin and simazine are herbicides widely used in the vineyards of the Barossa Valley, South Australia. The leaching behaviour of norflurazon, oxadiazon, oxyfluorfen and trifluralin was investigated on four key soils in the Barossa Valley. Leaching potential on packed soil columns and actual mobility using intact soil columns were investigated. On the packed soil columns, norflurazon was the most leachable herbicide. More of the herbicides were detected in the leachates from the sandy soils (Mountadam and Nuriootpa) than from the clayey soils (Lyndoch and Tanunda). Organic matter is generally low in soils in the Barossa region. Porosity and saturated conductivity significantly affect herbicide movement and in the sandy Mountadam and Nuriootpa soils, the water flux is greater than for the higher clay content Lyndoch and Tanunda soils. Increasing the time interval between herbicide application and the incidence of “rainfall”; reduced the amounts of herbicides found in the leachates. The use of intact soil columns and including simazine for comparison showed that both norflurazon and simazine were present in the leachates. Simazine was the first herbicide to appear in leachates. Sectioning of the intact soil columns after leaching clearly demonstrated that norflurazon and simazine reached the bottom of the soil columns for all soils studied. Greater amounts of norflurazon were retained in the soil columns compared with simazine. The other herbicides were mostly retained in the initial sections of the soil columns.     

Fenuron sorption on homoionic natural and modified smectites

Abstract

The adsorption isotherms of fenuron (l, l‐dimethyl‐3‐phenylurea) on three smectites (SWy and SAz montmorillonites and SH hectorite) differing in their layer charge (SH<SWy<SAz) and saturated with several inorganic and organic cations were determined. The isotherms and sorption parameters from Freundlich equation indicate low adsorptivity on inorganic clays, but medium sorption in organoclays (OCls). Fenuron adsorption on homoionic smectites increases with decreasing layer charge and hydratation power of the inorganic exchangeable cation (except Fe³⁺), indicating that fenuron adsorbs as neutral molecule on uncharged siloxane surface by hydrophobic bonding, with some contribution of polar bond (fenuron C=O group and water associated to exchangeable cation). In the case of Fe³⁺‐saturated smectite fenuron protonation, provided by the interlayer acidic environment, promotes further sorption of fenuron as cationic form. The sorption on organoclays is enhanced via hydrophobic interaction with organocations, which is favoured for high layer charge and basal spacing and organocation saturation close to CEC. Quaternary alkylamonium is more efficient in high layer charge smectite, whereas primary alkylammonium is more efficient in medium charge smectite. The low values of the maximum sorption obtained with homoionic inorganic and organic smectites (100 and 5000 μmol/Kg) represent one fenuron molecule for each 2000–200 exchange sites and indicate that fenuron sorption is mainly associated to the outer exchange sites. This low adsorptivity of fenuron, as consequence of its high water affinity (high water solubility) would suggest high mobility of fenuron in natural soil and water systems.     

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.