Herbicide sorption to concrete and asphalt

In order to accurately predict the fate and behaviour of herbicides following application to hard surfaces, an understanding of the processes involved is required. Previous studies have demonstrated that herbicides with a low soil organic carbon partition coefficient (K(oc)) are preferentially removed from concrete and asphalt surfaces. It is possible, therefore, that sorption may play a role in retaining herbicides to hard surfaces. This study provides an indication of the extent to which herbicides may sorb to concrete and asphalt, and examines the results in the light of other research to identify the significance of sorption in describing herbicide losses after application. There was measurable sorption of herbicides to concrete and asphalt although this was limited compared with that to soils, especially for concrete. An exponential relationship between experimentally derived values of K(p) and literature values of K(oc) for asphalt was established (r(2) = 0.931); there was a weaker relationship for concrete (r(2) = 0.606). The experimentally derived K(p) values could be used to enhance the prediction of herbicide loss to receiving waters following application. It is probable that the fate of herbicides applied to concrete and asphalt surfaces depends more heavily on physical processes than is the case in soils.     

Effect of phosphine dose on sorption in wheat

BACKGROUND: In spite of the extensive use of phosphine fumigation around the world to control insects in stored grain, and the knowledge that grain sorbs phosphine, the effect of concentration on sorption has not been quantified. A laboratory study was undertaken, therefore, to investigate the effect of phosphine dose on sorption in wheat. Wheat was added to glass flasks to achieve filling ratios of 0.25-0.95, and the flasks were sealed and injected with phosphine at 0.1-1.5 mg L(-1) based on flask volume. Phosphine concentration was monitored for 8 days at 25 degrees C and 55% RH. RESULTS: When sorption occurred, phosphine concentration declined with time and was approximately first order, i.e. the data fitted an exponential decay equation. Percentage sorption per day was directly proportional to filling ratio, and was negatively correlated with dose for any given filling ratio. Based on the results, a tenfold increase in dose would result in a halving of the sorption constant and the percentage daily loss. Wheat was less sorptive if it was fumigated for a second time. CONCLUSIONS: The results have implications for the use of phosphine for control of insects in stored wheat. This study shows that dose is a factor that must be considered when trying to understand the impact of sorption on phosphine concentration, and that there appears to be a limit to the capacity of wheat to sorb phosphine.     

Acetochlor sorption and degradation in limestone subsurface and aquifers

BACKGROUND: Acetochlor, introduced on the market in 1994, is used extensively worldwide, but sorption and degradation studies, including subsurface, are scarce, and there appear to be no such studies with aquifer sediment according to the present mini‐review. Sorption, degradation and mineralisation of acetochlor were investigated in heterogeneous limestone down to 43 m below surface (mbs) in four European aquifers (1.7–59 mbs), both aerobic and anaerobic. RESULTS: Sorption revealed K_d values of 3.39–4.96 L kg^?1 in topsoil, < 0.01–2.02 L kg^?1 in heterogeneous limestone, 0.06–0.72 L kg^?1 in aerobic aquifers and 1.03–4.60 L kg^?1 in microaerobic or anaerobic aquifers. The mineralisation half‐lives in the samples from 0.0–0.6 mbs were 0.8–2.1 years and 4.7–95 years in the unsaturated limestone samples from 1–43 mbs. Out of 22 samples from four different European aquifers, acetochlor was mineralised in five samples (half‐lives of 9–19 years), all from the same aquifer and core section (19.25–19.53 mbs). CONCLUSION: Sorption was weak in limestone and aerobic sandy aquifers, and strong in topsoils and in reduced sandy aquifers. Redox conditions controlled the extent of acetochlor sorption in aquifers, as reduced conditions induced increased sorption. Acetochlor was mineralised in deep subsurface, though slowly, and, as mineralisation is the only true removal mechanism in natural attenuation, even slow mineralisation in aquifers with long residence times can have a significant impact. Copyright © 2010 Society of Chemical Industry     

Time effect on bentazone sorption and degradation in soil

Previous sorption/desorption batch experiments have indicated that bentazone is weakly sorbed by soils. In addition, field experiments have shown that 4% of the bentazone sprayed can be leached to drainage water. In order to complete bentazone characterisation, we have assessed the effect of time on its behaviour in contrasting soils. In laboratory studies, bentazone was added to three topsoils (sandy, loamy and clay soils). Bentazone degradation, sorption/desorption kinetics and isotherm measurements were carried out at different times. At 160 days after treatment, bentazone mineralisation amounts varied from 2.1% (sandy soil) to 14% (clay soil). The extractable amounts became lower (from 97% after treatment to 12% after 160 days for the clay soil) and a greater number of desorption series was needed to obtain these products. Nevertheless, at the end of the experiments, a small amount of bentazone was still extracted by water. At the same time, bound residues of bentazone reached 65% in clay soil. Statistical analysis indicated effects of both residence time and soil type on bentazone behaviour.     

Enhanced soil sorption of methidathion using sewage sludge and surfactants

Batch experiments were carried out to examine the partitioning of an organophosphorus insecticide, methidathion, in non-amended agricultural soil and soil amended with urban sewage sludge and/or different types of surfactant. Kinetic data showed that sewage sludge significantly reduced adsorption rate, whereas amendment of the soil with the cationic surfactant tetradecyltrimethylammonium bromide (TDTMA) at 10 x CMC (critical micellar concentration) increased the adsorption rate by a factor of 10. The adsorption isotherms were evaluated using the Freundlich model. The soil adsorption capacity for methidathion was enhanced by amendment with sewage sludge and even more significantly with TDTMA at 10 x CMC or combined with sewage sludge. TDTMA conferred a high hydrophobic character to the soil, enhancing the adsorption capacity of the rather hydrophobic methidathion. The amendment of soil both with sewage sludge and TDTMA combines the increased hydrophobicity with a higher surfactant retention by organic matter, due to an increase in cation exchange capacity, which promotes even more the adsorption capacity for the insecticide. An anionic surfactant, linear alkylbenzene sulfonate, and the non-ionic Tween 80 only induced a slight modification in the kinetics and adsorption of methidathion.     

Inverse modelling for estimating sorption and degradation parameters for pesticides

The leaching model PESTRAS was used to estimate sorption and degradation values for bentazone from three lysimeter datasets using the inverse modelling package PEST. Investigations were undertaken to assess the influence on calibration results of (1) values attributed to uncertain parameters not included in the calibration, and (2) starting values supplied to the inverse modelling package. Automatic calibrations with different realistic values for the Freundlich exponent n(f) yielded different combinations of K(om) and DT50. Similarly, the supply of different starting values for K(om) and DT50 revealed that different combinations of these two parameters equally calibrated PESTRAS for two of the three lysimeters. Examination of the error surface, ie the forward running of the model for different combinations of K(om) and DT50 values, and the calculation of the goodness-of-fit to the experimental data, was found useful for identifying those instances where non-uniqueness in the calibration is likely to occur. Although the derivation of sorption and degradation values through inverse modelling is expected to offer significant benefits over laboratory determinations, care should be exercised when examining values derived through this approach. Research is needed to identify data requirements for robust estimation of sorption and degradation parameters through calibration of pesticide fate models against leaching data.     

Variation of pesticide sorption isotherm in soil at the catchment scale

The variation of the sorption isotherm of pesticides has seldom been explored at the catchment scale. Such a study was conducted at the scale of a 187-ha agricultural catchment for three herbicides: atrazine, isoproturon and metamitron. Partition coefficient (Kd) values were measured in batch experiments on 51 topsoil samples, and showed moderate variability at the catchment scale (coefficient of variation CV approximately 30%). Values of Kd ranged from 0.47 to 1.70 litre kg(-1) for atrazine, 0.47 to 1.81 for isoproturon, and 0.55 to 2.21 for metamitron. A clustering method was used to reduce the number of samples on which to measure sorption isotherms to 14. Sorption isotherms agreed with the Freundlich rather than the linear model. Kf parameters had CV values similar to those for Kd, with values ranging from 0.78 to 2.13 mg(1 - Nf) litre(Nf) kg(-1) for atrazine, 0.61 to 1.82 for isoproturon, and 0.69 and 2.58 for metamitron. Nf exponents showed little variation (CV < 5%). Nf values were between 0.86 and 0.98 for atrazine, 0.85 and 0.90 for isoproturon, and 0.82 and 0.87 for metamitron. More than 97% of the Kf catchment-scale variations could be explained by the variations of the soil organic carbon content.     

Pedotransfer functions for isoproturon sorption on soils and vadose zone materials

BACKGROUND: Sorption coefficients (the linear K_D or the non‐linear K_F and N_F) are critical parameters in models of pesticide transport to groundwater or surface water. In this work, a dataset of isoproturon sorption coefficients and corresponding soil properties (264 K_D and 55 K_F) was compiled, and pedotransfer functions were built for predicting isoproturon sorption in soils and vadose zone materials. These were benchmarked against various other prediction methods. RESULTS: The results show that the organic carbon content (OC) and pH are the two main soil properties influencing isoproturon K_D. The pedotransfer function is K_D = 1.7822 + 0.0162 OC^1.5 ? 0.1958 pH (K_D in L kg^?1 and OC in g kg^?1). For low‐OC soils (OC < 6.15 g kg^?1), clay and pH are most influential. The pedotransfer function is then K_D = 0.9980 + 0.0002 clay ? 0.0990 pH (clay in g kg^?1). Benchmarking K_D estimations showed that functions calibrated on more specific subsets of the data perform better on these subsets than functions calibrated on larger subsets. CONCLUSION: Predicting isoproturon sorption in soils in unsampled locations should rely, whenever possible, and by order of preference, on (a) site‐ or soil‐specific pedotransfer functions, (b) pedotransfer functions calibrated on a large dataset, (c) K_OC values calculated on a large dataset or (d) K_OC values taken from existing pesticide properties databases. Copyright © 2011 Society of Chemical Industry     

Changes in phosphine sorption in wheat after storage at two temperatures

BACKGROUND: Wheat can be stored for many months before being fumigated with phosphine to kill insects, so a study was undertaken to investigate whether the sorptive capacity of wheat changes as it ages. Wheat was stored at 15 or 25 °C and 55% RH for up to 5.5 months, and samples were fumigated at intervals to determine sorption. Sealed glass flasks (95% full) were injected with 1.5 mg L^?1 of phosphine based on flask volume. Concentrations were monitored for 11 days beginning 2 h after injection. Some wheat samples were refumigated after a period of ventilation. Several fumigations of wheat were conducted to determine the pattern of sorption during the first 24 h. RESULTS: Phosphine concentration declined exponentially with time from 2 h after injection. Rate of sorption decreased with time spent in storage at either 15 or 25 °C and 55% RH. Rate of sorption tended to be lower when wheat was refumigated, but this could be explained by time in storage rather than by refumigation per se. The data from the 24 h fumigations did not fit a simple exponential decay equation. Instead, there was a rapid decline in the first hour, with phosphine concentration falling much more slowly thereafter. CONCLUSIONS: The results have implications for phosphine fumigation of insects in stored wheat. Both the time wheat has spent in storage and the temperature at which it has been stored are factors that must be considered when trying to understand the impact of sorption on phosphine concentrations in commercial fumigations. Copyright © The state of Queensland (through the Department of Employment, Economic Development and Innovation) 2009. Published by John Wiley and Sons, Ltd.     

Role of sorption and degradation in the herbicidal function of isoxaflutole

BACKGROUND: The fate of isoxaflutole (IFT) in soil is closely related to soil sorption. Sorption and transformation of IFT were investigated in laboratory incubations with four soils, and these results were used to interpret greenhouse studies using IFT to control several weed species. RESULTS: Degradation proceeded by previously observed pathways to form diketonitrile (DKN) and benzoic acid (BA) derivatives, as well as traces of unidentified products. Over the course of the incubation, DKN was the dominant active form of the herbicide present in the experimental system, and was thus critical to the soil activity of the herbicide for weed control. CONCLUSION: Control of most weed species appeared to be a function of both sorption and biodegradation of DKN, with greatest weed control being observed in soils in which a significant portion of the DKN that was formed persisted and remained bioavailable over the course of the incubation. Copyright © 2009 Society of Chemical Industry     

Degradation of a sulfonamide herbicide as a function of soil sorption

The degradation of DE-498 (proposed common name flumetsulam) was studied in 21 US soils as a first step in developing a management plan for this new herbicide. Degradation half-lives were shorter in soils that adsorbed the compound less. Adsorption was lower in soils with higher pH and lower organic carbon content. Degradation half-lives were thus influenced by both pH and organic carbon: they were in the range 2–4 weeks in higher pH soils (pH 5 7.0) unless the organic carbon content was above 2.5%, at which half-lives were in the range 1–3 months. In medium pH soils (6.4 pH 6.9) half-lives were 1–2 months, while in lower pH soils (5.9 pH 6.3) they were 1–4 months. The laboratory data were supported by the response of sunflowers (Helianthus annuus L.) planted 1 year after application of flumetsulam to different soils. A quantitative model relating half-life to sorption K_d (r²= 0.85) was coupled with an additional equation relating sorption K_d to the proportion of neutral and anionic forms of the compound at different pH values. The study allows estimates of this herbicide's degradation in soil to be made if its pH and organic carbon content are known. Degradation d'un herbicide sulfonamide en fonction de la capacité d'absorption du sol La dégradation du flumetsulam a étéétudiée dans les sols aux Etats Unis comme premier stade dans le développement d'un plan d'utilisation de ce nouvel herbicide. Les demi-vies de dégradation étaient plus courtes dans les sols qui absorbaient moins le produit. L'absorption était plus faible dans les sols à pH élevé et à faible teneur en carbone organique. Les demi-vies étaient ainsi sous l'influence du pH et du carbone organique: elles étaient de 2 à 4 semaines pour les pH de sols élevés (pH 7) sauf si le carbone organique était au dessus de 2,5%, dans ce cas, les demi-vies etaient de 1 à 3 mois. Dans les sols à pH moyen (6,4 pH 6,9) les demi-vies étaient de 1 à 2 mois, tandis que dans les sols à pH faible (5,9 pH 6,3) elles étaient de 1 à 4 mois. Les résultats de laboratoire ont été confirmés par le comportement de tournesols plantés un an aprfès l'application de flumetsulam dans différents sols. Un modèle reliant la demi-vie au coefficient d'absorption Kd (r²= 0.85) a été couplé avec une équation additionelle reliant le coefficient d'absorption Kd à la proportion de particules neutres et anioniques de la molécule aux différents pH. L'étude permet de faire des estimations de la dégradation de cet herbicide dans le sol dès que le pH et la teneur en carbone organique sont connus. Abbau eines Sulfonamid-Herbizids als Funktion der Bodensorption Der Abbau von Flumetsulam (DE-498) wurde in 21 Böden untersucht, um eine Grundlage zur Produktentwicklung dieses neuen Herbizids zu gewinnen. Die 50%ige Verlustrate (DT₅₀) war in schwächer sorptiven Böden kürzer. Bei hohem pH-Wert und geringem Gehalt an organischer Substanz war die Adsorption schwächer. Die DT₅₀ wurde durch den pH-Wert und den Gehalt organischer Substanz wie folgt beeinflußt: Sie betrug 2 bis 4 Wochen in Böden mit pH >7,0 (wenn der C_org-Gehalt nicht über 2,5% lag; dort dann 1 bis 3 Monate), 1 bis 2 Monate bei 6,4 < pH < 6,9 und 1 bis 4 Monate bei 5,9 < pH < 6,3). Die Ergebnisse der Laboruntersuchungen wurden durch Untersuchungen an Sonnenblumen gestützt. die 1 Jahr nach Applikation von Flumetsulam auf verschiedenen Böden angebaut wurden. Ein quantitatives Modell über das Verhältnis der Verlustrate zum Sorptionskoeffizienten K_d (r²= 0,85) wurde mit einer zusätzhchen Gleichung der Beziehung des Sorptionskoeffizienten K_d zum Verhältnis der neutralen und der anionischen Verbindungen des Wirkstoffs bei verschiedenen pH-Werten verknüpft. Aufgrund der Untersuchungen kann der Abbau dieses Herbizids in Böden bekannten pH-Werts und C_org-Gehalts abgeschätzt werden.     

Cuticular sorption and desorption of a nonionic diethylene glycol monooleate surfactant

Sorption and desorption of ‘Pegosperse’ 100-O(PEG 100-O; diethylene glycol monooleate, containing 15% diester) surfactant by unaltered (CM) and dewaxed (DCM) adaxial cuticle membranes isolated from apple (Malus pumila M.) leaves were studied. The aim of this study was to understand interactions between surfactants and cuticles. Enzymatically isolated cuticles were soaked in buffer or PEG 100-O solution (pH 7–0). and the weight changes of cuticles were measured to determine the amount of surfactant sorbed or desorbed by the cuticles. For very low surfactant concentrations, sorption was measured by changes in the surface tension of the solutions. PEG 100-O sorption by both the CMs and the DCMs occurred mainly in the first three hours and was concentration-dependent. The DCMs always sorbed more surfactant than the CMs. Desorption of PEG 100-O from both CMs and DCMs was rapid in the first few hours and then decreased to a relatively low rate until the surfactant was totally desorbed from the cuticles after about two months. The sorption and complete desorption of the surfactant by both CMs and DCMs show that PEG 100-O interacts with both cutins and waxes of the cuticles and the interactions are reversible.     

高效液相色谱法测定二甲四氯在铁铝土中的吸附特征

二甲四氯 (MCPA) 是铁铝土区域广泛使用的一种除草剂,生物毒性大。吸附是控制MCPA在土壤中迁移/转化的关键过程。本研究建立了以C₁₈为色谱柱、V(甲醇):V[水 (乙酸调pH值至2.5)] = 80 : 20为流动相、PDA为检测器 (检测波长280 nm) 的MCPA高效液相色谱检测方法,并结合批量平衡法评估MCPA在铁铝土中的吸附特征。结果表明:在0.5~40 mg/L内,MCPA的质量浓度与对应的峰面积间呈良好线性关系 (R2 = 0.999 9),检出限为0.2 mg/L,定量限为0.5 mg/L;回收率为98%~103%,相对标准偏差为3.5%~4.0%,适用于MCPA吸附试验的测定。铁铝土对MCPA的等温吸附过程符合Freundlich模型,吸附自由能△G<0,|△G|为9.34~14.73 kJ/mol,是一个自发的、非均质的、多层的物理吸附过程。吸附常数K_f值在0.85~4.24 L/kg之间,属于难吸附污染物,对地下水具有环境风险。不同铁铝土对MCPA的吸附作用受土壤pH值、有机质、矿物影响,表现为水稻土>暗红湿润铁铝土>简育湿润铁铝土。氢键结合、偶极间作用是吸附发生的关键作用力。     

Modelling the kinetics of ethyl formate sorption by wheat using batch experiments

BACKGROUND: Ethyl formate formulations are being considered to replace methyl bromide for fast grain disinfestation. Grain adsorbs ethyl formate rapidly, which can result in inadequate fumigation concentrations and unacceptable grain residues. A model of ethyl formate sorption kinetics will enable fumigation approaches to be determined that meet disinfestation and food safety requirements. RESULTS: This paper identifies all mass transport processes involved in ethyl formate sorption by wheat from published and experimental evidence. The model accounts for reaction losses of ethyl formate in air and grain using first‐order kinetics, transport in the gas and solid phases with linear mass transfer coefficients and uses a linear partition relationship representation of sorption equilibrium. Batch experimental data were measured to determine model coefficients. Novel gaseous breakdown data for ethyl formate in air were measured, and first‐order kinetics was demonstrated, although the specific reactions involved were not identified. CONCLUSION: The model predicts air and grain fumigant concentrations relevant for grain disinfestation and food residue contamination successfully. The form of the model should be applicable to all fumigant–grain systems, as it accounts for the diffusion and reaction influences known to occur with all modern fumigants under concentration and exposure conditions relevant to industry. Copyright © 2009 CSIRO, Australia. Published by John Wiley & Sons, Ltd.     

Organic amendments affecting sorption, leaching and dissipation of fungicides in soils

Metalaxyl and tricyclazole are two fungicides widely used in Spain in vineyard and rice crops respectively. In this study an investigation has been made of the effect of three organic amendments [two commercial amendments, solid fertiormont (SF) and liquid fertiormont (LF), and a residue from the olive oil production industry, alperujo (OW)] on fungicide fate in soils. Changes in soil porosity on amendment were studied by mercury intrusion porosimetry, sorption-desorption studies were performed by the batch equilibration method, dissipation of metalaxyl and tricyclazole in the soil was studied at - 33 kPa moisture content and 20 degrees C and leaching was studied in hand-packed soil columns. Amendments with SF and LF reduced soil porosity, while OW increased porosity through an increase in pore volume in the highest range studied. Tricyclazole sorbed to soils to a much higher extent than metalaxyl. With some exceptions, sorption of both fungicides increased on amendment, especially in the case of SF-amended soils, which rendered the highest K(oc) values. In soils amended with the liquid amendment LF, sorption either remained unaffected or decreased, and this decrease was much higher in the case of metalaxyl and a soil with 70% clay. In this clay soil, amendment with OW, of very high soluble organic matter content, also decreased metalaxyl sorption. Tricyclazole is more persistent in soil than metalaxyl, and both fungicides were found to be more persistent in amended soils than in unamended soils. Leaching of metalaxyl and tricyclazole in soil columns was inversely related to sorption capacity. The low recoveries of tricyclazole in leachates and in soil columns when compared with metalaxyl, a less persistent fungicide, were attributed to diffusion into micropores and to increase in sorption with residence time in the soil, both processes favoured by the low mobility of tricyclazole.     

A kinetic model of fumigant sorption by grain using batch experimental data

BACKGROUND: Most fumigants are adsorbed by grain at differing rates depending on the fumigant or grain type. Sorption can reduce the concentrations of fumigation doses to sublethal levels before grain has been disinfested. A model to predict fumigant losses due to sorption in industrial scenarios is needed. RESULTS: This work reviews the kinetics of grain fumigant sorption and develops a new alternative model based upon key factors established from the literature and batch experimental results. The novel model accounts for linear mass transfer within the grain, irreversible 'binding' and linear partitioning of the fumigant to the grain. Model coefficients were estimated by minimizing the sum of squared residuals between model predictions and experimental data. The model was compared with other options including diffusion into spheres, and results for methyl bromide and phosphine are provided. CONCLUSION: The model describes the transient changes of fumigant concentrations in both the intergranular air and grain. It provides the capacity to predict fumigant concentrations throughout grain stacks for a wide range of scenarios of industrial importance.     

Mechanisms of herbicide sorption in microalgae and the influence of environmental factors

The sorption kinetics of photosystem II herbicides in the unicellular microalgae Ankistrodesmus braunii are independent of the herbicide concentration. While diuron-type herbicides attain an equilibrium state of sorption after at most 5 min, it takes up to 60 min for phenol-type herbicides. The kinetics of the inhibition of photosynthetic electron transport display a good correlation to the kinetics of sorption. For both types of herbicides, a phase of prevalent partitioning into the lipid phase of the cell membranes preceeds binding to thylakoid membranes. With phenol-type herbicides this phase is much more extended than with diuron-type compounds. As a consequence, there is no displacement of previously bound herbicides of this type from algal cells by addition of an excess of other photosystem II herbicides. The sorption of phenol-type herbicides to microalgae is under strong influence of environmental factors, such as light, temperature, pH, or oxygen concentration. Thus, besides the lipophilicity of these biocides, the response of the target cells to environmental factors is at least as important for herbicide sorption in the cells. From these results it is concluded that a prediction of the biocide accumulation in aquatic microorganisms can only be partly deduced from the properties of the pesticide molecule. The target cells and their complex responses to their environment strongly relativize correlations of chemical properties, e.g., lipophilicity and biological activity.     

Analysis,sorption and residues of a homologous series of isothiocyanates on wheat

A series of isothiocyanates (R-NCS, R, 1–6 carbon atoms) was applied in the vapour phase to wheat in sealed containers. The speed of sorption, as measured by the rate of loss from the intergranular air space, was inversely proportional to molecular weight; e.g. the time for 50% sorption of hexyl isothiocyanate was over 100 times longer than for the methyl analogue. Despite extensive sorption, most of the applied chemicals was recovered from the fumigated wheat seven days after dosing, indicating that sorption did not lead to extensive degradation. Purge and trap techniques proved suitable for recovery of low-boiling, but not high-boiling chemicals.