Differences in herbicide adsorption on soil using several soil ph modification techniques

Abstract

Effects of soil pH on weak acid and weak base herbicide adsorption by soil are often determined by modifying soil pH in the laboratory. Modification of soil pH with acidic or basic amendments such as HCl or NaOH can cause changes in the soil‐solution system that may affect pesticide adsorption. The partition coefficients (K_d) for atrazine and dicamba by Waukegan, Piano, and Walla Walla silt loam soils stabilized in the field at different pH levels were compared to the K_d obtained when the soil pH was adjusted with acidic or basic amendments before herbicide addition. NaOH addition to raise soil pH generally increased the soluble soil organic carbon (SSOC) concentration in solution compared to field soils at the same pH and to soil treated with Ca(OH)₂. NaOH decreased the soil solution ionic strength slightly. Acidifying soils increased the soil solution ionic strength, when compared to field soils at the same pH and had no effect on SSOC concentration. Dicamba adsorption to soil was minimal (K_d < 0.22) and not influenced by soil pH in the range of 4.1 to 6.0; adsorption by laboratory amended soils in some cases underestimated adsorption compared to nonamended soils. Atrazine adsorption increased with decreased pH in all soils, and was overestimated slightly by several laboratory treatments to reduce pH compared to adsorption by field soils. Treatments to raise the pH did not affect atrazine adsorption. Overall, herbicide adsorption differences due to pH modification were small (<30%), and were not affected by soil solution ionic strength, saturating cation, or SSOC concentration in solution.     

Adsorption studies of the herbicide simazine in agricultural soils of the Aconcagua valley, central Chile

Simazine is a s-triazine herbicide that has been applied worldwide for agriculture. This herbicide is the second most commonly detected pesticide in surface and groundwater in the United States, Europe and Australia. In this study, simazine adsorption behaviour was studied in two agricultural soils of the Aconcagua valley, central Chile. The two studied soils were soil A (loam, 8.5% organic matter content) and soil B (clay-loam, 3.5% organic matter content). Three times higher simazine adsorption capacity was observed in soil A (68.03 mg kg⁻¹) compared to soil B (22.03 mg kg⁻¹). The simazine adsorption distribution coefficients (K_d) were 9.32 L kg⁻¹ for soil A and 7.74 L kg⁻¹ for soil B. The simazine adsorption enthalpy in soil A was −21.0 kJ mol⁻¹ while in soil B the adsorption enthalpy value was −11.5 kJ mol⁻¹. These results indicate that simazine adsorption process in these soils is exothermic, governing H bonds the adsorption process of simazine in both the loam and clay-loam soils. These results and the potentiometric profiles of both soils, suggest that simazine adsorption in soil A is mainly governed by simazine–organic matter interactions and in soil B by simazine–clay interactions. The understanding of simazine sorption–desorption processes is essential to determine the pesticide fate and availability in soil for pest control, biodegradation, runoff and leaching.     

Sorption–desorption and transport of trimethoprim and sulfonamide antibiotics in agricultural soil: effect of soil type,dissolved organic matter,and pH

Use of animal manure is a main source of veterinary pharmaceuticals (VPs) in soil and groundwater through a series of migration processes. The sorption–desorption and transport of four commonly used VPs including trimethoprim (TMP), sulfapyridine, sulfameter, and sulfadimethoxine were investigated in three soil layers taken from an agricultural field in Chongming Island China and two types of aqueous solution (0.01 M CaCl₂ solution and wastewater treatment plant effluent). Results from sorption–desorption experiments showed that the sorption behavior of selected VPs conformed to the Freundlich isotherm equation. TMP exhibited higher distribution coefficients (K _d?=?6.73–9.21) than other sulfonamides (K _d?=?0.03–0.47), indicating a much stronger adsorption capacity of TMP. The percentage of desorption for TMP in a range of 8–12 % is not so high to be considered significant. Low pH (<pK _a of tested VPs) and rich soil organic matter (e.g., 0–20 cm soil sample) had a positive impact on sorption of VPs. Slightly lower distribution coefficients were obtained for VPs in wastewater treatment plant (WWTP) effluent, which suggested that dissolved organic matter might affect their sorption behavior. Column studies indicated that the transport of VPs in the soil column was mainly influenced by sorption capacity. The weakly adsorbed sulfonamides had a high recovery rate (63.6–98.0 %) in the leachate, while the recovery rate of TMP was only 4.2–10.4 %. The sulfonamides and TMP exhibited stronger retaining capacity in 20–80 cm and 0–20 cm soil samples, respectively. The transport of VPs was slightly higher in the columns leached by WWTP effluent than by CaCl₂ solution (0.01 M) due to their sorption interactions.     

Adsorption and desorption variability of four herbicides used in paddy rice production

This investigation was performed to determine the effect of physicochemical soil properties on penoxsulam, molinate, bentazon, and MCPA adsorption–desorption processes. Four soils from Melozal (35° 43′ S; 71° 41′ W), Parral (36° 08′ S; 71° 52′ W), San Carlos (36° 24′ S; 71° 57′ W), and Panimavida (35° 44′ S; 71° 24′ W) were utilized. Herbicide adsorption reached equilibrium after 4 h in all soils. The Freundlich L-type isotherm described the adsorption process, which showed a high affinity between herbicides and sorption sites mainly because of hydrophobic and H-bonds interaction. Penoxsulam showed the highest adsorption coefficients (4.23 ± 0.72 to 10.69 ± 1.58 mL g^?1) and were related to soil pH. Molinate showed K_d values between 1.72 ± 0.01 and 2.3 ± 0.01 mL g^?1and were related to soil pH and organic matter, specifically to the amount of humic substances. Bentazon had a high relationship with pH and humic substances and its K_d values were the lowest, ranging from 0.11 ± 0.01 to 0.42 ± 0.01 mL g^?1. MCPA K_d ranged from 0.14 ± 0.02 to 2.72 ± 0.01 mL g^?1, however its adsorption was related to humic acids and clay content. According to these results, the soil factors that could explain the sorption process of the studied herbicides under paddy rice soil conditions, were principally humic substances and soil pH. Considering the sorption variability observed in this study and the potential risk for groundwater contamination, it is necessary to develop weed rice management strategies that limit use of herbicides that exhibit low soil adsorption in areas with predisposing conditions to soil leaching.     

2,4-二氯苯酚在土壤中的吸附及其批实验与柱实验的分配系数比较

为了研究2,4-二氯苯酚在土壤中的吸附及比较其批实验与柱实验的分配系数Kd,开展了2,4-二氯苯酚的批实验（不同液固比条件下）和柱实验。通过分析结果可知,在批实验中,不同液固比条件下2,4-二氯苯酚达到平衡的时间类似,都在60～70 h,吸附动力学曲线符合伪二级动力学方程,吸附规律是：液固比越大,平衡吸附量增大,反应速率常数K2减小,初始吸附速率常数减小;Kd随液固比增大而降低,范围在2.91～2.12 L/kg。柱实验结果表明,2,4-二氯苯酚的贯穿曲线可以很好地用化学非平衡模型来拟合,通过模型拟合得到的Kd值要低于批实验的结果。该研究对表征2,4-二氯苯酚在环境中的行为、预测其对土壤和地下水的污染及其治理提供了依据。     

Adsorption-desorption and leaching of pyraclostrobin in Indian soils

Pyraclostrobin is a new broad-spectrum foliar applied and seed protectant fungicide of the strobilurin group. In this paper, adsorption-desorption of pyraclostrobin has been investigated in three different soils viz. Inceptisol (sandy loam, Delhi), Vertisol (sandy clay, Hyderabad) and Ultisol (sandy clay loam, Thrissur). Effect of organic matter and clay content on sorption was also studied in Inceptisol of Delhi. Leaching potential of pyraclostrobin as influenced by rainfall was studied in intact soil columns to confirm the results of adsorption-desorption studies. The adsorption studies were carried out at initial concentrations of 0.05, 0.1, 0.5, 1 and 1.5 μg mL^?1. The distribution coefficient (K_d) values in three test soils ranged from 4.91 to 18.26 indicating moderate to high adsorption. Among the three test soils, adsorption was the highest in Ultisol (K_d 18.26), followed by Vertisol (K_d 9.87) and Inceptisol (K_d 4.91). K_F value was also highest for Ultisol soil (66.21), followed by Vertisol (40.88) and Inceptisol (8.59). S-type adsorption isotherms were observed in all the three test soils. K_d values in organic carbon-removed soil and clay-removed soil were 3.57 and 2.83 respectively, indicating lower adsorption than normal Inceptisol. Desorption studies were carried out at initial concentrations of 0.5, 1 and 1.5 μg mL^?1. Desorption was the greatest in Inceptisol, followed by Vertisol and Ultisol. Amounts of pyraclostrobin desorbed in three desorption cycles for different concentrations were 23.1–25.3%, 9.4–20.7% and 8.1–13.6% in Inceptisol, Vertisol and Ultisol respectively. Desorption was higher in clay fraction-removed and organic carbonremoved soils than normal Inceptisol. Desorption was slower than adsorption in all the test soils, indicating hysteresis effect (with hysteresis coefficient values varying from 0.05 to 0.20). Low values of hysteresis coefficient suggest high hysteresis effect indicating easy and strong adsorption, and slow desorption, of pyraclostrobin in soils. Higher hysteresis coefficient values in organic carbon removed soil (0.25–0.30) and clay fraction removed soil (0.28–0.36) as compared to normal Inceptisol soil suggest relatively weak adsorption and easy desorption of pyraclostrobin. Results of regression analysis suggest that the organic matter and pH of the soil play a major role in adsorption of pyraclostrobin. Leaching studies were carried out in intact soil columns in Inceptisol. The columns were leached with different amounts of water simulating different amounts of rainfall. The results suggest that most of the pyraclostrobin residues will remain present in the top soil layers even under high rainfall conditions and chances of pyraclostrobin moving to lower soil depth are almost negligible.     

Inferences About Radionuclide Mobility in Soils Based on the Solid/Liquid Partition Coefficients and Soil Properties

To assist transport modeling in assessments of the radiological impact of a geological repository for radioactive wastes, the mobility of various elements was studied in arable and wetland soils in the Forsmark region, Sweden. Pore water and total element contents were determined for five types of unconsolidated deposits (regolith), spanning a wide range of soil properties with respect to pH and organic matter content. Two soil depths were sampled to capture element mobility in regolith layers affected and unaffected by soil-forming processes. The solid/liquid partition coefficients (K _d values) for most elements varied significantly among regolith types. For most elements, the observed variations in K _d values could be explained by variations in soil properties. For many elements, mobility increased with decreasing soil pH. The results provide a significant addition of data on radionuclide retention in soils, taking account of soil properties and processes.     

Effect on herbicide adsorption of organic forestry waste products used for soil remediation

Organic soil amendments can be useful for improving degraded soil, but this increase in organic matter (OM) may influence adsorption of herbicides subsequently applied to the treated soil, even though the particle size of amendments and their nature differ from typical soil OM. In this study, a batch equilibrium method was used to measure adsorption of five herbicides following application to two organic media, wood pulp and sawdust, comparing these with two cropping soils. Herbicide adsorption, quantified by distribution coefficients (k_d), was much higher in the two organic media than in the cropping soils. The increases in adsorption were strongly correlated to the percentage of organic carbon. When the k_d was normalized to adsorption coefficients corrected for OM content (k_oc), variation in results between the media was greatly reduced, indicating that OM is an important factor influencing adsorption in these media. The results of this study suggest that herbicides will be less effective when applied to soils in which sawdust and wood pulp have been added. Using organic amendments to remediate soil will increase adsorption of pesticides, reducing their bio-availability and efficacy, but also reducing their tendency to leach into root zones of deep-rooted crops and into groundwater.     

Fate of atrazine in a soil under different agronomic management practices

Agricultural management affects the movement of atrazine in soil and leaching to groundwater. The objective of this study was to determine atrazine adsorption in a soil after 20 years of atrazine application under agronomic management practices differing in tillage practice (conventional and zero tillage), residue management (with and without residue retention) and crop rotation (wheat-maize rotation and maize monoculture). Atrazine sorption was determined using batch and column experiments. In the batch experiment, the highest distribution coefficient K_d (1.1 L kg^?1) at 0–10 cm soil depth was observed under zero tillage, crop rotation and residue retention (conservation agriculture). The key factor in adsorption was soil organic matter content and type. This was confirmed in the column experiment, in which the highest K_d values were observed in treatments with residue retention, under either zero or conventional tillage (0.81 and 0.68 L kg^?1, respectively). Under zero tillage, the fact that there was no soil movement helped to increase the K_d. The increased soil organic matter content with conservation agriculture may be more important than preferential flow due to higher pore connectivity in the same system. The soil's capacity to adsorb 2-hydroxyatrazine (HA), an important atrazine metabolite, was more important than its capacity to adsorb atrazine, and was similar under all four management practices (K_d ranged from 30 to 40 L kg^?1). The HA adsorption was attributed to the type and amount of clay in the soil, which is unaffected by agronomic management. Soils under conservation agriculture had higher atrazine retention potential than soils under conventional tillage, the system that predominates in the study area.     

A comparison of octanol-water partitioning between organic chemicals and their metabolites in mammals

Bioaccumulation models take various elimination and uptake processes into account, estimating rates from chemical lipophilicity, expressed as the octanol-water partition ratio (K_ow). Here, we focussed on metabolism, which transforms parent compounds into usually more polar metabolites, thus enhancing elimination. The aim of this study was to quantify the change in lipophilicity of relevant organic pollutants undergoing various biotransformation reactions in mammals. We considered oxidation reactions catalyzed by three enzyme groups: cytochrome P450 (CYP), alcohol dehydrogenase (ADH), and aldehyde dehydrogenase (ALDH). Estimated log K_ow values of a selected dataset of parent compounds were compared with the log K_ow of their first metabolites. The log K_ow decreased by a factor that varies between 0 and −2, depending on the metabolic pathway. For reactions mediated by CYP, the decrease in K_ow was one order of magnitude for hydroxylated and epoxidated compounds and two orders of magnitude for dihydroxylated and sulphoxidated xenobiotics. On the other hand, no significant change in lipophilicity was observed for compounds N-hydroxylated by CYP and for alcohols and aldehydes metabolized by ADH and ALDH. These trends could be anticipated by the calculus method of log K_ow. Yet, they were validated using experimental log K_ow values, when available. These relationships estimate the extent to which the elimination of pollutants is increased by biotransformation. Thus, the quantification of the K_ow reduction can be considered as a first necessary step in an alternative approach to anticipate biotransformation rates, which are hard to estimate with existing methods.     

The use of hard- and soft-modelling to predict radiostrontium solid-liquid distribution coefficients in soils

The solid-liquid distribution coefficient (K_d) is the parameter that governs the incorporation of contaminants in soils. Its estimation allows the prediction of the fate of contaminants in the short- and long-term after a contamination event. Here, the K_d of radiostrontium (K_d(Sr)), a radionuclide of significant environmental interest, was predicted by hard models, which are based on knowledge of the mechanisms governing its sorption, and by soft models based on Partial Least Squares (PLS), using a large data set with the main soil parameters. The two approaches were tested and compared for 30 soils in Spain. Correlations between the predicted and experimental values of K_d(Sr) obtained using hard- and soft-modelling showed slopes close to 1 and regression coefficients higher than 0.95, which confirms that both approaches are able to obtain satisfactory estimates for K_d(Sr) from soil parameters.     

Estimation of octanol/water partition coefficients for organic pollutants using reverse-phase HPLC

Octanol/water partition coefficients (K_ow's) of organic solutes are estimated with reasonable accuracy (standard deviation ± 0.25 log K_ow units) by elution from a C-18 column with 75:25 (v/v) MeOH-H₂O, based on results with 37 test compounds. Changes in solute activity coefficients from water to 75% MeOH account for the slope of the log K_ow-log k' plot, where k' is the HPLC capacity factor. The method is used to estimate K_ow's for 25 additional organic compounds, and some disparities between the results and those calculated using group additivity-constitutive factors are noted.     

Sorption of polar and nonpolar organic contaminants by oil-contaminated soil

Sorption of nonpolar (phenanthrene and butylate) and polar (atrazine and diuron) organic chemicals to oil-contaminated soil was examined to investigate oil effects on sorption of organic chemicals and to derive oil–water distribution coefficients (K_oil). The resulting oil-contaminated soil–water distribution coefficients (K_d) for phenanthrene demonstrated sorption-enhancing effects at both lower and higher oil concentrations (C_oil) but sorption-reducing (competitive) effects at intermediate C_oil (approximately 1 g kg⁻¹). Rationalization of the different dominant effects was attempted in terms of the relative aliphatic carbon content which determines the accessibility of the aromatic cores to phenanthrene. Little or no competitive effect occurred for butylate because its sorption was dominated by partitioning. For atrazine and diuron, the changes in K_d at C_oil above approximately 1 g kg⁻¹ were negligible, indicating that the presently investigated oil has little or no effect on the two tested compounds even though the polarity of the oil is much less than soil organic matter (SOM). Therefore, specific interactions with the active groups (aromatic and polar domains) are dominantly responsible for the sorption of polar sorbates, and thus their sorption is controlled by available sorption sites. This study showed that the oil has the potential to be a dominant sorptive phase for nonpolar pollutants when compared to SOM, but hardly so for polar compounds. The results may aid in a better understanding of the role of the aliphatic and aromatic domains in sorption of nonpolar and polar organic pollutants.     

Surfactant solubilization of hydrophobic compounds in soil and water

The soil/water partition coefficient (K_d) of hexachlorobenzene (HCB) ranged from 220 1/kg to 1800 1/kg for eight soils having a wide range of physico-chemical properties. K_d normalised to soil organic carbon (K_oc) was found to be 28000 ± 4800 1/kg. Anionic surfactant dodecylsulphate (DS) present at concentrations above the critical micellar concentration (CMC) caused reductions in the apparent soil/water partition coefficient (K_d ^*) in the range of 3–26 times for most soils and up to 36–91 times for sandy soils. Below CMC, at environmentally relevant surfactant concentrations, K_d ^* was reduced by a factor of 1–13. For clay and calcareous soils significant adsorption/complexation/precipitation of DS occurred. At the lowest DS concentration this produced a two-fold increase in K_d ^*. At increasing DS concentrations this effect was shielded by the solubihzing effect from DS. Monomer (K_mn) and micellar (K_mc) surfactant/water partition coefficients for HCB were determined to be, 980 ± 190 1/kg and 21000 ± 1600 1/kg, respectively.     

ADSORPTION–DESORPTION,PERSISTENCE, AND LEACHING BEHAVIOR OF DITHIOPYR IN AN ALLUVIAL SOIL OF INDIA

Investigations were undertaken to determine the adsorption–desorption, persistence and leaching of dithiopyr (S,S′-dimethyl 2-difluoromethyl-4-isobutyl-6-trifluoromethyl pyridine-3,5-dicarbothioate) in an alluvial soil under laboratory condition. The adsorption–desorption studies were carried out using batch equilibration technique. The mass balance studies showed that 83–97% of the pesticide was recovered during adsorption–desorption studies. The results revealed strong adsorption of dithiopyr in alluvial soil with K_d values ranging from 3.97–5.78 and Freundlich capacity factor (K_F) value of 2.41. The strong adsorption was evident from the hysteresis effect observed during desorption. The hysteresis coefficients ranged from 0.17–0.40.

The persistence studies were carried out at two concentrations (1.0 and 10.0 μg g^?1 level) under field capacity moisture and submerged condition by incubating the treated soil at 25±1°C. In general, dithiopyr persisted beyond 90 days with half-life varying from 11.5–12.9 days under different conditions. The rate of application and moisture regimes had no overall effect on the persistence. The leaching studies carried out in packed column under saturated flow condition revealed that dithiopyr was highly immobile in alluvial soil. Only small amounts (0.02–0.04%) were recovered from leachate whereas major portion (99.9%) remained in top layer of the soil column. The data suggest that strong adsorption of dithiopyr will cause a greater persistence problem in the soil. However, the chances of its movement to ground water will be negligible due to its immobility.     

Bioaccumulation and bioavailability of polybrominated diphynel ethers (PBDEs) in soil

Earthworms were exposed to artificially contaminated soils of DE-71 and DE-79 to investigate the bioaccumulation and bioavailability of PBDEs in soil. All major congeners were bioavailable to earthworms. The uptake and elimination rate coefficients of PBDEs decreased with their logK_ows. The biota soil accumulation factors of PBDEs also declined with logK_ow. These may be due to the large molecular size and the high affinity of PBDEs to soil particles. The concentrations extracted by Tenax for 6 h correlated very well with those found in earthworms, suggesting that the bioavailability of PBDEs in soil is related to the fraction of rapid desorption from soil. This also indicates that 6 h Tenax extraction is a good proxy for the bioavailability of PBDEs to earthworms in soil. The BSAFs of PBDEs in aged soil decreased 22-84% compared to freshly spiked soil, indicating that aging may diminish the bioavailability of PBDEs in soil significantly.     

Sorption of chlorinated solvents and degradation products on natural clayey tills

The sorption of chlorinated solvents and degradation products on seven natural clayey till samples from three contaminated sites was investigated by laboratory batch experiments in order to obtain reliable sorption coefficients (K_d values). The sorption isotherms for all compounds were nearly linear, but fitted by Freundlich isotherms slightly better over the entire concentration range. For chloroethylenes, tetrachloroethylene (PCE) was most strongly sorbed to the clayey till samples (K_d = 0.84-2.45 L kg⁻¹), followed by trichloroethylene (TCE, K_d = 0.62-0.96 L kg⁻¹), cis-dichloroethylene (cis-DCE, K_d = 0.17-0.82 L kg⁻¹) and vinyl chloride (VC, K_d = 0.12-0.36 L kg⁻¹). For chloroethanes, 1,1,1-trichloroethane (1,1,1-TCA) was most strongly sorbed (K_d = 0.2-0.45 L kg⁻¹), followed by 1,1-dichloroethane (1,1-DCA, K_d = 0.16-0.24 L kg⁻¹) and chloroethane (CA, K_d = 0.12-0.18 L kg⁻¹). This is consistent with the order of hydrophobicity of the compounds. The octanol-water coefficient (log K_ow) correlated slightly better with log K_d values than log K_oc values indicating that the K_d values may be independent of the actual organic carbon content (f_oc). The estimated log K_oc or log K_d for chlorinated solvents and degradation products determined by regression of data in this study were significantly higher than values determined by previously published empirical relationships. The site specific K_d values as well as the new empirical relationship compared well with calculations on water and soil core concentration for cis-DCE and VC from the Rugårdsvej site. In conclusion, this study with a wide range of chlorinated ethenes and ethanes - in line with previous studies on PCE and TCE - suggest that sorption in clayey tills could be higher than typically expected.