Influence of soil aging on sorption and bioavailability of simazine

Characterization of pesticide bioavailability, particularly in aged soils, is of continued interest because this information is necessary for environmental risk assessment. However, pesticide bioavailability in aged soils has been characterized by a variety of methods with limited success, due in part to methodological limitations. The objective of this study was to use solvent extraction methods to correlate simazine residue bioavailability in aged soils to simazine mineralization using a simazine-mineralizing bacterium. Soils from Brazil, Hawaii, and the midwestern United States were treated with UL-ring-labeled [14C]simazine and incubated for up to 8 weeks. At the end of each incubation period, soils were either incubated further, extracted with 0.01 M CaCl2, or extracted with aqueous methanol (80:20 v/v methanol/water). In a parallel experiment, after each incubation period, soils were inoculated with the bacterium Pseudomonas sp. strain ADP, which is capable of rapidly mineralizing simazine, and 14CO2 was determined. The inoculated soil samples were then extracted with 0.01 N CaCl2 and with aqueous methanol. This allowed for the evaluation of the bioavailability of aged simazine residues, without the contribution of simazine desorption from soil. Results of these studies indicated that simazine sorption to soil increased with aging and that amounts of simazine in aged soils extracted by 0.01 M CaCl2 and aqueous methanol were highly correlated to amounts of simazine mineralized by Pseudomonas sp. strain ADP. Consequently, 0.01 M CaCl2/methanol-extractable simazine in aged soils can be used to estimate bioavailable residues. This technique may be useful in determining the bioavailability of other s-triazine compounds in soils.     

Field aging of insecticides after repeated application to a northern Thailand ultisol

Field aging immobilizes pollutants and reduces their toxicity, but it also boosts their accumulation and holds the risk of future release. We investigated the aging of six insecticides (water solubilities: 0.33 mg L (-1)-completely miscible) applied five times (10-day intervals) to a tropical fruit orchard under natural weather conditions. After sequential extractions of soil samples with 0.01 M CaCl 2, methanol (MeOH), and acetone/ethylacetate/water (AEW), a conventional ( K OC(app) = [ c(MeOH) + c(AEW)]/ c(CaCl 2), normalized to soil organic carbon) and a newly introduced distribution ratio (MAR = MeOH/AEW ratio; c(MeOH)/ c(AEW)) were calculated. Field half-lives of the insecticides correlated with K OC(app) but not with MAR, which might reflect that dissipation was significantly affected by abiotic processes. The extent of aging was related to hydrophobicity of the compounds and most pronounced for endosulfan (3-fold increase in K OC(app) within 84 days). For dimethoate, this increase was even steeper (5- to 10-fold within 10 days), which was, however, mostly caused by dissipation from labile pools rather than by aging. The K OC(app) of chlorpyrifos remained constant, but a significant decrease in MAR ( r = -0.78) revealed that sorption strength increased nevertheless. Results for malathion were ambiguous. Within the time frame of our study, neither K OC(app) nor MAR gave evidence for the aging of mevinphos. The different dynamics of K OC(app) and MAR for the six insecticides studied indicate that different aging mechanisms or rates, or both control the fate of the individual insecticides, which can potentially be revealed by sequential exctraction procedures.     

Sorption-desorption of two "aged" sulfonylaminocarbonyltriazolinone herbicide metabolites in soil

Aging (herbicide-soil contact time) has been shown to significantly affect the sorption-desorption characteristics of many herbicides, which in turn can affect the availability of the herbicide for transport, plant uptake, and microbial degradation. In contrast, very little work in this area has been done on herbicide metabolites in soil. The objective of this study was to characterize the sorption-desorption of sulfonylaminocarbonyltriazolinone herbicide metabolites incubated in soils at different soil moisture potentials. A benzenesulfonamide metabolite and a triazolinone metabolite from sulfonylaminocarbonyltriazolinone herbicides were incubated in clay loam and loamy sand soils for up to 12 weeks at -33 kPa and at water contents equivalent to 50 and 75% of that at -33 kPa. Chemicals were extracted sequentially with 0.01 N CaCl(2) and aqueous acetonitrile (solution and sorbed phase concentrations, respectively), and apparent sorption coefficients (K(d,app)) were calculated. Sufficient metabolite remained during the incubation (>55% of applied) to allow determination of the coefficients. The initial aging period (2 weeks after application) significantly increased sorption as indicated by increased K(d,app) values for the chemical remaining, after which they remained relatively constant. After 12 weeks of incubation at -33 kPa, K(d,app) values for benzenesulfonamide and triazolinone increased by a factor of 3.5 in the clay loam soil and by a factor of 5.9 in the loamy sand as compared to freshly treated soils. There was no effect of moisture potential on aged apparent K(d,app) values. These data show the importance of characterization of sorption-desorption in aged herbicide residues, including metabolites, in soil, particularly in the case of prediction of herbicide residue transport in soil. In this case, potential transport of sulfonylaminocarbonyltriazolinone herbicide metabolites would be overpredicted if freshly treated soil K(d) values were used to predict transport.     

Sorption and leaching of atrazine and MCPA in natural and peat-amended calcareous soils from Spain.

The sorption and leaching of atrazine and MCPA (0.02 M CaCl(2) aqueous solution at 25 degrees C) by a calcareous soil from Southeastern Spain, after organic carbon (OC) amendment with a commercial peat (from 0.18% to 4.61% OC), were studied in batch and soil column experiments. Adsorption capacity (K(f)) values, obtained by fitting the experimental data to the Freundlich equation, ranged from 0.24 mg kg(-)(1) for MCPA sorption on the original soil to 5.47 mg kg(-)(1) for atrazine sorption on the peat-amended soil containing 4.61% OC. The breakthrough curves obtained from the step-function soil column experiments indicated that the amount of herbicide adsorbed ranged from 17.5 mg kg(-)(1) for MCPA in the original soil to 331 mg kg(-)(1) for atrazine in the peat-amended soil containing 1.67% OC. The results obtained from the pulse experiments indicate that the mobility of MCPA is much greater than that corresponding to atrazine.     

Solvent extraction characterization of bioavailability of atrazine residues in soils

Characterization of pesticide bioavailability, particularly in aged soils, is of continued interest because this information is necessary for environmental risk assessment. The objective of this study was to correlate atrazine residue bioavailability in aged soils, as determined by solvent extraction methods, to atrazine mineralization by an atrazine-degrading bacterium. Webster clay loam and Zimmerman fine sand soils were treated with UL-ring-labeled [14C]atrazine and incubated for up to 8 weeks. At the end of each incubation period, soils were either not extracted, extracted with 0.01 M CaCl2, or extracted with 0.01 M CaCl2/aqueous methanol. Soils were then inoculated with the bacterium Pseudomonas sp. strain ADP, which is capable of rapidly mineralizing the atrazine ring. This allowed for the evaluation of the bioavailability of aged atrazine residues without the contribution of atrazine desorption from soil. Results of these studies indicated that the amounts of atrazine residues in aged soils extracted by 0.01 M CaCl2 and aqueous methanol were correlated to amounts of atrazine mineralized by Pseudomonas sp. strain ADP. Consequently, 0.01 M CaCl2/methanol extractable atrazine in aged soils may be used to estimate bioavailable residues, and this technique may be useful to determine the bioavailability of other compounds in soils, especially other triazine herbicides.     

Sorption-desorption of "aged" sulfonylaminocarbonyltriazolinone herbicides in soil

Sorption-desorption interactions of pesticides with soil determine the availability of pesticides in soil for transport, plant uptake, and microbial degradation. These interactions are affected by the physical and chemical properties of the pesticide and soil, and for some pesticides, their residence time in the soil. The objective of this study was to characterize sorption-desorption of two sulfonylaminocarbonyltriazolinone herbicides incubated in soils at different soil moisture potentials. The chemicals were incubated in clay loam and loamy sand soils for up to 12 wks at -33 kPa and at water contents equivalent to 50 and 75% of that at -33 kPa. Chemicals were extracted sequentially with 0.01 N CaCl(2) and aqueous acetonitrile, and sorption coefficients were calculated. Sufficient sulfonylaminocarbonyltriazolinone herbicides remained (>40% of that applied) during incubation to allow calculation of sorption coefficients. Aging significantly increased sorption as indicated by increased sorption coefficients. For instance, for sulfonylaminocarbonyltriazolinone remaining after a 12-wk incubation at -33 kPa, K(d) increased by a factor of 4.5 in the clay loam soils and by 6.6 in the loamy sand as compared to freshly treated soils. There was no effect of moisture potential on sorption K(d) values. These data show the importance of characterization of sorption-desorption in aged herbicide residues in soil, particularly in the case of prediction of herbicide transport in soil. In this case, potential transport of sulfonylaminocarbonyltriazolinone herbicides would be over-predicted if freshly treated soil K(d) values were used to predict transport.     

Changes in sorption/bioavailability of imidacloprid metabolites in soil with incubation time

Changes in sorption/bioavailability of two metabolites, imidacloprid-urea {1-[(6-chloro-3-pyridinyl)methyl]-2-imidazolidinone} and imidacloprid-guanidine {1-[(6-chloro-3-pyridinyl)methyl]-4,5-dihydro-1H-imidazol-2-amine} of the insecticide imidacloprid {1-[(6-chloro-3-pyridinyl)-methyl]-N-nitro-2-imidazolidinimine} with aging in different soils were determined. Soil moisture was adjusted to -33 kPa and ¹⁴C- and analytical-grade imidacloprid-urea and imidacloprid-guanidine were added to the soil at a rate of 1.0 mg kg^-1. Spiked soils were incubated at 25°C for 8 weeks. Replicate soil samples were periodically extracted successively with 0.01 N CaCl₂, acetonitrile, and 1 N HCl. Imidacloprid-urea sorption, as indicated by sorption coefficient values, was highest in the soil with highest organic C content, and increased by an average factor of 2.6 in three soils during the 8-week incubation period. Imidacloprid-guanidine sorption increased by a factor of 2.3 in the same soils. The increase in sorption was the result of a decrease in the metabolite extractable with CaCl₂ (solution phase); the amount of metabolite extractable with acetonitrile and HCl (sorbed phase) did not significantly change with incubation time. It appears the increase in sorption was because the rate of degradation in solution and on labile sites was faster than the rate of desorption from the soil particles. It may have also been due to metabolite diffusion to less accessible or stronger binding sites with time. Regardless of the mechanism, these results are further evidence that increases in sorption during pesticide aging should be taken into account during characterization of the sorption process for mathematical models of pesticide degradation and transport.     

长期定位施肥对土壤磷素吸持特性与淋失突变点影响的研究

通过对黄土旱塬地区长期(26a)定位施肥条件下的不同施肥处理的土壤磷素及其吸持参数的测定,以及通过室内模拟试验对土壤磷素淋失突变点的测定,研究了土壤磷素吸持参数、土壤磷素淋失突变点和部分土壤性质之间的关系。结果表明,经过26年的长期施肥,M75P60和M75N120P60处理的Olsen-P含量比CK处理的提高了10.7和9.8倍,全磷(T-P)含量比CK处理的提高了60.4%和57.7%。长期磷肥和有机肥投入可以减低土壤磷素的最大吸附量(Qm),而提高土壤磷素的吸附饱和度(DPSS),M75N120P60处理的Qm比CK的减低了49.92%,而DPSS比CK的提高了21.5倍。相关分析表明,黄土旱塬土壤的Qm与Olsen-P、T-P和CaCl2-P呈极显著的负相关关系(P<0.01),与土壤有机质呈显著负相关关系(P<0.05)。零净吸附浓度磷(EPC0)与Olsen-P和CaCl2-P呈极显著正相关关系,与T-P和SOM也达到显著正相关,而与pH值的关系不显著,但土壤磷最大缓冲能力(MBC)与pH值的关系达到极显著。DPSS与Olsen-P、T-P、CaCl2-P和SOM呈极显著正相关关系。土壤磷素淋失的Olsen-P突变点值与土壤吸持参数Qm呈极显著正相关,与MBC也达到显著正相关,与DPSS、Olsen-P、T-P和CaCl2-P呈极显著负相关关系。该地区土壤磷素淋失的Olsen-P突变点值与DPSS15%的值极为吻合,即可以用DPSS15%值作为该地土壤磷素淋失的突变点值。     

Effects of solid olive-mill waste addition to soil on sorption, degradation and leaching of the herbicide simazine

Abstract. A laboratory study was conducted to investigate the effects of adding an intermediary byproduct of olive oil extraction ( alperujo or solid olive-mill waste, SOMW) on the sorption, degradation and leaching of the herbicide simazine in a sandy loam soil. The effect of SOMW addition on soil porosity was also assessed. The soil was amended in the laboratory with SOMW at two different rates (5% and 10% w/w). Simazine sorption isotherms showed a great increase in herbicide sorption after SOMW addition to soil; sorption increased with the amount of SOMW added. Incubation studies showed extended persistence by reduced biodegradation of simazine in the soil amended with SOMW compared with the unamended soil. Although the addition of SOMW to soil increased the total porosity, breakthrough curves of simazine in handpacked soil columns showed that SOMW addition retarded the vertical movement of the herbicide through the soil and reduced the total amount of herbicide leached. It appeared that the longer residence time of simazine in the amended soil columns (>20 days) compared with that in the unamended soil column (<20 days) allowed enhanced degradation and/or irreversible sorption under column leaching conditions. The results revealed important changes in herbicide behaviour upon SOMW addition, confirming the need to assess these changes in order to optimize the combined use of organic wastes and soil-applied pesticides.     

洛克沙胂在土壤柱中的淋溶迁移

畜禽粪便中残留的兽药进入土壤后的移动性是评价其淋溶能力（对地下水的污染风险）的重要信息。通过土壤柱稳定流实验,考察了不同淋溶剂、粪浸液等对洛克沙胂在不同深度（0～20、20～50、50～80 cm）灰潮土中的迁移行为影响。结果表明,水、0.01mol.L^-1 CaCl2、0.01 mol.L^-1 EDTA-Na2淋溶剂,对不同深度土壤柱中洛克沙胂的淋溶穿透曲线（BTCs）呈现不同程度的不对称性,在不同深度土壤柱中对洛克沙胂的淋出率分别为：水为92.3%～97.1%,0.01 mol.L^-1 CaCl2为71.0%～84.9%,0.01 mol.L^-1 EDTA-Na2为75.4%～91.2%;土壤柱先用粪浸液通过后,洛克沙胂的穿透曲线峰时间均有不同程度的提前,淋出率均有增加,在不同深度土壤柱中的淋出率分别为：水为96.4%～110.4%,0.01 mol.L^-1 CaCl2为94.5%～106.8%,0.01 mol.L^-1 EDTA-Na2为90.8%～103.2%。说明洛克沙胂随粪便进入土壤后可较快地淋溶迁移,可进入地表水和地下水中,对水环境质量的影响较大。     

Sorption and mobility of 14C-labeled imazaquin and metolachlor in four soils as influenced by soil properties

Aqueous batch-type sorption-desorption studies and soil column leaching studies were conducted to determine the influence of soil properties, soil and suspension pH, and ionic concentration on the retention, release, and mobility of [14C]imazaquin in Cape Fear sandy clay loam, Norfolk loamy sand, Rion sandy loam, and Webster clay loam. Sorption of [14C]metolachlor was also included as a reference standard. L-type sorption isotherms, which were well described by the Freundlich equation, were observed for both compounds on all soils. Metolachlor was sorbed to soils in amounts 2-8 times that of imazaquin, and retention of both herbicides was related to soil organic matter (OM) and humic matter (HM) contents and to herbicide concentration. Metolachlor retention was also related to soil clay content. Imazaquin sorption to one soil (Cape Fear) increased as concentration increased and as suspension pH decreased, with maximum sorption occurring in the vicinity of pK(a1) = (1.8). At pH levels below pK(a1) imazaquin sorption decreased as hydronium ions (H3O+) increased and competed for sites. NaCl was more effective than water in desorption of imazaquin at pH levels near the pK(a1). Mechanisms of bonding are postulated and discussed. The mobility of imazaquin through soil columns was in the order Rion > or = Norfolk > Cape Fear > or = Webster, whereas for metolachlor it was Rion > or = Norfolk > Webster > or = Cape Fear. Imazaquin was from 2 to 10 times as mobile as metolachlor.     

Sorption-desorption of imidacloprid and its metabolites in soil and vadose zone materials

Sorption-desorption is one of the most important processes affecting the leaching of pesticides through soil because it controls the amount of pesticide available for transport. Subsurface soil properties can significantly affect pesticide transport and the potential for groundwater contamination. This research characterized the sorption-desorption of imidacloprid (1-[(6-chloro-3-pyridinyl)-methyl]-N-nitro-2-imidazolidinimine) and three of its metabolites, 1-[(6-chloro-3-pyridinyl)methyl]-2-imidazolidinone (imidacloprid-urea), 1-[(6-chloro-3-pyridinyl)methyl]-4,5-dihydro-1H-imidazol-2-amine (imidacloprid-guanidine), and 1-[(6-chloro-3-pyridinyl)methyl]-1H-imidazol-2-amine (imidacloprid-guanidine-olefin), as a function of changing soil properties with depth in two profiles extending from the surface to a depth of 1.8 or 8 m. Sorption of each compound was highly variable and hysteretic in all cases. Normalizing the sorption coefficients (K(f)) to the organic carbon or the clay content of the soil did not reduce the variability in sorption coefficients for any compound. These results illustrate the importance of evaluation of the sorption data used to predict potential mobility. Understanding the variability of soil properties and processes as a function of depth is necessary for accurate prediction of pesticide dissipation.     

伴随阴离子对马铃薯种植冲击土中钾素固持与淋溶的影响

A column study was carried out to assess the influence of accompanying anions on potassium (K) leaching at potato growing sites with different soil textures (sandy loam and clay loam) in northwestern India. Potassium was applied in the top 15 cm layer of soil column at 30 and 60 mg K kg^-1 through different sources having different accompanying anions (Cl^-, SO₄^2-, NO₃^- and H₂PO₄^-). Maximum K was retained in the top 0--15 cm layer with a sharp decrease in K content occurring in 15--30 cm layer of the soil column. The trend was similar for both levels of applied K as well as frequency of leaching and soil type. The decrease of K content in soil column after four leaching events was maximum in case of Khanaura sandy loam, while only minor decrease was observed in Hundowal clay loam when K was applied at 60 mg K kg^-1, indicating higher potential of clay rich soil to adsorb K. In general, the K leaching in presence of the accompanying anions followed the order of SO₄^2- ≤ H₂PO₄^2- < NO₃^- = Cl^-. Highest 1 mol L^-1 CH3COONH4-extractable K was retained when K was applied along with SO42- and H2PO4- anions, and the least was retained when accompanying anion was Cl^-1. The influence of anions was more pronounced in the light textured soil and at high amounts of K application. Higher levels of K application resulted in higher losses of K, especially in sandy loam soil as observed from the leachate concentration. Among the different K sources, the maximum amount of K leaching was noticed in the soil column amended with KCl. After four leachings, the maximum amount of K leached out was 6.40 mg L^-1 in Hundowal clay loam and 9.29 mg L^-1 in Khanaura sandy loam at 60 mg K kg^-1 of soil application through KCl. These concentrations were lower than the recommended guideline of the World Health Organisation (12.00 mg L^-1).     

Metsulfuron methyl sorption-desorption in field-moist soils

Pesticide sorption coefficients (K(d)) are generally obtained using batch slurry methods. As a consequence, the results may not adequately reflect sorption processes in field-moist or unsaturated soil. The objective of this study was to determine sorption of metsulfuron methyl, a weak acid, in field-moist soils. Experiments were performed using low density (i.e., 0.3 g mL(-)(1)) supercritical fluid carbon dioxide (SF-CO(2)) to convert anionic metsulfuron methyl to the molecular species and remove it from the soil water phase only, thus allowing calculation of sorption coefficients (K(d)) at low water contents. K(d) values for sorption of the metsulfuron methyl molecular species on sandy loam, silt loam, and clay loam soil at 11% water content were 120, 180, and 320 mL g(-)(1), respectively. Using neutral species K(d) values, the pK(a) of metsulfuron methyl, and the pH of the soil, we could successfully predict the K(d) values obtained using the batch slurry technique, which typically has a predominance of anionic species in solution during the sorption characterization. This application of supercritical fluid extraction to determine sorption coefficients, combined with sulfonylureas' pK(a) values and the soil pH, will provide an easy method to predict sorption in soil at different pH levels.     

Characterization of nicosulfuron availability in aged soils

Sorption-desorption interactions of pesticides with soil determine their availability for transport, plant uptake, and microbial degradation. These interactions are affected by the physical-chemical properties of the pesticide and soil, and for some pesticides, their residence time in the soil. This research evaluated changes in sorption/availability of nicosulfuron (2-[[[[(4,6-dimethoxy-2-pyrimidinyl]amino]carbonyl]amino]sulfonyl]-N,N-dimethyl-3-pyridinecarboxamide) herbicide with aging in different soils, using a radiolabeled ((14)C) tracer. Aging significantly increased sorption. For instance, after the 41-day incubation, calculated K d,app increased by a factor of 2 to 3 in Mollisols from the Midwestern United States and by a factor of 5 to 9 in Oxisols from Brazil and Hawaii, as compared to freshly treated soils. In view of this outcome, potential transport of nicosulfuron would be overpredicted if freshly treated soil K d values were used to predict transport. The fact that the nicosulfuron solution concentration decreased faster than the soil concentration with time suggested that the increase in sorption was because the rate of degradation in solution and on labile sites was faster than the rate of desorption of the neutral species from the soil particles. It may have also been due to nicosulfuron anion diffusion to less accessible sites with time, leaving the more strongly bound neutral molecules for the sorption characterization. Regardless of the mechanism, these results are further evidence that increases in sorption during pesticide aging should be taken into account during the characterization of the sorption process for mathematical models of pesticide degradation and transport.     

A potential method to incorporate quantity/intensity into routine soil test interpretations

Abstract

Exchangeable potassium (K), extracted with 1M ammonium acetate, widely used as the measure for plant available K does not estimate the K supplying capacity of the soil. This research was undertaken to quantity the K supplying capacities of some Missouri soils and evaluate a modified K Quantity‐Intensity (Q/I) approach for adaptation into routine soil analysis. The K supplying capacities as analyzed by the modified Q/I and plant removal were measured on the 0–20 cm and 20–40 cm depths of Broseley loamy fine sand (loamy, mixed, thermic Arenic Hapludalf), Mexico silt loam, (fine, montmorillonitic, mesic Udollic Ochraqualf), Waldron clay loam [fine, montmorillonitic (calcareous) mesic Arenic Fluvaquemt] and the 0–20 cm of Sharkey clay (very fine, montmorillonitic, nonacid, thermic Vertic Haplaquet). The dominant clays in the clay fractions were identified by X‐ray diffraction to be composed of montmorillonite and illite. The high linear coefficient of correlation (R₂ = 0.92**) between the potassium buffer capacity index (KBC Index) and cation exchange capacity [CEC, sum of exchangeable Ca, Mg, K, Na, and Neutralizable Acidity (NA)] suggests that KBC Index of soils with similar clay mineral compositions, but different clay quantities, could be estimated from the measured CEC. Plant K uptake was highly linearly correlated with K quantity (Kq, R₂ =0.98**) as measured by the modified Kq/i method. It appears to be possible, using the KBC Index derived from the CEC, to calculate a Kq/i value with a single measurement of the K in equilibrium with 0.01 M CaCl₂. With the modified Kq/i method, and using this approach, a total plant available K model is presented. This modified Kq/i approach offers the opportunity for soil testing laboratories to complete a calculation for total plant available K with only one additional measurement of the equilibrium K in 0.01 M CaCl2. This would facilitate the fine tuning of soil test interpretation by basing K fertilizer recommendations on the quantity of plant‐available K in the soil.     

石灰土壤原状土柱上硼和锌的迁移

Leaching of boron （B） and zinc （Zn） can be significant in some pedomorphic conditions, which can cause contamination of shallow groundwater and economic losses. Boron and Zn adsorption and transport was studied using 8.4 cm diameter × 28 cm long intact columns from two calcareous soil series with differing clay contents and vadose zone structures： Lyallpur soil series, clay loam （fine-silty, mixed, hyperthermic Ustalfic Haplargid）, and Sultanpur soil series, sandy loam （coarse-silty, mixed, hyperthermic Ustollic Camborthid）. The adsorption isotherms were developed by equilibrating soil with 0.01 tool L^-1 CaCl2 aqueous solution containing varying amounts of B and Zn and were fitted to the Langmuir equation. The B and Zn breakthrough curves were fitted to the two-domain convective-dispersive equation. At the end of the leaching experiment, 0.11 L 10 g L^-1 blue dye solution was also applied to each column to mark the flow paths. The Lyallpur soil columns had a slightly greater adsorption partition coefficient both for B and Zn than the Sultanpur soil columns. In the Lyallpur soil columns, B arrival was immediate but the peak concentration ratio （the concentration in solution at equilibrium/concentration applied） was lower than that in the Sultanpur soil columns. The breakthrough of B in the Sultanpur soil columns occurred after about 10 cm of cumulative drainage in both the columns; the rise in effluent concentration was fast and the peak concentration ratio was almost 1. Zinc leaching through the soil columns was very limited as only one column from the Lyallpur soil series showed Zn breakthrough in the effluent where the peak concentration ratio was only 0.05. This study demonstrates the effect of soil structure on B transport and has implications for the nutrient management in field soils.     

丁吡吗啉在土壤中的吸附及淋溶特性

化学农药在土壤中的吸附和淋溶特性是评价其环境行为的重要指标,也是新农药登记必须提供的环境影响资料。本文分别采用振荡平衡法、土壤薄层层析法和土柱淋溶法研究了丁吡吗啉在不同土壤中的吸附和淋溶特性。结果表明,丁吡吗啉在3种供试土壤上的吸附规律可以较好地用FreundLich方程描述,吸附常数Kd在10.42~37.72mL.g-1之间,在砂土中较难被吸附,在壤土和粘土中属中等吸附。丁吡吗啉在3种供试土壤中不易移动或不移动,3种土柱淋溶试验的结论均为难淋溶。根据综合试验结果,对相关影响因素进行了讨论,认为影响丁吡吗啉在土壤中吸附性的主要因素为土壤有机质含量和土壤粘粒含量,影响淋溶特性的主要因素为土壤吸附和丁吡吗啉在水中的溶解度。     

Linuron sorption-desorption in field-moist soils

Pesticide sorption or binding to soil is traditionally characterized using batch slurry techniques. The objective of this study was to determine linuron sorption in field-moist or unsaturated soils. Experiments were performed using low-density (i.e., 0.25 g mL(-)(1)) supercritical carbon dioxide to remove linuron from the soil water phase, thus allowing calculation of sorption coefficients (K(d)) at low water contents. Both soil water content and temperature influenced sorption. K(d) values increased with increased water content, if less than saturated. K(d) values decreased with increased temperature. K(d) values for linuron sorption on silty clay and sandy loam soils at 12% water content and 40 degrees C were 3.9 and 7.0 mL g(-)(1), respectively. Isosteric heats of sorption (DeltaH(i)) were -41 and -35 kJ mol(-)(1) for the silty clay and sandy loam soils, respectively. The sorption coefficient obtained using the batch method was comparable (K(f) for sandy loam soil = 7. 9 microg(1)(-)(1/)(n)() mL(1/)(n)() g(-)(1)) to that obtained using the SFE technique. On the basis of these results, pesticide sorption as a function of water content must be known to more accurately predict pesticide transport through soils.     

Lysimeter experiment to investigate the potential influence of diffusion-limited sorption on pesticide availability for leaching

Pesticide leaching from soil has been shown to decrease with increasing time from application to irrigation. It is hypothesized that the availability of compounds for leaching decreases due to diffusion and sorption inside soil aggregates. Previous work showed that pesticide sorption inside soil aggregates increases significantly during the first days after application. The study presented here tested if diffusion into aggregates could explain the leaching of four aged pesticides from manually irrigated soil cores. Azoxystrobin, chlorotoluron, cyanazine, and bentazone were applied to 30 undisturbed cores (25 cm long, 23.7 cm diameter) from a clay loam soil. The soil cores were irrigated 1, 3, 7, 14, and 28 days after application. Leachate was collected and analyzed. The amount of pesticide found in leachate decreased rapidly with time from application. Pesticide losses in leachate declined 2.5-27 times faster than total residues in soil. The decline was 4-5 times faster for the more strongly sorbed pesticides (azoxystrobin, chlorotoluron, and cyanazine) than for bentazone. In previous work, we derived a model to describe sorption and diffusion of the pesticides in small aggregates from the same soil. The diffusion model was used here to describe sorption inside the large aggregates in the soil cores and extended to describe pesticide leaching by interaggregate flow. The model showed a significant decline in leaching with time from application, which supports the theory that diffusion-limited sorption in aggregates influences the availability for pesticide leaching, although it does not exclude alternative explanations for this decline. The model well described the decline in leaching for three out of four pesticides. The interaggregate transport model could, however, not account for the amount of preferential flow in the cores and underestimated the leaching of bentazone.