Sorptive interactions of pesticides in soils treated with modified humic acids

Different structural changes in peat humic acid (HA) were induced through treatments leading to chemical derivatization and/or the removal of functional groups. Eleven humic products were obtained after acetylation, amidation, ammonia fixation, methylation, nitration, oximation, sulphonation, selective degradations and ‘fixation’ of stearic acid. The sorption of 12 pesticides (alachlor, atrazine, carbofuran, 2,4-D, 2,4-DB, methyl parathion, metoxuron, monouron, prometryne, propanil, fenoprop and chloranil) on the above products was determined by ultraviolet derivatographic spectroscopy. In addition, pesticide sorption was evaluated on samples from neutral and calcic soils treated with the corresponding potassium humates. The most intense interactions occurred in samples from the neutral plot, whereas the greatest effect of the humic matter in enhancing pesticide sorption was found with the calcic soil. As expected, the sorption patterns in HA-pesticide systems were poorly correlated with those in soil-HA-pesticide systems. In the former case, the sorption performance was influenced mainly by hydrophobic interactions, whereas in the latter it depended on the participation of multiple parameters suggesting that the molecular volume and the van der Waals energy of the pesticide molecule play a chief role. The HA characteristics most frequently correlated with pesticide sorption were those connected with the aromatic/aliphatic ratio and the particle size. In the calcic-soil-HA-pesticide systems, the base saturation of the exchange complex correlated negatively with pesticide sorption.     

An evaluation of methods for measurement of pesticides in sorption experiments

Abstract

The concentration of four pesticides (2,4‐D, atrazine, phorate, and terbufos) in soil solution during sorption experiments was measured using UV spectrophotometry, Gas Liquid Chromatography (GLC), High Performance Liquid Chromatography (HPLC), and radiotracer technique. The presence of water soluble organic matter in soil solution interfered with the measurement of pesticide using the UV spectrophotometry. The use of GLC, HPLC, and radiotracer technique involving ¹⁴C gave a good estimate of the concentration of pesticide in soil solution. The pesticide remaining in soil can be quantitatively analyzed by extracting with a scintillation solution containing an organic solvent such as toluene or dioxane. Among the various centrifuge tubes glass tubes with Teflon caps sorbed negligible amount of pesticides and these tubes can be used for the sorption measurements.     

Adsorption-desorption studies of selected herbicides in soil-Fly ash mixtures

Fly ash and soil mixtures with a range of fly ash content from 0 to 100% were used to study the adsorption and desorption of herbicides atrazine, propazine, prometryne, propanil, and molinate in batch experiments. The isotherms shapes according to Giles classification (Giles et al., 1960) were S, L, and H as the substrate changed from sandy clay loam (SCL) to fly ash, depending on the percent of fly ash in the mixture. The adsorption isotherms fit the Freundlich equation x/m = K(f) C(1/)(n)(). The K(f) values increase with the increase of the fly ash content. The mean percent amounts of herbicides, for a range of concentration 1-20 mg L(-)(1), adsorbed on the soil were 21.9% for atrazine, 50.7% for propazine, 29.04% for prometryne, 43.14% for molinate, 31.35% for propachlor, and 46.34% for propanil. Mass balance estimations show that the adsorbed amounts of the herbicides increase along with the fly ash content in the sorbent mixture and reach the 99% in the "pure" fly ash. In contrast, the amounts desorbed with water decrease as the fly ash content increases. The n values ranged from 0.82 to 3.05 indicating that the carbon content of fly ash plays a significant role during the sorption process and an increase of heterogenity of solid substrate. The increase of the amounts desorbed with acetone indicates that the sorption of organic compounds onto fly ash is believed to occur principally via the weak induction forces of London or dispersion forces which are characteristic of the physical adsorption process. The results of this research demonstrate that the fly ash shows a significant capacity for adsorption of organic compounds from aqueous solution.     

Impact of tillage on microbial activity and the fate of pesticides in the upper soil

The impact of two tillage systems, plow tillage (PT) and no-tillage (NT), on microbial activity and the fate of pesticides in the 0–5 cm soil layer were studied. The insecticides carbofuran and diazinon, and the herbicides atrazine and metolachlor were used in the study, which included the incubation and leaching of pesticides from untreated soils and soils in which microorganisms had been inhibited. The mineralization of ring¹⁴C labeled pesticides was studied. The study differentiated between biotic and abiotic processes that determine the fate of pesticides in the soil. Higher leaching rates of pesticides from PT soils are explaned by the relative importance of each of these processes. In NT soils, higher microbial populations and activity were associated with higher mineralization rates of atrazine, diazinon and carbofuran. Enhanced transformation rates played an important role in minimizing the leaching of metolachlor and carbofuran from NT soils. The role of abiotic adsorption/retention was important in minimizing the leaching of metolachlor, carbofuran and atrazine from NT soils. The role of fungi and bacteria in the biodegradation process was studied by selective inhibition techniques. Synergistic effects between fungi and bacteria in the degradation of atrazine and diazinon were observed. Carbofuran was also degraded in the soils where fungi were selectively inhibited. Possible mechanisms for enhanced biodegradation and decreased mobility of these pesticides in the upper layer of NT soils are discussed.     

Degradation of [carboxyl-14C] 2,4-D and [ring-U-14C] 2,4-D in 114 agricultural soils as affected by soil organic carbon content

This study compared the degradation of [carboxyl-¹⁴C] 2,4-dichlorophenoxyacetic acid (2,4-D) (C2,4-D) and [ring-U-¹⁴C] 2,4-D (R2,4-D) in 114 agricultural soils (0–15 cm) as affected by 2,4-D sorption and soil properties (organic carbon content, pH, clay content, carbonate content, cation exchange capacity, total microbial activity). The sample area was confined to Alberta, Canada, located 49–60° north longitude and 110–120° west latitude and soils were grouped by soil organic carbon content (SOC) (0–0.99%, 1–1.99%, 2–2.99%, 3–3.99% and >4% SOC). Degradation rates of C2,4-D and R2,4-D followed first-order kinetics in all soils. Although total microbial activity increased with increasing SOC, degradation rates and total degradation of C2,4-D and R2,4-D decreased with increasing SOC because of increased sorption of 2,4-D by soil and reduced bioavailability of 2,4-D and its metabolites. Rates of R2,4-D degradation were more limited by sorption than rates of C2,4-D degradation, possibly because of greater sorption and formation of bound residues of 2,4-D metabolites relative to the 2,4-D parent molecule. Based on the sorption and degradation parameters quantified, there were two distinct groups of soils, those with less than 1% SOC and those with greater than 1% SOC. Specifically, soils with less than 1% SOC had, on average, 2.4 times smaller soil organic carbon sorption coefficients and 1.4 times smaller 2,4-D half-lives than soils with more than 1% SOC. In regional scale model simulations of pesticide leaching to groundwater, covering many soils, input parameters for each pesticide include a single soil organic carbon sorption coefficient and single half-life value. Our results imply, however, that the approach to these regional scale assessments could be improved by adjusting the values of these two input parameters according to SOC. Specifically, this study indicates that for 2,4-D and Alberta soils containing less than 1% SOC, the 2,4-D pesticide parameters obtained from generic databases should be divided by 2.5 (soil organic carbon sorption coefficient) and 1.5 (half-life value).     

Dissolved organic matter enhances the sorption of atrazine by soil

The influence of dissolved organic matter (DOM) on the sorption of atrazine (2-chloro-4-ethylamino-6-isopylamino-1,3,5-triazine) by ten soils was investigated. Batch sorption isotherm techniques were used to evaluate the important physiochemical properties of soil determining the sorption of atrazine in the presence of DOM. The sorption of atrazine as a representative of nonionic organic contaminants (NOCs) by soil with and without DOM could be well described by the Linear and Freundlich models. The n values of the Freundlich model were generally near to 1, indicating that linear partitioning was the major mechanism of atrazine sorption by soil samples. The apparent distribution coefficient, value, for atrazine sorption in the presence of DOM initially increased and decreased thereafter as the DOM concentration increased in the equilibrium solution. DOM at relatively lower concentrations significantly enhanced the sorption of atrazine by soil, while it inhibited the atrazine sorption at higher concentrations. For all the soil samples, the maximum of was 1.1~3.1 times higher than its corresponding K _d value for the control (without DOM). The maximum enhancement of the distribution coefficient () in the presence of DOM was negatively correlated with the content of soil organic carbon (SOC) and positively correlated with the clay content. The critical concentration of DOM, below which DOM would enhance atrazine sorption, was negatively correlated with SOC. The influence of DOM on atrazine sorption could be approximately considered as the net effect of the cumulative sorption and association of atrazine with DOM in solution. Results of this study provide an insight into the retention and mobility of a NOC in the soil environment.     

Molecular approaches to investigate herbicide-induced bacterial community changes in soil microcosms

Since biochemical and microbiological methods used to study microbial community changes induced by anthropogenic activities can be biased, the impact of two herbicides on soil microorganisms was investigated by culture-independent molecular techniques. The effect of three different amounts (the recommended field dose, tenfold, and 100-fold the dose) of propanil or prometryne on the bacterial community of a clay soil, two modalities of incubation (soil moisture at 70% of the field capacity and a soil-herbicide suspension, 1:10, w:v), and time of incubation were investigated by denaturing gradient gel electrophoresis (DGGE) and amplified rDNA restriction analysis (ARDRA). Two sets of primers for 16S rDNA were used to amplify total soil DNA. Sterile and non-sterile samples were used to determine, by HPLC, the amounts of herbicides adsorbed on soil and transformed by soil microorganisms. Prometryne persisted in soil longer than propanil. Propanil was removed significantly more by non-sterile than by sterile samples, while for prometryne, slight differences were observed. 3,4-Dichloroaniline, a product of propanil hydrolysis, was detected in non-sterile samples and increased with incubation time. Propanil did not affect soil bacteria significantly as indicated by DGGE and ARDRA, with the only exception being the soil-herbicide suspension. Despite a lower utilization of prometryne by soil microorganisms, DGGE analysis showed a more diverse banding than with propanil. Some bands were also detected in the DNA sample extracted from the soil-prometryne suspension, and could be representative of bacterial species utilizing the herbicide as a carbon source, in two very different soil microcosms.     

Factors influencing degradation of pesticides in soil

Degradation and sorption of six acidic pesticides (2,4-D, dicamba, fluroxypyr, fluazifop-P, metsulfuron-methyl, and flupyrsulfuron-methyl) and four basic pesticides (metribuzin, terbutryn, pirimicarb, and fenpropimorph) were determined in nine temperate soils. Results were submitted to statistical analyses against a wide range of soil and pesticide properties to (i) identify any commonalities in factors influencing rate of degradation and (ii) determine whether there was any link between sorption and degradation processes for the compounds and soils studied. There were some marked differences between the soils in their ability to degrade the different pesticides. The parameters selected to explain variations in degradation rates depended on the soil-pesticide combination. The lack of consistent behavior renders a global approach to prediction of degradation unrealistic. The soil organic carbon content generally had a positive influence on degradation. The relationship between pH and degradation rates depended on the dominant mode of degradation for each pesticide. There were positive relationships between sorption and rate of degradation for metsulfuron-methyl, pirimicarb, and all acidic pesticides considered together (all P < 0.001) and for dicamba and all bases considered together (P < 0.05). No relationship between these processes was observed for the remaining seven individual pesticides.     

Natural soil colloids To retard simazine and 2,4-D leaching in soil

Natural or synthetic sorbents for pesticides can be used to reduce contamination of soils and natural waters. The sorption of simazine and 2,4-D on montmorillonite minerals has been studied and their potential use to retard pesticide leaching in soil evaluated. Simazine and 2,4-D did not sorb on high-layer charge montmorillonite, whereas sorption on the lower layer charge montmorillonite SWy varied depending on the saturating cation. Simazine sorption increased in the order Ca(2+)SWy < K(+)SWy < Fe(3+)SWy. Simazine molecules sorb on hydrophobic microsites of the montmorillonite. Once protonated, further sorption through cation exchange takes place in the interlamellar space of the montmorillonite, as corroborated by X-ray diffraction and FT-IR studies. 2,4-D does not sorb on K(+)SWy or Ca(2+)SWy, but does sorb on Fe(3+)SWy, because the acidic character of this sorbent allows the molecular form of 2, 4-D to sorb by hydrogen bonding and/or by hydrophobic interactions. Leaching experiments in hand-packed soil columns indicate that simazine and 2,4-D application as a complex with FeSWy renders later breakthrough and lower maximum concentration peaks, and the total herbicide leached is lower than when applied as the pure analytical grade compound. These results suggest the possible use of natural soil colloids as sorbents for herbicides such as simazine and 2,4-D to retard pesticide leaching in soil, thus reducing their ground water contamination potential.     

Humic acid and biochar as specific sorbents of pesticides

Purpose

The aim of the research was to compare the effect of two types of organic sorbents—humic acid (HA) and biochar (BC)—in sorption-desorption processes of different polar pesticides, which residues are commonly present in arable soils and are potentially harmful for the environment. It also aims to advance the understanding of behavior of both ionizable and nonionizable pesticides in the presence of BC and HA in soils.

Materials and methods

Three different classes of pesticides were investigated: carbamates (carbaryl and carbofuran), phenoxyacetic acids (2,4-dichlorophenoxyacetic acid (2,4-D) and 4-chloro-2-methylphenoxyacetic acid (MCPA)), and aniline derivatives (metolachlor). Investigated humic acid was extracted by Shnitzer’s method from topsoil horizon of arable Gleyic Phaeozem. Biochar was produced from wheat straw in gasification process at 550 °C, remaining 30 s in the reactor. To obtain the experimental goal structural properties of both sorbents were determined and sorption-desorption experiments conducted. To the investigated organic matter samples (HA or BC), 10 or 15 mg L^?1 pesticide solutions in 10 mM CaCl₂ were added and the mixtures were shaken for 24 h. Afterwards, the samples were centrifuged and supernatants analyzed by LC-MS/MS for the pesticide content. Analogous experiment was performed for desorption studies (samples refilled with 10 mM CaCl₂).

Results and discussion

Humic acids exhibited strong affinity for the ionic substances, for which high-percentage uptake (74.6 and 67.9% initial dose of 2,4-D and MCPA, respectively) was obtained. Retention of nonionic carbamates on HA was much weaker (35.4% of carbofuran and 10.2% of carbaryl sorbed). Sorption of carbamates to BC was significantly reduced (76.4–84.3%) by the alkaline hydrolysis. Metolachlor was bound comparably strong both by HA (72.9%) and BC (70.2%), although different mechanisms governed its sorption. Noticeable desorption occurred only in the case of 2,4-D bound to HA (over 50%), whereas other studied compounds were released from HA within the range of 4.4–10.8% of the dose sorbed. Oppositely to HA, desorption of all studied pesticides from BC was completely inhibited, except for 2,4-D (3.7% desorbed).

Conclusions

Investigated humic acid has high affinity to polar, ionic pesticides of high water solubility, which are sorbed via specific interactions with HA functional groups. Studied biochar, due to its moderately hydrophobic character, preferentially attracts nonionic pesticides of relatively high logP values and low water solubility. Hydrophobic bonding is postulated as a main mechanism of their attraction to BC. Besides sorbent structural properties, pH is the main factor governing sorption equilibria in the studied mixtures.

     

Pesticides and nitrogen fixation in a paddy soil

The influence of six pesticides, applied singly or in combination, on ¹⁵N₂ incorporation and C₂H₂ reduction in a submerged paddy soil was studied under laboratory conditions. While the application of diazinon had no marked effect, benomyl, carbofuran, parathion, nitrofen and γ-HCH, at concentrations close to recommended field application rates (5μg ^?1) significantly stimulated N₂ fixation. Synergistic stimulatory effects of the pesticides on N₂ fixation were evident particularly in combinations of carbofuran with benomyl, nitrofen and γ-HCH. On the contrary, diazinon slightly retarded the stimulatory effect of benomyl and carbofuran. Results indicated that the differential effects of pesticides on N₂ fixation could be attributed partly to fluctuations in the population of certain groups of N₂ fixers in submerged soil.     

Sorption of atrazine, 2,4‐D,nitrobenzene and pentachlorophenol by urban and industrial wastes

This study was carried out to investigate the sorption properties of man‐made soil developed from sewage sludge, municipal wastes, brick and mortar debris, harbour sludge, sand fills, fly ash, and wastes from coking plants and coal mines. The composition of organic matter in the samples was analysed, and the sorption isotherms of four reference chemicals (nitrobenzene, atrazine, 2,4‐D, pentachlorophenol) were determined. Fly ash, which contains up to 89% of its carbon as Black Carbon, showed a strong affinity to all four chemicals. For the other waste materials, a strong correlation between the logarithm of the Freundlich adsorption constant, K_f, and the logarithm of organic carbon, C_o, was established (r = 0.85–0.96). This holds for the non‐ionic nitrobenzene and also, within a certain pH range depending on the pK_a of the compound, for the three ionizable organic compounds (atrazine: pH > 4; 2,4‐D: pH > 5; PCP: pH > 6). At pH near the pK_a value the sorption is sensitive to pH. There were no statistically significant differences between the waste materials and the natural soils in the relations between logK_f and logC_o for either ionic or non‐ionic chemicals. This result suggests that the method devised for estimating the sorption of organic chemicals in natural soils based on their content of organic carbon is equally valuable for the waste materials, with the exception of fly ash which contains a large amount of Black Carbon.     

Seasonal pattern of total soil respiration in undisturbed and disturbed ecosystems of Central Himalaya

Summary The rates of CO₂ efflux were measured by an alkali absorption method (using 20 ml 0.5 N NaOH) from soils in four undisturbed sites [two evergreen oak forests, Quercus floribunda Lindl. (tilonj oak), Quercus leucotrichophora A Camus (banj oak), and two evergreen conifer forests, Cedrus deodara Loud. (deodar forest) and Pinus roxburghii Sarg. (chir pine forest)] and three disturbed sites. The sites were located between elevations of 1850 and 2360 m in the Central Himalaya. The seasonal pattern of soil respiration was similar in all the sites with a maximum during the rainy season, intermediate rates during the summer season and the lowest level of activity in winter. The rate of CO₂ efflux was higher in broadleaf than in conifer forests, and it was lowest in the disturbed sites. Among the edaphic conditions, soil moisture, N, organic C, pH, soil porosity, and root biomass positively affected total soil respiration. The proportion of root respiration to total soil respiration was higher in the disturbed sites than the undisturbed sites in winter. Conditions in the winter season were less favourable for microbial respiration than for root respiration.     

Pesticide adsorptivity of aged particulate matter arising from crop residue burns

Particulates (ashes) arising from the burning of crop residues are potentially effective adsorbents for pesticides in agricultural soils. To determine the long-term adsorptive sustainability of ashes, a wheat (Triticum aestivum L.) ash was aged under environmentally relevant conditions (in CaCl(2) solution at room temperature and pH 7) in soil extract for 1 month and in a soil (1% ash) for a period of up to 12 months. The aged ash and ash-amended soil were used to sorb diuron from water. The diuron sorption was also measured in the presence of atrazine as a competing pesticide. There was no observed microbial impact on the stability of the wheat ash in soil. All isotherms with the ash were nonlinear type-I curves, suggestive of the surface adsorption. On a unit mass basis, the ash in soil extract was 600-10000 times more effective than the soil in sorbing diuron. Adsorption of dissolved soil organic matter (DOM) during aging on the ash surfaces reduced the diuron adsorption by 50-60%. Surface competition from the atrazine adsorption also reduced the ash adsorption of diuron by 10-30%. A total of 55-67% reduction in diuron sorption by the ash-amended soil was observed. Due to its high initial adsorptivity, the ash fraction of the aged ash-amended soil contributed >50% to the total diuron sorption. Thus, the wheat ash aged in the soil remained highly effective in adsorbing diuron. As crop residues are frequently burned in the field, pesticides in agricultural soils may be highly immobilized due to the presence of ashes.     

Potential contributions of smectite clays and organic matter to pesticide retention in soils.

Soil organic matter (SOM) is often considered the dominant sorptive phase for organic contaminants and pesticides in soil-water systems. This is evidenced by the widespread use of organic-matter-normalized sorption coefficients (K(OM)) to predict soil-water distribution of pesticides, an approach that ignores the potential contribution of soil minerals to sorption. To gain additional perspective on the potential contributions of clays and SOM to pesticide retention in soils, we measured sorption of seven pesticides by a K-saturated reference smectite clay (SWy-2) and SOM (represented by a muck soil). In addition, we measured the adsorption of atrazine by five different K-saturated smectites and Ca-saturated SWy-2. On a unit mass basis, the K-SWy-2 clay was a more effective sorbent than SOM for 4,6-dinitro-o-cresol (DNOC), dichlobenil, and carbaryl of the seven pesticides evaluated, of which, DNOC was sorbed to the greatest extent. Atrazine was sorbed to a similar extent by K-SWy-2 and SOM. Parathion, diuron, and biphenyl were sorbed to a greater extent by SOM than by K-SWy-2. Atrazine was adsorbed by Ca-SWy-2 to a much lesser extent than by K-SWy-2. This appears to be related to the larger hydration sphere of Ca(2+) (compared to that of K(+)) which shrinks the effective size of the adsorption domains between exchangeable cations, and which expands the clay layers beyond the apparently optimal spacing of approximately 12.2 A for sorption of aromatic pesticide structures. Although a simple relation between atrazine adsorption by different K-smectites and charge properties of clay was not observed, the highest charge clay was the least effective sorbent; a higher charge density would result in a loss of adsorption domains. These results indicate that for certain pesticides, expandable soil clays have the potential to be an equal or dominant sorptive phase when compared to SOM for pesticide retention in soil.     

Sorption and desorption of non-ionic herbicides onto particulate organic matter from surface soils under different land uses

In vegetative filter strips used to intercept pesticides present in run‐off, particulate organic matter derived from the vegetation plays an important function in pesticide sorption processes, because it accumulates at the soil surface and quickly responds to changes in land use. Two herbicides with contrasted properties: isoproturon, moderately hydrophobic (log K_ow= 2.5), diflufenican, strongly hydrophobic (log K_ow= 4.9), and isopropylaniline, a metabolite of isoproturon, were used to characterize the sorption and desorption properties of POM originating from soils under three different land uses: a cropped plot under conventional wheat/maize rotation, an adjacent 10‐year‐old grassed strip and a nearby 80‐year‐old oak/chestnut forest. Chemical structural composition information obtained from solid‐state ¹³C CPMAS NMR and estimation of hydrophobicity from contact angle measurements were used to explain the different sorption capacities of POM according to their size and origins. Sorption of isoproturon and diflufenican increased with hydrophobicity of POM, which was greater in the forest soil. Aromaticity of POM was positively correlated to sorption coefficients (K_oc). Desorption of the more hydrophobic compounds, diflufenican and isopropylaniline was weak for all POM fractions, regardless of their origin and size. On the other hand, desorption of isoproturon depended on land use and POM characteristics. The sorption capacities of POM were not only controlled by their chemical composition, but also by their size, due to a greater number of sorptive sites related to a greater surface area with decreasing particle‐size.     

Pesticides and heterotrophic nitrogen fixation in paddy soils

The effect of three pesticides, benomyl, carbofuran and gamm-BHC at 5 parts 10⁶, rates equivalent to recommended field levels, on the heterotrophic N₂ fixation in five air-dried, cellulose-amended, submerged tropical soils was invevstigated employing ¹⁵N tracer technique under laboratory conditions. Addition of benomyl, a carbamate fungicide, to alluvial, laterite and two acid sulphate soils resulted in significant increases in N₂ fixation, while carbofuran, a methylcarbamate insecticide, exerted a stimulatory effect on N₂ fixation in alluvial, alterite and acid saline soils. Gamma-BHC, a chlorinated hydrocarbon insecticide, stimulated N₂ fixation in alluvial and acid sulphate pokkali solis, while considerable inhibition of N₂ fixation was evident inother soils. Results showed differential responses of specific groups of N₂-fixing organisms to the pesticides depending ont he soil type.     

农田尺度降雨入渗—重分布条件下阿特拉津在非饱和土壤中淋溶风险的评价

以农药阿特拉津为研究对象,通过在北京郊区一个面积为72 9m2 (2 7m×2 7m)的田间采集10 0个土壤样品,分别测定其主要理化特性,由土壤的机械组成和干容重测试数据,采用土壤传递函数生成了vanGenuchten型的水力学参数,并进一步间接计算得到阿特拉津运移的弥散度,同时,由实测的土壤有机碳含量估算了阿特拉津的吸附参数。在此基础上,根据柱模型假设,运用HYDRUS 1D软件,就所设计的由实际背景概化而来的降雨入渗—重分布算例,对阿特拉津在农田尺度非饱和土壤中的淋溶动态进行了数值模拟。结果表明:对一场雨量为90mm、雨强为30mmd-1的降雨,在连续3d降雨接着重分布2 0d的情况下,若忽略蒸散作用对土壤水分和阿特拉津运动的影响,则降雨入渗和降雨入渗—重分布过程结束时,通过土壤2 0cm耕层的阿特拉津的最大累积淋溶量分别占施用量的17.87%和75 .4 1% ;采样区域内阿特拉津淋溶通量的空间分布存在较大差异。所探明的阿特拉津易淋溶带,不仅为合理使用该农药、保护土壤环境提供了定量的依据,而且为预防该农药对浅层地下水的污染提供了重要的信息     

Prediction of atrazine sorption coefficients in soils using mid-infrared spectroscopy and partial least-squares analysis

This study explored the potential of mid-infrared spectroscopy (MIR) with partial least-squares (PLS) analysis to predict sorption coefficients (Kd) of pesticides in soil. The MIR technique has the advantage of being sensitive to both the content and the chemistry of soil organic matter and mineralogy, the important factors in the sorption of nonionic pesticides. MIR spectra and batch Kd values of atrazine were determined on a set of 31 soil samples as reference data for PLS calibration. The samples, with high variability in soil organic carbon content (SOC), were chosen from 10 southern Australian soil profiles (A1, A2, B, and C in one case). PLS calibrations, developed for the prediction of Kd from the MIR spectra and reference Kd data, were compared with predictions from Koc-based indirect estimation using SOC content. The reference Kd data for the 31 samples ranged from 0.31 to 5.48 L/kg, whereas Koc ranged from 30 to 680 L/kg. Both coefficients generally increased with total SOC content but showed a relatively poor coefficient of determination (R2 = 0.53; P > 0.0001) and a high standard error of prediction (SEP =1.22) for the prediction of Kd from Koc. This poor prediction suggested that total SOC content alone could explain only half of the variation in Kd. In contrast, the regression plot of PLS predicted versus measured Kd resulted in an improved correlation, with R2 = 0.72 ( P > 0.0001) and standard error of cross-validation (SECV) = 0.63 for three PLS factors. With the advantages of MIR-PLS in mind, (i) more accurate prediction of Kd, (ii) an ability to reflect the nature and content of SOC as well as mineralogy, and (iii) high repeatability and throughput, it is proposed that MIR-PLS has the potential for an improved and rapid assessment of pesticide sorption in soils.     

Adsorption von Pflanzenschutzmitteln und DOC an Saugkerzen aus Glas und Keramik

Sorption of pesticides and DOC on glass and ceramic suction cups Suction cups are widely used for the sampling of soil solution. Due to sorption and desorption processes the concentration of dissolved substances in the samples may vary considerably depending on the material of the suction cups. In order to minimize these losses, a new glass suction cup was developed. In laboratory studies, aqueous solutions of pesticides and DOC were percolated through both types of suction cups; the concentration of pesticides and DOC in the percolates was examined. The pesticides pendimethaline, terbuthylazine, metolachlor and chlortoluron were tested at concentrations of 2, 20, and 200 μg 1⁻¹. The average losses due to sorption by the suction cups were 10% (1.1—31%) for the ceramic cups and 3.1% (0—11%) for the glass cups. Sorption effects increased with increasing hydrophobicity of the pesticides and decreasing pesticide concentrations. Thus, at a concentration of 2 μg 1⁻¹ ceramic cups sorbed 31% of pendimethaline compared with 7.7% in the case of glass cups. Corresponding tests with soilborne DOC solutions yielded comparable results. Ceramic suction cups adsorbed up to 50% of the DOC input concentration, while glass cups retarded 2.4% on average. These results are especially noteworthy because soilborne dissolved organic substances are effective sorbents and carriers for pesticides. The new type of glass suction cups may help to improve the results of pesticide field studies and, in consequence, the assessment and prediction of the leaching behavior of pesticides.