Spatial distribution and characterization of long-term aged 14C-labeled atrazine residues in soil

The long-term behavior of the herbicide atrazine and its metabolites in the environment is of continued interest in terms of risk assessment and soil quality monitoring. Aqueous desorption, detection, and quantification of atrazine and its metabolites from an agriculturally used soil were performed 22 years after the last atrazine application. A lysimeter soil containing long-term aged atrazine for >20 years was subdivided into 10 and 5 cm layers (at the lysimeter bottom: soil 0-50 and 50-55 cm; fine gravel 55-60 cm depth, implemented for drainage purposes) to identify the qualitative and quantitative differences of aged (14)C-labeled atrazine residues depending on the soil profile and chemico-physical conditions of the individual soil layers. Deionized water was used for nonexhaustive cold water shaking extraction of the soil. With increasing soil depth, the amount of previously applied (14)C activity decreased significantly from 8.8% to 0.7% at 55-60 cm depth whereas the percentage of desorbed (14)C residues in each soil layer increased from 2% to 6% of the total (14)C activity in the sample. The only metabolite detectable by means of LC-MS/MS was 2-hydroxyatrazine while most of the residual (14)C activity was bound to the soil and was not desorbed. The amount of desorbed 2-hydroxyatrazine decreased with increasing soil depth from 21% to 10% of the total desorbed (14)C residue fraction. The amount of (14)C residues in the soil layers correlated well with the carbon content in the soil and in the aqueous soil extracts ( p value = 0.99 and 0.97, respectively), which may provide evidence of the binding behavior of the aged atrazine residues on soil carbon. The lowest coarse layer (55-60 cm) showed increased residual (14)C activity leading to the assumption that most (14)C residues were leached from the soil column over time.     

温和提取法评估老化前后土壤中菲的生物有效性

采用温和溶剂提取方法对不同老化时间土壤中的菲进行提取,研究了正丁醇、二氯甲烷、2-羟丙基-β-环糊精(2-Hydroxypropyl-beta cyclodextrin,HPCD)提取量与生物吸收之间的相关性。结果表明,温和有机溶剂(二氯甲烷、正丁醇)提取与温和HPCD提取法对菲的提取量与蚯蚓蓄积量有很好的相关性(p<0.05)。与其他温和试剂提取相比,温和正丁醇提取可以更好地预测菲在土壤中的生物有效性。     

Metabolism and persistence of atrazine in several field soils with different atrazine application histories

To assess the potential occurrence of accelerated herbicide degradation in soils, the mineralization and persistence of (14)C-labeled and nonlabeled atrazine was evaluated over 3 months in two soils from Belgium (BS, atrazine-treated 1973-2008; BC, nontreated) and two soils from Germany (CK, atrazine-treated 1986-1989; CM, nontreated). Prior to the experiment, accelerated solvent extraction of bulk field soils revealed atrazine (8.3 and 15.2 μg kg(-1)) in BS and CK soils and a number of metabolites directly after field sampling, even in BC and CM soils without previous atrazine treatment, by means of LC-MS/MS analyses. For atrazine degradation studies, all soils were incubated under different moisture conditions (50% maximum soil water-holding capacity (WHC(max))/slurried conditions). At the end of the incubation, the (14)C-atrazine mineralization was high in BS soil (81 and 83%) and also unexpectedly high in BC soil (40 and 81%), at 50% WHC(max) and slurried conditions, respectively. In CK soil, the (14)C-atrazine mineralization was higher (10 and 6%) than in CM soil (4.7 and 2.7%), but was not stimulated by slurried conditions. The results revealed that atrazine application history dramatically influences its degradation and mineralization. For the incubation period, the amount of extractable atrazine, composed of residues from freshly applied atrazine and residues from former field applications, remained significantly greater (statistical significance = 99.5 and 99.95%) for BS and CK soils, respectively, than the amount of extractable atrazine in the bulk field soils. This suggests that (i) mostly freshly applied atrazine is accessible for a complex microbial community, (ii) the applied atrazine is not completely mineralized and remains extractable even in adapted soils, and (iii) the microbial atrazine-mineralizing capacity strongly depends on atrazine application history and appears to be conserved on long time scales after the last application.     

Changes in the atrazine extractable residues in no-tilled Mollisols

The effect of application dose and soil organic matter (SOM) stratification on changes in atrazine (6-chloro-N²-ethyl-N⁴-isopropyl-1,3,5-triazine-2,4-diamine) extractable residues (ER) were investigated. Two soils [Entic Haplustoll (EH) and Typic Hapludoll (TH)] with contrasting SOM content and form and without previous atrazine exposure were selected. Sampling was carried out at two depths: 0–2 and 2–5 cm. Atrazine ER were measured at 0, 3, 7, 14, 28, and 56 days in laboratory incubation. Atrazine concentration recovered 1 h after of its application (C_t0) was used as an index of the soil capacity to reduce the atrazine extractable fraction. SOM stratification was studied by means of physical fractionation. In both soils, the higher OC concentration was found in the 200–2000 μm fraction (OC_{f 200–2000}). Soils differed in terms of the OC_f 50–200/OC_{f 200–2000} ratio. This ratio increased with depth in EH soil: 0.23 (0–2 cm) and 2.00 (2–5 cm). In TH soil, the ratio was 0.80 (0–2 cm) and 0.50 (2–5 cm). The t_1/2 values ranged from 9 to 19 days, depending on soil type and atrazine application dose. The upper layer C_t0 and k were higher for higher atrazine doses. Implementation of a split application dose of atrazine may be an effective alternative to extend its half-life in soil solution, as well as involving a lower potential risk of soil accumulation or vertical movement in the soil profile towards deep soil layers and groundwater.     

Adsorption-desorption of atrazine on four soils of Hyderabad

The adsorption-desorption equilibrium of atrazine (2-chloro, 4-ethylamino, 6-isopropyl amino-1, 3, 5 triazine) was studied by the batch equilibration method at 27 ± 1 °C on four soils of Hyderabad. Adsorption isotherms conformed to the Freundlich equation (A = KC^1/n ). K increased in the same order as the organic C content of the soils. Desorption studies were conducted by repeated replacement of 5 mL of the supernatant equilibrium solutions after adsorption, with 0.01 M CaCl₂. Desorption isotherms showed considerable hysteresis which was more prominent when the desorption was carried out with higher adsorbed concentration of atrazine. Desorption from the lowest level of adsorbed atrazine (3 to 5 μg g^?1 soil) was close to the adsorption isotherm. The cumulative desorption after four desorption steps covering five days was significantly different at the 1% level, for different initial adsorbed concentrations of atrazine. Desorption was significantly higher at the lowest adsorbed level of atrazine. The soils differed significantly at 6% level for desorption and the amount desorbed decreased in the inverse order of organic C. Desorption isotherms also conformed to Freundlich equation but K andn values were both higher than that for adsorption and increased with increase in initially adsorbed concentration of atrazine. Desorption thus confirmed the irreversible nature of the adsorption of atrazine on these soils. The quantitative factors and reasons for desorption are discussed.     

Degradation and binding of atrazine in surface and subsurface soils

Understanding the dissipation rates of chemicals in unsaturated and saturated zones of subsurface soils will help determine if reductions of concentrations to acceptable levels will occur. Chemical properties and microbial biomass and activity were determined for the surface (0-15 cm), lower root (50-105 cm), and vadose (175-220 cm) zones in a Huntington silty clay loam (Fluventic Hapludoll) collected from an agricultural field near Piketon, OH. The rates of sorption, mineralization, and transformation (formation of bound residues and metabolites) of atrazine were determined. Microbial activity was estimated from the mineralization of (14)C-benzoate. We observed decreased levels of nutrients (total organic carbon, N, and P) and microbial biomass with depth, while activity as measured with benzoate metabolism was higher in the vadose zone than in either the surface or the root zones. Sorption coefficients (K(f)) declined from 8.17 in the surface to 3.31 in the vadose zone. Sorption was positively correlated with organic C content. Rates of atrazine mineralization and bound residues formation were, respectively, 12-2.3-fold lower in the vadose than in the surface soil. Estimated half-lives of atrazine ranged from 77 to 101 days in the surface soil, but increased to over 900 days in the subsurface soils. The decreased dissipation of atrazine with increasing depth in the profile is the result of decreased microbial activity toward atrazine, measured either as total biomass or as populations of atrazine-degrading microorganisms. The combination of reduced dissipation and low sorption indicates that there is potential for atrazine movement in the subsurface soils.     

Glufosinate and ammonium sulfate inhibit atrazine degradation in adapted soils

The co-application of glufosinate with nitrogen fertilizers may alter atrazine cometabolism, thereby extending the herbicide’s residual weed control in adapted soils. The objective of this study was to assess the effects of glufosinate, ammonium sulfate, and the combination of glufosinate and ammonium sulfate on atrazine mineralization in a Dundee silt loam exhibiting enhanced atrazine degradation. Application of glufosinate at rates of 10 to 40 mg kg⁻¹ soil extended the lag phase 1 to 2 days and reduced the maximum degradation rate by 15% to 30%. However, cumulative atrazine mineralization averaged 85% 21 days after treatment and was independent of treatment. Maximum daily rates of atrazine mineralization were reduced from 41% to 55% by application of 1 to 8 g kg⁻¹ of ammonium sulfate. Similarly, cumulative atrazine mineralization was inversely correlated with ammonium sulfate rates ranging from 1.0 to 8 g kg⁻¹ soil. Under the conditions of this laboratory study, atrazine degradation was relatively insensitive to exogenous mineral nitrogen, in that 8 g (NH₄)₂SO₄ per kilogram soil repressed but did not completely inhibit atrazine mineralization. Moreover, an additive effect on reducing atrazine mineralization was observed when glufosinate was co-applied with ammonium sulfate. In addition, ammonium fertilization alters the partitioning of ¹⁴C-atrazine metabolite accumulation and nonextractable residues, indicating that ammonium represses cleavage of the triazine ring. Consequently, results indicate that the co-application of glufosinate with N may increase atrazine persistence under field conditions thereby extending atrazine residual weed control in adapted soils.     

Sequential extraction of low concentrations of pyrene and formation of non-extractable residues in sterile and non-sterile soils

In this study, temporal changes in the extractability of ¹⁴C-pyrene, at native concentrations, were followed in two soils with differing organic matter contents, under sterile and non-sterile conditions over 24 weeks by a sequential solvent extraction scheme. No significant loss of the added ¹⁴C-pyrene was observed during the incubation. Significant decreases in methanol:water and n-butanol extractability were observed with increasing soil-pyrene contact time. Significant non-extractable residues were formed in all soils, with the largest increases found in the non-sterile soils. After 8 weeks soil-pyrene contact time, there was a significant increase in the rate and extent of sequestration of pyrene in the biologically active soils. This indicated that the aging of pyrene was initially a physical process, with active microbial communities increasing the rate and extent of residue formation after 8 weeks soil-pyrene contact time. These findings suggest that there is a need for longer term ageing experiments following the role of microbial communities on the formation of solvent non-extractable residues. The humin fraction of the soil organic matter contained the majority of the ¹⁴C-pyrene associated activity which was not extractable using the scheme of sequential solvents. Saponification of the soil humin resulted in the release of similar amounts of ¹⁴C-pyrene associated activity from sterile and non-sterile soils. Solvent extraction with methanol:water was found to significantly underestimate the bioavailable fraction, whereas n-butanol overestimated the bioavailability of the ¹⁴C-pyrene-associated activity when assessed by bacterial mineralization after 24 weeks soil-pyrene contact time.     

Improved extraction of atrazine and metolachlor in field soil samples

A method was developed for extraction of weathered residues of atrazine and metolachlor from field soils; soils had last been treated with commercial formulations of the herbicides 8-15 months prior to sample collection. Maximum yields were obtained by batch extraction at 75 degrees C for 2-16 h with methanol-water (80 + 20) in a sealed vial. Hydrolysis or other decomposition reactions were minor or negligible, depending on the extraction time. This method is an improvement over published methods that are validated by spike recoveries; the proposed method gives 1.7-1.8 times higher yields compared to shaking for 2 h at room temperature, and 1.3-1.8 times higher yields compared to Soxhiet extraction. The reproducibility of the method was better than 12%. The results underscore the impact of nonequilibrium sorption of organic compounds on analytical methodology and emphasize the need to validate extraction methods with field samples.     

Predicting bioavailability of PAHs in soils to wheat roots with triolein-embedded cellulose acetate membranes and comparison with chemical extraction

Triolein-embedded cellulose acetate membrane (TECAM) was buried in 15 field-contaminated soils in parallel with the cultivation of wheat to predict bioavailability of naphthalene, phenanthrene, pyrene, and benzo[a]pyrene to wheat roots, and the method was compared with chemical extraction methods. Although a good linear relationship was found between PAH concentrations in chemical extractants and wheat roots, the percentage of PAH in soil removed by chemical extraction was much higher than the corresponding percentage removed by wheat roots. In contrast to chemical extraction, a nearly 1:1 relationship was found between the amount of each PAH taken up by TECAMs and wheat roots (r(2) = 0.798-0.925, P < 0.01). Furthermore, the uptake of PAHs by TECAMs and wheat roots had the same pathway of passive transport via the soil solution. Moreover, TECAM caused minimal disturbance to the soil and was easy to deploy. Therefore, TECAM is believed to be a useful tool to predict bioavailability of PAHs to wheat roots grown in contaminated soils.     

Ageing of vanadium in soils and consequences for bioavailability

Total vanadium (V) concentrations in soils commonly range from 20 to 120 mg kg^?1. Vanadium added directly to soils is more soluble than geogenic V and can be phytotoxic at doses within this range of background concentrations. However, it is unknown how slow sorption reactions change the fate and effect of added V in soils. This study addresses the changes in V solubility, toxicity and bioavailability in soils over time. Four soils were amended with pentavalent V in the form of a soluble vanadate salt, and extractable V concentrations were monitored over 100 days. The toxicity to barley and tomato plants was evaluated in freshly spiked soils and in the corresponding aged soils that were equilibrated for up to 330 days after spiking. The V concentrations in 0.01 m CaCl₂ soil extracts decreased approximately two‐fold between 14 and 100 days after soil spiking, and the reaction kinetics were similar for all soils. The phytotoxicity of added V decreased on average two‐fold between freshly spiked and aged soils. The reduced toxicity was associated with a corresponding decrease in V concentrations in the isolated soil solutions and in the shoots. The V speciation in the soil solution of the aged soils was dominated by V(V); less than 8% was present as V(IV). Oxalate extractions suggest that the V(V) added to soils is predominantly sorbed onto poorly crystalline oxyhydroxides. It is concluded that the toxicity of V measured in freshly spiked soils may not be representative of soils subject to a long‐term V contamination in the field.     

A simplified extraction schema to for the analytical characterization of apple orchard soils

Purpose

Standardized procedures for agricultural soil analysis use different extractant solutions, to determine one or just a few elements, which needs a lot of time and manpower. Within this work, it was tried to substitute traditional methods by the use of multi-element determination techniques, like inductively coupled plasma optical emission spectrometry (ICP-OES) and inductively coupled plasma mass spectrometry (ICP-MS) applied to a few solutions.

Material and methods

ICP-OES and ICP-MS have been applied to a sequence of extracts obtained with 0.16 M acetic acid and 0.1 M oxalate buffer pH 3, which are more suitable for the plasma than traditional salt extractant solutions. Dilute acetic acid should characterize exchangeables plus carbonates, and oxalate buffer the pedogenic oxides. Aqua regia extractions in glass have been replaced by pressure digestion with KClO₃ in dilute nitric acid, which yields results equivalent to aqua regia, and additionally permits the determination of total sulfur, as well as acid-leachable boron and silicon. Total digestion was done in PTFE beakers by fuming with HNO₃/HClO₄, subsequently with HF, and final uptake in 1?+?1 HCl.

Results and discussion

The method was applied to 44 soils from apple orchards of different soil types and climatic zones. P and K obtained from standard acetate-lactate extract as well as B obtained from the Baron extract correlated with the results from the acetic acid extract better than 0.9. Just Mg from the CaCl₂ extract (Schachtschabel) was independent from all other Mg fractions. The results of the total digests could be verified by XRF analysis of the solid, Ti recovery was the most critical item. The results for Ca, Cu, Mg, Mn, Sr, Pb, and Zn obtained from KClO₃ digest and from totals, were strongly correlated. Factor analysis showed that the fraction mobilized by dilute acetic acid contained Ca-Mg-carbonates as well as Al-Ba-Na in the first factor, K-P-S in a second, whereas Mn-La-Li formed a group of its own. The pedogenic oxides, obtained from Al-Fe-Mn-Ti released in oxalate, carry most of the cationic trace elements, whereas the anions P-S-B-Si and the essentials Cu-Mo form different groups. Among the main elements, the quasi-total data were much less intercorrelated than the totals. The rare earth elements formed a strongly intercorrelated group as well after total digestion as in the oxalate leach.

Conclusions

The proposed method permits to obtain information about common cations including trace elements, and the nonmetals phosphorus, silicon, sulfur, boron, and iodine simultaneously, which could be a gate to find new relations among them. The two-step procedure permits to predict availabilities in shorter and longer periods of time. Data from the extract in dilute acetic acid for K, P, and B can substitute traditional methods of soil analysis.

     

竹炭固定化微生物对土壤中阿特拉津的降解研究

采用环境友好材料竹炭为主要载体,壳聚糖和海藻酸钠为辅助载体,固定从污泥中分离出的阿特拉津降解菌株,研究不同固定材料对降解菌生长的影响,以及固定化微生物对土壤中阿特拉津的降解效果.结果表明,竹炭对阿特拉津降解菌具有较强的吸附固定能力,且竹炭粒径越小,固定化效果越好.利用壳聚糖和海藻酸钠交联并加固阿特拉津降解菌,增大了固定化空间,显著增加了降解菌的生物量,并提高了阿特拉津的降解效率.1％壳聚糖+5％海藻酸钠+竹炭+降解菌颗粒对阿特拉津降解菌的固定化效果最佳,施用该微生物固定化颗粒28天后,砂姜黑土及红壤中阿特拉津残留率分别为48.07％和47.23％.     

How increasing availabilities of carbon and nitrogen affect atrazine behaviour in soils

 The effect of increasing amounts of glucose and mineral N on the behaviour of atrazine was studied in two soils. One had been exposed to atrazine under field conditions (adapted soil), the other had not (non-adapted soil), resulting, respectively, in an accelerated degradation of atrazine in the adapted soil and in a slow degradation of the herbicide in the non-adapted soil. The dissipation of ¹⁴C-atrazine via degradation and formation of non-extractable "bound" residues was followed during laboratory incubations in soils supplemented or not with increasing amounts of glucose and mineral N. In both soils, glucose added at rates of up to 16 g C kg^–1 soil did not modify atrazine mineralization but increased the formation of bound residues; this was probably due to the retention of atrazine by the growing microbial biomass. Atrazine dealkylation was enhanced when a large amount of glucose was added. In both soils, the addition of the largest dose of mineral N (2.5 g N kg^–1 soil) decreased atrazine mineralization. The simultaneous addition of glucose and mineral N enhanced their effects. When the largest doses of mineral N and glucose were added, atrazine mineralization stopped in both soils, and the proportion of bound residues increased. Glucose and mineral N additions influenced atrazine mineralization to a greater extent in the adapted soil than in the non-adapted one, as revealed by ANOVA, although glucose addition had a greater effect than N. The competition for space and nutrients between atrazine-degrading microorganisms and the total heterotrophic microflora probably contributed to the decrease in atrazine mineralization. Received: 9 June 1998     

Biodegradation of aged residues of atrazine and alachlor in a mix-load site soil

A selected microbial consortium (SMC) capable of degrading two specific herbicides, alachlor (2-chloro-2′,6′-diethyl-N-[methoxymethyl]-acetanilide; AL) and atrazine (2-chloro-4-ethylamino-6-isopropylamino-S-triazine; AT) was isolated from a pesticide-contaminated mix-load site soil. Evaluation of bioaugmentation as a feasible bioremediation strategy for this mix-load site soil (Site 5A) was initiated in standard laboratory biometer flasks utilizing the isolated SMC. The biometer flasks were monitored for CO₂ evolution and pesticide degradation. The total amount of CO₂ evolved from the treated biometer flasks was significantly different from the control flasks. The rate of CO₂ evolution was 2.6 times faster in the treated soil (0.0123 mM CO₂ d⁻¹ vs. 0.0048 mM CO₂ d⁻¹). The total net CO₂ produced in the treated biometer flasks was 0.9481 mM, representing mineralization of approximately 10% of the AT and AL initially present. Forty-eight percent of AT and 70% of AL was degraded in the inoculated biometer flasks. The first-order rate constants were 0.0064 d⁻¹ and 0.1331 d⁻¹ for AT and AL, respectively. The calculated half-life of AT was 108 d while a 50% decrease in AL occurred by Day 5. In just 2 d, 20% of the AT was degraded while only 10% of the AL disappeared. The initial fast degradation rate of AT was followed by a much slower, more gradual degradation rate period that lasted about 35 d. Alternatively, the rate of AL degradation increased after the second day resulting in 60% of the AL being transformed by the end of the first week. Alachlor degradation appeared to be dependent upon AT degradation especially during the first several days of the incubation period. Complete disappearance of the herbicides over the study time was not achieved.     

Copper fungicide residues in Australian vineyard soils

Copper (Cu) concentrations were measured in Australian vineyard soils to assess the extent and magnitude of Cu accumulation resulting from the use of Cu-based fungicides and to indicate the likely risks to long-term soil fertility. Soil samples were collected from 98 vineyards across 10 grape-growing regions of Australia and analyzed for total Cu concentrations. Ninety-six percent of vineyards surveyed had elevated Cu concentrations in soil compared to the background Cu concentrations in nearby soil in its native state. Concentrations of total B, Co, Cr, Pb, and Zn were similar to background concentrations and below reported toxicity guideline values. Cu concentrations in Australian vineyard soils were generally much lower (6-150 mg kg (-1)) than those reported in the soils of vineyards in parts of Europe (i.e., 130-1280 mg kg (-1)). Concentrations of total Cu were generally below those concentrations reported to cause lethal effects to soil invertebrates; however, Cu exceeded concentrations known to cause sublethal effects (i.e., inhibit growth, affect reproduction, induce avoidance behavior) to those (or related) invertebrates.     

Organoclays reduce arsenic bioavailability and bioaccessibility in contaminated soils

Purpose  

Naturally occurring layer silicate clay minerals can be value added by modifying their surface properties to enhance their efficacy in the remediation of environmental contaminants. Silicate clay minerals modified by the introduction of organic molecules into the mineral structure are known as organoclays and show much promise for environmental remediation applications. The present study assesses the extent of decrease in bioavailable and bioaccessible arsenic (As) via enhanced adsorption by soil treated with organoclays.     

除草剂莠去津和灭草松单用和混用在土壤中的降解

The application of a mixture of bentazone （3-isopropyl-1H-2,1,3-benzothiadiazin-4（3H）-one-2,2-dioxide） and atrazine （6-chloro-N2-ethyl-N4-isopropyl-1,3,5-triazine-2,4-diamine） is a practical approach to enhance the herbicidal effect. Laboratory incubation experiments were performed to study the degradation of bentazone and atrazine applied in combination and individually in maize rhizosphere and non-rhizosphere soils. After a lag phase, the degradation of each individual herbicide in the non-autoclaved soil could be adequately described using a first-order kinetic equation. During a 30-d incubation, in the autoclaved rhizosphere soil, bentazone and atrazine did not noticeably degrade, but in the non-autoclaved soil, they rapidly degraded in both non-rhizosphere and rhizosphere soils with half-lives of 19.9 and 20.2 d for bentazone and 29.1 and 25.7 d for atrazine, respectively. The rhizosphere effect significantly enhanced the degradation of atrazine, but had no significant effect on bentazone. These results indicated that biological degradation accounted for the degradation of both herbicides in the soil. When compared with the degradation of the herbicide applied alone, the degradation rates of the herbicides applied in combination in the soils were lower and the lag phase increased. With the addition of a surfactant, Tween-20, a reduced lag phase of degradation was observed for both herbicides applied in combination. The degradation rate of bentazone accelerated, whereas that of atrazine remained nearly unchanged. Thus, when these two herbicides were used simultaneously, their persistence in the soil was generally prolonged, and the environmental contamination potential increased.     

土壤中重金属的生物有效性研究进展

综述了年十年来国内及国际上研究土壤中重金属的生物有效性的态势，尤其是影响土壤中重金属生物有效性的诸多因素，以期进一步推动国内的土壤中重金属生物有效的研究工作和重金属污染土壤的生物治理工作。