Glyphosate degradation as a soil health indicator for heavy metal polluted soils

Glyphosate is a commonly used herbicide in grassland soils and microorganisms control its degradation. We introduce the concept of using the degradation rate as an indicator for ecosystem health. Testing this concept, we used soils with a long history of heavy metal pollution (Cu, Pb, and Zn). We hypothesized lower degradation rates in metal-polluted compared to less polluted soils. The degradation rates were measured by repeated measurements of the parent compound in spiked soil-water slurries incubated at 20 °C over 21 days. Average rates showed no differences comparing among soils. We observed a positive correlation between glyphosate degradation rates and soil metal pollution. Therefore, we concluded that the expected impact of the metals on the bacteria responsible for the herbicide degradation was not established. We discuss the potential influence on biological degradation rates of soil pH and adsorption and implications using the concept of the soil health indicator.     

Influence of Cry1Ac toxin on mineralization and bioavailability of glyphosate in soil

The impact of transgenic plants containing Bacillus thuringiensis (Bt) toxin on soil processes has received recent attention. In these studies, we examined the influence of the lepidopterean Bt Cry1Ac toxin on mineralization and bioavailability of the herbicide glyphosate in two different soils. The addition of 0.25-1.0 microg g(-1) soil of purified Cry1Ac toxin did not significantly affect glyphosate mineralization and sorption in either a sandy loam or a sandy soil. In contrast, extractable glyphosate decreased over the 28 day incubation period in both soils. Our findings suggest that the reduction in the bioavailability of glyphosate was not influenced by the presence of Cry1Ac toxin but rather the results of aging or sorption processes. Results from this investigation suggest that the presence of moderate concentrations of Bt-derived Cry1Ac toxin would have no appreciable impact on processes controlling the fate of glyphosate in soils.     

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.     

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.     

Fate of diuron and terbuthylazine in soils amended with two-phase olive oil mill waste

The addition of organic amendments to soil increases soil organic matter content and stimulates soil microbial activity. Thus, processes affecting herbicide fate in the soil should be affected. The objective of this work was to investigate the effect of olive oil production industry organic waste (alperujo) on soil sorption-desorption, degradation, and leaching of diuron [3-(3,4-dichlorophenyl)-1,1-dimethylurea] and terbuthylazine [N2-tert-butyl-6-chloro-N4-ethyl-1,3,5-triazine-2,4-diamine], two herbicides widely used in olive crops. The soils used in this study were a sandy soil and a silty clay soil from two different olive groves. The sandy soil was amended in the laboratory with fresh (uncomposted) alperujo at the rate of 10% w/w, and the silty clay soil was amended in the field with fresh alperujo at the rate of 256 kg per tree during 4 years and in the laboratory with fresh or composted alperujo. Sorption of both herbicides increased in laboratory-amended soils as compared to unamended or field-amended soils, and this process was less reversible in laboratory-amended soils, except for diuron in amended sandy soil. Addition of alperujo to soils increased half-lives of the herbicides in most of the soils. Diuron and terbuthylazine leached through unamended sandy soil, but no herbicide was detected in laboratory-amended soil. Diuron did not leach through amended or unamended silty clay soil, whereas small amounts of terbuthylazine were detected in leachates from unamended soil. Despite their higher sorption capacity, greater amounts of terbuthylazine were found in the leachates from amended silty clay soils. The amounts of dissolved organic matter from alperujo and the degree of humification can affect sorption, degradation, and leaching of these two classes of herbicides in soils. It appears that adding alperujo to soil would not have adverse impacts on the behavior of herbicides in olive production.     

Effects of Wood Amendments on the Degradation of Terbuthylazine and on Soil Microbial Community Activity in a Clay Loam Soil

The herbicide terbuthylazine is widely used within the EU; however, its frequent detection in surface and groundwater, together with its intrinsic toxicological properties, may pose a risk both for human and environmental health. Organic amendments have recently been proposed as a possible herbicide sorbent in soil, in order to limit herbicide movement from soil to water. The environmental fate of terbuthylazine depends not only in its mobility but also in its persistence. The latter is directly dependent on microbial degradation. For this reason, the effects of pine and oak residues on terbuthylazine soil microbial community functioning and on the potential of this community for terbuthylazine degradation were studied. For this purpose, degradation kinetics, soil dehydrogenase activity and the number of live bacteria were assessed in a clay loam soil treated with terbuthylazine and either amended with pine or oak wood or unamended (sterilised and non-sterilised). At day 65, 85?% of the herbicide applied still persisted in the sterile soil, 73?% in the pine-amended one and 63?% in the oak-amended and unamended ones. Pine residues increased the sorption of terbuthylazine to soil and hampered microbial degradation owing to its high terbuthylazine sorption capacity and a decrease in the bioavailability of the herbicide. On the contrary, in the presence of oak residues, the herbicide sorption did not increase significantly. The overall results confirm the active role of the soil microbial community in terbuthylazine degradation in amended and unamended soils and in a liquid enrichment culture performed using an aliquot of the same soil as the inoculum. In this clay loam soil, in the absence of amendments, the herbicide was found to be quite persistent (t _1/2?>?95?days), while in the enrichment culture, the same natural soil bacterial community was able to halve terbuthylazine in 24?days. The high terbuthylazine persistence in this soil was presumably ascribable to its texture and in particular to the mineralogy of the clay fraction.     

Soil moisture and the rates of biodegradation of diallate and triallate

Degradation experiments were combined with biomass measurements and adsorption tests to determine how soil moisture content influences the rates of degradation of ⁴¹C-labelled diallate and triallate. In soils treated with 1 μg^?1 herbicide and incubated at constant temperature and moisture, degradation rates were regulated by two variables: the quantity of microbial biomass in the soil; and the quantity of herbicide dissolved in the soil solution. The quantity of biomass was influenced by soil water content and the duration of incubation. The amounts of herbicide in solution were determined by the amount of water present and the total quantity of herbicide in the soil. In all soil samples, the rates of degradation increased with increasing water content but decreased with prolonged incubation. The factors responsible for decrease with time were the loss of biomass during incubation and the decline in herbicide concentration in the soils as degradation proceeded.     

Effects of incorporated corn residues on glyphosate mineralization and sorption in soil

In modern agricultural systems employing conservation tillage practices, glyphosate is widely used as a preplant burndown herbicide in a wide range of crops. Conservation tillage systems are characterized by a significant presence of crop residues at the soil surface so that glyphosate is applied to a soil matrix rich in poorly decomposed crop residues. Incorporation of corn residues in the range from 0.5 to 4% caused different effects on mineralization and sorption of [14C]glyphosate in sandy and sandy loam soils. More specifically, low levels of incorporated corn residues did not affect or slightly stimulated herbicide mineralization in the sandy and sandy loam soils, respectively. In the sandy soil, incorporation of the highest level of corn residues (4%) caused a decrease in [14C]glyphosate mineralization. [14C]Glyphosate sorption on both soil types was reduced in samples receiving high amounts of incorporated corn residues.     

Influence of soil composition on adsorption of glyphosate and phosphate by contrasting Danish surface soils

The herbicide glyphosate and inorganic phosphate are strongly adsorbed by inorganic soil components, especially aluminium and iron oxides, where they seem to compete for the same adsorption sites. Consequently, heavy phosphate application may exhaust soil's capacity to bind glyphosate, which may lead to pollution of drain‐ and groundwater. Adsorption of phosphate and glyphosate to five contrasting Danish surface soils was investigated by batch adsorption experiments. The different soils adsorbed different amounts of glyphosate and phosphate, and there was some competition between glyphosate and phosphate for adsorption sites, but the adsorption of glyphosate and phosphate seemed to be both competitive and additive. The competition was, however, less pronounced than found for goethite and gibbsite in an earlier study. The soil's pH seemed to be the only important factor in determining the amount of glyphosate and phosphate that could be adsorbed by the soils; consequently, glyphosate and phosphate adsorption by the soils was well predicted by pH, though predictions were somewhat improved by incorporation of oxalate‐extractable iron. Other soil factors such as organic carbon, the clay content and the mineralogy of the clay fraction had no effect on glyphosate and phosphate adsorption. The effect of pH on the adsorption of glyphosate and phosphate in one of the soils was further investigated by batch experiments with pH adjusted to 6, 7 and 8. These experiments showed that pH strongly influenced the adsorption of glyphosate. A decrease in pH resulted in increasing glyphosate adsorption, while pH had only a small effect on phosphate adsorption.     

Sorption-desorption isotherms and biodegradation of glyphosate in two tropical soils aged with eucalyptus biochar

ABSTRACT

The objective of this study was to evaluate the sorption-desorption process and biodegradation of glyphosate in two tropical soils aged with biochar derived from eucalyptus. The biochar aging period was 30 d. There was little difference between the amounts of sorbed glyphosate in Ultisol (96.8, 96.8 and 96.4%) and Alfisol (97.1, 97.5 and 97.4%) soils that were unamended or amended with biochar aged for 0 or 30 d, respectively. Similar amounts of desorbed herbicide occurred in Ultisol (3.3, 3.3 and 3.4%) and Alfisol (4.1, 4.2 and 3.9%) soils, respectively. The degradation time half-life (DT50) of glyphosate in Ultisol unamended and initial amended were higher (38 and 36 d, respectively) than DT50 in the amended soil with 30 d of biochar aging (27 d); and in the Alfisol DT50 was higher in unamended soil (38 d), and similar in soil unamended at 0 and 30 d of biochar aging (21 and 26 d, respectively). The addition of biochar to two tropical soils or its aging did not have any effect on the sorption and desorption of glyphosate and its biodegradation in relation to the unamended soils, and it can did not affect the transport and persistence of this herbicide in soil.     

批实验中土壤对地乐酚吸附的差异

吸附是决定除草剂地乐酚在土壤中迁移的重要机制之一。通常用简单快捷的批实验来衡量土壤对除草剂的吸附。由大量的批实验确定地乐酚在不同土壤样本中的吸附参数,并对各土壤特性与吸附参数的相关性作统计分析。结果表明土壤有机C含量,粘粒含量及阳离子代换量与吸附参数显著正相关,土壤pH值与吸附参数显著负相关。方差分析表明地乐酚在土壤中的吸附表现出很强的空间差异,在不同地点的地乐酚吸附参数无显著区别,而在不同的深度区别显著。超过85%的地乐酚吸附参数的空间差异可由土壤有机C含量的空间差异来解释。     

Release of soil phosphate by sequential extractions as a function of soil properties and added phosphorus

Abstract

A study of sequential phosphate (P) extraction by water and iron oxide‐impregnated paper strip procedures was carried out on three Italian soils ranging widely in soil characteristics and enriched with three rates of fertilizer P. The degree of change was dependant on P addition, soil P properties, and type of extraction. For the Fe‐oxide strip procedure, a greater release of P than for water extraction was observed for soils with and without added P. At a given level of added P, more P was released from the soil with the lowest P sorption index (SI). However, at a given level of NaHCO₃‐extractable P, less P was released from the soil with lower SI than from soil with a higher SI, indicating that a greater available P content was necessary for low P sorbing soils to maintain a given rate of P release. The variation of SI accounted for 96% and 92% of the variation in amount of water‐extractable and Fe‐oxide strip P at a given P addition. Furthermore, SI accounted for 97% and 98% of the variation in water‐extractable and Fe‐oxide P at a given increase in available soil P. Inclusion in a soil testing program of an estimate of the P Sorption Index, that accounts for the overall effect of soil properties affecting sorption in soils (clay content and type, iron and aluminum oxide content, surface area, etc.), may improve fertilizer P requirements for optimum crop growth for certain soils.     

Influence of soil moisture on sorption and degradation of hexazinone and simazine in soil.

Sorption and degradation rates of hexazinone and simazine on soil were determined in a sandy loam soil incubated, during 44 days, at 25 degrees C with moisture contents ranging from 4% to 18%. Herbicide levels in soil solution were also measured, after extraction of this solution by a centrifugation method. All experiments were conducted with treated soil in plastic columns, and the results showed that this method is suitable for the simultaneous study of pesticide sorption and degradation in soil at different environmental conditions. In general, sorption of both herbicides was higher for aged herbicide residues compared to recently applied herbicides, and soil subjected to drying and rewetting cycles had the highest sorption values. K(f) values ranged from 0.5 to 1.2 for simazine and from 0.2 to 0.4 for hexazinone. Degradation rates increased with soil moisture content for both herbicides, and drying-rewetting of soil yielded degradation rates slower than that obtained at 10% soil moisture content. Hexazinone concentration in soil solution decreased with incubation time faster than simazine.     

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.     

Phosphorus sorption by four soils receiving long‐term applications of fertilizer

Abstract

A laboratory study was conducted to evaluate P sorption in the Ap horizon of four soil series in the Ultisol order (Benndale Is, Hartsells fsl, Lucedale fsl, and Dewey sicl) receiving the same fertility treatments since 1929. Soil was collected in the spring of 1985 from 4 treatments: i) no‐lime, plus P (total fertilizer P = 1584 kg/ha from 1929 to 1985); ii) no‐K, plus P (total fertilizer P = 1584 kg/ha); iii) low‐P (total fertilizer P = 442 kg/ha); 4) standard treatment (total fertilizer P = 2376 kg/ha). The soils and treatments within a soil varied in pH, total P, Mehlich 1 extractable P, K, Ca and Mg, and KC1 extractable Al. The four soils had large differences in P sorption capacity which increased with increasing clay content. The Dewey (27 % clay) soil had the highest P sorption capacity and the Benndale (4 % clay) soil had the smallest P sorption capacity. Sorption of P within a soil was affected by the rate of added P and past fertility treatment. Treatment differences in P sorption were due primarily to the level of extractable P and soil pH. Within a given soil, P sorption (at a given rate of added P) generally decreased as the level of extractable P increased. Regression analysis of P sorption data for equilibrium P concentrations of 1 to 32 μmol/L showed that the parti‐ tioning between sorbed and solution P (buffer power) had not been changed by 56 years of annual applications of P. The maximum P sorption capacity of the four soils was decreased slightly by P fertilization.     

The effect of soil type on phosphorus sorption capacity and desorption dynamics in Irish grassland soils

Abstract. The phosphorus (P) sorption and desorption dynamics of eleven major agricultural grassland soil types in Ireland were examined using laboratory techniques, so that soils vulnerable to P loss might be identified. Desorption of P from soil using the iron-oxide paper strip test (Pfeo), water extractable P (Pw) and calcium chloride extractable P (Pcacl₂) depended on soil P status in all soils. However, soil types with high organic matter levels (OM), namely peat soils (%OM >30), had lower Pfeo and Pw but higher Pcacl₂ values compared to mineral soils at similar soil test P levels. Phosphorus sorption capacity remaining (PSCr) was measured using a single addition of P to soils and used to calculate total P sorption capacities (PSCt) and degree of P saturation (DPS). Phosphorus sorption capacities correlated negatively with % OM in soils indicating that OM may inhibit P sorption from solution to soil. High organic matter soils exhibited low P sorption capacities and poor P reserves (total P, oxalate extractable P) compared to mineral soils. Low P sorption capacities (PSCt) in peat soils were attributed to OM, which blocked or eliminated sorption sites with organic acids, therefore, P remained in the soil solution phase (Pcacl₂). In this work, peat and high organic matter soils exhibited P sorption and desorption characteristics which suggest that these soils may not be suitable for heavy applications of manure or fertilizer P owing to their low capacities for P sorption and storage.     

土壤中14C-甲磺隆存在形态的动态研究

利用同位素示踪技术 ,在实验室条件下研究了1 4 C -甲磺隆在 1 5种不同土壤中存在形态的动态变化。结果表明 ,土壤pH值与甲磺隆1 4 C残留物的降解半衰期、残留量及可提取态残留量呈显著的正相关 ,而与结合态残留量呈显著负相关 ;土壤微生物的活性越强 ,甲磺隆降解速率越快 ,但结合态残留量也越高 ;土壤中各腐殖质组分和粘粒的含量也影响甲磺隆在土壤中的降解速率和存在形态。土壤中甲磺隆的残留符合一级反应动力学指数方程C =C0 e-kt,拟合方程的复相关系数达到极显著水平。甲磺隆残留与土壤性质之间经逐步回归分析可得到拟合效果较好的方程 ,由各自变量的决定系数可知 ,土壤pH值、微生物生物量碳和有机碳中富啡酸碳所占的比例是影响甲磺隆在土壤中残留的主要因素     

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.     

Effects of the herbicide glyphosate on nitrification in four soils from Atlantic Canada

The herbicide glyphosate, supplied as Roundup (Monsanto Canada Inc.), was tested for effects on nitrification in four soils from Atlantic Canada. These included a sandy loam (pH 6.8), two silt loam (pH 6.4 and 5.8) agricultural soils and a clay loam forest soil (pH 3.5). Glyphosate was tested at normal field exposure rates (FR) and levels up to 200 times higher. FR values ranged from 19.83 to 29.26 ppm (jig glyphosate g^?1 soil). Glyphosate had no deleterious effects on nitrification in any soil when tested at FR concentrations. In the sandy loam soil nitrification was significantly stimulated at a glyphosate level 50 times higher than FR. With this soil and one of the silt loam soils (pH 6.4) glyphosate levels of 100 times FR and higher were required for a significant inhibition of nitrification. With the other silt loam soil (pH 5.8) glyphosate significantly inhibited nitrification at concentrations 10 times FR and higher. Nitrification in the acidic forest soil was very low and accurate toxicity data could not be obtained. The EC₅₀ of glyphosate towards nitrification in soil ranged from 1435 to 2920 ppm, which corresponds to exposure levels from 67 to 150 times higher than recommended field application rates. The use of glyphosate in agriculture and forestry should have no toxic effects on nitrification in soil.