RESUMO
Chiral pesticides that are still commercialized and incorporated into the environment as racemic mixtures of enantiomers require evaluation of the enantioselectivity of their biological activity and environmental fate processes for a better prediction of their field efficacy and environmental risks. In this work, we successfully separated the enantiomers of the chiral herbicide ethofumesate (ETFM), determined their absolute configuration, and characterized their herbicidal activity as well as their adsorption, degradation, enantiomerization, and leaching in Mediterranean agricultural soils. While the herbicidal activity of R-ethofumesate to the sensitive species Portulaca grandiflora was greater than that of S-ethofumesate, the adsorption, degradation, and leaching of the herbicide showed negligible enantioselectivity and enantiomer interconversion did not occur in soils. The adsorption of both enantiomers showed a positive correlation with the soil organic carbon content (r = 0.856, P = 0.015), and their degradation in soils occurred slowly (DT50 > 60 days) and at similar rates independent of their application as individual enantiomers or as a racemic mixture of enantiomers. The addition of three highly adsorptive materials to a scarcely adsorptive soil increased the adsorption of the enantiomers of ETFM and delayed their degradation without affecting the non-enantioselective character of the processes. As a result of their high adsorption capacity, the materials were highly effective in reducing the leaching of both enantiomers of ETFM through soil columns. The results of this work indicate that the application of single-enantiomer ETFM formulations, based on a higher herbicidal activity or a lower toxicity to non-target organisms of the formulated enantiomer, would reduce considerable exposure risks associated with incorporating into the environment the less favorable enantiomer, as this would show long persistence and high leaching potential in soils similar to its optical isomer.
Assuntos
Benzofuranos , Carvão Vegetal , Fungicidas Industriais , Herbicidas , Mesilatos , Poluentes do Solo , Solo , Estereoisomerismo , Carbono , Fungicidas Industriais/metabolismo , Poluentes do Solo/metabolismo , Alanina/metabolismo , Biodegradação AmbientalRESUMO
We assessed the effect of three organic amendments and two organo-clays on sorption, persistence, and phytotoxicity of scopoletin, an allelochemical compound with potential as bioherbicide, in a Mediterranean alkaline soil. The aim was to elucidate whether the phytotoxicity of scopoletin could be expressed better in amended than unamended soil. The three organic amendments were fresh solid olive-mill waste (OMW), composted solid olive-mill waste (OMWc), and biochar (BC) prepared from OMWc. The two organo-clays were a commercial organo-montmorillonite (Cloi10) and lab-synthesized oleate-modified hydrotalcite (HT-OLE). The amendments enhanced sorption of scopoletin by the soil consistently with their individual affinities for the allelochemical: Cloi10 â« OMW > BC > OMWc > HT-OLE. The soil persistence of scopoletin increased significantly because of the addition of Cloi10, OMW, and BC. This increase was attributed to a combination of sorption, which protected the allelochemical from rapid biodegradation, and microbial activity changes. Although the inhibitory effect produced by the amendments themselves obscured the phytotoxicity of scopoletin to Lactuca sativa L. in soil treated with OMW and Cloi10, applying scopoletin to BC-amended soil led to a marked reduction in root length and aerial biomass of the emerged seedlings even though BC alone did not negatively affect these parameters. This inhibitory effect of scopoletin in BC-amended soil was in contrast to the negligible effect exerted by the allelochemical when applied to unamended soil. The results show that soils treated with suitable amendments, such as BC, might provide a scenario in which the herbicidal properties of 7-hydroxycoumarins could be better expressed.
Assuntos
Poluentes do Solo , Solo , Argila , Feromônios , Escopoletina , Poluentes do Solo/análiseRESUMO
Biochar is a nanoengineered sorbent proposed to control the contamination derived from the presence of residual concentrations of sulfonamides in soil. In this work, we evaluated the sorption of sulfanilamide (SFA) in commercial biochar (BC) produced at 500 °C from oak hardwood (Quercus ilex) and its analog activated with 2% (w/w) Fe (BC-Fe). Subsequently, the effect on dissipation and transport of SFA in untreated soil and soil treated with BC and BC-Fe was also assessed. Laboratory batch studies revealed that BC-Fe increased the sorption of SFA as compared to the pristine BC with Kd of 278 and 98 L/kg, respectively. The dissipation of SFA in either untreated soil or soil treated with BC or BC-Fe was similar, displaying half-lives ranging between 4 and 6.4 days. Conversely, the concurrent determination of sorption during the incubation experiment showed that lower amounts of SFA in solution at the beginning of the experiments were bioavailable in BC-Fe-treated soil when compared to the rest of the treatments shortly after application. Leaching column studies confirmed the amendment's capability to bind the SFA compound. Therefore, the decrease in bioavailability and movement of SFA in treated soils suggest that biochar soil application can reduce SFA soil and water contamination. According to our results, BC surface modification after Fe activation may be more appropriate for water decontamination than for soil since there were no significant differences between the two types of biochar when added to the soil. Therefore, these outcomes should be considered to optimize the SFA mitigation potential of biochar.
Assuntos
Poluentes do Solo , Solo , Poluentes do Solo/análise , Água , Sulfanilamida , Carvão VegetalRESUMO
We recently proposed that weak acids (AH) adsorb to partially oxidized carbonaceous materials in part by forming strong hydrogen bonds with acidic surface groups, depicted by (A···H···O-surf)(-), known as negative charge-assisted hydrogen bonds, (-)CAHBs. Here we use competition experiments to show that sorption of AH on carbon nanotubes (CNTs) can be described conceptually by a dual specific/nonspecific domain model, where one domain involves (-)CAHB sites that can become saturated. The trends observed in single-solute adsorption, including the stoichiometric release of hydroxide upon sorption of carboxyate or phenolate anions, were consistent with trends in the previous studies and pointed to the formation of (-)CAHB. 3,4-Dinitrophenolate formed (-)CAHBs more efficiently than did 2,6-dichloro-4-nitrophenolate because of alleviation of steric hindrance to approach by the ortho chlorines. Competition against a (-)CAHB-capable target compound was greater when the competitor was also (-)CAHB-capable than when it was not (e.g., benzoate as target vs 3,4-dinitrophenolate or nitrobenzene as competitor; mono-n-butyl phthalate as target vs methyl benzoate or p-tolyl acetate as competitor). Experiments also revealed competition between the nitroaromatic species for π-π electron donor-acceptor sites. The findings will contribute to a better understanding of the adsorption mechanism of ionizable compounds on carbonaceous materials.
Assuntos
Nanotubos de Carbono/química , Adsorção , Ligação de Hidrogênio , Compostos Orgânicos/química , OxirreduçãoRESUMO
[This corrects the article DOI: 10.1371/journal.pone.0291398.].
RESUMO
Biochars and organoclays have been proposed as efficient adsorbents to reduce the mobility of agrochemicals in soils. However, following their application to soils, these adsorbents undergo changes in their physicochemical properties over time due to their interaction with soil components. In this study, the adsorption capacity of a commercial biochar and a commercial organoclay for the antibiotic sulfamethoxazole (SFMX) and the pesticide ethofumesate (ETFM) was evaluated over aging periods of 3 months in the laboratory and 1 year in the field, subsequent to their application to a Mediterranean soil. The results showed that the adsorption of SFMX and ETFM in the soil amended with the adsorbents was greater than in the unamended soil, but for both chemicals, adsorption decreased with aging of the adsorbents in the soil. Characterization of the adsorbents before and after aging revealed physical blocking of adsorption sites by soil components. The loss of adsorption capacity of the adsorbents upon aging led to higher leaching of SFMX and ETFM in the soil containing field-aged adsorbents, although leaching remained lower than in unamended soil. Our findings reveal that, under the Mediterranean environment studied, the efficacy of the studied materials as adsorbents is maintained to a considerable extent for at least one year after their field application, which would have positive implications in their use for attenuating the dispersion of agricultural contaminants in the environment.
Assuntos
Carvão Vegetal , Poluentes do Solo , Solo , Sulfametoxazol , Sulfametoxazol/química , Carvão Vegetal/química , Adsorção , Poluentes do Solo/análise , Poluentes do Solo/química , Solo/química , Argila/químicaRESUMO
Certain soil management practices can affect the enantioselective behavior of chiral pesticide enantiomers in agricultural soils. In this work, laboratory experiments were conducted to study the effects of olive-mill waste (OMW) addition to a Mediterranean agricultural soil on the enantioselectivity of sorption, degradation, and leaching processes of the chiral fungicide metalaxyl. Sorption-desorption isotherms indicated that the sorption of metalaxyl enantiomers by unamended and OMW-amended soil (2% w/w) was non-enantioselective and that OMW addition had little effect on the extent of sorption of metalaxyl enantiomers by the soil. Soil incubation experiments revealed that the degradation of metalaxyl in unamended soil was highly enantioselective, with R-metalaxyl being degraded faster (t1/2 = 12 days) than S-metalaxyl (t1/2 = 39 days). OMW addition to the soil increased the half-life of the biologically-active R-metalaxyl enantiomer from 12 to 28 days, and decreased the half-life of the non-active S-metalaxyl enantiomer from 39 to 33 days. Consequently, the enantioselectivity of metalaxyl degradation in the soil was greatly reduced upon OMW addition. Column leaching data were consistent with batch sorption and incubation results, showing similar retardation of S- and R-metalaxyl in unamended and OMW-amended soil and enantioselective leaching of the fungicide only in unamended soil. The results have important implications regarding the biological efficacy and environmental impact of the fungicide when applied as a mixture of enantiomers or racemate to OMW-treated soils.
Assuntos
Alanina/análogos & derivados , Fertilizantes , Olea , Solo , Absorção , Agricultura , Alanina/química , Alanina/metabolismo , Biodegradação Ambiental , Meio Ambiente , Fungicidas Industriais/química , Fungicidas Industriais/metabolismo , Meia-Vida , Resíduos Industriais , Poluentes do Solo/química , Poluentes do Solo/metabolismo , Espanha , EstereoisomerismoRESUMO
Soil plays a primary role in the activity of plant allelochemicals in natural and agricultural systems. In this work, we compared the phytotoxicity of three natural hydroxycoumarins (umbelliferone, esculetin, and scopoletin) to different model plant species (Lactuca sativa, Eruca sativa, and Hordeum vulgare) in Petri dishes, and then selected the most phytotoxic compound (umbelliferone) to assess how its adsorption and dissipation in two distinct soils affected the expression of its phytotoxic activity. The root growth inhibitory effect of umbelliferone was significantly greater than that of esculetin and scopoletin, and the dicot species (L. sativa and E. sativa) were more sensitive to the hydroxycoumarins than the monocot species (H. vulgare). For all three plant species tested, the phytotoxicity of umbelliferone decreased in the following order: soilless (Petri dishes) > soil 1 > soil 2. In soil 2 (alkaline), umbelliferone displayed negligible adsorption (Kf < 0.01) and rapid biodegradation (t1/2 = 0.2-0.8 days), and its phytotoxicity was barely expressed. In soil 1 (acid), umbelliferone displayed enhanced adsorption (Kf = 2.94), slower biodegradation (t1/2 = 1.5-2.1 days), and its phytotoxicity was better expressed than in soil 2. When the microbial activity of soil 2 was suppressed by autoclaving, the phytotoxicity of umbelliferone, in the presence of soil, became similar to that observed under soilless conditions. The results illustrate how soil processes can reduce the allelopathic activity of hydroxycoumarins in natural and agricultural ecosystems, and suggest scenarios where the bioactivity of hydroxycoumarins may be better expressed.
RESUMO
Plant monoterpenes have received attention for their ecological functions and as potential surrogates for synthetic herbicides, but very little is known about the processes that govern their behavior in the soil environment, and even less about the possible enantioselectivity in the functions and environmental behavior of chiral monoterpenes. We characterized the adsorption and dissipation of the two enantiomers of the chiral monoterpene pulegone in different soils, and their phytotoxicity to different plant species through Petri dish and soil bioassays. R- and S-pulegone displayed a low-to-moderate non-enantioselective adsorption on the soils that involved weak interaction mechanisms. Soil incubation experiments indicated that, once in the soil, R- and S-pulegone are expected to suffer rapid volatilization and scarcely enantioselective, biodegradation losses. In Petri dishes, the phytotoxicity of pulegone and its enantioselectivity to Lactuca sativa, Hordeum vulgare, and Eruca sativa was species-dependent. Lactuca sativa was the most sensitive species and showed higher susceptibility to S- than to R-pulegone. Biodegradation and volatilization losses greatly reduced the phytotoxic activity of S-pulegone applied to soil, but the addition of a highly-adsorptive organoclay stabilized the monoterpene and increased its phytotoxic effect. Stabilization by adsorption may represent an important mechanism by which the bioactivity of plant monoterpenes in soils can be increased.
RESUMO
BACKGROUND: Allelochemicals can act as biopesticides or enhance the action of synthetic pesticides. In this work, we assessed the bioavailability of the allelochemical coumarin in soils amended with fresh or field-aged biochars (BCs). The fresh BC from oak wood (Fresh BC) was prepared at 550 °C and was buried for aging in two different places: in a sandy loam soil in Spain for 15 months (Aged BC_1) and a sandy loam soil in USA for six months (Aged BC_2). RESULTS: Sorption experiments showed that all BCs were able to increase the affinity of soil towards coumarin, with the distribution coefficient following the order: unamended soil < Aged BC_2-amended soil < Aged BC_1-amended soil < Fresh BC-amended soil. All biochars ensure greater persistence of coumarin and the effect was more pronounced at high chemical dose (10 mg kg-1 ). Conversely, leaching studies in soil columns revealed that BCs were able to maintain coumarin within the first 5 cm of top-soil with total amount extracted ranging between 17% and 22% for BC-amended soil and <1% for unamended soil. Leaching was only observed when coumarin was added at the highest rate. Likewise, the bioefficacy of coumarin against lettuce was enhanced only at 10 kg ha-1 with BC-amended soil. CONCLUSIONS: Biochar application to agricultural soils is a promising tool for the management of natural compounds with potential use as biopesticides, such as coumarin, because it increases sorption, persistence and, in some cases, bioefficacy. The results reveal that this effect still persists with aging of BC in soils.
Assuntos
Poluentes do Solo , Solo , Adsorção , Disponibilidade Biológica , Carvão Vegetal , Cumarínicos , Feromônios , Poluentes do Solo/análise , EspanhaRESUMO
This study investigates the changes in sorption/desorption, dissipation, and leaching of the two enantiomeric forms of the allelochemical carvone, R-carvone and S-carvone, after amending an agricultural soil sample with two nanoengineered sorbents: biochar (BC) and organoclay (OCl). The sorption of carvone enantiomers was nonenantioselective and similarly improved by the addition of OCl and BC to the soil. However, OCl-amended soil showed reversible sorption, whereas BC-amended soil displayed sorption-desorption hysteresis. Dissipation of carvone enantiomers was enantioselective. Both amendments increased the half-life of the enantiomers in the soil. This effect was more pronounced for BC-amended soil and for S-carvone. Leaching of R- and S-carvone through soil columns was scarce in unamended soil (<7%), due to their rapid degradation during leaching, and null for OCl- and BC-amended soil, for which much of the applied R- and S-carvone remained in the top 0-5 cm of the amended soil layer. Addition of biochars and organoclays could help increase the persistence of carvone enantiomers in the rhizosphere, which may favor their use as residual pest-management substances.
Assuntos
Monoterpenos/química , Feromônios/química , Poluentes do Solo/química , Adsorção , Carvão Vegetal/química , Argila/química , Monoterpenos Cicloexânicos , Nanotecnologia , Rizosfera , Solo/químicaRESUMO
Coumarins represent an important family of allelochemicals with fungicidal, bactericidal, insecticidal, nematicidal, and herbicidal properties. Like for other allelochemicals, the short persistence of coumarins in soils can reduce their biological activity and hamper their application as environmentally friendly agrochemicals. We evaluated the sorption of the coumarin umbelliferone by eight soils and six sorbent materials, and then selected two nanoengineered sorbents, hexadecyltrimethylammonium-modified Arizona montmorillonite (SA-HDTMA) and olive-mill waste biochar (BC), to assess the effect of their addition to two distinct soils on umbelliferone sorption, persistence, and leaching. Umbelliferone was sorbed to a greater extent by the acid soils (A1-A2, Kd > 4.0 L kg-1) than by the alkaline soils (B1-B6, Kd < 0.5 L kg-1). The addition of BC and SA-HDTMA at a rate of 4% to alkaline soil (B2) increased the umbelliferone sorption Kd value from 0.3 to 1.6-2.0 L kg-1, whereas their addition to acid soil (A1) increased the Kd value from 4.6 to 12.2-19.0 L kg-1. Incubation experiments showed that BC had more impact than SA-HDTMA on the persistence of umbelliferone in the soils, increasing its half-life from 0.3-2.5 to 1.2-14.4 days, depending on the soil. Furthermore, the addition of BC to the top 0-5 cm of soil columns reduced leaching of umbelliferone and led to accumulation of umbelliferone residues in the top 0-5 cm soil layer. The addition of nanoengineered materials, such as organoclays and biochars, could thus be a suitable strategy to increase the persistence and reduce the mobility of coumarins in the rhizosphere with the aim of prolonging their biological activity.
RESUMO
In this study, we assessed the sorption, dissipation, and leaching of the herbicide mesotrione in soil amended with fresh and field-aged biochars, when added to the soil. The aging process was performed by burying the fresh biochar at 10 cm depth in three soils located in different points across the USA [Wisconsin (ABC_WI), Idaho (ABC_ID), and South Carolina (ABC_SC)] for six months. ABC_ID and ABC_SC slightly increased the sorption of mesotrione in soils, whereas ABC_WI removed greater amounts of herbicide from the solution. This was attributed to differences in water-soluble components and metal content of this aged biochar. Consequently, the persistence of the herbicide in the amended soils with fresh biochar and ABC_ID and ABC_SC were similar to that in unamended soils, while ABC_WI slightly increased mesotrione half-life. Differences between treatments were detected in leaching studies although no direct relationship with the dissipation batch studies was observed. Mesotrione leaching could not be detected in soil columns amended with ABC_WI and was high for the rest of treatments. The outcomes from this work demonstrate that temporal variability of biochar sorption capacities due to soil exposure can occur altering mesotrione's behavior in biochar-amended soils.
Assuntos
Carvão Vegetal/química , Cicloexanonas/química , Herbicidas/química , Poluentes do Solo/química , Adsorção , Solo/química , Fatores de TempoRESUMO
A local low value bentonite from Southern Spain (Raw Bentonite), previously decarbonated (Bent), was modified to improve its pesticide adsorption capacity with Fe3+, hexadecyltrimethylammonium (HDTMA) and the biopolymer chitosan (CH). Adsorption of pesticides on powdered samples showed that Fe3+ and HDTMA were appropriate modifiers for this purpose. The modification was optimized by saturation with Fe3+ (Bent-Fe) and hexadecyltrimethylammonium (Bent-HDTMA) and the obtained adsorbents were characterized by several physicochemical techniques (X-ray diffraction, thermogravimetric analysis, X-ray fluorescence, physisorption of N2). Their adsorption capacity to remove three widely used pesticides in Andalusian crops (terbuthylazine, tebuconazole and MCPA) from water was assessed and compared with the commercial organoclay Cloisite® 10A (Clo10). The modified bentonites adsorbed the selected pesticides in a percentage ranging from 30 to 100%, whereas sorption on Clo10 ranged from 30 to 90%. For their possible use as filtering beds, Bent-HDTMA, Bent-Fe and Clo10 were granulated by using three different binders (colophony resin and carnauba and bee waxes) at three different mixing ratios and the water resistance and pesticide adsorption of the granules were measured. Results showed that the granulation process did not alter the pesticide adsorption capacity of the powdered modified bentonites, and both waxes granules (carnauba and bee wax) showed better behavior than resin granules. In this work, we succeeded in the preparation of granulated adsorbents derived from a low cost material with similar behavior against a high purity smectite (precursor of Cloisite® 10A). This raises an alternative for this waste material to be used in filter systems for removing pesticides from contaminated water.
RESUMO
Addition of biomass chars (biochar) to soil reportedly suppresses emissions of nitrous oxide (N2O), a potent greenhouse and ozone-depleting gas, but the causes and endurance of the effect are unclear. To determine whether adsorption may play a role, adsorption isotherms of N2O were constructed at 273â¯K on outgassed samples of anoxically-prepared wood-derived chars (300-700⯰C) and on a subset briefly reheated in air at 400⯰C. Sorption by the chars was greater and more reversible than sorption by soils or soil mineral phases. Adsorption by chars increased with pyrolysis temperature and upon post-pyrolysis air oxidation. The Langmuir maximum capacity correlates well with the CO2-determined (but not N2-B.E.T.-determined) surface area. At environmentally realistic partial pressures in soil, N2O adsorption correlates with CO2 adsorption, and is found to predominate in the micropores (<1.5â¯nm), especially ultramicropores (<0.7â¯nm). Neither adsorption nor adsorption reversibility was affected by coating the char with soil organic matter extract. It is concluded that char added at levels above 1% in soil would act as a strong and reversible sink for N2O, and could be responsible for the temporary nature of N2O emission suppression observed in some cases.
RESUMO
BACKGROUND: Biochar, a carbon-rich product of biomass pyrolysis, could limit glyphosate transport in soil and remediate contaminated water. The present study investigates the sorption/desorption behavior of glyphosate on biochars prepared from different hardwoods at temperatures ranging from 350 to 900 °C to elucidate fundamental mechanisms. RESULTS: Glyphosate (1 mg L-1 ) sorption on biochars increased with pyrolysis temperature and was highest on 900 °C biochars; however, total sorption was low on a mass basis (<0.1 mg g-1 ). Sorption varied across feedstock materials, and isotherms indicated concentration dependence. Biochars with a greater fraction of micropores exhibited lower sorption capacities, and specific surface groups were also found to be influential. Prepyrolysis treatments with iron and copper, which complex glyphosate in soils, did not alter biochar sorption capacities. Glyphosate did not desorb from biochar with CaCl2 solution; however, up to 86% of the bound glyphosate was released with a K2 HPO4 solution. CONCLUSION: Results from this study suggest a combined impact of surface chemistry and physical constraints on glyphosate sorption/desorption on biochar. Based on the observed phosphate-induced desorption of glyphosate, the addition of P-fertilizer to biochar-amended soils can remobilize the herbicide and damage non-target plants; therefore, improved understanding of this risk is necessary. © 2017 Society of Chemical Industry.
Assuntos
Carvão Vegetal/química , Glicina/análogos & derivados , Herbicidas/química , Poluentes do Solo/química , Adsorção , Cátions/química , Fenômenos Químicos , Glicina/química , Fenômenos Físicos , Temperatura , GlifosatoRESUMO
The potential use of allelopathic and signaling compounds as environmentally friendly agrochemicals is a subject of increasing interest, but the fate of these compounds once they reach the soil environment is poorly understood. This work studied how the sorption, persistence, and leaching of the two enantiomers of the phytohormone abscisic acid (ABA) in agricultural soil was affected by the amendments of two organoclays (SA-HDTMA and Cloi10) and a biochar derived from apple wood (BC). In conventional 24-h batch sorption experiments, higher affinity toward ABA enantiomers was displayed by SA-HDTMA followed by Cloi10 and then BC. Desorption could be ascertained only in BC, where ABA enantiomers presented difficulties to be desorbed. Dissipation of ABA in the soil was enantioselective with S-ABA being degraded more quickly than R-ABA, and followed the order unamended > Cloi10-amended > BC-amended > SA-HDTMA-amended soil for both enantiomers. Sorption determined during the incubation experiment indicated some loss of sorption capacity with time in organoclay-amended soil and increasing sorption in BC-amended soil, suggesting surface sorption mechanisms for organoclays and slow (potentially pore filling) kinetics in BC-amended soil. The leaching of ABA enantiomers was delayed after amendment of soil to an extent that depended on the amendment sorption capacity, and it was almost completely suppressed by addition of BC due to its irreversible sorption. Organoclays and BC affected differently the final behavior and enantioselectivity of ABA in soil as a consequence of dissimilar sorption capacities and alterations in sorption with time, which will affect the plant and microbial availability of endogenous and exogenous ABA in the rhizosphere.
Assuntos
Ácido Abscísico/química , Silicatos de Alumínio/química , Carvão Vegetal/química , Recuperação e Remediação Ambiental/métodos , Praguicidas/química , Poluentes do Solo/química , Adsorção , Argila , Recuperação e Remediação Ambiental/instrumentação , Solo/química , Estereoisomerismo , Madeira/químicaRESUMO
Biochar (BC), solid biomass subjected to pyrolysis, can alter the fate of pesticides in soil. We investigated the effect of soil amendment with several biochars on the efficacy of two herbicides, clomazone (CMZ) and bispyribac sodium (BYP). To this aim, we evaluated CMZ and BYP sorption, persistence, and leaching in biochar-amended soil. Sorption of CMZ and BYP was greater in soil amended with BC produced at high temperature (700 °C). Significant sorption of the neutral CMZ herbicide also occurred in amended soil with BC prepared at low temperature (350 and 500 °C). For both herbicides, desorption possessed higher hysteretic behavior in soil amended with BC made at 700 °C (pyrolysis temperature). Dissipation of CMZ was enhanced after addition of BCs to soil, but no correlation between persistence and sorption was observed. Persistence of BYP was up to 3 times greater when BC made at 700 °C was added to soil. All BCs suppressed the leaching of CMZ and BYP as compared to the unamended soil. Amendment with 700 °C BC inhibited the action of CMZ against weeds, but 350 and 500 °C BCs had no such effect when added to soil. BYP activity was similar to that exhibited by unamended soil after the addition of 700 °C BC. From these results, biochar amendments can be a successful strategy to reduce the environmental impact of CMZ and BYP in soil. However, the phytotoxicity of soil-applied herbicides will depend on BC sorption characteristics and the pesticide's chemical properties, as well as the pesticide application timing (e.g., pre- or postemergence). According to our results, proper biochar screening with intended pesticides in light of the application mode (pre- or postemergence) is required prior to use to ensure adequate efficacy.
Assuntos
Benzoatos/química , Carvão Vegetal/química , Herbicidas/química , Isoxazóis/química , Oxazolidinonas/química , Pirimidinas/química , Poluentes do Solo/química , Adsorção , Solo/química , Temperatura , Fatores de TempoRESUMO
Although enantioselective sorption to soil particles has been proposed as a mechanism that can potentially influence the availability of individual chiral pesticide enantiomers in the environment, environmental fate studies generally overlook this possibility and assume that only biotic processes can be enantioselective, whereas abiotic processes, such as sorption, are non-enantioselective. In this work, we present direct evidence for the effect of the enantioselective sorption of a chiral pesticide in a natural soil on the availability of the single pesticide enantiomers for transport. Batch sorption experiments, with direct determination of the sorbed amounts, combined with column leaching tests confirmed previous observations that from non-racemic aqueous solutions the sorption of the chiral fungicide metalaxyl on the soil appeared to be enantioselective, and further demonstrated that the enantiomer that was sorbed to a greater extent (R-metalaxyl, Kd = 1.73 L/kg) exhibited retarded leaching compared to its optical isomer (S-metalaxyl, Kd = 1.15 L/kg). Interconversion and degradation of the pesticide enantiomers, which are potential experimental artifacts that can lead to erroneous estimates of sorption and its enantioselectivity, were discarded as possible causes of the observed enantioselective behavior. The results presented here may have very important implications for a correct assessment of the environmental fate of chiral pesticides that are incorporated into the environment as non-racemic mixtures, and also of aged chiral pesticide residues that have been transformed from racemic to non-racemic by biologically-mediated processes.
Assuntos
Alanina/análogos & derivados , Biodegradação Ambiental , Fungicidas Industriais/química , Poluentes do Solo/química , Solo/química , Estereoisomerismo , Alanina/química , Humanos , Praguicidas/químicaRESUMO
A large number of pesticides are chiral and reach the environment as mixtures of optical isomers or enantiomers. Agricultural practices can affect differently the environmental fate of the individual enantiomers. We investigated how amending an agricultural soil with composted olive-mill waste (OMWc) or its biochar (BC) at 2% (w:w) affected the sorption, degradation, and leaching of each of the two enantiomers of the chiral fungicide metalaxyl. Sorption of metalaxyl enantiomers was higher on BC (Kd ≈ 145 L kg(-1)) than on OMWc (Kd ≈ 22 L kg(-1)) and was not enantioselective in either case, and followed the order BC-amended>OMWc-amended>unamended soil. Both enantiomers showed greater resistance to desorption from BC-amended soil compared to unamended and OMWc-amended soil. Dissipation studies revealed that the degradation of metalaxyl was more enantioselective (R>S) in unamended and OMWc-amended soil than in BC-amended soil. The leaching of both S- and R-metalaxyl from soil columns was almost completely suppressed after amending the soil with BC and metalaxyl residues remaining in the soil columns were more racemic than those in soil column leachates. Our findings show that addition of BC affected the final enantioselective behavior of metalaxyl in soil indirectly by reducing its bioavailability through sorption, and to a greater extent than OMWc. BC showed high sorption capacity to remove metalaxyl enantiomers from water, immobilize metalaxyl enantiomers in soil, and mitigate the groundwater contamination problems particularly associated with the high leaching potential of the more persistent enantiomer.