Characterization of Diastereo‐ and Enantioselectivity in Degradation of Synthetic Pyrethroids in Soils

Permethrin (PM), cypermethrin (CP), and cyfluthrin (CF) are three important synthetic pyrethroids, which contain two, four, and four enantiomeric pairs (diastereomers) and thus have four, eight, and eight stereoisomers, respectively. In this study, the stereo‐ and enantioselective degradation of PM, CP, and CF in a Shijiazhuang alkaline yellow soil and a Wuhan acidic red soil were studied in detail by a combination of achiral and chiral high‐performance liquid chromatography (HPLC). The results showed that PM, CP, and CF degraded faster in Shijiazhuang soil than in Wuhan soil, and the dissipation rate followed an order of PM > CF > CP in both soils. The three pyrethroids exhibited similar diastereomer selectivity, while CP and CF showed higher enantioselectivity than PM. Moreover, the trans‐diastereomers degraded faster, and showed higher enantioselectivity than the corresponding cis‐diastereomers. For PM, the enantiomer 1S‐trans‐PM degraded most rapidly in both soils. As for CP and CF, the highest enantioselectivity was observed for diastereomer trans‐3, and the insecticidally active enantiomer 1R‐trans‐αS degraded fastest among the 8 CP or CF stereoisomers in both soils. In addition, the Wuhan acidic soil displayed higher diastereomer and enantiomer selectivity than the Shijiazhuang alkaline soil for the three pyrethroids. Further incubation of CF in an alkaline‐treated Wuhan soil showed that the dissipation rate greatly increased and the diastereo‐ and enantioselectivity significantly decreased after the alkaline treatment process. Chirality 28:72–77, 2016. © 2015 Wiley Periodicals, Inc.     

The influence of microbial communities for triadimefon enantiomerization in soils with different pH values

Enantiomers of chiral molecules can undergo interconversion leading to markedly different toxicities, which can introduce significant uncertainty when evaluating biological and environmental fates. However, enantiomerization (the reversible conversion of one enantiomer into the other) related to soil microorganism is rarely understood. For better understanding, S‐triadimefon and R‐triadimefon enantiopure were incubated in different soils with different pH value. Both high‐performance liquid chromatography and high‐throughput sequencing technology were used to explore target analytes quantitatively and microbial taxa related to the conversion process. Results revealed a significant enantiomerization among the soils. The alkaline soil from Beijing had a faster conversion than neutral soil from Changchun, while acidic soil from Wuhan had no conversion. At the same results, analysis of bacteria community showed higher abundance of Arthrobacter and Halomonas genus in alkaline soil than neutral soil after treatments, but the acidic soil was lower. Moreover, Arthrobacter and Halomonas were responsible for converting S‐triadimefon to R‐triadimefon and R‐triadimefon to S‐triadimefon in alkaline and neutral soil, respectively. Thus, these genera may be one of the reasons to explain the enantiomerization in different soils observed in this study. Thus, research at microbial level is necessary for efficient ecological risk assessment of chiral fungicide.     

Enhanced Biodegradation of Anthracene in Acidic Soil by Inoculated <Emphasis Type="Italic">Burkholderia</Emphasis> sp. VUN10013

The ability of Burkholderia sp. VUN10013 to degrade anthracene in microcosms of two acidic Thai soils was studied. The addition of Burkholderia sp. VUN10013 (initial concentration of 10(5) cells g(-1) dry soil) to autoclaved soil collected from the Plew District, Chanthaburi Province, Thailand, supplemented with anthracene (50 mg kg(-1) dry soil) resulted in complete degradation of the added anthracene within 20 days. In contrast, under the same test conditions but using autoclaved soil collected from the Kitchagude District, Chanthaburi Province, Thailand, only approximately 46.3% of the added anthracene was degraded after 60 days of incubation. In nonautoclaved soils, without adding the VUN10013 inocula, 22.8 and 19.1% of the anthracene in Plew and Kitchagude soils, respectively, were degraded by indigenous bacteria after 60 days. In nonautoclaved soil inoculated with Burkholderia sp. VUN10013, the rate and extent of anthracene degradation were considerably better than those seen in autoclaved soils or in uninoculated nonautoclaved soils in that only 8.2 and 9.1% of anthracene remained in nonautoclaved Plew and Kitchagude soils, respectively, after 10 days of incubation. The results showed that the indigenous microorganisms in the pristine acidic soils have limited ability to degrade anthracene. Inoculation with the anthracene-degrading Burkholderia sp. VUN10013 significantly enhanced anthracene degradation in such acidic soils. The indigenous microorganisms greatly assisted the VUN10013 inoculum in anthracene degradation, especially in the more acidic Kitchagude soil.     

Stereoselective Degradation and Microbial Epimerization of Triadimenol in Soils

Triadimenol is a widely used triazole fungicide and consists of four stereoisomers with 1R,2S, 1S,2R, 1R,2R, and 1S,2S configurations. The trans‐enantiomeric pair (1R,2S‐isomer and 1S,2R‐isomer) is also called triadimenol‐A and the cis‐enantiomeric pair (1R,2R‐isomer and 1S,2S‐isomer) triadimenol‐B. In this study, the stereoselective degradation and chiral stability of triadimenol in two soils were investigated in details. The dissipation of technical triadimenol, a 6:1 mixture of triadimenol‐A and triadimenol‐B, showed significant epimerization from triadimenol‐A to triadimenol‐B occurred along with the dissipation process. The degradation exhibited some stereoselectivity, resulting in a concentration order of 1S,2S > 1R,2R > 1R,2S > 1S,2R or 1S,2S > 1R,2R > 1S,2R > 1R,2S at the end of the 100 days incubation for Baoding soil or Wuhan soil, respectively. Further incubation of triadimenol‐B revealed no epimerization, i.e. triadimenol‐B was configurationally stable in soil, and 1R,2R‐triadimenol degraded slightly slower in the former part and slightly faster in the later part of the incubation than 1S,2S‐triadimenol. Moreover, by incubation of enantiopure 1S,2R‐triadimenol and 1R,2S‐triadimenol, the results documented the epimerization for each enantiomer occurred at both C‐1 and C‐2 positions. Finally, the present work also documented that the enantiomerization reaction for all the four stereoisomers was nearly negligible in the soils. Chirality 25:355‐360:, 2013. © 2013 Wiley Periodicals, Inc.     

Effect of corn plant on survival and phenanthrene degradation capacity of Pseudomonas sp. UG14LR in two soils

A study was undertaken to assess if corn (Zea mays L.) can enhance phenanthrene degradation in two soils inoculated with Pseudomonas sp. UG14Lr. Corn increased the number of UG14Lr cells in both soils, especially in the acidic soiL Phenanthrene was degraded to a greater extent in UG14Lr-inoculated or corn-planted soils than uninoculated and unplanted soils. The spiked phenanthrene was completely removed within 70 days in all the treatments in slightly alkaline soil. However, in acidic soil, complete phenanthrene removal was found only in the corn-planted treatments. The shoot and root lengths of corn grown in UG14Lr-inoculated soils were not different from those in non-inoculated soil between the treatments. The results showed that in unplanted soil, low pH adversely affected the survival and phenanthrene degradation ability of UG14Lr. Planting of corn significantly enhanced the survival of UG14Lr cells in both the bulk and rhizospheric soil, and this in turn significantly improved phenanthrene degradation in acidic soil. Re-inoculation of UG14Lr in the acidic soil increased the number of UG14Lr cells and enhanced phenanthrene degradation in unplanted soil. However, in corn-planted acidic soils, re-inoculation of UG14Lr did not further enhance the already active phenanthrene degradation occurring in both the bulk or rhizospheric soils.     

垃圾渗滤液在土壤中的生物降解动态

通过室内好氧、厌氧2种培养,研究了3种不同填埋年限垃圾渗滤液在红壤和潮土中的生物降解动态.鲜样、天井洼样、水阁样垃圾渗滤液分别为填埋0年、4～5年和12年的垃圾渗滤液.结果表明,垃圾渗滤液在前7 d降解相对较快.在好氧培养条件下,红壤鲜样、天井洼样、水阁样渗滤液在前7 d的表观降解率为88.9%、60.5%、25.0%;潮土中的表观降解率更大,分别为96.6%、80.4%和65.0%;7 d后下降趋势均趋于平缓.在相同土壤中,填埋龄越短的垃圾渗滤液的表观降解率越大,在厌氧培养条件下的情况与此类似,但降解率不如好氧条件下高.在没有土壤介质参与的条件下(如低洼处积存的渗滤液),3种垃圾渗滤液自身降解速率均符合一级动力学方程.鲜样垃圾渗滤液降解的半衰期为12～16 d,其余垃圾渗滤液降解的半衰期为20～30 d.垃圾渗滤液一旦进入土壤环境,降解速率会大大加快.土壤处理垃圾渗滤液有一定的功效.     

Relationship between enantioselective transformation of racemic quizalofop‐ethyl and soil bacterial diversity: A destructive approach

This study investigated the resilience of bacterial diversity in soils restored after autoclaving, in terms of richness, evenness and community structure, and its feedback on the enantioselective transformation of racemic quizalofop‐ethyl (rac‐QE). Microbial biomass carbon (MBC) and bacterial richness (indexed by operational taxonomic units [OTUs]) in restored soil recovered to approximately 50% and 29%, respectively, of the native soil within 43 days. Bacterial evenness was much lower in restored soil than in native soil. The relative proportions of dominant bacterial genera differed significantly (P < .05) between restored and native soils. Importantly, two major bacterial genera that recolonized restored soil were not detected in native soil. Highly enantioselective transformation of rac‐QE was observed in restored soils, whereas QE enantiomers exhibited comparable transformation rates in native soils. The second‐round enantioselective transformation of rac‐QE was altered by the first‐round transformation of enantiopure quizalofop‐P‐ethyl (R‐P‐QE) in restored and native soils through selective effects of R‐P‐QE on the bacterial community. The transformation rate of rac‐QE was predominantly determined by bacterial abundance and richness, while the enantioselectivity was correlated more with bacterial structure.     

Functional Establishment of Introduced Chlorobenzoate Degraders Following Bioaugmentation with Newly Activated Soil

Introduced degraders often do not survive when applied to polluted sites; however, the potential for successful bioaugmentation may be increased if newly activated soil (containing indigenous degrader populations recently exposed to the contaminant) or potentially active soil (containing indigenous degrader populations not previously exposed to the contaminant) is used as the inoculant. To investigate this concept, Madera and Oversite soils were amended with 0 or 500 micrograms of 2-, 3-, or 4-chlorobenzoate per gram soil. The Madera degraded 2-chlorobenzoate while the Oversite degraded 3- and 4-chlorobenzoate. After 22 days of incubation, non-active soils that had not degraded chlorobenzoate were bioaugmented with the appropriate activated soil that had been exposed to and degraded chlorobenzoate. Thus, Oversite soil that had not degraded 2-chlorobenzoate was bioaugmented with Madera soil that had degraded 2-chlorobenzoate. Likewise, Madera soil that had not degraded 3- or 4-chlorobenzoate was bioaugmented with the Oversite soil that had degraded 3- or 4-chlorobenzoate. Additionally, the non-active soils were bioaugmented with the corresponding potentially active soils. The Oversite soil amended with activated Madera soil degraded the 2-chlorobenzoate within 3 days of bioaugmentation. The Madera soil amended with activated Oversite soils degraded the 3- and 4-chlorobenzoate within 20 and 6 days, respectively. Large degrader populations developed in microcosms bioaugmented with activated soil, and shifts in the 3- and 4-CB degrader community structures occurred following bioaugmentation. In contrast, bioaugmentation with potentially active soil did not impact degradation. The results indicate the potential for bioaugmentation with newly activated soil to enhance contaminant degradation.     

Biodegradation of polycyclic aromatic hydrocarbons (PAHs) by Cladosporium sphaerospermum isolated from an aged PAH contaminated soil

The ability of a Deuteromycete fungus, Cladosporium sphaerospermum, previously isolated from soil of an aged gas manufacturing plant, to degrade polycyclic aromatic hydrocarbons was investigated. This strain was able to degrade PAHs in non-sterile soils (average 23%), including high molecular weight PAHs, after 4 weeks of incubation. In a microcosm experiment, PAH depletion was clearly correlated to fungal establishment. In liquid culture, this strain degraded rapidly benzo(a)pyrene during its early exponential phase of growth (18% after 4 days of incubation). Among extracellular ligninolytic enzyme activities tested, only laccase activity was detected in liquid culture in the absence or in presence of benzo(a)pyrene. C. sphaerospermum might be a potential candidate for an effective bioremediation of aged PAH-contaminated soils.     

Lime Treatment of Explosives-Contaminated Soil from Munitions Plants and Firing Ranges

Microcosms were prepared using soils from munitions plants and active firing ranges and treated with hydrated lime. The presence of particulate explosives and co-contaminants, and the concentration of soil total organic carbon (TOC) on the alkaline hydrolysis reaction were studied. Trinitrobenzene (TNB) and dinitrobenzene (DNB) were sensitive to alkaline hydrolysis under these experimental conditions. The TNT metabolites, 2A- and 4A-DNT, were also removed, although more slowly than the parent compound, and the reaction required a higher pH (>12). RDX retention in the soil was proportional to the TOC content. The degradation intermediates of the alkaline hydrolysis reaction partitioned in the soil matrix in a manner similar to the parent. Solid particles of explosives are also degraded by alkaline hydrolysis. RDX and HMX exhibited 74 and 57% removal, respectively, in 21 days. TNT, as whole and broken grains, showed 83 and 99.9% removal in 21 days, respectively. The propellants, 2,4- and 2,6-DNT, were insensitive to alkaline hydrolysis. Alkaline hydrolysis is an inexpensive and effective means of reducing the varied explosives contamination.     

百菌清对土壤氧化亚氮和二氧化碳排放的影响

在25 ℃、60%WHC（最大持水量）的好氧条件下进行14 d的培养试验,研究杀菌剂百菌清在添加水平为0 mg·kg^-1（CK）、5.5 mg·kg^-1（田间施用量,FR）及110 mg·kg^-1(20FR)和220 mg·kg^-1（40FR）时对酸性、中性和碱性土壤中N₂O和CO₂排放的影响.结果表明：百菌清对N₂O和CO₂排放的影响取决于土壤类型和施用浓度.与对照相比,百菌清在20FR和40FR时显著抑制了酸性土壤N₂O的产生与排放;3种施用量均显著促进了中性土壤N₂O的排放,其中FR水平的促进效果最显著;高浓度（20FR和40FR）的百菌清在培养初期抑制了碱性土壤N₂O的排放,而在培养后期显著促进了N₂O的排放.田间用量的百菌清对土壤CO₂排放量没有明显影响;高浓度（20FR和40FR）时显著促进了酸性土壤CO₂的排放,显著抑制了中性和碱性土壤CO₂的排放.     

Abscisic acid in soils: What is its function and which factors and mechanisms influence its concentration?

Abscisic acid (ABA) was detected in aqueous extracts of a range of different soils, beneath a range of crops, pasture and forest species. Assuming that all the ABA is dissolved in the soil solution concentrations ranged from 0.6–2.8 nM. This is in the range which computer simulations predict is required in soils in order to prevent ABA release from the root hair zones of plant roots. The concentration of ABA in the soil solution was highest in acid soils and in soils with reduced moisture, and was lowest in moist, neutral and moderately alkaline soils. ABA in the soil solution of maize fields increased during the vegetative period. After incubation in soil for 72 h, radioactive ABA was degraded by 30–40%. Tetcyclacis, an inhibitor of the oxidative breakdown of ABA, completely prevented the degradation of ABA in the soil solution. Acid conditions and high salt concentrations significantly retarded ABA breakdown.     

Effects of soil pH on rhizoctonia damping-off of sugar beet and disease suppression induced by soil amendment with crop residues

Effects of soil pH on damping-off of sugar beet by R. solani (AG2-2) and soil suppressiveness against the disease were studied by comparing disease incidences in pasteurized versus non-pasteurized, infested soils. Soil pH was correlated neither to disease incidence in five soils ranging from pH 4.5 to 7.2 nor to indigenous disease suppressiveness, the difference in disease incidences between non-treated soil and its pasteurized counterpart. When an alkaline soil was acidified with H₂SO₄, disease suppression markedly declined, increasing disease incidence in the non-pasteurized soil. Inversely, disease suppression was enhanced when an acidic soil was neutralized by adding Ca(OH)₂. Soil amendment with dried peanut plant residue suppressed the disease in two pasteurized, near-neutral soils, lowering the incidence to the levels in the non-pasteurized soils, but was less effective in two pasteurized, acidic soils. In vitro mycelial growth of the pathogen and seedling growth was optimal at pH 4.5–5.5 and 6.0–6.5, respectively, and declined as the pH became higher or lower. (Conclusions) These results suggest that the seedlings were inhibited more than the pathogen at low pH, and that indigenous disease suppressiveness through the activity of antagonistic soil microorganisms operates effectively in near-alkaline soils, but is weakened or nullified in acidic soils.     

Fungal communities associated with degradation of polyester polyurethane in soil

Soil fungal communities involved in the biodegradation of polyester polyurethane (PU) were investigated. PU coupons were buried in two sandy loam soils with different levels of organic carbon: one was acidic (pH 5.5), and the other was more neutral (pH 6.7). After 5 months of burial, the fungal communities on the surface of the PU were compared with the native soil communities using culture-based and molecular techniques. Putative PU-degrading fungi were common in both soils, as <45% of the fungal colonies cleared the colloidal PU dispersion Impranil on solid medium. Denaturing gradient gel electrophoresis showed that fungal communities on the PU were less diverse than in the soil, and only a few species in the PU communities were detectable in the soil, indicating that only a small subset of the soil fungal communities colonized the PU. Soil type influenced the composition of the PU fungal communities. Geomyces pannorum and a Phoma sp. were the dominant species recovered by culturing from the PU buried in the acidic and neutral soils, respectively. Both fungi degraded Impranil and represented >80% of cultivable colonies from each plastic. However, PU was highly susceptible to degradation in both soils, losing up to 95% of its tensile strength. Therefore, different fungi are associated with PU degradation in different soils but the physical process is independent of soil type.     

不同肥力棕壤溶解性有机碳、氮生物降解特性

溶解性有机碳、氮在土壤全碳、全氮含量中所占的比例很小,但却是土壤有机质中最为重要和活跃的部分。研究利用土壤溶解性有机碳、氮生物降解的测定方法,分别选取沈阳农业大学试验站不同肥力及与定位试验地紧密相连的自然林地棕壤为研究对象,开展棕壤溶解性有机碳、氮的生物降解特性的研究,为了解溶解性有机碳、氮在土壤生态系统碳、氮循环中的作用,探讨棕壤溶解性有机碳、氮与土壤肥力的关系提供理论依据。研究结果表明,棕壤林地溶解性有机碳、氮的含量最高,高肥处理次之,低肥处理含量最低。棕壤溶解性有机碳、氮与全碳、全氮和微生物量碳、氮的相关性达到极显著水平,与土壤肥力紧密相关,可以作为指示土壤肥力的重要指标。不同肥力棕壤溶解性有机碳、氮的降解速率在培养初期较快,而后逐渐减慢,降解数据符合双指数衰变模型。棕壤溶解性有机碳分别由降解速率不同的两个库组成：周转时间在1d的易分解部分和周转时间大约为400d的难分解部分。棕壤溶解性有机氮是由周转速率大约为2d的易降解部分和周转速率在99～105d左右的难分解部分组成． 经过42d的培养,浸提液中剩余溶解性有机质碳氮比值较培养前有所增加。     

Initial-phase optimization for bioremediation of munition compound-contaminated soils.

We examined the bioremediation of soils contaminated with the munition compounds 2,4,6-trinitrotoluene (TNT), hexahydro-1,3,5-trinitro-1,3,5-triazine, and octahydro-1,3,5,7-tetranitro-1,3,5,7-tetraazocine by a procedure that produced anaerobic conditions in the soils and promoted the biodegradation of nitroaromatic contaminants. This procedure consisted of flooding the soils with 50 mM phosphate buffer, adding starch as a supplemental carbon substrate, and incubating under static conditions. Aerobic heterotrophs, present naturally in the soil or added as an inoculum, quickly removed the oxygen from the static cultures, creating anaerobic conditions. Removal of parent TNT molecules from the soil cultures by the strictly anaerobic microflora occurred within 4 days. The reduced intermediates formed from TNT and hexahydro-1,3,5-trinitro-1,3,5-triazine were removed from the cultures within 24 days, completing the first stage of remediation. The procedure was effective over a range of incubation temperatures, 20 to 37 degrees C, and was improved when 25 mM ammonium was added to cultures buffered with 50 mM potassium phosphate. Ammonium phosphate buffer (50 mM), however, completely inhibited TNT reduction. The optimal pH for the first stage of remediation was between 6.5 and 7.0. When soils were incubated under aerobic conditions or under anaerobic conditions at alkaline pHs, the TNT biodegradation intermediates polymerized. Polymerization was not observed at neutral to slightly acidic pHs under anaerobic conditions. Completion of the first stage of remediation of munition compound-contaminated soils resulted in aqueous supernatants that contained no munition residues or aminoaromatic compounds.     

Biotic and Abiotic Soil Properties Influence Survival of Listeria monocytogenes in Soil

Listeria monocytogenes is a food-borne pathogen responsible for the potentially fatal disease listeriosis and terrestrial ecosystems have been hypothesized to be its natural reservoir. Therefore, identifying the key edaphic factors that influence its survival in soil is critical. We measured the survival of L. monocytogenes in a set of 100 soil samples belonging to the French Soil Quality Monitoring Network. This soil collection is meant to be representative of the pedology and land use of the whole French territory. The population of L. monocytogenes in inoculated microcosms was enumerated by plate count after 7, 14 and 84 days of incubation. Analysis of survival profiles showed that L. monocytogenes was able to survive up to 84 days in 71% of the soils tested, in the other soils (29%) only a short-term survival (up to 7 to 14 days) was observed. Using variance partitioning techniques, we showed that about 65% of the short-term survival ratio of L. monocytogenes in soils was explained by the soil chemical properties, amongst which the basic cation saturation ratio seems to be the main driver. On the other hand, while explaining a lower amount of survival ratio variance (11%), soil texture and especially clay content was the main driver of long-term survival of L. monocytogenes in soils. In order to assess the effect of the endogenous soils microbiota on L. monocytogenes survival, sterilized versus non-sterilized soils microcosms were compared in a subset of 9 soils. We found that the endogenous soil microbiota could limit L. monocytogenes survival especially when soil pH was greater than 7, whereas in acidic soils, survival ratios in sterilized and unsterilized microcosms were not statistically different. These results point out the critical role played by both the endogenous microbiota and the soil physic-chemical properties in determining the survival of L. monocytogenes in soils.     

A Previously Unexposed Forest Soil Microbial Community Degrades High Levels of the Pollutant 2,4,6-Trichlorophenol

2,4,6-Trichlorophenol (2,4,6-TCP) is a hazardous pollutant that is efficiently degraded by some aerobic soil bacterial isolates under laboratory conditions. The degradation of this pollutant in soils and its effect on the soil microbial community are poorly understood. We report here the ability of a previously unexposed forest soil microbiota to degrade high levels of 2,4,6-TCP and describe the changes in the soil microbial community found by terminal restriction fragment length polymorphism (T-RFLP) analysis. After 30 days of incubation, about 50% degradation of this pollutant was observed in soils amended with 50 to 5,000 ppm of 2,4,6-TCP. The T-RFLP analysis showed that the soil bacterial community was essentially unchanged after exposure to up to 500 ppm of 2,4,6-TCP. However, a significant decrease in richness was found with 2,000 and 5,000 ppm of 2,4,6-TCP, even though the removal of this pollutant remained high. The introduction of Ralstonia eutropha JMP134 or R. eutropha MS1, two efficient 2,4,6-TCP degraders, to this soil did not improve degradation of this pollutant, supporting the significant bioremediation potential of this previously unexposed, endogenous forest soil microbial community.     

Transformation of urea and ammonium sulphate in different soils

Summary The transformation of urea and ammonium sulphate in Ladwa sandy loam and Balsamand sand was studied in laboratory. Urea took at least one week in sandy loam and 2 weeks in sandy soils to hydrolyse completely. The process of hydrolysis was faster in finer soil with high organic matter than in coarse soil having low organic matter. There was no nitrification upto 3 days in sandy loam and upto 7 days in sandy soils, respectively, but there was immobilization of NO₃-N during these initial periods. The NO₃-N content at the end of incubation period (35 days) was more in case of urea than in case of ammonium sulphate treated samples in sandy loam soil and reverse was true in sandy soil. The hydrolysis of urea did not follow zero or first order kinetics as proposed in previous studies.