Microbial degradation pathways of the herbicide dichlobenil in soils with different history of dichlobenil-exposure

This is the first detailed study of metabolite production during degradation of the herbicide 2,6-dichlorobenzonitrile (dichlobenil). Degradation of dichlobenil and three potential metabolites: 2,6-dichlorobenzamide (BAM), 2,6-dichlorobenzoic acid (2,6-DCBA) and ortho-chlorobenzamide (OBAM) was studied in soils either previously exposed or not exposed to dichlobenil using a newly developed HPLC method. Dichlobenil was degraded in all four soils; BAM and 2,6-DCBA were only degraded in soils previously exposed to dichlobenil (100% within 35-56 days and 85-100% in 56 days, respectively), and OBAM in all four soils (25-33% removal in 48 days). BAM produced from dichlobenil was either hydrolyzed to 2,6-DCBA or dechlorinated to OBAM, which was further hydrolyzed to ortho-chlorobenzoic acid. BAM was rapidly mineralized in previously exposed soils only. All potential metabolites and the finding that BAM was a dead-end metabolite of dichlobenil in soils not previously exposed to dichlobenil needs to be included in risk assessments of the use of dichlobenil.     

Degradation and sorption of imidacloprid in dissimilar surface and subsurface soils

Degradation and sorption/desorption are important processes affecting the leaching of pesticides through soil. This research characterized the degradation and sorption of imidacloprid (1-[(6-chloro-3-pyridinyl)-methyl]-N-nitro-2-imidazolidinimine) in Drummer (silty clay loam) and Exeter (sandy loam) surface soils and their corresponding subsurface soils using sequential extraction methods over 400 days. By the end of the incubation, approximately 55% of imidacloprid applied at a rate of 1.0 mg kg^?1 degraded in the Exeter sandy loam surface and subsurface soils, compared to 40% of applied imidacloprid within 300 days in Drummer surface and subsurface soils. At the 0.1 mg kg^?1 application rate, dissipation was slower for all four soils. Water-extractable imidacloprid in Exeter surface soil decreased from 98% of applied at day 1 to > 70% of the imidacloprid remaining after 400 d, as compared to 55% in the Drummer surface soil at day 1 and 12% at day 400. These data suggest that imidacloprid was bioavailable to degrading soil microorganisms and sorption/desorption was not the limiting factor for biodegradation. In subsurface soils > 40% of ¹⁴C-benzoic acid was mineralized over 21 days, demonstrating an active microbial community. In contrast, cumulative ¹⁴CO₂ was less than 1.5% of applied ¹⁴C-imidacloprid in all soils over 400 d. Qualitative differences in the microbial communities appear to limit the degradation of imidacloprid in the subsurface soils.     

Degradation and sorption of imidacloprid in dissimilar surface and subsurface soils

Degradation and sorption/desorption are important processes affecting the leaching of pesticides through soil. This research characterized the degradation and sorption of imidacloprid (1-[(6-chloro-3-pyridinyl)-methyl]-N-nitro-2-imidazolidinimine) in Drummer (silty clay loam) and Exeter (sandy loam) surface soils and their corresponding subsurface soils using sequential extraction methods over 400 days. By the end of the incubation, approximately 55% of imidacloprid applied at a rate of 1.0 mg kg(-1) degraded in the Exeter sandy loam surface and subsurface soils, compared to 40% of applied imidacloprid within 300 days in Drummer surface and subsurface soils. At the 0.1 mg kg(-1) application rate, dissipation was slower for all four soils. Water-extractable imidacloprid in Exeter surface soil decreased from 98% of applied at day 1 to >70% of the imidacloprid remaining after 400 d, as compared to 55% in the Drummer surface soil at day 1 and 12% at day 400. These data suggest that imidacloprid was bioavailable to degrading soil microorganisms and sorption/desorption was not the limiting factor for biodegradation. In subsurface soils > 40% of (14)C-benzoic acid was mineralized over 21 days, demonstrating an active microbial community. In contrast, cumulative (14)CO(2) was less than 1.5% of applied (14)C-imidacloprid in all soils over 400 d. Qualitative differences in the microbial communities appear to limit the degradation of imidacloprid in the subsurface soils.     

Determination of acibenzolar-S-methyl and its acidic metabolite in soils by HPLC-diode array detection

A simple and accurate method for the analysis of acibenzolar-S-methyl (benzo[1,2,3]thiadiazole-7-carbothioic acid-S-methyl ester; CGA 245 704; ASM) and its major conversion product, benzo[1,2,3]thiadiazole-7-carboxylic acid (CGA 210 007; BTC), in soils is presented. ASM extraction from soil samples was performed using acetonitrile and BTC was extracted with a mixture of potassium phosphate buffer (0.5 M, pH 3) and acetonitrile (70:30 %, v/v). Both extracts were directly analyzed in a high-performance liquid chromatography-diode array detection (HPLC-DAD) system. Pesticide separation was achieved on a C18 (4.6 mm × 150 mm, 5 μm) analytical column with a isocratic elution of acetonitrile:water 40:60 % (v/v) with 0.6 mL L?1 acetic acid at a flow rate of 1 mL min?1. Linear regression coefficients (r (2)) of the external calibration curves were always above 0.9997. The limits of detection (LOD) and quantification (LOQ) of the method were 0.005 and 0.02 mg kg?1 for ASM, and 0.01 and 0.05 mg kg?1 for BTC, respectively. Recoveries were investigated at six fortification levels and were in the range of 90-120 % for ASM and 74-96 % for BTC with relative standard deviations (RSDs) below 11 % in all cases. The method was also validated by analyzing freshly spiked soil samples with 2.7% organic matter content at 0.5 mg kg?1 level, with slightly lower recovery values only for ASM. Moreover, recoveries for intermediate aged residues of the analytes were similar to fresh residues. This method was also applied to determine ASM half-life (t(?) = 8.7 h) and the rate of the acidic metabolite formation.     

Sorption characteristics of cyromazine and its metabolite melamine in typical agricultural soils of China

A myriad of physical, chemical, and biological processes controls the fate of organic contaminants in soils. The knowledge of bioavailability of a contaminant in soil can be useful to conduct environmental risk assessment. We conducted batch equilibrium experiments to investigate the sorption of cyromazine (CA) and its metabolite melamine (MA) onto five typical soils of China belonging to suborders Ali-Perudic Ferrosols, Udic Argosols, Gleyic-Stagnic Anthrosols, Ustic Cambosols, and Udic Isohumosols. Results showed that sorption of CA and MA onto soils was linear, as indicated by the Freundlich and Langmuir models. Different sorption behaviors of CA and MA were observed on the five agricultural soils, with lgK _f values (Freundlich model) of 1.6505–2.6557 and 1.632–2.549, respectively. Moreover, the K _f values for CA and MA were positively correlated with soil organic matter (r?=?0.989, r?=?0.976) and significantly negatively correlated with pH (r?=??0.938, r?=??0.964). The free energy of sorption of CA and MA ranged from ?20.8 to ?23.0 kJ mol^?1 and ?20.8 to ?22.8 kJ mol^?1, respectively, suggesting that the sorption of CA and MA onto the soils is primarily a physical process.     

Aerobic biodegradation of dichloroethylenes in surface and subsurface soils

Laboratory studies were conducted to examine the aerobic biodegradation of dichloroethylenes (cis-1,2-DCE, trans-1,2-DCE and 1,1-DCE) in soil and groundwater. Authentic surface and subsurface materials with no reported DCE exposure history were used. All DCE isomers were observed to biodegrade to varying degrees in the soils examined. Use of radiolabeled [14C] test chemicals allowed correlation of DCE disappearance with mineralization to 14CO2. Study results indicate that naturally occurring microorganisms in soil and groundwater are capable of degrading cis-1,2-, trans-1,2- and 1,1-DCE without laboratory supplementation of exogenous organic nutrients, or previous exposure history. The data further suggest that degradative potential may vary with soil type, DCE isomer structure, and concentration.     

The flame retardant tetrabromobisphenol-A and its metabolite found in river and marine sediments in Japan

Tetrabromobisphenol-A (TBBP), used as a flame retardant, was detected in river sediments collected in Osaka, Japan, at a concentration range from 22 to 140 μg/kg (ppb), as determined on a dry weight basis. TBBP was also found in marine sediments collected at Osaka Bay, though the TBBP levels of these samples were much lower than those from river sediments. Dimethyl ether derivative of TBBP (TBBP-DM), thought to be a decomposition product from microbial methylation, was found in the river sediments but in none of the marine sediments. TBBP-DM residues were about one-hundredth of the TBBP levels.     

Fate of napropamide herbicide in selected Malaysian soils

This study was carried out to determine the sorption-desorption, degradation and leaching of napropamide in selected Malaysian soils. The sorption capacities of the selected Malaysian soils for napropamide were the following in descending order: Linau > Teringkap > Gunung Berinchang > Jambu > Rudua > Baging soil. The results indicate that napropamide degradation decreased with increasing soil sorption capacity. Napropamide was leached out earlier in the Baging soil than the other soils. Overall, the application of napropamide in the selected Malaysian soils would not pose a threat to the environment except in soil with low organic matter and clay content and high hydraulic conductivity, such as the Baging soil.     

Persistence of herbicide fenoxaprop ethyl and its acid metabolite in soil and wheat crop under Indian tropical conditions

The persistence of fenoxaprop ethyl {Ethyl (RS)-2-[4-(6-chloro-1,3-benzoxazol-2-yloxy) phenoxy] propionate} herbicide and its active metabolite fenoxaprop acid was investigated in soil and wheat crop. Fenoxaprop acid was prepared by alkaline hydrolysis of fenoxaprop ethyl. A HPLC method was developed in which fenoxaprop ethyl herbicide and its acid metabolite showed sharp single peak at 6.44 and 2.61 min respectively. The sensitivity of the method for ester and acid was 2 and 1 ng respectively with limit of detection of 0.1 and 0.05 μg mL^?1. The recovery of fenoxaprop ethyl and fenoxaprop acid from soil, wheat straw and grain ranged between 73.8–80.2%. In a field experiment fenoxaprop ethyl (Puma super® 10 EC) when applied to wheat crop at the rate of 120 g and 240 g a.i. ha^-1 as post emergence spray, fenoxaprop ethyl converted to fenoxaprop acid. Residues of fenoxaprop ethyl and acid dissipated in soil with a half-life of 0.5 and 7.3 days, respectively. At harvest no detectable residues of fenoxaprop ethyl or acid were observed in soil, wheat grain and straw samples.     

Degradation of monocrotophos in soils

The degradation of a widely used organophosphorus insecticide, monocrotophos (dimethyl (E)-1-methyl-2-methylcarbamoyl vinyl phosphate) in two Indian agricultural soils at two concentration levels, 10 and 100 microg g(-1) soil under aerobic conditions at 60% water-holding capacity at 28+/-4 degrees C was studied in a laboratory. The degradation of monocrotophos at both concentrations in black vertisol and red alfinsol soils was rapid accounting for 96-98% of the applied quantity and followed the first-order kinetics with rate constants (k) of 0.0753 and 0.0606 day(-1) and half-lives (t1/2) of 9.2 and 11.4 days, respectively. Degradation of monocrotophos in soils proceeded by hydrolysis with formation of N-methylacetoacetamide. Even three additions of monocrotophos at 10 microg g(-1) soil did not result in its enhanced degradation. However, there was cumulative accumulation of N-methylacetoacetamide in soils pretreated with monocrotophos to the tune of 7-15 microg g(-1) soil. Both biotic and abiotic factors were involved in degradation of monocrotophos in soils.     

Microbial physiology-based model of ethanol metabolism in subsurface sediments

Dense non-aqueous phase liquids (DNAPLs) present in the subsurface may contain surface active compounds that impact DNAPL migration and distribution. While a number of studies have revealed the role surface active compounds play in altering the wettability of quartz sand, few have considered the implications for other minerals common to contaminated sites. This study extends understanding of DNAPL/surfactant wettability to iron oxide surfaces. Specifically, quartz and iron oxide-coated sands in a tetrachloroethene (PCE)/water system containing the organic base (an organic molecule that acts as a base) dodecylamine (DDA) were compared at a variety of scales. Wettability of the minerals' surfaces, and the impact of wettability on capillary resistance to DNAPL entry, were assessed as a function of pH through: (i) advancing and receding contact angles, (ii) primary drainage capillary pressure-saturation experiments, and (iii) small, two-dimensional, flow cell experiments. The work revealed that, at neutral pH and under identical boundary capillary pressures, DNAPL invaded quartz sand but not iron oxide-coated sand; however, at low pH, DNAPL invaded both sands equally. These differences were demonstrated to be due to wettability alterations associated with the strength of attractive forces between DDA and the mineral surface, dictated by the isolectric point of the minerals and system pH. Observed differences in DNAPL invasion behavior were consistent with measured intrinsic contact angles and P(c)-S relationships, the latter requiring scaling by the operative contact angle inside the porous medium for a meaningful comparison. This study suggests that the distribution of minerals (and, more specifically, their isoelectric points), as well as the aqueous phase pH at a given site, may have a significant impact on the DNAPL source zone architecture.     

Sorption and desorption of the diketonitrile metabolite of isoxaflutole in soils

Isoxaflutole is a new pre-emergence corn herbicide that undergoes rapid conversion to a diketonitrile derivative (DKN) in soils. Sorption-desorption studies were conducted in five different soils varying in physical and chemical properties. A batch equilibration technique was used with total initial aqueous solution concentrations of DKN at 0.25, 0.75, 2.0, 8.0, 25, 75, 150, and 250 mg l(-1). After the sorption process, two subsequent desorptions were conducted with an equilibration period of 7 days. A high correlation existed between the desorption coefficient, K(Fd) and the organic matter content of soils (r(2)=0.844 for the first desorption and r(2)=0.861 for the second desorption), while the clay content did not greatly influence the desorption of DKN. Although the sorption of DKN was generally reversible, a sorption-desorption hysteresis was apparent in all soils. The site energy distribution curves emphasized the fact that DKN binds tightly to soils with higher organic matter content and greater proportion of DKN was retained by those soils     

Sorption behavior of a new acidic herbicide in soils

The sorptive behavior of the experimental herbicide quinmerac (7-chloro-3-methyl-quinoline-8-carboxylic acid) was investigated in soils of different organic carbon content. Distribution coefficients are low (K_d = 0.03 - 12 mL g⁻¹) and are mainly determined by the soil organic carbon content. The adsorption mechanism operating in neutral to slightly acid agricultural soils is supposed to be cation bridging with the anionic form of quinmerac. Under acid conditions (pH 5.2) the predominating sorption mechanism is hydrophobic interaction. Therefore soil pH and cationic composition are also major factors determining the sorptive capacity of soils for quinmerac.

Adsorption kinetics, equilibrium adsorption and desorption isotherms were determined in batch experiments. Sorption kinetics were investigated at various times from 15 min to 96 hours. A two-step sorption behavior with time was found for the anionic form indicating two types of sorption mechanisms or sorption sites. Equilibrium for the first type was reached at a time-scale of minutes and for the second type after 24 hours. Adsorption isotherms were determined for two soil/solution ratios 1/5 and 1/3. Alteration of the adsorbent concentration exerted a strong influence on the adsorption isotherms. An increase of sorption was found with increasing adsorbent concentration. Under natural soil conditions sorption is therefore expected to be higher compared to the batch experiments. Desorption isotherms were obtained using the consecutive desorption method. Desorption hysteresis was not observed which indicates weak interactions. Implications of the results for the movement of quinmerac under field conditions and for models describing transport are discussed.     

黑麦草对土壤中残留抗生素的降解及其对微生物活性的影响

为了研究抗生素污染土壤的修复方法,利用黑麦草对土壤中残留抗生素进行降解,并探讨土壤微生物生态活性及根系体表特征的响应。结果表明：黑麦草对土壤中四环素、金霉素、恩诺沙星、洛美沙星、环丙沙星、诺氟沙星的降解速率均显著大于对照（pr=-0.948,p<0.05）。     

Sorption and oxic degradation of the explosive CL-20 during transport in subsurface sediments

The abiotic sorption and oxic degradation processes that control the fate of the explosive CL-20, Hexanitrohexaazaisowurtzitane, in the subsurface environment were investigated to determine the potential for vadose and groundwater contamination. Sorption of aqueous CL-20 is relatively small (K(d) = 0.02-3.83 cm3 g(-1) for 7 sediments and 12 minerals), which results in only slight retardation relative to water movement. Thus, CL-20 could move quickly through unsaturated and saturated sediments of comparable composition to groundwater, similar to the subsurface behavior of RDX. CL-20 sorption was mainly to mineral surfaces of the sediments, and the resulting isotherm was nonlinear. CL-20 abiotically degrades in oxic environments at slow rates (i.e., 10s to 100s of hours) with a wide variety of minerals, but at fast rates (i.e., minutes) in the presence of 2:1 phyllosilicate clays (hectorite, montmorillonite, nontronite), micas (biotite, illite), and specific oxides (MnO2 and the ferrous-ferric iron oxide magnetite). High concentrations of surface ferrous iron in a dithionite reduced sediment degraded CL-20 the fastest (half-life < 0.05 h), but 2:1 clays containing no structural or adsorbed ferrous iron (hectorite) could also quickly degrade CL-20 (half-life < 0.2 h). CL-20 degradation rates were slower in natural sediments (half-life 3-800 h) compared to minerals. Sediments with slow degradation rates and small sorption would exhibit the highest potential for deep subsurface migration. Products of CL-20 oxic degradation included three high molecular weight compounds and anions (nitrite and formate). The 2-3.5 moles of nitrite produced suggest CL-20 nitro-groups are degraded, and the amount of formate produced (0.2-1.2 moles) suggests the CL-20 cage structure is broken in some sediments. Identification of further degradation products and CL-20 mineralization rates is needed to fully assess the impact of these CL-20 transformation rates on the risk of CL-20 (and degradation product) subsurface movement.     

Organochlorine compounds in soils and sediments of the mountain Andean Lakes

Semi-volatile organochlorine compounds (OC) were analyzed in remote Andean soils and lake sediments. The sampling sites covered a wide latitudinal gradient from 18 degrees S to 46 degrees S along Chile and an altitudinal gradient (10-4500 m). The concentrations were in the order of background levels, involving absence of major pollution sources in the high mountain areas. Significant correlations were found between log-transformed concentrations of hexachlorobenzene, alpha- and gamma-hexachlorocyclohexane in soils and total organic content (TOC). In addition, TOC-normalized concentrations of the most volatile OC showed a significant linear dependence with air temperature. This good agreement points to temperature as a significant factor for the retention of long range transported OC in remote ecosystems such as the Andean mountains, although other variables should not be totally excluded. The highest concentrations of OCs were achieved in the sites located at highest altitude and lowest temperature of the dataset.     

Fate of 14C‐allylalcohol herbicide in soils and crop residues

Abstract

Residue disappearance and leaching of ¹⁴C‐allyl‐alcohol from different soils were studied in laboratory experiments. Additionally, the uptake of residues by lettuce and carrots was investigated in the greenhouse. In laboratory experiments, residue disappearance and leaching from soils was correlated negatively to the organic matter content. In greenhouse experiments with a sandy loam soil at an application rate normally used in practice, an average of 12.5 % of the applied radioactivity was recovered after an eight day interval between application and sowing. Furthermore, an average of 8 % (sum in soil and plants) of the applied radioactivity was recovered after lettuce or carrot growing. Uptake of residues was higher by carrots than by lettuce, and higher by lettuce roots than by lettuce tops. No bioaccumulation was observed. The residues in soils and plants were, to a high percentage, unextractable and, to a smaller extent, fully water‐soluble products. Unchanged allylalcohol could not be detected by the analytical methods used.     

PBDEs and PCBs in sediments of the Thi Nai Lagoon (Central Vietnam) and soils from its mainland

Concentration and distribution of PCBs, PCB 11, and PBDEs in both surficial sediment and soil samples, taken from a zone subject to recent accelerated development, were investigated to assess the environmental quality and understand both natural and anthropogenic processes that influence contaminant behaviors. Values of PCB and PBDE are in the lower range of those reported in literature, typical of low impacted coastal zones. This could be due to efficient processes of resuspension and removal. Contaminants in the lagoon showed higher concentrations in sediments from sites close to the city and the outfalls of the industrial area, while soils showed maximum values in the northern samples. In addition, congener patterns and statistical analyses suggest the presence of effective degradation processes, especially for PBDEs, with the exception of the most concentrated samples that may indicate a direct input. PCB 11 is a significant component (up to 18%) in most lagoon sediments. Its presence is strongly associated with fine particles, thus the distribution seems to be driven mainly by the system hydrodynamic and does not trace the sources. Due to evaporation, only flooded agricultural soils show a similar relative abundance of this congener.     

Degradation of telone II in contaminated and noncontaminated soils

Abstract

Degradation of the nematicide Telone II (cis‐ and trans‐1,3‐dichloropropene comprise the active ingredients) in soil was studied using ¹⁴C‐l,3‐dichloropropene (DCP) along with soil samples collected from a field test site near Quincy, Florida. A mixed bacterial culture isolated from the soil in the presence of a second carbon source, glucose or yeast extract, completely degraded ¹⁴C‐DCP to ¹⁴CO₂, water‐soluble products, and microbial mass. ¹⁴C‐DCP in soil was also degraded to ¹⁴CO₂. After 28 days of incubation, the labeled chemical was completely degraded to ¹⁴CO₂, water‐soluble metabolites, bound‐residues, and possibly some microbial mass. Little or no difference was observed in the degradation of ¹⁴C‐DCP in soil samples collected one week prior to field application of Telone II, or two weeks and two years after application.