Biotic and abiotic degradation of illicit drugs, their precursor, and by-products in soil

This study presents the first systematic information on the degradation patterns of clandestine drug laboratory chemicals in soil. The persistence of five compounds - parent drugs (methamphetamine, 3,4-methylenedioxymethamphetamine (MDMA)), precursor (pseudoephedrine), and synthetic by-products N-formylmethylamphetamine and 1-benzyl-3-methylnaphthalene) - were investigated in laboratory scale for 1 year in three different South Australian soils both under non-sterile and sterile conditions. The results of the degradation study indicated that 1-benzyl-3-methylnaphthalene and methamphetamine persist for a long time in soil compared to MDMA and pseudoephedrine; N-formylmethylamphetamine exhibits intermediate persistence. The role of biotic versus abiotic soil processes on the degradation of target compounds was also varied significantly for different soils as well as with the progress in incubation period. The degradation of methamphetamine and 1-benzyl-3-methylnaphthalene can be considered as predominantly biotic as no measureable changes in concentrations were recorded in the sterile soils within a 1 year period. The results of the present work will help forensic and environmental scientists to precisely determine the environmental impact of chemicals associated with clandestine drug manufacturing laboratories.     

Application of microbial hot spots enhances pesticide degradation in soils

Through transfer of an active, isoproturon degrading microbial community, pesticide mineralization could be successfully enhanced in various soils under laboratory and outdoor conditions. The microbes, extracted from a soil having high native ability to mineralize this chemical, were established on expanded clay particles and distributed to various soils in the form of microbial "hot spots". Both, diffusion controlled isoproturon mass flow towards these "hot spots" (6microg d(-1)) as well as microbial ability to mineralize the herbicide (approximately 5microg d(-1)) were identified as the main processes enabling a multiple augmentation of the native isoproturon mineralization even in soils with heavy metal contamination. Soil pH-value appears to exert an important effect on the sustainability of this process.     

A sensitivity analysis of adsorption and degradation parameters in the modeling of pesticide transport in soils

The increasing use of deterministic models in predicting the movement of pesticides in soils, has focused attention on the evaluation of major parameters which represent attenuation factors of organics in the subsurface. These parameters are the degradation rate constant and the adsorption constant for the pesticide. In view of the large in situ variability of these parameters and of the difficulty in obtaining accurate field data, there is a high degree of uncertainty associated with the results obtained from deterministic models. A sensitivity analysis is performed here to quantify the impact of such variation in each of these input parameters on the output results of an unsaturated zone transport model (PRZM). Results show that variations in these parameters about their respective mean values greatly affect the predicted concentration distributions, obtained after three years, of the pesticide aldicarb in all the soil profile. A 15–22% variation in the degradation constant, or a 24% variation in the adsorption constant, lead to a 100% uncertainty in the various simulation results defined as the cumulative quantity of aldicarb or the dissolved aldicarb concentration leached below the root zone (or the unsaturated zone) of the soil. Such a deterministic model presents a high degree of sensitivity to these input parameters. Accurate field data are then needed to obtain reliable model results in predicting pesticide movement inthe unsaturated zone.     

Biotic and abiotic transformations of methyl tertiary butyl ether (MTBE)

Background Methyl tertiary butyl ether (MTBE) is a fuel additive which is used all over the world. In recent years it has often been found in groundwater, mainly in the USA, but also in Europe. Although MTBE seems to be a minor toxic, it affects the taste and odour of water at concentrations of < 30 μg/L. Although MTBE is often a recalcitrant compound, it is known that many ethers can be degraded by abiotic means. The aim of this study was to examine biotic and abiotic transformations of MTBE with respect to the particular conditions of a contaminated site (former refinery) in Leuna, Germany. Methods Groundwater samples from wells of a contaminated site were used for aerobic and anaerobic degradation experiments. The abiotic degradation experiment (hydrolysis) was conducted employing an ion-exchange resin and MTBE solutions in distilled water. MTBE, tertiary butyl formate (TBF) and tertiary butyl alcohol (TBA) were measured by a gas chromatograph with flame ionisation detector (FID). Aldehydes and organic acids were respectively analysed by a gas chromatograph with electron capture detector (ECD) and high-performance ion chromatography (HPIC). Results and Discussion Under aerobic conditions, MTBE was degraded in laboratory experiments. Only 4 of a total of 30 anaerobic experiments exhibited degradation, and the process was very slow. In no cases were metabolites detected, but a few degradation products (TBF, TBA and formic acid) were found on the site, possibly due to the lower temperatures in groundwater. The abiotic degradation of MTBE with an ion-exchange resin as a catalyst at pH 3.5 was much faster than hydrolysis in diluted hydrochloric acid (pH 1.0). Conclusion Although the aerobic degradation of MTBE in the environment seems to be possible, the specific conditions responsible are widely unknown. Successful aerobic degradation only seems to take place if there is a lack of other utilisable compounds. However, MTBE is often accompanied by other fuel compounds on contaminated sites and anaerobic conditions prevail. MTBE is often recalcitrant under anaerobic conditions, at least in the presence of other carbon sources. The abiotic hydrolysis of MTBE seems to be of secondary importance (on site), but it might be possible to enhance it with catalysts. Recommendation and Outlook MTBE only seems to be recalcitrant under particular conditions. In some cases, the degradation of MTBE on contaminated sites could be supported by oxygen. Enhanced hydrolysis could also be an alternative. - * The basis of this peer-reviewed paper is a presentation at the 9th FECS Conference on 'Chemistry and Environment', 29 August to 1 September 2004, Bordeaux, France.     

农药污染土壤的生物修复技术

本文综述了土壤农药有机污染的生物修复技术 ,重点分析了植物、微生物对土壤农药污染的修复机制以及影响因子 ,介绍了几种生物修复技术     

Bound pesticide residues in soils: a review

This article is a review of the current state of knowledge regarding the formation and biological/environmental significance of bound pesticide residues in soils. We begin by defining various terms used in our discussions and identifying the types/classes of pesticides which may be added to soil and interact with it. We then consider various soil properties and aspects of land management which will influence the nature and degree of the soil-pesticide association and discuss the possible physical and chemical binding mechanisms. We then move on to consider the role of microorganisms and other forms of soil biota in bound residue formation and the bioavailability of soil-borne pesticide residues. The review ends with a consideration of the significance of bound pesticide residues.     

Characterizing the uncertainty of pesticide leaching in agricultural soils

A Monte-Carlo numerical simulation procedure for making regional assessments of pesticide leaching has been developed. This procedure uses probability density functions for organic matter, field capacity, and wilting point developed from information on approximately 3000 soils. Variations in climatic conditions were incorporated by random selection of yearly rainfall data. The procedure was demonstrated for aldicarb applied to corn grown in Ohio. A total of 2000 parameter sets were evaluated using the unsaturated zone model PRZM. The simulation results indicated that convergence of the 90th, 95th, and 99th percentiles for movement past 0.3, 0.6, 0.9, and 1.5 m was obtained after 500 simulations. The relative uncertainty associated with these percentiles was approximately 50% after 1500 simulations. The downward movement of aldicarb residues was most sensitive to changes in field capacity. These simulations, coupled with additional soil-specific simulations, indicated no significant movement of aldicarb residues beyond 1.8 m for applications to Ohio corn.     

Bioavailability and degradation of phenanthrene in compost amended soils

Bioavailability in soil of organic xenobiotics such as phenanthrene is limited by mechanisms of diffusion of the xenobiotics within soil micropores and organic matter. The agricultural utilization of compost may reduce the risk connected to organic xenobiotic contamination by means of: (i) a reduction of the bioavailable fraction through an increased adsorption and (ii) an enhanced degradation of the remaining bioavailable fraction through an inoculum of degrading microorganisms. Aim of this work is to test this hypothesis by assessing the effects of compost amendment on the bioavailability and degradation of phenanthrene in soil. Experiments were carried out in both sterilized and non-sterilized conditions, and chemical and microbiological analyses were carried out in order to determine the extent of degradation and bioavailability and to monitor the evolution of the soil micro flora in time. Bioavailability was assessed in sterilized microcosms, in order to assess the physical effects of compost on aging processes without the influence of microbial degradation. Results showed that bioavailability is significantly reduced in soils amended with compost, although no differences were found at the 2 doses of compost studied. In non-sterilized soils the amount of phenanthrene degraded was always higher in the amended soils than in the non-amended one. Microbiological analyses confirmed the presence of a higher number of phenanthrene degraders in the amended soils and in samples of compost alone. These results suggest that compost induces the degradation in soils of easily degradable compounds such as phenanthrene, when the proper bacteria are in the compost; more resistant xenobiotics may instead be trapped by the compost organic matter, thus becoming less available.     

Sorption and degradation of neonicotinoid insecticides in tropical soils

ABSTRACT

Neonicotinoids are the most widely applied class of insecticides in cocoa farming in Ghana. Despite the intensive application of these insecticides, knowledge of their fate in the Ghanaian and sub-Saharan African environment remains low. This study examined the behavior of neonicotinoids in soils from cocoa plantations in Ghana by estimating their sorption and degradation using established kinetic models and isotherms. Studies of sorption were conducted using the batch equilibrium method on imidacloprid, thiamethoxam, clothianidin, acetamiprid and thiacloprid, while degradation of imidacloprid, thiamethoxam and their respective deuterated counterparts was studied using models proposed by the European forum for coordination of pesticide fate and their use (FOCUS). Analytes were extracted using the quick, easy, cheap, effective, rugged and safe (QuEChERS) procedure and quantified by liquid chromatography-tandem mass spectrometry (LC–MS/MS). Average recoveries were high (≥ 85%) for all analytes. The findings from the study suggest that neonicotinoid insecticides may be persistent in the soils studied based on estimated half-lives > 150 days. The study also revealed generally low-sorption coefficients for neonicotinoids in soils, largely influenced by soil organic carbon.     

Kinetic degradation processes of butyl- and phenyltins in soils

The degradation of organotin compounds (OTC) in agricultural and forest soils is studied in sandy soil samples. Individual experiments involving the three butyl- and the three phenyltins were carried out during 90 d in controlled conditions (darkness, 28 degrees C, aerobic conditions, 13% moisture) and with spiking concentration representative of environmental levels (20-50 micrg(Sn) kg(-1)). After the validation of first-order degradation kinetic model, mechanisms involved throughout the study were considered. Degradation pathways are proposed for butyl- and phenyltins and discussed according to literature data. The degradation of mono- (MBT, MPhT), di-organotins (DBT, DPhT) and TBT is clearly identified as a single successive loss of an organic group whereas TPhT is directly degraded to MPhT. The half-life times were dependent on their substitution degree, ranging from 24 (TPhT) to 220 (MBT) d. The less substituted the OTC is, the more persistent it is. In the range 4.3-5.7, pH does not seem to influence OTC degradation under the present operating conditions. Finally this study shows the significant persistence in soil samples in our experimental conditions for most of studied organotins and highlights the potential impact on soil quality.     

Adsorption and desorption characteristics of hydrophobic pesticide endosulfan in four Indian soils

Adsorption and desorption characteristics of endosulfan in four Indian soils were studied extensively. The soils used were clayey soil (CL--lean clay with sand), red soil (GM--silty gravel with sand), sandy soil (SM--silty sand with gravel) and composted soil (PT--peat) as per ASTM (American Society for Testing and Materials) standards. Adsorption and desorption rates were calculated from kinetic studies. These values varied for alpha and beta endosulfan depending on the soil type. Maximum specific adsorption capacities (qmax) for different soils were calculated by Langmuir model. The values varied from 0.1 to 0.45 mg g(-1) for alpha endosulfan and 0.0942-0.2722 mg g(-1) for beta endosulfan. Maximum adsorption took place in clay soil followed by composted soil and red soil. Adsorptions of alpha and beta endosulfan were negligible in sand. The binding characteristics of various functional groups were calculated using Scatchard plot. Effect of functional groups was more predominant in clayey soil. Organic matter also played a significant role in adsorption and desorption of endosulfan. Endosulfan adsorption decreased drastically in clay soil when the pH was reduced. Desorption was higher at both acidic and alkaline pH ranges compared to neutral pH. Results indicated that alpha endosulfan is more mobile compared to beta endosulfan and mobility of endosulfan is maximum in sandy soil followed by red soil. It can be inferred that crystal lattice of the clay soil plays a significant role in endosulfan adsorption and desorption. Immobilization of endosulfan is more advisable in clay soil whereas biological and or chemical process can be applied effectively for the remediation of other soil types.     

Enhanced degradation of carbofuran in Pacific Northwest soils

Persistence of 14C-carbonyl carbofuran was measured in Pacific Northwest soils that had received 1-14 applications of the insecticide for root weevil control on perennial crops. Insecticide decay curves were obtained in nonautoclaved soil and several autoclaved soil samples from previously-treated fields and in nonautoclaved soils from paired control sites not previously treated with carbofuran. The insecticide usually degraded faster in soil from previously-treated fields than in soil from corresponding control fields. Among 26 previously-treated fields, the pseudo half-life (time for 50% loss) of carbofuran was less than one wk in 11 soils, 1-3 wks in 8 soils and greater than 4 wks in the remaining soils. Among the nontreated control fields the pseudo half-life was greater than 2 wks in all cases and greater than 15 wks in 5 of the soils. The carbofuran decay curve always possessed an initial lag phase where soil mixing enhanced insecticide decline. Carbofuran degraded very slowly in autoclaved soil samples. The half-life of carbofuran exceeded 16 wk in all autoclaved soils tested and in most instances 85-90% of the original dosage remained when the tests were terminated 112 days after treatment. These results provided evidence that many of the soils which received applications of carbofuran over the past several years have developed a capacity to degrade carbofuran very rapidly.     

Enhanced degradation of carbofuran in pacific northwest soils

Abstract

Persistence of ¹⁴C‐carbonyl carbofuran was measured in Pacific Northwest soils that had received 1–14 applications of the insecticide for root weevil control on perennial crops. Insecticide decay curves were obtained in nonautoclaved soil and several autoclaved soil samples from previously‐treated fields and in nonautoclaved soils from paired control sites not previously treated with carbofuran. The insecticide usually degraded faster in soil from previously‐treated fields than in soil from corresponding control fields. Among 26 previously‐treated fields, the pseudo half‐life (time for 50% loss) of carbofuran was < one wk in 11 soils, 1–3 wks in 8 soils and > 4 wks in the remaining soils. Among the nontreated control fields the pseudo half‐life was > than 2 wks in all cases and > than 15 wks in 5 of the soils. The carbofuran decay curve always possessed an initial lag phase where soil mixing enhanced insecticide decline. Carbofuran degraded very slowly in autoclaved soil samples. The half‐life of carbofuran exceeded 16 wk in all autoclaved soils tested and in most instances 85–90% of the original dosage remained when the tests were terminated 112 days after treatment. These results provided evidence that many of the soils which received applications of carbofuran over the past several years have developed a capacity to degrade carbofuran very rapidly.     

Fate and antibacterial potency of anticoccidial drugs and their main abiotic degradation products

The antibacterial potency of eight anticoccidial drugs was tested in a soil bacteria bioassay (pour plate method), EC₅₀-values between 2.4 and 19.6 μM were obtained; however, one compound, nicarbazin exhibited an EC₅₀-value above the maximum tested concentration (21 μM, 9.1 mg L⁻¹). The potency of mixtures of two of the compounds, narasin and nicarbazin, was synergistic (more than additive) with 10-fold greater antibacterial potency of the mixture than can be explained by their individual EC₅₀-values. The influence of pH, temperature, oxygen concentration and light on the transformation of robenidine and salinomycin was investigated. Robenidine was transformed by photolysis (DT₅₀ of 4.1 days) and was unstable at low pH (DT₅₀ of approximately 4 days); salinomycin was merely transformed at low pH, the latter into an unknown number of products. The antibacterial potency of the mixtures of transformation products of robenidine after photolysis and at low pH was comparable with that of the parent compound. Finally five photo-transformation products of robenidine were structural elucidated by accurate mass measurements, i-FIT values (isotopic pattern fit) and MS/MS fragmentation patterns.     

Key parameters and practices controlling pesticide degradation efficiency of biobed substrates

We studied the contribution of each of the components of a compost-based biomixture (BX), commonly used in Europe, on pesticide degradation. The impact of other key parameters including pesticide dose, temperature and repeated applications on the degradation of eight pesticides, applied as a mixture, in a BX and a peat-based biomixture (OBX) was compared and contrasted to their degradation in soil. Incubation studies showed that straw was essential in maintaining a high pesticide degradation capacity of the biomixture, whereas compost, when mixed with soil, retarded pesticide degradation. The highest rates of degradation were shown in the biomixture composed of soil/compost/straw suggesting that all three components are essential for maximum biobed performance. Increasing doses prolonged the persistence of most pesticides with biomixtures showing a higher tolerance to high pesticide dose levels compared to soil. Increasing the incubation temperature from 15 °C to 25 °C resulted in lower t(1/2) values, with biomixtures performing better than soil at the lower temperature. Repeated applications led to a decrease in the degradation rates of most pesticides in all the substrates, with the exception of iprodione and metalaxyl. Overall, our results stress the ability of biomixtures to perform better than soil under unfavorable conditions and extreme pesticide dose levels.     

Influence of kinetic sorption and diffusion on pesticide movement through aggregated soils

Laboratory studies were carried out to investigate solute leaching at different times from application in relation to temperature and initial soil moisture. Aggregates of a heavy clay soil were treated with a non-interactive solute (bromide) and the herbicides chlorotoluron, isoproturon and triasulfuron. The soil was incubated at 90% field capacity and either 5 or 15 degrees C. The influence of application to initially dry and initially wet aggregates on the behaviour of isoproturon was also investigated. At intervals, samples were either leached in small columns, centrifuged to characterise the fraction of chemical available in pore water under natural moisture conditions or extracted with organic solvents to assess total residues in soil. Bromide concentrations in leachate and in pore water extracted by centrifugation were constant with time. In contrast, availability for leaching and concentration in pore water of the herbicides decreased with increasing time from application in soil incubated at 15 degrees C. The effect of residence time was much smaller at 5 than at 15 degrees C. At the higher temperature, pesticide concentrations in leachate and pore water declined faster than would be expected from degradation alone, probably due to slow diffusion of the pesticides into soil aggregates where they are less available for leaching and/or slow sorption-desorption. The faster decline in availability for leaching at 15 than at 5 degrees C was attributed to faster degradation of the readily available fraction. There was no significant influence of initial soil moisture on either the leaching behaviour of isoproturon or its availability in soil water.     

Field studies of ethoprop movement and degradation in two Florida soils

Unsaturated- and saturated-zone field studies were conducted under two different agricultural conditions in Florida, U.S.A., to measure the movement and degradation of ethoprop.When ethoprop was applied to a sand soil in an orange grove located on the Florida central ridge, soil residues declined with a half-life of 13 days to near the limit of detection (0.01 μg g⁻¹ within 2 months. Ethoprop residues were generally contained in the upper 2 m of soil. Although low levels of ethoprop were found in four groundwater samples within the first 3 months after application, the cause of these isolated and transient residues could not be determined. The data show that there was no widespread plume of ethoprop residues beneath or downgradient from the treated area.On a flatwood soil on the west coast of Florida, ethoprop was incorporated into raised beds and protected by a plastic mulch in which tomatoes were grown. When the plastic mulch was present, ethoprop soil residues declined with a half-life of 40 days and were confined to the upper 0.3 m of soil. After the mulch was removed at crop harvest, the remaining ethoprop dissipated with a half-life of 12 days. Groundwater residues in excess of 1 μg L⁻¹ were confined to a single sample collected after the well had been damaged during a rototilling operation. Resides of < 1 μg L⁻¹ were present in three later samples from this well. At the sampling interval where the highest residues were detected in the damaged well, ethoprop residues of < 1 μg L⁻¹ were also found in three other wells but no residues were detected in these wells in later samples.     

Characterisation of the abiotic degradation pathways of oxytetracyclines in soil interstitial water using LC-MS-MS

The fate of oxytetracyclines (OTCs) in soil interstitial water was investigated and the structure of a number of degradation products elucidated in a time-related experiment. A previously developed separation method for LC–MS–MS able to base separate and quantify OTC and three of its epimers and degradation products was applied. Compounds detected were 4-epi-oxytetracycline (EOTC) (t_R=3.0 min), OTC (t_R=4.4 min), -apo-oxytetracycline (-apo-OTC) (t_R=11.4 min) and β-apo-oxytetracycline (β-apo-OTC) (t_R=18.4 min). Furthermore, we tentatively identified 4-epi-N-desmethyl-oxytetracycline (E-N-DM-OTC) (t_R=3.0 min), N-desmethyl-oxytetracycline (N-DM-OTC) (t_R=3.5), N-didesmethyl-oxytetracycline (N-DDM-OTC), 4-epi-N-didesmethyl-oxytetracycline (E-N-DDM-OTC) (t_R=3.7 and 4.7 min) and 2-acetyl-2-decarboxamido-oxytetracycline (t_R=8.7) in all samples. Most compounds were only present in trace concentrations (less than 2%) relative to the parent OTC. EOTC was on the other hand formed up to a ratio of 0.6 relative to parent OTC concentration. Only EOTC, E-N-DM-OTC, N-DM-OTC, N-DDM-OTC and E-N-DDM-OTC were formed during the time-related experiment. All other compounds were probably only present as impurities in the spiked OTC formulation as they declined in concentration from the start of the experiment. Half-lives (T_1/2, days) of the OTCs in soil interstitial water were in the order of 2 days (EOTC) to 270 days (β-apo-OTC).     

漂浮负载型光催化剂制备及降解草甘膦研究

以漂珠(FP)为载体,采用溶胶-凝胶-浸渍法制备了漂浮负载型CdS/TiO2/FP复合膜光催化剂,通过SEM、XRD对其结构进行了表征.以甘草膦农药的光催化降解为模型反应,使用不同光源研究了CdS/TiO2/FP的光催化性能,探讨了影响催化剂活性的因素及采用太阳光做光源处理草甘膦的可行性.结果表明,经4层镀膜500℃热处理的20%(w/w)CdS/TiO2/FP光催化剂具有良好的光催化性能,最佳降解条件为:催化剂加入量3 g/L,初始pH 7～9,Fe2 浓度为2.0×10-3 mol/L.通气量200 mL/min.在最佳条件下,对135 mg/L草甘膦溶液降解率可以分别达到96.3%(125 W高压汞灯,60 min)和82.4%(太阳光,180 min).     

Characterizing pesticide sorption and degradation in microscale biopurification systems using column displacement experiments

Biopurification systems treating pesticide contaminated water are very efficient, however they operate as a black box. Processes inside the system are not yet characterized. To optimize the performance, knowledge of degradation and retention processes needs to be generated. Therefore, displacement experiments were carried out for four pesticides (isoproturon, bentazone, metalaxyl, linuron) in columns containing different organic mixtures. Bromide, isoproturon and bentazone breakthrough curves (BTCs) were well described using the convection-dispersion equation (CDE) and a first-order degradation kinetic approach. Metalaxyl and linuron BTCs were well described using the CDE model expanded with Monod-type kinetics. Freundlich sorption, first-order degradation and Monod kinetics coefficients were fitted to the BTCs. Fitted values of the distribution coefficient K_f,column were much lower than those determined from batch experiments. Based on mobility, pesticides were ranked as: bentazone > metalaxyl - isoproturon > linuron. Based on degradability, pesticides were ranked as: linuron > metalaxyl - isoproturon > bentazone.