Biomassbed: a biological system to reduce pesticide point contamination at farm level

A potential method for cleaning water from point-source pollution by organic compounds is using biological reactors. In this study, four reactors were tested for their ability to retain and degrade pesticides. The pesticides tested were the insecticide chlorpyrifos, the fungicide metalaxyl and the herbicide imazamox. The reactors were filled with differing mixtures of vine-branch, citrus peel, urban waste and public green compost. The reactor volume was 188 l. Forced circulation of the contaminated solution was programmed to decontaminate the solution. Both retention and degradation of the compounds by the reactors was studied. Chlorpyrifos was the best retained, due to its physico-chemical characteristics, while only one substrate effectively retained metalaxyl and imazamox (citrus peel+urban waste compost). Degradation of the pesticides in the reactors was faster than published values for degradation in soil. The half-life of all pesticides in the reactors was less than 14 days, compared to literature values of 60-70 days in soil. The combined retention and fast degradation make the biofilter a feasible technique to reduce spill-related and point environmental contamination by pesticides. The technique is most effective against persistent pesticides, while for mobile pesticides, the efficiency can be improved with several passages of the contaminated solution through biofilters.     

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.     

Hydrolysis of chlorpyrifos in natural waters of the Chesapeake Bay

Chlorpyrifos is the most widely used insecticide in the Chesapeake Bay region. Recent studies show that this organophospate chemical is consistently present in the air, rain and surface waters of the Chesapeake Bay region, suggesting a long environmental half-life. Hydrolytic degradation of chlorpyrifos is likely a dominant removal process, but existing hydrolysis data do not reflect conditions in the Chesapeake Bay. In this project, hydrolysis rates of chlorpyrifos were measured in sterilized, ambient water from the mouth of four Chesapeake Bay tributaries ranging in salinity from 0 to 17 ppt. The measured hydrolysis half-lives varied from 24 d in the Patuxent River to 126 d in the Susquehanna River. These results indicate that pH alone cannot be used as a single parameter to predict hydrolysis under field conditions. The influence of copper concentration, and other water constituents, need to be further evaluated as they may emerge as independent predictors to assess the fate of pesticides in natural systems.     

Comparison of two methods for obtaining degradation half-lives

Given the paucity of experimental degradation half-life data for most organic chemicals, there is a compelling incentive to use available estimation software when undertaking assessments of chemical persistence and mass balance modeling studies. In this study, half-life data obtained from estimation software for a set of 233 organic chemicals in air, water, soil and sediments were shown to differ significantly from half-life data listed in handbooks. It is suggested that the widely available and used estimation software, EPIWIN (Estimations Program's Interface for Windows), overestimates the reactivity of persistent organic pollutants (POPs). Reasons for this overestimation are explored. It is concluded that the maximum "default half-life values" used by the EPIWIN software are too short for estimating half-lives of highly persistent chemicals such as PCBs. There is a need for estimation software such as EPIWIN to be more thoroughly calibrated against experimental derived half-life data for a wide range of chemicals, including potential POPs, thus improving their reliability.     

Degradation of atrazine, metolachlor, and pendimethalin in pesticide-contaminated soils: effects of aged residues on soil respiration and plant survival

This study was conducted to determine the effects of pesticide mixtures on degradation patterns of parent compounds as well as effects on soil microbial respiration. Bioavailability of residues to sensitive plant species was also determined. Soil for this study was obtained from a pesticide-contaminated area within an agrochemical dealer site. Degradation patterns were not affected by the presence or absence of other herbicides in this study. Atrazine concentrations were significantly lower at 21 through 160 days aging time compared to day 0 concentrations. Metolachlor and pendimethalin concentrations were not significantly different over time and remained high throughout the study. Microbial respiration was suppressed in treated soils from day 21 to day 160. Soybean and canola were the most successful plant species in the germination and survival tests. Generally, with increased aging of pesticides in soil, germination time decreased. Survival time of plants increased over time for some treatments indicating possible decreased bioavailability of pesticide residues. In some cases, survival time decreased at the longer 160-day aging period, possibly indicating a change in bioavailability, perhaps as the result of formation of more bioavailable and phytotoxic metabolites. No interactive effects were noted for mixtures of pesticides compared to individually applied pesticides in terms of degradation of the parent compound or on seed germination, plant survival, or microbial respiration.     

Degradation of zearalenone and ochratoxin A in three Danish agricultural soils

Degradation of two mycotoxins: zearalenone (ZON) produced by species of Fusarium and ochratoxin A (OTA) produced by species of Penicillium were followed in pot experiments using agricultural topsoils from Danish experimental farms: a sandy soil, a sandy clay soil and a gyttja soil with a high content of silt. Experiments with unplanted soil and pots planted with barley were included. Soil samples were withdrawn during a period of 225 days and analysed for the content of OTA and ZON. The degradation of both toxins consisted of an initial fast degradation followed by a slower transformation step and was described well by a sum of two first-order kinetic equations. The decay first-order rate constants for the first step (k1) were in the range 0.73-2.91 d(-1) for OTA and 0.0612-0.108 d(-1) for ZON, respectively. Half-lives (t0.5) for ZON using data from the first phase were between 6.4 and 11 days, whereas the half-lives for OTA were about 0.2-1 day. The slowest degradation was measured in soil rich in clay. After 225 days, neither OTA nor ZON was detected in any of the soil types. Generally, the degradation of ZON and OTA was faster in planted soil than in unplanted soil, probably due to higher microbial activity. Due to the fast degradation of ZON and OTA in surface soil leaching as soluble substances appears to be limited.     

Estimating biodegradation half-lives for use in chemical screening

Biodegradation half-lives are needed for many applications in chemical screening, but these data are not available for most chemicals. To address this, in phase one of this work we correlated the much more abundant ready and inherent biodegradation test data with measured half-lives for water and soil. In phase two, we explored the utility of the BIOWIN™ models (in EPI Suite™) and molecular fragments for predicting half-lives. BIOWIN™ model output was correlated directly with measured half-lives, and new models were developed by re-regressing the BIOWIN™ fragments against the half-lives. All of these approaches gave the best results when used for binary (fast/slow) classification of half-lives, with accuracy generally in the 70–80% range. In the last phase, we used the collected half-life data to examine the default half-lives assigned by EPI Suite™ and the PBT Profiler™ for use as input to their level III multimedia models. It is concluded that estimated half-lives should not be used for purposes other than binning or prioritizing chemicals unless accuracy improves significantly.     

Parameters affecting azoxystrobin and imidacloprid degradation in biobed substrates in the North Indian tropical environment

Abstract

This study reports degradation of azoxystrobin (AZOXY) and imidacloprid (IMIDA) in the rice straw (RS)/corn cob (CC) and peat (P)/compost (C)-based biomixtures. The effect of biomixture preconditioning (10?days incubation prior to pesticide application), pesticide concentration and moisture content was evaluated. Results suggested that conditioning of biomixture greatly affected IMIDA degradation where half-life (t_1/2) was reduced by 5–9 times. This was attributed to higher microbial biomass carbon content and dehydrogenase activity in the conditioned biomixtures. Pesticide application in the conditioned biomixture did not show any negative impact on soil microbial parameters. Both pesticides degraded at faster rate in the rice straw-based biomixtures than in the corn cob-based biomixtures. Degradation slowed down with increase in initial concentration of pesticides in biomixture and 1.6–3.0 (AZOXY) and 2.4–3.6 (IMIDA) times increase in t_1/2 values was observed. The moisture content of biomixture showed positive effect on degradation which increased when moisture content was increased from 60 to 80% water holding capacity. The effect was significant for IMIDA degradation in the corn cob-based biomixtures and AZOXY degradation in the peat biomixtures. The rice straw-based biomixtures were better in degrading AZOXY and IMIDA and can be used in biopurification systems.     

Degradation of atrazine,metolachlor, and pendimethalin in pesticide‐contaminated soils: Effects of aged residues on soil respiration and plant survival

Abstract

This study was conducted to determine the effects of pesticide mixtures on degradation patterns of parent compounds as well as effects on soil microbial respiration. Bioavailability of residues to sensitive plant species was also determined. Soil for this study was obtained from a pesticide‐contaminated area within an agrochemical dealer site. Degradation patterns were not affected by the presence or absence of other herbicides in this study. Atrazine concentrations were significantly lower at 21 through 160 days aging time compared to day 0 concentrations. Metolachlor and pendimethalin concentrations were not significantly different over time and remained high throughout the study. Microbial respiration was suppressed in treated soils from day 21 to day 160. Soybean and canola were the most successful plant species in the germination and survival tests. Generally, with increased aging of pesticides in soil, germination time decreased. Survival time of plants increased over time for some treatments indicating possible decreased bioavailability of pesticide residues. In some cases, survival time decreased at the longer 160‐day aging period, possibly indicating a change in bioavailability, perhaps as the result of formation of more bioavailable and phytotoxic metabolites. No interactive effects were noted for mixtures of pesticides compared to individually applied pesticides in terms of degradation of the parent compound or on seed germination, plant survival, or microbial respiration.     

Effects of temperature and water content on degradation of isoproturon in three soil profiles

The phenylurea herbicide isoproturon, 3-(4-isopropylphenyl)-1,1-dimethylurea (IPU), is widely used to control pre- and post-emergence of grass and broad-leaved weeds in cereal crops. Its degradation in soils is a key process for assessing its leaching risk to groundwater resources. The degradation properties of various samples from surface and subsurface soil (down to 1m depth) of a heterogeneous agricultural field were studied using (14)C-IPU. Laboratory incubations were carried out at 22 and 10 degrees C and at water contents 90% and 50% of the estimated water holding capacity (eWHC) corresponding to water potentials between -56 kPa and -660 MPa. Degradation was found to be more sensitive to water content variations than to temperature variations in the ranges that we used. For surface layers, at 10 and 22 degrees C, the degradation half-life increased by a factor 10 and 15, respectively, when water content decreased from 90% to 50% eWHC. Under optimal degradation conditions (i.e. 22 degrees C and 90% eWHC), 3-(4-isopropylphenyl)-1-methylurea (MDIPU) was the main metabolite in surface samples. At subsurface depths, IPU half-lives were larger than 100 d, IPU was the main compound after 92 d of incubation and the main metabolite was an unidentified polar metabolite. These results suggest a metabolic pathway involving hydroxylations for subsurface materials. IPU degradation was largely affected by water availability in both surface and subsurface horizons. Clay content seemed to play a major role in degradation processes in subsurface soil by determining through sorption IPU availability in soil solution and/or by limiting water availability for microorganisms.     

Investigations of the determination and transformations of diazinon and malathion under environmental conditions using gas chromatography coupled with a flame ionisation detector

Degradation of two model insecticides, diazinon and malathion, and their degradation products 2-isopropyl-6-methyl-4-pyrimidinol--IMP (diazinon hydrolysis product) and malaoxon (malathion oxidation product) was compared and studied in the environment. The pesticides and their metabolites were extracted from samples (water, soil, chicory) with ethyl acetate and subsequently the extracts were analyzed by GC/FID. It was shown that hydrolysis is the major process in the degradation of these pesticides in water. In fact, 95% of diazinon was degraded, and only 10% of malathion was oxidised. In soil 30% of diazinon exposed to the sunlight was decomposed by photolysis, whereas in soil left in the darkness no degradation products were observed. In soil left under environmental conditions, 90% of diazinon was degraded and 40% from its initial concentration was transformed into IMP. The concentrations of the pesticides after 21 days on chicory were under maximal allowable concentration, which is 0.5 ppm for malathion and for diazinon. The concentration of malaoxon was more than twice as high as the allowable value, which is for the sum of malathion and malaoxon 3 ppm.     

Biodegradation of lindane, methyl parathion and carbofuran by various enriched bacterial isolates

In the present study, lindane (1,2,3,4,5,6-hexachlorocyclohexane), methyl parathion (O-dimethylO-(4-nitro-phenyl) phosphorothioate) and carbofuran (2,3-dihydro-2,2-dimethyl-7-benzofuranyl methylcarbamate) degradation potential of different enriched bacterial cultures were evaluated under various environmental conditions. Enriched cultures behaved differently with different pesticides. Degradation was more in a facultative anaerobic condition as compared to that in aerobic condition. A specific pesticide enriched culture showed maximum degradation of that pesticide irrespective of pesticides and environmental conditions. Lindane and endosulfan enriched cultures behaved almost similarly. Degradation of lindane by lindane enriched cultures was 75 +/- 3% in aerobic co-metabolic process whereas 78 +/- 5% of lindane degradation occurred in anaerobic co-metabolic process. Degradation of methyl parathion by methyl parathion enriched culture was 87 +/- 1% in facultative anaerobic condition. In almost all the cases, many intermediate metabolites were observed. However, many of these metabolites disappeared after 4-6 weeks of incubation. Mixed pesticide-enriched culture degraded all the three pesticides more effectively as compared to specific pesticide- enriched cultures. It can be inferred from the results that a bacterial consortium enriched with a mixture of all the possible pesticides that are present in the site seems to be a better option for the effective bioremediation of multi-pesticide contaminated site.     

Modelling the fate of organic chemicals in the soil plant environment: Model study of root uptake of pesticides

The fate of organic chemicals in the soil-plant-atmosphere environment and the governing processes were studied with a coupled dynamic soil transport and plant compartment model. Scenarios with applications of pesticides on sand and loam soils with chemical uptake in barley and wheat were used in the model calculations. Root uptake and concentrations in the plant compartments stem, leave and fruit were calculated for the pesticides terbuthylazine, isoproturon and carbofuran.

The effectivity of uptake from soils with different soil sorption coefficients had been shown for sand and loam soils. The processes degradation in plant and volatilization from leaves to atmosphere are especially effective for carbofuran and terbuthylazine. Although the concentrations in corn at harvest are lower than the maximum allowed concentrations, the peak concentrations in the course of the vegetation period are significantly higher (factor ≤ 200).     

Using polymer mats to biodegrade atrazine in groundwater: laboratory column experiments

Large-scale column experiments were undertaken to evaluate the potential of in situ polymer mats to deliver oxygen into groundwater to induce biodegradation of the pesticides atrazine, terbutryn and fenamiphos contaminating groundwater in Perth, Western Australia. The polymer mats, composed of woven silicone (dimethylsiloxane) tubes and purged with air, were installed in 2-m-long flow-through soil columns. The polymer mats proved efficient in delivering dissolved oxygen to anaerobic groundwater. Dissolved oxygen concentrations increased from <0.2 mg l(-1) to approximately 4 mg l(-1). Degradation rates of atrazine in oxygenated groundwater were relatively high with a zero-order rate of 240-380 microg l(-1) or a first-order half-life of 0.35 days. Amendment with an additional carbon source showed no significant improvement in biodegradation rates, suggesting that organic carbon was not limiting biodegradation. Atrazine degradation rates estimated in the column experiments were similar to rates determined in laboratory culture experiments, using pure cultures of atrazine-mineralising bacteria. No significant degradation of terbutryn or fenamiphos was observed under the experimental conditions within the time frames of the study. Results from these experiments indicate that remediation of atrazine in a contaminated aquifer may be achievable by delivery of oxygen using an in situ polymer mat system.     

Dissipation of some organochlorine insecticides in cropped and uncropped soil

Dissipation of four organochlorine insecticides, viz. aldrin, HCH, chlordane and heptachlor was studied in a sandy loam soil with and without crops during a period of 10 cropping seasons. Dissipation of all chemicals followed first-order kinetics (r(2)=0.537 - 0.976) with almost similar persistence in cropped and uncropped soils for all the insecticides. The average half-lives, (t(1/2) values) for total residues of aldrin, HCH, chlordane, and heptachlor in cropped treatments were 80.7, 58.8, 93.2, and 110 days. Their respective values in fallow plots were 78.4, 83.8, 154, and 116 days. None of the parent compounds or their isomers could be detected below the 20 cm depth at the termination of the experiment. Highest residue concentrations were observed in the surface 10 cm layer in fallow plots, but in the deeper (10-20 cm) layer in cropped plots. Analysis of plants and grains showed significant residues of all the chemicals. Degradation of these compounds in cropped and uncropped plots is discussed with regard to their volatilization, microbial degradation, leaching, and plant uptake.     

The adsorption and degradation of chlorpyriphos-methyl, pendimethalin and metalaxyl in solid urban waste compost

To evaluate the feasibility of using compost to prepare substrates for the disposal of pesticide residues, adsorption and degradation studies were carried out on three widely used agricultural pesticides: chlorpyriphos-methyl, pendimethalin and metalaxyl. Obtained from solid urban waste, this compost has been shown to be able to adsorb high levels of chlorpyriphos-methyl and pendimethalin (85%, 100%) whereas metalaxyl was only adsorbed at a level of 37%. However, adding smectite to the compost increased the adsorption of metalaxyl by 117%. Chlorpyriphos-methyl and pendimethalin degraded quickly with half-lives of 1.7 and 14.5 days, respectively, whereas metalaxyl proved more persistent (a half-life of 84 days). Adding ammonium nitrate to the compost accelerated metalaxyl degradation to a half-life of 15 days.     

Rhizoremediation of pentachlorophenol by Sphingobium chlorophenolicum ATCC 39723

Sphingobium chlorophenolicum is well known as a pentachlorophenol (PCP) degrader. The objective of this study was to evaluate PCP degradation in a loamy sandy soil artificially contaminated with PCP using phytoremediation and bioaugmentation. Measurements of PCP concentrations were carried out using high performance liquid chromatography analyses (HPLC). The toxic effect of PCP on plants was studied through the monitoring of weight plant and root length. The biodegradation of PCP by S. chlorophenolicum in soil was assessed with a bioluminescence assay of Escherichia coli HB101 pUCD607. Bacterial analyses were carried out by plating on Mineral Salt Medium (MSM) for S. chlorophenolicum, MSM for PCP-degrading/tolerant organisms and Trypticase Soy Broth Agar (TSBA) for heterotrophic organisms. The introduction of S. chlorophenolicum into soil with plants showed a faster degradation when compared to the non-inoculated soil. The monitoring of the plant growth showed a protective role of S. chlorophenolicum against the toxicity of PCP. The bioassay confirmed that initial toxicity was lowered while degradation progressed. There was a significant increase of organisms tested in the roots in comparison to those in the soil. This study showed that the presence of S. chlorophenolicum enhanced the PCP degradation in a loamy soil and also it had a protective role to prevent phytotoxic effects of PCP on plant growth. The combined use of bioaugmentation and plants suggests that the rhizosphere of certain plant species may be important for facilitating microbial degradation of pesticides in soil with important implications for using vegetation to stabilize and remediate surface soils.     

Degradation of the potential rodent contraceptive quinestrol and elimination of its estrogenic activity in soil and water

Quinestrol has shown potential for use in the fertility control of the plateau pika population of the Qinghai–Tibet Plateau. However, the environmental safety and fate of this compound are still obscure. Our study investigated degradation of quinestrol in a local soil and aquatic system for the first time. The results indicate that the degradation of quinestrol follows first-order kinetics in both soil and water, with a dissipation half-life of approximately 16.0 days in local soil. Microbial activity heavily influenced the degradation of quinestrol, with 41.2 % removal in non-sterile soil comparing to 4.8 % removal in sterile soil after incubation of 10 days. The half-lives in neutral water (pH 7.4) were 0.75 h when exposed to UV light (λ?=?365 nm) whereas they became 2.63 h when exposed to visible light (λ?>?400 nm). Acidic conditions facilitated quinestrol degradation in water with shorter half-lives of 1.04 and 1.47 h in pH 4.0 and pH 5.0 solutions, respectively. Moreover, both the soil and water treatment systems efficiently eliminated the estrogenic activity of quinestrol. Results presented herein clarify the complete degradation of quinestrol in a relatively short time. The ecological and environmental safety of this compound needs further investigation.     

Sorption and degradation of pharmaceuticals and personal care products (PPCPs) in soils

Pharmaceuticals and personal care products (PPCPs) are one class of the most urgent emerging contaminants, which have drawn much public and scientific concern due to widespread contamination in aquatic environment. Most studies on the environmental fate and behavior of PPCPs have focused on nonsteroidal anti-inflammatory drugs. Some other compounds with high concentrations were less mentioned. In this study, sorption and degradation of five selected PPCPs, including bisphenol A (BPA), carbamazepine (CBZ), gemfibrozil (GFB), octylphenol (OP), and triclosan (TCS) have been investigated using three different soils. Sorption isotherms of all tested PPCPs in soils were well described by Freundlich equation. TCS and OP showed moderate to strong sorption, while the sorption of GFB and CBZ in soils was negligible. Degradation of PPCPs in three soils was generally fitted first-order exponential decay model, with half-lives (t _1/2) varying from 9.8 to 39.1 days. Sterilization could prolong the t _1/2 of PPCPs in soil, indicating that microbial activity played an important role in the degradation of these chemicals in soils. Degradation of PPCPs in soils was also influenced by the soil organic carbon (f _oc) contents. Results from our data show that sorption to the soils varied among the different PPCPs, and their sorption affinity on soil followed the order of TCS > OP > BPA > GFB > CBZ. The degradation of the selected PPCPs in soil was influenced by the microbial activity and soil type. The poor sorption and relative persistence of CBZ suggest that it may pose a high leaching risk for groundwater contamination when recycled for irrigation.     

Dichlobenil and 2,6-dichlorobenzamide (BAM) dissipation in topsoil and deposits from groundwater environment within the boreal region in southern Finland

BAM (2,6-dichlorobenzamide) is a metabolite of pesticide dichlobenil and a common groundwater contaminant. Dichlobenil and BAM half-lives were determined in five Finnish subsurface deposits and in topsoil. Aerobic and anaerobic conditions with sterilized controls were included in this 1.4-year incubation experiment. In subsurface deposits, dichlobenil half-life varied from 157 days to no degradation and that of BAM from 314 days to no degradation. Microbes and oxygen enhanced dichlobenil and BAM dissipation rates in some deposits. However, dichlobenil and BAM concentrations were most significantly affected by deposit characteristics, especially carbon and nitrogen amounts. Also low pH, cadmium, iron, zinc, manganese and lead correlated with low dichlobenil and/or BAM concentrations. In mineral topsoil, dissipation was faster with half-lives of 41–54 days for dichlobenil, and 182–261 days for BAM. Dichlobenil was depleted completely in surface soil, but BAM was not dissipated below 55–81 % of the initial concentration. Generally, dichlobenil and BAM dissipation in samples from the northern boreal region was similar to that reported for the temperate region. BAM was persistent in topsoil and subsurface deposits, indicating long-term persistence problems in groundwater also within the northern boreal region.