Pesticide decontamination from fabric by laundering and simulated weathering1

Abstract

This laboratory study investigated the effectiveness of selected detergents and the phenomenon of simulated environmental conditions (weathering) on the removal of a commercial‐grade mixture of parathion and methyl parathion from a three‐layer laminated fabric. The weathering treatment consisted of exposure and non‐exposure to simulated environmental conditions of heat, light, and humidity. Contaminated fabric samples were laundered in one of three detergents containing an anionic, a nonionic, and a combined anionic and nonionic surfactant. The test fabric, a three‐layer fabric containing an impermeable microporous film laminated between two layers of nylon, was pipette‐contaminated with 400 microliters of field strength pesticide solution and allowed to dry. Half of the contaminated samples were weathered in an Atlas Fade‐Ometer. All of the contaminated samples were subsequently laundered in a Launder‐Ometer. Percent of pesticide residue was determined by gas chromatography. Weathering did significantly reduce both parathion and methyl parathion residues remaining in the test fabric. No statistically significant difference was found among the three detergents. High amounts of both parathion and methyl parathion remained in the test fabric after weathering and laundry treatments. Before the test fabric can be recommended for use in protective garments further research is needed to develop more effective decontamination procedures.     

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.     

A study on the environmental degradation of pesticides azinphos methyl and parathion methyl

The effect of environmental parameters (temperature and relative humidity) on the degradation rate of azinphos methyl and parathion methyl was studied. Proprietary emulsifiable concentrates were diluted and added to each of 90 glass Petri dishes for each pesticide and were left overnight to dry. Petri dishes were placed in 18 air-tight containers (9 for each pesticide) in which were created environments with relative humidity (RH) of 60, 82, and 96%. The containers were stored at 0, 20, and 40 degrees C. From the experimental results best fit curves, kinetic equations, rate constants, and half-lives were calculated. Half-lives of azinphos methyl for the RH studied were, from 124 to 267 days at 0 degrees C, from 89 to 231 days at 20 degrees C, and from 25 to 71 days at 40 degrees C. Corresponding half-lives for parathion methyl were from 48 to 57 days at 0 degrees C, from 9.2 to 10.5 days at 20 degrees C and from 1.3 to 1.5 days at 40 degrees C. The results were correlated with relevant results from the decomposition of the same or similar pesticides on apples both, on the trees and during refrigerated storage. These correlations are suggesting that biological factors strongly affected the decomposition rate of azinphos methyl. On the contrary the decomposition of parathion methyl was mainly affected by environmental rather than biological factors.     

Biodegradation of mixed pesticides by mixed pesticide enriched cultures

This paper discusses the degradation kinetics of mixed (lindane, methyl parathion and carbofuran) pesticides by mixed pesticide enriched cultures (MEC) under various environmental conditions. The bacterial strains isolated from the mixed microbial consortium were identified as Pseudomonas aeruginosa (MTCC 9236), Bacillus sp. (MTCC 9235) and Chryseobacterium joostei (MTCC 9237). Batch studies were conducted to estimate the biokinetic parameters like the maximum specific growth rate (μ_max), Yield Coefficient (Y_T), half saturation concentration (K_s) and inhibition concentration (Ki) for individual and mixed pesticide enriched cultures. The cultures enriched in a particular pollutant always showed high growth rate and low inhibition in that particular pollutant compared to MEC. After seven weeks of incubation, mixed pesticide enriched cultures were able to degrade 72% lindane, 95% carbofuran and 100% of methyl parathion in facultative co-metabolic conditions. In aerobic systems, degradation efficiencies of lindane methyl parathion and carbofuran were increased by the addition of 2g L^{? 1} of dextrose. Though many metabolic compounds of mixed pesticides were observed at different time intervals, none of the metabolites were persistent. Based on the observed metabolites, a degradation pathway was postulated for different pesticides under various environmental conditions.     

A Study on the Environmental Degradation of Pesticides Azinphos Methyl and Parathion Methyl

Abstract

The effect of environmental parameters (temperature and relative humidity) on the degradation rate of azinphos methyl and parathion methyl was studied. Proprietary emulsifiable concentrates were diluted and added to each of 90 glass Petri dishes for each pesticide and were left overnight to dry. Petri dishes were placed in 18 air-tight containers (9 for each pesticide) in which were created environments with relative humidity (RH) of 60, 82, and 96%. The containers were stored at 0, 20, and 40°C. From the experimental results best fit curves, kinetic equations, rate constants, and half-lives were calculated. Half-lives of azinphos methyl for the RH studied were, from 124 to 267 days at 0°C, from 89 to 231 days at 20°C, and from 25 to 71 days at 40°C. Corresponding half-lives for parathion methyl were from 48 to 57 days at 0°C, from 9.2 to 10.5 days at 20°C and from 1.3 to 1.5 days at 40°C. The results were correlated with relevant results from the decomposition of the same or similar pesticides on apples both, on the trees and during refrigerated storage. These correlations are suggesting that biological factors strongly affected the decomposition rate of azinphos methyl. On the contrary the decomposition of parathion methyl was mainly affected by environmental rather than biological factors.     

Genotoxicity of methyl parathion in short-term bacterial test systems

Genotoxicity of the insecticide methyl parathion was investigated in Salmonella typhimurium and Escherichia coli bacterial test systems for the detection of back mutations and DNA-damage. Methyl parathion was mutagenic to S. typhimurium strain TA100 after activation with rat liver microsomal and cytosolic enzymes. In DNA repair tests, methyl parathion was effective in inducing damage to the S. typhimurium strain TA1538 which lack excision repair compared to the strain TA1978 which is proficient in excision repair mechanisms. Normal laboratory light conditions had no effect on the mutagenicity tests, however, exposure of methyl parathion in the petri dish containing the tester strain TA100 and rat liver microsomal and cytosolic enzymes reduced the mutagenic activity and increased the toxic effects of methyl parathion.     

Influence of vegetation in mitigation of methyl parathion runoff

A pesticide runoff event was simulated on two 10 m x 50 m constructed wetlands (one non-vegetated, one vegetated) to evaluate the fate of methyl parathion (MeP) (Penncap-M). Water, sediment, and plant samples were collected at five sites downstream of the inflow for 120 d. Semi-permeable membrane devices (SPMDs) were deployed at each wetland outflow to determine exiting pesticide load. MeP was detected in water at all locations of the non-vegetated wetland (50 m), 30 min post-exposure. MeP was detected 20 m from the vegetated wetland inflow 30 min post-exposure, while after 10d it was detected only at 10 m. MeP was measured only in SPMDs deployed in non-vegetated wetland cells, suggesting detectable levels were not present near the vegetated wetland outflow. Furthermore, mass balance calculations indicated vegetated wetlands were more effective in reducing aqueous loadings of MeP introduced into the wetland systems. This demonstrates the importance of vegetation as sorption sites for pesticides in constructed wetlands.     

Genotoxicity of methyl parathion in short‐term bacterial test systems

Abstract

Genotoxicity of the insecticide methyl parathion was investigated in Salmonella typhimurium and Escherichia coli bacterial test systems for the detection of back mutations and DNA‐damage. Methyl parathion was mutagenic to S. typhimurium strain TA100 after activation with rat liver microsomal and cytosolic enzymes. In DNA repair tests, methyl parathion was effective in inducing damage to the S. typhimurium strain TA1538 which lack excision repair compared to the strain TA1978 which is proficient in excision repair mechanisms. Normal laboratory light conditions had no effect on the mutagenicity tests, however, exposure of methyl parathion in the petri dish containing the tester strain TA100 and rat liver microsomal and cytosolic enzymes reduced the mutagenic activity and increased the toxic effects of methyl parathion.     

Catalytic properties of cyclodextrins on the hydrolysis of parathion and paraoxon in aquatic medium containing humic acids

The inclusion catalysis effects of -,β- and γ-cyclodextrins(CyDs) on the hydrolysis rate of parathion, methyl parathion and paraoxon were investigated at 25°C in alkaline buffer solution(pH=8.5) containing humic acids. The hydrolysis rate of these pesticides was increased by the presence of humic acids. The inclusion catalysis of β-CyD inhibited parathion hydrolysis but promoted paraoxon hydrolysis. The CyD inclusion catalysis showed characteristic correlation with relative magnitudes of the inclusion-depth parameters of the pesticides which could be determined by the rotational-strength analysis of the induced circular dichroism. The essential properties of the CyD inclusion catalysis were explained in terms of the geometries of the CyD-pesticide inclusion complexes which determine degree of the proximity between the pesticide reaction site and the CyD catalytic site.     

Enhanced desorption of phenanthrene from contaminated soil using anionic/nonionic mixed surfactant

A new approach using an anionic/nonionic mixed surfactant, sodium dodecyl sulphate (SDS) with Triton X-100 (TX100), was utilized for the desorption of phenanthrene from an artificial contaminated natural soil in an aim to improve the efficiency of surfactant remediation technology. The experimental results showed that the presence of SDS not only reduced the sorption of TX100 onto the natural soil, but also enhanced the solubilization of TX100 for phenanthrene, both of which resulted in the distribution of phenanthrene in soil-water systems decreasing with increasing mole fraction of SDS in surfactant solutions. These results can be attributed to the formation of mixed micelles in surfactant solution and the corresponding decrease in the critical micelle concentration of TX100 in mixed solution. The batch desorption experiments showed that the desorption percentage of phenanthrene from the contaminated soil with mixed solution was greater than that with single TX100 solution and appeared to be positively related to the mole fraction of SDS in surfactant solution. Thus, the anionic/nonionic mixed surfactants are more effective for the desorption of phenanthrene from the contaminated soil than a single nonionic surfactant.     

Evaluation of the susceptibility of the cultured shrimp Litopenaeus vannamei to vibriosis when orally exposed to the insecticide methyl parathion

The causes of disease in cultured shrimp are difficult to ascertain but there is evidence that disease is correlated with environmental factors. Crustaceans are particularly sensitive to insecticides due to their close phylogenetic relationship with insects. The objective of this study was to investigate whether there was an increased susceptibility of the shrimp Litopenaeus vannamei to Vibrio parahaemolyticus, when exposed to methyl parathion. The outline of the study was the following: An LC50 96 h was determined to methyl parathion orally offered to juvenile shrimp. Further experiments were carried out in order to determine a concentration that affected the shrimp (verified by measuring the acethylcholinesterase activity) while producing minimal mortalities. This sublethal concentration was used in a susceptibility experiment where methyl parathion was offered to shrimp which were later injected with V. parahaemolyticus in a dose expected to kill less than 15%. Probit analysis estimated a 96 h median lethal concentration (LC50) of 1.56 microg g(-1). Mortality and AChE activity showed a concentration-response relationship in the exposure treatments. The median inhibitory concentration (IC50) determined was 0.029 microg g(-1). These results suggested that a concentration of 0.1 microg g(-1) was appropriate for the bacteria-pesticide interaction test as it was able to elicit 11.1% mortality after 10 days of exposure, while producing an AChE inhibition of 57.12%. Cumulative mortalities were significantly increased (P<0.01) in the treatment that combined exposure to methyl parathion and V. parahaemolyticus (35.19%) in comparison with methyl parathion or V. parahaemolyticus alone (9.26% and 7.41%, respectively).     

Comparison of homologous and heterologous formats in nanocolloidal gold-based immunoassays for parathion residue determination

The effectiveness of homologous and heterologous formats in a nanocolloidal gold-based immunoassay for pesticide residue determination was investigated. Parathion, one of the most toxic organophosphorus pesticides, was used as the target analyte. One-step homologous and heterologous test strips based on a nanocolloidal gold-labeled monoclonal antibody were developed for the rapid detection of parathion residues. The results showed that the heterologous format was more effective than the homologous format, being more sensitive, more specific to parathion and more tolerant of matrix interferences. The best competitive hapten was found to have a moderate heterology and the opposite electronic distribution to the immunizing hapten. The detection limits for parathion using the preferred heterologous strip were 1 μg/L in water samples and 5 μg/kg in soil and food samples.     

Comparison of homologous and heterologous formats in nanocolloidal gold-based immunoassays for parathion residue determination

The effectiveness of homologous and heterologous formats in a nanocolloidal gold-based immunoassay for pesticide residue determination was investigated. Parathion, one of the most toxic organophosphorus pesticides, was used as the target analyte. One-step homologous and heterologous test strips based on a nanocolloidal gold-labeled monoclonal antibody were developed for the rapid detection of parathion residues. The results showed that the heterologous format was more effective than the homologous format, being more sensitive, more specific to parathion and more tolerant of matrix interferences. The best competitive hapten was found to have a moderate heterology and the opposite electronic distribution to the immunizing hapten. The detection limits for parathion using the preferred heterologous strip were 1 μg/L in water samples and 5 μg/kg in soil and food samples.     

Determination of pesticide residues in IPM and non-IPM samples of mango (Mangifera indica)

Studies were conducted to analyze the residue of commonly used pesticides viz. methyl parathion, chloropyrifos, endosulfan, cypermethrin, fenvalerate, carbendazim, imidacloprid and carbaryl in mango, Dashehari variety, integrated pest management (IPM) and non-IPM samples were collected from the IPM and non-IPM orchards, Lucknow, India. We also present a method for the simultaneous determination of these pesticides in mango samples. Residues of methyl parathion, chloropyriphos, endosulfan, cypermethrin, fenvalerate were extracted from the samples with acetone: cyclohexane: ethyl acetate in the ratio 2:1:1 followed by cleanup using neutral alumina. Analysis was performed by gas chromatography-electron capture detector (GC-ECD) with a megabore column (OV-1). Residues of carbendazim, imidacloprid and carbaryl were extracted with acetone and after cleanup, analysis was performed by high performance liquid chromatography (HPLC) using photo diode array (PDA) detector. Recoveries of all the pesticides ranged between 72.7 – 110.6%, at 0.1 and 1.0 μg g^{? 1} level of fortification. The residues detected in non-IPM samples of mango were found to be below the prescribed limits of maximum residue limit (MRL) while IPM samples were free from pesticide residues.     

Determination of pesticide residues in IPM and non-IPM samples of mango (Mangifera indica)

Studies were conducted to analyze the residue of commonly used pesticides viz. methyl parathion, chloropyrifos, endosulfan, cypermethrin, fenvalerate, carbendazim, imidacloprid and carbaryl in mango, Dashehari variety, integrated pest management (IPM) and non-IPM samples were collected from the IPM and non-IPM orchards, Lucknow, India. We also present a method for the simultaneous determination of these pesticides in mango samples. Residues of methyl parathion, chloropyriphos, endosulfan, cypermethrin, fenvalerate were extracted from the samples with acetone: cyclohexane: ethyl acetate in the ratio 2:1:1 followed by cleanup using neutral alumina. Analysis was performed by gas chromatography-electron capture detector (GC-ECD) with a megabore column (OV-1). Residues of carbendazim, imidacloprid and carbaryl were extracted with acetone and after cleanup, analysis was performed by high performance liquid chromatography (HPLC) using photo diode array (PDA) detector. Recoveries of all the pesticides ranged between 72.7-110.6%, at 0.1 and 1.0 microg g(-1) level of fortification. The residues detected in non-IPM samples of mango were found to be below the prescribed limits of maximum residue limit (MRL) while IPM samples were free from pesticide residues.     

Probabilistic approaches in the effect assessment of toxic chemicals. What are the benefits and limitations?

There is an ongoing discussion whether in the environmental risk assessment for chemicals the so called 'deterministic' approach using point estimates of exposure and effect concentrations is still appropriate. Instead, the more detailed and scientifically sounder probabilistic methods that have been developed over the last years are widely recommended. Here, we present the results of a probabilistic effect assessment for the aquatic environment performed for the pesticide methyl parathion and compare them with the results obtained with the common deterministic approach as described in the EU Technical Guidance Document. Methyl parathion was chosen because a sufficient data set (acute toxicity data for about 70 species) was available. The assumptions underlying the probabilistic effect assessment are discussed in the light of the results obtained for methyl parathion. Two important assumptions made by many studies are: (i) a sufficient number of ecologically relevant toxicity data is available, (ii) the toxicity data follow a certain distribution such as log-normal. Considering the scarcity of data for many industrial chemicals, we conclude that these assumptions would not be fulfilled in many cases if the probabilistic assessment was applied to the majority of industrial chemicals. Therefore, despite the well-known limitations of the deterministic approach, it should not be replaced by probabilistic methods unless the assumptions of these methods are carefully checked in each individual case, which would significantly increase the effort for the assessment procedure.     

Isolation of a selected microbial consortium capable of degrading methyl parathion and p-nitrophenol from a contaminated soil site

A bacterial consortium with the ability to degrade methyl parathion and p-nitrophenol, using these compounds as the only carbon source, was obtained by selective enrichment in a medium with methyl parathion. Samples were taken from Moravia, Medellin; an area that is highly contaminated, owing to the fact that it was used as a garbage dump from 1974 to 1982. Acinetobacter sp, Pseudomonas putida, Bacillus sp, Pseudomonas aeruginosa Citrobacter freundii, Stenotrophomonas sp, Flavobacterium sp, Proteus vulgaris, Pseudomonas sp, Acinetobacter sp, Klebsiella sp and Proteus sp were the microorganisms identified within the consortium. In culture, the consortium was able to degrade 150 mg L?1 of methyl-parathion and p-nitrophenol in 120 h, but after adding glucose or peptone to the culture, the time of degradation decreased to 24 h. In soil, the consortium was also able to degrade 150 mg L?1 of methyl parathion in 120 h at different depths and also managed to decrease the toxicity.     

Mixtures of quaternary ammonium compounds and anionic organic compounds in the aquatic environment: Elimination and biodegradability in the closed bottle test monitored by LC-MS/MS

Quaternary ammonium compounds (QACs) are widely used as disinfectants, detergents and fabric softeners. Anionic detergents are one of the most widely used chemical substances. QACs and anionic surfactants can form ionic pairs. In the present study we investigated the biodegradability of QACs in the presence of different anionic surfactants. The biodegradability of three QACs, namely benzalkonium chloride (BAC), didecyldimethylammonium chloride (DDMAC) and ethacridine lactate (EL), when applied as single substances and in combination with anionic surfactants such as benzene sulfonic acid (BSA), LAS, naphthalene sulfonic acid (NSA) and sodium dodecylsulfonate (SDS) was studied applying the closed bottle test (CBT) [OECD 301D, 1992. Guidelines for Testing of Chemicals. Closed bottle test. Organisation of Economic Cooperation and Development, Paris] at a ratio of 1:1 (mol:mol). Biodegradation was monitored by measuring oxygen concentration in the test vessels with an oxygen electrode in accordance with international standard methods [ISO 5414, 1990. Water quality - determination of dissolved oxygen. In: German Standard Methods for the Examination of Water, Wastewater and Sludge. VCH Verlagsgesellschaft, Weinheim, New York, Basel Cambridge]. Primary elimination of the QACs and of LAS was monitored by LC-MS/MS. There was little biodegradability of the QACs as either single compounds or in the presence of organic counter ions. The biodegradability of the organic counter ions was lower in the presence of QACs as compared to the single substances. Primary elimination of the QACs by sorption took place.     

Assessment of pesticide contamination in three Mississippi Delta oxbow lakes using Hyalella azteca

Three oxbow lakes in northwestern Mississippi, USA, an area of intensive agriculture, were assessed for biological impairment from historic and current-use pesticide contamination using the amphipod, Hyalella azteca. Surface water and sediment samples from three sites in each lake were collected from Deep Hollow, Beasley, and Thighman Lakes from September 2000 to February 2001. Samples were analyzed for 17 historic and current-use pesticides and selected metabolites. Ten-day H. azteca survival and growth (as length and dry weight) were measured to determine the degree of biological impairment. Maximum number of detectable pesticides in surface water from Deep Hollow, Beasley and Thighman Lakes was 10, 11, and 17, respectively. Maximum number of detectable pesticides in lake sediments was 17, 17, and 15, respectively. Bioassay results indicated no observable survival effects on H. azteca exposed to surface water or sediment from any lake examined and no growth impairment in animals exposed to lake sediments. However, growth was significantly impaired in surface water exposures from Deep Hollow Lake (2 sites) and Beasley Lake (1 site). Statistically significant relationships between growth impairment (length) and cyanazine, methyl parathion, λ-cyhalothrin, chlorfenapyr, and pp′DDE surface water concentrations in Deep Hollow Lake as well as trifluralin, atrazine, and methyl parathion in Beasley Lake were observed. Although pesticide frequency and concentrations were typically greater in sediment than surface water, bioassay results indicated decreased availability of these pesticides in sediment due to the presence of clay and organic carbon. Growth impairment observed in surface water exposures was likely due to complex interaction of pesticide mixtures that were present.     

Removal of alkylphenols from polluted sites using surfactant-assisted soil washing and photocatalysis

Background and purpose  

Surfactant-assisted soil washing and photocatalysis are well-known remediation processes of environmental concern. The application of photocatalysis to treat soil washing extracts containing 4-methylphenol, 4-ethylphenol and 4–tert-butylphenol in the presence of nonionic (C₁₂E₈ and C₁₂E₂₃) and anionic (SDS) surfactants and some of their binary mixtures was investigated in this work by studying the pollutants degradation in the presence of TiO₂ dispersions irradiated with simulated solar light.