Organic amendments to enhance herbicide biodegradation in contaminated soils

Pesticide contamination of soil and groundwater at agricultural chemical distribution sites is a widespread problem in the USA. Alternatives to land-farming or solid waste disposal include biostimulation and phytoremediation. This research investigated the ability of compost, corn stalks, corn fermentation byproduct, peat, manure, and sawdust at rates of 0.5% and 5% (w/w) to stimulate biodegradation of atrazine [6-chloro-N-ethyl-N'-(1-methyethyl)-1,3,5-triazine-2,4-diamine], metolachlor [2-chloro-N-(2-ethyl-6-methylphenyl)-N-(2-methoxy-1-methylethyl)acetamide], and trifluralin [2,6-dinitro-N,N-dipropyl-4-(trifluoromethyl)benzenamine] added as a mixture to soil. Initial concentrations were 175ᆾ mg atrazine kg^-1 soil, 182ᆭ mg metolachlor kg^-1 soil, and 165ᆫ mg trifluralin kg^-1 soil. After amendment addition, 30% of the atrazine, 33% of the metolachlor, and 44% of the trifluralin was degraded over 245 days, which included 63 days' aging prior to amendment additions. Atrazine degradation was enhanced by 0.5% manure, 5% peat, and 5% cornstalk amendments compared to nonamended soils. Metolachlor degradation was enhanced by all amendments at the 5% level, except for compost and peat. Amendments had no effect on trifluralin degradation. The 5% addition of compost, manure, and cornstalks resulted in significant increases in bacterial populations and dehydrogenase activity. A second experiment compared the persistence of atrazine, metolachlor, and trifluralin applied in a mixture to their persistence in soil individually. A combined average of 123 mg atrazine kg^-1 remained in soil treated with the three-herbicide mixture compared to 31 mg atrazine kg^-1 remaining in soil treated with atrazine only. Atrazine mineralization and atrazine-degrading microorganisms were suppressed by high concentrations of metolachlor, but not by trifluralin.     

Adsorption of atrazine and metolachlor in three soils from Blue Creek wetlands, Waterville, Ohio

Atrazine and metolachlor are extensively used pesticides in agricultural activities in northwest Ohio. Adsorption coefficients are often used to model pesticide fate and transport. Many physical-chemical parameters, such as organic matter, clay content, pH, and ionic strength, affect pesticide adsorption. Adsorption kinetics and adsorption isotherms were studied by batch experiment. Effects of humic acid, solution pH, and ionic strength on atrazine and metolachlor adsorption were also approached. After 24 h, both atrazine and metolachlor reached adsorption equilibrium in three local soils. Adsorption isotherms were described by Freundlich equations. The Freundlich coefficient (Kf) ranged from 0.14 to 4.47 (L kg^–1) for atrazine, and 0.04 to 5.30 (L kg^–1) for metolachlor. Adsorption capacity decreased in the order Sloan loam > Del Rey loam > Ottokee fine sand. Koc values varied considerably for both pesticides: metolachlor > in Sloan loam, atrazine metolachlor in Del Rey loam, and atrazine > metolachlor in Ottokee fine sand. In addition to organic matter content, clay played a key role in adsorption in the Del Rey loam and Ottokee fine sand. Higher adsorption was observed at pH 5 for both pesticides. As pH decreased to 3 and increased to 11, adsorption decreased. Adsorption increased as ionic strength increased.     

Pesticide occurrence in selected South Florida canals and Biscayne Bay during high agricultural activity

Climate and soil conditions in South Florida along with an extensive canal system facilitate movement of agricultural pesticides into surface waters. In a two-year study (2002-2004) of the currently used pesticides in South Florida, atrazine, endosulfan, metolachlor, chlorpyrifos, and chlorothalonil were the most frequently detected in the canals and in Biscayne Bay, with average concentrations of 16, 11, 9.0, 2.6, and 6.0 ng/L, respectively. Concentrations of atrazine and chlorpyrifos were highest near corn production. Chlorothalonil and endosulfan concentrations were highest near vegetable production, with no clear trend for metolachlor, which is used on multiple crops. Concentration data were used to calculate an aquatic life hazard potential for the planting period (November) versus the harvest period (March). This analysis indicated that a higher hazard potential occurs during harvest, primarily from the use of endosulfan. These data will also serve to document canal conditions prior to implementation of the Comprehensive Everglades Restoration Plan (CERP).     

Environmental distribution of acetochlor, atrazine, chlorpyrifos, and propisochlor under field conditions

The environmental behavior, movement, distribution, persistence, and runoff by rainfall of the pesticides acetochlor, atrazine, chlorpyrifos, and propisochlor were studied under field conditions during a five-month period at normal weather conditions. The pesticide concentrations in soil depths of 0-5 and 5-20 cm, and in sediment and runoff water samples (collected from an artificial reservoir built in the lower part of the experimental plot) were measured every second week and following every runoff event. The contamination of a stream running across the lowest part of the plot was also monitored. The weather conditions were also recorded at the experimental site. The pesticide residues were quantified by a capillary gas chromatograph equipped with a nitrogen phosphorus selective detector (GC-NPD). There was a consistent decrease in pesticide residues in the 0-5 cm soil layer with time after spaying. At 140 days after treatment only atrazine and chlorpyrifos were present; acetochlor and propisochlor were not detected in this soil layer. Atrazine and chlorpyrifos in the soil at a depth of 5-20 cm were detectable during the whole experimental interval, whereas acetochlor and propisochlor concentrations were below the limit of detection. Pesticide losses by the surface runoff process and the contamination of the stream were closely related to the time of rainfall elapsed after treatment and amount of rain at the experimental plots. Losses were primarily dependent on surface rainfall volume and intensity. The maximum detected residues of atrazine and acetochlor in stream water were 1 order of magnitude higher than the maximum residue limit specified by the European Union (EU) for environmental and drinking water (0.1 microg/L for individual compounds and 0.5 microg/L for total pesticides). Chlorpyrifos and propisochlor were not detected in this matrix.     

Atrazine and metolachlor in surface runoff under typical rainfall conditions in southern Louisiana

Atrazine and metolachlor are commonly detected in surface water bodies in southern Louisiana. These herbicides are frequently applied in combination to corn, and atrazine to sugarcane, in this region. A study was conducted on the runoff of atrazine and metolachlor from 0.21 ha plots planted to corn on Commerce silt loam, a Mississippi River alluvial soil. The study, carried out over a three-year period characterized by rainfall close to the 30-year average, provided data on persistence in the surface soil (top 2.5 cm layer) and in the runoff active zone of the soil, as measured by decrease in runoff concentrations with time after application. Regression equations were developed that allow an estimate of the runoff extraction coefficients for each herbicide. Atrazine showed soil half-lives in the range 10.5-17.3 days, and metolachlor exhibited half-lives from 15.8-28.0 days. Concentrations in successive runoff events declined much faster than those in the surface soil layer: Atrazine runoff concentrations decreased over successive runoff events with a half-life from 0.6 to 5.7 days, and metolachlor in runoff was characterized by half-lives of 0.6-6.4 days. That is, half-lives of the two herbicides in the runoff-active zone were one-tenth to one-half as long as the respective half-lives in the surface soil layer. Within years, the half-lives of these herbicides in the runoff active zone varied from two-thirds longer for metolachlor in 1996 to one-fifth longer for atrazine in 1995. The equations relating runoff concentrations of atrazine and metolachlor to soil concentrations contain extraction coefficients of 0.009. Losses in runoff for atrazine were 5.2-10.8% of applied, and for metolachlor they were 3.7-8.0%; atrazine losses in runoff were 20-40% higher than those for metolachlor. These relatively high percent of application losses indicate the importance of practices that reduce runoff of these chemicals from alluvial soils of southern Louisiana.     

Impact of tillage on microbial activity and the fate of pesticides in the upper soil

The impact of two tillage systems, plow tillage (PT) and no-tillage (NT), on microbial activity and the fate of pesticides in the 0–5 cm soil layer were studied. The insecticides carbofuran and diazinon, and the herbicides atrazine and metolachlor were used in the study, which included the incubation and leaching of pesticides from untreated soils and soils in which microorganisms had been inhibited. The mineralization of ring¹⁴C labeled pesticides was studied. The study differentiated between biotic and abiotic processes that determine the fate of pesticides in the soil. Higher leaching rates of pesticides from PT soils are explaned by the relative importance of each of these processes. In NT soils, higher microbial populations and activity were associated with higher mineralization rates of atrazine, diazinon and carbofuran. Enhanced transformation rates played an important role in minimizing the leaching of metolachlor and carbofuran from NT soils. The role of abiotic adsorption/retention was important in minimizing the leaching of metolachlor, carbofuran and atrazine from NT soils. The role of fungi and bacteria in the biodegradation process was studied by selective inhibition techniques. Synergistic effects between fungi and bacteria in the degradation of atrazine and diazinon were observed. Carbofuran was also degraded in the soils where fungi were selectively inhibited. Possible mechanisms for enhanced biodegradation and decreased mobility of these pesticides in the upper layer of NT soils are discussed.     

Influence of microbial inoculation (Pseudomonas sp. strain ADP), the enzyme atrazine chlorohydrolase,and vegetation on the degradation of atrazine and metolachlor in soil

The concentrations of atrazine in the freshly added soils and the soils that had been incubated for 50 days significantly decreased 1 day after the addition of the enzyme atrazine chlorohydrolase or the soil bacterium Pseudomonas sp. strain ADP as compared with those in the uninoculated soils. Atrazine chlorohydrolase or ADP had no effect on the degradation of metolachlor. The half-lives of atrazine in the freshly added soils and in the aged soils after the treatment with atrazine chlorohydrolase or ADP markedly decreased as compared with those in the uninoculated soils. The half-lives of metolachlor in the aged soils were much longer than those of freshly added metolachlor. The percentage atrazine degraded in the freshly treated soils was much higher than that in the aged soils. This indicates that aging significantly decreased the bioavailability of atrazine. Vegetation significantly decreased the concentration of metolachlor. However, vegetation showed no effect on the degradation of atrazine.     

Algal degradation of a known endocrine disrupting insecticide, alpha-endosulfan, and its metabolite, endosulfan sulfate, in liquid medium and soil

The role of algae in the persistence, transformation, and bioremediation of two endocrine disrupting chemicals, alpha-endosulfan (a cyclodiene insecticide) and its oxidation product endosulfan sulfate, in soil (incubated under light or in darkness) and a liquid medium was examined. Incubation of soil under light dramatically decreased the persistence of alpha-endosulfan and enhanced its transformation to endosulfan sulfate, over that of dark-incubated soil samples, under both nonflooded and flooded conditions. This enhanced degradation of soil-applied alpha-endosulfan was associated with profuse growth of indigenous phototrophic organisms such as algae in soil incubated under light. Inoculation of soil with green algae, Chlorococcum sp. or Scenedesmus sp., further enhanced the degradation of alpha-endosulfan. The role of algae in alpha-endosulfan degradation was convincingly demonstrated when these algae degraded alpha-endosulfan to endosulfan sulfate, the major metabolite, and endosulfan ether, a minor metabolite, in a defined liquid medium. When a high density of the algal inoculum was used, both metabolites appeared to undergo further degradation as evident from their accumulation only in small amounts and the appearance of an endosulfan-derived aldehyde. Interestingly, beta-endosulfan was detected during degradation of alpha-endosulfan by high density algal cultures. These algae were also capable of degrading endosulfan sulfate but to a lesser extent than alpha-endosulfan. Evidence suggested that both alpha-endosulfan and endosulfan sulfate were immediately sorbed by the algae from the medium, which then effected their degradation. Biosorption, coupled with their biotransformation ability, especially at a high inoculum density, makes algae effective candidates for remediation of alpha-endosulfan-polluted environments.     

Thermodynamic, spectroscopic, and computational evidence for the irreversible conversion of beta- to alpha-endosulfan.

Previous studies have provided unequivocal evidence for the symmetry of beta-endosulfan and the corresponding asymmetry of alpha-endosulfan; the conversion of beta-endosulfan to alpha-endosulfan was identified. In this study, evidence from differential scanning calorimetry (DSC) and nuclear magnetic resonance (NMR) experiments combined with computational chemistry calculations was used to propose a molecular mechanism for the corresponding conformational changes that occur in this process. DSC and NMR data of mixtures indicated that both isomers can influence the conformer populations in the solid, solution, and vapor phase. Computational chemistry demonstrated that the relative S==O configuration between alpha- and beta-isomers can be the intermediate state through which the conformations of alpha- and beta-isomers affect each other. Furthermore, calculations for mixtures indicated that the asymmetrical conformation of the sulfite in alpha-endosulfan can induce asymmetry in beta-endosulfan, and conversion to alpha-endosulfan occurs from this transition state.     

Wet deposition of current use pesticides at a rural location on the Delmarva Peninsula: impact of rainfall patterns and agricultural activity

Event-based precipitation samples were collected during the main agricultural season (April-September) over 4 years (2000-2003) at one site in the Choptank River Watershed on the Delmarva Peninsula. The samples were analyzed for 19 agricultural pesticides to determine the contribution of wet deposition as a source of these compounds to the Chesapeake Bay and the factors affecting the temporal trends in deposition. Chlorothalonil was detected most frequently (92% samples) followed by metolachlor (66%) and endosulfans (49%). Although chlorothalonil is the single biggest contributor to pesticide flux (33-46%), pesticide wet deposition is dominated by herbicides (46-61%), with the greatest fluxes occurring during the time of herbicide application on corn and soybeans. The analysis suggests that the extent of wet deposition of herbicides depends on the timing of precipitation relative to herbicide application. The insecticide and fungicide flux was greater in years with above-average rainfall (2001 and 2003), suggesting that for these pesticides deposition flux is dependent on the total amount of rainfall in the agricultural season. The data indicate that the use of chlorpyrifos, an organophosphate insecticide which is on the Toxics of Concern list for the Bay, is on the increase. Total pesticide flux ranged from 90 microg/m2 (2001) to 180 microg/m2 (2000). Wet deposition can account for up to 10-20% of the annual loadings of pesticides to the Bay.     

Pesticide extraction efficiency of two solid phase disk types after shipping

An interlaboratory study was conducted to compare pesticide recovery from Empore C(18) and Speedisks C(18)XF solid phase extraction disks after shipping. Four pesticides were used for the comparison of the two disk extraction materials: atrazine, diazinon, metolachlor, and tebuconazole. These pesticides were chosen to provide a range of physiochemical properties. Water samples were extracted onto the disk types and shipped to a cooperating laboratory for elution and analysis. The mean recoveries from Empore disks were atrazine, 95%; diazinon, 91%; metolachlor, 92%; and tebuconazole, 83%. The recoveries from Speedisks C(18)XF were atrazine, 89%; diazinon, 87%; metolachlor, 86%; and tebuconazole, 79%. Means for each of the pesticides using the different disk types were not statistically different (alpha = 0.05), but results were more variable when using Speedisks C(18)XF as compared to Empore disks. Reasons for the increased variability are discussed, but overall results indicate that Speedisks C(18)XF could be used as an alternative to Empore disks. Speedisks C(18)XF are enclosed in a plastic housing, so they can be used more easily in remote sampling sites without the possibility of glassware breakage, no prefiltration of samples is needed, and there are realignment problems that can be associated with the Empore disks.     

Blind inlets: conservation practices to reduce herbicide losses from closed depressional areas

Purpose

In a 6-year study, we investigated the effectiveness of blind inlets as a conservation practice in reducing pesticide losses compared to tile risers from two closed farmed depressional areas (potholes) in the US Midwest under a 4-year cropping rotation.

Materials and methods

In two adjacent potholes within the same farm and having similar soils, a conventional tile riser and blind inlet were installed. Each draining practice could be operated independent of each other in order to drain and monitor each depression with either practice. Sampling events (runoff events) were collected from the potholes from 2008 to 2013 using autosamplers. The samples were analyzed for atrazine, metolachlor, 2,4-D, glyphosate, and deethylatrazine.

Results and discussion

The results of this study demonstrated that the blind inlet reduced analyzed pesticide losses; however, the level of reduction was compound dependent: atrazine (57 %), 2,4-D (58 %), metolachlor (53 %), and glyphosate (11 %).

Conclusions

Results from this study corroborate previous research findings that blind inlets are an effective conservation practice to reduce discharge and pollutants, including pesticides from farmed pothole surface runoff in the US Midwest.

     

Physiological and Genetic Responses to Pesticide Mixture Treatment of Veronica beccabunga

The effects of a five-pesticide mixture on pesticide accumulation, phytohormone levels (indole-3-acetic acid, gibberellic acid, jasmonic acid, and salicylic acid), pigment contents (total chlorophyll and carotenoid), antioxidant enzyme (catalase and guaiacol peroxidase) activities, lipid peroxidation product (malondialdehyde), and DNA profiles were investigated in the leaves of Veronica beccabunga. Laboratory-acclimatized plants were treated with a mix of five pesticides (atrazine, disulfoton, chlorpyrifos, metalaxyl, and ethion) in doses of 50?ppt, 1?ppb, 100?ppb, and 1?ppm for 1, 3, and 6?days. The accumulation of each pesticide, from highest to lowest, was as follows: chlorpyrifos, atrazine, metalaxyl, disulfoton, and ethion. The amounts of total chlorophyll and protein decreased with increased pesticide concentration. Antioxidant enzyme activities and malondialdehyde amount increased linearly with increasing pesticide exposure. However, the highest pesticide concentration caused decreases in guaiacol peroxidase (POD) activity and malondialdehyde (MDA) content at all treatment times. Both jasmonic and salicylic acid levels increased with pesticide exposure and decreased gradually after. It was also determined that application of the pesticide mixture affected the DNA profiles of V. beccabunga. The most band changes were detected on the sixth day of treatment.     

Fate of (14)C-labeled soybean and corn pesticides in tropical soils of Brazil under laboratory conditions

The dissipation rate of seven currently used soybean and corn pesticides in two tropical soils (Ustox and Psamments) of Brazil was studied in a laboratory incubation experiment. Dissipation half-lives of pesticides ranged between 2 (monocrotofos) and 90 days (endosulfan-beta). The contrasting clay contents of the studied tropical soils (130 versus 470 g of clay kg(-1) of soil) did not influence the dissipation dynamics of pesticides substantially. Mineralization to CO(2) was high [up to 78% of the applied radioactivity (AR)] for the studied organophosphorus compounds and deltamethrin, which also formed considerable amounts of bound residues (>20% of AR) during the 80 days of incubation. The highest portion of nonextractable residues was found for alachlor and simazine (55-60% of AR). In contrast, the nonpolar trifluralin and endosulfan formed only small amounts of bound residues (mostly <20% of AR) but showed the highest dissipation half-lives (>14 days) in the studied soils, also due to a low mineralization rate. When endosulfan-sulfate, as the main metabolite of endosulfan, was considered, the half-life time of endosulfan compounds (sum of -alpha, -beta, and -sulfate) was enhanced to >160 days in both soils. In comparison with the laboratory experiments, dissipation half-life times of chlorpyrifos, endosulfan-alpha, and trifluralin were shortened by a factor of 10-30 in field trials with the same soils, which was related to the volatilization potential of pesticides from soils.     

Multi-Year Measurements of Field-Scale Metolachlor Volatilization

Volatilization is a critical pathway for herbicide loss from agricultural fields, and subsequently deposited downwind from the edge of the field. To better understand the volatilization process, field-scale turbulent volatilization fluxes of metolachlor (2-chloro-N-(2-ethyl-6-methylphenyl)-N-(2-methoxy-1-methylethyl) acetamide) were quantified for 13 consecutive years using a combination of herbicide concentration profiles and eddy diffusivities derived from turbulent fluxes of heat and water vapor. Site location, type of herbicides, and agricultural management practices remained unchanged during this study in order to evaluate the effect of soil moisture on metolachlor volatilization. Twenty gravimetric surface soil moisture samples (0–5 cm) were collected immediately after herbicide application and then at 0430 hours each morning to determine the impact of surface moisture on herbicide volatilization. Five days after application, cumulative herbicide volatilization ranged from 5 to 63% of that applied for metolachlor. Metolachlor volatilization remained an important loss process more than 5 days after application when the soil surface was moist. Conversely, if the soil surface was dry, negligible volatilization occurred beyond 5 days. Furthermore, the total amount of metolachlor volatilized into the atmosphere increased exponentially with surface soil water content during application (r ²?=?0.78). Metolachlor volatility was found to be governed largely by surface soil moisture.     

Impact of grass filter strips length on exported dissolved masses of metolachlor,atrazine and deethylatrazine: a four‐season study under natural rain conditions

Herbicides atrazine and metolachlor have been detected in water bodies across the world. The objective of this study was to assess the efficiency of 0‐m, 3‐m, 6‐m and 9‐m grass filter strips to reduce masses of dissolved metolachlor, atrazine and deethylatrazine (a degradation product of atrazine) exported in runoff. For that purpose, 16 uncultivated plots (3‐m wide × 65‐m long) with 0‐m‐, 3‐m‐, 6‐m‐ and 9‐m‐long grass filter strips were setup in a completely randomized block design. During four seasons, masses of dissolved atrazine, metolachlor and deethylatrazine were determined for the first four to five rain events, under natural rain conditions, after atrazine and metolachlor application. Generally, grass filter strips reduced exported herbicide masses by more than 90% and influenced atrazine and metolachlor dissipation kinetics in the field. The 3‐m grass filter strip (area ratio source/strip of 22:1) usually provided a reduction in exported herbicide masses similar to the 6‐ or 9‐m grass filter strips. Therefore, under the present experimental soil and climate conditions, a grass filter strip of 3 m would be a good compromise between environmental protection of surface waters against atrazine and metolachlor contamination and conservation of agricultural land use. Such an approach contributes to the acceptability by producers to implement optimized best management practices such as vegetated filter strips for the preservation of the quality of water resources.     

Acute Toxicity of Seven Selected Pesticides (Alachlor, Atrazine, Dieldrin, Diuron, Pirimiphos-Methyl, Chlorpyrifos, Diazinon) to the Marine Fish (Turbot, Psetta maxima)

The present study evaluated the short-term toxicity of seven selected pesticides: four insecticides (chlorpyrifos, dieldrin, diazinon and pirimiphos-methyl) and three herbicides (diuron, alachlor and atrazine). With this aim, a standard toxicity test with the highly sensitive early life stages (ELS) of a marine fish was used. The turbot, Psetta maxima, is abundant in shallow estuarine and costal habitats and is currently the most commonly cultivated fish species in Galicia, NW Spain. According to the turbot ELS test results, chlorpyrifos was the most toxic pesticide tested for both embryos and larvae and was followed in order of decreasing toxicity by dieldrin, pirimiphos-methyl, diazinon, alachlor, atrazine and diuron. Larvae were more sensitive than embryos to the seven pesticides. The median lethal concentrations of the selected pesticides during a 48- and a 96-h exposure for turbot embryos and larvae were, respectively (in micrograms per litre): chlorpyrifos, 116.6 and 94.65; dieldrin, 146 and 97; pirimiphos-methyl, 560 and 452; diazinon, 1,837 and 1,230; alachlor, 2,177 and 2,233; diuron, 10,076 and 7,826; and atrazine, 11,873 and 9,957. According to their acute toxicity, the insecticides were more toxic than the herbicides. Furthermore, all insecticides and herbicides appear to be teratogenic to turbot ELS.     

Comparison of the persistence of atrazine and metolachlor under field and laboratory conditions

A study was carried out in a loamy soil to evaluate the degradation of atrazine and metolachlor under laboratory-controlled and field-variable conditions as a function of temperature and soil moisture content. In laboratory trials, metolachlor showed fast degradation, with half-lives from 100 to 5.7 days in a temperature range from 5 to 35 degrees C at 100% of field capacity, whereas in the same conditions the degradation rate of atrazine was relatively slow, with half-lives from 407 to 23 days. Modeling of laboratory degradation data to predict field persistence was carried out. Field persistence of atrazine and metolachlor was measured in the same soil during the corn growing seasons in 1993, 1994, and 1996. In the three years the mean half-dissipation times for atrazine and metolachlor were 36 and 21 days, respectively. Calculations from model equations gave acceptable prediction of field dissipation of both herbicides. Limitations and perspectives of employed modelization procedure are discussed.     

Multiclass pesticide determination in olives and their processing factors in olive oil: comparison of different olive oil extraction systems

The processing factors (pesticide concentration found in olive oil/pesticide concentration found in olives) of azinphos methyl, chlorpyrifos, lambda-cyhalothrin, deltamethrin, diazinon, dimethoate, endosulfan, and fenthion were determined in olive oil production process in various laboratory-scale olive oil extractions based on three- or two-phase centrifugation systems in comparison with samples collected during olive oil extractions in conventional olive mills located at different olive oil production areas in Greece. Pesticide analyses were performed using a multiresidue method developed in our laboratory for the determination of different insecticides and herbicides in olive oil by solid-phase extraction techniques coupled to gas chromatography detection (electron capture detection and nitrogen phosphorus detection), optimized, and validated for olive fruits sample preparation. Processing factors were found to vary among the different pesticides studied. Water addition in the oil extraction procedure (as in a three-phase centrifugation system) was found to decrease the processing factors of dimethoate, alpha-endosulfan, diazinon, and chlorpyrifos, whereas those of fenthion, azinphos methyl, beta-endosulfan, lambda-cyhalothrin, and deltamethrin residues were not affected. The water content of olives processed was found to proportionally affect pesticide processing factors. Fenthion sulfoxide and endosulfan sulfate were the major metabolites of fenthion and endosulfan, respectively, that were detected in laboratory-produced olive oils, but only the concentration of fenthion sulfoxide was found to increase with the increase of water addition in the olive oil extraction process.     

Influence of rhamnolipids and triton X-100 on the biodegradation of three pesticides in aqueous phase and soil slurries.

The effect of surfactants on the biodegradation of trifluralin and atrazine (by Streptomyces PS1/5) and coumaphos (by degrading consortia from a contaminated cattle dip) in liquid cultures and soil slurries was tested at different concentrations of a rhamnolipid mixture (Rh-mix) and Triton X-100 (TX-100). The extent of trifluralin biodegradation in liquid culture was improved at high concentrations of both surfactants. The extent of atrazine degradation dropped in the presence of either surfactant. Coumaphos biodegradation improved slightly at Rh-mix dosages >3000 microM; however, it was readily inhibited by TX-100 at amounts above the critical micelle concentration. In soil slurries, the extent of both trifluralin and atrazine biodegradation was higher in Hagerstown A (HTA) soil than in Hagerstown B (HTB) soil and was not significantly affected by the presence of either surfactant. The onset of trifluralin biodegradation was retarded at higher concentrations of surfactants. In the absence of surfactant, up to 98% of coumaphos in both soil slurries was transformed. At increasing dosages of Rh-mix, the onset of coumaphos biodegradation was retarded, but the removal efficiency of the pesticide increased. Rh-mix and TX-100 depletion was observed during Streptomyces PS1/5 growth in liquid cultures. Rh-mix concentration also decreased during coumaphos biodegradation, whereas TX-100 concentration was not affected. These results suggest that surfactants, added for the purpose of increasing the apparent water solubility of hydrophobic organic compounds, may have unintended effects on both the rate and extent of biodegradation of the target compounds if the surfactants can also be degraded by the microorganisms in the system.