Procedure for the determination of 2,4-D and dicamba in inhalation, dermal, hand-wash, and urine samples from spray applicators

Analytical procedures for the simultaneous determination of residues of 2,4-D and dicamba from polyurethane foam plug air samplers, ethylene glycol impregnated glass-fiber filter paper dermal samplers, 1% sodium bicarbonate hand wash solution, and urine are presented. Residues were derivatized with diazomethane and quantitated using electron capture gas chromatography. Recoveries were greater than 80% at the limit of detection in all substrates. The limits of detection for both herbicides were 0.1 microgram/foam plug and 0.5 micrograms/filter paper, and in the urine, 1.7 micrograms/100 mL and 5.0 micrograms/100 mL for dicamba and 2,4-D, respectively.     

Exposure of homeowners and bystanders to 2,4-dichlorophenoxyacetic acid (2,4-D).

Total body dose received in home gardeners applying 2,4-D and bystanders living within the household, but not applying the pesticide was measured. Levels of 2,4-D were monitored in air samples both inside the home and downwind of the application site. Homeowners were divided into protective and non-protective apparel groups and applied both a granular and liquid formulation of 2,4-D on two separate dates. Analyses of urine collected from homeowners for 96 hours following applications found total body doses ranging from non-detectable to 0.0071 mg/kg of body weight. The highest exposures occurred in the non-protected group and were consistently associated with spills of the liquid concentrate or excessive contact with the dilute mixture on the hands or forearms. Residues of 2,4-D were not detected in urine samples supplied by bystanders to home applicators. Residues of 2,4-D were detected in five of the 76 air samples taken during the home applications. Two of these air samples coincided with measurable applicator exposure but it is unlikely that this was a major route of exposure.     

2,4-D levels in the South Saskatchewan River in 1973 as determined by GLC method.

2,4-D levels in the South Saskatchewan River near Saskatoon in 1973 at the height of the spraying season, and at harvestime, were determined by a method involving direct glc analysis, ankaline hydrolysis, followed by n-butylation of the liberated free acid after acidification of the alkaline solution, and confirmed by subsequent n-octylation. GC/MS also confirmed the presence of 2,4-D. 2,4-D was detected during the spraying season but not at harvest time or in river mud samples. The average level was ca. 2mug of acid equivalent to 2,4-D per liter of river water at the height of the spraying season.     

Determination of 2,4-Dichlorophenoxyacetic acid in food and water samples using a modified graphene oxide sorbent and high-performance liquid chromatography

Abstract

In the present work, dispersive micro-solid phase extraction (D-μ-SPE) method using magnetic graphene oxide tert-butylamine (GO/Fe₃O₄/TBA) nanocomposite, as an efficient sorbent, was applied for determining 2,4-dichlorophenoxyacetic acid (2,4-D) in water and food samples. Detection was carried out using high-performance liquid chromatography (HPLC) instrument. Influential parameters of D-μ-SPE such as sorbent and its amount, elution solvent and its volume, adsorption and desorption times and pH of sample solution were investigated and optimized. Under the optimized conditions, limit of detection and quantitation values were 0.007 and 0.02?μg/mL, respectively. Recovery data for several real samples were obtained within the range of 88.0–94.0% with a relative standard deviation (RSD) less than 7.5%. The proposed method was successfully applied to quantitative determination of 2,4-D in several vegetables and water samples.     

Exposure of Florida airboat aquatic weed applicators to 2,4-Dichlorophenoxyacetic acid (2,4-D)

Florida airboat handgun applicators were monitored for exposure to 2,4-Dichlorophenoxyacetic acid (2,4-D). Four applicators were monitored with air samplers, α -cellulose patches, and 24 hr urine samples on 10 separate days. Estimated total body exposure averaged 15 ± 2 mg/hr, of which 74% was to the legs and feet with an additional 18% to the hands and arms. Estimated respiratory exposure was about 0.03% of the total body exposure. Twenty-four hr urinary 2,4-D ranged from 0.190–0.645 mg. The use of disposable coveralls and effective hand protection would markedly reduce this exposure.     

Spiking solvent, humidity and their impact on 2,4-D and 2,4-DCP extractability from high humic matter content soils

The 2,4-dichlorophenoxyacetic acid (2,4-D) is a hormone-like herbicide widely used in agriculture. Although its half life in soil is approximately two weeks, the thousands of tons introduced in the environment every year represent a risk for human health and the environment. Considering the toxic properties of this compound and its degradation products, it is important to assess and monitor the 2,4-D residues in agricultural soils. Furthermore, experiments of phyto/bioremediation are carried out to find economic and environmental friendly tools to restore the polluted soils. Accordingly, it is essential to accurately measure the amount of 2,4-D and its metabolites in soils. There is evidence that 2,4-D extraction from soil samples seriously depends on the physical and chemical properties of the soil, especially in those soils with high content of humic acids. The aim of this work was to assess the variables that influence the recovery and subsequent analysis of 2,4-D and its main metabolite (2,4-dichlorophenol) from those soils samples. The results showed that the recovery efficiency depends on the solvent and method used for the extraction, the amount and kind of solvent used for dissolving the herbicide and the soil water content at the moment of spiking. An optimized protocol for the extraction and quantification of 2,4-D and its main metabolite from soil samples is presented.     

Concurrent 2,4-D and triclopyr biomonitoring of backpack applicators, mixer/loader and field supervisor in forestry

Two herbicides, 2,4-D and triclopyr esters (application ratio 1.6:1 acid equivalents) were applied as a tank mix by a crew of 8 backpack sprayer applicators, a mixer/loader, and a field supervisor. The crew was employed in a conifer release program in northern California during the summer of 2002. Biomonitoring (urine, 24 h) utilized 2,4-D and triclopyr (a.e.) as rapidly excreted exposure biomarkers. The absorbed dosages of 2,4-D and triclopyr were calculated based upon cotton whole body suits and biomonitoring. Dosages based upon accumulation of the herbicides on body suits averaged 42.6 μg (a.e.) 2,4-D/kg-d and 8.0 μg (a.e.) triclopyr/kg-d. Six consecutive days of concurrent urine collections showed that backpack applicators excreted an average of 11.0 μg (a.e.) 2,4-D/kg-d and 18.9 μg (a.e.) triclopyr/kg-d. Estimates based upon curve fitting were 17.1 and 29.3 μg (a.e.)/kg-d, respectively. Results suggest that passive dosimetry for 2,4-D consistently overestimated the dosage measured using biomonitoring by a factor of 2-3 fold, while for triclopyr, passive dosimetry underestimated the absorbed dose based on biomonitoring by a factor of 2-4 fold.     

2,4-Dichlorophenoxyacetic acid (2,4-D) biodegradation in river sediments of Northeast-Scotland and its effect on the microbial communities (PLFA and DGGE)

A bench-scale study was conducted to investigate 2,4-D biodegradation rates at different concentrations (10, 100 and 1000 microg per gram of dry weight) in distinct sediments samples collected on the River Ythan, Northeast-Scotland. Mineralisation of 14C 2,4-D occurred mostly within 30 days for all tested concentrations with a degradation rate ranging from 5 to 750 microg d(-1). Biodegradation rates were affected by the biological and biochemical characteristics of the indigenous microbial community in the studied sediments rather than factors such as compound bioavailability and/or toxicity. PLFA-profiling provided evidences of the effect of 2,4-D amendments on the microbial communities and DGGE-profiling showed changes in the genetic potential of the microbial populations which might affect metabolic characteristics of the sediment. PLFAs biomarkers suggested that the pathway of alpha-ketoglutarate-dependent dioxygenase was the main route of 2,4-D biodegradation. This pathway is commonly found in microorganisms of the beta-subdivision of proteobacteria.     

Survey of Airborne 2,4-D in South-Central Washington

The extensive application of 2,4-D herbicides to wheat and other agricultural crops in the states of Washington and Oregon can produce "off-target" damage when the 2,4-D formulations are transported by the atmosphere to sensitive crops, such as grapes. During May-June of 1973 and April-June of 1974, a 2,4-D monitoring network in south-central Washington collected samples for subsequent herbicide analysis. The daily, 24 hr field samples were collected with differential Impactor-impinger air samplers and were routinely analyzed in the analytical laboratory by electron-capture gas chromatography. In addition, gas chromatography/mass spec-trometry was employed for positive identification of the 2,4-D esters and for comparative quantitative analysis. The complete sampling and analytical methodology, the 2,4-D concentration data for 1973 and 1974, the agricultural 2,4-D application records and crop Injury reports, and the concomitant meteorological data are described in this paper.     

Fungal bioconversion of 2,4-dichlorophenoxyacetic acid (2,4-D) and 2,4-dichlorophenol (2,4-DCP)

Ninety strains of fungi from the collection of our mycology laboratory were tested in Galzy and Slonimski (GS) synthetic liquid medium for their ability to degrade the herbicide 2,4-dichlorophenoxyacetic acid (2,4-D) and its by-product, 2,4-dichlorophenol (2,4-DCP) at 100 mg l(-1), each. Evolution of the amounts of each chemical in the culture media was monitored by HPLC. After 5 days of cultivation, the best results were obtained with Aspergillus penicilloides and Mortierella isabellina for 2,4-D and with Chrysosporium pannorum and Mucor genevensis for 2,4-DCP. The data collected seemed to prove, on one hand, that the strains responses varied with the taxonomic groups and the chemicals tested, and, on the other hand, that 2,4-D was less accessible to fungal degradation than 2,4-DCP. In each case, kinetics studies with the two most efficient strains revealed that there was a lag phase of 1 day before the onset of 2,4-D degradation, whereas there was none during 2,4-DCP degradation. Moreover, 2,4-DCP was detected transiently during 2,4-D degradation. Finally, M. isabellina improved its degradation potential in Tartaric Acid (TA) medium relative to GS and Malt Extract (ME) media.     

Procedure for the determination of 2,4‐D and dicamba in inhalation,dermal, hand‐wash,and urine samples from spray applicators

Abstract

Analytical procedures for the simultaneous determination of residues of 2,4‐D and dicamba from polyurethane foam plug air samplers, ethylene glycol impregnated glass‐fiber filter paper dermal samplers, 1% sodium bicarbonate hand wash solution, and urine are presented. Residues were derivatized with diazomethane and quantitated using electron capture gas chromatography. Recoveries were greater than 80% at the limit of detection in all substrates. The limits of detection for both herbicides were 0.1 μg/foam plug and 0.5 μg/filter paper, and in the urine, 1.7 μg/100 mL and 5.0 μg/100 mL for dicamba and 2,4‐D, respectively.     

Human exposure to 2,4-D following controlled activities on recently sprayed turf.

Total body dose of 2,4-D was determined in 10 volunteers following exposure to sprayed turf 1 hour following application and in 10 volunteers exposed 24 hours following application. Each group of 10 volunteers was divided in half and five wore long pants, a short-sleeved shirt, socks and closed footwear. The other five wore shorts and a short-sleeved shirt and were barefoot. All volunteers were exposed to a 2 by 15 m area of turf for 1 hour during which they alternated between walking and sitting or lying on the turf surface for intervals of 5 minutes. Dislodgeable residues of 2,4-D taken during the exposure sessions showed a rapid decline from 1 hour following application (8%) to 24 hours following application (1%). No detectable residues were found in 4-day urine samples supplied by volunteers except for 3 people who were barefoot and wearing shorts and contacted the turf 1 hour following 2,4-D application. The highest dose was measured in a volunteer who removed his shirt for 30 minutes of the exposure session (426 micrograms). Exposure levels of the other two volunteers who wore the prescribed clothing were lower (153 and 103 micrograms). No detectable residues were found in urine samples supplied by volunteers exposed to sprayed turf 24 hours following application. These results indicate that at the doses measured, exposure to sprayed turf should present little risk in humans. However, people can reduce exposure to non-detectable levels by remaining off treated turf for a period of 24 hours or until after rainfall or irrigation so that dislodgeable residues and therefore potential exposure are essentially zero.     

Sampling and Analysis of Volatile Organic Compounds Evolved During Thermal Processing of Acrylonitrile Butadiene Styrene Composite Resins

Abstract

The evaluation of emissions of volatile organic compounds (VOCs) during processing of resins is of interest to resin manufacturers and resin processors. An accurate estimate of the VOCs emitted from resin processing has been difficult due to the wide variation in processing facilities. This study was designed to estimate the emissions in terms of mass of emitted VOC per mass of resin processed.

A collection and analysis method was developed and validated for the determination of VOCs present in the emissions of thermally processed acrylonitrile butadiene styrene (ABS) resins. Four composite resins were blended from automotive, general molding, pipe, and refrigeration grade ABS resins obtained from the manufacturers. Emission samples were collected in evacuated 6-L Summa canisters and then analyzed using gas chromatography/flame ionization detection/mass selective detection (GC/FID/MSD). Levels were determined for nine target analytes detected in canister samples, and for total VOCs detected by an inline GC/FID. The emissions evolved from the extrusion of each composite resin were expressed in terms of mass of VOCs per mass of processed resin. Styrene was the principal volatile emission from all the composite resins. VOCs analyzed from the pipe resin sample contained the highest level of styrene at 402 μg/g. An additional collection and detection method was used to determine the presence of aerosols in the emissions. This method involved collecting particulates on glass fiber filters, extracting them with solvents, and analyzing them using gas chromatography/mass spectrometry (GC/MS). No significant levels of any of the target analytes were detected on the filters.     

2,4-Dichlorophenoxyacetic acid (2,4-D) sorption and degradation dynamics in three agricultural soils

The fate and transport of 2,4-dichlorophenoxyacetic acid (2,4-D) in the subsurface is affected by a complex, time-dependent interplay between sorption and mineralization processes. 2,4-D is biodegradable in soils, while adsorption/desorption is influenced by both soil organic matter content and soil pH. In order to assess the dynamic interactions between sorption and mineralization, 2,4-D mineralization experiments were carried using three different soils (clay, loam and sand) assuming different contact times. Mineralization appeared to be the main process limiting 2,4-D availability, with each soil containing its own 2,4-D decomposers. For the clay and the loamy soils, 45 and 48% of the applied dose were mineralized after 10 days. By comparison, mineralization in the sandy soil proceeded initially much slower because of longer lag times. While 2,4-D residues immediately after application were readily available (>93% was extractable), the herbicide was present in a mostly unavailable state (<2% extractable) in all three soils after incubation for 60 days. We found that the total amount of bound residue decreased between 30 and 60 incubation days. Bioaccumulation may have led to reversible immobilization, with some residues later becoming more readily available again to extraction and/or mineralization.     

Adsorption characteristics of 2,4-dichlorophenoxyacetic acid (2,4-D) from aqueous solution on powdered activated carbon

The removal of 2,4-dichlorophenoxyacetic acid (2,4-D), one of the most commonly used phenoxy acid herbicides, from aqueous solution was studied by using acid-washed powdered activated carbon (PAC) as an adsorbent in a batch system. Adsorption equilibrium, kinetics, and thermodynamics were investigated as a function of initial pH, temperature, and initial 2,4-D concentration. Powdered activated carbon exhibited the highest 2,4-D uptake capacity of 333.3 mg g(-1) at 25 degrees C and an initial pH value of 2.0. Freundlich, Langmuir, and Redlich-Peterson isotherm models were used to express the equilibrium data of 2,4-D depending on temperature. Equilibrium data fitted very well to the Freundlich equilibrium model in the studied concentration range of 2,4-D at all the temperatures studied. Three simplified models including pseudo-first-order, pseudo-second-order, and saturation-type kinetic models were used to test the adsorption kinetics. It was shown that the adsorption of 2,4-D on PAC at 25, 35, and 45 degrees C could be best fitted by the saturation-type kinetic model with film and intraparticle diffusions being the essential rate-controlling steps. The activation energy of adsorption (EA) was determined as--1.69 kJ mole(-1). Using the thermodynamic equilibrium coefficients obtained at different temperatures, the thermodynamic constants of adsorption (deltaG degrees, deltaH degrees, and deltaS degrees) were also evaluated.     

Effects of nozzle types and 2,4-D formulations on spray deposition

The objective of this study was to evaluate the effects of nozzle types and 2,4-D formulations on spray deposition on different targets. Two field experiments were carried out in a completely randomized design, and treatments were arranged in a factorial scheme. Species in experiment 1 were Sumatran fleabane (Conyza sumatrensis) and Brazil pusley (Richardia brasiliensis) and in experiment 2 were soybeans (Glycine max) and Benghal dayflower (Commelina benghalensis). For both experiments, the first factor corresponded to spray nozzles with different settings (AD 110.015 – 61 and 105 L ha^?1; AD 015-D – 75 and 146 L ha^?1; XR 110.0202 – 200 L ha^?1; and ADIA-D 110.02 – 208 L ha^?1) and the second factor consisted of two formulations of 2,4-D (amine and choline). The formulation of 2,4-D choline has contained Colex-D? Technology. Similar or higher spray deposition was observed on the leaves and artificial targets when using 2,4-D choline as compared to the 2,4-D amine formulation, and these differences in deposition were more evident for nozzles applying lower spray volumes. Deposition was more affected by nozzle type when amine formulation was used, compared to choline formulation.     

Treatment of 2,4-D, mecoprop, and dicamba using membrane bioreactor technology

Phenoxyacetic and benzoic acid herbicides are widely used agricultural, commercial, and domestic pesticides. As a result of high water solubility, mobility, and persistence, 2,4-dichlorophenoxyacetic acid (2,4-D), methylchlorophenoxypropionic acid (mecoprop), and 3,6-dichloro-2-methoxybenzoic acid (dicamba) have been detected in surface and waste waters across Canada. As current municipal wastewater treatment plants do not specifically address chronic, trace levels of contaminants like pesticides, an urgent need exists for an efficient, environmentally friendly means of breaking down these toxic herbicides. A commercially available herbicide mix, WeedEx, containing 2,4-D, mecoprop, and dicamba, was subjected to treatment using membrane bioreactor (MBR) technology. The three herbicides, in simulated wastewater with a chemical oxygen demand of 745 mg/L, were introduced to the MBR at concentrations ranging from 300 μg/L to 3.5 mg/L. Herbicides and biodegradation products were extracted from MBR effluent using solid-phase extraction followed by detection using high-performance liquid chromatography coupled with mass spectrometry. 2,4-D was reduced by more than 99.0 % within 12 days. Mecoprop and dicamba were more persistent and reduced by 69.0 and 75.4 %, respectively, after 112 days of treatment. Half-lives of 2,4-D, mecoprop and dicamba during the treatment were determined to be 1.9, 10.5, and 28.3 days, respectively. Important water quality parameters of the effluent such as dissolved oxygen, pH, ammonia, chemical oxygen demand, etc. were measured daily. MBR was demonstrated to be an environmentally friendly, compact, and efficient method for the treatment of toxic phenoxyacetic and benzoic acid herbicides.     

2,4-Dichlorophenoxy acetic acid mineralization in amended soil

The application of municipal biosolid or liquid hog manure to agricultural soils under laboratory conditions at 20 degrees C influenced the fate of the herbicide 2,4-D [2,4-(dichlorophenoxy)acetic acid] in soil. When 2,4-D was added to soil at agronomic rates immediately after the addition of manure or biosolids to a coarse-textured soil, the percentage of 2,4-D mineralized at 100 days was about 47% for both treatments, compared to only 31% for control soils without amendments. The enhanced 2,4-D mineralization as a result of amendment addition was due to an increased heterotrophic microbial activity, with the greatest increases in soil respiration occurring for soils amended with biosolids. When additions of 2,4-D were delayed for one, two, or four weeks after the amendments were applied, the additions of amendments generally reduced 2,4-D mineralization in soil, particularly for manure, indicating that the effect of amendments on enhancing soil microbial activities diminished over time. In contrast, the mineralization of 2,4-D in control soils was less dependent on when 2,4-D was applied in relation to pre-incubations of soil for zero, one, two, or four weeks. The effect of manure on decreasing 2,4-D mineralization in specific soils was as large as the effect of soil texture on differences in 2,4-D mineralization across soils. Because manure was not found to impact 2,4-D sorption by soil, it is possible that 2,4-D mineralization decreased because 2,4-D transformation products were strongly sorbed onto organic carbon constituents in manure-amended soils and were therefore less accessible to microorganisms. Alternatively, microorganisms were less likely to metabolize the herbicide because they preferentially consumed the type of organic carbon in manure that is a weak sorbent for 2,4-D.     

Treatment and reuse of wastewater in pesticide 2,4-D production

Waste-water from the production of pesticide 2,4-D often contains high concentrations of 2,4-DCP and 2,6-D as the primary pollutants. Treatment of waste-water collected from a 2,4-D manufacturer was carried out using a technology combining acidification with hyper-crosslinked resin NDA-150 adsorption process. The overall process recovered 5.4 kg of 2,4-DCP and 0.6 kg of 2,6-D per cubic metre of the wastewater. The treatment reduced the concentration of 2,4-DCP in the wastewater from >6000 mg/L to <0.5 mg/L. The optimal operation parameters of adsorption and desorption were determined. The hyper-crosslinked resin adsorbent can be re-used after regeneration by NaOH aqueous solution. The recovered 2,4-DCP with a sufficiently high purity may be re-used in the production of 2,4-D. The technology may thus be applied to the treatment of waste-water for reclamation of chemicals for 2,4-D production while minimising the environmental nuisances and hazards that may be caused by these chemicals.     

2,4-Dichlorophenoxy Acetic Acid Mineralization in Amended Soil

The application of municipal biosolid or liquid hog manure to agricultural soils under laboratory conditions at 20°C influenced the fate of the herbicide 2,4-D [2,4-(dichlorophenoxy)acetic acid] in soil. When 2,4-D was added to soil at agronomic rates immediately after the addition of manure or biosolids to a coarse-textured soil, the percentage of 2,4-D mineralized at 100 days was about 47% for both treatments, compared to only 31% for control soils without amendments. The enhanced 2,4-D mineralization as a result of amendment addition was due to an increased heterotrophic microbial activity, with the greatest increases in soil respiration occurring for soils amended with biosolids. When additions of 2,4-D were delayed for one, two, or four weeks after the amendments were applied, the additions of amendments generally reduced 2,4-D mineralization in soil, particularly for manure, indicating that the effect of amendments on enhancing soil microbial activities diminished over time. In contrast, the mineralization of 2,4-D in control soils was less dependent on when 2,4-D was applied in relation to pre-incubations of soil for zero, one, two, or four weeks. The effect of manure on decreasing 2,4-D mineralization in specific soils was as large as the effect of soil texture on differences in 2,4-D mineralization across soils. Because manure was not found to impact 2,4-D sorption by soil, it is possible that 2,4-D mineralization decreased because 2,4-D transformation products were strongly sorbed onto organic carbon constituents in manure-amended soils and were therefore less accessible to microorganisms. Alternatively, microorganisms were less likely to metabolize the herbicide because they preferentially consumed the type of organic carbon in manure that is a weak sorbent for 2,4-D.