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.     

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.     

Determination of 2,4-dichlorophenoxyacetic acid (2,4-D) in human urine with mass selective detection.

Method development and validation studies have been completed on an assay that will allow the determination of 2,4-dichlorophenoxyacetic acid (2,4-D) in human urine. The accurate determination of 2,4-D in urine is an important factor in monitoring worker and population exposure. These studies successfully validated a method for the detection of 2,4-D in urine at a limit of quantitation (LOQ) of 5.00 ppb (parts per billion) using gas chromatography with mass selective detection (GC/MSD). The first study involved the determination of 2,4-D in control human urine and urine samples fortified with 2,4-D. Due to chromatographic interference, a second study was conducted using 14C-2,4-D to verify the recoverability of 2,4-D from human urine at low levels using the GC/MSD method. The second study supports the results of the original data. The 2,4-D was extracted from human urine using a procedure involving hydrolysis using potassium hydroxide, followed by a liquid-liquid extraction into methylene chloride. The extracted samples were derivatized with diazomethane. The methylated fraction was analyzed by GC/MSD. Quantitation was made by comparison to methylated reference standards of 2,4-D. Aliquots fortified at 5-, 50-, and 500-ppb levels were analyzed. The overall mean recovery for all fortified samples was 90.3% with a relative standard deviation of 14.31%.     

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.     

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-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.     

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.     

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.     

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.     

Dicamba and 2,4-D residues following applicator cleanout: A potential point source to the environment and worker exposure

This paper presents a survey of pesticide residues in tanks following application and throughout the cleanout procedure as conducted by 46 volunteer operators across Colorado. While many pesticides were detected, this paper focuses on dicamba and 2,4-D, which were detected by liquid chromatography/tandem mass spectroscopy (LC-MS/MS). An exponential decrease in concentration was observed with sequential rinses, although this decrease may be more rapid for more water-soluble pesticides. More than 95% of the pesticide in the prerinse solution was removed by the end of the third rinse in all but three operator samples. Concentrations after three rinses were 0.41 ± 0.25 and 3.3 ± 1.1 mg/L for dicamba and 2,4-D, respectively. These concentrations suggest that the recommended practice of three rinses may not be adequate to eliminate off-target effects or point sources of pesticide waste, and that the recommended standard of personal protective equipment is essential to prevent worker exposure to the chemicals.

Implications:?This paper demonstrates that the waste generated during cleanout of pesticide application devices constitutes a potential source of pollution and worker exposure. In particular, while the first rinse of pesticide containers is often treated as hazardous waste and reapplied to crops, the remaining rinses are not. This work demonstrates that the wastewater generated in subsequent rinses can have high enough concentrations to impact worker health, cause off-target effects on crops, and potentially constitute a point source of pesticides. The practical implication is for improved recommendations and regulations regarding pesticide applicators and their cleanout process.     

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.     

Residues of 2,4‐D in air samples from Saskatchewan: 1966–1975

Abstract

Residues of 2,4‐D (2,4‐dichlorophenoxyacetic acid) in air samples from several sampling sites in central and southern Saskatchewan during the spraying seasons in the 1966–68 and 1970–75 periods were determined by gas‐liquid Chromatographic techniques. Initially, individual esters of 2,4‐D were characterized by retention times and confirmed further by co‐injection and dual column procedures. Since 1973, however, only total 2,4‐D acid levels in air samples have been determined after esterification to the methyl ester and confirmed by gc/ms techniques whenever possible.

Up to 50% of the daily samples collected during the spraying season at any of the locations and during any given year contained 2,4‐D, with butyl esters being found most frequently. The daily 24‐hr mean atmospheric concentrations of 2,4‐D ranged from 0.01 to 1.22 μg/m³, 0.01 to 13.50 μg/m³, and 0.05 to 0.59 μg/m for the iso‐propyl, mixed butyl and iso‐octyl esters, respectively. Even when the samples were analysed for the total 2,4‐D content, i.e. from 1973 onwards, the maximum level of the total acid reached only 23.14 μg/m. In any given year and at any of the sampling sites, about 30% of the samples contained less than 0.01 μg/m³ of 2,4‐D. In another 40% of the samples, the levels of 2,4‐D ranged from 0.01 to 0.099 yg/m. Only about 30% of the samples contained 2,4‐D concentrations higher than 0.1 μg/m³, with only 10% or less exceeding 1 μg/m³.

None of the samples, obtained with the high volume particu‐late sampler, showed any detectable levels of 2,4‐D, indicating little or no transport of 2,4‐D adsorbed on dust particles or as crystals of amine salts.     

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.     

Biodegradation and transfer of ingested 2,4-D herbicide by a polyphagous saturniid caterpillar.

A herbicide containing 2,4-dichlorophenoxyacetic acid (2,4-D) and related chemicals was fed to caterpillars of Eupackardia calleta, and the fate of the substances in the larvae and during further ontogenesis was followed by combined gas chromatography/mass spectrometry. The compounds were found in differing amounts in larval midgut, faeces, fat body/haemolymph, and even in an exocrine secretion produced by integumental glands. Furthermore, they were detected in samples from the resulting adult moths, indicating an intraindividual transfer. Since the individual development of E. calleta was distinctly accelerated by 2,4-D, possible impacts of the herbicide on the life history of the animals in the field are discussed. Based on the chemical data, hypothetical metabolic pathways for 2,4-D in E calleta larvae are proposed.     

Duplicate sampling reproducibility of atmospheric residues of herbicides for paired pan and high-volume air samplers

The reproducibility of collection of atmospheric residues of the herbicides 2,4-D and triallate as bulk (wet plus dry) deposition samples by paired pan samplers and as particulate (filter) and vapour (PUF/XAD-2 resin cartridge) samples by paired high-volume air samplers was determined. Variability of herbicide concentrations in paired bulk deposition samples was within 25% for 65 and 80% of the samples for 2,4-D and triallate, respectively, with approximately 90% of the paired samples being within a factor of 2 for both herbicides. The vapour samples of 2,4-D and triallate showed similar reproducibilities. The highest reproducibility was observed for the filter samples with 92% of the paired data sets for 2,4-D being within 25% variability. No triallate was detected in the filter samples.     

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.     

Effect of day time climatic conditions associated with different 2,4-D formulations on spray deposition and weed control

Abstract

The aim of this study was to evaluate the effect of time of the day and their associated climatic conditions on spray deposition of two 2,4-D formulations, as well as the influence on weed control. The experiment was installed in the field in complete randomized design. Treatments were arranged in factorial design 8?×?2, with 20 repetitions. First factor corresponded to different application time (1:00, 4:00, 7:00, 10:00, 13:00, 16:00, 19:00, and 22:00) with their respective climatic conditions. The second factor consisted of two formulations of 2,4-D applied at 776?g a.e. ha^?1 (2,4-D amine and 2,4-D choline salt with Colex-D? Technology) + glyphosate (816?g a.e. ha^?1). There was more spray deposition when 2,4-D choline formulation was used, and such differences were more evident for applications performed under adverse climatic conditions. More spray deposition was found in applications performed at times of day with more favorable temperature and humidity of the air conditions. Only the initial control of the evaluated species was affected by the time of application.     

Pesticide risk assessment: A study on inhalation and dermal exposure to 2,4-D and paraquat among Malaysian paddy farmers

A cross-section analytical study was conducted to evaluate the risk of pesticide exposure to those applying the Class II pesticides 2,4-D and paraquat in the paddy-growing areas of Kerian, Perak, Malaysia. It investigated the influence of weather on exposure as well as documented health problems commonly related to pesticide exposure. Potential inhalation and dermal exposure for 140 paddy farmers (handlers of pesticides) were assessed. Results showed that while temperature and humidity affected exposure, windspeed had the strongest impact on pesticide exposure via inhalation. However, the degree of exposure to both herbicides via inhalation was below the permissible exposure limits set by United States National Institute of Occupational Safety and Health (NIOSH). Dermal Exposure Assessment Method (DREAM) readings showed that dermal exposure with manual spraying ranged from moderate to high. With motorized sprayers, however, the level of dermal exposure ranged from low to moderate. Dermal exposure was significantly negatively correlated with the usage of protective clothing. Various types of deleterious health effects were detected among users of manual knapsack sprayers. Long-term spraying activities were positively correlated with increasing levels of the gamma-glutamyl transpeptidase (GGT) liver enzyme. The type of spraying equipment, usage of proper protective clothing and adherence to correct spraying practices were found to be the most important factors influencing the degree of pesticide exposure among those applying pesticides.     

Pesticide risk assessment: A study on inhalation and dermal exposure to 2,4-D and paraquat among Malaysian paddy farmers

A cross-section analytical study was conducted to evaluate the risk of pesticide exposure to those applying the Class II pesticides 2,4-D and paraquat in the paddy-growing areas of Kerian, Perak, Malaysia. It investigated the influence of weather on exposure as well as documented health problems commonly related to pesticide exposure. Potential inhalation and dermal exposure for 140 paddy farmers (handlers of pesticides) were assessed. Results showed that while temperature and humidity affected exposure, windspeed had the strongest impact on pesticide exposure via inhalation. However, the degree of exposure to both herbicides via inhalation was below the permissible exposure limits set by United States National Institute of Occupational Safety and Health (NIOSH). Dermal Exposure Assessment Method (DREAM) readings showed that dermal exposure with manual spraying ranged from moderate to high. With motorized sprayers, however, the level of dermal exposure ranged from low to moderate. Dermal exposure was significantly negatively correlated with the usage of protective clothing. Various types of deleterious health effects were detected among users of manual knapsack sprayers. Long-term spraying activities were positively correlated with increasing levels of the gamma-glutamyl transpeptidase (GGT) liver enzyme. The type of spraying equipment, usage of proper protective clothing and adherence to correct spraying practices were found to be the most important factors influencing the degree of pesticide exposure among those applying pesticides.     

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.