Air concentrations of currently used herbicides and legacy compounds in the Canadian prairies,subarctic, and arctic

Passive air samplers were installed in the summers of 2005 and 2007 for 90 days at four locations in the agricultural region of the Canadian Prairies and at five locations in the Canadian Subarctic and Arctic. The presence and masses of ten currently used herbicides and three legacy compounds in the polyurethane foam disks were quantified. Herbicides 2,4-D, bromoxynil and MCPA were detected at all locations in the Canadian Prairies and in both years because these herbicides are widely applied to control broadleaf weeds in cereal crops that are an integral part of Prairie agricultural production systems. MCPA was also detected at one location in the Arctic in 2007. The detection of the other seven herbicides in the 2 years combined ranged from no detections (atrazine only) to five detections for the relatively volatile herbicides trifluralin and triallate. Triallate was the only other herbicide detected in the Arctic (2005). Legacy compounds were either not detected (alachlor) or at levels near their detection level (γ-HCH and α-HCH). γ-HCH and α-HCH were more frequently detected in 2005 than in 2007 indicating that their concentrations in Canadian air have decreased over time. γ-HCH, widely used as an insecticide in Prairie oilseed production until 2002, was detected at larger concentrations in the Canadian Prairies than in the Subarctic and Arctic. α-HCH, a manufacturing by-product in technical HCH prior to 1971 in Canada, was not detected in the Canadian Prairies but was at detectable levels in the Subarctic and Arctic as the Arctic Ocean is reported to be a major source of α-HCH to the atmosphere. We conclude that some of the most widely used herbicides in Canadian agriculture today are commonly present in the air in regions where they are applied and that a portion of these herbicides may be traveling as parent molecules to the Canadian Arctic. To the authors’ knowledge, this is the first evidence of the presence of MCPA and triallate in Arctic air samples, perhaps because previous research has seldomly monitored for currently used herbicides in this region.     

Herbicide levels in rivers draining two prairie agricultural watersheds (1984)

A monitoring survey was conducted during 1984 on the Ochre and Turtle Rivers, which flow into Dauphin Lake in western Manitoba, Canada, to determine levels of the herbicides MCPA, diclofop-methyl, dicamba, bromoxynil, 2,4-D, triallate and trifluralin which were widely used in each watershed. Triallate concentrations exceeded 4 ng/L in 50% and 10% of the 21 samples taken from each of the Turtle and Ochre River, respectively, during the period March to October 1984. Trifluralin concentrations exceeded 3 ng/L in 14% and 10% of the samples from the respective rivers. Maximum concentrations did not exceed 25 ng/L and were unrelated to changes in river flow. Bromoxynil and diclofop were detected in the Turtle River, at concentrations of 113 and 476 ng/L, respectively, following a major high water event in late June, but were undetectable (less than 2 and 12 ng/L, respectively) at other sampling times. Dicamba and 2,4-D were detectable throughout most of the sampling period in both rivers at low levels (less than 100 ng/L). High levels of dicamba and 2,4-D (5476 and 2568 ng/L respectively) were found in water from the Turtle River prior to the high water event event possibly caused by spraying of ditches or rights-of-way near the river. Discharges (grams/year) of all seven herbicides monitored in the study represented less than 0.1% of the amounts estimated to be used in each watershed. Unit loadings (mg/ha/year) of 2,4-D and dicamba were similar to those reported for Southern Ontario streams in the mid-1970's. The results indicate that herbicide contamination of Manitoba streams draining agricultural areas is generally low except when major runoff occurs during the application period in May and June.     

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.     

Evaluation of polyurethane foam as a trapping medium for herbicide vapor in air monitoring and worker inhalation studies

Polyurethane foam was an efficient adsorbent for trapping vapors of butyl esters of 2,4-D (2,4-dichlorophenoxyacetic acid) and triallate (S-(2,3,3-trichloroallyl)diisopropylthiocarbamate) in high volume air monitoring studies and of butyl esters of 2,4-D, iso-octyl ester of 2,4-D, n-butyl ester of 2,4,5-T (2,4,5-trichlorophenoxyacetic acid), bromoxynil octanoate (2,5-dibromo-4-hydroxybenzonitrile), triallate, and trifluralin (alpha, alpha, alpha-trifluoro-2,6-dinitro-N-N-dipropyl-p-toluidine) in short-term, low volume, worker inhalation exposure studies. The collected herbicide vapor was readily desorbed under soxhlet extraction with n-hexane and subsequently analyzed with electron-capture GLC. The overall efficiencies, for both trapping and extraction, were over 90%, using a single plug, for all herbicides, except triallate. In the case of triallate, two plugs in series were required for efficient trapping under the high volume air monitoring situation.     

Adsorption of 2,4-dichlorophenoxyacetic acid and 4-chloro-2-metylphenoxyacetic acid onto activated carbons derived from various lignocellulosic materials

Adsorption of 2,4-dichlorophenoxyacetic acid (2,4-D) and 4-chloro-2-metylphenoxyacetic acid (MCPA) from aqueous solution onto activated carbons derived from various lignocellulosic materials including willow, miscanthus, flax, and hemp shives was investigated. The adsorption kinetic data were analyzed using two kinetic models: the pseudo-first order and pseudo-second order equations. The adsorption kinetics of both herbicides was better represented by the pseudo-second order model. The adsorption isotherms of 2,4-D and MCPA on the activated carbons were analyzed using the Freundlich and Langmuir isotherm models. The equilibrium data followed the Langmuir isotherm. The effect of pH on the adsorption was also studied. The results showed that the activated carbons prepared from the lignocellulosic materials are efficient adsorbents for the removal of 2,4-D and MCPA from aqueous solutions.     

A new sampler for collecting separate dry and wet atmospheric depositions of trace organic chemicals

Studies conducted in Saskatchewan and elsewhere have demonstrated the atmospheric transport of agricultural pesticides and other organic contaminants and their deposition into aquatic ecosystems. To date these studies have focused on ambient concentrations in the atmosphere and in wet precipitation. To measure the dry deposition of organic chemicals, a new sampler was designed which uses a moving sheet of water to passively trap dry particles and gasses. The moving sheet of water drains into a reservoir and, during recirculation through the sampler, is passed through an XAD-2 resin column which adsorbs the trapped organic contaminants. All surfaces which contact the process water are stainless steel or Teflon. Chemicals collected can be related to airborne materials depositing into aquatic ecosystems. The sampler has received a United States patent (number 5,413,003 – 9 May 1996) with the Canadian patent pending.XAD-2 resin adsorption efficiencies for 10 or 50 μg fortifications of ten pesticides ranged from 76% for atrazine (2-chloro-4-ethylamino-6-isopropylamino-S-triazine) to 110% for triallate [S-(2,3,3-trichloro-2-phenyl)bis(1-methylethyl)carbamothioate], dicamba (2-methoxy-3,6-dichlorobenzoic acid) and toxaphene (chlorinated camphene mixture). Field testing using duplicate samplers showed good reproducibility and amounts trapped were consistent with those from high volume and bulk pan samplers located on the same site. Average atmospheric dry deposition rates of three chemicals, collected for 5 weeks in May and June, were: dicamba, 69 ng m^-2 da^-1; 2,4-D (2,4-dichlorophenoxyacetic acid), 276 ng m^-2 da^-1: and, γ-HCH (γ-1, 2, 3, 4, 5, 6-hexachlorocyclohexane), 327 ng m^-2 da^-1.     

Electrochemical degradation of chlorophenoxy and chlorobenzoic herbicides in acidic aqueous medium by the peroxi-coagulation method

The degradation of 4-chlorophenoxyacetic acid (4-CPA), 4-chloro-2-methylphenoxyacetic acid (MCPA), 2,4-dichlorophenoxyacetic acid (2,4-D) and 2,4,5-trichlorophenoxyacetic acid (2,4,5-T) as chlorophenoxy herbicides, as well as of 3,6-dichloro-2-methoxybenzoic acid (dicamba) as chlorobenzoic herbicide, has been studied by peroxi-coagulation. This electrochemical method yields a very effective depollution of all compounds in acidic aqueous medium of pH 3.0 working under pH regulation, since they are oxidized with hydroxyl radicals produced from Fenton's reaction between Fe(2+) and H(2)O(2) generated by the corresponding Fe anode and O(2)-diffusion cathode. Their products can then be removed by mineralization or coagulation with the Fe(OH)(3) precipitate formed. Both degradative paths compete at low currents, but coagulation predominates at high currents. The peroxi-coagulation process of dicamba at I>or=300 mA leads to more than 90% of coagulation, being much more efficient than its comparative electro-Fenton treatment with a Pt anode and 1 mM Fe(2+), where only mineralization takes place. For the chlorophenoxy compounds, electro-Fenton gives a slightly lower depollution than peroxi-coagulation, because more easily oxidable products are produced. Oxidation of chlorinated products during peroxi-coagulation is accompanied by the release of chloride ion to the solution. The efficiency of this method decreases with increasing electrolysis time and current. The decay of all herbicides follows a pseudo-first-order reaction, with a similar constant rate for 4-CPA, MCPA, 2,4-D and 2,4,5-T, and a higher value for dicamba.     

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.     

Strategies to evaluate biodegradability: application to chlorinated herbicides

The biodegradability of nitrochlorinated (diuron and atrazine) and chlorophenoxy herbicides (2,4-D and MCPA) has been studied through several bioassays using different testing times and biomass/substrate ratios. A fast biodegradability test using unacclimated activated sludge yielded no biodegradation of the herbicides in 24 h. The inherent biodegradability test gave degradation percentages of around 20–30 % for the nitrochlorinated herbicides and almost complete removal of the chlorophenoxy compounds. Long-term biodegradability assays were performed using sequencing batch reactor (SBR) and sequencing batch membrane bioreactor (SB-MBR). Fixed concentrations of each herbicide below the corresponding EC₅₀ value for activated sludge were used (30 mg L^?1 for diuron and atrazine and 50 mg L^?1 for 2,4-D and MCPA). No signs of herbicide degradation appeared before 35 days in the case of diuron and atrazine and 21 days for 2,4-D, whereas MCPA was partially degraded since the early stages. Around 25–36 % degradation of the nitrochlorinated herbicides and 53–77 % of the chlorophenoxy ones was achieved after 180 and 135 days, respectively, in SBR, whereas complete disappearance of 2,4-D was reached after 80 days in SB-MBR.     

Ability of O-anisate degrading microorganisms to come tabolize dicamba and other related herbicides

O-anisate degrading microorganisms were isolated from soil samples and identified. 80, 24, 64 and 64% of the isolates showed cometabolism to the herbicides dicamba, 2, 3, 6-TBA, 2, 4-D and MCPA, respectively.     

Toxicity assessment of 2,4-D and MCPA herbicides in primary culture of fish hepatic cells

In this study, we used primary cultures of fish hepatic cells as a tool for evaluating the effects of environmental contamination. Primary hepatic cell cultures derived from the subtropical fish Metynnis roosevelti were exposed to different concentrations (0.275, 2.75 and 27.5 μg L^?1) of the herbicides 2,4-dichlorophenoxyacetic acid (2,4-D) and 4-chloro-2-methylphenoxyacetic acid (MCPA). Cellular respiratory activity was evaluated by polarography using three substrates: 0.5 M glucose, 0.5 M succinate and 0.5 M α-ketoglutarate. Significant changes were observed in cellular oxygen consumption with 0.5 M α-ketoglutarate. Even at low concentrations, 2,4-D and MCPA were potent uncouplers of oxidative phosphorylation. Primary cultures of M. roosevelti liver cells may provide a useful tool for the evaluation of environmental contaminant effects. A review of regulations regarding permitted concentrations of these herbicides is needed.     

Temporal trends of persistent organochlorine residues in human adipose tissue from Japan, 1928-1985

The presence of pesticide residues in rain, throughfall, stemflow and in ambient air in two Italian forests affected by the forest damage phenomenon were investigated. Pesticides measured were: alachlor, atrazine, carbaryl, 2,4-D, diazinon, dichlobenil, fluazifop-butyl, MCPA, parathion, phorate and trifluralin. Rainwater samples were collected from May to October 1988 at Vallombrosa and Renon, air and atmospheric particulates were sampled during April-June 1989, only at Vallombrosa. A total of 146 samples of rainfall and 20 samples of ambient air were analysed and 49 out of 166 samples contained at least one active ingredient. Herbicides were more frequent than insecticides, and their concentrations were also higher (max 3.44 microg litre(-1)).     

Determination of commonly used polar herbicides in agricultural drainage waters in Australia by HPLC

The present study describes the application of different extraction techniques for the preconcentration of ten commonly found acidic and non-acidic polar herbicides (2,4-D, atrazine, bensulfuron-methyl, clomazone, dicamba, diuron, MCPA, metolachlor, simazine and triclopyr) in the aqueous environment. Liquid-liquid extraction (LLE) with dichloromethane, solid-phase extraction (SPE) using Oasis HLB cartridges or SBD-XC Empore disks were compared for extraction efficiency of these herbicides in different matrices, especially water samples from contaminated agricultural drainage water containing high concentrations of particulate matter. Herbicides were separated and quantified by high performance liquid chromatography (HPLC) with an ultraviolet detector. SPE using SDB-XC Empore disks was applied to determine target herbicides in the Murrumbidgee Irrigation Area (NSW, Australia) during a two-week survey from October 2005 to November 2005. The daily aqueous concentrations of herbicides from 24-h composite samples detected at two sites increased after run-off from a storm event and were in the range of: 0.1-17.8 microg l(-1), < 0.1-0.9 microg l(-1) and 0.2-17.8 microg l(-1) at site 1; < 0.1-3.5 microg l(-1), < 0.1-0.2 microg l(-1) and < 0.2-3.2 microg l(-1) at site 2 for simazine, atrazine and diuron, respectively.     

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.     

Analysis of acidic pesticides using in situ derivatization with alkylchloroformate and solid-phase microextraction (SPME) for GC-MS.

A solid-phase microextraction (SPME) method was developed for the analysis of acidic pesticide residues in water. The method utilizes in situ derivatization with butylchloroformate (BuCF), followed by on-line SPME extraction using a PDMS fibre, and analysis by GC-MS. Derivatives of the phenoxy acids mechlorprop (MCPP), dichlorprop (DCPP), MCPA and 2,4-D and their phenol degradation products 4-chloro-2-methylphenol and 2,4-dichlorophenol (DCP) were identified. Detection limits at 0.16-2.3 microg/l were achieved. Optimization of derivatization, ion strength, extraction time, SPME-fibre, desorption time and temperature are described. Standard curves in the range 0.5-10.0 microg/l were fitted to a second-degree polynomial. Standard deviation (n = 5) was below 10% for the phenol derivatives, but 20-50% for the phenoxy acids. For method verification groundwater samples from a field experiment were screened for content of MCPP and compared to the results from the HPLC analysis. A good agreement was obtained with respect to identification of positive samples, even though concentrations measured by the SPME were lower than with HPLC. Even if the precision and accuracy do not meet the demands for a strictly quantitative analysis, the SPME method is suitable for screening, because it is cheap, it can be automated, and uses smaller amounts of potential harmful solvents. Also, the method is less labour-intensive, as it requires a minimum of sample preparation when compared to traditional analyses. The acidic pesticides bentazon, dicamba, bromoxynil, ioxynil, dinoseb and DNOC were included in the study but could not be analysed by the current method.     

A comparison of five pesticides adsorption and desorption processes in thirteen contrasting field soils

Batch adsorption and desorption experiments were performed using thirteen agricultural soil samples and five pesticides. Experimental data indicated a gradient in pesticide adsorption on soil: trifluralin > 2,4-D > isoproturon> atrazine > bentazone. Atrazine, isoproturon and trifluralin adsorption were correlated to soil organic matter content (r2 = 0.7, 0.82, 0.79 respectively). Conversely, bentazone adsorption was governed by soil pH (r2 = 0.68) while insignificant effect has been shown in the case of 2,4-D. Multiple linear regressions were used to combine relationships between the various soil parameters and the Freundlich adsorption coefficient (K(f)) of each pesticide. Then desorption was assessed since it may reflect some of the interactions involved between the pesticides and the soil components. Adsorbed molecules were released into aqueous solution in the following order: bentazone > atrazine> isoproturon> 2,4-D > trifluralin. The occurrence of hysteresis did not allow an accurate interpretation of the pesticide desorption data because of the possible interplay of several processes.     

Oxidation of MCPA and 2,4-D by UV radiation, ozone, and the combinations UV/H2O2 and O3/H2O2

The phenoxyalkyl acid derivative herbicides MCPA (4-chloro 2-methylphenoxyacetic acid) and 2,4-D (2,4-dichlorophenoxyacetic acid) were oxidized in ultrapure water by means of a monochromatic UV irradiation and by ozone, as well as by the combinations UV/H2O2 and O3/H2O2. In the direct photolysis of MCPA, the quantum yield at 20 degrees C was directly evaluated and a value of 0.150 mol Eins(-1) was obtained in the pH range 5-9, while a lower value of 0.41 x 10(-2) mol Eins(-1) was determined at pH=3. Similarly, for 2,4-D a value of 0.81 x 10(-2) mol Eins(-1) was deduced, independent of the pH of work. The influence of the additional presence of hydrogen peroxide was established in the combined process UV/H2O2, and the specific contribution of the radical pathway to the global photo-degradation was evaluated. The oxidation by ozone and by the combination O3/H2O2 was also studied, with the determination of the rate constants for the reactions of both herbicides with ozone and hydroxyl radicals at 20 degrees C. These rate constants for the direct reactions with ozone were 47.7 and 21.9 M(-1) s(-1) for MCPA and 2,4-D respectively, while the found values for the rate constants corresponding to the radical reactions were 6.6 x 10(9) and 5.1 x 10(9) M(-1) s(-1).     

Utilization of long duration high-volume sampling coupled to SPME-GC-MS/MS for the assessment of airborne pesticides variability in an urban area (Strasbourg,France) during agricultural application

Atmospheric samples have been collected between 14 March and 12 September 2012 on a 2-week basis (15 days of sampling and exchange of traps each 7 days) in Strasbourg (east of France) for the analysis of 43 pesticides. Samples (particle and gas phases) were separately extracted using Accelerated Solvent Extraction (ASE) and pre-concentrated by Solid Phase Micro-Extraction (SPME) before analysis by gas chromatography coupled to tandem mass spectrometry (GC-MS/MS). Four SPME consecutive injections at distinct temperatures were made in order to increase the sensitivity of detection for the all monitored pesticides. Currently used detected pesticides can be grouped in four classes; those used in maize crops (acetochlor, benoxacor, dicamba, s-metolachlor, pendimethalin, and bromoxynil), in cereal crops (benoxacor, chlorothalonil, fenpropimorph, and propiconazole), in vineyards (tebuconazole), and as herbicides for orchards, meadows of green spaces (2,4-MCPA, trichlopyr). This is in accordance with the diversity of crops found in the Alsace region and trends observed are in accordance with the period of application of these pesticides. Variations observed permit also to demonstrate that the long time sampling duration used in this study is efficient to visualize temporal variations of airborne pesticides concentrations. Then, long time high-volume sampling could be a simple method permitting atmospheric survey of atmospheric contamination without any long analysis time and consequently low cost.     

Toxicity of chlorinated phenoxyacetic acid herbicides in the experimental eukaryotic model Saccharomyces cerevisiae: role of pH and of growth phase and size of the yeast cell population

The inhibitory effect of the herbicides 2-methyl-4-chlorophenoxyacetic acid (MCPA) and 2,4-dichlorophenoxyacetic acid (2,4-D) in Saccharomyces cerevisiae growth is strongly dependent on medium pH (range 2.5-6.5). Consistent with the concept that the toxic form is the liposoluble undissociated form, at values close to their pK(a) (3.07 and 2.73, respectively) the toxicity is high, decreasing with the increase of external pH. In addition, the toxicity of identical concentrations of the undissociated acid form is pH independent, as observed with 2,4-dichlorophenol (2,4-DCP), an intermediate of 2,4-D degradation. Consequently, at pH values above 3.5 (approximately one unit higher than 2,4-D pK(a)), 2,4-DCP becomes more toxic than the original herbicide. A dose-dependent inhibition of growth kinetics and increased duration of growth latency is observed following sudden exposure of an unadapted yeast cell population to the presence of the herbicides. This contrasts with the effect of 2,4-DCP, which essentially affects growth kinetics. Experimental evidences suggest that the acid herbicides toxicity is not exclusively dependent on the liposolubility of the toxic form, as may essentially be the case of 2,4-DCP. An unadapted yeast cell population at the early stationary-phase of growth under nutrient limitation is significantly more resistant to short-term herbicide induced death than an exponential-phase population. Consequently, the duration of growth latency is reduced, as observed with the increase of the size of the herbicide stressed population. However, these physiological parameters have no significant effect either on growth kinetics, following growth resumption under herbicide stress, or on the growth curve of yeast cells previously adapted to the herbicides, indicating that their role is exerted at the level of cell adaptation.     

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.