2,4-D Mineralization in soil profiles of a cultivated hummocky landscape in Manitoba,Canada

The objective of this study was to quantify 2,4-D (2,4-dichlorophenoxyacetic acid) mineralization in soil profiles characteristic of hummocky, calcareous-soil landscapes in western Canada. Twenty-five soil cores (8 cm inner diameter, 50 to 125 cm length) were collected along a 360 m transect running west to east in an agricultural field and then segmented by soil-landscape position (upper slopes, mid slopes, lower slopes and depressions) and soil horizon (A, B, and C horizons). In the A horizon, 2,4-D mineralization commenced instantaneously and the mineralization rate followed first-order kinetics. In both the B and C horizons, 2,4-D mineralization only commenced after a lag period of typically 5 to 7 days and the mineralization rate was biphasic. In the A horizon, 2,4-D mineralization parameters including the first-order mineralization rate constant (k ₁), the growth-linked mineralization rate constant (k ₂) and total 2,4-D mineralization at the end of the experiment at 56 days, were most strongly correlated to parameters describing 2,4-D sorption by soil, but were also adequately correlated to soil organic carbon content, soil pH, and carbonate content. In both B and C horizons, there was no significant correlation between 2,4-D mineralization and 2,4-D sorption parameters, and the correlation between soil properties and 2,4-D mineralization parameters was very poor. The k ₁ significantly decreased in sequence of A horizon (0.113% day^?1) > B horizon (0.024% day^?1) = C horizon (0.026% day^?1) and in each soil horizon was greater than k ₂. Total 2,4-D mineralization at 56 days also significantly decreased in sequence of A horizon (42%) > B horizon (31%) = C horizon (27%). In the A horizon, slope position had little influence on k ₁ or k ₂, except that k ₁ was significantly greater in upper slopes (0.170% day^?1) than in lower slopes (0.080% day^?1). Neither k ₁ nor k ₂ was significantly influenced by slope position in the B or C horizons. Total 2,4-D mineralization at 56 days was not influenced by slope positions in any horizon. Our results suggest that, when predicting 2,4-D transport at the field scale, pesticide fate models should consider the strong differences in 2,4-D mineralization between surface and subsurface horizons. This suggests that 2,4-D mineralization is best predicted using a model that has the ability to describe a range of non-linear mineralization curves. We also conclude that the horizontal variations in 2,4-D mineralization at the field scale will be difficult to consider in predictions of 2,4-D transport at the field scale because, within each horizon, 2,4-D mineralization was highly variable across the twenty-five soil cores, and this variability was poorly correlated to soil properties or soil-landscape position.     

2,4-D mineralization in unsaturated and near-saturated surface soils of an undulating, cultivated Canadian prairie landscape

The herbicide 2,4-D [2,4-(dichlorophenoxy) acetic acid] is one of the most widely used pesticides in the Canadian prairies and is frequently detected as a ground and surface water contaminant. The objective of this paper was to determine the magnitude and extent of variation of 2,4-D mineralization in a cultivated undulating prairie landscape. Microcosm incubation experiments, using a 4 x 3 x 2 factorial experimental design (soil moisture, 4 levels: 60, 85, 110, 135% of field capacity; slope position, 3 levels: upper-, mid- and lower-slopes; soil depth, 2 levels: 0-5 and 5-15 cm), were used to assess 2,4-D mineralization. The first-order mineralization rate constant (k(1)) varied from 0.03 to 0.22 day(- 1), while total 2,4-D mineralization varied from 31 to 52%. At near-saturated conditions (110 and 135% of field capacity), the onset of 2,4-D degradation was delayed in soil obtained from the upper- and mid-slopes but not in soils obtained from the lower-slope position. The k(1) and total 2,4-D mineralization was significantly influenced by all three factors and their interactions. The Freundlich sorption coefficient of 2,4-D ranged from 0.83 to 2.46 microg (1-1/n)g(- 1) mL(1/n) and was significantly influenced by variations in soil organic carbon content across slope positions. The infield variability of 2,4-D sorption and mineralization observed across slope positions in this undulating field was comparable in magnitude and extent to the regional variability of 2,4-D sorption and mineralization observed in surface soils across Manitoba. The large variability of 2,4-D mineralization and sorption at different slope positions in this cultivated undulating field suggests that landform segmentation models, which are used to delineate slope positions, are important considerations in pesticide fate studies.     

Factors Influencing 2,4-D Sorption and Mineralization in Soil

Abstract

This study quantified 2,4-D [(2,4-dichlorophenoxy)acetic acid] sorption and mineralization rates in five soils as influenced by soil characteristics and nutrient contents. Results indicated that 2,4-D was weakly sorbed by soil, with Freundlich distribution coefficients ranging from 0.81 to 2.89 µg^1?1/n  g^?1 mL^{1/ n} . First-order mineralization rate constants varied from 0.03 to 0.26, corresponding to calculated mineralization half-lives of 3 and 22 days, respectively. Herbicide sorption generally increased with increasing soil organic carbon content, but the extent of 2,4-D sorption per unit organic carbon varied among the soils due to differences in soil pH, clay content and/or organic matter quality. Herbicide mineralization rates were greater in soils that sorbed more 2,4-D per unit organic carbon, and that had greater soil nitrogen contents. We conclude that the effect of sorption on herbicide degradation cannot be generalized without a better understanding of the effects of soil characteristics and nutrient content on herbicide behavior in soil.     

Factors influencing 2,4-D sorption and mineralization in soil

This study quantified 2,4-D [(2,4-dichlorophenoxy)acetic acid] sorption and mineralization rates in five soils as influenced by soil characteristics and nutrient contents. Results indicated that 2.4-D was weakly sorbed by soil, with Freundlich distribution coefficients ranging from 0.81 to 2.89 microg(1 - 1/n) g(-1) mL(1/n). First-order mineralization rate constants varied from 0.03 to 0.26, corresponding to calculated mineralization half-lives of 3 and 22 days, respectively. Herbicide sorption generally increased with increasing soil organic carbon content, but the extent of 2,4-D sorption per unit organic carbon varied among the soils due to differences in soil pH, clay content and/or organic matter quality. Herbicide mineralization rates were greater in soils that sorbed more 2,4-D per unit organic carbon, and that had greater soil nitrogen contents. We conclude that the effect of sorption on herbicide degradation cannot be generalized without a better understanding of the effects of soil characteristics and nutrient content on herbicide behavior in soil.     

Leaching of 2,4-D from a soil in the presence of beta-cyclodextrin: laboratory columns experiments

This study reports on the effect of the presence of beta-cyclodextrin (beta-CD) on the adsorption and mobility of the pesticide 2,4-dichlorophenoxyacetic acid (2,4-D) through soil columns. The previous application of beta-CD to the soil produced a retarded leaching of 2,4-D through the soil column, due probably to herbicide adsorption on the soil through beta-CD adsorbed. However, the application of beta-CD solution to the soil column where 2,4-D had been previously adsorbed, led to the complete desorption of the herbicide, due to the formation of water-soluble 1:1 inclusion complexes between 2,4-D and beta-CD. Beta-CD can be viewed as a microscopic organic-phase extractant. It can be an advantage to remove from soil pesticides which are able to form inclusion complexes with cyclodextrins, making them possible candidates for use in in situ remediation efforts.     

Concentrations of lead in aquatic macrophytes from Shoal Lake, Manitoba, Canada

The ability of aquatic macrophytes to accumulate lead was examined in the context of sample site, sample date, depth, organ and species. Considerable variations in lead concentrations were found between the 11 species of macrophytes studied. The mean lead concentration for all species sampled was 16 microg/g (dry weight) ranging from 0-78 microg/g. Analysis of variance indicated that there were significant differences in the mean lead content of macrophytes collected from different sample sites. Similarly, significantly higher values were observed for plants collected from the upper 2m of water. Seasonal trends in lead accumulation were not observed for Shoal Lake macrophytes.     

In-field variation in 2,4-D mineralization in relation to sorption and soil microbial communities

This study was undertaken to assess 2,4-D mineralization in an undulating cultivated field, along a sloping transect (458 m to 442 m above sea level), as a function of soil type, soil microbial communities and the sorption of 2,4-D to soil. The 2,4-D soil sorption coefficient (Kd) ranged from 1.81 to 4.28 L kg^?1, the 2,4-D first-order mineralization rate constant (k) ranged from 0.04 to 0.13 day^?1 and the total amount of 2,4-D mineralized at 130 days (M₁₃₀) ranged from 24 to 39%. Both k and M₁₃₀ were significantly negatively associated (or correlated) with soil organic carbon content (SOC) and Kd. Both k and M₁₃₀ were significantly associated with two fatty-acid methyl esters (FAME), i17:1 and a18, but not with twenty-two other individual FAME. Imperfectly drained soils (Gleyed Dark Grey Chernozems) in lower-slopes showed significantly lesser 2,4-D mineralization relative to well-drained soils (Orthic Dark Grey Chernozems) in mid- and upper-slopes. Well-drained soils had a greater potential for 2,4-D mineralization because of greater abundance and diversity of the microbial community in these soils. However, the reduced 2,4-D mineralization in imperfectly drained soils was predominantly because of their greater SOC and increased 2,4-D sorption, limiting the bioavailability of 2,4-D for degradation. The wide range of 2,4-D sorption and mineralization in this undulating cultivated field is comparable in magnitude and extent to the variability of 2,4-D sorption and mineralization observed at a regional scale in Manitoba. As such, in-field variations in SOC and the abundance and diversity of microbial communities are determining factors that require greater attention in assessing the risk of movement of 2,4-D by runoff, eroded soil and leaching.     

In-field variation in 2,4-D mineralization in relation to sorption and soil microbial communities

This study was undertaken to assess 2,4-D mineralization in an undulating cultivated field, along a sloping transect (458 m to 442 m above sea level), as a function of soil type, soil microbial communities and the sorption of 2,4-D to soil. The 2,4-D soil sorption coefficient (Kd) ranged from 1.81 to 4.28 L kg(-1), the 2,4-D first-order mineralization rate constant (k) ranged from 0.04 to 0.13 day(-1) and the total amount of 2,4-D mineralized at 130 days (M(130)) ranged from 24 to 39%. Both k and M(130) were significantly negatively associated (or correlated) with soil organic carbon content (SOC) and Kd. Both k and M(130) were significantly associated with two fatty-acid methyl esters (FAME), i17:1 and a18, but not with twenty-two other individual FAME. Imperfectly drained soils (Gleyed Dark Grey Chernozems) in lower-slopes showed significantly lesser 2,4-D mineralization relative to well-drained soils (Orthic Dark Grey Chernozems) in mid- and upper-slopes. Well-drained soils had a greater potential for 2,4-D mineralization because of greater abundance and diversity of the microbial community in these soils. However, the reduced 2,4-D mineralization in imperfectly drained soils was predominantly because of their greater SOC and increased 2,4-D sorption, limiting the bioavailability of 2,4-D for degradation. The wide range of 2,4-D sorption and mineralization in this undulating cultivated field is comparable in magnitude and extent to the variability of 2,4-D sorption and mineralization observed at a regional scale in Manitoba. As such, in-field variations in SOC and the abundance and diversity of microbial communities are determining factors that require greater attention in assessing the risk of movement of 2,4-D by runoff, eroded soil and leaching.     

Ageing processes and soil microbial community effects on the biodegradation of soil C-2,4-D nonextractable residues

The biodegradation of nonextractable residues (NER) of pesticides in soil is still poorly understood. The aim of this study was to evaluate the influence of NER ageing and fresh soil addition on the microbial communities responsible for their mineralisation. Soil containing either 15 or 90-day-old NER of ¹³C-2,4-D (NER15 and NER90, respectively) was incubated for 90 days with or without fresh soil. The addition of fresh soil had no effect on the mineralisation of NER90 or of SOM, but increased the extent and rate of NER15 mineralisation. The analyses of ¹³C-enriched FAME (fatty acids methyl esters) profiles showed that the fresh soil amendment only influenced the amount and structure of microbial populations responsible for the biodegradation of NER15. By coupling biological and chemical analyses, we gained some insight into the nature and the biodegradability of pesticide NER.     

Carbaryl, 2,4-D, and Triclopyr adsorption in thatch-soil ecosystems

Thatch development in intensively managed turf sites may cause environmental concerns for greater sorption or leaching of applied chemicals in terrestrial ecosystems. To determine the adsorption potential of Carbaryl (1-Napthyl N-methylcarbamate), 2,4-D (2,4-dichloro-phenoxyacetic acid), and Triclopyr (3,5,6-trichloro-2-pyridinyloxyacetic acid) in turf ecosystems, composite thatch and underlying soil samples from three-and six-year-old stands of cool-season Southshore creeping bentgrass (Agrostis palustris Huds.) and warm-season Meyer zoysiagrass (Zoysia japonica Steud.) were collected. The samples were processed and analyzed for total organic carbon (COrg); extractable (CExt), humic (CHA) and fulvic acid (CFA); anthrone reactive nonhumic carbon (ARC) fractions; and CHA and CFA associated iron (Fe) contents. Pesticide adsorption capacity (Kf) and intensity (1/n), organic carbon partition coefficient (KOC) and Gibbs free energy change (deltaG) were calculated for thatch materials and the underlying soils using a modified batch/flow technique. Both bentgrass (BT) and zoysiagrass thatch (ZT) contained a greater concentration of CExt, CFA, CHA, and ARC than the respective soils (BS and ZS). The CExt, CFA, CHA, and ARC concentration was higher in BT compared with ZT. The BT contained a greater concentration of bound Fe in both CFA and CHA fractions than in BS, whereas ZT had more bound Fe in CHA fraction than in ZS. On average, the BT had a greater concentration of bound Fe in CExt, CFA, and CHA fractions than in the ZT. Among the pesticides, Carbaryl had higher Kf and 1/n values than 2,4-D and Triclopyr for both thatch and soil. Although the KOC and deltaG values of Carbaryl were higher in both BT and ZT than in the underlying soils, the KOC and deltaG values of 2,4-D were significantly higher in BS and ZS than in the overlying thatch materials. The 2,4-D and Triclopyr had higher leaching indices (LI) than Carbaryl for both BT and ZT materials than the respective soils. The Carbaryl, however, had a higher LI for soils than for thatch materials. Averaged across thatch materials and soils, COrg accounted for 96, 85, and 84% variations in Carbaryl, 2,4-D, and Triclopyr adsorption, respectively. Among the COrg fractions, lignin followed by CFA and CHA accounted for greater adsorption of pesticides, especially Carbaryl. The concentration of CHA and CFA bound Fe did not correlate with Kf and 1/n values of pesticides.     

Carbaryl, 2,4-D,and Triclopyr Adsorption in Thatch-Soil Ecosystems

Thatch development in intensively managed turf sites may cause environmental concerns for greater sorption or leaching of applied chemicals in terrestrial ecosystems. To determine the adsorption potential of Carbaryl (1-Napthyl N-methylcarbamate), 2,4-D (2,4-dichloro-phenoxyacetic acid), and Triclopyr (3,5,6-trichloro-2-pyridinyloxyacetic acid) in turf ecosystems, composite thatch and underlying soil samples from three- and six-year-old stands of cool-season Southshore creeping bentgrass (Agrostis palustris Huds.) and warm-season Meyer zoysiagrass (Zoysia japonica Steud.) were collected. The samples were processed and analyzed for total organic carbon (C_Org); extractable (C_Ext), humic (C_HA) and fulvic acid (C_FA); anthrone reactive nonhumic carbon (ARC) fractions; and C_HA and C_FA associated iron (Fe) contents. Pesticide adsorption capacity (K _f ) and intensity (1/n), organic carbon partition coefficient (K _OC ) and Gibbs free energy change (Δ G) were calculated for thatch materials and the underlying soils using a modified batch/flow technique. Both bentgrass (BT) and zoysiagrass thatch (ZT) contained a greater concentration of C_Ext, C_FA, C_HA, and ARC than the respective soils (BS and ZS). The C_Ext, C_FA, C_HA, and ARC concentration was higher in BT compared with ZT. The BT contained a greater concentration of bound Fe in both C_FA and C_HA fractions than in BS, whereas ZT had more bound Fe in C_HA fraction than in ZS. On average, the BT had a greater concentration of bound Fe in C_Ext, C_FA, and C_HA fractions than in the ZT. Among the pesticides, Carbaryl had higher K _f and 1/n values than 2,4-D and Triclopyr for both thatch and soil. Although the K _OC and Δ G values of Carbaryl were higher in both BT and ZT than in the underlying soils, the K _OC and Δ G values of 2,4-D were significantly higher in BS and ZS than in the overlying thatch materials. The 2,4-D and Triclopyr had higher leaching indices (LI) than Carbaryl for both BT and ZT materials than the respective soils. The Carbaryl, however, had a higher LI for soils than for thatch materials. Averaged across thatch materials and soils, C_Org accounted for 96, 85, and 84% variations in Carbaryl, 2,4-D, and Triclopyr adsorption, respectively. Among the C_Org fractions, lignin followed by C_FA and C_HA accounted for greater adsorption of pesticides, especially Carbaryl. The concentration of C_HA and C_FA bound Fe did not correlate with K _f and 1/n values of pesticides.     

Polynomial response of 2,4-D mineralization to temperature in soils at varying soil moisture contents,slope positions and depths

The herbicide 2,4-D [2,4-(dichlorophenoxy) acetic acid] is a widely used broadleaf control agent in cereal production systems. Although 2,4-D soil-residual activity (half-lives) are typicaly less than 10 days, this herbicide also has as a short-term leaching potential due to its relatively weak retention by soil constituents. Herbicide residual effects and leaching are influenced by environmental variables such as soil moisture and temperature. The objective of this study was to determine impacts of these environmental variables on the magnitude and extent of 2,4-D mineralization in a cultivated undulating Manitoba prairie landscape. Microcosm incubation experiments were utilized to assess 2,4-D half-lives and total mineralization using a 4 × 4 × 3 × 2 factorial design (with soil temperature at 4 levels: 5, 10, 20 and 40°C; soil moisture at 4 levels: 60, 85, 110, 135 % of field capacity; slope position at 3 levels: upper-, mid- and lower-slopes; and soil depth at 2 levels: 0–5 cm and 5–15 cm). Half-lives (t_1/2) varied from 3 days to 51 days with the total 2,4-D mineralization (M _T ) ranging from 5.8 to 50.9 %. The four-way interaction (temperature × moisture × slope × depth) significantly (p< 0.001) influenced both t_1/2 and M _T. Second-order polynomial equations best described the relations of temperature with t_1/2 and M_T as was expected from a biological system. However, the interaction and variability of t_1/2 and M_T among different temperatures, soil moistures, slope positions, and soil depth combinations indicates that the complex nature of these interacting factors should be considered when applying 2,4-D in agricultural fields and in utilizing these parameters in pesticide fate models.     

Polynomial response of 2,4-D mineralization to temperature in soils at varying soil moisture contents, slope positions and depths

The herbicide 2,4-D [2,4-(dichlorophenoxy) acetic acid] is a widely used broadleaf control agent in cereal production systems. Although 2,4-D soil-residual activity (half-lives) are typically less than 10 days, this herbicide also has as a short-term leaching potential due to its relatively weak retention by soil constituents. Herbicide residual effects and leaching are influenced by environmental variables such as soil moisture and temperature. The objective of this study was to determine impacts of these environmental variables on the magnitude and extent of 2,4-D mineralization in a cultivated undulating Manitoba prairie landscape. Microcosm incubation experiments were utilized to assess 2,4-D half-lives and total mineralization using a 4 × 4 × 3 × 2 factorial design (with soil temperature at 4 levels: 5, 10, 20 and 40°C; soil moisture at 4 levels: 60, 85, 110, 135 % of field capacity; slope position at 3 levels: upper-, mid- and lower-slopes; and soil depth at 2 levels: 0-5 cm and 5-15 cm). Half-lives (t(?)) varied from 3 days to 51 days with the total 2,4-D mineralization (M(T)) ranging from 5.8 to 50.9 %. The four-way interaction (temperature × moisture × slope × depth) significantly (p < 0.001) influenced both t(?) and M(T). Second-order polynomial equations best described the relations of temperature with t(?) and M(T) as was expected from a biological system. However, the interaction and variability of t(?) and M(T) among different temperatures, soil moistures, slope positions, and soil depth combinations indicates that the complex nature of these interacting factors should be considered when applying 2,4-D in agricultural fields and in utilizing these parameters in pesticide fate models.     

Effect of 2,4-D contamination on soil functional stability evaluated using the relative soil stability index (RSSI)

Soil functional stability is the capacity of soil functions to resist and recover from an environmental perturbation and can be used to evaluate soil health. It can be influenced by the presence of xenobiotics such as herbicides. The impact of a fresh 2,4-D contamination (36 mg kg(-1) dry soil) on soil functional stability was evaluated by comparing the capacity of soil enzyme activities to resist and recover from a heat perturbation for both a clean and 2,4-D-contaminated soil. The functional stabilities of the soils (uniform sands, pH 6.9, 7% (w/w) organic matter) were calculated using the relative soil stability index (RSSI). The RSSI scores indicate the proportion of potential enzyme activity the soil retains after a perturbation compared to the potential activity of an unperturbed soil. Six extra-cellular enzyme activities (acid and alkaline phosphatases, arylsulfatase, urease, protease and beta-glucosidase) were monitored in soil microcosms during a 15-day period. During this period, a 60 degrees C heat perturbation was applied to the soil for 24 h. The activities of arylsulfatase and protease were found to be the most stable following heat perturbation obtaining the highest RSSI scores (87% and 77%, respectively). Urease activity showed the lowest RSSI score (38%). Although all enzyme activities were inhibited by the presence of 2,4-D, the RSSI results indicated that contamination lowered the stability of only three enzyme activities (arylsulfatase, beta-glucosidase and urease). The RSSI adequately described resistance, recovery and recovery rate parameters and enabled differentiation between functional stabilities of clean and contaminated soil and between different soil types.     

Bioavailability of 2,4-D sorbed to a chlorite-like complex.

An Al(OH)x-montmorillonite (chlorite) complex (AM18) was prepared and 2,4-dichlorophenoxyacetic acid (2,4-D) sorbed to saturation. After several washing cycles the 'strongly sorbed' 2,4-D was 507 micrograms g-1 AM18. The bioavailability of sorbed 2,4-D was assessed in a minimal salts medium with the AM18-2,4-D as the sole C and energy source. Over a 28-day period a Pseudomonas sp. degraded 23% more of the sorbed 2,4-D than could be accounted for by desorption from AM18 in the non-inoculated controls. Possible explanations for the increase in bioavailability are presented.     

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.     

Dissipation of 2,4-D in soils of the Humid Pampa region, Argentina: a microcosm study

Phenoxy herbicides like 2,4-dichlorophenoxyacetic acid (2,4-D) are widely used in agricultural practices. Although its half life in soil is 7-14d, the herbicide itself and its first metabolite 2,4-dichlorophenol (2,4-DCP) could remain in the soil for longer periods, as a consequence of its intensive use. Microcosms assays were conducted to study the influence of indigenous microflora and plants (alfalfa) on the dissipation of 2,4-D from soils of the Humid Pampa region, Argentina, with previous history of phenoxy herbicides application. Results showed that 2,4-D was rapidly degraded, and the permanence of 2,4-DCP in soil depended on the presence of plants and soil microorganisms. Regarding soil microbial community, the presence of 2,4-D degrading bacteria was detected even in basal conditions in this soil, possibly due to the adaptation of the microflora to the herbicide. There was an increment of two orders of magnitude in herbicide degraders after 15d from 2,4-D addition, both in planted and unplanted microcosms. Total heterotrophic bacteria numbers were about 1x10(8) CFUg(-1) dry soil and no significant differences were found between different treatments. Overall, the information provided by this work indicates that the soil under study has an important intrinsic degradation capacity, given by a microbial community adapted to the presence of phenoxy herbicides.     

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.     

Light regime, riboflavin, and pH effects on 2,4-D photodegradation in water

A laboratory study was conducted to determine the effects of light regime, riboflavin, and pH on photodegradation of 2,4-D in aqueous solution. In controlled-environment chamber experiments, riboflavin sensitized 2,4-D photolysis in a concentration-dependent manner under both attenuated UV (-UV) and enhanced UV (+UV) light regimes. The photolysis half-life of 2,4-D in solutions containing 10 mg L-1 riboflavin was 9.7 and 12.5 h when exposed to +UV and -UV, respectively, compared to no photolysis in the absence of riboflavin. In contrast, the extrapolated half-life of 2,4-D in solutions containing 2.5 mg L-1 riboflavin was 46 h under +UV and 72 h under -UV. The rate of 2,4-D photolysis in the presence of riboflavin increased under both light regimes as initial pH of the solution was decreased from 7.5 to 4.5. The half-life of 2,4-D in the presence of 10 mg L-1 riboflavin at pH 4.5 and exposed to +UV was 1.6 h. Lumichrome, a principal photoproduct of riboflavin, did not photosensitize 2,4-D. Concentrations of 2,4-dichlorophenol formed as a result of riboflavin-sensitized 2,4-D photolysis were higher under the -UV than the +UV regime. These results indicate that riboflavin concentration, solution pH, and light regime are interacting factors that may be manipulated to enhance rates of aqueous 2,4-D photolysis.