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.     

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.     

Dissipation of glyphosate and aminomethylphosphonic acid in water and sediment of two Canadian prairie wetlands

Glyphosate [N-(phosphonomethyl)glycine] is the active ingredient of several herbicide products first registered for use in 1974 under the tradename Roundup. The use of glyphosate-based herbicides has increased dramatically over the last two decades particularly in association with the adoption of glyphosate-tolerant crops. Glyphosate has been detected in a range of surface waters but this is the first study to monitor its fate in prairie wetlands situated in agricultural fields. An ephemeral wetland (E) and a semi-permanent wetland (SP) were each divided into halves using a polyvinyl curtain. One half of each wetland was fortified with glyphosate with the added mass simulating an accidental direct overspray. Glyphosate dissipated rapidly in the water column of the two prairie wetlands studied (DT(50) values of 1.3 and 4.8 d) which may effectively reduce the impact of exposure of aquatic biota to the herbicide. Degradation of glyphosate to its major metabolite aminomethylphosphonic acid (AMPA) and sorption of the herbicide to bottom sediment were more important pathways for the dissipation of glyphosate from the water column than movement of the herbicide with infiltrating water. Presently, we are not aware of any Canadian guidelines for glyphosate residues in sediment of aquatic ecosystems. Since a substantial portion of glyphosate entering prairie wetlands will become associated with bottom sediments, particularly in ephemeral wetlands, guidelines would need to be developed to assess the protection of organisms that spend all or part of their lifecycle in sediment.     

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.     

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.     

17 β-estradiol and 17 α-ethinylestradiol mineralization in sewage sludge and biosolids

Natural steroid estrogens (e.g., 17 β-estradiol, E2), synthetic steroid estrogens (e.g., 17 α-ethinylestradiol, EE2) and pharmaceutical antibiotics (e.g., ciprofloxacin) are chemicals detected in biosolids and sewage sludges because they partition into the solids fraction during the wastewater treatment process. This research utilized a three-way factorial design (six media × two estrogens × three antibiotic treatments) to quantify cumulative E2 and EE2 mineralization over 133 d (MAX) in a range of sewage sludge and biosolid samples in the presence (4 and 40 mg kg^?1) and absence of ciprofloxacin. The same three-way factorial design was utilized to quantify the impact of the six media, E2 or EE2, and ciprofloxacin on cumulative soil respiration over 133 d (RESP). Minimal ciprofloxacin mineralization was observed (<0.05% over 133 d), but despite its persistence, ciprofloxacin had no significant effect on MAX of E2 or EE2, and, in general, no significant effect on RESP. MAX ranged from 38.38% to 48.44% for E2 but from only 0.72% to 24.27% for EE2 although RESP was relatively similar, ranging from 101.00 to 866.54 mg CO₂ in the presence of E2 and from 69.55 to 893.95 mg CO₂ in the presence of EE2. The sorption-limited bioavailability of EE2, which is inherently resistant to biodegradation due to chemical structure, as MAX and Freundlich sorption coefficients (K_f) were negatively correlated. As such, the K_f values of EE2 were largest in composted biosolids in which EE2 was particularly resistant to microbial degradation as the MAX of EE2 was <3%. In contrast, the MAX of E2 showed a positive association with the K_f values of E2 because some steps in the E2 transformation process have been found to occur in the sorbed phase. The MAX of E2 was significantly greater in the biosolid and composted biosolid media than in any other media, whereas the MAX of E2 decreased in the following order: secondary sewage sludge > primary sewage sludge > biosolid = composted biosolid. This suggests that sewage sludges in municipal lagoons and pre-treatment holding lagoons are a more favorable media for mineralization of EE2, whereas biosolids in post-treatment storage lagoons are a more favorable media for the mineralization of E2. The presence of ciprofloxacin will have no impact on the potential E2 or EE2 mineralization rates in these cases.     

Influence of crop residues on trifluralin mineralization in a silty clay loam soil

Trifluralin is typically applied onto crop residues (trash, stubble) at the soil surface, or onto the bare soil surface after the incorporation of crop residues into the soil. The objective of this study was to quantify the effect of the type and amount of crop residues in soil on trifluralin mineralization in a Wellwood silty clay loam soil. Leaves and stubble of Potato (Solanum tuberosum) (P); Canola (Brassica napus) (C), Wheat (Triticum aestivum) (W), Oats (Avena sativa), (O), and Alfalfa (Medicago sativa) (A) were added to soil microcosms at rates of 2%, 4%, 8% and 16% of the total soil weight (25 g). The type and amount of crop residues in soil had little influence on the trifluralin first-order mineralization rate constant, which ranged from 3.57E-03 day^?1 in soil with 16% A to 2.89E-02 day^?1 in soil with 8% W. The cumulative trifluralin mineralization at 113 days ranged from 1.15% in soil with 16% P to 3.21% in soil with 4% C, again demonstrating that the observed differences across the treatments are not of agronomic or environmental importance.     

Sorption of atrazine and metolachlor by earthworm surface castings and soil

Abstract

Atrazine and metolachlor were more strongly retained on earthworm (Lumbricus terrestris L.) castings than on soil, suggesting that earthworm castings at the surface or at depth can reduce herbicide movement in soil. Herbicide sorption by castings was related to the food source available to the earthworms. Both atrazine and metolachlor sorption increased with increasing organic carbon (C) content in castings, and Freundlich constants (K_f values) generally decreased in the order: soybean‐fed > corn‐fed > not‐fed‐earthworm‐castings. The amount of atrazine or metolachlor sorbed per unit organic carbon (K_oc values) was significantly greater for corn‐castings compared with other castings, or soil, suggesting that the composition of organic matter in castings is also an important factor in determining the retention of herbicides in soils. Herbicide desorption was dependent on both the initial herbicide concentration, and the type of absorbent. At small equilibrium herbicide concentrations, atrazine desorption was significantly greater from soil than from any of the three casting treatments. At large equilibrium herbicide concentrations, however, the greater organic C content in castings had no significant effect on atrazine desorption, relative to soil. For metolachlor, regardless of the equilibrium herbicide concentration, desorption from soybean‐ and corn‐castings treatments was always less than desorption from soil and not‐fed earthworm castings treatments. The results of this study indicate that, under field conditions, the extent of herbicide retention on earthworm castings will tend to be related to crop and crop residue management practices.     

Regional assessment of herbicide sorption and degradation in two sampling years

Sorption and degradation of the herbicide 2,4-D [2,4-dichlorophenoxyacetic acid] were determined for 123 surface soils (0 to 15 cm) collected in 2002 and in 2004 between 49 degrees to 60 degrees north longitude and 110 degrees to 120 degrees west latitude in Alberta, Canada. The soils were characterized by soil organic carbon content (SOC), pH, electrical conductivity, soil texture, cation exchange capacity, carbonate content, and total soil microbial activity. The 2,4-D sorption coefficients, Kd and Koc, were highly variable with coefficients of variation of 89 and 59%, respectively, at the provincial scale. Both Kd and Koc were well described by regression models with SOC and soil pH as variables, regardless of scale. Surprisingly, variations in 2,4-D mineralization were much smaller than variations in sorption. Variability in total 2,4-D mineralization was particularly low, with a coefficient of variation of only 7% at the provincial scale. Average 2,4-D half-lives in ecoregions ranged from 1.7 to 3.5 d, much lower than the field dissipation half-life of 10 d reported for 2,4-D in general pesticide property databases. Regression models describing degradation parameters were generally poor or not significant because 2,4-D mineralization was only weakly associated with measured 2,4-D sorption parameters and soil properties. As such, regional variations in herbicide sorption coefficients should be measured or calculated based on soil properties, to assign distinct pesticide fate model input parameters when estimating 2,4-D off-site transport at the provincial scale. Spatial variations in herbicide degradation appear less important for Alberta as 2,4-D half-lives were similar in soils across the province. The rapid mineralization of 2,4-D is noteworthy because 2,4-D is widely used in Alberta and perhaps adaptation of soil microbial communities allowed for accelerated degradation regardless of soil properties or the extent of 2,4-D sorption by soil.     

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.