Uniformly (14)C-ring-labeled 2,4-dichlorophenoxyacetic acid: a metabolism study in bluegill sunfish, Lepomis macrochirus.

The fate of 2,4-dichlorophenoxyacetic acid (2,4-D), a mixture of [phenyl(U)-(14)C]-2,4-D and unlabeled 2,4-D, in bluegill sunfish was investigated after exposure to approximately 11 ppm under static conditions for 4 days. Total radioactive residues (TRR) in whole fish increased from 0.41 ppm on day 1 to 0.60 ppm on day 3. TRR levels in fillet (edible) and viscera (nonedible) of treated fish on day 4 were 0.41 and 1.9 ppm, respectively. Most residues in both matrices were acetonitrile soluble; small amounts were hexane soluble or unextractable with solvents. Acid and base hydrolyses with ethyl acetate partitioning were used to release the fillet unextractable residues. The identification of 2,4-D and 2,4-dichlorophenol (2,4-DCP) in the fillet was conclusively confirmed by GC-MS analysis. On the basis of the experimental data from this study, a metabolic pathway for 2,4-D in bluegill sunfish in which the 2,4-D is metabolized to 2,4-DCP and conjugates of 2,4-D and 2,4-DCP is proposed.     

Uptake and metabolic fate of [14C]-2,4-dichlorophenol and [14C]-2,4-dichloroaniline in wheat (Triticum aestivum) and soybean (Glycine max)

The uptake and metabolism of [14C]-2,4-dichlorophenol (DCP) and [14C]-2,4-dichloroaniline (DCA) were investigated in wheat and soybean. Seeds were exposed to a nutrient solution containing 50 microM of one of two radiolabeled compounds, and plant organs were harvested separately after 18 days of growth. In wheat, uptake of [14C]-2,4-DCP was 16.67 +/- 2.65 and 15.50 +/- 2.60% of [14C]-2,4-DCA. In soybean, uptake of [14C]-2,4-DCP was significantly higher than [14C]-2,4-DCA uptake, 38.39 +/- 2.56 and 18.98 +/- 1.64%, respectively. In the case of [14C]-2,4-DCP, the radioactivity absorbed by both species was found mainly associated with roots, whereas [14C]-2,4-DCA and related metabolites were associated with aerial parts, especially in soybean. In wheat, nonextractable residues represented 7.8 and 8.7% of the applied radioactivity in the case of [14C]-2,4-DCP and [14C]-2,4-DCA, respectively. In soybean, nonextractable residues amounted to 11.8 and 5.8% of the total radioactivity for [14C]-2,4-DCP and [14C]-2,4-DCA, respectively. In wheat, nonextractable residues were nearly equivalent to extractable residues for [14C]-2,4-DCP, whereas they were greater for [14C]-2,4-DCA. In soybean, the amount of extractable residues was significantly greater for both chemicals. However, in both species, nonextractable residues were mainly associated with roots. Isolation of soluble residues was next undertaken using excised shoots (wheat) or excised fully expanded leaves including petioles (soybean). Identification of metabolite structures was made by comparison with authentic standards, by enzymatic hydrolyses, and by electrospray ionization-mass spectrometric analyses. Both plant species shared a common metabolism for [14C]-2,4-DCP and [14C]-2,4-DCA since the malonylated glucoside conjugates were found as the final major metabolites.     

2,4-Dichlorophenoxyacetic acid metabolism in transgenic tolerant cotton (Gossypium hirsutum)

The metabolic fate of 2,4-dichlorophenoxyacetic acid (2,4-D) was studied in leaves of transgenic 2,4-D-tolerant cotton (Gossypium hirsutum), which is obtained by transfer of the tfdA gene from the bacterium Alcaligenes eutrophus. The tdfA gene codes for a dioxygenase catalyzing the degradation of 2,4-D to 2, 4-dichlorophenol (2,4-DCP). [phenyl-(14)C]-2,4-D was administered by petiolar absorption followed by an 18 h water chase or converted to the isopropyl ester and sprayed onto the leaf surface; the leaves were harvested 48 h later. The herbicide was degraded to 2,4-DCP by the bacterial enzyme expressed in the plants. 2,4-DCP was rapidly converted to more polar metabolites and was never found in detectable amounts. Metabolite structures were deduced from enzymatic hydrolysis studies and mass spectrometric analyses. The first metabolite was the glucoside conjugate of 2,4-DCP (2, 4-DCP-beta-O-glucoside). The major terminal metabolites were two more complex glucosides: 2,4-DCP-(6-O-malonyl)glucoside and 2, 4-DCP-(6-O-sulfate)glucoside.     

Comparative degradation of [14C]-2,4-dichlorophenoxyacetic acid in wheat and potato after Foliar application and in wheat, radish, lettuce, and apple after soil application

The fate of 2,4-dichlorophenoxyacetic acid (2,4-D) applied foliarly as the 2-ethylhexyl ester (EHE) to wheat and potatoes, to the soil as the dimethylamine (DMA) salt under apple tree canopies, and preplant as the free acid for wheat, lettuce, and radish was studied to evaluate metabolic pathways. Crop fractions analyzed for (14)C residues included wheat forage, straw, and grain; potato vine and tubers; and apple fruit. The primary metabolic pathway for foliar application in wheat is ester hydrolysis followed by the formation of base-labile 2,4-D conjugates. A less significant pathway for 2,4-D in wheat was ring hydroxylation to give NIH-shift products 2,5-dichloro-4-hydroxyphenoxyacetic acid (4-OH-2,5-D), 4-OH-2,3-D, and 5-OH-2,4-D both free and as acid-labile conjugates. The primary metabolic pathway in potato was again ester hydrolysis. 2,4-D acid was further transformed to 4-chlorophenoxyacetic acid and 4-OH-2,5-D. For the soil applications, (14)C residues in the crops were low, and characterization of the (14)C residues indicated association with or incorporation into the biochemical matrix of the tissue. The degradative pathways observed in wheat are similar to those characterized in other intact plant studies but differ from those in studies in wheat cell suspension culture in that no amino acid conjugates were observed.     

Metabolic fate of 2,4-dichlorophenol and related plant residues in rats

This study compared the metabolic fate of [(14)C]-DCP, [(14)C]-residues from radish plants, and purified [(14)C]-DCP-(acetyl)glucose following oral administration in rats. A rapid excretion of radioactivity in urine occurred for [(14)C]-DCP, [(14)C]-DCP-(acetyl)glucose, and soluble residues, 69, 85, and 69% within 48 h, respectively. Radio-HPLC profiles of 0-24 h urine from rats fed [(14)C]-DCP and [(14)C]-DCP-(acetyl)glucose were close and qualitatively similar to those obtained from plant residues. No trace of native plant residues was detected under the study conditions. The structures of the two major peaks were identified by MS as the glucuronide and the sulfate conjugates of DCP. The characterization of a dehydrated glucuronide conjugate by MS and NMR of DCP was unusual. In contrast to soluble residues, bound residues were mainly excreted in feces, 90% within 48 h, whereas total residues were eliminated in both urine and feces. For total residues, the radioactivity in feces was higher than expected from the percentage of soluble and bound residues in radish plants. This result highlighted that less absorption took place when residues were present in the plant matrix as compared to plant-free residues and DCP.     

Gas chromatographic method for analysis of 2,4-D in wheat: interlaboratory study

A procedure is described for the determination of 2,4-D (2,4-dichlorophenoxyacetic acid) in dried green plant material. Samples are first extracted with dilute sodium hydroxide, and then after acidification and solvent extraction, the residues are methylated using boron trifluoride-methanol reagent. The methyl ester of 2,4-D is cleaned up on a Florisil column and quantitated using a gas chromatograph equipped with an electron capture detector. Six laboratories made quadruplicate determinations on control, dried green wheat check samples, on 4 similar samples fortified at the 0.50 ppm level, and on 4 samples fortified at the 1.00 ppm level with 2,4-D. Based on the data from 5 laboratories, the plant fortifications of 0.50 and 1.00 ppm yielded average interlaboratory recoveries of 2,4-D of 83.3 and 88.2%, respectively. The procedure also has potential for the determination of 2,4-D in wheat straw and wheat grain.     

Soil metabolism of a new herbicide, [14C]Pyribenzoxim, under flooded conditions

To elucidate the fate of a new pyrimidinyloxybenzoic herbicide, pyribenzoxim, a soil metabolism study was carried out with [14C]pyribenzoxim applied to a sandy loam soil under flooded conditions. The material balance of applied radioactivity ranged from 96.4 to 104.4% and from 96.1 to 101.9% for nonsterile and sterile soils, respectively. The half-life of [14C]pyribenzoxim was calculated to be approximately 1.3 and 9.4 days for nonsterile and sterile soils, respectively. The metabolites identified during the study were 2,6-bis(4,6-dimethoxypyrimidin-2-yloxy)benzoic acid (M1) and 2-hydroxy-6-(4,6-dimethoxypyrimidin-2-yloxy)benzoic acid (M2), resulting from the cleavage of the ester bond and subsequent hydrolysis. The nonextractable radioactivity levels increased to 37.8% for nonsterile conditions at 50 days after treatment and to 38.2% for sterile conditions at 60 days after treatment. Fractionation of the nonextractable soil residues indicated that bound radioactivity was associated mainly with humin fraction. No significant volatile products or [14C]carbon dioxide was observed during the study. On the basis of these results, pyribenzoxim is considered to undergo rapid degradation in soil by microbial and chemical reactions, mainly hydrolysis, which limits its transfer to and accumulation in lower soil layers and groundwater. Therefore, the possibility of environmental contamination from the use of pyribenzoxim is expected to be very low.     

Bioavailability of the herbicide 2,4-D formulated with organoclays

Research on organoclays as sorbents of pesticides has shown the usefulness of these materials as pesticide supports to prolong the efficacy of soil-applied pesticides and to reduce the large transport losses that usually affect pesticides applied in an immediately available form. Nevertheless, little information exists on the availability of organoclay-formulated pesticides for bacterial degradation. In this work, laboratory experiments were conducted to determine the adsorption-desorption behavior of two hexadecyltrimethylammonium-treated Arizona montmorillonites (SA-HDTMA₅₀ and SA-HDTMA₁₀₀) for the herbicide 2,4-dichlorophenoxyacetic acid (2,4-D), and to evaluate the ability of these organoclays to slow the release of the herbicide and to reduce herbicide leaching losses as compared to the free (technical) compound. The kinetics of mineralization of free and formulated 2,4-D by adapted bacteria was also determined. Organoclay-based formulations of 2,4-D displayed slow release properties in water and reduced herbicide leaching through soil columns, while maintained a herbicidal efficacy similar to that of the free (technical) 2,4-D. The total amount of ¹⁴C-2,4-D mineralized at the end of the biodegradation experiment (t=130 h) ranged between 30% and 46% of the formulated herbicide, which represented 53-81% of the amount of free 2,4-D mineralized in the same conditions. The release, leaching, and mineralization patterns of the formulated herbicide were found to depend both on the affinity of the organoclay for the herbicide and on the degree of interaction promoted during the preparation of the herbicide-organoclay complex. This suggests the possibility to select diverse preparations to achieve the desired release, leaching and biodegradation behavior.     

Biodegradation of chlorinated phenols in subsurface soils

Microcosm studies were employed to determine the subsurface biodegradation rates of phenol, 2-chlorophenol (2-CP), 2,4-dichlorophenol (2,4-DCP), 2,4,6-trichlorophenol (2,4,6-TCP), and pentachlorophenol (PCP). Soil samples were taken from sites in Pennsylvania and Virginia from depths up to 31 m, and all samples contained significant microbial populations. Soil from both sites readily biodegraded all five compounds. Biodegradation rates increased as initial concentrations increased, and all biodegradation rates appeared to follow first-order kinetics with regard to the initial compound concentrations. Biodegradation rates for the five compounds followed the order: phenol = 2-CP > 2,4,6-TCP > 2,4-DCP. PCP was degraded more slowly than phenol or 2-CP, but similarly to 2,4,6-TCP and 2,4-DCP. Different soils exhibited different degradation rates, and the soil characteristics that may influence the rates are discussed. The data suggest that biological degradation is a significant attenuation mechanism for phenol and its chlorinated derivatives in subsurfaces saturated and unsaturated zones.     

Oxidation of Chlorophenols in Aqueous Solution by Excess Potassium Permanganate

A simple spectrophotometric method was developed to quantify chlorophenol (CP) concentrations after reaction with potassium permanganate and quenching with sodium sulfite. Other quenching agents (peroxide, sodium thiosulfate and hydroxylamine hydrochloride) were found to create absorbance in the spectral range required for CP quantification. Analysis at pH 12 gave greater absorption and sensitivity for the method compared with pH 5.6. The calibration curves of the proposed methods were linear in the concentration ranges 0.0061–0.61 and 0.0078–0.78 mM with detection limit of 0.0006 and 0.0008 mM for dichlorophenols and monochlorophenols, respectively. The oxidation kinetics of five chlorophenols in aqueous solution with excess potassium permanganate were evaluated using the analytical method. The pseudo-first-order reaction rates were found to be relatively rapid 1.42 × 10⁻³ to 0.024 s⁻¹ and followed the sequence 2-chlorophenol (2-CP) > 2,6-dichlorophenol (2,6-DCP) > 4-chlorophenol (4-CP) > 2,4-dichlorophenol (2, 4-DCP) > 3-chlorophenol (3-CP). The apparent second-order rate constant was calculated from the measured pseudo-first-order rate constant with respect to CP with initial KMnO₄ concentration (1.5 mM) and follows the same sequence of pseudo-first-order rate constant. This shows that chlorine atoms in the structure of chlorophenol had a significant influence on the oxidation of chlorophenols by potassium permanganate. Permanganate can be used for the treatment of chlorophenol-contaminated soil and groundwater.     

Rhizodeposits of Trifolium pratense and Lolium perenne: their comparative effects on 2,4-D mineralization in two contrasting soils

Rhizosphere enhanced biodegradation of organic pollutants has been reported frequently and a stimulatory role for specific components of rhizodeposits postulated. As rhizodeposit composition is a function of plant species and soil type, we compared the effect of Lolium perenne and Trifolium pratense grown in two different soils (a sandy silt loam: pH 4, 2.8% OC, no previous 2,4-D exposure and a silt loam: pH 6.5, 4.3% OC, previous 2,4-D exposure) on the mineralization of the herbicide 2,4-D (2,4-dichlorophenoxyacetic acid). We investigated the relationship of mineralization kinetics to dehydrogenase activity, most probable number of 2,4-D degraders (MPN_2,4-D) and 2,4-D degrader composition (using sequence analysis of the gene encoding α-ketoglutarate/2,4-D dioxygenase (tfdA)). There were significant (P<0.01) plant-soil interaction effects on MPN_2,4-D and 2,4-D mineralization kinetics (e.g. T. pratense rhizodeposits enhanced the maximum mineralization rate by 30% in the acid sandy silt loam soil, but not in the neutral silt loam soil). Differences in mineralization kinetics could not be ascribed to 2,4-D degrader composition as both soils had tfdA sequences which clustered with tfdAs representative of two distinct classes of 2,4-D degrader: canonical R. eutropha JMP134-like and oligotrophic α-proteobacterial-like. Other explanations for the differential rhizodeposit effect between soils and plants (e.g. nutrient competition effects) are discussed. Our findings stress that complexity of soil-plant-microbe interactions in the rhizosphere make the occurrence and extent of rhizosphere-enhanced xenobiotic degradation difficult to predict.     

Metabolism of 2,4-dichlorophenoxyacetic acid in laying hens and lactating goats

2,4-Dichlorophenoxyacetic acid (2,4-D) labeled with (14)C was found to be rapidly eliminated by laying hens and lactating goats dosed orally for 7 consecutive days at 18 mg/kg of food intake and for 3 consecutive days at 483 mg/kg of food intake, respectively. Excreta of hens and goats contained >90% of the total dose within 24 h after the final dose. Tissue residues were low and accounted for <0.1% of the dose in these animals. For hens, the residues in muscle, liver, and eggs (0.006-0.030 ppm) were lower than those found in fat and kidney (0.028-0.714 ppm), 2,4-D equivalents. The tissue with highest residue in goat was the kidney at 1.44 ppm, 2,4-D equivalents. Milk, liver, composite fat, and composite muscle had significantly lower residue levels of 0.202, 0.224, 0.088, and 0.037 ppm, respectively. The most abundant tissue residue was 2,4-D and acid/base releasable residues of 2,4-D. A minor metabolite was identified as 2,4-dichlorophenol.     

The influence of nitrogen on atrazine and 2,4-dichlorophenoxyacetic acid mineralization in grassland soils

The influence of fertilizer N on the mineralization of atrazine [2-chloro-4(ethylamino)-6(isopropylamino)-s-triazine] and 2,4-D (2,4-dichlorophenoxyacetic acid) in soils was assessed in microcosms using radiometric techniques. N equivalent to 0, 250, and 500 kg N as NH₄NO₃ ha^-1 was added to three grassland soils. Compared to the control, the 250- and 500-kg treatments suppressed mineralization of atrazine by 75 and 54%, respectively, and inhibited mineralization of 2,4-D by 89 and 30%, respectively. Active fungal biomass responded to the N treatments in an opposite manner to herbicide mineralization. Compared to the control, the 250- and 500-kg treatments increased the active fungal biomass by more than 300 and 30%, respectively. These results agree with other observations that N can suppress the decomposition of resistant compounds but stimulate the primary growth of fungi. The degree of suppression was not related to the amount of N added nor to the inherent soil N levels before treatment. The interaction between the N additions and the active fungal biomass in affecting herbicide mineralization suggests that N may alter microbial processes and their use of C sources and thus influence rates of herbicide degradation in the field.     

Transformation and binding of 13C and 14C-labelled atrazine in relation to straw decomposition in soil

As a source of organic matter, crop residues affect the behaviour of pesticides in agricultural soils. The fate of [U‐ring‐¹³C] and [U‐ring‐¹⁴C] atrazine (6‐chloro‐N‐ethyl‐N‐isopropyl‐1,3,5‐triazine‐2,4‐diamine) was investigated during laboratory incubation under controlled conditions in a loamy soil amended with wheat straw at two different states of decomposition: no preliminary decomposition or 6 months’ preliminary decomposition. After 3 months, non‐extractable, so‐called ‘bound’, ¹³C‐atrazine residues were recovered in three particle‐size fractions (> 200, 50–200 and < 50 μm), and investigated with solid‐state ¹³C‐NMR spectroscopy. Parallel incubations with [U‐ring‐¹⁴C] atrazine were carried out to quantify the bound residues as well as the extractable and mineralized fractions. The effect of straw residues on atrazine behaviour depended on whether they had been previously decomposed or not. When straw was decomposed for 6 months prior to incubation, atrazine mineralization was enhanced to 50% of the initial ¹⁴C in contrast to 15% of the initial ¹⁴C in soil alone and soil amended with fresh straw. In parallel, atrazine bound residues were formed in greater amount representing up to 20% of the initial ¹⁴C. CP/MAS ¹³C‐NMR on soil size fractions of soil–straw mixtures after incubation with ¹³C‐atrazine showed that bound residues contained mostly triazinic C, corresponding to atrazine or primary metabolites. Non‐humified organic materials recovered in size fractions > 200 and 50–200 μm contained significant amounts of bound residues, especially when straw was added to the soil. CP/MAS ¹³C‐NMR analysis of humic acids obtained from < 50‐μm fractions was difficult due to overlapping of the native carboxyl ¹³C signal with the ¹³C‐atrazine signal.     

Laboratory incubation studies of chlorophenoxyacetic acids in chernozemic soils

The relative persistence of 2,4-D, MCPA and 2,4,5-T in some Saskatchewan soils was assessed under laboratory conditions. Under moist conditions, 2,4-D and MCPA showed half-life times of between 14 and 41 days but the MCPA half-life was usually 1 or 2 days longer. 2,4,5-T exhibited a half-life period over twice the length of the other chemicals. The half-life times were directly correlated to microbial plate counts, the larger numbers of soil microorganisms being associated with shorter residence times. Half-lives depended on soil moisture content and the best moisture levels for chemical loss appeared to be just less than field capacity. The use of ¹⁴C in 2,4-D incubation studies showed that the initial cleavage of the 2,4-D molecule was associated with the ether linkage and was not a decarboxylation.     

养殖水体中氯酚残留特征及其与环境因子关系初探

采用固相微萃取（SPME）与气-质联用方法,测定分析了3种养殖模式水体中氯酚化合物（CPs）的污染特征。结果表明,19种CPs类化合物在一般四大家鱼养殖水体（A）、猪-鱼综合养殖模式水体（B）以及鸭-鱼综合养殖模式水体（C）表层水中的分布特征相似。总CPs及10种CPs化合物在不同养殖方式水体中浓度由高到低的顺序为A〉B〉C。表层水中残留浓度比较高的一氯酚、二氯酚、三氯酚和四氯酚分别是3-CP和4-CP、2,4-DCP、2,4,6-TCP、2,3,4,6-TCP。回归分析表明,铁、锰总含量与总CPs和PCP含量存在显著负相关。     

Microbial mineralization of atrazine and 2,4-dichlorophenoxyacetic acid in riparian pasture and forest soils

Microbial biomass and mineralization of atrazine [2-chloro-4(ethylamino)-6(isopropylamino)s-triazine] and 2,4-D (2,4-dichlorphenoxyacetic acid) were examined in the top 10 cm of riparian pasture soils and in the litter layer and top 10 cm of mineral soils of riparian forest ecosystems. The riparian forest litter had higher levels of active and total fungal biomass than forest or pasture mineral soils in winter, spring, and fall. Active bacterial biomass was higher in forest litter than in forest and pasture mineral soils in spring and autumn, and higher in forest mineral soils than in pasture soils in summer. Total bacterial biomass was higher in forest mineral soils than in pasture soils during all seasons. In spring, it was also higher in forest litter than in pasture soils. Atrazie and 2,4-D mineralization in pasture soils was exceeded by that in forest litter in spring and autumn and by that in forest mineral soils in summer and autumn. There was no correlation between either active or total fungal and bacterial biomass with pesticide degradation.     

Degradation of [carboxyl-14C] 2,4-D and [ring-U-14C] 2,4-D in 114 agricultural soils as affected by soil organic carbon content

This study compared the degradation of [carboxyl-¹⁴C] 2,4-dichlorophenoxyacetic acid (2,4-D) (C2,4-D) and [ring-U-¹⁴C] 2,4-D (R2,4-D) in 114 agricultural soils (0–15 cm) as affected by 2,4-D sorption and soil properties (organic carbon content, pH, clay content, carbonate content, cation exchange capacity, total microbial activity). The sample area was confined to Alberta, Canada, located 49–60° north longitude and 110–120° west latitude and soils were grouped by soil organic carbon content (SOC) (0–0.99%, 1–1.99%, 2–2.99%, 3–3.99% and >4% SOC). Degradation rates of C2,4-D and R2,4-D followed first-order kinetics in all soils. Although total microbial activity increased with increasing SOC, degradation rates and total degradation of C2,4-D and R2,4-D decreased with increasing SOC because of increased sorption of 2,4-D by soil and reduced bioavailability of 2,4-D and its metabolites. Rates of R2,4-D degradation were more limited by sorption than rates of C2,4-D degradation, possibly because of greater sorption and formation of bound residues of 2,4-D metabolites relative to the 2,4-D parent molecule. Based on the sorption and degradation parameters quantified, there were two distinct groups of soils, those with less than 1% SOC and those with greater than 1% SOC. Specifically, soils with less than 1% SOC had, on average, 2.4 times smaller soil organic carbon sorption coefficients and 1.4 times smaller 2,4-D half-lives than soils with more than 1% SOC. In regional scale model simulations of pesticide leaching to groundwater, covering many soils, input parameters for each pesticide include a single soil organic carbon sorption coefficient and single half-life value. Our results imply, however, that the approach to these regional scale assessments could be improved by adjusting the values of these two input parameters according to SOC. Specifically, this study indicates that for 2,4-D and Alberta soils containing less than 1% SOC, the 2,4-D pesticide parameters obtained from generic databases should be divided by 2.5 (soil organic carbon sorption coefficient) and 1.5 (half-life value).     

The millimetre-scale distribution of 2,4-D and its degraders drives the fate of 2,4-D at the soil core scale

The biodegradation of organic compounds in soil is a key process that has major implications for different ecosystem services such as soil fertility, air and water quality, and climate regulation. Due to the complexity of soil, the distributions of organic compounds and microorganisms are heterogeneous on sub-cm scales, and biodegradation is therefore partly controlled by the respective localizations of organic substrates and degraders. If they are not co-localized, transfer processes become crucial for the accessibility and availability of the substrate to degraders. This spatial interaction is still poorly understood, leading to poor predictions of organic compound dynamics in soils. The objectives of this work were to better understand how the mm-scale distribution of a model pesticide, 2,4-dichlorophenoxyacetic acid (2,4-D), and its degraders drives the fate of 2,4-D at the cm soil core scale. We constructed cm-scale soil cores combining sterilized and “natural” soil aggregates in which we controlled the initial distributions of 2,4-D and soil microorganisms with the following spatial distributions: i) a homogeneous distribution of microorganisms and 2,4-D at the core-scale, ii) a co-localized distribution of microorganisms and 2,4-D in a single spot (360 mm³) and iii) a disjoint localization of microorganisms and 2,4-D in 2 soil spots (360 mm³) separated by 2 cm. Two sets of experiments were performed: one used radiolabeled ¹⁴C-2,4-D to study the fate of 2,4-D, and the other used ¹²C-2,4-D to follow the dynamics of degraders. Microcosms were incubated at 20 °C and at field capacity (−31.6 kPa). At the core scale, we followed 2,4-D mineralization over time. On three dates, soil cores with microorganisms and 2,4-D localized in soil spots, were cut out in slices and then in 360 mm³ soil cubes. The individual soil cubes were then independently analysed for extractable and non-extractable ¹⁴C and for degraders (quantitative PCR of tfdA genes). Knowing the initial position of each soil cube allowed us to establish 3D maps of 2,4-D residues and degraders in soil. The results indicated that microorganisms and pesticide localizations in soil are major driving factors of i) pesticide biodegradation, by regulating the accessibility of 2,4-D to degrading microorganisms (by diffusion); and ii) the formation of non-extractable residues (NER). These results also emphasized the dominant role of microorganisms in the formation and localization of biogenic NER at a mm-scale. To conclude, these results demonstrate the importance of considering micro-scale processes to better understand the fate of pesticides and more generally of soil organic substrates at upper scales in soil and suggest that such spatial heterogeneity should not be neglected when predicting the fate of organic compounds in soils.     

Mineralization of organic contaminants under aerobic and anaerobic conditions in sludge-soil mixtures

Background and Main Features  The mineralization of eight organic chemicals (surfactants, substituted aromatic compounds, di(2-ethylhexyl)phthalate and phenanthrene) was examined in sludge-soil mixtures under aerobic, denitrifying and methanogenic conditions. Results and Discussion  Most of the chemicals were extensively or partially mineralized under aerobic conditions with mineralization half-lives between 1.5 and 12.5 days. Linear tridecyl tetra ethoxylate, di(2-ethylhexyl)phthalate and 2,4-dinitrophenol were also mineralized partially under denitrifying conditions. No mineralization of the chemicals was observed under methanogenic conditions, with the exception of a minor mineralization of linear tridecyl tetraethoxylate. Conclusion  This study indicates that the examined organic chemicals may be rapidly degraded in sludge-amended fields under aerobic conditions, and that some of the chemicals may also be degraded during denitrification. Recommendations and Outlook  When investigating the degradation of sludge-bound chemicals in soil, it is relevant to consider both aerobic and anaerobic soil regimes due to spatial and temporal variations in the redox conditions within sludge and soil. The approach presented in this article may be used for evaluation of the long-term fate of sludge-bound chemicals in soil.