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.     

Impact of carbon nanomaterials on the behaviour of 14C-phenanthrene and 14C-benzo-[a] pyrene in soil

The impact of fullerene soot (FS), single-walled (SWCNTs) and multi-walled (MWCNTs) carbon nanotubes on the behaviour of two ¹⁴C-PAHs in sterile soil was investigated. Different concentrations of carbon nanomaterials (0, 0.05, 0.1 and 0.5%) were added to soil, and ¹⁴C-phenanthrene and ¹⁴C-benzo[a]pyrene extractability assessed over 80 d through dichloromethane (DCM) and hydroxypropyl-β-cyclodextrin (HPCD) shake extractions. Total ¹⁴C-PAH activity in soils was determined by combustion, and mineralisation of ¹⁴C-phenanthrene was monitored over 14 d, using a catabolically active pseudomonad inoculum. No significant loss of ¹⁴C-PAH-associated activity from CNM-amended soils was observed over the ‘aging’ period. CNMs had a significant impact on HPCD-extractability of ¹⁴C-PAHS; extractability decreased with increasing CNM concentration. Additionally, ¹⁴C-phenanthrene mineralisation was inhibited by the presence of CNMs at concentrations of ≥0.05%. Differences in overall extents of ¹⁴C-mineralisation were also apparent between CNM types. It is suggested the addition of CNMs to soil can reduce PAH extractability and bioaccessibility, with PAH sorption to CNMs influenced by CNM type and concentration.     

Effects of 2,4-dichlorophenol, pentachlorophenol and vegetation on microbial characteristics in a heavy metal polluted soil

The aim of this study was to evaluate the soil microbial characteristics in historically heavy-metal polluted soil, which was also affected by organic co-contaminants, 2,4-dichlorophenol or pentachlorophenol, which often occur due to the conventional use of pesticides. It was observed that the normalized microbial biomass (microbial biomass per unit soil organic C) of the contaminated soil was very low, less than 1% in both non-planted and ryegrass planted soil, and showed a decreasing trend with the treatment of organic co-contaminants. The microbial biomass and substrate-induced respiration (SIR) in the ryegrass planted soil were much larger, as compared with the non-planted soil with or without organic pollutants. The different resistant bacterial community and its physiological diversity in the rhizosphere further suggested that the effect of vegetation on microbial activity was not just a general increase in the mass or activity of pre-existing microorganisms, but rather acted selectively on microbial growth so that the relative abundance of different microbial groups in soil was changed. In sum, high concentrations of organic co-contaminants, especially pentachlorophenol (PCP), could strengthen the deterioration of microbial ecology. The adverse effect of heavy metal-organic pollutants on the soil microbial biomass and activity might be the reason for the slow degradation of PCP that has high chlorinated and high toxicity. Vegetation might be the efficient way to assist in improving and restoring the utilization of agricultural ecosystems. The beneficial microbial effect of vegetation could cause the rapid dissipation of 2,4-dichlorophenol (2,4-DCP) that has less chlorinated and less toxicity in the planted soils.     

Effects of 2,4-dichlorophenol,pentachlorophenol and vegetation on microbial characteristics in a heavy metal polluted soil

The aim of this study was to evaluate the soil microbial characteristics in historically heavy-metal polluted soil, which was also affected by organic co-contaminants, 2,4-dichlorophenol or pentachlorophenol, which often occur due to the conventional use of pesticides. It was observed that the normalized microbial biomass (microbial biomass per unit soil organic C) of the contaminated soil was very low, less than 1% in both non-planted and ryegrass planted soil, and showed a decreasing trend with the treatment of organic co-contaminants. The microbial biomass and substrate-induced respiration (SIR) in the ryegrass planted soil were much larger, as compared with the non-planted soil with or without organic pollutants. The different resistant bacterial community and its physiological diversity in the rhizosphere further suggested that the effect of vegetation on microbial activity was not just a general increase in the mass or activity of pre-existing microorganisms, but rather acted selectively on microbial growth so that the relative abundance of different microbial groups in soil was changed. In sum, high concentrations of organic co-contaminants, especially pentachlorophenol (PCP), could strengthen the deterioration of microbial ecology. The adverse effect of heavy metal-organic pollutants on the soil microbial biomass and activity might be the reason for the slow degradation of PCP that has high chlorinated and high toxicity. Vegetation might be the efficient way to assist in improving and restoring the utilization of agricultural ecosystems. The beneficial microbial effect of vegetation could cause the rapid dissipation of 2,4-dichlorophenol (2,4-DCP) that has less chlorinated and less toxicity in the planted soils.     

Biogenic volatile organic compounds as a potential stimulator for organic contaminant degradation by soil microorganisms

The effects of monoterpenes on the degradation of ¹⁴C-2,4-dichlorophenol (DCP) were investigated in soils collected from areas surrounding monoterpene and non-monoterpene-emitting vegetation. Indigenous microorganisms degraded ¹⁴C-2,4-DCP to ¹⁴CO₂, after 1 d contact time. Degradation was enhanced by prior exposure of the soils to 2,4-DCP for 32 d, increasing extents of mineralisation up to 60%. Monoterpene amendments further enhanced 2,4-DCP degradation, but only following pre-exposure to both 2,4-DCP and monoterpene, with total 2,4-DCP mineralisation extents of up to 71%. Degradation was greatest at the higher monoterpene concentrations (≥1 μg kg⁻¹). Total mineralisation extents were similar between concentrations, but higher than the control and the 0.1 μg kg⁻¹ amendment, indicating that increases in monoterpene concentration has a diminishing enhancing effect. We suggest that monoterpenes can stimulate the biodegradation of 2,4-DCP by indigenous soil microorganisms and that monoterpene amendment in soils is an effective strategy for removing organic contaminants.     

Atrazine and simazine degradation in Pennisetum rhizosphere

The ability of rhizosphere of four plant species to promote the degradation of charcoal-fixed atrazine and simazine in cement blocks of a long-term contaminated soil when mixed with a normal soil at 1:1 ratio was tested. Of the four selected plants viz., rye grass (Lolium perenne), tall fescue (Festuca arundinacae), Pennisetum (Pennisetum clandestinum) and a spring onion (Allium sp.) used in this study, only P. clandestinum was able to survive in herbicide contaminated soil while other plants died within few days after germination/transplanting. Both atrazine and simazine were degraded at a faster rate in contaminated soil planted to P. clandestinum than in unplanted soil. Within 80 days, nearly 45% and 52% of atrazine and simazine, respectively, were degraded in soil planted to P. clandestinum while only 22% and 20% of the respective herbicide were degraded in the unplanted soil. During 80-day experimental period, both microbial biomass and soil dehydrogenase activity were significantly increased (7-fold) in soil planted to P. clandestinum over that in unplanted soil. The suspension of contaminated rhizosphere soil, planted to P. clandestinum exhibited an exceptional capability to degrade both atrazine (300 microg) and simazine (50 microg) in a mineral salts medium over that of non-rhizosphere soil suspension. Results indicate that P. clandestinum, a C4 plant, may be useful for remediation of soils contaminated with atrazine and simazine.     

Mobilization of phenol and dichlorophenol in unsaturated soils by non-uniform electrokinetics

The poor mobility of organic pollutants in contaminated sites frequently results in slow remediation processes. Organics, especially hydrophobic compounds, are generally retained strongly in soil matrix as a result of sorption, sequestration, or even formation into non-aqueous-phase liquids and their mobility is thus greatly reduced. The objective of this study was to evaluate the feasibility of using non-uniform electrokinetic transport processes to enhance the mobility of organic pollutants in unsaturated soils with no injection reagents. Phenol and 2,4-dichlorophenol (2,4-DCP), and kaolin and a natural sandy loam soil were selected as model organics and soils, respectively. The results showed that non-uniform electrokinetics can accelerate the desorption and movement of phenol and 2,4-DCP in unsaturated soils. Electromigration and electroosmotic flow were the main driving forces, and their role in the mobilization of phenol and 2,4-DCP varied with soil pH. The movement of 2,4-DCP in the sandy loam towards the anode (about 1.0 cmd(-1)V(-1)) was 1.0-1.5 cmd(-1)V(-1) slower than that in the kaolin soil, but about 0.5 cmd(-1)V(-1) greater than that of phenol in the sandy loam. When the sandy loam was adjusted to pH 9.3, the movement of phenol and 2,4-DCP towards the anode was about twice and five times faster than that at pH 7.7, respectively. The results also demonstrated that the movement of phenol and 2,4-DCP in soils can be easily controlled by regulating the operational mode of electric field. It is believed that non-uniform electrokinetics has the potential for practical application to in situ remediation of organics-contaminated sites.     

Ozone treatment of soil contaminated with aniline and trifluralin

Column studies were conducted to determine the ability of ozone to degrade aniline and trifluralin in soil. Ozone rapidly degraded aniline from soil under moist soil conditions, 5% (wt). Removal of 77-98% of [UL-14C]-aniline was observed from soil columns (15 ml, i.d. = 2.5 cm), exposed to 0.6% O(3) (wt) at 200 ml/min after 4 min. Initial ozonation products included nitrosobenzene and nitrobenzene, while further oxidation led to CO(2). Ring-labeled-[UL-14C]-trifluralin removal rates were slower, requiring 30 min to achieve removals of 70-97%. Oxidation and cleavage of the N-propyl groups of trifluralin was observed, affording 2,6-dinitro-4-(trifluoromethyl)-aniline, 2,6-dinitro-N-propyl-4-(trifluoromethyl)-benzamine, and 2,6-dinitro-N-propyl-N-acetonyl-4-(trifluoromethyl)-benzamine. Base solutions revealed that trifluralin was similarly oxidized to CO(2), where 72-83% of the activity recovered comprised 14CO(2). Use of ozone-rich water improved contaminant removal in trifluralin-amended soil columns, but did not improve removal in aniline, pentachloroaniline, hexachlorobenzene amended soil columns, suggesting that ozonated water may improve contaminant removal for reactive contaminants of low solubility.     

The impact of synthetic pyrethroid and organophosphate sheep dip formulations on microbial activity in soil

Sheep dip formulations containing organophosphates (OPs) or synthetic pyrethroids (SPs) have been widely used in UK, and their spreading onto land has been identified as the most practical disposal method. In this study, the impact of two sheep dip formulations on the microbial activity of a soil was investigated over a 35-d incubation. Microbial utilisation of [1-(14)C] glucose, uptake of (14)C-activity into the microbial biomass and microbial numbers (CFUs g(-1) soil) were investigated. In control soils and soils amended with 0.01% sheep dip, after 7d a larger proportion of added glucose was allocated to microbial biomass rather than respired to CO(2). No clear temporal trends were found in soils amended with 0.1% and 1% sheep dips. Both sheep dip formulations at 0.1% and 1% concentrations resulted in a significant increase in CFUs g(-1) soil and [1-(14)C] glucose mineralisation rates, as well as a decline in microbial uptake of [1-(14)C] glucose, compared to control and 0.01% SP- or OP-amended soils. This study suggests that the growth, activity, physiological status and/or structure of soil microbial community may be affected by sheep dips.     

Adsorption behavior of 2,4-dichlorophenol and pentachlorophenol in an allophanic soil

The adsorption of 2,4-dichlorophenol (2,4-DCP) and pentachlorophenol (PCP) by a variable-charge soil from southern Chile was studied in a series of batch equilibration experiments. 2,4-DCP and PCP adsorption behavior was evaluated as a function of pH (pH values of 4.5, 6.0 and 7.5) in a 0.1M KCl (25 degrees C) background solution for soil material collected at three different depths (0-20 cm, 20-40 cm, and 40-60 cm). 2,4-DCP and PCP adsorption decreased with increasing soil pH, suggesting that the undissociated species were adsorbed more readily and that electrostatic repulsion may inhibit partitioning as pH increases. The PCP adsorption was greater than observed for 2,4-DCP and decreased with soil depth. Multiple regression analysis between K(d) and various soil properties indicated that the soil organic carbon content is a strong indicator of chlorophenol adsorption, and in addition to organic carbon, the soil pH is an important property controlling adsorption behavior.     

2,4-Dichlorophenoxy Acetic Acid Mineralization in Amended Soil

The application of municipal biosolid or liquid hog manure to agricultural soils under laboratory conditions at 20°C influenced the fate of the herbicide 2,4-D [2,4-(dichlorophenoxy)acetic acid] in soil. When 2,4-D was added to soil at agronomic rates immediately after the addition of manure or biosolids to a coarse-textured soil, the percentage of 2,4-D mineralized at 100 days was about 47% for both treatments, compared to only 31% for control soils without amendments. The enhanced 2,4-D mineralization as a result of amendment addition was due to an increased heterotrophic microbial activity, with the greatest increases in soil respiration occurring for soils amended with biosolids. When additions of 2,4-D were delayed for one, two, or four weeks after the amendments were applied, the additions of amendments generally reduced 2,4-D mineralization in soil, particularly for manure, indicating that the effect of amendments on enhancing soil microbial activities diminished over time. In contrast, the mineralization of 2,4-D in control soils was less dependent on when 2,4-D was applied in relation to pre-incubations of soil for zero, one, two, or four weeks. The effect of manure on decreasing 2,4-D mineralization in specific soils was as large as the effect of soil texture on differences in 2,4-D mineralization across soils. Because manure was not found to impact 2,4-D sorption by soil, it is possible that 2,4-D mineralization decreased because 2,4-D transformation products were strongly sorbed onto organic carbon constituents in manure-amended soils and were therefore less accessible to microorganisms. Alternatively, microorganisms were less likely to metabolize the herbicide because they preferentially consumed the type of organic carbon in manure that is a weak sorbent for 2,4-D.     

2,4-Dichlorophenoxy acetic acid mineralization in amended soil

The application of municipal biosolid or liquid hog manure to agricultural soils under laboratory conditions at 20 degrees C influenced the fate of the herbicide 2,4-D [2,4-(dichlorophenoxy)acetic acid] in soil. When 2,4-D was added to soil at agronomic rates immediately after the addition of manure or biosolids to a coarse-textured soil, the percentage of 2,4-D mineralized at 100 days was about 47% for both treatments, compared to only 31% for control soils without amendments. The enhanced 2,4-D mineralization as a result of amendment addition was due to an increased heterotrophic microbial activity, with the greatest increases in soil respiration occurring for soils amended with biosolids. When additions of 2,4-D were delayed for one, two, or four weeks after the amendments were applied, the additions of amendments generally reduced 2,4-D mineralization in soil, particularly for manure, indicating that the effect of amendments on enhancing soil microbial activities diminished over time. In contrast, the mineralization of 2,4-D in control soils was less dependent on when 2,4-D was applied in relation to pre-incubations of soil for zero, one, two, or four weeks. The effect of manure on decreasing 2,4-D mineralization in specific soils was as large as the effect of soil texture on differences in 2,4-D mineralization across soils. Because manure was not found to impact 2,4-D sorption by soil, it is possible that 2,4-D mineralization decreased because 2,4-D transformation products were strongly sorbed onto organic carbon constituents in manure-amended soils and were therefore less accessible to microorganisms. Alternatively, microorganisms were less likely to metabolize the herbicide because they preferentially consumed the type of organic carbon in manure that is a weak sorbent for 2,4-D.     

Aged and bound herbicide residues in soil and their bioavailability. Part 2: Uptake of aged and non-extractable (bound) [carbonyl-14C]methabenzthiazuron residues by maize

[Carbonyl-14C]methabenzthiazuron (MBT) was applied to growing winter wheat in an outdoor lysimeter. The amount applied corresponded to 4 kg Tribunil/ha. 140 days after application the 0-2.5 cm soil layer was removed from the lysimeter. This soil contained about 40% of the applied radioactivity. Using 0,01 M CaCl2 solution or organic solvents, the extractable residues were removed from the soil. The bioavailability of the non-extractable as well as aged residues remaining in the soil was investigated in standardized microecosystems containing 1.5 kg of dry soil. During a 4 weeks period the total uptake (4 maize plants/pot) amounted up to 3.6; 2.2; and 0.9% of the radioactivity from soils containing aged MBT residues, MBT residues non-extractable with 0.01 M CaCl2 or MBT residues non-extractable with organic solvents, respectively. About 20% of the radioactivity found in maize leaves represented chromatographically characterized parent compound. At the end of the plant experiment the soil was extracted again with 0.01 M CaCl2 and with organic solvents. The soil extracts and also the organic phases obtained from the aqueous fulvic acid solution contained unchanged parent compound.     

Comparison of microbial pyrene and benzo[a]pyrene mineralization in liquid medium, soil slurry, and soil

The microbial degradation of 14C-pyrene and 14C-benzo[a]pyrene by a bacterial mixed culture was studied within a mixture of the PAHs phenanthrene, anthracene, pyrene, fluoranthene, and benzo[a]pyrene as sole carbon source in the different culture systems: (i) liquid medium, (ii) soil slurry (surface and grinding influence), and (iii) soil. The fate of these two labeled compounds was followed in these systems with an emphasis on mineralization to carbon dioxide, extractability, and adsorption to humic materials and formation of unextractable residual. Mineralization showed the most obvious differences: soil slurries achieved the best results both concerning the extent of mineralization and the time required. The highest extent of pyrene mineralization (54% within 21 days) was observed in soil slurries; in liquid media, pyrene mineralization was slower, but reached approximately the same extent (54% in 150 days); in soils, mineralization reached only 36% of added pyrene after 160 days. Benzo[a]pyrene was mineralized in a mixture of PAHs in soil slurries to an extent of 34% within 70 days, whereas mineralization in liquid medium and soil occurred in the range of 5% (70 days). Mineralization of benzo[a]pyrene in sand slurries was lower compared to soil slurries (19% in sand slurries vs. 32% in soil slurries within 50 days).     

Copolymerization of 2,4-dichlorophenol with humic substances by oxidative and photo-oxidative biomimetic catalysis

We evaluated the catalytic activity of a water-soluble iron-porphyrin in an oxidative coupling reaction to form covalent bonds between 2,4-dichlorophenol (2,4-DCP) and humic molecules. The biomimetic catalysis in the presence of H₂O₂ was tested in the dark and in daylight, and changes in reaction products were revealed by high-performance liquid chromatography (HPLC) and nuclear magnetic resonance (NMR) spectroscopy. In all conditions, iron-porphyrin was effective in promoting complete disappearance of 2,4-DCP, although catalyst activity was enhanced in daylight (with a maximum turnover number of 85.13). Further evidence of the occurred covalent coupling between 2,4-DCP and humic molecules was revealed by diffusion-ordered nuclear magnetic resonance (DOSY-NMR) spectroscopy that showed a reduced diffusivity of 2,4-DCP after the catalytic reaction. These findings indicate that iron-porphyrin is an efficient catalyst for the covalent binding of polyhalogenated phenols to humic molecules, thereby suggesting that the copolymerization reactions may become a useful technology to remediate soils and waters contaminated by halogenated phenols and their analogues.     

Sorption behavior of metolachlor, isoproturon, and terbuthylazine in soils

The sorption-desorption of metolachlor [2-chloro-N-(ethyl-6-methyl phenyl)-N-(2-methoxy-1-methyl ethyl) acetamide], isoproturon [3-(4-isopropyl phenyl)-1,1-dimethyl urea] and terbuthylazine [N6-tert butyl-6-chloro-N4-ethyl-1,3,5-triazine-2,4-diamine] herbicides was studied in two German soils at 1:10 soil to water ratio by batch method. Equilibrium of herbicides between soil and water (0.01 M CaCl2) was attained in 2 h. Sorption data fitted very well to Freundlich equation, represented by very high correlation coefficient (r2 > 0.934). Comparison of Freundlich K values indicated that sorption of all the three herbicides was most pronounced in soil having higher organic carbon content. Koc values were as expected nearly identical for each herbicide in the two soils. The Freundlich constant (1/n) was about 1 for metolachlor and less than 1 for terbuthylazine and isoproturon indicating a L-type of sorption isotherms. Desorption of all the three herbicides showed hysteresis. Nearly equal amounts of metolachlor, isoproturon and terbuthylazine were desorbed from both soils. There was a good correlation between Koc and solubility.     

Phytoremediation of an aged petroleum contaminated soil using endophyte infected and non-infected grasses

Phytoremediation is a promising technique for cleaning petroleum contaminated soils. In this study, the effects of two grass species (Festuca arundinacea Schreb. and Festuca pratensis Huds.), infected (E(+)) and non-infected (E(-)) by endophytic fungi (Neotyphodium coenophialum and Neotyphodium uncinatum, respectively) on the degradation of petroleum hydrocarbons in an aged petroleum contaminated soil was investigated. Plants were grown in the soil for 7 months and unplanted soil considered as control. At the end of the experiment, total and oil-degrading bacteria, dehydrogenase activity, water-soluble phenols, total petroleum hydrocarbons (TPH) and polycyclic aromatic hydrocarbons (PAHs) contents were measured in the soil. The results demonstrated that E(+) plants contained more root and shoot biomass than E(-) plants and created higher levels of water-soluble phenols and dehydrogenase activity in the soil, while there was no significant difference in bacterial counts of planted soils. Planting stimulated total and oil-degrading bacterial numbers, dehydrogenase activity and the soil content of water-soluble phenols. Regardless of endophyte infection, PAH and TPH removal in the rhizosphere of plants were 80-84 and 64-72% respectively, whereas the removals in controls were 56 and 31%, respectively. It was revealed that TPHs in retention time range of n-alkanes with C(10)-C(25) chain lengths and TPH were more degraded in the rhizosphere of E(+) plants compared to E(-) ones. Thus, grasses infected with endophytic fungi could be more efficient for removal of TPH from oil-contaminated soils.     

Comparison of Microbial Pyrene and Benzo[a]Pyrene Mineralization in Liquid Medium,Soil Slurry,and Soil

The microbial degradation of ¹⁴C-pyrene and ¹⁴C-benzo[a]pyrene by a bacterial mixed culture was studied within a mixture of the PAHs phenanthrene, anthracene, pyrene, fluoranthene, and benzo[a]pyrene as sole carbon source in the different culture systems: (i) liquid medium, (ii) soil slurry (surface and grinding influence), and (iii) soil. The fate of these two labeled compounds was followed in these systems with an emphasis on mineralization to carbon dioxide, extractability, and adsorption to humic materials and formation of unextractable residual. Mineralization showed the most obvious differences: soil slurries achieved the best results both concerning the extent of mineralization and the time required. The highest extent of pyrene mineralization (54% within 21 days) was observed in soil slurries; in liquid media, pyrene mineralization was slower, but reached approximately the same extent (54% in 150 days); in soils, mineralization reached only 36% of added pyrene after 160 days. Benzo[a]pyrene was mineralized in a mixture of PAHs in soil slurries to an extent of 34% within 70 days, whereas mineralization in liquid medium and soil occurred in the range of 5% (70 days). Mineralization of benzo[a]pyrene in sand slurries was lower compared to soil slurries (19% in sand slurries vs. 32% in soil slurries within 50 days).     

Study on the possibility of hydrogen peroxide pretreatment and plant system to remediate soil pollution

Hydrogen peroxide was widely selected as the chemical oxidant in chemical remediation or as the donor of oxygen in in situ aerobic bioremediation of organic pollutants. In this paper, hydrogen peroxide pretreatment and plant system was done to examine its possibility to remediate the heavy metal contaminated soil or heavy metal-organic combined contaminated soil. Heavy metal contaminated soil was collected from the heavily industrialized area, in Fuyang county, Zhejiang province, China. And heavy metal-organic combined contaminated soil was prepared from the same contaminated soil by spiking 100 microg g(-1) 2,4-dichlorophenol (2,4-DCP). Results showed that H2O2 could improve the dissipation of 2,4-DCP and enhance the availability of Cu and Zn in soil. The greatly increased DOC (dissolved organic carbon) in the oxidation process was probably the main reason for the greatly increased water soluble Cu in higher pH condition. Water soluble Zn, however, easily rebound to soil components with the time being and had no positive relation with dissolved organic carbon. Planting with ryegrass influenced the behavior of pollutants in soil. It was observed that the dissipation of 2,4-DCP could be enhanced by the presence of plant roots and the availability of Cu and Zn in the planted soil was changed due to the mobilization and rebound mechanisms in the rhizosphere. Co-contamination of 2,4-DCP caused the greater availability of Cu and Zn in H2O2 pretreatment. But with the ryegrass planting, it was easier to rebound to the less available phase in the rhizosphere. Both Cu and Zn concentration in shoots increased with the H2O2 treatment. Therefore our results suggested that H2O2 pretreatment was probably a promising way for promoting the dissipation of persistent organic pollutants and enhancing the solubility of Cu and Zn in soil. A combination of H2O2 pretreatment and suitable plant might be an efficient alternative for remedying heavy metal or heavy metal-organic contaminated soil.     

Fate in soil of 14C-sulfadiazine residues contained in the manure of young pigs treated with a veterinary antibiotic

The fate of (14)C-labeled sulfadiazine ((14)C-SDZ) residues was studied in time-course experiments for 218 days of incubation using two soils (A(p) horizon of loamy sand, orthic luvisol; A(p) horizon of silt loam, cambisol) amended with fresh and aged (6 months) (14)C-manure [40 g kg(-1) of soil; 6.36 mg of sulfadiazine (SDZ) equivalents per kg of soil], which was derived from two shoats treated with (14)C-SDZ. Mineralization of (14)C-SDZ residues was below 2% after 218 days depending little on soil type. Portions of extractable (14)C (ethanol-water, 9:1, v/v) decreased with time to 4-13% after 218 days of incubation with fresh and aged (14)C-manure and both soils. Non-extractable residues were the main route of the fate of the (14)C-SDZ residues (above 90% of total recovered (14)C after 218 days). These residues were high immediately after amendment depending on soil type and aging of the (14)C-manure, and were stable and not remobilized throughout 218 days of incubation. Bioavailable portions (extraction using CaCl(2) solution) also decreased with increasing incubation period (5-7% after 218 days). Due to thin-layer chromatography (TLC), 500 microg of (14)C-SDZ per kg soil were found in the ethanol-water extracts immediately after amendment with fresh (14)C-manure, and about 50 microg kg(-1) after 218 days. Bioavailable (14)C-SDZ portions present in the CaCl(2) extracts were about 350 microg kg(-1) with amendment. Higher concentrations were initially detected with aged (14)C-manure (ethanol-water extracts: 1,920 microg kg(-1); CaCl(2) extracts: 1,020 microg kg(-1)), probably due to release of (14)C-SDZ from bound forms during storage. Consistent results were obtained by extraction of the (14)C-manure-soil samples with ethyl acetate; portions of N-acetylated SDZ were additionally determined. All soluble (14)C-SDZ residues contained in (14)C-manure contributed to the formation of non-extractable residues; a tendency for persistence or accumulation was not observed. SDZ's non-extractable soil residues were associated with the soluble HCl, fulvic acids and humic acids fractions, and the insoluble humin fraction. The majority of the non-extractable residues appeared to be due to stable covalent binding to soil organic matter.