Impact of pH buffer capacity of sediment on dechlorination of atrazine using zero valent iron

This research investigated the role of the pH buffer capacity of sediment on the dechlorination of atrazine using zero valent iron (ZVI). The buffer capacity of the sediment was quantified by batch experiments and estimated to be 5.0 cmol OH^? · pH^?1. The sediments were spiked with atrazine at 7.25-36.23 mg kg^?1 (6.21 × 10^?7–3.09 × 10^?6 mol atrazine · g^?1 sediment) for the batch experiments. The buffer capacity of the sediment maintained the sediment suspension at neutral pH, thereby enabling continuous dechlorination until the buffer capacity of the sediment was depleted. The pseudo-first order dechlorination constants were estimated to be in the range of 1.19 × 10^?2?7.04 × 10^?2 d^?1 for the atrazine-spiked sediments.     

Rapid reductive dechlorination of atrazine by zero-valent iron under acidic conditions

The dechlorination of atrazine (2-chloro-4-ethylamino-6-isopropylamino-1,3,5-triazine) via reaction with metallic iron under low-oxygen conditions was studied using reaction mixture pH values of 2.0, 3.0, and 3.8. The pH control was achieved through addition of sulfuric acid throughout the duration of the reaction. The lower the pH of the reaction mixture, the faster the degradation of atrazine. The surface area of the sulfuric acid-treated iron particles was 0.31 (+/- 0.01) m2 g-1 and the surface area normalized initial pseudo-first order rate constants (kSA, where rate = kSA x (surface area/l) x [Atrazine]) at pH values of 2.0, 3.0, and 3.8 were equal to, respectively, 3.0 (+/- 0.4) x 10(-3) min-1 m-2 l, 5 (+/- 3) x 10(-4) min-1 m-2 l, and 1 (+/- 1) x 10(-4) min-1 m-2 l. The observed products of the degradation reaction were dechlorinated atrazine (2-ethylamino-4-isopropylamino-1,3,5-triazine) and possibly hydroxyatrazine (2-ethylamino-4-isopropylamino-6-hydroxy-s-triazine). Triazine ring protonation may account, at least in part, for the observed effect of pH on atrazine dechlorination via metallic iron.     

Degradation of terbutylazine (2-chloro-4-ethylamino-6-terbutylamino-1,3,5-triazine), deisopropyl atrazine (2-amino-4-chloro-6-ethylamino-1,3,5-triazine), and chlorinated dimethoxy triazine (2-chloro-4,6-dimethoxy-1,3,5-triazine) by zero valent iron and electrochemical reduction

To help elucidate the mechanism of dechlorination of chlorinated triazines via metallic iron, terbutylazine (TBA: 2-chloro-4-ethylamino-6-terbutylamino-1,3,5-triazine), deisopropyl atrazine (DIA: 2-amino-4-chloro-6-ethylamino-1,3,5-triazine), and chlorinated dimethoxy triazine (CDMT: 2-chloro-4,6-dimethoxy-1,3,5-triazine) were degraded via zero valent iron under controlled pH conditions. The lower the solution pH the faster the degradation, with surface area normalized pseudo first order rate constants ranging from 2 (+/- 1)x10(-3) min(-1) m(-2) l for TBA at pH 2.0 to 4 (+/- 2)x10(-5) min(-1) m(-2) l for CDMT at pH 4.0. Hydrogenolysis (dechlorinated) products were observed for TBA and CDMT. Electrochemical reduction on mercury showed similar behavior for all of the triazines studied; the initial product of CDMT bulk electrolysis was the dechlorinated compound. The iron results are consistent with a mechanism involving the addition of surface hydrogen to the surface associated triazine.     

Effect of surfactants at low concentrations on the sorption of atrazine by natural sediment.

A series of experiments were carried out to determine the effect of surfactants at low concentrations on the sorption of atrazine by natural sediments. With surfactant concentrations ranging from 0 to 20 mg/ L, anionic and cationic surfactants appreciably reduce the adsorption of atrazine, while nonionic surfactant decreases the adsorption of atrazine at concentrations equal to or less than 1 mg/L and increases adsorption at higher concentrations. Desorption of atrazine in the presence of different sodium dodecylbenzene sulfonate (SDBS) concentrations shows that a portion of the bound pesticide resists desorption in the SDBS free system. However, the addition of SDBS accelerates the desorption of atrazine. Furthermore, the nature of sediment and the contacting sequence of SDBS, at 10 mg/L, with the sediment, also influence the adsorption of atrazine. The conclusions in this study could be explained partially by the effect of the type and concentration of surfactants and the characteristics of sediments.     

Anaerobic transformation of chlorophenols in methanogenic sludge unexposed to chlorophenols

Transformation of all 19 chlorophenol (CP) isomers was investigated in a laboratory anaerobic methanogenic sludge that had not been exposed to synthetic chemicals. Concentration of CP was analyzed over time to calculate disappearance rate constants using first-order reaction kinetics and all possible CP degradation pathways were estimated. The rate constants ranged between 0.46 x 10(-3) and 0.161 day(-1). CPs were transformed via dechlorination. The chlorine atom at the ortho-position was the most easily dechlorinated, whereas dechlorination rate at the para-position was lowest. The overall pathways of CP transformation were much less diverse than that we previously found for contaminated sediment. The Dolfing hypothesis of microbial selection of the most thermodynamically favorable pathways was not applicable for CP transformation in this study as well as previous study performed by our group.     

Experimental in situ chemical peroxidation of atrazine in contaminated soil

Lab-scale experiments of in situ chemical oxidation (ISCO), were performed on soil contaminated with 100 mg kg(-1) of atrazine (CIET). The oxidant used was hydrogen peroxide catalysed by naturally occurring minerals or by soluble Fe(II) sulphate, added in aqueous solution. The oxidation conditions were: CIET:H2O2=1:1100, 2 PV or 3 PV reaction volume, Fe(II):H2O2=0, 1:22, 1:11. Stabilized (with KH2PO4 at a concentration of 16 g l(-1)) or non-stabilized hydrogen peroxide was used. The pH of the reagents was adjusted to pH=1 with sulphuric acid, or was not altered. Results showed that the addition of soluble Fe(II) increased the temperature of the soil slurry and the use of stabilized hydrogen peroxide resulted in a lower heat generation. The treatment reduced the COD of the soil of about 40%, pH was lowered and natural organic matter became less hydrophobic. The highest atrazine conversion (89%) was obtained in the conditions: 3 PV, Fe(II):H2O2=1:11 with stabilized hydrogen peroxide added in two steps. The stabilizer only increased H2O2 life-time significantly when soluble Fe(II) was added. Results indicate as preferential degradation pathway of atrazine in soil dechlorination instead of dealkylation.     

Sorption of atrazine and phenanthrene by organic matter fractions in soil and sediment

Atrazine and phenanthrene (Phen) sorption by nonhydrolyzable carbon (NHC), black carbon (BC), humic acid (HA) and whole sediment and soil samples was examined. Atrazine sorption isotherms were nearly linear. The single-point organic carbon (OC)-normalized distribution coefficients (K_OC) of atrazine for the isolated HA1, NHC1 and BC1 from sediment 1 (ST1) were 36, 550, and 1470 times greater than that of ST1, respectively, indicating the importance of sediment organic matter, particularly the condensed fractions (NHC and BC). Similar sorption capacity of atrazine and Phen by NHC but different isotherm nonlinearity indicated different sorption domains due to their different structure and hydrophobicity. The positive relationship between (O + N)/C ratios of NHC and atrazine log K_OC at low concentration suggests H-bonding interactions. This study shows that sediment is probably a less effective sorbent for atrazine than Phen, implying that atrazine applied in sediments or soils may be likely to leach into groundwater.     

Reductive dechlorination of polychlorinated biphenyls as affected by sediment characteristics

The effect of sediment sources on the selection of polychlorinated biphenyl (PCB) dechlorinating competence was investigated using sediments from two different locations, the Grasse River and Owasco Lake. These two sediments had a similar organic carbon content but different particle size distribution. The two PCB-free sediments were spiked with Aroclor 1248 and inoculated with microorganisms from the Reynolds and General Motors sites in the St. Lawrence River, which exhibited different dechlorination patterns. When each inoculum was serially transferred into fresh sediments four times (every 8-10 weeks), they still maintained the initial dechlorination patterns regardless, the source of sediments and the number of transfers, and dechlorination patterns of the two inocula in the same sediments did not converge. In a parallel approach, when the acclimated microorganisms from the Reynolds site were inoculated into fresh sediments from both sources as well as sediments enriched with organic carbon (2%, w/v), the dechlorination pattern remained unchanged after a 40-week incubation. These results suggest that the sediment characteristics or organic carbon content did not play a role in the selection of dechlorinating populations.     

Dehalogenation of 2,6-dibromobiphenyl and 2,3,4,5,6-pentachlorobiphenyl in contaminated estuarine sediment

Estuarine sediments from a USEPA Superfund site in coastal Georgia were extensively contaminated with Aroclor 1268, a mixture of highly chlorinated polychlorinated biphenyls used by a former chlor-alkali plant. Batch slurries of contaminated sediment were incubated for 1 yr with amendments of 2,6-dibromobiphenyl (26-BB) and 2,3,4,5,6-pentachlorobiphenyl (23456-CB) under anaerobic, sulfate-reducing conditions and different pH (5.5-7.5). Organic extracts of slurry sub-samples in a time series were analyzed by congener-specific GC-MS. Dechlorination of 23456-CB was pH dependent and occurred via two routes with the sequential loss of (1) meta and para chlorines and (2) para, ortho, and meta chlorines. Quantitative dehalogenation of 26-BB was observed at all pH. Supplementation of nonachlorobiphenyls (as primers) did not induce dechlorination of native Aroclor 1268 nor of the primers themselves. While contaminated estuarine sediments possess microbial consortia with diverse dehalogenating activities, lack of dechlorination of Aroclor 1268 and spiked nonachlorobiphenyl congeners suggests a bioavailability limitation or enzyme-substrate incompatibilities.     

Batch and column studies of the stabilization of toxic heavy metals in dredged marine sediments by hematite after bioremediation

The management of dredged sediments is an important issue in coastal regions where the marine sediments are highly polluted by metals and organic pollutants. In this paper, mineral-based amendments (hematite, zero-valent iron and zeolite) were used to stabilize metallic pollutants (As, Cd, Cu, Mo, Ni, Pb, and Zn) in a contaminated marine sediment sample. Mineral-based amendments were tested at three application rates (5 %, 10 %, and 15 %) in batch experiments in order to select the best amendment to perform column experiments. Batch tests have shown that hematite was the most efficient amendment to stabilize inorganic pollutants (As, Cd, Cu, Mo, Ni, Pb, and Zn) in the studied sediment. Based on batch tests, hematite was used at one application rate equal to 5 % to conduct column experiments. Column tests confirmed that hematite was able to decrease metal concentrations in leachates from stabilized sediment. The stabilization rates were particularly high for Cd (67 %), Mo (80 %), and Pb (90 %). The Microtox solid phase test showed that hematite could decrease significantly the toxicity of stabilized sediment. Based on batch and column experiments, it emerged that hematite could be a suitable adsorbent to stabilize metals in dredged marine sediment.     

Biotransformation and antioxidant enzymes of Lumbriculus variegates as biomarkers of contaminated sediment exposure

In this study the black worm Lumbriculus variegatus was tested for suitability as biomonitor for moderately contaminated sediments. The response capacity of the biotransformation system phase II enzyme glutathione-S-transferase (GST) and the oxidative defense enzyme catalase (CAT) to contaminated sediment and atrazine was investigated to establish them as sensitive biomarkers. To get an integrated view on the enzyme activity kinetics, increasing concentrations of the herbicide atrazine were applied to stimulate GST response, and relationship between enzyme activity and herbicide concentration was observed at various exposure durations. Furthermore, animals were exposed for up to 1 week to sediments of four typical urban river sections with high anthropogenic impact. L. variegatus was capable to accomplish the environmental stress and the selected enzymes showed elevation. Significant changes of GST (membrane-bound and soluble) were detected after at least 4 days of exposure to atrazine and contaminated sediments. Although CAT increase could be observed already after 1 day of exposure to sediments, an exposure time of one week is considerable for accurate interpretation of the enzymatic response. The clear enzymatic response of especially the membrane-bound GST indicated charges with organic lipophilic substances at all sampling sites.     

Interactions of sodium azide with triazine herbicides: effect on sorption to soils

Sodium azide (NaN(3)) is one of the biocides commonly used to inhibit microbial growth during sorption experiments. However, a few reports have suggested that NaN(3) can react with the analyte of interest. In this study, the interactions of NaN(3) with triazine herbicides were investigated and the effect of atrazine transformation on its sorption to soil was evaluated. The concentration of atrazine in the presence of NaN(3) decreased significantly over period of time. After 14 days, only 38% of the initial atrazine concentration (10 mg l(-1)) was detected in a solution containing 1,000 mg l(-1) NaN(3) at pH 5.5. The magnitude and the rate of atrazine transformation increased with increase in NaN(3) load and with decrease in pH. In contrast to atrazine behavior, the concentrations of prometon and ametryn did not change during the experiment. GC/MS analysis indicated that the chlorine atom of atrazine is replaced by the azide group yielding 2-azido-4-(ethylamino)-6-(isopropylamino)-s-triazine. Atrazine transformation by NaN(3) significantly affected sorption of herbicide to soil. The presence of NaN(3) affects indirectly the sorption of atrazine due to competitive effect of its derivative. Our results demonstrated that the application of NaN(3) as a biocide in sorption-desorption experiments must be carefully evaluated. This issue is vital for sorption experiments conducted over long periods of time or/and with concentration of NaN(3) higher than 100 mg l(-1).     

Constructed wetlands for mitigation of atrazine-associated agricultural runoff

Atrazine was amended into constructed wetlands (59-73x14x0.3 m) for the purpose of monitoring transport and fate of the pesticide to obtain information necessary to provide future design parameters for constructed wetlands mitigation of agricultural runoff. Following pesticide amendment, a simulated storm and runoff event equal to three volume additions was imposed on each wetland. Targeted atrazine concentrations were 0 microg/l (unamended control), 73 microg/l, and 147 microg/l. Water, sediment, and plant samples were collected weekly for 35 days from transects longitudinally distributed throughout each wetland and were analyzed for atrazine using gas chromatography. Between 17 and 42% of measured atrazine mass was within the first 30-36 m of wetlands. Atrazine was below detection limits (0.05 microg/kg) in all sediment and plant samples collected throughout the duration of this study. Aqueous half lives ranged from 16 to 48 days. According to these data, conservative buffer travel distances of 100-280 m would be necessary for effective runoff mitigation.     

Sorption of Cr(VI) from dilute solutions and wastewater by live and pretreated biomass of Aspergillus flavus

Sorption of Cr(VI) was carried out from dilute solutions using live and pretreated biomass in a batch mode. Effects of agitation time, adsorbent dosage and pH were examined. The autoclaved biomass that showed maximum adsorption capacity (Q(0)=0.335 mg g(-1)) was used as an adsorbent in column studies. The optimized flow rate of 2.5 ml min(-1) and bed height 10 cm were used to determine the effect of metal ion concentration on removal of Cr(VI). Applying the BDST model to calculate the adsorption capacity (N(0)) of column, which showed 4.56 x 10(-5), 7.28 x 10(-5), 6.89 x 10(-5), 3.07 x 10(-5), 2.80 x 10(-5)mg g(-1) for 4, 8, 12, 16 and 20 mg dm(-3) of Cr(VI), respectively. Batch sorption proved to be more efficient than the column sorption and hence batch sorption was used to remove Cr(VI) from a textile dyeing industry wastewater. The phytotoxic effect of treated and untreated wastewater was studied against Zea mays. Toxicity was reduced by 50% in the treated effluent.     

Sorption of imidazolium-based ionic liquids to aquatic sediments

Ionic liquids (ILs) have received much attention as "green" alternatives to traditional solvents because they do not evaporate, eliminating concerns over fugitive emissions. However, if ionic liquids are used in industrial applications, they may enter aquatic systems via effluent, and their fate and transport may be influenced by sorption to sediments. In this study, we conducted batch mixing experiments with four alkylmethylimidizolium-based ILs and four types of aquatic sediments to asses the capacity for natural aquatic sediments to remove these chemicals from the water column. The concentration isotherms were non linear with point estimates of the distribution coefficient (K(d)) decreasing with increasing concentration. Apparent distribution coefficients ranged from 7.9 to 95.7l kg(-1) at an initial concentration of 0.5mM and were positively related to sediment organic matter (SOM) content. These K(d) values indicate that the ILs did not sorb strongly to the tested sediments. Increased alkyl chain length did not lead to increased sorption suggesting that hydrophobic interactions were not the most important sorption mechanism. We conclude that aquatic sediments have a limited capacity to sorb alkylmethylimidazolium ILs and that the transport of these contaminants in aquatic systems will not be strongly attenuated by sediments.     

Particle-size-fractioned transfer of dioxins from sediments to water columns by resuspension process

Particle-size-fractioned transfer of dioxins from sediments to water columns by resuspension process was investigated, using supernatant samples obtained from shaking experiments of sediment-water pairs simulating natural disturbances. The concentrations (dry-matter mass basis) of individual compounds (Cfraction) in two particle size fractions (0.1-1 and 1-10 μm) in the supernatants were generally slightly higher than those in the original sediment (Csed). Cfraction/Csed ratios ranged from 0.45 to 5.9 (median 1.5) without consistent differences among congener groups or consistent correlations against the number of chlorine atoms. The dioxin concentrations in the water column associated with the remaining sediment particles can therefore be estimated by those in the original sediment and by the concentration of suspended sediment particles in the water. The concentration of each compound in the remaining sediment particles (mostly 0.1-10 μm in size) can be roughly estimated by multiplying the concentration in the original sediment by 1.5.     

Microbial dechlorination of 2,4,6-trichlorophenol in anaerobic sewage sludge

The dechlorination of 2,4,6-trichlorophenol (TCP) in municipal sewage sludge with a chlorophenol (CP)-adapted consortium was investigated. Results show that dechlorination rates differed according to the source of the sludge samples used in the batch experiments. No significant differences in 2,4,6-TCP dechlorination were observed following treatment with inoculum at densities ranging from 10% to 50% (V/V), but a significant delay was noted at 5% (V/V) density. Overall, results show that the higher the 2,4,6-TCP concentration, the slower the dechlorination rate. The addition of acetate, lactate, pyruvate, vitamin B12 or manganese dioxide did not results in a significant change in 2,4,6-TCP dechlorination. Data collected from a bioreactor experiment revealed that pH 7.0 and a total solid concentration of 10 g/L were optimal for dechlorination. Dechlorination rates decreased significantly at higher agitation speeds. 2,4,6-TCP dechlorination was enhanced under methanogenic conditions, but it was inhibited under denitrifying and sulfate-reducing conditions.     

Pesticide storage and release in unsaturated soil in Illinois, USA.

The chemical fate and movement of pesticides may be subject to transient storage in unsaturated soils during periods of light rainfall, and subsequent release into shallow groundwater by increased rainfall. The objective of this study was to conduct field-scale experiments to determine the relative importance of transient storage and subsequent release of agrichemicals from the vadose zone into potential aquifers. Two field-scale experiments were conducted under a rain exclusion shelter. In the 1x experiment, atrazine and chlorpyrifos were applied at application-rate equivalents (1.6 kg ha(-1) and 1.3 kg ha(-1), respectively). In the 4x experiment, atrazine was applied in an amount that was four times greater than that usually applied to fields (6.7 kg ha(-1)). Water was either applied to simulate rain or withheld to simulate dry periods. In the 1x experiment, atrazine was detected in the water samples whereas chlorpyrifos was not detected in the majority of the samples. The dry period imposed on the treatment plot did not appear to result in storage of the chemicals, whereas the wet period resulted in greater leaching of atrazine, although the concentrations remained less than the Maximum Contaminant Level of 3 microg L(-1). Both chemicals were detected in soil samples collected from a 20- to 30-cm depth, but it appeared that both chemicals dissipated before the field experiment was concluded. It appeared that the one-time application of atrazine and chlorpyrifos at the label rates did not result in a sufficient mass to be stored and flushed in significant concentrations to the saturated zone. When atrazine was applied at 4x and a longer drought period was imposed on the treatment plot, the resulting concentrations of dissolved atrazine were still less than 3 microg L(-1) . Atrazine was detected in only the near-surface (0 to 15 cm) soil samples and the herbicide dissipated before the onset of the dry period in the treatment plot. The results of this field study demonstrated that atrazine and chlorpyrifos were not sufficiently persistent to be stored and then released in significantly large concentrations to the saturated zone. The dissipation half-life of atrazine in the 4x application was about 44 days. This study, in addition to others, suggested that atrazine may be less persistent in surface soil than has been generally reported.     

Biodegradation of coplanar polychlorinated biphenyls by anaerobic microorganisms from estuarine sediments.

In this study, we investigated the biodegradability of biphenyl and 5 congeners (one non-planar and four coplanar) of polychlorinated biphenyl (PCB). Biphenyl, the non-planar congener 2,3',4',5-tetrachlorobiphenyl (25-34 CB), and the four coplanar congeners 3,3',4,4'-tetrachlorobiphenyl (34-34 CB), 3,4,4',5-tetrachlorobiphenyl (345-4 CB), 3,3',4,4',5-pentachlorobiphenyl (345-34 CB), and 3,3',4,4',5,5'-hexachlorobiphenyl (345-345 CB) were amended at a concentration of 10 mg/L into anoxic sediment slurries collected from the estuaries of the Tansui River and the Erjen River. During 2 years' incubation under sulfidogenic conditions, biphenyl was persistent, while all other chlorinated congeners, except for 345-345 CB, were dechlorinated with or without a lag period in sediment slurries collected from both rivers. Dechlorination of coplanar and non-planar congeners began with para chlorine removal. All para chlorines from the mono-, di-, and trichlorobiphenyl groups could be removed by sediment slurries from both rivers. Microbial communities in sediment from the Erjen River additionally fostered meta-dechlorination activity, but only after removal of all the para chlorines. Addition of Tween 20 (0.05%, v/v) into sediment slurries from the Tansui River did not enhance dechlorination rates or extents, but the addition of toluene- or 3-chlorobenzoate-adapted sediments enhanced dechlorination of 34-34 CB and 345-4 CB.     

Formation pathways of polychlorinated dibenzofurans (PCDFs) in sediments contaminated with PCBs during the thermal desorption process

Thermal desorption has attracted considerable interest as a remediation technology for the removal of dioxins and polychlorinated biphenyls (PCBs) from contaminated soils and sediments. Although several research groups have confirmed that polychlorinated dibenzofurans (PCDFs) are formed from PCBs during the thermal desorption of sediments contaminated with PCB, the formation pathways remain poorly understood. Herein, thermal desorption has been used to develop a greater understanding of the formation pathways of PCDFs from sediments contaminated with PCBs. PCB decomposition experiments of sediments contaminated with PCBs were performed over 5 min at 450 °C with a gas composition of 10% O(2)/90% N(2), either in the absence (Run 1) or presence (Run 2-4) of one of three different (13)C(12)-labeled PCB individual standards. The results of Run 1 showed that 99.96% of PCBs and 98.40% of polychlorinated dibenzo-p-dioxins (PCDDs) in the treated sediments had decomposed, whereas the concentration levels of PCDFs had increased by a factor of 31. The addition of different (13)C(12)-labeled PCBs to the sediment sample yielded different (13)C(12)-PCDFs isomer patterns, with formation pathways including loss of ortho-Cl(2), loss of HCl involving a 2,3-chlorine shift, loss of ortho-H(2) and dechlorination.