Herbicide Leaching on a Recharge Area of the Guarany Aquifer in Brazil

Abstract

The region of Ribeirão Preto City, located in Southeast of Brazil, São Paulo State, is an important sugarcane, soybean, and corn producing area with a high level of pesticides utilization. This region is also an important recharge area for groundwater supply of the Guarany aquifer. Since the past ten years atrazine, simazine, ametryn, tebuthiuron, diuron, 2,4-D, picloram, and hexazinone are the main herbicides used in this area. In order to study a possible leaching of some of these herbicides into the aquifer, surface, and groundwater samples were collected in a watershed during the years of 1996 to 2003, from different locations. To detect and quantify the herbicides a GC-MS (gas chromatograph/mass spectrometry) method was used. The response of the herbicides analyzed was linear over the concentration range of 0.02 to 2.0 μg/L. Analysis of groundwater revealed that the herbicides tebuthiuron, diuron, atrazine, simazine, and ametryn were not present in the samples. In the surface water collected in 1997, ametryn was present in two out of nine locations with concentrations ranging from 0.17 and 0.23 μg/L, which is above the allowable 0.1 μg/L according to the European safety level. The leaching potential of tebuthiuron, diuron, atrazine, simazine, 2,4-D, picloram, and hexazinone has been evaluated using CMLS-94, “Chemical Movement in Layered Soil,” as simulation model. No leaching into the depth of the water table at 40 m was found.     

Herbicide leaching on a recharge area of the Guarany aquifer in Brazil

The region of Ribeir?o Preto City, located in Southeast of Brazil, S?o Paulo State, is an important sugarcane, soybean, and corn producing area with a high level of pesticides utilization. This region is also an important recharge area for groundwater supply of the Guarany aquifer. Since the past ten years atrazine, simazine, ametryn, tebuthiuron, diuron, 2,4-D, picloram, and hexazinone are the main herbicides used in this area. In order to study a possible leaching of some of these herbicides into the aquifer, surface, and groundwater samples were collected in a watershed during the years of 1996 to 2003, from different locations. To detect and quantify the herbicides a GC-MS (gas chromatograph/mass spectrometry) method was used. The response of the herbicides analyzed was linear over the concentration range of 0.02 to 2.0 microg/L. Analysis of groundwater revealed that the herbicides tebuthiuron, diuron, atrazine, simazine, and ametryn were not present in the samples. In the surface water collected in 1997, ametryn was present in two out of nine locations with concentrations ranging from 0.17 and 0.23 microg/L, which is above the allowable 0.1 microg/L according to the European safety level. The leaching potential of tebuthiuron, diuron, atrazine, simazine, 2,4-D, picloram, and hexazinone has been evaluated using CMLS-94, "Chemical Movement in Layered Soil," as simulation model. No leaching into the depth of the water table at 40 m was found.     

Sorption and mass fluxes of sulfonated naphthalene formaldehyde condensates in aquifers

Sulfonated naphthalene formaldehyde condensates (SNFC) and their monomeric analogues were used as superplasticizers for cement suspension injections at two tunnel construction sites that are in direct contact with groundwater. Because in one case the aquifer is an important drinking water resource, the behavior of SNFC in the groundwater was carefully investigated. Chemical analyses showed that SNFC leached to the groundwater in concentrations of up to 58 microg/l of total SNFC at a distance of about 60 m down-gradient from the construction site. Of the individual SNFC components, only monomers and oligomers with up to four units could be detected in the groundwater. Oligomers with more than four units did not leach from the cement paste. The leached oligomers were transported in the groundwater at different velocities, which can be explained by sorption experiments. Mass fluxes of SNFC used at the tunnel construction sites were evaluated. Most SNFC were immobilized in the cement, but 5% (w/w) of the applied SNFC were found to leach into the aquifer. This corresponds to a total amount of leached SNFC of approximately 100 kg, of which about 80% are biodegraded in the aquifer and 20% (20 kg) still remain in the groundwater.     

Multivariate analysis of photo-Fenton degradation of the herbicides tebuthiuron, diuron and 2,4-D

The degradation of herbicides in aqueous solution by photo-Fenton process using ferrioxalate complex (FeOx) as source of Fe2+ was evaluated under blacklight irradiation. The commercial products of the herbicides tebuthiuron, diuron and 2,4-D were used. The multivariate analysis, more precisely, the response surface methodology was applied to evaluate the role of FeOx and hydrogen peroxide concentrations as variables in the degradation process, and in particular, to define the concentration ranges that result in the most efficient degradation of the herbicides. The degradation process was evaluated by the determination of the remaining total organic carbon content (TOC), by monitoring the decrease of the concentrations of the original compounds using HPLC and by the chloride ion release in the case of diuron and 2,4-D. Under optimized conditions, 20 min were sufficient to mineralize 93% of TOC from 2,4-D and 90% of diuron, including oxalate. Complete dechlorination of these compounds was achieved after 10 min reaction. It was found that the most recalcitrant herbicide is tebuthiuron, while diuron shows the highest degradability. However, under optimized conditions the initial concentration of tebuthiuron was reduced to less than 15%, while diuron and 2,4-D were reduced to around 2% after only 1 min reaction. Furthermore, it was observed that the ferrioxalate complex plays a more important role than H2O2 in the photodegradation of these herbicides in the ranges of concentrations investigated.     

Effects of sewage sludge amendments on pesticide sorption and leaching through undisturbed Mediterranean soils

The Gharb region in Morocco is an important agricultural zone where soils receive pesticide treatments and organic amendments to increase yields. The groundwater aquifer in the Gharb region is relatively shallow and thus vulnerable. The objective of this work was to study the influence of organic amendments on diuron, cyhalofop-butyl and procymidone leaching through undisturbed soil columns. Two soils were sampled from the Gharb region, a Dehs (sandy soil) and a R'mel (loamy clay soil). Following elution (124.5 mm), the amount of pesticide residues in the leachates of the sandy soil (0.06-0.21 %) was lower than in those of the loamy clay soil (0.20-0.36 %), which was probably due to preferential flow through the loamy clay soil. The amount of procymidone leached through the amended soil columns was greater than the control for the sandy soil only. The organic amendments did not significantly influence diuron and cyhalofop-butyl leaching in either of the soils. The application of organic amendments affected the amounts of dissolved organic matter (DOM) eluted and thus pesticide leaching as a function of soil-type. Nevertheless, in some case, the formation of pesticide-DOM complexes appeared to promote pesticide leaching, thus increasing groundwater contamination risks.     

Effects of sewage sludge amendments on pesticide sorption and leaching through undisturbed Mediterranean soils

The Gharb region in Morocco is an important agricultural zone where soils receive pesticide treatments and organic amendments to increase yields. The groundwater aquifer in the Gharb region is relatively shallow and thus vulnerable. The objective of this work was to study the influence of organic amendments on diuron, cyhalofop-butyl and procymidone leaching through undisturbed soil columns. Two soils were sampled from the Gharb region, a Dehs (sandy soil) and a R’mel (loamy clay soil). Following elution (124.5 mm), the amount of pesticide residues in the leachates of the sandy soil (0.06–0.21 %) was lower than in those of the loamy clay soil (0.20–0.36 %), which was probably due to preferential flow through the loamy clay soil. The amount of procymidone leached through the amended soil columns was greater than the control for the sandy soil only. The organic amendments did not significantly influence diuron and cyhalofop-butyl leaching in either of the soils. The application of organic amendments affected the amounts of dissolved organic matter (DOM) eluted and thus pesticide leaching as a function of soil-type. Nevertheless, in some case, the formation of pesticide-DOM complexes appeared to promote pesticide leaching, thus increasing groundwater contamination risks.     

Leaching of oryzalin and diuron through undisturbed vineyard soil columns under outdoor conditions

Field studies monitoring herbicide pollution in the vineyards of Burgundy (France) have revealed that drinking water reservoirs are contaminated with several pre-emergence herbicides. An assessment of the leaching of two such herbicides, diuron and oryzalin, was therefore performed using lysimeters, under outdoor conditions, from May 2001 to May 2002. Four vineyard soils from Vosne-Romanée (Burgundy) were chosen along a topolithosequence: a rendosol and three calcosols. After 673 mm of rainfall, greater amounts of diuron than oryzalin were measured in percolates: respectively 0.10-0.84% and 0.02-0.43% of applied herbicide, depending on soils. Measurements for diuron metabolites detected greater amounts of DCPMU than DCPU in the percolates: respectively 0.05-0.13% and 0-0.04% of the applied diuron. At the end of the monitoring period, more residues of diuron than oryzalin were recovered in the soil profiles: respectively 4.6-9% and 1.4-4.4%. The oryzalin residues were found mainly in the upper 10 cm of soil columns, whereas diuron residues were present in the whole core. The mobility of both oryzalin and diuron seems fairly well-related to soil organic carbon content; the mobility of diuron is also related to soil texture (sand and coarse material contents). Under such experimental conditions, this study confirms that diuron leaching, and therefore potential groundwater contamination, is greater than that of oryzalin.     

Transport of Escherichia coli and solutes during waste water infiltration in an urban alluvial aquifer

Recharge of waste water in an unconsolidated poorly sorted alluvial aquifer is a complex process, both physically and hydrochemically. The aim of this paper is to analyse and conceptualise vertical transport mechanisms taking place in an urban area of extensive wastewater infiltration by analysing and combining the water balance, the microbial (Escherichia coli) mass balance, and the mass balance for dissolved solutes. For this, data on sediment characteristics (grain size, organic carbon, reactive iron, and calcite), groundwater levels, and concentrations of E. coli in groundwater and waste water were collected. In the laboratory, data on E. coli decay rate coefficients, and on bacteria retention characteristics of the sediment were collected via column experiments. The results indicated that shallow groundwater, at depths of 50 m below the surface, was contaminated with E. coli concentrations as high as 10(6) CFU/100 mL. In general, E. coli concentrations decreased only 3 log units from the point of infiltration to shallow groundwater. Concentrations were lower at greater depths in the aquifer. In laboratory columns of disturbed sediments, bacteria removal was 2-5 log units/0.5 cm column sediment. Because of the relatively high E. coli concentrations in the shallow aquifer, transport had likely taken place via a connected network of pores with a diameter large enough to allow bacterial transport instead of via the sediment matrix, which was inaccessible for bacteria, as was clear from the column experiments. The decay rate coefficient was determined from laboratory microcosms to be 0.15 d(-1). Assuming that decay in the aquifer was similar to decay in the laboratory, then the pore water flow velocity between the point of infiltration and shallow groundwater, coinciding with a concentration decrease of 3 log units, was 0.38 m/d, and therefore, transport in this connected network of pores was fast. According to the water balance of the alluvial aquifer, determined from transient groundwater modelling, groundwater flow in the aquifer was mainly in vertical downward direction, and therefore, the mass balance for dissolved solutes was simulated using a 1D transport model of a 200 m column of the Quaternary Alluvium aquifer. The model, constructed with PHREEQC, included dual porosity, and was able to adequately simulate removal of E. coli, cation-exchange, and nitrification. The added value of the use of E. coli in this study was the recognition of relatively fast transport velocities occurring in the aquifer, and the necessity to use the dual porosity concept to investigate vertical transport mechanisms. Therefore, in general and if possible, microbial mass balances should be considered more systematically as an integral part of transport studies.     

Degradation and leaching of the herbicides metolachlor and diuron: a case study in an area of Northern Italy

In this work the degradation of the herbicides metolachlor, diuron, monuron and of the metabolites 2-ethyl-6-methylaniline (EMA), and 3,4-dichloroaniline (DCA) was assessed in laboratory experiments on microbiologically active and sterilized soils. Their leaching potentials were calculated, using Gustafson's equation, by determining their mobility (as Koc) and persistence (expressed as DT50). Lysimeter experiments were also conducted to assess the actual leaching of the studied herbicides in a cereal crop tillage area vulnerable to groundwater contamination. The data obtained from the field were compared to the laboratory results. Moreover, some compounds of particular concern were searched for in the groundwater located near the experimental area in order to evaluate actual contamination and to test the reliability of the leaching potential. The GUS index, computed on data from microbiologically active soil, shows monuron as a leacher compound, EMA and DCA as non-leachers, metolachlor and diuron as transient ones. The presence of metolachlor in the groundwater monitored, even at concentrations up to 0.1 mug/l, confirms the possibility that transient compounds can be leached if microbial activity has not completely occurred in active surface soil.     

Temporal variability of groundwater chemistry in shallow and deep aquifers of Araihazar, Bangladesh

Samples were collected every 2-4 weeks from a set of 37 monitoring wells over a period of 2-3 years in Araihazar, Bangladesh, to evaluate the temporal variability of groundwater composition for As and other constituents. The monitoring wells are grouped in 6 nests and span the 5-91 m depth range. Concentrations of As, Ca, Fe, K, Mg, Mn, Na, P, and S were measured by high-resolution ICPMS with a precision of 5% or better; concentrations of Cl were measured by ion chromatography. In shallow wells <30 m deep, As and P concentrations generally varied by <30%, whereas concentrations of the major ions (Na, K, Mg, Ca and Cl) and the redox-sensitive elements (Fe, Mn, and S) varied over time by up to +/-90%. In wells tapping the deeper aquifers >30 m often below clay layers concentrations of groundwater As were much lower and varied by <10%. The concentrations of major cations also varied by <10% in these deep aquifers. In contrast, the concentration of redox-sensitive constituents Fe, S, and Mn in deep aquifers varied by up to 97% over time. Thus, strong decoupling between variations in As and Fe concentrations is evident in groundwaters from shallow and deep aquifers. Comparison of the time series data with groundwater ages determined by (3)H/(3)He and (14)C dating shows that large seasonal or inter-annual variations in major cation and chloride concentrations are restricted to shallow aquifers and groundwater recharged <5 years ago. There is no corresponding change in As concentrations despite having significant variations of redox sensitive constituents in these very young waters. This is attributed to chemical buffering due to rapid equilibrium between solute and solid As. At two sites where the As content of groundwater in existing shallow wells averages 102 microg/L (range: <5 to 648 microg/L; n=118) and 272 microg/L (range: 10 to 485 microg/L; n=65), respectively, a systematic long-term decline in As concentrations lends support to the notion that flushing may slowly deplete an aquifer of As. Shallow aquifer water with >5 years (3)H/(3)He age show a constant As:P molar ratio of 9.6 over time, suggesting common mechanisms of mobilization.     

Hydraulic constraints on the performance of a groundwater denitrification wall for nitrate removal from shallow groundwater

Denitrification walls are a practical approach for decreasing non-point source pollution of surface waters. They are constructed by digging a trench perpendicular to groundwater flow and mixing the aquifer material with organic matter, such as sawdust, which acts as a carbon source to stimulate denitrification. For efficient functioning, walls need to be permeable to groundwater flow. We examined the functioning of a denitrification wall constructed in an aquifer consisting of coarse sands. Wells were monitored for changes in nitrate concentration as groundwater passed through the wall and soil samples were taken to measure microbial parameters inside the wall. Nitrate concentrations upstream of the wall ranged from 21 to 39 g N m(-3), in the wall from 0 to 2 g N m(-3) and downstream from 19 to 44 g N m(-3). An initial groundwater flow investigation using a salt tracer dilution technique showed that the flow through the wall was less than 4% of the flow occurring in the aquifer. Natural gradient tracer tests using bromide and Rhodamine-WT confirmed groundwater bypass under the wall. Hydraulic conductivity of 0.48 m day(-1) was measured inside the wall, whereas the surrounding aquifer had a hydraulic conductivity of 65.4 m day(-1). This indicated that during construction of the wall, hydraulic conductivity of the aquifer had been greatly reduced, so that most of the groundwater flowed under rather than through the wall. Denitrification rates measured in the center of the wall ranged from 0.020 to 0.13 g N m(-3) day(-1), which did not account for the rates of nitrate removal (0.16-0.29 g N m(-3) day(-1)) calculated from monitoring of groundwater nitrate concentrations. This suggested that the rate of denitrification was greater at the upstream face of the wall than in its center where it was limited by low nitrate concentrations. While denitrification walls can be an inexpensive tool for removing nitrate from groundwater, they may not be suitable in aquifers with coarse textured subsoils where simple inexpensive construction techniques result in major decreases in hydraulic conductivity.     

Effects of a reactive barrier and aquifer geology on metal distribution and mobility in a mine drainage impacted aquifer

The Nickel Rim aquifer has been impacted for five decades by a metal-rich plume generated from the Nickel Rim mine tailings impoundment. Metals released by the oxidation of pyrrhotite in the unsaturated zone of the tailings migrate into the downgradient aquifer, affecting both the groundwater and the aquifer solids. A reactive barrier has been installed in the aquifer to remove sulfate and metals from the groundwater. The effect of the reactive barrier on metal concentrations in the aquifer solids has not previously been studied. In this study, a series of selective extraction procedures was applied to cores of aquifer sediment, to ascertain the distribution of metals among various solid phases present in the aquifer. Extraction results were combined with groundwater chemistry, geochemical modelling and solid-phase microanalyses, to assess the potential mobility of metals under changing geochemical conditions. Reactions within the reactive barrier caused an increase in the solid-phase carbonate content downgradient from the barrier. The concentrations of poorly crystalline, oxidized phases of Mn and Fe, as well as concentrations of Cr(III) associated with oxidized Fe, and poorly crystalline Zn, are lower downgradient from the barrier, whereas total solid-phase metal concentrations remain constant. Iron and Mn accumulate as oxidized, easily extractable forms in a peat layer overlying the aquifer. Although these oxides may buffer reducing plumes, they also have the potential to release metals to the groundwater, should a reduced condition be imposed on the aquifer by remedial actions.     

Distribution of metals in a polluted aquifer: A comparison of aquifer suspended material to fine sediments of the adjacent environment

Metal concentrations were determined for groundwater suspended matter from a site in the coastal aquifer of Israel which has been irrigated with secondary sewage effluents since the 1960's. Suspended matter was collected from the aquifer saturated zone by pumping and by a multi-layer sampler. Fine sediments were collected from both the unsaturated and saturated zones of the contaminated aquifer, as well as from an adjacent uncontaminated environment. Ag, Cu, Fe, Mn and Zn were leached from the samples in three sequential chemical extractions which are taken to represent the carbonate, organic and oxide phases. Comparison of the aquifer samples to those of the adjacent environment showed that Fe and Mn are primarily enriched in non-mobile fine sediments and not in suspended matter, whereas the concentrations of Zu, Cu and Ag show up to an order of magnitude enrichment in the mobile suspended matter in groundwater. The enrichment of these metals in the suspended matter indicates that metals from sewage effluents and agricultural activities have reached the groundwater.     

Plume persistence caused by back diffusion from thin clay layers in a sand aquifer following TCE source-zone hydraulic isolation

This paper concludes that back diffusion from one or a few thin clayey beds in a sand aquifer can cause contaminant persistence above MCLs in a sand aquifer long after the source zone initially causing the plume is isolated or removed. This conclusion is based on an intensive case study of a TCE contaminated site in Florida, with the processes evaluated using numerical modeling. At this site, the TCE DNAPL zone formed decades ago, and was hydraulically isolated by means of an innovative system performing groundwater extraction, treatment and re-injection. Treated water is re-injected in a row of injection wells situated a short distance downgradient of the extraction wells, creating a clean-water displacement front to efficiently flush the downgradient plume. This scheme avoids the creation of stagnation zones typical of most groundwater pump-and-treat systems, thereby minimizing the time for aquifer flushing and therefore downgradient cleanup. The system began operation in August 2002 and although the performance monitoring shows substantial declines in concentrations, detectable levels of TCE and degradation products persist downgradient of the re-injection wells, long after the TCE should have disappeared based on calculations assuming a nearly homogenous sand aquifer. Three hypotheses were assessed for this plume persistence: 1) incomplete source-zone capture, 2) DNAPL occurrence downgradient of the re-injection wells, and 3) back diffusion from one or more thin clay beds in the aquifer. After careful consideration, the first two hypotheses were eliminated, leaving back diffusion as the only plausible hypothesis, supported by detailed measurements of VOC concentrations within and near the clay beds and also by numerical model simulations that closely represent the field site hydrogeologic conditions. The model was also used to simulate a more generalized, hypothetical situation where more thin clayey beds occur in a sand aquifer with an underlying aquitard. While there is no doubt that DNAPL source mass reduction can eventually improve downgradient groundwater quality, the magnitude and time scale over which the improvement occurs is the major uncertainty given current characterization approaches. This study shows that even one thin clay bed, less than 0.2 m thick, can cause plume persistence due to back diffusion for several years or even decades after the flux from the source is completely isolated. Thin clay beds, which have a large storage capacity for dissolved and sorbed contaminant mass, are common in many types of sandy aquifers. However, without careful inspection of continuous cores and sampling, such thin clay beds, and their potential for causing long-term back-diffusion effects, can easily go unnoticed during site characterization.     

Groundwater-surface water interaction and its role on TCE groundwater plume attenuation

A field investigation of a TCE plume in a surficial sand aquifer shows that groundwater-surface water interactions strongly influence apparent plume attenuation. At the site, a former industrial facility in Connecticut, depth-discrete monitoring along three cross-sections (transects) perpendicular to groundwater flow shows a persistent VOC plume extending 700 m from the DNAPL source zone to a mid-size river. Maximum TCE concentrations along a transect 280 m from the source were in the 1000s of microg/L with minimal degradation products. Beyond this, the land surface drops abruptly to a lower terrace where a shallow pond and small streams occur. Two transects along the lower terrace, one midway between the facility and river just downgradient of the pond and one along the edge of the river, give the appearance that the plume has strongly attenuated. At the river, maximum TCE concentrations in the 10s of microg/L and similar levels of its degradation product cis-DCE show direct plume discharge from groundwater to the river is negligible. Although degradation plays a role in the strong plume attenuation, the major attenuation factor is partial groundwater plume discharge to surface water (i.e. the pond and small streams), where some mass loss occurs via water-air exchange. Groundwater and stream mass discharge estimates show that more than half of the plume mass discharge crossing the first transect, before surface water interactions occur, reaches the river directly via streamflow, although river concentrations were below detection due to dilution. This study shows that groundwater and surface water concentration measurements together provide greater confidence in identifying and quantifying natural attenuation processes at this site, rather than groundwater measurements alone.     

Diuron mobility through vineyard soils contaminated with copper

The herbicide diuron is frequently applied to vineyard soils in Burgundy, along with repeated treatments with Bordeaux mixture (a blend of copper sulfate and calcium hydroxide) that result in elevated copper concentrations. Cu could in principle affect the fate and transport of diuron or its metabolites in the soil either directly by complexation or indirectly by altering the populations or activity of microbes involved in their degradation. To assess the effect of high Cu concentrations on diuron transport, an experiment was designed with ten undisturbed columns of calcareous and acidic soils contaminated with 17--509 mg kg(-1) total Cu (field-applied). Grass was planted on three columns. Diuron was applied to the soils in early May and in-ground lysimeters were exposed to outdoor conditions until November. Less than 1.2% of the diuron applied was found in the leachates as diuron or its metabolites. Higher concentrations were found in the effluents from the grass-covered columns (0.1--0.45%) than from the bare-soil columns (0.02--0.14%), and they were correlated with increases in dissolved organic carbon. The highest amounts of herbicide were measured in acidic-soil column leachates (0.98--1.14%) due to the low clay and organic matter contents of these soils. Cu also leached more readily through the acidic soils (32.8--1042 microg) than in the calcareous soils (9.5--63.4 microg). Unlike in the leachates, the amount of diuron remaining in the soils at the end of the experiment was weakly related to the Cu concentrations in the soils.     

Effect of grass cover on water and pesticide transport through undisturbed soil columns, comparison with field study (Morcille watershed, Beaujolais)

The purpose of this work is to assess the effectiveness of two grass covers (buffer zone and grass-covered inter-row), to reduce pesticide leaching, and subsequently to preserve groundwater quality. Lower amounts of pesticides leached through grass-cover soil columns (2.7-24.3% of the initial amount) than the bare soil columns (8.0-55.1%), in correspondence with their sorption coefficients. Diuron was recovered in higher amounts in leachates (8.9-32.2%) than tebuconazole (2.7-12.9%), in agreement with their sorption coefficients. However, despite having a sorption coefficient similar to that of diuron, more procymidone was recovered in the leachates (10.2-55.1%), probably due to its facilitated transport by dissolved organic matter. Thus even in this very permeable soil, higher organic matter contents associated with grass-cover reduce the amount of pesticide leaching and limit the risk of groundwater contamination by the pesticides. The results of diuron and tebuconazole transfer through undisturbed buffer zone soil columns are in agreement with field observations on the buffer zone.     

Effects of operating parameters on advanced oxidation of diuron by the Fenton's reagent: a statistical design approach

Advanced oxidation of diuron in aqueous solution by Fenton's reagent using FeSO(4) as source of Fe(II) was investigated in the absence of light. Effects of operating parameters namely the concentrations of pesticide (diuron), H(2)O(2) and Fe(II) on oxidation of diuron was investigated by using Box-Behnken statistical experiment design and the surface response analysis. Diuron oxidation by the Fenton reagent was evaluated by determining the total organic carbon (TOC), diuron, and adsorbable organic halogen (AOX) removals. Concentration ranges of the reagents resulting in the highest level of diuron oxidation were determined. Diuron removal increased with increasing H(2)O(2) and Fe(II) concentrations up to a certain level. Diuron concentration had a more profound effect than H(2)O(2) and Fe(II) in removal of diuron, TOC and AOX from the aqueous solution. Nearly complete (98.5%) disappearance of diuron was achieved after 15min reaction period. However, only 58% of diuron was mineralized after 240min under optimal operating conditions indicating formation of some intermediate products. Optimal H(2)O(2)/Fe(II)/diuron ratio resulting in the maximum diuron removal (98.5%) was found to be 302/38/20 (mgl(-1)).     

Metabolites of the phenylurea herbicides chlorotoluron, diuron, isoproturon and linuron produced by the soil fungus Mortierella sp.

Phenylurea herbicides are used worldwide, and often pollute surface- and groundwater in concentrations exceeding the limit value for drinking water (0.1 μg l⁻¹). Bacteria degrade phenylurea herbicides by successive N-dealkylation to substituted aniline products. Little is known about the corresponding fungal pathways, however. We here report degradation of chlorotoluron, diuron, isoproturon and linuron by the soil fungus Mortierella sp. Gr4. Degradation was fastest with linuron and resulted in successively dealkylated metabolites and 3,4-dichloroaniline. A major new metabolite was detected that has not yet been fully identified. Thin layer chromatography and nuclear magnetic resonance spectroscopy indicate that it is a non-aromatic diol. Degradation of isoproturon, chlorotoluron and diuron involved successive N-demethylation and, in the case of isoproturon and chlorotoluron, additional hydroxylation. A new hydroxylated isoproturon metabolite was detected. The study thus shows that the fungal pathways differ from the bacterial pathways and yield new metabolites of possible environmental concern.     

Movement of trichloroethene in a discontinuous permafrost zone

At a site with discontinuous permafrost in Fairbanks, Alaska, releases of trichloroethene (TCE), an industrial solvent, have caused contamination of the groundwater. The objective of this study was to investigate the relationship between the migration pathway of the TCE groundwater plume and the distribution of the discontinuous permafrost at the site. The TCE plume configuration is substantially different than what regional hydrology trends would predict. Using GIS, we conducted a geostatistical analysis of field data collected during soil-boring installations and groundwater monitoring well sampling. With the analysis results, we constructed maps of the permafrost-table elevation (top of permafrost) and of the groundwater gradients and TCE concentrations from multiyear groundwater sampling events. The plume concentrations and groundwater gradients were overlain on the permafrost map to correlate permafrost locations with groundwater movement and the spatial distribution of TCE moving with groundwater. Correlation of the overlay maps revealed converging and diverging groundwater flow in response to the permafrost-table distribution, the absence of groundwater contamination in areas with a high permafrost-table elevation, and channeling of contaminants and water between areas of permafrost. In addition, we measured groundwater elevations in nested wells to quantify vertical gradients affecting TCE migration. At one set of nested wells down gradient from an area of permafrost we measured an upward vertical gradient indicating recharge of groundwater from the subpermafrost region of the aquifer causing dilution of the plume. The study indicates that the variable distribution of the permafrost is affecting the way groundwater and TCE move through the aquifer. Consequently, changes to the permafrost configuration due to thawing would likely affect both groundwater movement and TCE migration, and areas that were contaminant-free may become susceptible to contamination.