Fluorescence imaging applied to tracer distributions in variably saturated fractured clayey till

The study of mechanisms controlling preferential flow and transport in variably saturated fractured clayey till is often hindered by insufficient spatial resolution or unknown measuring volume. With the objective to study these mechanisms while circumventing the obstacles, tracer experiments with two fluorescent tracers Acid Yellow 7 (AY7) and Sulforhodamine B (SB) were performed at three different rain events for a fall and a summer season. Irrigated areas were excavated down to depths of 2.8 m and the movement of both tracers in the exposed profiles was delineated simultaneously by high spatial resolution apparent concentration maps (pixel approximately 1 mm(2)) obtained with an imaging device. The device consists of a light source and a CCD camera, both equipped with tracer-specific-filters for fluorescent light. The fluorescence images were corrected for nonuniform lighting, changing surface roughness, and varying optical properties of the soil profile. The resulting two-dimensional apparent concentration distribution profiles of the tracers showed that: (i) relative low water content in the upper 10 cm of the irrigated till in summer had a pronounced retardation effect on the AY7-migration and no effect on the SB-migration; (ii) the dead-end biopores were not activated in the fall season; (iii) only 3D fracture-plans connected to hydraulically active 1D-biopores contributed to the leaching; (iv) the tracer migration primary followed macropores during both seasons, though AY7 also followed a topsoil piston transport in summer; (v) the highest tracer pixel apparent concentrations were often found in macropores and most pronounced in the summer season; and (vi) 3D-dilution in fractures seems to play a dominating role in AY7-migration in the fall season.     

Influence of flow rate on transport of bacteriophage in shale saprolite

The objective of this study was to investigate the influence of flow rate on transport and retention of bacteriophage tracers in a fractured shale saprolite, which is a highly weathered, fine-grained subsoil that retains much of the fabric of the parent bedrock. Synthetic ground water containing PRD-1, MS-2, and bromide was passed through a saturated column of undisturbed shale saprolite at rates ranging from 0.0075 to 0.96 m d '. First arrival of the bacteriophage tracers in effluent samples in each of the experiments occurred within 0.01 to 0.04 pore volumes (PV) of the start of injection, indicating that bacteriophage were advectively transported mainly through fractures or macropores. Bacteriophage transport velocities, based on first arrival in the effluent, were very similar to fracture flow velocities calculated using the cubic law for flow in a fractured material. For MS-2, maximum concentration and mass of tracer recovered both increased steadily as flow rate increased. For PRD-1, these values initially increased, but were nearly constant at flow rates above 0.039 m d(-1), indicating that approximately 50% of the observed losses were independent of flow rate. Evaluation of the data indicates that physical straining and electrostatic or hydrophobic attachment to fracture or macropore walls were the dominant retention processes. Inactivation and gravitational settling playing secondary roles, except at the slowest flow rates. The study suggests that microbial contamination from sources such as septic fields and sewage ponds may pose a threat to the quality of ground water and surface water in areas with saprolitic subsoils.     

In situ push-pull method to determine ground water denitrification in riparian zones

To quantify ground water denitrification in discrete locations of riparian aquifers, we modified and evaluated an in situ method based on conservative tracers and 15N-enriched nitrate. Ground water was "pushed" (i.e., injected) into a mini-piezometer and then "pulled" (i.e., extracted) from the same mini-piezometer after an incubation period. This push-pull method was applied in replicate mini-piezometers at two Rhode Island riparian sites, one fresh water and one brackish water. Conservative tracer pretests were conducted to determine incubation periods, ranging from 5 to 120 h, to optimize recovery of introduced plumes. For nitrate push-pull tests, we used two conservative tracers, sulfur hexafluoride and bromide, to provide insight into plume recovery. The two conservative tracers behaved similarly. The dosing solutions were amended with 15N-enriched nitrate that enabled us to quantify the mass of denitrification gases generated during the incubation period. The in situ push-pull method detected substantial denitrification rates at a site where we had previously observed high denitrification rates. At our brackish site, we found high rates of ground water denitrification in marsh locations and minimal denitrification in soils fringing the marsh. The push-pull method can provide useful insights into spatial and temporal patterns of denitrification in riparian zones. The method is robust and results are not seriously affected by dilution or degassing from ground water to soil air. In conjunction with measurements of ground water flow-paths, this method holds promise for evaluating the influence of site and management factors on the ground water nitrate removal capacity of riparian zones.     

Regression models for estimating concentrations of atrazine plus deethylatrazine in shallow groundwater in agricultural areas of the United States

Tobit regression models were developed to predict the summed concentration of atrazine [6-chloro--ethyl--(1-methylethyl)-1,3,5-triazine-2,4-diamine] and its degradate deethylatrazine [6-chloro--(1-methylethyl)-1,3,5,-triazine-2,4-diamine] (DEA) in shallow groundwater underlying agricultural settings across the conterminous United States. The models were developed from atrazine and DEA concentrations in samples from 1298 wells and explanatory variables that represent the source of atrazine and various aspects of the transport and fate of atrazine and DEA in the subsurface. One advantage of these newly developed models over previous national regression models is that they predict concentrations (rather than detection frequency), which can be compared with water quality benchmarks. Model results indicate that variability in the concentration of atrazine residues (atrazine plus DEA) in groundwater underlying agricultural areas is more strongly controlled by the history of atrazine use in relation to the timing of recharge (groundwater age) than by processes that control the dispersion, adsorption, or degradation of these compounds in the saturated zone. Current (1990s) atrazine use was found to be a weak explanatory variable, perhaps because it does not represent the use of atrazine at the time of recharge of the sampled groundwater and because the likelihood that these compounds will reach the water table is affected by other factors operating within the unsaturated zone, such as soil characteristics, artificial drainage, and water movement. Results show that only about 5% of agricultural areas have greater than a 10% probability of exceeding the USEPA maximum contaminant level of 3.0 μg L. These models are not developed for regulatory purposes but rather can be used to (i) identify areas of potential concern, (ii) provide conservative estimates of the concentrations of atrazine residues in deeper potential drinking water supplies, and (iii) set priorities among areas for future groundwater monitoring.     

Pesticide and Transformation Product Detections and Age‐Dating Relations from Till and Sand Deposits1

Abstract:  Pesticide and transformation product concentrations and frequencies in ground water from areas of similar crop and pesticide applications may vary substantially with differing lithologies. Pesticide analysis data for atrazine, metolachlor, alachlor, acetochlor, and cyanazine and their pesticide transformation products were collected at 69 monitoring wells in Illinois and northern Indiana to document occurrence of pesticides and their transformation products in two agricultural areas of differing lithologies, till, and sand. The till is primarily tile drained and has preferential fractured flow, whereas the sand primarily has surface water drainage and primary porosity flow. Transformation products represent most of the agricultural pesticides in ground water regardless of aquifer material – till or sand. Transformation products were detected more frequently than parent pesticides in both the till and sand, with metolachlor ethane sulfonic acid being most frequently detected. Estimated ground‐water recharge dates for the sand were based on chlorofluorocarbon analyses. These age‐dating data indicate that ground water recharged prior to 1990 is more likely to have a detection of a pesticide or pesticide transformation product. Detections were twice as frequent in ground water recharged prior to 1990 (82%) than in ground water recharged on or after 1990 (33%). The highest concentrations of atrazine, alachlor, metolachlor, and their transformation products, also were detected in samples from ground water recharged prior to 1990. These age/pesticide detection relations are opposite of what would normally be expected, and may be the result of preferential flow and/or ground‐water mixing between aquifers and aquitards as evident by the detection of acetochlor transformation products in samples with estimated ground‐water ages predating initial pesticide application.     

Atrazine and alachlor transport in claypan soils as influenced by differential antecedent soil water content

Increased attention to ground water contamination has encouraged an interest in mechanisms of solute transport through soils. Few studies have investigated the effect of the initial soil water content on the transport and degradation of herbicides for claypan soils. We investigated the effect of claypan soils at initial field capacity vs. permanent wilting level on atrazine and alachlor transport. The soil studied was Mexico silt loam (fine, smectitic, mesic Aeric Vertic Epiaqualf) with a subsoil clay content, primarily montmorillonite, of >40%. Strontium bromide, atrazine, and alachlor were applied to plots; half were at field capacity (Wet treatment), and half were near the permanent wilting point (Dry treatment). Soil cores were removed at selected depths and times, and cores were analyzed for bromide and herbicide concentrations. Bromide, atrazine, and alachlor were detected at the 0.90-m depth in dry plots within 15 d after experiment initiation. Bromide was detected 0.15 m deeper (P < 0.05) in the Dry compared with the Wet treatment at 1, 7, and 60 d after application and >0.30 m deeper (P < 0.01) in the Dry treatment at 15 and 30 d after application; similar treatment results were found for atrazine and alachlor, although on fewer dates with significant differences. The mobility order of the applied chemicals was bromide > atrazine > alachlor. The atrazine apparent half-life was significantly longer in the Dry plots compared with the Wet plots. The retardation factor determined from the relative velocity of each herbicide to that of bromide was higher for alachlor than for atrazine. This study identifies the impact that shrinkage cracks have for different moisture conditions on preferential transport of herbicides in claypan soils.     

Fate of atrazine in sandy soil cropped with sorghum

A field study was conducted to determine the fate of atrazine (6-chloro-N2-ethyl-N4-isopropyl-1,3,5-triazine-2,4-diamine) within the root zone (0 to 90 cm) of a sandy soil cropped with sorghum [Sorghum bicolor (L.) Moench] in Gainesville, Florida. Atrazine was uniformly applied at a rate of 1.12 kg ai. ha(-1) to a sorghum crop under moderate irrigation, optimum irrigation, and no irrigation (rainfed), 2 d after crop emergence. Bromide as a tracer for water movement was applied to the soil as NaBr at a rate of 45 kg Br ha(-1), 3 d before atrazine application. Soil water content, atrazine, and Br concentrations were determined as a function of time using soil samples taken from the root zone. Atrazine sorption coefficients and degradation rates were determined by depth for the entire root zone in the laboratory. Atrazine was strongly adsorbed within the upper 30 cm of soil and most of the atrazine recovered from the soil during the growing season was in that depth. The estimated half-life for atrazine was 32 d in topsoil to 83 d in subsoil. Atrazine concentration within the root zone decreased from 0.44 kg ai. ha(-1) 2 days after application (DAA) to 0.1 kg a.i. ha(-1) 26 DAA. Negligible amounts of atrazine (approximately 5 microg kg(-1)) were detected below the 60-cm soil depth by 64 DAA. Most of the decrease in atrazine concentration in the root zone over time was attributed to degradation. In contrast, all applied bromide had leached past the 60-cm soil depth during the same time interval.     

Determining long-term (decadal) deep drainage rate using multiple tracers

The deep drainage rate is a critical hydrological parameter in understanding contamination mechanisms of soil and groundwater. Little research has been conducted on the temporal variations in deep drainage rate during the last century. The objective of this study was to determine the long-term deep drainage rate on a cultivated loamy soil in the Canadian Prairies. Three tracers were used: KCl applied in 1971, fallout tritium in 1963, and NO3* released during the initial cultivation of the field (1923). Two soil cores to a depth of 3.6 m were taken along a flat portion of the field, and soil Cl(-), 3H, and NO3* concentrations were measured as a function of depth. An additional four cores were taken for soil water content measurements between 2000 and 2003. Distinct peaks in the depth distribution of these three tracers were located at 1.27 m for Cl(-), 1.31 m for 3H, and 1.52 m for NO3*, 32, 40, and 80 yr after the application of Cl(-), 3H, and NO3*, respectively. The average deep drainage rates, calculated as the product of the estimated tracer velocity and volumetric soil water content below the active root zone, were 2.0 mm yr(-1) from the Cl(-) tracer, 2.2 mm yr(-1) from 3H, and 2.5 mm yr(-1) from the NO3* tracer. Therefore, there was little temporal variability in the groundwater recharge over the eight decades that the field has been cultivated. The recharge rates are less than 1% of the mean annual precipitation (333 mm).     

Residual and contact herbicide transport through field lysimeters via preferential flow

Usage of glyphosate [N-(phosphonomethyl)-glycine] and glufosinate [2-amino-4-(hydroxy-methylphosphinyl)butanoic acid] may reduce the environmental impact of agriculture because they are more strongly sorbed to soil and may be less toxic than many of the residual herbicides they replace. Preferential flow complicates the picture, because due to this process, even strongly sorbed chemicals can move quickly to ground water. Therefore, four monolith lysimeters (8.1 m(2) by 2.4 m deep) were used to investigate leaching of contact and residual herbicides under a worst-case scenario. Glufosinate, atrazine (6-chloro-N(2)-ethyl-N(4)-isopropyl-1,3,5-triazine-2,4-diamine), alachlor [2-chloro-N-(2,6-diethylphenyl)-N-(methoxymethyl) acetamide], and linuron (3-3,4-dichlorophenyl-1-methoxy-1-methylurea) were applied in 1999 before corn (Zea mays L.) planting and glyphosate, alachlor, and metribuzin [4-amino-6-(1,1-dimethylethyl)-3-(methylthio)-1,2,4-triazin-5(4H)-one] were applied in 2000 before soybean [Glycine max (L.) Merr.] planting. A high-intensity rainfall was applied shortly after herbicide application both years. Most alachlor, metribuzin, atrazine, and linuron losses occurred within 1.1 d of rainfall initiation and the peak concentration of the herbicides coincided (within 0.1 d of rainfall initiation in 2000). More of the applied metribuzin leached compared with alachlor during the first 1.1 d after rainfall initiation (2.2% vs. 0.035%, P < 0.05). In 1999, 10 of 24 discrete samples contained atrazine above the maximum contaminant level (atrazine maximum contaminant level [MCL] = 3 mug L(-1)) while only one discrete sample contained glufosinate (19 mug L(-1), estimated MCL = 150 mug L(-1)). The results indicate that because of preferential flow, the breakthrough time of herbicides was independent of their sorptive properties but the transport amount was dependent on the herbicide properties. Even with preferential flow, glyphosate and glufosinate were not transported to 2.4 m at concentrations approaching environmental concern.     

Phosphorus flux from bottom sediments in Lake Eucha, Oklahoma

Phosphorus inputs into reservoirs include external sources from the watershed and internal sources from the reservoir bottom sediments. This study quantified sediment P flux in Lake Eucha, northeastern Oklahoma, USA, and evaluated the effectiveness of chemical treatment to reduce sediment P flux. Six intact sediment-water columns were collected from three sites in Lake Eucha near the reservoir channel at depths of 10 to 15 m. Three intact sediment and water columns from each site were incubated for 21 d at approximately 22 degrees C under aerobic conditions, and three were incubated under anaerobic conditions (N2 with 300 ppm CO2); sediment P flux was estimated over the 21 d for each core. The overlying water in the cores was bubbled with air for approximately 1 wk and then treated with aluminum sulfate (alum). The cores were incubated at approximately 22 degrees C for an additional 14 d under aerobic or anaerobic conditions, and sediment P flux after alum treatment was estimated for each core. Sediment P flux was approximately four times greater under anaerobic conditions compared with aerobic conditions. Alum treatment of the intact sediment-water columns reduced (8x) sediment P flux under anaerobic conditions. Internal P flux (1.03 and 4.40 mg m(-2) d(-1) under aerobic and anaerobic conditions, respectively) was greater than external P flux (0.13 mg m(-2) d(-1)). The internal P load (12 Mg yr(-1)) from reservoir bottom sediments was almost 25% of the external P load (approximately 48 Mg yr(-1)) estimated using a calibrated watershed model.     

Evaluating microbial purification during soil treatment of wastewater with multicomponent tracer and surrogate tests

Soil treatment of wastewater has the potential to achieve high purification efficiency, yet the understanding and predictability of purification with respect to removal of viruses and other pathogens is limited. Research has been completed to quantify the removal of virus and bacteria through the use of microbial surrogates and conservative tracers during controlled experiments with three-dimensional pilot-scale soil treatment systems in the laboratory and during the testing of full-scale systems under field conditions. The surrogates and tracers employed included two viruses (MS-2 and PRD-1 bacteriophages), one bacterium (ice-nucleating active Pseudomonas), and one conservative tracer (bromide ion). Efforts have also been made to determine the relationship between viruses and fecal coliform bacteria in soil samples below the wastewater infiltrative surface, and the correlation between Escherichia coli concentrations measured in percolating soil solution as compared with those estimated from analyses of soil solids. The results suggest episodic breakthrough of virus and bacteria during soil treatment of wastewater and a 2 to 3 log (99-99.9%) removal of virus and near complete removal of fecal coliform bacteria during unsaturated flow through 60 to 90 cm of sandy medium. Results also suggest that the fate of fecal coliform bacteria may be indicative of that of viruses in soil media near the infiltrative surface receiving wastewater effluent. Concentrations of fecal coliform in percolating soil solution may be conservatively estimated from analysis of extracted soil solids.     

Measured concentrations of herbicides and model predictions of atrazine fate in the Patuxent River estuary

The environmental fate of herbicides in estuaries is poorly understood. Estuarine physical transport processes and the episodic nature of herbicide release into surface waters complicate interpretation of water concentration measurements and allocation of sources. Water concentrations of herbicides and two triazine degradation products (CIAT [6-amino-2-chloro-4-isopropylamino-s-triazine] and CEAT [6-amino-2-chloro-4-ethylamino-s-triazine]) were measured in surface water from four sites on 40 d from 4 Apr. through 29 July 19% in the Patuxent River estuary, part of the Chesapeake Bay system. Atrazine (2-chloro-4-ethylamino-6-isopropylamino-1,3,5-triazine) was most persistent and present in the highest concentrations (maximum = 1.29 microg/L). Metolachlor [2-chloro-6'-ethyl-N-(2-methoxy-1-methylethyl)-o-acetoluidide], CIAT, CEAT, and simazine (1-chloro-3,5-bisethylamino-2,4,6-triazine) were frequently detected with maximum concentration values of 0.61, 1.1, 0.76, and 0.49 microg/L, respectively. A physical transport model was used to interpret atrazine concentrations in the context of estuarine water transport, giving estimates of in situ degradation rates and total transport. The estimated half-life of atrazine in the turbid, shallow upper estuary was t(1/2) = 20 d, but was much longer (t(1/2) = 100 d) in the deeper lower estuary. Although most (93%) atrazine entered the estuary upstream via the river, simulations suggested additional inputs directly to the lower estuary. The total atrazine load to the estuary from 5 April to 15 July was 71 kg with 48% loss by degradation and 31% exported to the Chesapeake Bay. Atrazine persistence in the estuary is directly related to river flows into the estuary. Low flows will increase atrazine residence time in the upper estuary and increase degradation losses.     

Depth distribution of sulfonamide antibiotics in pore water of an undisturbed loamy grassland soil

Despite the concern raised by the detections of veterinary antibiotics like sulfonamides (SA) in the environment, their fate in soils is still not sufficiently understood. In a previous article, we demonstrated that manure may substantially influence losses of SA via runoff from soils. Here, we report on the effect of manure on SA availability in soil pore water. Three sulfonamides (sulfadimidine, sulfadiazine, sulfathiazole) and two tracers (bromide and Brilliant Blue) were either applied in manure or as aqueous solution on grassland plots. After 1 and 3 d contact time, the plots were irrigated with deionized water. One day after irrigation, soil cores were taken and profiles of pore water concentrations were determined. The median SA concentrations of the top layer on manured plots varied between 40 and 60 microg L(-1) and between 10 and 30 microg L(-1) on the controls. For the conservative tracer Br the mass recovery was about 60 to 75% and much lower for the SA (2 to 14%). Apparent distribution coefficients K(d,app) of the SA in the topsoil ranged between 3 and 15 L kg(-1) on the manured plots and between 30 to 35 kg L(-1) on the controls. Below the top layer, the concentration distribution showed a pattern typical for preferential flow. Locally, SA concentrations down to 30- to 50-cm depth were as high as in the top 5 cm with little effect of the two application matrices. In the topmost layer, the data indicate that 10 to 25% of sulfadimidine were transformed to its acetyl-metabolite.     

Runoff and drainage losses of atrazine, metribuzin, and metolachlor in three water management systems

Rainfall can transport herbicides from agricultural land to surface waters, where they become an environmental concern. Tile drainage can benefit crop production by removing excess soil water but tile drainage may also aggravate herbicide and nutrient movement into surface waters. Water management of tile drains after planting may reduce tile drainage and thereby reduce herbicide losses to surface water. To test this hypothesis we calculated the loss of three herbicides from a field with three water management systems: free drainage (D), controlled drainage (CD), and controlled drainage with subsurface irrigation (CDS). The effect of water management systems on the dissipation of atrazine (6-chloro-N2-ethyl-N4-isopropyl-1,3,5-triazine-2,4-diamine), metribuzin [4-amino-6-(1,1-dimethylethyl)-3-(methylthio)-1,2,4-triazine-5(4H)-one), and metolachlor [2-chloro-N-(2-ethyl-6-methylphenyl)-N-(2-methoxy-1-methylethyl)acetamide] in soil was also monitored. Less herbicide was lost by surface runoff from the D and CD treatments than from CDS. The CDS treatment increased surface runoff, which transported more herbicide than that from D or CD treatments. In one year, the time for metribuzin residue to dissipate to half its initial value was shorter for CDS (33 d) than for D (43 d) and CD (46 d). The half-life of atrazine and metolachlor were not affected by water management. Controlled drainage with subsurface irrigation may increase herbicide loss through increased surface runoff when excessive rain is received soon after herbicide application. However, increasing soil water content in CDS may decrease herbicide persistence, resulting in less residual herbicide available for aqueous transport.     

Impact of climatic and soil conditions on environmental fate of atrazine used under plantation forestry in Australia

We studied the leaching and dissipation of atrazine (2-chloro-4-ethylamino-6-isopropylamino-1, 3, 5-s-triazine) and its two principal metabolites (desethylatrazine and desisopropylatrazine) for more than two years through soil profiles at five forestry sites across Australia (representing subtropical, temperate and Mediterranean climatic conditions with rainfall ranging from 780 to 1536 mm yr^?1). Following atrazine applications at local label rates, soil cores were collected at regular intervals (up to depths of 90–150 cm), and the residues of the three compounds in soil were analysed in composite samples using liquid chromatography. Bromide was applied simultaneously with atrazine to follow the movement of the soil water. While bromide ion rapidly leached through the entire profile, in most cases the bulk of atrazine, desethylatrazine and desisopropylatrazine remained in the top 45 cm of the soil profile. However, a small fraction of residue moved deeper into the soil profile and at a subtropical site (Toolara) trace levels (ng L^?1) of atrazine and one of its metabolites (DEA) were detected in perched groundwater located at a depth of 1.8 m. Data on the total residues of atrazine in soil profiles from all sites except the Tasmanian site fitted a first-order decay model. The half-life of atrazine in surface soils at the subtropical sites (Toolara and Imbil) ranged from 11 to 21 days. Four separate applications of atrazine at Toolara resulted in a narrow range of half-lives (16 ± 3.6 days), confirming relatively rapid dissipation of atrazine under subtropical conditions (Queensland). In contrast, a prominent biphasic pattern of initial rapid loss followed by very slow phase of degradation of atrazine was observed under the colder temperate climate of Highclere (Tasmania). The data showed that while its 50% (DT₅₀) loss occurred relatively rapidly (36 days), more than 10% of herbicide residue was still detectable in the profile even a year after application (DT₉₀ = 375 days). The rate of dissipation of atrazine at warm subtropical Queensland sites (Imbil and Toolara) was 2–3 times faster than sites located in colder climate of Tasmania. The marked contrast in DT₅₀ values between subtropical and temperate sites suggest that climatic conditions (soil temperature) is one of the key factors affecting atrazine dissipation. At the Tasmanian site, the combination of leaching of the herbicide in subsoil and slower microbial activity at cooler temperatures would have caused a longer persistence of atrazine.     

Distance and flow effects on microsphere transport in a large gravel column

Consumption of microbially contaminated ground water can cause adverse health effects and the processes involved in pathogen transport in aquifers need to be understood. The influences of distance, flow velocity, and colloid size on colloid transport were examined in homogenous pea-gravel media using an 8-m column and three sizes (1, 5, and 10 microm) of microspheres. Experiments were conducted at three flow rates by simultaneously injecting microspheres with a conservative tracer, bromide. Observed concentrations were simulated with CXTFIT and analyzed with filtration theory. The results demonstrate that colloid concentration is strongly log-linearly related to transport distance (as suggested by filtration theory) in coarse gravels, similar to our previous field studies. In contrast, the log-linear relationship is often reported to be invalid in fine porous media. The observed log-linear relationship is possibly because straining is negligible in the coarse gravels investigated. This has implications in predicting setback distances for land disposal of effluent, and suggests that setback distances in gravel aquifers can be estimated using constant spatial removal rates (f). There was an inverse relationship between transport distance and colloidal concentration, but not with temporal attachment rate (katt) and collision coefficient (alpha). Increases in flow velocity result in increasing colloidal recovery, katt and alpha but decreasing f. Increases in sphere size result in decreasing colloidal recovery with increasing katt, f, alpha, and velocity enhancement. Diffusion is the dominant collision mechanism for 1-microm spheres (81-88%), while settling dominates for 5- and 10-microm spheres (> 87%), and interception is very small for all spheres investigated.     

Improving saline-sodic coalbed natural gas water quality using natural zeolites

Management of saline-sodic water from the coalbed natural gas (CBNG) industry in the Powder River Basin (PRB) of Wyoming and Montana is a major environmental challenge. Clinoptilolie zeolites mined in Nevada, California, and New Mexico were evaluated for their potential to remove sodium (Na+) from CBNG waters. Based on the exchangeable cation composition, naturally occurring calcium (Ca2+)-rich zeolites from New Mexico were selected for further evaluation. Batch adsorption experiments were conducted to evaluate the potential of the Ca(2+)-rich natural clinoptilolites to remove Na+ from saline-sodic CBNG waters. Batch adsorption experiments indicated that Na+ adsorption capacity ofclinoptilolite ranged from 4.3 (4 x 6 mesh) to 7.98 g kg(-1) (14 x 40 mesh). Among the different adsorption isotherms investigated, the Freundlich Model fitted the data best for smaller-sized (6 x 8, 6 x 14, and 14 x 40 mesh) zeolites. Passing the CBNG water through Ca(2+)-rich zeolite columns reduced the salt content (electrical conductivity [EC]) by 72% with a concurrent reduction in sodium adsorption 10 mmol 1/2 L(-1/2). Zeolite technology appears to be an effective water treatment alternative to industrial membrane treatment for removing Na+ from poor-quality CBNG waters.     

Evaluating changes in matrix-based, recovery-adjusted concentrations in paired data for pesticides in groundwater

Pesticide concentration data for waters from selected carbonate-rock aquifers in agricultural areas of Pennsylvania were collected in 1993-2009 for occurrence and distribution assessments. A set of 30 wells was visited once in 1993-1995 and again in 2008-2009 to assess concentration changes. The data include censored matched pairs (nondetections of a compound in one or both samples of a pair). A potentially improved approach for assessing concentration changes is presented where (i) concentrations are adjusted with models of matrix-spike recovery and (ii) area-wide temporal change is tested by use of the paired Prentice-Wilcoxon (PPW) statistical test. The PPW results for atrazine, simazine, metolachlor, prometon, and an atrazine degradate, deethylatrazine (DEA), are compared using recovery-adjusted and unadjusted concentrations. Results for adjusted compared with unadjusted concentrations in 2008-2009 compared with 1993-1995 were similar for atrazine and simazine (significant decrease; 95% confidence level) and metolachlor (no change) but differed for DEA (adjusted, decrease; unadjusted, increase) and prometon (adjusted, decrease; unadjusted, no change). The PPW results were different on recovery-adjusted compared with unadjusted concentrations. Not accounting for variability in recovery can mask a true change, misidentify a change when no true change exists, or assign a direction opposite of the true change in concentration that resulted from matrix influences on extraction and laboratory method performance. However, matrix-based models of recovery derived from a laboratory performance dataset from multiple studies for national assessment, as used herein, rather than time- and study-specific recoveries may introduce uncertainty in recovery adjustments for individual samples that should be considered in assessing change.     

Effect of corn root exudates on the degradation of atrazine and its chlorinated metabolites in soils

DIMBOA (3,4-dihydro-2,4-dihydroxy-7-methoxy-2H-1,4-benzoxazin-3-one), a major benzoxazinone of Poaceae plants, was isolated and purified from corn seedlings. The effect of isolated and purified DIMBOA on the degradation of atrazine [2-chloro-4-(ethylamino)-6-(isopropylamino)-s-triazine], and its toxic breakdown products, desethylatrazine [2-chloro-4-amino-6-(isopropylamino)-s-triazine; DEA] and desisopropylatrazine [2-chloro-4-(ethylamino)-6-amino-s-triazine; DIA], was studied in the absence of plants using batch experiments, while the effect of corn root exudates on these compounds was determined in hydroponic experiments. Degradation experiments were performed in the presence and absence of 50 microM, 1 mM, or 5 mM DIMBOA resulting in ratios of DIMBOA to pesticide of 1:1, 20:1, and 100:1. We observed a 100% degradation of atrazine to hydroxyatrazine within 48 h at a ratio of DIMBOA to atrazine of 100:1. DIMBOA had the largest effect on atrazine, while it was about three times less effective on DEA and DIA. Corn (Zea mays L. cv. LG 2185) was exposed to 10 mg L(-1) of either atrazine, DEA, or DIA for 11 d in a growth chamber experiment. Up to 4.3 micromol L(-1) d(-1) of hydroxyatrazine were formed in the nutrient solutions by plants exposed to atrazine, while the formation of hydroxylated metabolites from plants exposed to DEA and DIA was smaller and also delayed. The formation of hydroxylated metabolites increased in the solution with plant age in all atrazine, DEA, and DIA treatments. HMBOA (3,4-dihydro-2-hydroxy-7-methoxy-2H-1,4-benzoxazin-3-one), the lactam precursor of DIMBOA, and a tentatively identified derivative of MBOA (2,3-dihydro-6-methoxy-benzoxazol-2-one) were detected in the corn root exudates. Mass balance calculations revealed that up to 30% of the disappearance of atrazine and DEA, and up to 10% of DIA removal from the solution medium in our study could be explained by the formation of hydroxylated metabolites in the solution itself. Our results show that higher plants such as corn have the potential to promote the hydrolysis of triazine residues in soils by exudation of benzoxazinones.     

Transport of gellan gum microbeads through sand: an experimental evaluation for encapsulated cell bioaugmentation

Transport of 10-40 microm gellan gum microbeads was studied in horizontal sand columns to evaluate the feasibility of using gel-encapsulated bacteria for bioaugmentation of contaminated aquifers. Three 5.2 x 110 cm columns were packed with sand (column A: 0.5-2 mm, column B: 0.25-2 mm, and column C: 0.125-2 mm). Microbeads in artificial groundwater were injected at 0.5 l h(-1) during intermittent 12-h periods. Breakthrough of microbeads increased with injection time, varying as a descending function of travel distance. After 72 h of injection, about 75% of injected microbeads were dispersed across a 5-110 cm distance from the inlet in column A, compared to 78% across a 5-50 cm in column B, and 76% across a 5-20 cm in column C. The wider dispersion of microbeads across the length of column A, compared to those observed in columns B and C, suggests a higher potential for the formation of a uniform bioactive zone of encapsulated cells across a sandy aquifer with such grain size distribution and hydrodynamic properties.