Investigating the role of gas bubble formation and entrapment in contaminated aquifers: Reactive transport modelling

In many natural and contaminated aquifers, geochemical processes result in the production or consumption of dissolved gases. In cases where methanogenesis or denitrification occurs, the production of gases may result in the formation and growth of gas bubbles below the water table. Near the water table, entrapment of atmospheric gases during water table rise may provide a significant source of O(2) to waters otherwise depleted in O(2). Furthermore, the presence of bubbles will affect the hydraulic conductivity of an aquifer, resulting in changes to the groundwater flow regime. The interactions between physical transport, biogeochemical processes, and gas bubble formation, entrapment and release is complex and requires suitable analysis tools. The objective of the present work is the development of a numerical model capable of quantitatively assessing these processes. The multicomponent reactive transport code MIN3P has been enhanced to simulate bubble growth and contraction due to in-situ gas production or consumption, bubble entrapment due to water table rise and subsequent re-equilibration of the bubble with ambient groundwater, and permeability changes due to trapped gas phase saturation. The resulting formulation allows for the investigation of complex geochemical systems where microbially mediated redox reactions both produce and consume gases as well as affect solution chemistry, alkalinity, and pH. The enhanced model has been used to simulate processes in a petroleum hydrocarbon contaminated aquifer where methanogenesis is an important redox process. The simulations are constrained by data from a crude oil spill site near Bemidji, MN. Our results suggest that permeability reduction in the methanogenic zone due to in-situ formation of gas bubbles, and dissolution of entrapped atmospheric bubbles near the water table, both work to attenuate the dissolved gas plume emanating from the source zone. Furthermore, the simulations demonstrate that under the given conditions more than 50% of all produced CH(4) partitions to the gas phase or is aerobically oxidised near the water table, suggesting that these processes should be accounted for when assessing the rate and extent of methanogenic degradation of hydrocarbons.     

Aquifer storage and recovery: recent hydrogeological advances and system performance.

Aquifer storage and recovery (ASR) is part of the solution to the global problem of managing water resources to meet existing and future freshwater demands. However, the metaphoric "ASR bubble" has been burst with the realization that ASR systems are more physically and chemically complex than the general conceptualization. Aquifer heterogeneity and fluid-rock interactions can greatly affect ASR system performance. The results of modeling studies and field experiences indicate that more sophisticated data collection and solute-transport modeling are required to predict how stored water will migrate in heterogeneous aquifers and how fluid-rock interactions will affect the quality of stored water. It has been well-demonstrated, by historic experience, that ASR systems can provide very large volumes of storage at a lesser cost than other options. The challenges moving forward are to improve the success rate of ASR systems, optimize system performance, and set expectations appropriately.     

Development of a solid phase microextraction-gas chromatography-mass spectrometry method for the determination of pentachlorophenol in human plasma using experimental design

A new method, headspace solid-phase microextraction (HS-SPME) with in situ derivatization and gas chromatography-mass spectrometry (GC-MS), which was used for the determination of trace amount of pentachlorophenol (PCP) in human plasma was presented. The acetylation derivatization reaction was firstly optimized using a Doehlert design. Then a series of parameters relevant to the headspace SPME procedure, including fiber coating, extraction temperature, extraction time and salt addition, were optimized using a two-level full factorial design expanded further to a central composite design. The validation of method showed that the optimized method had good linearity (R(2)=0.999) within the concentration ranges 0.1-50.0ngml(-1), and was sensitive with the limit of detection of 0.02ngml(-1). Intra- and inter-day precision for pentachlorophenol in human plasma samples were not greater than 11.9% and 12.6%, respectively. The proposed method, to our knowledge, describes the first application of HS-SPME with GC-MS for analysis of PCP in blood plasma sample. Application of the method to real human plasma samples, PCP was successfully detected in some cases at concentration levels 1.2-6.3ngml(-1).     

Role of protein, amino acids, and enzyme activity on odor production from anaerobically digested and dewatered biosolids.

The main objective of this research was to test the hypothesis that bioavailable protein and, more specifically, the sulfur-containing amino acids within the protein, can be degraded by proteolytic enzymes to produce odor-causing compounds--mainly volatile sulfur compounds (VSCs)--during biosolids storage. To achieve these objectives, samples of digester effluent and cake solids were collected at 11 different wastewater treatment plants in North America, and the samples were analyzed for protein and amino acid content and general protein-degrading enzyme activity. At the same time, cake samples were stored using headspace bottles, the concentration of VSCs were measured using gas chromatography, and olfactometry measurements were made by a trained odor panel. The results showed that the bound cake protein content and methionine content was well-correlated with VSC production and the detection threshold measured by the odor panel.     

Evaluation of high volume particle sampling and sample handling protocols for ambient urban air mutagenicity determinations.

An investigation of high volume particle sampling and sample handling procedures was undertaken to evaluate variations of protocols being used by the U.S. Environmental Protection Agency. These protocols are used in urban ambient air studies which collect ambient and source samples for subsequent mutagenicity analysis of the organic extracts of the aerosol fraction. Specific protocol issues investigated include: (a) duration of sampling period, (b) type of filter media used to collect air particles, (c) necessity for cryogenic field site storage and dry ice shipping of filter samples, and (d) sample handling at the receiving laboratory. Six PM10 Hi-Vol samplers were collocated at an urban site in downtown Durham, North Carolina and operated simultaneously to evaluate 12 h versus 24 h collection periods and filter media choices of glass fiber, Teflon impregnated glass fiber (TIGF), and quartz fiber. Filters from the samplers plus field blanks were collected during each of 25 sampling periods. TIGF filters from two samplers were immediately placed on dry ice in the field and transported directly to cryogenic storage. TIGF, quartz, and glass fiber filters from three samplers were transported at ambient and maintained at room temperature for three to six days prior to cryogenic storage. One TIGF sample, which was collected on a previously tared filter, was subjected to controlled environment equilibration (40 percent relative humidity, 22 degrees C) for 8 to 24 h and weighed prior to cryogenic storage. All filters were subsequently stored at -70 degrees C to -80 degrees C prior to a one-time extraction and Salmonella (Ames) mutagenicity bioassay of the entire sample set.(ABSTRACT TRUNCATED AT 250 WORDS)     

Characterization of odor released during handling of swine slurry: Part I. Relationship between odorants and perceived odor concentrations

Odor emission from livestock production systems is a major nuisance in many rural areas. This study aimed at determining the major airborne chemical compounds responsible for the unpleasant odor perceived in swine facilities during slurry handling, and at proposing predictive models of odor concentration (OC) based on the concentrations of specific odorants in the air. A multivariate data analysis strategy involving principal components analysis and multiple linear regressions was implemented to analyze the relationships between concentration of 35 gases (measured by GC/MS or gas detection tubes), and the overall OC perceived by sensory analysis. The study compiled data on the concentration of odor and odorants, measured in the headspace of 24 unstored and stored slurry samples collected from three different types of production units on 8 commercial swine farms. Among all the measured constituents, OC was found to have the highest correlation with the sulfur containing compounds (i.e. hydrogen sulfide, dimethylsulfide, dimethyldisulfide, dimethyltrisulfide). The concentration of hydrogen sulfide accounted for 68% of the variation in OC above the stirred slurry samples. The highest concentrations of volatile organic compounds were observed for phenols and indoles, which made a significant contribution to the overall OC when the slurry was fresh. The contribution of ammonia to the OC was only significant in the absence of hydrogen sulfide. The precision of predictive models of OC based on the concentration of specific odorants in the air was satisfactory (R² between 0.66 and 0.89). Hence, this study suggests that monitoring of specific odor compounds released from agitated swine slurry can be used to predict the concentration of odor perceived close to the source (e.g. at storage units), allowing the assessment of odor nuisance potentials.     

Filtration and transport of Bacillus subtilis spores and the F-RNA phage MS2 in a coarse alluvial gravel aquifer: implications in the estimation of setback distances

Filtration of Bacillus subtilis spores and the F-RNA phage MS2 (MS2) on a field scale in a coarse alluvial gravel aquifer was evaluated from the authors' previously published data. An advection-dispersion model that is coupled with first-order attachment kinetics was used in this study to interpret microbial concentration vs. time breakthrough curves (BTC) at sampling wells. Based on attachment rates (katt) that were determined by applying the model to the breakthrough data, filter factors (f) were calculated and compared with f values estimated from the slopes of log (cmax/co) vs. distance plots. These two independent approaches resulted in nearly identical filter factors, suggesting that both approaches are useful in determining reductions in microbial concentrations over transport distance. Applying the graphic approach to analyse spatial data, we have also estimated the f values for different aquifers using information provided by some other published field studies. The results show that values of f, in units of log (cmax/co) m(-1), are consistently in the order of 10(-2) for clean coarse gravel aquifers, 10(-3) for contaminated coarse gravel aquifers, and generally 10(-1) for sandy fine gravel aquifers and river and coastal sand aquifers. For each aquifer category, the f values for bacteriophages and bacteria are in the same order-of-magnitude. The f values estimated in this study indicate that for every one-log reduction in microbial concentration in groundwater, it requires a few tens of meters of travel in clean coarse gravel aquifers, but a few hundreds of meters in contaminated coarse gravel aquifers. In contrast, a one-log reduction generally only requires a few meters of travel in sandy fine gravel aquifers and sand aquifers. Considering the highest concentration in human effluent is in the order of 10(4) pfu/l for enteroviruses and 10(6) cfu/100 ml for faecal coliform bacteria, a 7-log reduction in microbial concentration would comply with the drinking water standards for the downgradient wells under natural gradient conditions. Based on the results of this study, a 7-log reduction would require 125-280 m travel in clean coarse gravel aquifers, 1.7-3.9 km travel in contaminated coarse gravel aquifers, 33-61 m travel in clean sandy fine gravel aquifers, 33-129 m travel in contaminated sandy fine gravel aquifers, and 37-44 m travel in contaminated river and coastal sand aquifers. These recommended setback distances are for a worst-case scenario, assuming direct discharge of raw effluent into the saturated zone of an aquifer. Filtration theory was applied to calculate collision efficiency (alpha) from model-derived attachment rates (katt), and the results are compared with those reported in the literature. The calculated alpha values vary by two orders-of-magnitude, depending on whether collision efficiency is estimated from the effective particle size (d10) or the mean particle size (d50). Collision efficiency values for MS-2 are similar to those previously reported in the literature (e.g. ) [DeBorde, D.C., Woessner, W.W., Kiley, QT., Ball, P., 1999. Rapid transport of viruses in a floodplain aquifer. Water Res. 33 (10), 2229-2238]. However, the collision efficiency values calculated for Bacillus subtilis spores were unrealistic, suggesting that filtration theory is not appropriate for theoretically estimating filtration capacity for poorly sorted coarse gravel aquifer media. This is not surprising, as filtration theory was developed for uniform sand filters and does not consider particle size distribution. Thus, we do not recommend the use of filtration theory to estimate the filter factor or setback distances. Either of the methods applied in this work (BTC or concentration vs. distance analyses), which takes into account aquifer heterogeneities and site-specific conditions, appear to be most useful in determining filter factors and setback distances.     

Trihalomethane formation during water disinfection in four water supplies in the Somes river basin in Romania

Background, aim and scope

After the discovery of chloroform in drinking water, an extensive amount of work has been dedicated to the factors influencing the formation of halogenated disinfections by-products (DBPs). The disinfection practice can vary significantly from one country to another. Whereas no disinfectant is added to many water supplies in Switzerland or no disinfectant residual is maintained in the distribution system, high disinfectant doses are applied together with high residual concentrations in the distribution system in other countries such as the USA or some southern European countries and Romania. In the present study, several treatment plants in the Somes river basin in Romania were investigated with regard to chlorine practice and DBP formation (trihalomethanes (THMs)). Laboratory kinetic studies were also performed to investigate whether there is a relationship between raw water dissolved organic matter, residual chlorine, water temperature and THM formation.

Materials and methods

Drinking water samples were collected from different sampling points in the water treatment plant (WTP) from Gilau and the corresponding distribution system in Cluj-Napoca and also from Beclean, Dej and Jibou WTPs. The water samples were collected once a month from July 2006 to November 2007 and stored in 40-mL vials closed with Teflon lined screw caps. Water samples were preserved at 4°C until analysis after sodium thiosulfate (Na₂S₂O₃) had been added to quench residual chlorine. All samples were analysed for THMs using headspace GC-ECD between 1 and 7 days after sampling. The sample (10 mL) was filled into 20-mL headspace vials and closed with a Teflon-lined screw cap. Thereafter, the samples were equilibrated in an oven at 60°C for 45 min. The headspace (1 mL) was then injected into the GC (Cyanopropylphenyl Polysiloxane column, 30 m × 53 mm, 3 μm film thickness, Thermo Finnigan, USA). The MDLs for THMs were determined from the standard deviation of eight standards at 1 μg/L. The MDLs for CHCl₃, CHBrCl₂, CHBr₂Cl and CHBr₃ were 0.3, 0.2, 0.3 and 0.6 μg/L, respectively. All kinetic laboratory studies were carried out only with water from the WTP Gilau. The experiments were conducted under two conditions: baseline conditions (pH 7, 21°C, 2.5 mg/L Cl₂) to gain information about the change of the organic matter in the raw water and seasonally variable conditions to simulate the actual process at the treatment plant and the distribution system.

Results and discussion

This study shows that the current chlorination practice in the investigated plants complies with the THM drinking water standards of the EU. The THM concentrations in all samples taken in the four treatment plants and distributions systems were below the EU drinking water standard for TTHMs of 100 μg/L. Due to the low bromide levels in the raw waters, the main THM formed in the investigated plants is chloroform. It could also be seen that the THM levels were typically lower in water supplies with groundwater as their water resource. In one plant (Dej) with a pre-ozonation step, a significantly lower (50%) THM formation during post-chlorination was observed. Laboratory chlorination experiments revealed a good correlation between chloroform formation and the consumed chlorine dose. Also, these experiments allowed a semi-quantative prediction of the chloroform formation in the distribution system of Cluj-Napoca.

Conclusions

CHCl₃ was the most important trihalomethane species observed after the chlorination of water in all of the sampled months. However, TTHM concentrations did not exceed the maximum permissible value of 100 μg/L (EU). The THM formation rates in the distribution system of Cluj-Napoca have a high seasonal variability. Kinetic laboratory experiments could be used to predict chloroform formation in the Cluj-Napoca distribution system. Furthermore, an empirical model allowed an estimation of the chloroform formation in the Gilau water treatment plant.

     

Comparison of PCE and TCE disappearance in heated volatile organic analysis vials and flame-sealed ampules

The rates of hydrolysis reported for tetrachloroethylene (PCE) and trichloroethylene (TCE) at elevated temperatures range over two orders-of-magnitude, where some of the variability may be due to the presence of a gas phase. Recent studies suggest that volatile organic analysis (VOA) vials provide a low-cost and readily available zero headspace system for measuring aqueous-phase hydrolysis rates. This work involved measuring rates of PCE and TCE disappearance and the corresponding appearance of dechlorination products in water-filled VOA vials and flame-sealed ampules incubated at 21 and 55 °C for up to 95.5 days. While PCE and TCE concentrations readily decreased in the VOA vials to yield first-order half lives of 11.2 days for PCE and 21.1 days for TCE at 55 °C, concentrations of anticipated dechlorination products, including chloride, remained constant or were not detected. The rate of PCE disappearance was 34 times faster in VOA vials at 55 °C compared to values obtained with flame-sealed ampules containing PCE-contaminated water. In addition, the concentration of TCE increased slightly in flame-sealed ampules incubated at 55 °C, while a decrease in TCE levels was observed in the VOA vials. The observed losses of PCE and TCE in the VOA vials were attributed to diffusion and sorption in the septa, rather than to dechlorination. These findings demonstrate that VOA vials are not suitable for measuring rates of volatile organic compound hydrolysis at elevated temperatures.     

Anaerobic biotransformation of explosives in aquifer slurries amended with ethanol and propylene glycol

Hexahydro-1,3,5-trinitro-1,3,5-triazine (RDX), octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine (HMX), and 2,4,6-trinitrotoluene (TNT) are explosives that are frequently found as environmental contaminants on military installations. Hydrogen has been shown to support the anaerobic transformation of these explosives. We investigated ethanol and propylene glycol as electron donors for providing syntrophically produced H2 for stimulating the anaerobic biodegradation of explosives in contaminated soil. The study was conducted using anoxic microcosms constructed with slurries of the contaminated soil and groundwater. The addition of 5mM ethanol and propylene glycol enhanced the biodegradation of RDX and HMX relative to the control bottles. Ethanol was depleted within about 20 days, resulting in the transient formation of hydrogen, acetate, and methane. The hydrogen headspace concentration increased from 8 ppm to 1838 ppm before decreasing to background concentrations. Propylene glycol was completely degraded after 15 days, forming hydrogen, propionate, and acetate as end-products. The hydrogen headspace concentrations increased from 56 ppm to 628 ppm before decreasing to background concentrations. No methane formation was observed during the incubation period of 48 days. Our findings indicate the addition of ethanol and propylene to the aquifer slurries increased the hydrogen concentrations and enhanced the biotransformation of RDX and HMX in the explosive-contaminated soil.     

MTBE and aromatic hydrocarbons in North Carolina stormwater runoff

A total of 249 stormwater samples were collected from 46 different sampling locations in North Carolina over an approximate 1-year period and analyzed to identify land use types where fuel oxygenates and aromatic hydrocarbons may be present in higher concentrations and at greater frequency. Samples were analyzed by gas chromatography-mass spectrometry in ion selective mode to achieve a quantitation limit of 0.05 microg/l. m-,p-Xylene and toluene were detected in over half of all samples analyzed, followed by MTBE: o-xylene: 1,3,5-trimethylbenzene: ethylbenzene; and 1,2,4-trimethylbenzene. Benzene, DIPE, TAME and 1,2,3-trimethylbenzene were detected in < 10% of the samples analyzed. Median contaminant concentrations (when detected) varied from 0.07 microg/l for ethylbenzene to 0.11 microg/l for toluene. All of the locations with significantly higher contaminant concentrations were associated with direct runoff from a gas station or discharge of contaminated groundwater from a former leaking underground storage tank. For all of the aromatic hydrocarbons, the maximum observed contaminant concentrations were over an order of magnitude lower than current drinking water standards.     

Landfill Gas Effects on Groundwater Samples at a Municipal Solid Waste Facility

A study was performed to determine the source of low concentrations of volatile organic compounds (VOCs) detected in groundwater samples at a solid waste management facility. The affected wells were identified as hydraulically upgradient of an old unlined facility, but downgradient of a new clay-lined landfill. These monitoring wells are close to both sites. Subsurface landfill gas migration was identified after a low permeability cap was installed on the older site. Subsurface gas pressure was monitored to identify horizontal landfill gas migration. Monitoring well headspace gases were evaluated to identify depressed oxygen concentrations and methane because of landfill gas migration into the well. Monitoring well headspace gas VOC concentrations were compared to groundwater VOC concentrations to determine the direction of phase transfer. A ratio above 1.0 of the observed well headspace gas concentration of a VOC to the concentration that would be in equilibrium with the groundwater concentration indicates gas-to-water phase transfer within the well. For the major gas-phase and aqueous-phase VOC, cis-1,2-dichloroethene, gas-to-water phase transfer is clearly indicated from the data for two of the four wells. Fifteen other VOCs were detected in monitoring well headspace gases but not in groundwater samples from the four wells studied. Only one compound in one well was detected in the groundwater sample but not in the headspace gases, and only one compound in one well was detected in both matrices at concentrations that suggested water-to-gas phase transfer. This study suggests that if landfill gas is suspected as the source of detected VOCs, monitoring well construction and stratigraphy are important considerations when attempting to differentiate between groundwater contamination by landfill gas and contamination from other sources.     

MTBE oxidation byproducts from the treatment of surface waters by ozonation and UV-ozonation

In recent years, there has been considerable concern over the release of methyl tert-butyl ether (MTBE), a gasoline additive, into the aquifers used as potable water sources. MTBE readily dissolves in water and has entered the environment via gasoline spills and leaking storage tanks. In this paper, we investigate ozonation and UV-ozonation for treatment of MTBE in contaminated drinking water sources. We report the test protocol and results of using solid-phase microextraction (SPME) to determine the level of MTBE and its oxidation byproducts in samples drawn from laboratory-scale ozone and UV-ozone reactors being evaluated at a US EPA research facility. Analysis of a prepared MTBE standard indicated a detection limit on the order of 0.1 microgl(-1) with a repeatability of +/-0.4%. Results show that the overall rate of removal of MTBE via UV-ozonation in a relatively turbid surface water (15 ntu) is twice that of ozonation alone. In addition, GC-MS analysis of decomposition products showed that tert-butyl formate (TBF), methyl acetate, butene, acetone, and acetaldehyde were produced by both processes. TBF and butene reach similar maximum yields from the two processes, but are more efficiently degraded by UV-ozonation treatment. This indicates that these treatment processes also degrade these byproducts. In contrast, the remaining byproducts (methyl acetate, acetone, and acetaldehyde) are formed at similar levels during treatment, but are not degraded once formed. These byproducts may be resistant to hydrogen abstraction by hydroxyl radical.     

Assessing the aerobic biodegradability of 14 hydrocarbons in two soils using a simple microcosm/respiration method.

The aerobic biodegradability of 14 hydrocarbons in two soils was determined using a simple microcosm/respirometric method based on oxygen consumption. Biodegradability was assessed indirectly by measuring the depletion of oxygen over time in the headspace of microcosms containing soil and test chemicals. The microcosms consisted of small glass vials fitted with valves that allowed headspace gas samples to be collected, essentially resulting in a sealed system. Respiration data from control microcosms were obtained from identically treated microcosms with no test chemical. Control data were necessarily included in all calculations of percent of theoretical oxygen demand (%ThOD) for any given test chemical. Two experiments were performed to verify this simple biodegradation test method. First, an experiment was performed in which disappearance of n-tetradecane from the microcosms was measured directly by standard soil extraction and analytical techniques while simultaneously performing this simple respirometric method based on %ThOD with the same test chemical. Second, the method was compared to a well-established radiochemical technique using 14C-phenanthrene. Results of both comparisons showed that the method is both accurate and reliable. The consistent manner with which the data were produced in two different soils show that the method is also very reproducible. The method described here provides a simple and inexpensive method for determining the aerobic biodegradability of organic compounds in soils.     

Presence of bacteriophages in animal feed as indicators of fecal contamination

The objectives of this study were to determine if indigenous male specific and somatic bacteriophages could be detected in animal feeds and if isolated phages contained RNA or DNA. Seven fresh feeds, 2 fresh feed ingredients, 7 stored feeds, 2 stored feed ingredients, and 8 samples of poultry diets suspected to contain Salmonella spp. were enriched and spot plated for indigenous phages using Escherichia coli Famp and CN-13 as hosts. Bacteriophage numbers were below detection without enrichment, but both male specific and somatic coliphages were detected in all animal feeds, feed ingredients, and poultry diets after 16 h of enrichment, even after the samples had been stored for 14 months of storage at -20 C. Five out of 9 fresh feeds and 7 out of 8 stored feeds contained RNA somatic phages.     

Cationic surfactant as a sensitizer for the spectrophotometric determination of hydrogen sulphide in air and evaluation of a new absorbing medium containing triethanolamine-zinc acetate-sodium hydroxide

An extractive spectrophotometric method for the determination of trace amounts of hydrogen sulphide after fixing the gas in triethanolamine (TEA)-zinc acetate-sodium hydroxide solution is described. The method is based on the reaction of iodate with hydrogen sulphide in the presence of acid and excess chloride ion leading to the formation of ICl2- species which is used to iodinate 2',7'-dichlorofluorescein to form 2',7'-dichloro-4',5'-diiodofluorescein. The iodinated product formed is extracted into an organic solvent and sensitized by equilibrating with a cationic surfactant, cetrimide, in the presence of acetate buffer (pH 5.9 +/- 0.1). The colour system obeys Beer's law over the range 0-1 microg of hydrogen sulphide and the relative standard deviation is 2.4% for 10 determinations at 0.75 microg of hydrogen sulphide. The effect of interfering gases on the determination is discussed. The proposed absorbing solution has been evaluated using a hydrogen sulphide permeation device. This absorbing solution has an absorption efficiency of > 93% at a flow rate of 1.5 litre min(-1) for a sampling period of 2 h. The fixed H2S is stable for 40 days. The method has been applied to determine residual H2S levels in a laboratory fume hood and in the vicinity of sewage pumping station. The method can be used to determine as little as 0.05 microg of hydrogen sulphide.     

Dynamic air sampling of volatile organic compounds using solid phase microextraction

A new dynamic air sampling system was devised and evaluated in conjunction with solid phase microextraction (SPME) fiber materials for extracting odor-causing volatile organic compounds (VOCs) present in swine building environments. Utilizing a standard solution consisting of 11 compounds (i.e., volatile fatty acids, indoles, and phenol), sampling times, volumes, and flow rates were adjusted to establish optimal extraction conditions. Results indicated that the sampling system was effective with the Carboxen/Polydimethylsiloxane (CAR/PDMS) fiber in extracting all 11 standard compounds. The best sampling conditions for the extraction were a 100-mL sampling vial subjected to a continuous flow of 100 mL/min for 60 min. The gas chromatographic analysis showed that the reproducibility was within acceptable ranges for all compounds (RSD=4.24-17.26% by peak areas). In addition, field tests revealed that the sampling system was capable of detecting over 60 VOCs in a swine house whose major components were identified by gas chromatography-mass spectrometry (GC-MS) and by their retention times as volatile fatty acids, phenols, indole, and skatole. The field tests also showed that considerably different levels of VOCs were present in various parts of the swine building.     

Cloud point extraction for the preconcentration of palladium and lead in environmental samples and determination by flow injection flame atomic absorption spectrometry

Purpose

An online cloud-point extraction (CPE) coupled with flow injection method is developed for the separation and preconcentration of palladium and lead from various matrices using flame atomic absorption spectrometry (FAAS).

Method

The method employs the formation of complexes of the metallic species with dimethylglyoxime, which are subsequently entrapped in the micelles of the surfactant Triton X-114, upon increase of the solution temperature to 60°C and loaded into the flow injection system at a flow rate of 4.6?mL?min^?1. The surfactant rich-phase was retained in a minicolumn packed with animal wool at pH?6 and eluted with 1.0?mol?L^?1 nitric acid in methanol at a flow rate of 1.1?mL?min^?1 directly into the nebulizer of the FAAS. The CPE variables and flow injection conditions affecting the analytical performance of the combined methodology was studied and optimized.

Results

Under the optimized conditions for 25?mL of preconcentrated solution, the enrichment factors were 51 and 44, and the limit of detections were 1.0 and 1.4?ng?mL^?1 for palladium and lead, respectively. Finally, the developed method was applied for the determination of palladium and lead in street dust, soil, radiology waste, catalytic converter, and urban aerosol samples.

Conclusions

Cloud-point extraction coupled with flow injection-FAAS was proposed as an effective preconcentration and separation method for Pd and Pb determination in radiology waste, road dust, soil, and urban aerosol samples. The most favorable feature of this method is its much higher selectivity, sensitivity, rapidity, good extraction efficiency, and employs the green chemistry concept, as it does not require the addition of toxic chemicals. In addition, this proposed method gives very low detection limits and good relative standard.     

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.     

Preparation of antibodies and development of an enzyme immunoassay for determination of atrazine in environmental samples

An indirect competitive enzyme-linked immunosorbent assay (ELISA) has been developed and optimized for atrazine determination in soil at different depths (0-10, 10-20, and 20-30 cm) before and after 48 h of application, corn shoot and cow milk samples collected from Dina farm, Egypt. This assay was based on a specific polyclonal antibodies (PAb) raised by immunizing New Zealand rabbits with an immunogen prepared by coupling 3-{4-(ethylamino)-6-(isopropylamino)-1,3,5-triazine-2-yl} thiopropanoic acid to bovine serum albumin (BSA) via N-hydroxysuccinimide (NHS) active ester method. The sensitivity (estimated as IC?? value) was 17.5 μg mL?1 with a detection limit of 0.1 ng mL?1. The maximum atrazine concentration was found in soil especially in the deepest layer (325 and 890 μg kg?1 before and after application, respectively). Atrazine concentration in corn shoot was 333.28, μg kg?1 dry plant, while there was no detectable amount in milk. All samples screened by ELISA were validated by gas chromatography mass spectrometer procedure (GC/MS). Good correlation was achieved between the two methods (r = 0.997 for soil and 0.9814 for plant). This study demonstrates the utility and convenience of the simple, practical and cost-effective ELISA method in the laboratory for analysis of environmental samples. The method is ideal for the rapid screening of large numbers of samples in laboratories where access to GC/MS facilities, is limited or lacking.