Effect of Different Sampling Methodologies on Measured Methane Concentrations in Groundwater Samples

Analysis of dissolved light hydrocarbon gas concentrations (primarily methane and ethane) in water supply wells is commonly used to establish conditions before and after drilling in areas of shale gas and oil extraction. Several methods are currently used to collect samples for dissolved gas analysis from water supply wells; however, the reliability of results obtained from these methods has not been quantified. This study compares dissolved methane and ethane concentrations measured in groundwater samples collected using three sampling methods employed in pre‐ and post‐drill sampling programs in the Appalachian Basin. These include an open‐system collection method where 40 mL volatile organic analysis (VOA) vials are filled directly while in contact with the atmosphere (Direct‐Fill VOA) and two alternative methods: (1) a semi‐closed system method whereby 40 mL VOA vials are filled while inverted under a head of water (Inverted VOA) and (2) a relatively new (2013) closed system method in which the sample is collected without direct contact with purge water or the atmosphere (IsoFlask^®). This study reveals that, in the absence of effervescence, the difference in methane concentrations between the three sampling methods was relatively small. However, when methane concentrations equaled or exceeded 20 mg/L (the approximate concentration at which effervescence occurs in the study area), IsoFlask^® (closed system) samples yielded significantly higher methane concentrations than Direct‐Fill VOA (open system) samples, and Inverted VOA (semi‐closed system) samples yielded lower concentrations. These results suggest that open and semi‐closed system sample collection methods are adequate for non‐effervescing samples. However, the use of a closed system collection method provides the most accurate means for the measurement of dissolved hydrocarbon gases under all conditions.     

The Effect of Air Bubbles and Headspace on the Aqueous Concentrations of Volatile Organic Compounds in Sampling Vials

The presence of headspace and air bubbles in volatile organic analysis sampling vials lowers the actual aqueous concentration of these compounds due to the partitioning of solutes into the gaseous phase. This could make the sample invalid for analysis.
In this work, the effects of air bubbles and headspace on the aqueous concentration of 60 volatile organic compounds listed in U.S.Environmental Protection Agency (U.S. EPA) Method 8260 were evaluated experimentally and theoretically. The results showed that for air to water ratios of 1 to 20 and less, there was no significant effect on the aqueous concentrations of target organic solutes in the sampling vials. When the air to water ratio was increased to 1 to 10, the recovery rates of four organic compounds were lower than the control. Laboratory experiments on sampling vials showed that the presence of air bubbles or headspace with the volumetric air to water ratios of 1 to 20 and less do not produce any significant effect on the original concentrations for most targeted volatile organic compounds.
The experimental results also indicated that in 40 mL sampling vials with headspace range of 2 to 8 mL, the recovery rates of most volatile organic compounds with high values of Henry's law constant (> 0.01 Atm m³/mol. at 25°C) were larger than the calculated rates.     

The Effect of Oxygen on Anaerobic Color Removal of Azo Dye in a Sequencing Batch Reactor

In this study, various amounts of oxygen were added to the anaerobic phase of an anaerobic‐aerobic sequencing batch reactor (SBR) receiving azo dye remazol brilliant violet 5R to mimic the input of oxygen into the anaerobic zones of biological textile wastewater treatment plants. The effect of oxygen on the anaerobic biodegradative capability of the mixed microbial culture for remazol brilliant violet 5R was investigated. To investigate the effect of oxygen on anaerobic azo dye biodegradation, the anaerobic phase of the SBR cultures were exposed to a very low limited amount of oxygen for various air flow rates. Initially, an air flow rate of 20 mL/min was applied, further on the air flow rate in the anaerobic phase was increased up to 40 mL/min. System performance was determined by monitoring chemical oxygen demand, color removal rate, activities of anaerobic (azo reductase) and aerobic enzymes (catechol 2,3‐dioxygenase, catechol 1,2‐dioxygenase). The results of percentage COD reduction at each stage were similar for all runs, giving an overall reduction of 96%. Anaerobic color removal efficiency and azo reductase activity of anaerobic microorganisms were adversely affected by the addition of oxygen. Color removal efficiencies of the anaerobic phases decreased from 80% down to 42 and 38% for the limited oxygen conditions of 20 mL/min and 40 mL/min, respectively. It was observed that the activity of catechol 2,3‐dioxygenase and catechol 1,2‐dioxygenase, involved in breakage of aromatic rings, increased after they are exposed to oxygen limited conditions compared to fully anaerobic conditions. It was also observed that catechol 1,2‐dioxygenase enzyme activity increased by increasing the oxygen level on oxygen limited conditions in the anaerobic zone.     

Epigenetic gorges in fluvial landscapes

Epigenetic gorges form when channels that have been laterally displaced during episodes of river blockage or aggradation incise down into bedrock spurs or side‐walls of the former valley rather than excavating unconsolidated fills and reinhabiting the buried paleovalley. Valley‐filling events that promote epigenetic gorges can be localized, such as a landslide dam or an alluvial/debris flow fan deposit at a tributary junction, or widespread, such as fluvial aggradation in response to climate change or fluctuating base‐level. The formation of epigenetic gorges depends upon the competition between the resistance to transport, strength and roughness of valley‐filling sediments and a river's ability to sculpt and incise bedrock. The former affects the location and lateral mobility of a channel incising into valley‐filling deposits; the latter determines rates of bedrock incision should the path of the incising channel intersect with bedrock that is not the paleovalley bottom. Epigenetic gorge incision, by definition, post‐dates the incision that originally cut the valley. Strath terraces and sculpted bedrock walls that form in relation to epigenetic gorges should not be used to directly infer river incision induced by tectonic activity or climate variability. Rather, they are indicative of the variability of short‐term bedrock river incision and autogenic dynamics of actively incising fluvial landscapes. The rate of bedrock incision associated with an epigenetic gorge can be very high (>1 cm/yr), typically orders of magnitude higher than both short‐ and long‐term landscape denudation rates. In the context of bedrock river incision and landscape evolution, epigenetic gorges force rivers to incise more bedrock, slowing long‐term incision and delaying the adjustment of rivers to regional tectonic and climatic forcing. Copyright © 2008 John Wiley & Sons, Ltd.     

Application of AMD to the Determination of Cropprotection Agents in Drinking Water. Part III: Solid Phase Extraction and Affecting Factors Anwendung der AMD-Technik zur Bestimmung von Pflanzenbehandlungsmittel-Wirkstoffen im Trinkwasser. Teil III: Festphasenextraktion und ihre Einflußfaktoren

The more sensitive an analysis method the more care must be given to sample preparation. Solid phase extraction (SPE) onto RP 18 phases has established itself as a general purification and enrichment technique for trace components in aqueous samples. Various factors may thereby influence the recovery rate. For example, the ratio amount of sorbent and sample volume should be taken into account to avoid breakthrough of the investigated substance. Extracting phenylurea herbicides from drinking water, the ratio should be 1 g RP 18 sorbent per 1 L water sample. Concerning the flow rate for the fungicides procymidone, vinclozolin, and iprodione, the recovery rate decreases using higher flow rates than 3 or 6 mL/min. In the case of phenylurea herbicides, a flow rate of 10 or 14 mL/min showed best results. Even the coefficient of variation is below ± 5% at these flow rates. Furthermore, the company dependence should be considered because the recovery rate might differ by up to 40% using the nominally identical material. The same applies to the batch dependence of quality from the same company. The concentration of the eluate must also be monitored and carried out with great care to avoid decreasing the recovery rate. Considering these factors of influence, SPE is a very useful tool in sample preparation, particularly if an automated system is used.     

Groundwater Sampling at ISCO Sites: Binary Mixtures of Volatile Organic Compounds and Persulfate

In situ chemical oxidation involves the introduction of a chemical oxidant into the subsurface for the purpose of transforming groundwater contaminants into harmless by‐products. Owing to oxidant persistence, groundwater samples collected at hazardous waste sites may contain both the contaminant(s) and the oxidant in a “binary mixture.” Binary mixtures composed of sodium persulfate (2.5 g/L; 10.5 mM) and volatile organic compounds (VOCs) (benzene, toluene, m‐xylene, perchloroethylene, trichloroethylene) were analyzed to assess the impact on the quality of the sample. A significant decline (49 to 100%) in VOC concentrations was measured in binary mixtures using gas chromatography (GC) purge and trap, and GC mass spectroscopy headspace methods. Preservation of the binary mixture samples was achieved through the addition of ascorbic acid (99 to 100% VOC average recovery). High concentrations of ascorbic acid (42 to 420 mM) did not interfere in the measurement of the VOCs and did not negatively impact the analytical instruments. High concentrations of ascorbic acid favored the reaction between persulfate and ascorbic acid while limiting the reaction between persulfate and VOCs. If an oxidant is detected and the binary sample is not appropriately preserved, the quality of the sample is likely to be compromised.     

Sampling of VOCs with the BAT Ground Water Sampling System

In the BAT ground water sampling system, a stainless steel probe with a porous filter element is pushed vertically to the desired sampling depth. An evacuated glass sampling tube is then lowered down the penetration rods where it makes contact with the filter via a hypodermic needle and draws a pore fluid sample.
An investigation of the system was carried out at a number of sites contaminated by leaking underground gasoline storage tanks. Ground water samples obtained using the BAT system and adjacent monitoring wells were analyzed for volatile organic compounds (VOCs).
Because the BAT system is an in situ penetration device with a small filter length, it is possible to determine variations in contaminant concentration with depth. BAT samples in general exhibited higher recovery of VOCs than did bailer samples from adjacent monitoring wells screened over large intervals.
Much higher levels of VOCs were recovered when the probe was used with its 316 stainless steel filter than when using the high-density polyethylene (HDPE) filter. Significant sorption apparently occurred on the latter filter.
Because the BAT sample tubes are sealed and remain a closed system, the in situ water pressure is maintained. No significant loss of VOCs was found in sampling tubes containing headspace. Samples from the upper tube in the cascaded setup with headspace recovered levels of VOCs as high, or in a few cases higher, than the lower, no-headspace tubes.     

Online Preconcentration and Determination of Trace Levels Cadmium in Water Samples Using Flow Injection Systems Coupled with Flame AAS

A rapid and sensitive method for the determination of trace levels cadmium in water samples by flame atomic absorption spectrometry was developed. It is based on the online sorption of Cd(II) ions on a microcolumn packed with HCl treated bamboo charcoal. In a pH range of 5.0–7.5, Cd(II) ions were effectively retained on the microcolumn, which exhibited fast kinetics, permitting the use of high sample flow rates up to at least 12.8 mL/min without the loss of retention efficiency. The retained Cd(II) ions were quantitatively eluted with HCl (2.0 mol/L) for an online determination. With a preconcentration time of 80 s at a sample loading flow rate of 8.6 mL/min, a sensitivity enhancement factor of 63 was obtained compared with the slope of the linear portion of the calibration curves before and after preconcentration. The calibration graph using the preconcentration system for cadmium was linear with a correlation coefficient of 0.9997, at levels from 1–40 ng/mL. The precision (RSD) for 11 replicate measurements were 3.2% for the determination of 5 ng/mL Cd(II) and 1.8% for 20 ng/mL Cd(II), respectively, and the detection limit (3s) was 0.36 ng/mL. The accuracy was assessed through the determination of a certified reference material, and also through recovery experiments.     

Research note: Laboratory study of the influence of changing the injection rate on the geometry of the fluid front and on P‐wave ultrasonic velocities in sandstone

Forced imbibition was performed in reservoir sandstone by injecting water into a dry sample. The injection was monitored with X‐ray computed tomography and acoustic acquisition to simultaneously visualize the displacement of the fluid and quantify its presence by calculating saturation and P‐wave velocities. We observed a strong influence when changing the injection rates on the acoustic response. Upon decreasing the injection rate from 5 mL/h to 0.1 mL/h, P‐wave velocities decreased sharply: 100 m/s in 1 h. This behaviour is related to the partially saturated conditions of the sample (76% of saturation) before decreasing the injection rate. The air that is still trapped is free to move due to a decrease of pore pressure that is no longer forced by the higher injection rate. After 1 hour, P‐wave velocities started increasing with small changes in saturation. Stopping injection for 16 hrs decreased saturation by 8% and P‐wave velocities by 100 m/s. Restarting injection at 5 mL/h increased saturation to 76% while P‐wave velocities fluctuated considerably for 2 hrs until they stabilized at 2253 m/s. Through the computed tomography scans we observed a water front advancing through the sample and how its shape changed from a plane to a curve after decreasing the injection rate.     

Optimization of the Sampling Technique for the Determination of Dissolved Hydrogen in Groundwater

In this study a field‐sampling technique for dissolved hydrogen (H₂) in groundwater will be presented which allows the transport of gaseous samples into the laboratory for further analysis. The method consists of transferring the headspace trapped in a gas‐sampling bulb which is continuously purged by groundwater into previously evacuated vials using a gas‐tight syringe. Three transfer steps with preceding evacuation of the vial led to a H₂‐recovery of 100 % in laboratory experiments. The method has been applied to determine H₂ concentrations in an aquifer contaminated with chlorinated solvents. Tests concerning the effect of different pumping techniques on H₂ concentrations revealed that most reliable values were obtained with a bladder pump, while an electrically driven submersible pump generated considerable amounts of hydrogen due to electrochemical interactions with the sampled water. Concentrations of dissolved hydrogen in field and laboratory samples were about two orders of magnitude higher when sampling was performed with the electrically driven submersible pump compared to sampling with the bladder pump and a peristaltic pump. Lab experiments with a Plexiglas reservoir to produce H₂‐enriched water were used to study the effect of two tubing materials (PVC, polyamide) on H₂ losses. PVC tubing turned out to allow transfer of H₂‐enriched water over 25 m without significant losses, while PA‐tubing was not suitable for sampling of H₂.     

On‐Site Vapor‐Phase Analysis as a Novel Approach for Monitoring Groundwater Wells

The results of comprehensive field testing of on‐site vapor‐phase‐based groundwater monitoring methods are presented to demonstrate their utility as a robust and cost‐effective approach for rapidly obtaining volatile organic compounds (VOCs) concentration data from a monitoring well. These methods—which rely on sensitive, commercially available field equipment to analyze vapor in equilibrium with groundwater—proved easy to implement and can be tailored to site‐specific needs, including multilevel sampling. During field testing, low‐flow groundwater concentrations could be reasonably estimated using submerged passive vapor diffusion samplers or field equilibration of collected groundwater (R² = 0.85 to 0.96). These two methods are not as reliant on in‐well mixing to overcome vertical stratification within wells as simpler headspace methods. The importance of well and aquifer‐specific factors on concentration data (and therefore method selection) is highlighted, including the effect of changing in‐well patterns due to seasonal temperature gradients. Results indicated that vertical stratification was relatively limited within the set of wells included in these studies, resulting in similar performance for short depth‐discrete passive vapor diffusion samplers (constructed from 40‐mL vials) and longer samplers (2.5 to 5 feet in length) designed to cover a larger portion of the screened interval. A year‐long, multi‐event evaluation demonstrated that vapor‐phase‐based monitoring methods are no more variable than conventional groundwater monitoring methods, with both types subject to similar spatial and temporal variability that can be difficult to reduce. Vapor sampling methods represent a promising approach for estimation of groundwater concentrations by reducing the cost liabilities associated with monitoring while providing a more sustainable approach.     

Comparison of Downhole and Surface Sampling for the Determination of Volatile Organic Compounds (VOCs) in Ground Water

The relative precision and accuracy of sampling and analysis methods for the determination of trace concentrations of volatile organic compounds (VOCs) in ground water were compared. Samples were collected from a well containing nanogram-per-liter (ng/L) to microgram-per-liter (μg/L) levels of VOCs. A Keck helical rotor submersible pump was used to collect samples at the surface for analysis by purge and trap (P&T) and for analysis by adsorption/thermal desorption (ATD). Downhole samples were collected by passing water through an ATD cartridge. Although slight spontaneous bubble outgassing occurred when the water was brought to the surface, the relative precisions and comparabilities of the surface and downhole methods were generally found to be equivalent from a statistical point of view. A main conclusion of this study is that bringing sample water to the surface for placement in VOC vials (and subsequent analysis by P&T) can be done reliably under many circumstances. However, care must still be taken to prevent adsorption losses and cross contamination. Samples subject to strong bubble outgassing will need to be handled in a special fashion (e.g., by downhole ATD) to minimize volatilization losses. Additionally, the higher sensitivity of the ATD method allows lower detection limits than are possible with P&T. For example, several compounds present at the ng/L level could be determined with confidence by ATD, but not by P&T.     

Removal of Volatile Organic Compounds in Vertical Flow Filters: Predictions from Reactive Transport Modeling

Vertical flow filters are containers filled with porous medium that are recharged from top and drained at the bottom, and are operated at partly saturated conditions. They have recently been suggested as treatment technology for groundwater containing volatile organic compounds (VOCs). Numerical reactive transport simulations were performed to investigate the relevance of different filter operation modes on biodegradation and/or volatilization of the contaminants and to evaluate the potential limitation of such remediation mean due to volatile emissions. On the basis of the data from a pilot‐scale vertical flow filter intermittently fed with domestic waste water, model predictions on the system’s performance for the treatment of contaminated groundwater were derived. These simulations considered the transport and aerobic degradation of ammonium and two VOCs, benzene and methyl tertiary butyl ether (MTBE). In addition, the advective‐diffusive gas‐phase transport of volatile compounds as well as oxygen was simulated. Model predictions addressed the influence of depth and frequency of the intermittent groundwater injection, degradation rate kinetics, and the composition of the filter material. Simulation results show that for unfavorable operation conditions significant VOC emissions have to be considered and that operation modes limiting VOC emissions may limit aerobic biodegradation. However, a suitable combination of injection depth and composition of the filter material does facilitate high biodegradation rates while only little VOC emissions take place. Using such optimized operation modes would allow using vertical flow filter systems as remediation technology suitable for groundwater contaminated with volatile compounds.     

Effects of hillslope topography on hydrological responses in a weathered granite mountain,Japan: comparison of the runoff response between the valley‐head and the side slope

To evaluate the effects of hillslope topography on storm runoff in a weathered granite mountain, discharge rate, soil pore water pressures, and water chemistry were observed on two types of hillslope: a valley‐head (a concave hillslope) and a side slope (a planar hillslope). Hydrological responses on the valley‐head and side slope reflected their respective topographic characteristics and varied with the rainfall magnitude. During small rainfall events (<35 mm), runoff from the side slope occurred rapidly relative to the valley‐head. The valley‐head showed little response in storm runoff. As rainfall amounts increased (35–60 mm), the valley‐head yielded a higher flow relative to the side slope. For large rainfall events (>60 mm), runoff from both hillslopes increased with rainfall, although that from the valley‐head was larger than that from the side slope. The differences in the runoff responses were caused by differences in the roles of lower‐slope soils and the convergence of the hillslope. During small rainfall events, the side slope could store little water; in contrast, all rainwater could be stored in the soils at the valley‐head hollow. As the amount of rainfall increased, the subsurface saturated area of the valley‐head extended from the bottom to the upper portion of the slope, with the contributions of transient groundwater via lateral preferential flowpaths due to the high concentration of subsurface water. Conversely, saturated subsurface flow did not contribute to runoff responses, and the subsurface saturated area at the side slope did not extend to the upper slope for the same storm size. During large rainfall events, expansion of the subsurface saturated area was observed in both hillslopes. Thus, differences in the concentration of subsurface water, reflecting hillslope topography, may create differences in the extension of the subsurface saturated area, as well as variability in runoff responses. Copyright © 2007 John Wiley & Sons, Ltd.     

Determination of Copper in Water Samples after Solid‐phase Extraction Using Dimethylglyoxime‐modified Silica

This work describes the modification of silica gel with dimethylglyoxime, in order to prepare an effective sorbent for the preconcentration and determination of copper. The sorption capacity of dimethylglyoxime‐modified silica‐gel (DMGMS) was 71.37 mg g^–1 and the optimum pH for the quantitative recovery of copper was found to be 5.0. The optimum flow rate, sorbent amount, and sample volume were 1 mL min^–1, 300 mg, and 50 mL, respectively. 10 mL of 0.1 mol L^–1 HCl was the most suitable eluent. The detection limit of copper was 6.0 ng mL^–1. The recommended method, for the determination of copper, is simple and reliable, without any notable matrix effect and can be successfully applied to environmental water samples. Copper recovery in the range from 99–100% was obtained from seawater and thermal spring water using this method. The method was applied to standard reference materials, NIST‐1515 (apple leaves) and NIST‐1643e (simulated fresh water), for the determination of copper and the results were in good agreement with certified values.     

Effect of the Dead Sea–Red Sea canal modelling on the prediction of the Dead Sea conditions

A project to link the Dead Sea to the Red Sea via a canal is undergoing extensive study. In previous works, a generalized mathematical model describing the state of the Dead Sea and a simulation model to implement it have been developed. The model is extended to include the proposed canal project and investigates two alternative modelling canal scenarios: (1) introducing the canal water inflow into the bottom layer or (2) the top layer of the sea. The predicted general effects of the canal are the restoration of the water level of the sea to pre‐1970s level; an increase in the total evaporation rate and a decrease in the top layer salinity. Implementing scenario 1, the model predicts that: the water level of the Dead Sea will exceed the desired level design value and therefore shorter filling time can be used; seasonal stratification will persist; total evaporation rate will increase Modestly; there will a small decrease in the salinity of the top layer but a substantial decrease in the salinity of the bottom layer, which will hurt industries severely; there will be a continuation of seasonal crystallization of aragonite and gypsum. Implementing scenario 2 the model predicts that: the water level of the Dead Sea will be maintained at the desired level design value; stratification will be re‐established, with the formation of a permanent two‐layer system; there will be a substantial increase in the total evaporation rate; the salinity of the top layer will decrease significantly but there will be continuous slower salinity increase in the bottom layer; the crystallization of aragonite will cease, but seasonal gypsum crystallization can be expected to continue as soon as the filling period ends and the canal shifts into normal operation. Copyright © 2003 John Wiley & Sons, Ltd.     

Historic range of variability in geomorphic processes as a context for restoration: Rocky Mountain National Park,Colorado, USA

Evaluation of historic range of variability (HRV) is an effective tool for determining baseline conditions and providing context to researchers and land managers seeking to understand and enhance ecological function. Incorporating HRV into restoration planning acknowledges the dynamic quality of landscapes by allowing variability and disturbance at reasonable levels and permitting riverine landscapes to adapt to the physical processes of their watersheds. HRV analysis therefore represents a practical (though under‐utilized) method for quantifying process‐based restoration goals. We investigated HRV of aggradational processes in the subalpine Lulu City wetland in Rocky Mountain National Park to understand the impacts of two centuries of altered land use and to guide restoration planning following a human‐caused debris flow in 2003 that deposited up to 1 m of sand and gravel in the wetland. Historic aerial photograph interpretation, ground penetrating radar surveys, and trenching, coring, and radiocarbon dating of valley‐bottom sediments were used to map sediment deposits, quantify aggradation rates, and identify processes (in‐channel and overbank fluvial deposition, direct hillslope input, beaver pond filling, peat accumulation) creating alluvial fill within the wetland. Results indicate (i) the Lulu City wetland has been aggrading for several millennia, (ii) the aggradation rate of the past one to two centuries is approximately six times higher than long‐term pre‐settlement averages, (iii) during geomorphically active periods, short‐term aggradation rates during the pre‐settlement period were probably much higher than the long‐term average rate, and (iv) the processes of aggradation during the last two centuries are the same as historic processes of aggradation. Understanding the HRV of aggradation rates and processes can constrain management and restoration scenarios by quantifying the range of disturbance from which a landscape can recover without active restoration. Copyright © 2011 John Wiley & Sons, Ltd.     

Macro- and Micro-Purge Soil-Gas Sampling Methods for the Collection of Contaminant Vapors

Purging influence on soil‐gas concentrations for volatile organic compounds (VOCs), as affected by sampling tube inner diameter and sampling depth (i.e., system volume) for temporary probes in fine‐grained soils, was evaluated at three different field sites. A macro‐purge sampling system consisted of a standard, hollow, 3.2‐cm outer diameter (OD) drive probe with a retractable sampling point attached to an appropriate length of 0.48‐cm inner diameter (ID) Teflon^® tubing. The macro‐purge sampling system had a purge system volume of 24.5 mL at a 1‐m depth. In contrast, the micro‐purge sampling systems were slightly different between the field sites and consisted of a 1.27‐cm OD drive rod with a 0.10‐cm ID stainless steel tube or a 3.2‐cm OD drive rod with a 0.0254‐cm inner diameter stainless steel tubing resulting in purge system volumes of 1.2 and 7.05 mL at 1‐m depths, respectively. At each site and location within the site, with a few exceptions, the same contaminants were identified in the same relative order of abundances indicating the sampling of the same general soil atmosphere. However, marked differences in VOC concentrations were identified between the sampling systems, with micro‐purge samples having up to 27 times greater concentrations than their corresponding macro‐purge samples. The higher concentrations are the result of a minimal disturbance of the ambient soil atmosphere during purging. The minimal soil‐gas atmospheric disturbance of the micro‐purge sampling system allowed for the collection of a sample that is more representative of the soil atmosphere surrounding the sampling point. That is, a sample that does not contain an atmosphere that has migrated from distance through the geologic material or from the surface in response to the vacuum induced during purging soil‐gas concentrations. It is thus recommended that when soil‐gas sampling is conducted using temporary probes in fine‐grained soils, the sampling system use the smallest practical ID soil‐gas tubing and minimize purge volume to obtain the soil‐gas sample with minimal risk of leakage so that proper decisions, based on more representative soil‐gas concentrations, about the site can be made.     

Electrical resistivity imaging of hydrologic flow through surface coal mine valley fills with comparison to other landforms

Surface coal mining has altered land cover, near‐surface geologic structure, and hydrologic processes of large areas in central Appalachia, USA. These alterations are associated with changes in water quality such as elevated total‐dissolved solids, which is usually measured via its surrogate, specific conductance (SC). The SC of valley fill effluent streams is a function of fill construction methods, materials, and age; yet hydrologic studies that relate these variables to water quality are sparse due to the difficulty of conducting traditional hydrologic studies in mined landscapes. We used electrical resistivity imaging (ERI) to visualize the subsurface geologic structure and hydrologic flow paths within a valley fill. ERI is a noninvasive geophysical technique that maps spatiotemporal changes in resistivity of the subsurface. We paired ERI with artificial rainfall experiments to track infiltrated water as it moved through the valley fill. Results indicate that ERI can be used to identify subsurface geologic structure and track advancing wetting fronts or preferential flow paths. Our results suggest that the upper portion of the fill contains significant fines, whereas the deeper profile is primarily large rocks and void spaces. Water tended to pond on the surface of compacted areas until it reached preferential flow paths, where it appeared to infiltrate quickly down to >15 m depth in 75 min. ERI applications can improve understanding of how fill construction techniques influence subsurface water movement, and in turn may aid in the development of valley fill construction methods to reduce water quality effects.     

Separation and Preconcentration of Cobalt Using a New Schiff Base Derivative on Amberlite XAD‐7

In this study, a new solid‐phase extraction procedure has been developed for preconcentration and determination of Co ions in different water samples by flame atomic absorption spectrometry (FAAS). Cobalt was preconcentrated as N,N′‐bis(pyridine‐2‐yl‐methyl)benzene‐1,4‐diamine (Co‐BPMBDA) from sample solutions using a column containing Amberlite XAD‐7 and was determined. In order to achieve the best performance for the method, effects of several parameters such as pH, concentrations of ligand, sample flow rate, eluent, and matrix ions on the method efficiency were investigated. Under optimum conditions, the preconcentration factor was found to be 200 for 1000 mL waters samples. Detection limit based on the 3S_b criterion was calculated as 0.24 µg/L for 100 mL of sample solution and relative standard deviation was found to be 1.8%. The method was applied to determine the trace amounts of cobalt in water samples.