Sources of Ground Water Salinization in Parts of West Texas

Abstract
Determination of chemical constituent ratios allows distinction between two salinization mechanisms responsible for shallow saline ground water and vegetative-kill areas in parts of west Texas. Mixing of deep-basin (high Cl) salt water and shallow (low Cl) ground water results in saline waters with relatively low Ca/Cl, Mg/Cl, SO₄4/ Cl, Br/Cl, and NO₃/Cl ratios. In scattergrams of major chemical constituents vs. chloride, plots of these waters indicate trends with deep-basin brines as high Cl end members. Evaporation of ground water from a shallow water table, in contrast, results in saline water that has relatively high Ca/Cl, Mg/Cl, SO₄/Cl, and Br/CL ratios. Trends indicated by plots of this water type do not coincide with trends indicated by plots of sampled brines. Leaching of soil nitrate in areas with a shallow water table accounts for high NO₃ concentrations in shallow ground water.     

Generation of Hydrogen Gas as a Result of Drilling Within the Saturated Zone

Hydrogen gas was discovered within the steel casing above standing water in a percussion-drilled borehole on the Hanlord Site in south-central Washington state. In situ measurements of the borehole fluids indicated anoxic, low-Eh (<-400 mV) conditions. Ground water sampled from adjacent wells in the same formation indicated that the ground water was oxygenated. H₂ was generated during percussion drilling, due to the decomposition of borehole waters as a result of aqueous reactions with drilled sediment and steel from the drilling tools or casing. The generation of H₂ within percussion-drilled boreholes that extend below the water table may be more common than previously realized. The ambient concentration of H₂ produced during drilling was limited by microbial activity within the casing-resident fluids. H₂ was generated abiotically in the laboratory, whereby sterilized borehole slurry samples produced 100 times more H₂ than unsterilizcd samples. It appears that H₂ is metabolized by microorganisms and concentrations might be significantly greater if not for microbial metabolism.     

Tracing coalbed natural gas-coproduced water using stable isotopes of carbon

Recovery of hydrocarbons commonly is associated with coproduction of water. This water may be put to beneficial use or may be reinjected into subsurface aquifers. In either case, it would be helpful to establish a fingerprint for that coproduced water so that it may be tracked following discharge on the surface or reintroduction to geologic reservoirs. This study explores the potential of using δ¹³C of dissolved inorganic carbon (DIC) of coalbed natural gas (CBNG)–coproduced water as a fingerprint of its origin and to trace its fate once it is disposed on the surface. Our initial results for water samples coproduced with CBNG from the Powder River Basin show that this water has strongly positive δ¹³C_DIC (12‰ to 22‰) that is readily distinguished from the negative δ¹³C of most surface and ground water (−8‰ to −11‰). Furthermore, the DIC concentrations in coproduced water samples are also high (more than 100 mg C/L) compared to the 20 to 50 mg C/L in ambient surface and ground water of the region. The distinctively high δ¹³C and DIC concentrations allow us to identify surface and ground water that have incorporated CBNG-coproduced water. Accordingly, we suggest that the δ¹³C_DIC and DIC concentrations of water can be used for long-term monitoring of infiltration of CBNG-coproduced water into ground water and streams. Our results also show that the δ¹³C_DIC of CBNG-coproduced water from two different coal zones are distinct leading to the possibility of using δ¹³C_DIC to distinguish water produced from different coal zones.     

A Field Test of Electromigration as a Method for Remediating Sulfate from Shallow Ground Water

Eloctromigraiion offers a potential tool for remediating ground water contaminated with highly soluble components, such as Na⁺, Cl, NO₃ and SO₄⁻. A field experiment was designed to lest the efficacy of electromigration for preconcontrating dissolved SO₄² in ground water associated with a fossil-fuel power plant. Two shallow wells, 25 feel apart (one 25 feel deep, the other 47 feet deep), were constructed in the upper portion of an unconfined alluvial aquifer. The wells were constructed with a double-wall design, with an outer casing of 4-inch PVC and an inner lube of 2-inch FVC; both were fully slotted (0.01 inch). Electrodes were constructed by wrapping the inner lulling with a 100-foot length of rare-earth metal oxide/copper wire. An electrical potential of 10.65 volts DC Was applied, and tests were run for periods of 12, 44, and 216 hours. Results showed large changes in the pH from the initial pH of ground water of about 7.5 to values of approximately 2 and 12 at the anode and cathode, respectively. Despite the fact that the test conditions were far from ideal, dissolved SO₄^2-; was significantly concentrated at the anode. Over a period of approximately nine days, the concentration of SO₄^2- at the anode reached what appeared to he a steady-state value of 2200 mg/L. compared lo the initial value in ground water of approximately 1150 mg/L. The results of this field lest should encourage further investigation of electromigration as a tool in the remediation of contaminated ground water.     

Monitoring the Removal of Phosphate from Ground Water Discharging through a Pond-Bottom Permeable Reactive Barrier

Installation of a permeable reactive barrier to intercept a phosphate (PO₄) plume where it discharges to a pond provided an opportunity to develop and test methods for monitoring the barrier's performance in the shallow pond-bottom sediments. The barrier is composed of zero-valent-iron mixed with the native sediments to a 0.6-m depth over a 1100-m² area. Permanent suction, diffusion, and seepage samplers were installed to monitor PO₄ and other chemical species along vertical transects through the barrier and horizontal transects below and near the top of the barrier. Analysis of pore water sampled at about 3-cm vertical intervals by using multilevel diffusion and suction samplers indicated steep decreases in PO₄ concentrations in ground water flowing upward through the barrier. Samples from vertically aligned pairs of horizontal multiport suction samplers also indicated substantial decreases in PO₄ concentrations and lateral shifts in the plume's discharge area as a result of varying pond stage. Measurements from Lee-style seepage meters indicated substantially decreased PO₄ concentrations in discharging ground water in the treated area; temporal trends in water flux were related to pond stage. The advantages and limitations of each sampling device are described. Preliminary analysis of the first 2 years of data indicates that the barrier reduced PO₄ flux by as much as 95%.     

Field vs. Lab Alkalinity and pH: Effects on Ion Balance and Calcite Saturation Index

Ground water samples for a hydrochemical investigation were collected from 92 observation wells completed in a shallow, unconfined aquifer in southeastern North Dakota. The samples showed predominantly an increase in HCO₃- (positive bias) and both a pH decrease (positive bias) and a pH increase (negative bias) from field to lab. Positive pH bias generally was associated with ground water characterized by dissolved-solids concentrations less than 400 mg/L. Negative pH bias generally was associated with ground water characterized by dissolvedsolids concentrations greater than 400 mg/L.
Observed HCO₃- bias from field to lab slightly distorted ion balance distribution. Excess anions greater than 2 percent generally corresponded to increased HCO₃- from field to lab.
Observed HCO₃- and pH bias significantly distorted the distribution of calcite saturation indices. Samples with dissolved-solids concentrations less than 400 mg/L that generally showed a positive pH bias had a mean change in calcite saturation index of -0.214 (toward undersaturation). Samples with dissolved-solids concentrations greater than 400 mg/L that generally showed a negative pH bias had a mean change in calcite saturation of +0.132 (toward over saturation).
Calcite saturation indices were much more sensitive to observed pH bias than to observed HCO₃- bias. Linear regression analysis indicates % percent of the variability in calcite saturation index change from field to lab is attributed to change in pH from field to lab. Field pH should be used to compute calcite saturation index.     

Associations Between Rural Land Uses and Ground Water Quality in the Ogallala Aquifer, Northwest Texas

Recent nitrate, chloride, and bromide concentrations were studied in the Ogallala Aquifer of northwest Texas. The study included 361 wells with a median depth of 92 m in a rural area dominated by agricultural activity and oil and gas production. Only five observations surpassed the 44.3 mg/L standard for nitrate (10 mg/L NO₃-N). Four other observations, and one from the preceding set, exceeded the secondary standard of 250 mg/L for chloride. Maximum concentrations were 91.2 mg/L, 1530 mg/L, and 0.70 mg/L for nitrate, chloride, and bromide, respectively. Chloride/bromide ratios covered a broad range, from 30.4 to 10930, but medians were < 160 for each of two years analyzed. There were statistically significant correlations between nitrate and chloride, and chloride and well depth. Results of this study suggest that agricultural activity has locally impacted ground water in north-west Texas. Regionally, low aquifer recharge rates have curtailed ground water contamination from potentially adverse land uses.     

Long-term trends in chloride concentrations in shallow aquifers near Chicago

The rapid expansion of major cities throughout the world is resulting in the degradation of water quality in local aquifers. Increased use of road deicers since the middle of the 20th century in cities in the northern United States, Canada, and Europe has been linked to degraded ground water quality. In this article, Chicago, Illinois, and its outlying suburban areas are used as an example of the effects of urbanization in a historical context. A statistical study of historical water quality data was undertaken to determine how urbanization activities have affected shallow (<60 m) ground water quality. Chloride (Cl⁻) concentrations have been increasing, particularly in counties west and south of Chicago. In the majority of shallow public supply wells in the western and southern counties, Cl⁻ concentrations have been increasing since the 1960s. About 43% of the wells in these counties have rate increases greater than 1 mg/L/year, and 15% have increases greater than 4 mg/L/year. Approximately 24% of the samples collected from public supply wells in the Chicago area in the 1990s had Cl⁻ concentrations greater than 100 mg/L (35% in the western and southern counties); median values were less than 10 mg/L before 1960. The greater increase in Cl⁻ concentrations in the outer counties is most likely due to both natural and anthropogenic factors, including the presence of more significant and shallower sand and gravel deposits, less curbing of major highways and streets, and less development in some parts of these counties.     

Preserving Ground Water Samples With Hydrochloric Acid Does Not Result in the Formation of Chloroform

Water samples collected for the determination of volatile organic compounds (VOCs) are often preserved with hydrochloric acid (HCl) to inhibit the biotransformation of the analytes of interest until the chemical analyses can he performed. However, it is theoretically possible that residual free chlorine in the HCl can react with dissolved organic carbon (DOC) to form chloroform via the haloform reaction. Analyses of 1501 ground water samples preserved with HCl from the U.S. Geological Survey's National Water-Quality Assessment Program indicate that chloroform was the most commonly detected VOC among 60 VOCs monitored. The DOC concentrations were not significantly larger in samples with detectable chloroform than in those with no delectable chloroform, nor was there any correlation between the concentrations of chloroform and DOC. Furthermore, chloroform was detected more frequently in shallow ground water in urban areas (28.5% of the wells sampled) than in agricultural areas (1.6% of the wells sampled), which indicates that its detection was more related to urban land-use activities than to sample acidification. These data provide strong evidence that acidification with HCl does not lead to the production of significant amounts of chloroform in ground water samples. To verify these results, an acidification study was designed to measure the concentrations of all trihalomethanes (THMs) that can form as a result of HCl preservation in ground water samples and to determine if ascorbic acid (C₆H₈O₆) could inhibit this reaction if it did occur. This study showed that no THMs were formed as a result of HCl acidification, and that ascorbic acid had no discernible effect on the concentrations of THMs measured.     

In Situ Electromigration as a Method for Removing Sulfate, Metals, and Other Contaminants from Ground Water

Electromigration is proposed as an in situ method for preconcentrating contaminants in ground water prior to pumping and treating. In earlier investigations by the senior author and co-workers, it was found that Cu in synthetic ground water migrated strongly to a Pt cathode and plated out as metallic copper. In the present study, carbon electrodes were inserted into a laboratory column of fine quartz sand that was saturated with a lower concentration of CuSO₄ solution. A fixed potential of 2.5 V was applied, causing dissolved Cu and SO₄ to accumulate strongly at the cathode and anode, respectively. Only minor plating-out of Cu took place on the carbon electrodes. In addition to the use of carbon electrodes, the present research also investigated the effects of a lower concentration of metal, accumulation of SO₄ adjacent to the anodes, adsorption of Cu on the sand, and competition by moving ground water.
At an imposed voltage of 2.5 V and in the presence of 65 mg/L of dissolved Cu and 96 mg/L of SO₄ (0.001 M CuSO₄ solution), electrolysis of water caused large changes in the pH and speciation of the aqueous components, as well as precipitation of solid Cu-hydroxides. Significant retardation of Cu occurred in the presence of ground water flowing at an average intergranular velocity of 0.2 m/day, but only minor retardation at water velocities of 1.9 and 2.9 m/day.
Sulfate tends to migrate strongly to the anodes, suggesting that in situ electromigration may offer a useful new method for preconcentrating such highly soluble ions as SO₄, NO₃, and CI that are difficult to remove by conventional pump-and-treat methods. A number of potential problems exist that should be addressed in a field test.     

Empirical Assessment of Ground Water–to-Indoor Air Attenuation Factors for the CDOT-MTL Denver Site

The area surrounding the Colorado Department of Transportation Materials Testing Laboratory in Denver was the subject of intense investigation, involving the collection of thousands of ground water, soil-gas, and indoor air samples in order to investigate indoor air impacts associated with a subsurface release of chlorinated solvents. The preremediation portion of that data set is analyzed and reduced in this work to ground water–to-indoor air attenuation factors (α_gw= the ratio of the measured indoor air concentration to the soil-gas concentration predicted to be in equilibrium with the local ground water concentration). The empirical α_gw values for this site range from about 10⁻⁶ to 10⁻⁴ with an overall average of 3 × 10⁻⁵ (μg/L indoor air)/(μg/L soil gas). The analysis of this data set highlights the need for a thorough data review and data screening when using large data sets to derive empirical relationships between subsurface concentrations and indoor air. More specifically, it is necessary to identify those parts of the data that contain a strong vapor intrusion pathway signal, which generally will require concentrations well above reported detection levels combined with spatial or temporal correlation of subsurface and indoor concentrations.     

Reduction of Nitrate Loadings to Ground Water

Non-point source pollution of ground water systems has become a national concern in recent years. Researchers and regulatory agencies are investigating the source and processes of the contamination. Agricultural best management practices (BMPs) traditionally developed to reduce non-point source pollution of surface water resources are being investigated for their impact on ground water quality. This study used the CREAMS model to simulate the long-term effects of seven different BMPs on nitrate nitrogen (NO₃-N) loadings to a shallow, unconfined ground water system. Two representative watersheds, 5.8 and 8.9 hectares (14.3 and 22 acres) in area, in the Coastal Plain physiographic region of Maryland were selected for study. Soils in these watersheds belong to the Matapeake silt loam series and have moderate infiltration capacity. Results from this study indicated that BMPs used in conjunction with winter cover (barley) reduced NO₃-N leaching to the ground water system. It was also found that turfgrass reduced surface losses of water and nitrogen, but increased leaching losses of water and NO₃-N significantly. All of the BMPs simulated in this study resulted in leachate NO₃-N concentrations exceeding 10 ppm, the U.S. EPA health standard for public drinking water, indicating a need for alternate practices for reducing nitrate leaching.     

Sampling the Chemistry of Shallow Aquifer Systems — A Case Study

Pumped waters from 14 Pennsylvania wells, located in shallow sandstone, siltstone and shale aquifers, were continuously monitored for dissolved oxygen (D. O.), nitrate (NO₃), pH, electrical conductivity (EC) and water temperature in a discharge manifold at the well head. The amount of pumping or purging required to stabilize these parameter readings varied by well site and parameter being analyzed. However, the purging required was generally greatest for D. O. and least for water temperature where: D. O. < NO₃ pH < EC < water temperature. Wells located near the siltstone-shale interface generally required far more purging than did wells located elsewhere. Although parameter stability was often achieved within purging one bore volume, the complexity, diversity, and variability in the data and these well-ground water systems, suggest that no single purging rule is appropriate. Instead, the extent of purging required before sampling these shallow aquifers should be determined by incorporating on-site monitoring of target or related parameters into the purging process.
From a sampling perspective, the relationship between NO₃ and D. O. concentrations during purging were analyzed relative to aquifer type. For most wells located in sandstone or siltstone, NO₃ concentrations remained relatively constant during purging irrespective of changes in D. O. For most wells located in shale, these two were positively and similarly correlated, suggesting that a general relationship exists.     

Simulation of a Ground Water Recirculation Well with a Dual-Column Laboratory Setup

This paper describes a dual-column laboratory setup consisting of a glass column and a stainless-steel column filled with aquifer material. The setup was used to replicate a ground water recirculation well that serves as an in situ reactor and a combined injection/withdrawal well. The treatment solution consisted of a buffered titanium (III) citrate/vitamin B₁₂ mixture. The first column, representing the well, was made of glass, allowing for visual inspection of the mixing. The stainless-steel column was instrumented with redox (Eh) probes to monitor the changes in redox conditions. The redox measurement showed that, although the sand contained large quantities of iron oxides, the oxidation rate was relatively slow and the titanium solution would remain reduced for some time in the aquifer, continuing to react with the contaminants. This laboratory setup was used to optimize the reagent concentrations and rate of delivery for field implementation. It was found that 4 mM titanium citrate and 3 mg/L vitamin B₁₂ were sufficient to degrade 1,1,2,2-tetrachloroethane and carbon tetrachloride within one day, but not trichloroethylene, which required five days with 10 mM titanium citrate and 5 mg/L vitamin B₁₂.     

Nitrate Source Identification Using δ15N in a Ground Water Plume Near an Intensive Swine Operation

Nitrate-contaminated ground water beneath and adjacent to an intensive swine ( Sus scrofa domesticus ) production facility in the Middle Coastal Plain of North Carolina was analyzed for δ¹⁵N of nitrate (δ¹⁵N-NO₃). Results show that the isotopic signal of animal waste nitrogen is readily identifiable and traceable in nitrate in this ground water. The widespread land application of animal wastes from intensive livestock operations constitutes a potential source of nitrogen contamination to natural water throughout large regions of the United States and other countries. The site of the present study has been suspected as a nitrate contamination source to nearby domestic supply wells and has been monitored for several years by government and private water quality investigators through sampling of observation wells, ditches, and streams. δ¹⁵N of nitrate allowed direct identification of animal waste-produced nitrate in 11 of 14 wells sampled in this study, as well as recognition of nitrate contributions from non-animal waste agricultural sources in remaining wells.     

Remediation of Dissolved BTEX Through Surface Application: A Prototype Field Investigation

The feasibility of surface application for remediating monoaromatic hydrocarbons (benzene, toluene, ethylbenzene, and xylenes — termed BTEX as a croup) dissolved in ground water under field conditions was investigated at a site within Canadian Forces Base. Borden. Ontario. The surface area was 25 m² and underlain by 3 to 3.5 m of unsaturated sands soil. For periods of at least 216 hours, between 43 and 72 cm/d of water containing BTEX at concentrations that averaged between 8 and 11 mg/L were continuously applied by drip irrigation. Nitrogen was added to the soil as a nutrient for the final third of the investigation.
Before the applied water reached the water table. BTEX mass losses ranged from of to essentially KM) percent. Less than 6 percent of the BTEX mass losses could be attributed to volatilization from the unsaturated soil. The remaining BTEX mass losses were attributed to biodegradation, mostly in the top 50 cm of the soil, which contained more inorganic nitrogen and organic carbon than the deeper soil. Biodegradation rates increased with applied concentration, nitrogen addition, and exposure to BTEX. Benzene concentrations in ground water attained compliance with Canadian and American drinking water standards only after nitrogen application.     

Urban Ground Water Pollution: A Case Study in Cuttack City, India

A large number of ground water samples (360) was collected from 60 stations over six consecutive seasons to study the influence of the main sewerage drain on shallow ground water table beneath the municipal area of Cuttack, India. A majority of the samples collected from stations close to the drain exceeded the maximum permissible limits set by the World Health Organization (WHO). Almost all the samples near the drain exceeded the WHO limit for NO₃^- and Na⁺. However, the concentrations decreased as the distance from the drain increased. The winter season registered the maximum concentrations of NH₄⁺, NO₃^-, and SO₄^2- ions whereas the minimum values always coincided with the rainy season. R-mode factor analysis was conducted to find relationships amongst the 16 chemical parameters studied. Fluoride showed a negative correlation with Cl^-, Na⁺, NO₃^-, SO₄^2-, and PO₄^3-. The concentration of F^- may be lower in raw waste water than naturally occurs in the ground water. Therefore, a decrease in the concentration of F^- near the drain may be attributed to dilution by contributions of waste water to the ground water. The rest of the parameters were found to be directly related to the distance of collection points to the sewerage. The distribution of nutrients is strongly affected by leaching of waste water into the ground water.     

Partial melting controls on the northwest Kyushu basalts from Saga-Futagoyama

Abstract   The major element and compatible trace element compositions of the northwest Kyushu basalts (NWKBs) collected from Saga-Futagoyama were analyzed to examine the petrogenesis of these basalts. Although nepheline-normative alkaline basalts are not found in the basalts from Saga-Futagoyama, the Saga-Futagoyama basalts almost cover the major element variations of NWKBs. The basalts can be chemically divided into two groups: an Fe-poor group (IPG) and an Fe-rich group (IRG). The compositional variation of IPG basalts is essentially controlled by the partial melting of the source as suggested by the following: (i) bulk rock MgO, FeO and NiO compositions indicate that some IPG samples were equilibrated with mantle olivine; and (ii) correlations between Al₂O₃, CaO and MgO are consistent with those of experimental partial melts of peridotites. The inconsistent behaviors of the elements compatible with clinopyroxene (Cpx), such as V (Sc and Cu), preclude the significant role of the fractional crystallization of Cpx and spinel in IPG variation. IPG basalts have low Al and high Fe concentrations compared to the products of melting experiments involving peridotites and pyroxenites, suggesting that the IPG source would have a lithology and bulk rock composition different from those of typical peridotites and pyroxenites. IRG basalts have negative correlations between Fe₂O₃* and MgO, and between V and Fe₂O₃*/MgO, indicating that IRG basalts would have fractionated Cpx. However, the anomalously Fe-rich feature of IRG basalts compared with NWKBs collected from other areas suggests that the role of Cpx fractionation in NWKBs is minor. Relatively low melting temperatures would have principally caused the large chemical variation of NWKBs.     

Predicting ground water nitrate concentration from land use

Ground water nitrate concentrations on Nantucket Island, Massachusetts, were analyzed to assess the effects of land use on ground water quality. Exploratory data analysis was applied to historic ground water nitrate concentrations to determine spatial and temporal trends. Maximum likelihood Tobit and logistic regression analyses of explanatory variables that characterize land use within a 1000-foot radius of each well were used to develop predictive equations for nitrate concentration at 69 wells. The results demonstrate that historic nitrate concentrations downgradient from agricultural land are significantly higher than nitrate concentrations elsewhere. Tobit regression results demonstrate that the number of septic tanks and the percentages of forest, undeveloped, and high-density residential land within a 1000-foot radius of a well are reliable predictors of nitrate concentration in ground water. Similarly, logistic regression revealed that the percentages of forest, undeveloped, and low-density residential land are good indicators of ground water nitrate concentration > 2 mg/L. The methodology and results outlined here provide a useful tool for land managers in communities with shallow water tables overlain with highly permeable materials to evaluate potential effects of development on ground water quality.     

An Analysis of Nitrate-Nitrogen in Ground Water Beneath Unsewered Subdivisions

Water samples from private water supply wells in five unsewered subdivisions were tested for nitrate-nitrogen to determine the possible impact of septic systems on ground water quality. Three subdivisions are located in Eau Claire County and two in LaCrosse County, Wisconsin.
The nitrate-nitrogen concentrations in the wells were analyzed in relation to ground water flow direction, the location of septic systems within the subdivision, and the hydrogeologic and physical characteristics of the subdivisions. A comparison of three nitrogen mass balance models helped to identify the possible sources of nitrate-nitrogen in the wells.
The results indicate that nitrogen from septic systems and lawn fertilizer cause nitrate-nitrogen to increase in the ground water beneath the downgradient side of the subdivisions. In three of the five subdivisions the highest nitrate-nitrogen value exceeds the drinking water standard of 10 mg/L.