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%.     

MTBE, TBA, and TAME Attenuation in Diverse Hyporheic Zones

Groundwater contamination by fuel-related compounds such as the fuel oxygenates methyl tert -butyl ether (MTBE), tert -butyl alcohol (TBA), and tert -amyl methyl ether (TAME) presents a significant issue to managers and consumers of groundwater and surface water that receives groundwater discharge. Four sites were investigated on Long Island, New York, characterized by groundwater contaminated with gasoline and fuel oxygenates that ultimately discharge to fresh, brackish, or saline surface water. For each site, contaminated groundwater discharge zones were delineated using pore water geochemistry data from 15 feet (4.5 m) beneath the bottom of the surface water body in the hyporheic zone and seepage-meter tests were conducted to measure discharge rates. These data when combined indicate that MTBE, TBA, and TAME concentrations in groundwater discharge in a 5-foot (1.5-m) thick section of the hyporheic zone were attenuated between 34% and 95%, in contrast to immeasurable attenuation in the shallow aquifer during contaminant transport between 0.1 and 1.5 miles (0.1 to 2.4 km). The attenuation observed in the hyporheic zone occurred primarily by physical processes such as mixing of groundwater and surface water. Biodegradation also occurred as confirmed in laboratory microcosms by the mineralization of U- ¹⁴C-MTBE and U-¹⁴C-TBA to ¹⁴CO₂ and the novel biodegradation of U- ¹⁴C-TAME to ¹⁴CO₂ under oxic and anoxic conditions. The implication of fuel oxygenate attenuation observed in diverse hyporheic zones suggests an assessment of the hyporheic zone attenuation potential (HZAP) merits inclusion as part of site assessment strategies associated with monitored or engineered attenuation.     

Fate of MTBE Relative to Benzene in a Gasoline-Contaminated Aquifer (1993–98)

Methyl tert -butyl ether (MTBE) and benzene have been measured since 1993 in a shallow, sandy aquifer contaminated by a mid-1980s release of gasoline containing fuel oxygenates. In wells downgradient of the release area, MTBK was detected before benzene, reflecting a chromatographic-like separation of these compounds in the direction of ground water flow. Higher concentrations of MTBE and benzene were measured in the deeper sampling ports of multilevel sampling wells located near the release area, and also up to 10 feet (3 m) below the water table surface in nested wells located farther from the release area. This distribution of higher concentrations at depth is caused by recharge events that deflect originally horizontal ground water flowlines. In the laboratory, microcosms containing aquifer material incubated with uniformly labeled ¹⁴C-MTBE under aerobic and anaerobic. Fe(III)-reducing conditions indicated a low but measurable biodegradation potential (<3%¹⁴C-MTBW as ¹⁴CO₂) after a seven-month incubation period, Tert -butyl alcohol (TBA), a proposed microbial-MTBE transformation intermediate, was detected in MTBE-contaminated wells, but TBA was also measured in unsaturated release area sediments. This suggests that TBA may have been present in the original fuel spilled and does not necessarily reflect microbial degradation of MTBE. Combined, these data suggest that milligram per liter to microgram per liter decreases in MTBE concentrations relative to benzene are caused by the natural attenuation processes of dilution and dispersion with less-contaminated ground water in the direction of flow rather than biodegradation at this point source gasoline release site.     

Flowpath Independent Monitoring of Reductive Dechlorination Potential in a Fractured Rock Aquifer

The flowpath dependent approaches that are typically employed to assess biodegradation of chloroethene contaminants in unconsolidated aquifers are problematic in fractured rock settings, due to difficulties defining discrete groundwater flowpaths in such systems. In this study, the variation in the potential for chloroethene biodegradation with depth was evaluated in a fractured rock aquifer using two flowpath independent lines of field evidence: (1) the presence of the three biochemical prerequisites [electron donor(s), chloroethene electron acceptor(s), and chlororespiring microorganism(s)] for efficient chloroethene chlororespiration and (2) the in situ accumulation of chloroethene reductive dechlorination daughter products. The validity of this approach was assessed by comparing field results with the results of [1, 2-¹⁴C] cis -DCE microcosm experiments. Microcosms were prepared with depth-specific core material, which was crushed and emplaced in discrete packer intervals for 1 year to allow colonization by the indigenous microbial community. Packer intervals characterized by significant electron donor concentrations, elevated numbers of chlororespiring microorganisms, and high reductive dechlorination product to parent contaminant ratios correlated well with the production of ¹⁴C-labeled reductive dechlorination products in the microcosm experiments. These results indicate that, in the absence of information on discrete groundwater flowpaths, a modified approach emphasizing flowpath independent lines of evidence can provide insight into the temporal and spatial variability of contaminant biodegradation in fractured rock systems.     

Determining Hydraulic Conductivity Using Pumping Data from Low-Flow Sampling

Hydraulic conductivity values computed using the steady-state discharge and drawdown attained while low-flow sampling were evaluated to determine if they were equivalent to those determined from slug testing. Based on testing 12 wells, it was found that the results were statistically equivalent. Conductivity values computed using low-flow sampling parameters were also evaluated as to their reproducibility in actual practice by analyzing consultant data for three wells sampled over three quarterly monitoring periods by four field technicians. The results were found to be reproducible within about a factor of 2 or better. Since the method is based on only one pair of parameters, diligence is required in attaining steady state and in accurately measuring the flow rate and drawdown. Conductivity values computed using this approach can enhance the use of low-flow data gathered in water quality sampling, avoid the need for slug testing in a subsequent phase of investigation, and help reduce the cost of characterizing sites when multilevel samplers are used. Given the practical range of discharge in low-flow sampling, the method was found to be applicable at conductivity values somewhat greater than 10⁻⁶ cm/s. Given the typical accuracy of water level meters and pressure transducers and a maximum discharge of 1 L/min, as mandated by regulatory guidance, the method has a calculated upper conductivity limit in the range of 10⁻³ to 10⁻² cm/s.     

Hydrogen Peroxide Treatment of Septic Systems and Its Negative Effects on Shallow Ground Water

Soil-solution samplers and shallow ground water monitoring wells were utilized to monitor nitrate movement to ground water following H₂O₂ application to a clogged soil absorption system. Nitrate-nitrogen concentrations in soil water and shallow ground water ranged from 29 to 67 mg/L and 9 to 22 mg/L, respectively, prior to H₂O₂ treatment. Mean nitrate-nitrogen concentrations in soil water and ground water increased and ranged from 67 to 115 mg/L and 23 to 37 mg/L, respectively, one week after H₂O₂ application. Elevated concentrations of nitrate-nitrogen above background persisted for several weeks following H₂O₂ treatment. The H₂O₂ treatment was unsuccessful in restoring the infiltrative capacity of a well-structured soil. Application of H₂O₂ to the soil absorption system poses a threat of nitrate contamination of ground water and its usefulness should be fully evaluated before rehabilitation is attempted.     

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.     

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.     

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.     

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.     

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.     

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.     

Eolian Transport of Geogenic Hexavalent Chromium to Ground Water

A conceptual model of eolian transport is proposed to address the widely distributed, high concentrations of hexavalent chromium (Cr⁺⁶) observed in ground water in the Emirate of Abu Dhabi, United Arab Emirates. Concentrations (30 to more than 1000 μg/L Cr⁺⁶) extend over thousands of square kilometers of ground water systems. It is hypothesized that the Cr is derived from weathering of chromium-rich pyroxenes and olivines present in ophiolite sequence of the adjacent Oman (Hajar) Mountains. Cr⁺³ in the minerals is oxidized to Cr⁺⁶ by reduction of manganese and is subsequently sorbed on iron and manganese oxide coatings of particles. When the surfaces of these particles are abraded in this arid environment, they release fine, micrometer-sized, coated particles that are easily transported over large distances by wind and subsequently deposited on the surface. During ground water recharge events, the readily soluble Cr⁺⁶ is mobilized by rain water and transported by advective flow into the underlying aquifer. Chromium analyses of ground water, rain, dust, and surface (soil) deposits are consistent with this model, as are electron probe analyses of clasts derived from the eroding Oman ophiolite sequence. Ground water recharge flux is proposed to exercise some control over Cr⁺⁶ concentration in the aquifer.     

Revisiting a classification scheme for U.S.-Mexico alluvial basin-fill aquifers

Intermontane basins in the Trans-Pecos region of westernmost Texas and northern Chihuahua, Mexico, are target areas for disposal of interstate municipal sludge and have been identified as possible disposal sites for low-level radioactive waste. Understanding ground water movement within and between these basins is needed to assess potential contaminant fate and movement. Four associated basin aquifers are evaluated and classified; the Red Light Draw Aquifer, the Northwest Eagle Flat Aquifer, the Southeast Eagle Flat Aquifer, and the El Cuervo Aquifer. Encompassed on all but one side by mountains and local divides, the Red Light Draw Aquifer has the Rio Grande as an outlet for both surface drainage and ground water discharge. The river juxtaposed against its southern edge, the basin is classified as a topographically open, through-flowing basin. The Northwest Eagle Flat Aquifer is classified as a topographically closed and drained basin because surface drainage is to the interior of the basin and ground water discharge occurs by interbasin ground water flow. Mountains and ground water divides encompass this basin aquifer on all sides; yet, depth to ground water in the interior of the basin is commonly >500 feet. Negligible ground water discharge within the basin indicates that ground water discharges from the basin by vertical flow and underflow to a surrounding basin or basins. The most likely mode of discharge is by vertical, cross-formational flow to underlying Permian rocks that are more porous and permeable and subsequent flow along regional flowpaths beneath local ground water divides. The Southeast Eagle Flat Aquifer is classified as a topographically open and drained basin because surface drainage and ground water discharge are to the adjacent Wildhorse Flat area. Opposite the Eagle Flat and Red Light Draw aquifers is the El Cuervo Aquifer of northern Chihuahua, Mexico. The El Cuervo Aquifer has interior drainage to Laguna El Cuervo, which is a phreatic playa that also serves as a focal point of ground water discharge. Our evidence suggests that El Cuervo Aquifer may lose a smaller portion of its discharge by interbasin ground water flow to Indian Hot Springs, near the Rio Grande. Thus, El Cuervo Aquifer is a topographically closed basin that is either partially drained if a component of its ground water discharge reaches Indian Hot Springs or undrained if all its natural ground water discharge is to Laguna El Cuervo.     

Modeling decadal timescale interactions between surface water and ground water in the central Everglades, Florida, USA

Surface-water and ground-water flow are coupled in the central Everglades, although the remoteness of this system has hindered many previous attempts to quantify interactions between surface water and ground water. We modeled flow through a 43,000 ha basin in the central Everglades called Water Conservation Area 2A. The purpose of the model was to quantify recharge and discharge in the basin's vast interior areas. The presence and distribution of tritium in ground water was the principal constraint on the modeling, based on measurements in 25 research wells ranging in depth from 2 to 37 m. In addition to average characteristics of surface-water flow, the model parameters included depth of the layer of ‘interactive’ ground water that is actively exchanged with surface water, average residence time of interactive ground water, and the associated recharge and discharge fluxes across the wetland ground surface. Results indicated that only a relatively thin (8 m) layer of the 60 m deep surfical aquifer actively exchanges surface water and ground water on a decadal timescale. The calculated storage depth of interactive ground water was 3.1 m after adjustment for the porosity of peat and sandy limestone. Modeling of the tritium data yielded an average residence time of 90 years in interactive ground water, with associated recharge and discharge fluxes equal to 0.01 cm d⁻¹. ³H/³He isotopic ratio measurements (which correct for effects of vertical mixing in the aquifer with deeper, tritium-dead water) were available from several wells, and these indicated an average residence time of 25 years, suggesting that residence time was overestimated using tritium measurements alone. Indeed, both residence time and storage depth would be expected to be overestimated due to vertical mixing. The estimate of recharge and discharge (0.01 cm d⁻¹) that resulted from tritium modeling therefore is still considered reliable, because the ratio of residence time and storage depth (used to calculated recharge and discharge) is much less sensitive to vertical mixing compared with residence time alone. We conclude that a small but potentially significant component of flow through the Everglades is recharged to the aquifer and stored there for years to decades before discharged back to surface water. Long-term storage of water and solutes in the ground-water system beneath the wetlands has implications for restoration of Everglades water quality.     

Vitamin B12-Catalyzed Dechlorination of Perchloroethylene Present as Residual DNAPL

The goal of this study was the cleanup of residual solvents in the saturated zone using an in situ biochemical treatment. Perchloroethylene (PCE) was chosen as a model compound because it is the most commonly found organic ground water contaminant. A mixture of vitamin B₁₂ with titanium citrate was pumped as the remedial solution through a column containing 100 μL of PCE residual. The rate of reaction was found to be first order with respect 10 the concentration of PCE and to the concentration of vitamin B₂. At 10 ppm B₁₂, more than 85 percent PCM was degraded to trichloroelhylene (TCE) and dichloroelhylene (DCE) in two hours. The presence of low to moderate concentrations of organic carbon had no significant effect on the reaction. Vitamin B₁₂ reduced by titanium citrate was found lo be compatible with the survival of anaerobic bacteria. The four major advantages of the biochemical system over the use of anaerobic bacteria are that (1) the rate is faster: (2) there is no need for the careful balance of nutrients or the addition of an extraneous carbon source: (3) there is no restriction in the concentration range of the compound to be treated; and (4) the remedial solution is mobile, even in the presence of organic carbon.     

Analysis of Petroleum-Contaminated Water by GC/FID with Direct Aqueous Injection

A direct aqueous injection capillary gas chromatography/flame ionization (GC/FID) procedure for the analysis of petroleum-contaminated water was developed and applied to seven water samples saturated with different petroleum products. Separation of C₁ to C₄ alcohols, C₆ to C₉ monoaromatics, MTBE, phenol, aniline, and other compounds, and the detection of BTEX compounds at concentrations at or below their maximum contaminant levels (MCLs) is reported. Among the test compounds analyzed, the only pair found to coelute were 1-butanol and benzene. A method for confirmation of alcohols and polar compounds in the presence of dissolved petroleum hydrocarbons was also evaluated. In this case, water samples were analyzed before and after purging. Polar compounds were found to be significant components of the water soluble fractions of commercial petroleum products.     

A Geostatistically Based Ground Water Monitoring Study of Nonpoint Source No3--N Concentrations

Geostatistical interpretations of ground water monitoring data are presented to define the spatial distributions of NO₃^--N in the ground water at two demonstration test sites in the Idaho Snake River Plain. Sequential Gaussian simulation was used to delineate monthly ground water NO₃^--N changes during and after implementation of a prescribed crop rotation at test site 1. Trend surface analyses were used to illustrate monthly ground water NO₃^--N changes during and after a prescribed irrigation practice was implemented at test site 2. These evaluations suggest that geostatistically based ground water monitoring can be effective in the delineation of changes in ground water quality in shallow, unconfined aquifers in agricultural areas such as those in southern Idaho. Geostatistical methods showed spatial and temporal changes in ground water NO₃^--N inferred to be a result of the agricultural practices implemented.     

Natural Gradient Tracer Test to Evaluate Natural Attenuation of MTBE Under Anaerobic Conditions

A natural gradient tracer test using perdeuterated MTBE was conducted in an anaerobic aquifer to determine the relative importance of dispersion and degradation in reducing MTBE concentrations in ground water. Preliminary ground water chemistry and hydraulic conductivity data were used to place the tracer within an existing dissolved MTBE plume at Port Hueneme, California. Following one year of transport, the tracer plume was characterized in detail.
Longitudinal dispersion was identified as the dominant mechanism for lowering the perdeuterated MTBE concentrations. The method of moments was used to determine the longitudinal and lateral dispersion coefficients (0.85 m²/day and 0.08 m²/day, respectively). A mass-balance analysis, carried out after one year of transport, accounted for 110% of the injected mass and indicated that no significant mass loss occurred. The plume structure created by zones of higher and lower hydraulic conductivity at the site was complex, consisting of several localized areas of high tracer concentration in a lower concentration plume. This is important because the aquifer has generally been characterized as exhibiting fairly minor heterogeneity. In addition, the tracer plume followed a curved flowpath that deviated from the more macroscopic direction of ground water flow inferred from local ground water elevation measurements and the behavior of the existing plume. Understanding the mass balance, plume structure, curvature of the tracer plume, and consequently natural attenuation behavior required the detailed sampling approach employed in this study. These data imply that a detailed understanding of site hydrogeology and an extensive sampling network may be critical for the correct interpretation of monitored natural attenuation of MTBE.     

Oxygen Transfer Through Flexible Tubing and Its Effects on Ground Water Sampling Results

A model for the diffusion of gases through polymeric tubing was derived which predicts that the amount of gas transferred is proportional to the tubing length and inversely proportional to the pumping rate. The model was experimentally tested and confirmed for oxygen transfer through fluorinated ethylene-propylene copolymer (FEP) tubing using tubing lengths and flow rates typical of ground water sampling. Diffusion can introduce measurable concentrations of oxygen into initially anoxic water. Diffusive loss of carbon dioxide from water that is oversaturated with respect to atmospheric CO₂ does not measurably affect pH under similar usage conditions.