A simple method for calculating growth rates of petroleum hydrocarbon plumes

Consumption of aquifer Fe(III) during biodegradation of ground water contaminants may result in expansion of a contaminant plume, changing the outlook for monitored natural attenuation. Data from two research sites contaminated with petroleum hydrocarbons show that toluene and xylenes degrade under methanogenic conditions, but the benzene and ethylbenzene plumes grow as aquifer Fe(III) supplies are depleted. By considering a one-dimensional reaction front in a constant unidirectional flow field, it is possible to derive a simple expression for the growth rate of a benzene plume. The method balances the mass flux of benzene with the Fe(III) content of the aquifer, assuming that the biodegradation reaction is instantaneous. The resulting expression shows that the benzene front migration is retarded relative to the ground water velocity by a factor that depends on the concentrations of hydrocarbon and bioavailable Fe(III). The method provides good agreement with benzene plumes at a crude oil study site in Minnesota and a gasoline site in South Carolina. Compared to the South Carolina site, the Minnesota site has 25% higher benzene flux but eight times the Fe(III), leading to about one-sixth the expansion rate. Although it was developed for benzene, toluene, ethylbenzene, and xylenes, the growth-rate estimation method may have applications to contaminant plumes from other persistent contaminant sources.     

Rapid evolution of redox processes in a petroleum hydrocarbon-contaminated aquifer

Ground water chemistry data collected over a six-year period show that the distribution of contaminants and redox processes in a shallow petroleum hydrocarbon-contaminated aquifer has changed rapidly over time. Shortly after a gasoline release occurred in 1990, high concentrations of benzene were present near the contaminant source area. In this contaminated zone, dissolved oxygen in ground water was depleted, and by 1994 Fe(III) reduction and sulfate reduction were the predominant terminal electron accepting processes. Significantly, dissolved methane was below measurable levels in 1994, indicating the absence of significant methanogenesis. By 1996, however, depletion of solid-phase Fe(III)-oxyhydrox ides in aquifer sediments and depletion of dissolved sulfate in ground water resulted in the onset of methanogenesis. Between 1996 and 2000, water-chemistry data indicated that methanogenic metabolism became increasingly prevalent. Molecular analysis of 16S-rDNA extracted from sediments shows the presence of a more diverse methanogenic community inside as opposed to outside the plume core, and is consistent with water-chemistry data indicating a shift toward methanogenesis over time. This rapid evolution of redox processes reflects several factors including the large amounts of contaminants, relatively rapid ground water flow (approximately 0.3 m/day [approximately foot/day]), and low concentrations of microbially reducible Fe(III) oxyhydroxides ( approximately 1 micromol/g) initially present in aquifer sediments. These results illustrate that, under certain hydrologic conditions, redox conditions in petroleum hydrocarbon-contaminated aquifers can change rapidly in time and space, and that the availability of solid-phase Fe(III)-oxyhydroxides affects this rate of change.     

Iron and Manganese in Groundwater: Using Kriging and GIS to Locate High Concentrations in Buncombe County,North Carolina

For health, economic, and aesthetic reasons, allowable concentrations (as suggested by the United States Environmental Protection Agency) of the secondary contaminants iron (Fe) and manganese (Mn) found present in drinking water are 0.3 and 0.05 mg/L, respectively. Water samples taken from private drinking wells in rural communities within Buncombe County, North Carolina contain concentrations of these metals that exceed secondary water quality criteria. This study predicted the spatial distribution of Fe and Mn in the county, and evaluated the effect of site environmental factors (bedrock geology, ground elevation, saprolite thickness, and drinking water well depth) in controlling the variability of Fe and Mn in groundwater. A statistically significant correlation between Fe and Mn concentrations, attributable to bedrock geology, was identified. Prediction models were created using ordinary kriging and cokriging interpolation techniques to estimate the presence of Fe and Mn in groundwater where direct measurements are not possible. This same procedure can be used to estimate the trend of other contaminants in the groundwater in different areas with similar hydrogeological settings.     

Dynamic Study of Common Well Screen Materials

Experiments simulating the dynamics of compliance sampling via a monitoring well were performed to assess the effects of common well screen materials (rigid polyvinyl chloride, polytetrafluoroethylene, stainless steel 304. and stainless steel 316) on several metals and tri- chloroethylene (TCE) in ground water. This was achieved by using a continuous flow-through chamber system capable of exposing monitoring well screens to ground water for periods ranging from 0.25 to 8 hours. The findings of this study are more representative than static laboratory experiments for assessing the potential effects well casing materials have on ground water samples. Under dynamic flow conditions stainless steel 304 and 316 screens were found to influence solution concentrations of Pb, Cd, Cr, Ni, and Fe, while ground water TCE concentrations were not affected by any of the materials tested.     

Creation of a Subsurface Permeable Treatment Zone for Aqueous Chromate Contamination Using In Situ Redox Manipulation

An in situ redox manipulation (ISRM) method for creating a permeable treatment zone in the subsurface has been developed at the laboratory bench and intermediate scales and deployed at the field scale for reduction/immobilization of chrornate contamination. At other sites, the same redox technology is currently being tested for dechlorination of TCE. The reduced zone is created by injected reagents that reduce iron naturally present in the aquifer sediments from Fe(III) to surface-bound and structural Fe(II) species. Standard ground water wells are used, allowing treatment of contaminants too deep below the ground surface for conventional treneh-and-fill technologies.
A proof-of-principle field experiment was conducted in September 1995 at a chromate (hexavalent chromium) contaminated ground water site on the Hartford Site in Washington. The test created a 15 m (˜50 feet) diameter cylindrical treatment zone. The three phases of the test consisted of (1) injection of 77, 000 L (20, 500 gallons) of buffered sodium dithionite solution in 17.1 hours, (2) reaction for 18.5 hours, and (3) withdrawal of 375, 000 L (99, 600 gallons) in 83 hours. The withdrawal phase recovered 87% to 90% of the reaction products. Analysis of post-experimental sediment cores indicated that 60% to 100% of the available reactive iron in the treated zone was reduced. The longevity of the reduced zone is estimated between seven and 12 years based on the post-experiment core samples. Three and half years after the field test, the treatment zone remains anoxic, and hexavalent chromium levels have been reduced from 0.060 mg/L to below detection limits (0.008 mg/L). Additionally, no significant permeability changes have been detected during any phase of the experiment.     

淮河流域平原区浅层地下水铁锰分布特征及成因浅析

结合淮河流域平原区水文地质条件,阐述了淮河流域平原区铁锰元素在浅层地下水（埋深0～50 m）中的赋存特征和分布规律.结合前人研究成果并总结现有水质资料,认为淮河流域地下水中铁锰的形成和分布特征除了受含水介质成分、上覆土层性质、酸碱条件等影响外,主要受氧化还原环境控制.建议通过适当除铁锰工艺或改变地下水循环条件等方式来改变研究区浅层水地下水水质状况.     

Fe/O ratio variations during the disturbed stage in the development of the solar cosmic ray fluxes: Manifestations of the first ionization potential effect in the solar cosmic ray composition

The accelerated particle energy spectra in different energy intervals (from 0.06 to 75.69 MeV n^–1) have been constructed for various powerful flare events (1997–2006) with the appearance of solar cosmic rays (SCRs) based on the processing of data from the Advanced Composition Explorer (ACE) and WIND spacecraft. Flares were as a rule accompanied by coronal mass ejections. Different specific features in the particle spectra behavior, possibly those related to different acceleration processes, were revealed when the events developed. The Fe/O abundance ratio in different energy intervals during the disturbed development of flareinduced fluxes has been qualitatively estimated. It has been established that ground level event (GLE) fluxes represent an individual subclass of gradual events according to the character of Fe/O variations. The manifestations of the first ionization potential (FIP) effect in the composition of SCRs during their propagation have been qualitatively described.     

Potential of Common Well Casing Materials to Influence Aqueous Metal Concentrations

Static leaching and sorption laboratory studies were performed to assess the potential of polyvinyl chloride (PVC), polytetrafluoroethylene (PTFE), and two types of stainless steel (SS 304 and SS 316) well casing materials to influence metal concentrations in ground water solutions with low dissolved oxygen. Overall, PTFE was inert, whereas one or both stainless steels significantly altered the solution concentrations of Cd, Cr, Cu, Pb, Fe, and Ni. PVC was generally more reactive than PTFE, but did not significantly alter the solution metal concentrations as often, or as greatly, as either of the stainless casings.     

MNA as a Remedy for Arsenic Mobilized by Anthropogenic Inputs of Organic Carbon

The potential application of monitored natural attenuation (MNA) as a remedy for ground water contaminated with arsenic (As) is examined for a subset of contaminated sites, specifically those where naturally occurring As has been mobilized due to localized anthropogenic organic carbon (OC) releases. This includes sites subject to petroleum releases, exposure to landfill leachates, and OC additions for biostimulation of reductive dechlorination of chlorinated solvents. The key characteristic of these sites is that, under conditions prevailing before the anthropogenic OC introduction, the naturally occurring As in the subsurface was not mobile and did not adversely affect ground water quality. This suggests that, in the far-field (where background conditions are (re) established), As may be sequestered upon contact of the contaminated ground water with either or both the (uncontaminated) ambient ground water and the background aquifer minerals. The observed extents of elevated concentrations (or "footprints") of As and other chemical species, such as dissolved OC and iron (Fe), and related parameters, such as redox potential ( E _h) and dissolved oxygen, and their evolution over time can be used to assess the mobilization and sequestration of As and the potential feasibility of MNA as a remedial option. Ultimately, the capacity for As sequestration must be assessed in the context of the OC loading to the site, which may require "active" measures for source control. Monitoring is needed to confirm the continuing effectiveness of the MNA remedy or to indicate if contingency measures must be implemented.     

Tracer Method to Determine Residence Time in a Permeable Reactive Barrier

A method is presented to evaluate ground water residence time in a zero‐valent iron (ZVI) permeable reactive barrier (PRB) using radon‐222 (²²²Rn) as a radioactive tracer. Residence time is a useful indicator of PRB hydraulic performance, with application to estimating the volumetric rate of ground water flow through a PRB, identifying flow heterogeneity, and characterizing flow conditions over time as a PRB matures. The tracer method relies on monitoring the decay of naturally occurring aqueous ²²²Rn as ground water flows through a PRB. Application of the method at a PRB site near Monticello, Utah, shows that after 8 years of operation, residence times in the ZVI range from 80 to 486 h and correlate well with chemical parameters (pH, Ca, SO₄, and Fe) that indicate the relative residence time. Residence times in this case study are determined directly from the first‐order decay equation because we show no significant emanation of ²²²Rn within the PRB and no measurable loss of ²²²Rn other than by radioactive decay.     

柴达木盆地苏干湖表层沉积与尘暴事件——元素示踪的初步结果

通过分析苏干湖地区10个地表表层沉积物、9个大气降尘(含2个尘暴降尘)、16个湖泊表层沉积物等样品的8种常量-微量元素和11种稀土元素的含量,以及同类沉积不同元素含量和不同沉积同一元素含量的相关性,结果表明,在湖泊沉积体系中Al、Fe、Sc含量的变化与强风-尘暴过程有关,指示了湖泊沉积碎屑颗粒风成输入的可能性．元素Fe、Sc含量在3种不同的沉积物中差异不大,与尘暴事件的强度和频次有关．稀土元素结果显示3类沉积具有同源性．苏干湖沉积可以用来重建研究区尘暴演化历史．     

Analysis of recharge-induced geochemical change in a contaminated aquifer

Recharge events that deliver electron acceptors such as O2, NO3, SO4, and Fe3+ to anaerobic, contaminated aquifers are likely important for natural attenuation processes. However, the specific influence of recharge on (bio)geochemical processes in ground water systems is not well understood. The impact of a moderate-sized recharge event on ground water chemistry was evaluated at a shallow, sandy aquifer contaminated with waste fuels and chlorinated solvents. Multivariate statistical analyses coupled with three-dimensional visualization were used to analyze ground water chemistry data (including redox indicators, major ions, and physical parameters) to reveal associations between chemical parameters and to infer processes within the ground water plume. Factor analysis indicated that dominant chemical associations and their interpreted processes (anaerobic and aerobic microbial processes, mineral precipitation/dissolution, and temperature effects) did not change significantly after the spring recharge event of 2000. However, the relative importance of each of these processes within the plume changed. After the recharge event, the overall importance of aerobic processes increased from the fourth to the second most important factor, representing the variability within the data set. The anaerobic signatures became more complex, suggesting that zones with multiple terminal electron-accepting processes (TEAPs) likely occur in the same water mass. Three-dimensional visualization of well clusters showed that water samples with similar chemical associations occurred in distinct water masses within the aquifer. Water mass distinctions were not based on dominant TEAPs, suggesting that the recharge effects on TEAPs occurred primarily at the interface between infiltrating recharge water and the aquifer.     

Evidence for Enhanced Mineral Dissolution in Organic Acid-Rich Shallow Ground Water

Total concentrations of formate, acetate, and isobutyrate varied from less than 5 to greater than 9,000 μmol/l over distances of < 3 m in ground water from a shallow hydrocarbon contaminated aquifer. Laboratory incubations of aquifer material indicate that organic acid concentrations were dependent on the amount of hydrocarbon loading in the sediment and the relative rates of microbial organic acid production and consumption. In heavily contaminated sediments, production greatly exceeded consumption and organic acid concentrations increased. In lightly contaminated sediments rates were essentially equal and organic acid concentrations remained low. Concentrations of dissolved calcium, magnesium, and iron generally were one to two orders of magnitude higher in organic acid-rich ground water than in ground water having low organic acid concentrations. Carbonate and Fe(III)-oxyhydroxide minerals were the likely sources of these elements. Similarly, concentrations of dissolved silica, derived from quartz and k-feldspar, were higher in organic acid-rich ground water than in other waters. The positive relation (r = 0.60, p < .05, n = 16) between concentrations of silica and organic acids suggests that the microbially mediated buildup of organic acids in ground water enhanced quartz/k-feldspar dissolution in the aquifer, although it was not the only factor influencing their dissolution. A model that included organic acid microequivalents normalized by cation microequivalents significantly strengthened the correlation (r = 0.79, p < .001, n = 16) between dissolved silica and organic acid concentrations, indicating that competition between silica and cations for complexation sites on organic acids also influenced quartz/k-feldspar dissolution. Physical evidence for enhanced mineral dissolution in organic acid-rich waters included scanning electron microscopy images of highly corroded quartz and k-feldspar grains from portions of the aquifer containing organic acid-rich ground water. Microporosity generated in hydrocarbon contaminated sediments may adversely affect remediation efforts that depend on the efficient injection of electron acceptors into an aquifer or on the recovery of solutes from an aquifer.     

In Situ Abiotic Detoxification and Immobilization of Hexavalent Chromium

Detailed site characterization data from the former electroplating shop at the U.S. Coast Guard Air Support Center, Elizabeth City, North Carolina, suggested that the elevated Cr(VI) in the capillary fringe area had contaminated the ground water at the site. Most of the mobile Cr(VI) is present in the capillary fringe zone of the aquifer under an oxidizing environment. Current literature suggests that the reduction of Cr(VI) to Cr(III) through in situ redox manipulation in the presence of a reductant is an innovative technique for remediating chromate-contaminated sediments and ground water. The objective of this study was to evaluate the effectiveness of sodium dithionite in creating a reductive environment to remediate Cr(VI) present in soil. Sodium dithionite, a strong reductant, was injected into a small area of the vadose zone where elevated Cr(VI) was identified. Several striking changes observed in the target zone during the post-injection monitoring periods include a significant decrease in Eh(SHE), as much as ∼700 mV, absence of dissolved oxygen for 48 weeks, and the increase of Fe(II) concentrations. Results indicated that the in situ remedial treatment of Cr(VI) in the capillary fringe area was effective and consequently the concentration of Cr(VI) in ground water dropped below the MCLG level. This research demonstrated the effectiveness of in situ abiotic remediation by reducing Cr(VI) concentrations, mobility, and toxicity in soils and ground water within a short period of time. Therefore, sodium dithionite would be a feasible and cost-effective option for a full-scale remedial approach for the contaminated site at the U.S. Coast Guard Facility.     

Experimental examination of the possible influence of the 1.87 Å line emission on the fine structure of the lower ionosphere ionization

Summary From the theoretical investigation ofLetfus andApostolov (1974) it follows that under flare conditions the intensive X-ray emission lines in the 1–8 Å range have an insignificant contribution to the ionization state of the lower ionosphere in comparison with the enhanced emission of the continuum. This result is experimentally confirmed by direct comparison of the intensity variations of the emission line 1.87 Å (Fe XXV) during the solar flare of 25 July 1967 measured onboard of the OSO III satellite with simultaneous ground observations of the ionization state variations of the lower ionosphere made by the A3 method.     

Multicomponent simulations of contrasting redox environments at an LNAPL site

A two-dimensional multicomponent reactive transport modeling approach was used to simulate contaminant transport and the evolution of redox processes at a large-scale kerosene-contaminated site near Berlin, Germany. In contrast to previous site-scale modeling studies that focused either on one or two contaminants or on steady-state redox conditions, multiple contaminants and electron acceptors, including mineral phase Iron (III), were considered with an evolving redox zonation. Inhibition terms were used to switch between the different electron acceptor processes in the reaction scheme. The transient evolution of redox zones and contaminant plumes was simulated for two separate transects of the site, which have different geology and ground water recharge distributions and where quite different downstream contaminant and terminal electron–accepting process (TEAP) distributions are observed. The same reaction system, calibrated to measured concentrations along one of the transects, was used in both cases, achieving a reasonable match with observed concentrations. The differences between the two transects could thus to some extent be attributed to the different hydrological and hydrogeological conditions, in particular ground water recharge distributions. Long-term simulations showed that the distribution of TEAPs evolves as Fe(III) becomes depleted, with conditions becoming increasingly methanogenic, leading to changes in contaminant plume lengths. The models were applied to assess the potential effects of planned changes in land use at the site that may affect the ground water recharge distribution. The simulated redox zonation responded strongly to changes in recharge, which in turn led to changes in the contaminant plume lengths.     

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.     

The blueberry (iron nodule) from the Shark Bay area,Western Australia and its implication to the genetic environments of iron nodules on Mars

Fist-sized iron nodules, extensively found on the ground of Western Australia, were investigated by element analysis (XRF, ICP-MS and ICP-AES), electron microscopes, X-ray diffraction and Mössbauser spectroscopy. Loosely-packed pisoidic structures of a few to >10 mm in size were observed in the cross-section of nodules. Chemically, the nodules are majorly made of O, Si, Fe and Al, and share similar REE pattern with the loess sourced Greatford concretions from New Zealand. Angular quartz particles, nano-sized goethite and hematite are found to be the major mineral phases. Other minerals, such as detrital zircon, barite and Ce-containing particles can also be observed but of very low abundance. No detectable carbonate or amorphous silica implies that these nodules have experienced little underground fluid alteration. The quartz particles showing particularly three sections of fractal size-distributions, together with their extensive broken features and conchoidal fractures, strongly suggest in situ fragmentation of the host rock with minimum later dynamic sorting. These observations indicate the genetic environment of those nodules is always close to the surface of the tectonically stable ground since their formation. Because of the similarity of climatic and geological features, the genesis and preservation environment of these nodules in Western Australia may provide clues on the formation of Martian iron concretions     

Humic Substances as a Mediator for Microbially Catalyzed Metal Reduction

The potential for humic substances to serve as a terminal electron acceptor in microbial respiration and to function as an electron shuttle between Fe(III)-reducing microorganisms and insoluble Fe(III) oxides was investigated. The Fe(III)-reducing microorganism Geobacter metallireducens conserved energy to support growth from electron transport to humics as evidenced by continued oxidation of acetate to carbon dioxide after as many as nine transfers in a medium with acetate as the electron donor and soil humic acids as the electron acceptor. Growth of G. metallireducens with poorly crystalline Fe(III) oxide as the electron acceptor was greatly stimulated by the addition of as little as 100 μM of the humics analog, anthraquinone-2,6-disulfonate. Other quinones investigated, including lawsone, menadione, and anthraquinone-2-sulfonate, also stimulated Fe(III) oxide reduction. A wide phylogenetic diversity of microorganisms capable of Fe(III) reduction were also able to transfer electrons to humics. Microorganisms which can not reduce Fe(III) could not reduce humics. Humics stimulated the reduction of structural Fe(III) in clay and the crystalline Fe(III) forms, goethite and hematite. These results demonstrate that electron shuttling between Fe(III)-reducing microorganisms and Fe(III) via humics not only accelerates the microbial reduction of poorly crystalline Fe(III) oxide, but also can facilitate the reduction of Fe(III) forms that are not typically reduced by microorganisms in the absence of humics. Addition of humic substances to enhance electron shuttling between Fe(III)-reducing microorganisms and Fe(III) oxides may be a useful strategy to stimulate the remediation of soils and sediments contaminated with organic or metal pollutants.     

A Full-Scale Porous Reactive Wall for Prevention of Acid Mine Drainage

The generation and release of acidic drainage containing high concentrations of dissolved metals from decommissioned mine wastes is an environmental problem of international scale. A potential solution to many acid drainage problems is the installation of permeable reactive walls into aquifers affected by drainage water derived from mine waste materials. A permeable reactive wall installed into an aquifer impacted by low-quality mine drainage waters was installed in August 1995 at the Nickel Rim mine site near Sudbury, Ontario. The reactive mixture, containing organic matter, was designed to promote bacterially mediated sulfate reduction and subsequent metal sulfide precipitation. The reactive wall is installed to an average depth of 12 feet (3.6 m) and is 49 feet (15 m) long perpendicular to ground water flow. The wall thickness (flow path length) is 13 feet (4 m). Initial results, collected nine months after installation, indicate that sulfate reduction and metal sulfide precipitation is occurring. Comparing water entering the wall to treated water exiting the wall, sulfate concentrations decrease from 2400 to 4600 mg/L to 200 to 3600 mg/L; Fe concentrations decrease from 250 to 1300 mg/L to 1.0 to 40 mg/L; pH increases from 5.8 to 7.0; and alkalinity (as CaCO₃) increases from 0 to 50 mg/L to 600 to 2000 mg/L. The reactive wall has effectively removed the capacity of the ground water to generate acidity on discharge to the surface. Calculations based on comparison to previously run laboratory column experiments indicate that the reactive wall has potential to remain effective for at least 15 years.