释放化学物质耗空电离层电子密度的研究

电离层作为电波传播的主要通道和载体,影响着无线电通信的质量,因此人工电离层扰动具有广阔的应用前景,在电离层中释放具有较强电子亲和力的化学物质可以耗空电离层F区的电子密度,是人工电离层扰动的有效手段之一.本文通过对CO2和SF6气体在电离层中的扩散和离子化学反应过程的分析,理论计算了在我国北京地区上空释放这两种气体后电离...     

Low-Cost On-Site Treatment of Landfill Leachate Using Infiltration Beds: Preliminary Field Trial

A small-scale field experiment was carried out to demonstrate the effectiveness of using septic system -type infiltration beds for on-site treatment of landfill leachate. Using an infiltration bed with a 3-m-thick vadose zone of medium sand, and loaded at a rate 01 18 cm/day, a treatment efficiency of >99 percent was obtained for Fe, 94 percent for NH₄⁺, and 54 percent for dissolved organic carbon (DOC). Attenuation occurred during one- to two-day residency in the aerobic vadose zone (pore gas O₂ > 12 percent by volume) as a result of oxidation reactions that caused nitrification of NH₄⁺, convened Fe²⁺ to Fe³⁺ allowing subsequent precipitation of sparingly soluble Fe oxyhydroxide minerals, and biodegraded DOC. Attenuation of an aerobically degradable trace volatile organic compound (dichlorobenzene) was also noted, although other less degradable compounds (trichloroethylene and tetrachloroethylene) persisted.
Fe mineral precipitation caused a discontinuous hardpan layer to occur in the zone immediately below the infiltration pipes. However, this layer did not become impermeable or continuous enough to significantly impede infiltration during the 82-day experiment.
Advantages of this technology for leachate treatment are that it is low cost, it is simple to construct and operate. and treatment occurs on-site, avoiding the cost of transporting leachate off-site for treatment.     

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.     

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.     

Chemical reaction diversity of geofluids revealed by hydrothermal experiments under sub- and supercritical states

Abstract   Hydrothermal experiments of dissolution of granite and quartz with pure water up to 600°C and 60 MPa were carried out in order to evaluate chemical reaction under sub- and supercritical conditions. The supercritical region beyond the critical point for water has been inferred to be a homogeneous state, which does not correspond to either a true liquid phase, or a true vapor phase. Results of dissolution experiments of granite and quartz in a supercritical state (artificially defined as higher pressures and temperatures than the critical point), show this fluid can be subdivided into two apparent phases comprising a 'liquid-like' region and a 'vapor-like' region. Chemical phenomena with respect to dissolution reactions in the 'liquid-like' region are more similar to those of subcritical water, whilst those reactions in the 'vapor-like' region even in the supercritical state are considered to be weak. The critical point of various kinds of geofluids, composed of solutions in the H₂O-CO₂-NaCl system was experimentally determined using a visible type autoclave. Chemical reaction diversity, depending on location of the critical point for a given solution and apparent phase boundary in terms of chemical reaction within the supercritical state, was recognized by hydrothermal experiments.     

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.     

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%.     

Computer Modeling of Scale Formation During Treatment of Ground Water in Air Strippers

During treatment to remove volatile organic compounds from contaminated ground water, inorganic scale sometimes precipitates in an air stripper tower. This leads to increased costs and down-time associated with tower media replacement. In order to determine the kind, quantity, and rate of scale formation, the ground water from five locations in Florida was simulated using an aqueous equilibrium chemistry and flow process model. In all cases the pH of the outflow water is higher than that of the inflow water because of degassing of CO₂. This often results in the precipitation of calcium carbonate. The addition of air to reduced ground water results in the oxidation of iron and the precipitation of ferric hydroxides. Model estimates of scale formation are about a factor of two to five too high. This indicates that the precipitation reactions do not reach equilibrium within the air stripper. Future work will require the inclusion of biological fouling and a kinetic expression to account for the observed non-equilibrium.     

Chemical mass balance in a reaction zone between serpentinite and metapelites in the Nishisonogi metamorphic rocks, Kyushu, Japan: Implications for devolatilization

Abstract   Reaction zones of 0.5–10.0 m thick are commonly observed between serpentinite and pelitic schist in the Nishisonogi metamorphic rocks, Kyushu, Japan. Each reaction zone consists of almost monomineralic or bimineralic layers of talc + carbonates, actinolite (or carbonates + quartz), chlorite, muscovite and albite from serpentinite to pelitic schist. Magnesite + quartz veins extend into the serpentinite from the talc + carbonates layer, while dolomite veins extend into the pelitic schist from the muscovite layer. These veins are filled by subhedral minerals with oriented growth features. Primary fluid inclusions yield the same homogenization temperatures (145–150°C) both in the reaction zone and in the veins, suggesting their simultaneous formation. Mass-balance calculations using the isocon method indicate that SiO₂, MgO, H₂O and K₂O are depleted in the reaction zone relative to the protoliths. These components were probably extracted from the reaction zone as fluids during the formation of the reaction zone.     

Denitrification and Phosphate Removal in Experiments Using Al Stearate

Hydrophobic Al monostearate was tested as a low-solubility denitrification substrate for anaerobic bacteria and a source of aluminum for phosphate precipitation. Flow-through laboratory columns at 25 ± 2°C were used with O₂-saturated solutions containing 1x, 2x, 8x, and 16x concentrations of 2.26 mg/L NO₃-N and 3.26 mg/L PO₄-P. Denitrification was exponential, approximating first-order reaction kinetics with the rate constant being a function of the initial nitrate concentration. The half life in minutes can be approximated by 5.29 (mg/L NO₃- N°)^1/2 where NO₃-N° was the initial input nitrate concentration. The reaction times were significantly shorter than those required using Ca distearate as a carbon source and much shorter than those using cellulose (white pine shavings) as a carbon source. Al stearate has potential for use in a flow-through container for denitrification of oxidized effluent from home sewage systems.
Aqueous phosphate removal with Al stearate depended upon dissolution of the Al stearate followed by precipitation of Al phosphate. Only 5% to 10% of the phosphate was removed from the solution. The amounts removed were similar to those obtained using bauxite grains as an aluminum source, following saturation of sorption sites with phosphate on bauxite. Aqueous phosphate removal with Ca stearate was insignificant, as the released calcium was apparently precipitated as calcite rather than as hydroxyapatite.     

Chrome-rich clinopyroxene in orthopyroxenite from Maowu, Dabie Mountains, central China: A second record and its implications for petrogenesis

A second occurrence of chrome-rich clinopyroxene has been discovered as inclusions in orthopyroxene in orthopyroxenite from Maowu, the Dabie Mountains, Central China. The average formula for chrome-rich clinopyroxene can be expressed as (Na_0.39Ca_0.54)_0.93(Mg_0.57Fe²⁺_0.06Fe³⁺_0.01Cr_0.24Al_0.15)_1.03Si_2.02O₆, with a maximum amount of kosmochlor component of 28.52 mol%. The unit cell parameters obtained from a single-crystal are a  = 9.614 Å, b  = 8.800 Å, c =  5.240 Å, β = 106.59°, space group C2 / c . The indices of refraction are α = 1.697, β = 1.704, γ = 1.726. Chrome-rich clinopyroxene, which coexists with chromite, chromian rutile and chromian pyrope, crystallized at a temperature of 1025 °C and very high pressure, and therefore represents a mantle relic. Together with the appearance of low-pressure inclusion mineral assemblage and the estimation of physical–chemical conditions for matrix minerals, the Maowu eclogite–ultramafic complex is considered to be formed during ultrahigh-pressure metamorphism from the mantle-derived protolith.     

Robust inversion of vertical electrical sounding data using a multiple reweighted least-squares method

The root cause of the instability problem of the least-squares (LS) solution of the resistivity inverse problem is the ill-conditioning of the sensitivity matrix. To circumvent this problem a new LS approach has been investigated in this paper. At each iteration, the sensitivity matrix is weighted in multiple ways generating a set of systems of linear equations. By solving each system, several candidate models are obtained. As a consequence, the space of models is explored in a more extensive and effective way resulting in a more robust and stable LS approach to solving the resistivity inverse problem. This new approach is called the multiple reweighted LS method (MRLS). The problems encountered when using the L ₁- or L ₂-norm are discussed and the advantages of working with the MRLS method are highlighted. A five-layer earth model which generates an ill-conditioned matrix due to equivalence is used to generate a synthetic data set for the Schlumberger configuration. The data are randomly corrupted by noise and then inverted by using L ₂, L ₁ and the MRLS algorithm. The stabilized solutions, even though blurred, could only be obtained by using a heavy ridge regression parameter in L ₂- and L ₁-norms. On the other hand, the MRLS solution is stable without regression factors and is superior and clearer. For a better appraisal the same initial model was used in all cases. The MRLS algorithm is also demonstrated for a field data set: a stable solution is obtained.     

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.     

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.     

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.     

Diamond-bearing and diamond-free metacarbonate rocks from Kumdy–Kol in the Kokchetav Massif, northern Kazakhstan

Abstract Dolomite marble from the Kumdy–Kol area of the Kokchetav Massif contains abundant microdiamond, mainly in garnet and a few in diopside. The mineral assemblage at peak metamorphic condition consists of dolomite + diopside + garnet (+ aragonite) ± diamond. Inclusions of very low MgCO₃ calcite and almost pure calcite occur in diopside and are interpreted as aragonite and/or aragonite + dolomite. Single-phase Mg–calcite in diopside with a very high MgCO₃ component (up to 21.7 mol%) was also found in diamond-free dolomitic marble, and is interpreted as a retrograde product from aragonite + dolomite to Mg–calcite. The dolomite stability constrains the maximum pressure (P) at < 7 GPa using previous experimental data, whereas the occurrence of diamond yields the minimum peak pressure–temperature (P–T) condition at 4.2 GPa and 980 °C at X co ₂ = 0.1. The highest MgCO₃ in Mg–calcite constrains the minimum P–T condition higher than 2.5 GPa and 800 °C for the exhumation stage. As these marbles were subjected to nearly identical P–T metamorphic conditions, the appearance of diamond in some carbonate rocks was explained by high X co ₂. A low X co ₂ condition refers to high oxidized conditions and diamond (and/or graphite) becomes unstable. Difference in X co ₂ for marble from the same area suggests local heterogeneity of fluid compositions during ultrahigh-pressure metamorphism.     

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.     

Extent of immobilisation of phosphate during aeration of nutrient-rich, anoxic groundwater

Nutrient-rich exfiltrating groundwater may impose a heavy phosphate load on surface water systems. However, iron oxides that bind PO₄ precipitate fast upon oxygenation at neutral pH and PO₄ may also become bound in Ca precipitates following upon pH increase, so load estimates based on conservative behaviour during exfiltration will be overestimates. Aeration experiments using natural groundwater were performed to characterise the immobilisation of PO₄ within one day after aeration started. Groundwaters having a wide variety in composition, were sampled in the coastal lowlands of the Western Netherlands. Three models were considered to describe the fast binding of PO₄ by Fe oxide type phases that form upon the oxygenation of dissolved Fe(II), each based on a different concept. The concepts were surface complexation, solid-solution precipitation and two-mineral precipitation. When the experimental data were compared with model results, all three models were found to be inadequate. Frequently, more immobilisation of PO₄ occurred than could be explained by binding to a Fe oxide type of phase alone. Uptake by Ca phosphates and/or Ca carbonates must additionally have played a role; alternatively, a non-ideal phase consisting of Ca, Fe and PO₄ precipitated upon oxygenation and CO₂ degassing. A predictive multiple regression model with two primary variables that reflect the driving forces for PO₄ immobilisation was deduced that describes immobilisation of phosphate after aeration of anoxic groundwater. The two primary variables are the log value of the groundwater Fe to PO₄ molar ratio and the saturation state for hydroxyapatite after the CO₂ degassing of groundwater. The model is useful for calculating the PO₄ load of surface water from exfiltration groundwater, taking into account fast immobilisation (<1 day) during exfiltration.     

Hydraulic Conductivity Measurements in the Unsaturated Zone Using Improved Well Analyses

The flow of ponded water into and through the unsaturated zone depends on both the saturated and unsaturated components of the hydraulic conductivity. Recent studies indicate that the ratio of the saturated (K_fs) to the unsaturated (φ_m) components (K_fs/φ_m=α*) of flow lies within prescribed bounds for most field soils, i.e., 1m⁻¹≤α*≤ 100 m⁻¹. In addition, the fact that the calculation of K_fs and φ_m is not strongly dependent on the choice of α*, suggests that a site estimation of α* leads to reasonable "best estimates" of K_fs and φ_m when using the constant head well permeameter technique. As a consequence, measurement of the steady flow rate using only one ponded head may be all that is necessary for many practical applications. Multiple head measurements or independent measurements of α* or φ_m can be used, however, to give more accurate estimates of K_fs if required.