δ34S isotope values of dissolved sulfate (SO4 2−) as a tracer for battery acid (H2SO4) contamination in groundwater

The application of sulfur isotope (³⁴S) values of sulfate in groundwater provided the information necessary to evaluate the source, transport and fate of battery acid and associated contaminants at the Gulf Coast Recycling (GCR) facility. The chemical and isotopic composition of groundwater beneath the (GCR) property, a battery recycling facility in east Tampa, Florida, varies more than expected for an area of comparable size. Sulfate (SO₄^2–) values, for example, range from 1.2 to 11,500 mg/L and oxygen and hydrogen isotopes do not attenuate towards the weighted annual mean. Those samples that are high in sulfate generally have a low pH, which immediately indicates battery acid (H₂SO₄) contamination as a potential source for the sulfate. The low pH and high reactivity of the sulfuric acid groundwater cause the formation of hydrogeological microenvironments due to preferential dissolution of carbonate minerals, which in turn causes enhanced recharge and groundwater flow in certain areas; thus, the extreme scatter in the data set. Because of the difficult hydrogeology it is not straightforward to delineate the point-sources of contamination and up to five potential scenarios have to be evaluated: (1) seawater intrusion, (2) upwelling of high-sulfate groundwater, (3) local dissolution of gypsum, (4) an up-gradient contaminant source to the northeast of the GCR property and (5) battery acid contamination.     

Oxidation and Origin of Organic Matter in Surficial Eastern Mediterranean Hemipelagic Sediments

Aerobic mineralisation of C_org in surface sedimentsof the deep (>2000 m water depth) eastern Mediterranean Sea has been quantified by analysis of detailedbox core C_org concentration versus depth profiles and the modelling environment for early diageneticproblems MEDIA. The reactive fraction comprises 60–80% of the total C_org reachingthe sediments and is largely oxidised within the surficial 10 cm. A non-reactive C _orgfraction (G_NR) dominates at depths >10 cm, and makes up20–40% of the total C _org flux to the sediments. First-order rateconstants for decomposition of the reactive fraction calculated from theC _org profiles range from 5.4 × 10^-3 to8.0 × 10^-3 y^-1 to 8.0 × 10^-3 y^-1. Total mineralization rates in thesurface sediment are between 1.7 and 2.6 mol C cm^-2 y^-1 and thus are typical for oligotrophic, deep-seaenvironments. The low fluxes and rapid remineralisation of C _org are accompanied by²¹⁰Pb_excess surface mixed layers which are only 2 cm deep, among the thinnest reported for oxygenated marine sediments.Model results indicate a mismatch between the C _org profiles and O₂ microprofileswhich were measured onboard ship. This can be attributed to a combination of decompression artefactsaffecting onboard measurement of the O₂ profiles or the leakage ofoxygen into the core during handling on deck. Furthermore, the used D_b values, based on ²¹⁰Pb, may not befully appropriate; calculations with higher D_b values improve the O₂ fits. The surficial sediment¹³C _org values of -22 become less negative with increasing depth and decreasing C _orgconcentrations. The major ¹³C change occurs in the top 3 to 4 cm and coincides with the interval weremost of the organic carbon oxidation takes place. This indicates that the reactive fractionof organic matter, commonly assumed to be marine, has a more negative ¹³C _orgthan the refractory fraction, usually held to be terrestrial. Palaeoproductivity estimates calculated from thesediment data by means of literature algorithms yield low surface productivities(12–88 gC m^-2 y^-1), which are in good agreement with field measurements of primary productivity in otherstudies. Such values are, however, significantly lower than those indicated by recent productivitymaps of the area derived from satellite imagery (>100 gC m^-2 y^-1).     

Groundwater quality and its suitability for drinking and agricultural use in Chithar River Basin, Tamil Nadu, India

Hydrochemistry of groundwater in Chithar Basin, Tamil Nadu, India was used to assess the quality of groundwater for determining its suitability for drinking and agricultural purposes. Physical and chemical parameters of groundwater such as electrical conductivity, pH, total dissolved solids (TDS), Na⁺, K⁺, Ca²⁺, Mg²⁺, Cl^–, HCO₃^–, CO₃^2–, SO₄^2–, NO^–₃, F^–, B^– and SiO₂ were determined. Concentrations of the chemical constituents in groundwater vary spatially and temporarily. Interpretation of analytical data shows that mixed Ca–Mg–Cl, Ca–Cl and Na–Cl are the dominant hydrochemical facies in the study area. Alkali earths (Ca²⁺, Mg²⁺) and strong acids (Cl^–, SO₄^2–) are slightly dominating over alkalis (Na⁺, K⁺) and weak acids (HCO₃^–, CO₃^2–). The abundance of the major ions is as follows: Na⁺ Ca²⁺ Mg²⁺ > K⁺ = Cl^– > HCO₃^–> SO₄^2– > NO₃^– > CO₃^2– . Groundwater in the area is generally hard, fresh to brackish, high to very high saline and low alkaline in nature. High total hardness and TDS in a few places identify the unsuitability of groundwater for drinking and irrigation. Such areas require special care to provide adequate drainage and introduce alternative salt tolerance cropping. Fluoride and boron are within the permissible limits for human consumption and crops as per the international standards.     

Space group and hydrogen sites of δ-AlOOH and implications for a hypothetical high-pressure form of Mg(OH)<Subscript>2</Subscript>

The space group and hydrogen positions of -(Al_0.84Mg_0.07Si_0.09)OOH are investigated using a single crystal synthesized using a multi-anvil apparatus under conditions of 1000 °C and 21 GPa. The space group determined by single-crystal X-ray diffraction is to Pnn2, with unit-cell parameters of a=4.6975(8) Å, b= 4.2060(6) Å, c=2.8327(4) Å, and V=55.97(1) ų. Partial occupancy of the Al site by Mg and Si suggests the possibility of a limited solid solution between -AlOOH, stishovite, and a hypothetical CaCl₂-type Mg(OH)₂ that is 16% denser than brucite. Difference-Fourier maps reveal two small but significant Fourier peaks attributable to hydrogen atoms. Atomic distances and angles around the first peak indicate a hydrogen bond with O···O distances of 2.511 Å, while those around the second peak are suggestive of a bifurcated hydrogen bond with O···O distances of 2.743 and 2.743 Å.     

Identifying sources of groundwater in the lower Colorado River valley, USA, with δ18O, δD, and 3H: implications for river water accounting

Isotope measurements (¹⁸O, D, ³H) indicate groundwater origin in the Lower Colorado River Valley (LCRV) and provide an alternative, or supplement, to the US Bureau of Reclamations proposed accounting surface method. The accounting surface method uses a hydraulic criterion to identify certain wells away from the flood plain that will eventually yield mainstream Colorado River water. New isotope data for 5 surface-water and 18 groundwater sites around Topock Marsh, Arizona, are compared with river-water data (1974–2002) from 11 sites between Utah and Mexico and with groundwater data from previous LCRV studies. Three groundwater sources are repeatedly identified in the LCRV: (1) local recharge derived from precipitation, usually winter rain, plots slightly below the global meteoric water line (GMWL) and has D values that are 20 greater than those of recent river water; (2) older (pre-1950) upper basin river-water plots on or near the GMWL, distinct from local rainfall and recent river water; and (3) recent (post-1950) Colorado River water, including Topock Marsh samples, plots below the GMWL along an evaporation trend. Large floods, as in 1983, complicate interpretation by routing less evaporated upper basin water into the LCRV; however, tritium content can indicate the age of a water. River-water tritium has declined steadily from its peak of 716 TU in 1967 to about 11 TU in 2002. Mixtures of all three groundwater sources are common.

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Resumen Mediciones isotópicas (¹⁸O, D, ³H) indican cual es el origen del agua subterránea en el Valle Bajo del Río Colorado (LCRV) y aportan una alternativa, o complemento, para el método superficie de conteo propuesto por el Buró de Reclamación de Estados Unidos. El método superficie de conteo utiliza un criterio hidráulico para identificar ciertos pozos alejados de la planicie de inundación que eventualmente producirán agua a partir de la corriente principal del Río Colorado. Los nuevos datos isotópicos para 18 sitios de agua subterránea y 5 sitios de agua superficial cerca de los Pantanos Topock, Arizona, se comparan con datos de agua de río (1974–2002) provenientes de 11 sitios localizados entre Utah y México, y con datos de aguas subterráneas de estudios previos realizados en el LCRV. Se identifican reiteradamente tres fuentes de aguas subterráneas en el LCRV: (1) recarga local derivada de precipitación, generalmente lluvia de invierno, cuya composición cae ligeramente por debajo de la línea de agua meteórica global (GMWL) y tiene valores D que son 20 mayores que los reportados para agua de río reciente; (2) el agua de río más vieja (pre-1950) de la cuenca alta cuya composición cae sobre o cerca de la GMWL, diferente de la lluvia local y del agua de río reciente; (3) agua reciente (post-1950) del Río Colorado, incluyendo muestras de los Pantanos Topock, con composición por debajo de la GMWL a lo largo de una tendencia a la evaporación. Inundaciones grandes, como en 1983, complican la interpretación al transmitir menos agua evaporada de la cuenca alta hacia el LCRV; sin embargo, el contenido de tritio puede indicar la edad del agua. El contenido de tritio en agua de río ha disminuido constantemente desde la concentración pico de 716 TU en 1967 a cerca de 11 TU en 2002. Es común que exista mezclas de las tres fuentes de agua subterránea.

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Résumé Les mesures isotopiques (d18O, dD, 3H) indiquent les origine de leaux souterraines dans la Vallée de la Rivière du Bas Colorado (LCRV) et sont une alternative, ou un supplément, à la méthode des bilans hydrologiques proposée par du «US Bureau of Reclamation». Cette méthode de bilan hydrologique utilise un critère hydraulique permettant didentifier certains puits hors de la plaine dinondation qui pomperaient une part non négligeable de leur eau dans la rivière Colorado. De nouvelles données isotopiques provenant de 5 sites deau de surface et 18 deaux souterraines autour de Topock Marsh en Arizona, sont comparées avec les données (1974–2000) de 11 sites localisés entre Utah et Mexico, ainsi que des données dautres études sur la LCRV. Ces sources deaux souterraines sont identifiées à plusieurs reprises dans la LCRV: (1) la recharge locale dérivant des précipitations, généralement les pluies hivernales, se retrouvent légèrement sous la ligne deau météoritique globale (GMWL) et possède des valeurs de dD 20% supérieures aux valeurs des eaux récentes de la rivière; (2) les eaux vieilles (pre-1950) du bassin supérieur de la rivière possèdent une valeurs très proches de la GMWL, distinctes des valeurs de la pluie locale et des eaux récentes de la rivière; et (3) les eaux récentes (post-1950) de la Rivière Colorado, incluant les échantillons de Topock Marsh, se positionnent à côté de la GMWL sur une droite dévaporation. Les grandes inondations, par exemple celle de 1983, compliquent linterprétation en reprenant dans la LCRV moins deaux marquées comme évaporées et provenant du bassin supérieur; par ailleurs le pic de tritium est descendu de 716 TU en 1967 à 11 TU en 2002. Les mélanges de ces trois sources sont assez fréquentes.

     

天然气水合物成因探讨

天然气水合物是未来的能源资源。其分布于极地地区、深海地区及深水湖泊中。在海洋里,天然气水合物主要分布于外大陆边缘和洋岛的周围,其分布与近代火山的分布范围具有一致性。同位素组成表明天然气水合物甲烷主要是由自养产甲烷菌还原CO₂形成的。典型的大陆边缘沉积物有机碳含量低（＜0．5％～1．0％）,不足以产生天然气水合物带高含量的甲烷。赋存天然气水合物的沉积物时代主要为晚中新世-晚上新世,具有一定的时限性,并且天然气水合物与火山灰或火山砂共存,表明其形成与火山-热液体系有一定联系。火山与天然气水合物空间上的一致性表明,天然气水合物甲烷的底物可能主要是由洋底火山喷发带来的CO2。由前人研究结果推断 HCO^－₃在脱去两个O原子的同时,可能发生了亲核重排,羟基 H原子迁移到 C原子上,形成了甲酰基（HCO^－）,使甲烷的第一个 H原子来源于水。探讨了甲烷及其水合物的形成机制,提出了天然气水合物成因模型。     

Epithermal gold veins in a caldera setting: Banská Hodruša, Slovakia

The central zone of the large Miocene tiavnica stratovolcano in the Western Carpathians hosts epithermal Au mineralization of intermediate-sulfidation type, located at deep levels of the historic Rozália base-metal mine at Banská Hodrua. The Au mineralization occurs as subhorizontal veins at the base of pre-caldera andesites, close to the roof of a subvolcanic granodiorite intrusion. The veins are dismembered by a set of quartz–diorite porphyry sills and displaced by the younger, steeply dipping, Rozália base-metal vein, and parallel structures. The base-metal vein structures are related to resurgent horst uplift in the caldera center. The Au mineralization formed during two stages. Based on fluid inclusion evidence, both stages formed from fluids of low salinity (0–3 wt% NaCl eq.), which underwent extensive boiling at moderate temperatures (280–330°C). Variable pressure conditions (39–95 bars, neglecting the effect of CO₂) indicate continual opening of the system and a transition from suprahydrostatic towards hydrodynamic conditions at shallow depths (~550 m). The fluid inclusions of the Rozália base-metal vein show homogenization temperature peaks at ~285 and 187°C and salinities between 1 and 4 wt% NaCl eq. Precipitation of Au is considered to be the result of prolonged boiling of fluids and associated decrease in Au solubility. Oxygen and hydrogen isotope data for quartz and carbonate from the Au veins show a relatively homogeneous fluid composition (–2.7 to 1.1¹⁸O, –78 to –62D). The combined ¹⁸O_fluid and D_fluid values suggest a mixed character of fluids, falling between the fields of typical magmatic and meteoric water influenced by ¹⁸O_fluid shift due to fluid–rock isotopic exchange. End stages of open-system boiling and fractionation could have been reached, at least locally. Significantly lower isotopic composition of meteoric fluids associated with Au mineralization compared to those associated with the intrusion-related mineralizations could have resulted from changing paleoclimate and/or analytical problems of extraction of water from fluid inclusions. The proposed genetic model for the Au deposit at Rozália mine highlights the importance of hydrothermal activity during the early stage of caldera collapse. Caldera subsidence established new, convective, fluid-flow paths along marginal caldera faults, which acted as infiltration zones. Major metal precipitation occurred within subhorizontal structures that formed as the result of a collapse-related stress field. A shallow, differentiated magma chamber at the base of the volcano was the likely source of heat and magmatic components for the mineralizing fluids.Editorial handling: S. Nicolescu     

Vibrational spectroscopy of beta-eucryptite (LiAlSiO<Subscript>4</Subscript>): optical phonons and phase transition(s)

The structural behavior of -eucryptite (LiAlSiO₄) has been investigated using infrared (IR) spectroscopy over a temperature range of 20 to 900 K and FT-Raman spectroscopy at room temperature. IR reflectance measurements show that -eucryptite possesses high reflectivity in the far-IR region, as is consistent with its reported superionic conductivity along the c-axis. On heating, the Li-related IR bands near 246 and 300 cm^–1 (with A₂ symmetry) broadened and weakened dramatically, presumably as a result of Li⁺ positional disordering along the structural channels parallel to c. The disordering process appears to induce a framework distortion, as is evidenced by the broadening of some vibrations of Si(Al)–O with increasing temperature. A change in slope in the temperature dependence of the phonon frequency near 300 cm^–1 and the linewidth of the 760 cm^–1 band at 715 K indicates that Li becomes completely disordered above this temperature. In addition, the temperature dependence of the linewidth for the 760 cm^–1 band exhibits an additional change in slope at 780 K, implying the existence of an intermediate state within this temperature range. The detailed structure of this intermediate phase, however, needs further study. Our IR data provide no indication of structural changes between room temperature and 20 K.     

The Speciation of (CH3)2Sn2+ in Electrolyte Solution Containing the Major Components of Natural Waters

Hydrolysis constants of dimethyltin(IV) cation, in different salt solutions (CaCl₂: 0.15 I 0.90; MgCl₂: 0.30 I 0.60; NaCl-–NaClO₄, NaCl-–NaNO₃ mixtures: I = 3; NaCl-–Na₂SO₄ mixtures: I = 1 mol dm^-3) were determined by potentiometric ([H⁺]-glass electrode) measurements. These data, together with previous data (De Stefano et al., 1996b) were interpreted in terms of DHT (Debye–Hückel type) and Pitzer equations. The mixed electrolyte solution results also allowed us to obtain and parameters for the Pitzer equation. Calorimetric measurements were made at different ionic strengths in order to find the temperature dependence of hydrolysis constants and of the relative interaction parameters. The body of results allows us to determine the speciation of natural waters in a wide range of ionic strengths and temperatures.     

Major ion chemistry of groundwaters in the Bahar area, Hamadan, western Iran

Hydrochemical investigations were carried out in Bahar area, Hamadan, western Iran, to assess the chemical composition of groundwater. The area falls in a semi-arid type of climate. In this area, groundwater has been exploited over the past century mainly for irrigation and water supply. A total of 135 representative groundwater samples were collected from different wells to monitor the water chemistry of various ions. Chemical analysis of the groundwater shows that the mean concentration of the cations is of the order Ca²⁺>Mg ²⁺>Na⁺>K⁺, while that for anions is SO₄^2–>HCO₃^–>Cl^–>NO₃^–. Statistical analyses indicate positive correlation between the following pairs of parameters Cl^– and Mg ²⁺ (r=0.71), Cl^– and Na⁺ (r=0.76), HCO₃^– and Na⁺ (r=0.56), SO₄^2– and Mg²⁺ (r=0.76), SO₄^2– and Na⁺ (r=0.69). Water presents a large spatial variability of the chemical facies (Ca-HCO₃, Ca-SO₄, Mg-HCO₃, Mg-SO₄, Na-HCO₃) which is in relation to their interaction with the geological formations of the basin (carbonates, dolomite and various silicates) and evaporation. The hydrochemical types Ca-HCO₃ and Ca-SO₄ dominate the largest part of the studied area. The dissolution of halite, calcite, dolomite, and gypsum explains part of the contained Na ⁺, Ca²⁺, Mg²⁺, Cl^–, SO₄^2– and HCO₃^–, but other processes, such as cation exchange and weathering of aluminosilicates also contribute to the water composition.     

The threshold value of epikarst runoff in forest karst mountain area

Hydrochemical investigations were carried out in Damagh area, Hamadan, western Iran, to assess chemical composition of groundwater. Forty representative groundwater samples were collected from different wells to monitor the water chemistry of various ions. Chemical analysis of the groundwater showed that the mean concentration of the cations is in the order Na⁺ > Ca²⁺ > Mg²⁺ > K⁺, while that for anions was HCO₃⁻ > Cl⁻ > SO₄^{2 −} > NO₃⁻. All of the investigated groundwaters present two different chemical facies (Ca–HCO₃ and Na–HCO₃) which is in relation with their interaction with the geological formations of the basin, cation exchange between groundwater and clay minerals and anthropogenic activities. The principal component analysis (PCA) performed on groundwater identified three principal components controlling their variability in groundwater. Electrical conductivity, Mg²⁺, Na⁺, SO₄²⁻, and Cl⁻ content were associated in the same component (PC1) (salinity), determined principally by anthropogenic activities. The pH, CO₃^{2 −}, HCO₃⁻, and Ca²⁺ (PC2) content were related to the geogenic factor. Finally, the NO₃⁻, Cl⁻ and K⁺ (PC3) were controlled by anthropogenic activity as a consequence of inorganic fertilizers.     

A method for determining the reversibility of a Markov sequence

This paper describes, given a tally matrix with strictly positive entries, a method to determine whether the associated Markov process is reversible, and (for reversible Markov processes) methods to compute the reversibility matrix from the tally matrix. If the tally matrixN is symmetric, then it is shown that the Markov process must be reversible and the reversibility matrixC equalss (R ^–1NR^–1), whereR is the diagonal matrix whosei ^th diagonal entry is the sum of the entries of thei ^th row ofN (for everyi) ands denotes the sum of all the entries ofN. Because a symmetric tally matrix is of special importance in applications, a ² test is proposed for determining, in the presence of experimental errors, whether such a matrix is symmetric.     

地下水中高锰酸盐指数和硝酸根铵根稳定性研究

高锰酸盐指数(CODMn)、硝酸根(NO-3)、铵根(NH+4)是判断水体是否受到三氮污染的重要指标。对于测定这三个指标的水样保存方式和时间,地质行业标准和国内外主要国家标准间存在明显差异。地质行业标准规定地下水样品原水室温保存,CODMn和NH+4在3天内测定;NO-3在20天内测定;国家标准和美国标准推荐样品硫酸酸化,避光或冷藏保存,在2~7天内完成CODMn和NO-3和1~7天内完成NH+4测试。为了分析各类标准在样品保存要求上的差异对检测结果的影响,确保检测数据能真实地反映水体污染状况,找寻简便的保存方式,本文在广州地区采集地下水,按照地质行业标准与国家标准进行处理和保存,并在不同时间段对三个指标进行测试。分析验证结果表明:地质行业标准与国家和美国标准关于水样的保存方法均非常可靠。地质行业标准主要针对静态地下水,保存方法相对宽松;国家标准和美国标准适用范围除了地下水,还包括动态的地表水和废水,采样对象成分更为复杂,更不稳定,更容易受外界影响发生变化,故保存条件高于地质标准。在广州地区,采用原水室温避光保存水样,CODMn、NH+4保存时间可为5天,NO-3保存时间可为30天;采用酸化水室温保存水样,CODMn、NO-3和NH+4保存时间可长达30天。这两种方式均比地质行业标准和国家标准推荐的有效时间长,且原水和酸化水室温保存方式相对于冷藏保存方式更为方便。本文提出,如果采集的水样能方便、快速送达实验室,可采用原水保存;如果不能在短时间内送达实验室检测,可采用硫酸酸化保存。     

Authigenic sericite record of a fossil geothermal system: the Offenburg trough,central Black Forest,Germany

A fossil geothermal area is hosted by the Carboniferous, Permian and Bunter sandstones of the Offenburg intramontane trough in the central Black Forest. The hydrothermal alteration is identified on the basis of newly formed sericites, which appear as pseudomorphs after feldspar and filling of pore spaces. According to K–Ar dating of sericite, serititization occurred about 145 Ma ago (Jurassic). On the basis of ¹⁸O analyses of sericite, sericite composition and vitrinite reflectance, the hydrothermal fluids had temperatures of 150–210 °C. Because their electrolyte content was low, these fluids are assumed to have derived from meteoric water. A second pulse of electrolyte-rich hydrothermal fluids resulted in quartz overgrowths. Fluid mobilization seems to be linked to the disintegration of Pangaea and to reactivated fault systems extending from the crystalline basement into the intramontane sediments.     

Selenium fractionation and speciation in rocks, soils, waters and plants in polluted surface mine environment

A fractionation and speciation was performed to determine the distribution of selenium (Se) species in major components of quartzite surface mine environment (rocks, mine tailings, soils, stream sediments, surface waters and plants) in obov, Slovakia. A three-step sequential extraction procedure was utilised for the fractionation of Se in mine tailings and soils. The first extractant in order to evaluate the soluble and ligand exchangeable fraction of Se (0.1 mol/l K₂HPO₄ + KH₂PO₄ at pH 7.0) solubilized up to 15% of total Se content. The second step (0.1 mol/l K₂S₂O₈ at 90°C) which extracted Se associated or occluded with organic matter released 13 – 45% of total selenium. The decomposition of the residue (HNO₃ + H₂SO₄ 1+1) was used to solubilize the remaining 35–88% of total Se as the final step. The recovery of the procedure was between 97 and 106%. Selenate predominated in natural river and lake waters about pH 7.0 (>95%) but in acid mine leakings up to 40% of selenite was found. In the plants (birch leaves, grass leaves and roots) collected from the area acidified by mine leakings no significant accumulation of selenium was observed. The correlation between total Se and S in the rocks from the mine gives an evidence of the common origin of these elements in the studied area.     

Evaluation of hydrogeochemistry and water quality in Bist-Doab region,Punjab, India

Agricultural activities act as dominant polluter of groundwater due to increased fertilizers and pesticides usage. Bist-Doab region, Punjab, India, is one such region facing deterioration of groundwater quality due to usage of fertilizers. This study aims in delineating and evaluating the groundwater quality in the region. Water samples are collected from canals, reservoir, and shallow and deep groundwater. Water types in canal and reservoir in Kandi region are Mg²⁺HCO₃ ^? and Mg²⁺Ca²⁺Na⁺HCO₃ ^?, respectively. While water types of shallow and deep groundwaters are found to be of two types: Na⁺Mg²⁺Ca²⁺HCO₃ ^? and Ca²⁺Mg²⁺Na⁺HCO₃ ^?. Presence of Mg²⁺ in groundwater at locations adjoining canals indicates recharge due to canal. The major ion (Na⁺, Mg²⁺, Ca²⁺, HCO₃ ^?) chemistry of the region is due to weathering of rocks that are rich in sodic minerals and kankar. Deep groundwater quality in the region meets BIS and WHO standards for drinking purpose, unlike shallow groundwater which is of poor quality at many locations. Both shallow and deep groundwater with high sodium concentration (>1.5 meq/l) affect cropping yield and permeability of soil matrix. High concentration of SO₄ ^2? and NO₃ ^2? (>1 meq/l) in shallow groundwater at few locations indicates influence of anthropogenic (fertilizer) activity. Factor analysis indicates that the major cations, bicarbonate and chloride are derived from weathering/dissolution of source rocks. Higher concentration of nitrate and presence of sulphate in shallow groundwater at few locations is due to usage of fertilizers and pesticides.     

Valent state and coordination of cobalt Ions in beryl and chrysoberyl crystals

We have studied the polarized optical absorption and EPR spectra of Co-doped beryls grown by hydrothermal, flux, and gas-transport methods, and chrysoberyl grown by the Czochralski method. In beryls three groups of bands, belonging to three various Co centers, were distinguished by analysis of the absorption band intensities. The first group, bands with maxima at 22 220 (E c), 17 730 (E c), and 9090 (E c), 7520 (E c) cm^–1 are due to Co²⁺ in octahedral site of Al³⁺. The second group is bands at 18 940, 18 250, 17 700 (E c), 18 300, 17 700, 17 000 (E c) and 8830 (E c), 7350 (E c) cm^–1 and 5320 (E c), 3880 (E c) cm^–1, which are caused by Co²⁺ in tetrahedral site of Be²⁺. A weak wide band in flux and gas-transport beryl in the region of 12 500–8300 cm^–1 (E , c) is related to Co³⁺ in octahedral Al³⁺ site. In hydrothermal beryl, bands 13 200 (E c), 10 900 (E c), and 8500 (E c) cm^–1 are caused by an uncontrolled impurity of Cu²⁺ ions. For Co-doped chrysoberyl one type of center of Co has been established: Co²⁺ in the octahedral site of Al³⁺. In the approximation of the trigonal field with regard to Trees correction, the energy levels of Co²⁺ have been calculated in octahedral and tetrahedral coordination. There is good agreement between the obtained experimental and calculated data. The polarization dependence of the optical absorption bands is explained well in terms of the spin-orbit interaction.     

Geochemical Eccentricity of Ground Water Allied to Weathering of Basalts from the Deccan Volcanic Province,India: Insinuation on CO<Subscript>2</Subscript> Consumption

Analyses of 72 samples from Upper Panjhara basin in the northern part of Deccan Plateau, India, indicate that geochemical incongruity of groundwater is largely a function of mineral composition of the basaltic lithology. Higher proportion of alkaline earth elements to total cations and HCO₃>Cl + SO₄ reflect weathering of primary silicates as chief source of ions. Inputs of Cl, SO₄, and NO₃ are related to rainfall and localized anthropogenic factors. Groundwater from recharge area representing Ca + Mg–HCO₃ type progressively evolves to Ca + Na–HCO₃ and Na–Ca–HCO₃ class along flow direction replicates the role of cation exchange and precipitation processes. While the post-monsoon chemistry is controlled by silicate mineral dissolution + cation exchange reactions, pre-monsoon variability is attributable chiefly to precipitation reactions + anthropogenic factors. Positive correlations between Mg vs HCO₃ and Ca + Mg vs HCO₃ supports selective dissolution of olivine and pyroxene as dominant process in post-monsoon followed by dissolution of plagioclase feldspar and secondary carbonates. The pre-monsoon data however, points toward the dissolution of plagioclase and precipitation of CaCO₃ supported by improved correlation coefficients between Na + Ca vs HCO₃ and negative correlation of Ca vs HCO₃, respectively. It is proposed that the eccentricity in the composition of groundwater from the Panjhara basin is a function of selective dissolution of olivine > pyroxene followed by plagioclase feldspar. The data suggest siallitization (L < R and R _k) as dominant mechanism of chemical weathering of basalts, stimulating monosiallitic (kaolinite) and bisiallitic (montmorillonite) products. The chemical denudation rates for Panjhara basin worked out separately for the ground and surface water component range from 6.98 to 36.65 tons/km²/yr, respectively. The values of the CO₂ consumption rates range between 0.18 × 10⁶ mol//km²/yr (groundwater) and 0.9 × 10⁶ mol/km²/yr (surface water), which indicates that the groundwater forms a considerable fraction of CO₂ consumption, an inference, that is, not taken into contemplation in most of the studies.     

Static compression of α-Fe<Subscript>2</Subscript>O<Subscript>3</Subscript>: linear incompressibility of lattice parameters and high-pressure transformations

The high-pressure behavior of -Fe₂O₃ has been studied under static compression up to 60 GPa, using a laser-heated diamond anvil cell. Synchrotron-based angular-dispersive X-ray diffraction shows that the sample remains in the corundum structure up to 50 GPa, but with the appearance of coexisting diffraction lines from a high-pressure phase at pressures above 45 GPa. A least-squares fit of low-pressure phase data to an Eulerian finite-strain equation of state yields linear incompressibilities of K _{a 0}=749.5 (± 18.4) GPa and K _{c 0}= 455.7 (± 21.4) GPa, differing by a factor of 1.6 along the two directions. The enhanced compressibility of the c axis may lead to breaking of vertex- or edge-sharing bonds between octahedra, inducing the high-pressure phase transformation at 50 GPa. Analysis of linear compressibilities suggests that the high-pressure phase above 50 GPa is of the Rh₂O₃ (II) structure. Continuous laser heating reveals a new structural phase transformation of -Fe₂O₃ at 22 GPa, to an orthorhombic structure with a=7.305(3) Å, b=7.850(3) Å, and c=12.877(14) Å, different from the Rh₂O₃ (II) structure.     

Sources and transformations of N in reclaimed coastal tidelands: evidence from soil δ<Superscript>15</Superscript>N data

Electrical conductivity of saturated soil extracts (EC_e) in three reclaimed tideland (RTL) soils on the west coast of Korea decreased with time since reclamation, indicating natural desalinization through leaching of salts by precipitation water. Soil N concentration increased with decreasing EC_e. With the increase in soil N concentration, the δ¹⁵N decreased, likely caused by the input of ¹⁵N-depleted N sources. As N₂-fixing plant species were found in the oldest RTL, atmospheric N₂ fixation likely contributed to the increase in soil N concentration in the oldest RTL. Negative δ¹⁵N (−7.1 to −2.0‰) of total inorganic N (NH₄ ⁺+NO₃ ⁻) and published data on N deposition near the study area indicate that atmospheric N deposition might be another source of N in the RTLs. Meanwhile, the consistently negative δ¹⁵N of soil NO₃ ⁻ excluded N input from chemical fertilizer through groundwater flow as a potential N source, since NO₃ ⁻ in groundwater generally have a positive δ¹⁵N. The patterns of δ¹⁵N of NH₄ ⁺ (+2.3 to +5.1‰) and NO₃ ⁻ (−9.2 to −5.0‰) suggested that nitrification was an active process that caused ¹⁵N enrichment in NH₄ ⁺ but denitrification was probably minimal which would otherwise have caused ¹⁵N enrichment in NO₃ ⁻. A quantitative approach on N budget would provide a better understanding of soil N dynamics in the studied RTLs.