Localized zones of denitrification in a floodplain aquifer in southern Wisconsin, USA

A floodplain aquifer within an agricultural watershed near Madison, Wisconsin (USA), was studied to determine whether denitrification was occurring below the surface organic layer. Groundwater levels and concentrations of O₂, Cl^?, NO ₃ ^? , SO ₄ ^2? , dissolved organic carbon (DOC), and major cations were monitored over a 1-year period along a 230-m transect between an agricultural field and a stream discharge point. Seventeen groundwater samples were analyzed for δ¹⁵N_NO3 and δ¹⁸O_NO3 composition. Samples in which NO ₃ ^? was too low for stable isotope analysis were analyzed for excess dissolved N₂. Groundwater NO ₃ ^? concentrations declined between the agricultural field and the discharge point. Chloride and δ¹⁵N_NO3/δ¹⁸O_NO3 data indicated that the drop in NO ₃ ^? was caused primarily by dilution of shallow NO ₃ ^? -rich water with deeper, NO ₃ ^? -depleted groundwater. Two localized zones of denitrification were identified in the upland-wetland transition by their δ¹⁵N_NO3 and δ¹⁸O_NO3 signatures, and two in the stream hyporheic zone by the presence of excess dissolved N₂. The combined stratigraphic, hydrologic, and geochemical data in these locations correspond to groundwater mixing zones where NO ₃ ^? is delivered to subsurface layers that support denitrification fueled by dissolved (e.g. DOC or dissolved Fe(II)) and/or solid-phase (e.g. particulate organic carbon, solid-associated Fe(II), or pyrite) electron donors.     

Submarine Groundwater Discharge-Derived Nutrient Loads to San Francisco Bay: Implications to Future Ecosystem Changes

Submarine groundwater discharge (SGD) was quantified at select sites in San Francisco Bay (SFB) from radium (²²³Ra and ²²⁴Ra) and radon (²²²Rn) activities measured in groundwater and surface water using simple mass balance box models. Based on these models, discharge rates in South and Central Bays were 0.3?C7.4?m³?day^?1?m^?1. Although SGD fluxes at the two regions (Central and South Bays) of SFB were of the same order of magnitude, the dissolved inorganic nitrogen (DIN) species associated with SGD were different. In the South Bay, ammonium (NH ₄ ⁺ ) concentrations in groundwater were three-fold higher than in open bay waters, and NH ₄ ⁺ was the primary DIN form discharged by SGD. At the Central Bay site, the primary DIN form in groundwater and associated discharge was nitrate (NO ₃ ^? ). The stable isotope signatures (??¹⁵N_NO3 and ??¹⁸O_NO3) of NO ₃ ^? in the South Bay groundwater and surface waters were both consistent with NO ₃ ^? derived from NH ₄ ⁺ that was isotopically enriched in ¹⁵N by NH ₄ ⁺ volatilization. Based on the calculated SGD fluxes and groundwater nutrient concentrations, nutrient fluxes associated with SGD can account for up to 16?% of DIN and 22?% of DIP in South and Central Bays. The form of DIN contributed to surface waters from SGD may impact the ratio of NO ₃ ^? to NH ₄ ⁺ available to phytoplankton with implications to bay productivity, phytoplankton species distribution, and nutrient uptake rates. This assessment of nutrient delivery via groundwater discharge in SFB may provide vital information for future bay ecological wellbeing and sensitivity to future environmental stressors.     

First principles quantum mechanical calculation of the electric dipole polarizabilities of the borate,carbonate, nitrate and related ions

Electric dipole polarizabilities have been calculated from first principles of quantum mechanics for the BO ₃ ^3? , CO ₃ ^2? , NO ₃ ^? series and for NO ₂ ^? and LiNO₃(g). Calculated trends in average polarizability and polarizability anisotropy in the BO ₃ ^3? -NO ₃ ^? series are in agreement with experiment and can be qualitatively interpreted in terms of the varying energies of the a₁′, a₂″ and e′ symmetry unoccupied MO's of the oxyanions. Embedding a CO ₃ ^2? ion in a D_3h symmetry array of divalent cations reduces both the average polarizability and its anisotropy, particularly when diffuse s and p functions are included in the calculation. Calculations on the gas phase LiNO₃ molecule and on the free NO ₃ ^? ion in the distorted geometry found in LiNO₃(g) allow us to separate polarizability contributions internal to the NO ₃ ^? and Li⁺ ions from those which arise from the Li⁺-NO ₃ ^? interaction. The Li⁺-NO ₃ ^? interaction term so obtained is much smaller than the NO ₃ ^? contribution but is in turn larger than the Li⁺ contribution, suggesting that the inclusion of this interaction term is essential for obtaining accurate results for ion pairs. Although static polarizabilities are in reasonable agreement with experiment for NO ₃ ^? the wavelength dispersion of the polarizability is underestimated by about a factor of two, apparently as a result of inadequacies in the quantum mechanical method. Calculated values are also presented for ¹⁴N NMR shieldings in the nitrogen oxyanions but these are in only qualitative agreement with the experimental values. Similarly, calculated values of magnetic susceptibility are in only qualitative agreement with experiment although trends along the BO ₃ ^3? -NO ₃ ^? series are properly reproduced.     

Assessment of hydrogeochemical processes in a coastal region: Application of multivariate statistical model

Hydrogeochemical studies have been carried out in a coastal region, using multivariate statistical model, for better understanding the controlling processes that influence the aquifer chemistry. Two principal components (PC1 and PC2) are extracted from the data set of chemical variables (pH, TDS, Ca²⁺, Mg²⁺, Na⁺, K⁺, HCO ₃ ^? , Cl^?, SO ₄ ^2? , NO ₃ ^? and F^?), which account for 79% of the total variation in the quality of groundwater. The PC1 (salinity controlled process) includes the concentrations of TDS, Mg²⁺, Na⁺, K⁺, Cl^?, SO ₄ ^2? and NO ₃ ^? , while the PC2 (alkalinity controlled process) comprises the concentrations of pH, HCO ₃ ^? and F^?. The spatial distribution of PC scores identifies the locations of high salinity and alkalinity processes. The first process corresponds to the influences of geogenic, anthropogenic and marine sources, and the second one to the influence of water-soil-rock interaction. Thus, the present study shows the usefulness of multivariate statistical model as an effective means of interpretation of spatial controlling processes of groundwater chemistry.     

Impacts of agricultural irrigation recharge on groundwater quality in a basalt aquifer system (Washington, USA): a multi-tracer approach

Irrigation in semi-arid agricultural regions can have profound effects on recharge rates and the quality of shallow groundwater. This study coupled stable isotopes (²??, ¹⁸O), age-tracers (³H, CFCs, ¹⁴C), ⁸⁷Sr/⁸⁶Sr ratios, and elemental chemistry to determine the sources, residence times, and flowpaths of groundwater and agricultural contaminants (e.g. NO ₃ ^?C ) in the Saddle Mountains Basalt Aquifer in central Washington, USA, where over 80% of the population depend on groundwater for domestic use. Results demonstrate the presence of two distinct types of water: contaminated irrigation water and pristine regional groundwater. Contaminated irrigation water has high NO ₃ ^?C concentrations (11?C116? mg/l), ⁸⁷Sr/⁸⁶Sr ratios (0.70659?C0.71078) within range of nitrogen-based fertilizers, detectable tritium (2.8?C13.4 TU), CFC ages 20?C40?years, high ??¹⁸O values (?16.9 to ?13.5??), and ??100 percent modern ¹⁴C. Pristine regional groundwater has low NO ₃ ^?C concentrations (1?C5? mg/l), no detectable tritium (??0.8 TU), low ??¹⁸O values (?18.9 to ?17.3??) and ¹⁴C ages from ??15 to 33?ky BP. Nitrogen and oxygen isotopes of NO ₃ ^?C , combined with high dissolved oxygen values, show that denitrification is not an important process in the organic-poor basalt aquifers resulting in transport of high NO ₃ ^?C irrigation water to depths greater than 40?m in less than 30? years.     

Characterisation and quality assessment of groundwater with a special emphasis on irrigation utility: Thirumanimuttar sub-basin, Tamil Nadu, India

Thirumanimuttar sub-basin is of particular importance in the study of groundwater quality due to the release of effluents from industries, agricultural, sewage and urban runoff, brining considerable change in water quality. An investigation was carried out by collecting a total of 194 groundwater samples for two seasons to decipher hydrogeochemistry and groundwater quality for determining its suitability for agricultural purposes. The water is neutral to alkaline in nature with pH ranging from 6.78 to 9.22 with an average of 7.37. Higher electrical conductivity (EC) was noted in NW and mid-downstream parts of the study area. Higher NO ₃ ^? was observed during post-monsoon (POM) due to the action of leaching and anthropogenic process. The piper plot reveals the dominance of Na⁺?CCl^? and Na⁺?CHCO ₃ ^? , mixed Ca²⁺?CNa⁺?CHCO ₃ ^? , mixed Ca²⁺?CMg²⁺?CHCO ₃ ^? and Ca²⁺?CSO ₄ ^? types of hydrogeochemical facies. Higher total hardness in the groundwater is due to the effect of dyeing and bleaching industries discharging effluents affects the quality of water. Residual Sodium Carbonate value indicates 56% of the samples are not suitable for irrigation purposes in both seasons. Higher sodium percentage is noted during PRM indicating the dominance of ion exchange and weathering. Higher sodium adsorption ratio was observed during POM indicating the effect of leaching and dissolution of salts into the aquifer matrix. USSL plot indicates 15% of samples record high salinity to medium sodicity. The Permeability Index indicates water is moderate to good for irrigation purposes. In general, groundwater in the study area is influenced by both natural and anthropogenic activities.     

Characterization, classification, and determination of drinkability of some Algerian thermal waters

In this study, the physicochemical parameters (Conductivity, pH, Cl^?, HCO ₃ ^? , PO ₄ ^3? , SO ₄ ^2? , NO ₃ ^? , NO ₂ ^? , F^?, TH, Ca²⁺, K⁺, Mg²⁺, Na⁺, and DS) were determined for 41 samples collected from fourteen places in Algeria. The temperature of the thermal water samples at collection sites varied from 26°C to 86°C. pH values varied from 6.5 to 8.5 (i.e., from slightly acidic to moderately alkaline); 90.24% of the samples exhibited relatively high salinity (DS?=?550–5,500 mg L^?1). Total hardness measurements indicated these waters to be moderately hard. Forty-six percent of the samples are Na–Cl in character. The ratios Na⁺/Ca²⁺, Na⁺/Mg²⁺, and (Na⁺ + K⁺)/(Ca²⁺ + Mg²⁺) were high in 90.24% of the samples. This indicates the ion exchange process is important, which indicates that most of the Algerian thermal waters had developed over a long period at a depth sufficient to react with the rock. Statistical analyses of the physicochemical data gave positive correlation values, thereby enabling good interpretation of the results and revealing the composition of ions present in the thermal waters, as well as some information about their origin. The therapeutic properties associated with thermal waters encourage people at spas to drink the water they bathe in. Therefore, we examined the drinkability of these thermal waters. World Health Organization (WHO 1993) standards were used to evaluate the thermal water quality for drinking. With respect to hardness, the samples were classified as moderately hard (58.54% of the samples), very hard (36.58% of the samples), and soft (4.88% of the samples). The drinkability study shows that only 16 samples of the investigated waters were drinkable and thus could be consumed without special precaution.     

Hydrogen and carbon in solid solution in oxides and silicates

The dissolution of H₂O and CO₂ in structurally dense, nominally anhydrous and non-carbonate oxide matrices such as MgO and CaO is reviewed. H₂O and CO₂ are treated as gaseous oxide components which enter into solid solution with the refractory oxide hosts. They form anion complexes associated with cation vacancy sites. Evidence is presented that OH^? pairs which derive from the dissolution of H₂O are subject to a charge transfer (CT) conversion into peroxy moieties and molecular hydrogen, O ₂ ^2? ... H₂. Because the O ₂ ^2? moiety is small (O^?-O^? distance ≈ 1.5 Å) high pressure probably favors the CT conversion. Mass spectroscopic studies show that molecular H₂ may be lost from the solid which retains excess oxygen in the form of O ₂ ^2? , leading to the release of atomic O. The dissociation of O ₂ ^2? moieties into a vacancy-bound O^? state and an unbound O^? state can be followed by measuring the internal redox reactions involving transition metal impurities, the transient paramagnetism of the O^? and their effect on the d.c. conductivity. Evidence is presented that CO₂ molecules dissolve dissociatively in the structurally dense oxide matrix, as if they were first to dissociate into CO+O and then to form separate solute moieties CO ₂ ^2? and O ₂ ^2? , both associated with cation vacancy sites. In the CO ₂ ^2? moiety (C-O^? distance 1.2–1.3 Å, OCO angle ≈ 130°) the C atom probably sits off center. The transition of the C atom into interstitial sites is accompanied by dissociation of the CO ₂ ^2? moiety into CO^? and O^?. This transition can be followed by infrared spectroscopy, using OH^? as local probes. Further support derives from magnetic susceptibility, thermal expansion, low frequency dielectric loss and low temperature deformation measurements. The recently observed emission of O and Mg atoms besides a variety of molecules such as CO, CO₂, CH₄, HCN and other hydrocarbons during impact fracture of MgO single crystals is presented and discussed in the light of the other experimental data.     

Hydrochemical characteristics of groundwater in the plains of Phalgu River in Gaya, Bihar, India

Assessment of groundwater quality is essential to ensure sustainable use of it for drinking, agricultural, and industrial purposes. The chemical quality of groundwater of Gaya region has been studied in detail in this work to delineate the potable groundwater zones. A total of 30 groundwater samples and 2 surface water samples were collected in and around Gaya district of Bihar. The major cations follow the trend: Ca²⁺?>?Mg²⁺?>?Na⁺?>?K⁺. The domination of calcium ions in the groundwater is due to weathering of rocks. The K⁺ ranged between 0.2 and 47.95 ppm, suggesting its abundance the below desired limit; but some samples were found to be above permissible limit. K⁺ weathering of potash silicate and the use of potash fertilizer could be the source. The major anions abundance followed the order HCO ₃ ^? ?>?Cl^??>?SO ₄ ^2? ?>?NO ₃ ^? ?>?PO ₄ ^3? . Dissolution of carbonates and reaction of silicates with carbonic acid accounts for the addition of HCO ₃ ^? to the groundwater and oxidation of sulphite may be the source of SO ₄ ^2? . Principal component analysis was utilized to reflect those chemical data with the greatest correlation and seven major principal components (PCs) representing >80 % of cumulative variance were able to interpret the most information contained in the data. PC1, PC2 and PC3 reflect the hydrogeochemical processes like mineral dissolution, weathering and anthropogenic sources. PC4, PC5, PC6 and PC7 show monotonic, random and independent relationships.     

Geochemical characterization of groundwater from shallow aquifer surrounding Fetzara Lake N. E. Algeria

Hydrogeochemical investigations were carried out around Fetzara Lake, Northeast Algeria, to assess the quality of groundwater for its suitability for drinking and irrigation purposes. The groundwater chemistry is mainly controlled by the water?Crock interactions, but also influenced by other processes such as evapotranspiration and ion exchange. Groundwater samples collected, during two periods (1993 and 2007) from wells in the area were analyzed for pH, EC, TDS, Ca²⁺, Mg²⁺, Na⁺, K⁺, CO ₃ ^2? , HCO ₃ ^? , Cl^?, SO ₄ ^2? , and NO ₃ ^? . The chemical relationships in Piper??s diagram and Gibbs??s diagram suggest that groundwaters mainly belong to noncarbonate alkali type and Cl^? group and are controlled by evaporation dominance, respectively, due to the sluggish drainage conditions, greater water?Crock interaction, and anthropogenic activities. A comparison of the groundwater quality in relation to drinking water quality standards proves that most of the water samples are not suitable for drinking. US Salinity Laboratory??s and Wilcox??s diagrams and %Na⁺ used for evaluating the water quality for irrigation suggest that the majority of the groundwater samples are not good for irrigation.     

Heterogeneous redox conditions, arsenic mobility, and groundwater flow in a fractured-rock aquifer near a waste repository site in New Hampshire, USA

Anthropogenic sources of carbon from landfill or waste leachate can promote reductive dissolution of in situ arsenic (As) and enhance the mobility of As in groundwater. Groundwater from residential-supply wells in a fractured crystalline-rock aquifer adjacent to a Superfund site in Raymond, New Hampshire, USA, showed evidence of locally enhanced As mobilization in relatively reducing (mixed oxic-anoxic to anoxic) conditions as determined by redox classification and other lines of evidence. Redox classification was determined from geochemical indicators based on threshold concentrations of dissolved oxygen (DO), nitrate (NO ₃ ^– ), iron (Fe²⁺), manganese (Mn²⁺), and sulfate (SO ₄ ^2– ). Redox conditions were evaluated also based on methane (CH₄), excess nitrogen gas (N₂) from denitrification, the oxidation state of dissolved As speciation (As(III) and As(V)), and several stable isotope ratios. Samples from the residential-supply wells primarily exhibit mixed redox conditions, as most have long open boreholes (typically 50–100?m) that receive water from multiple discrete fractures with contrasting groundwater chemistry and redox conditions. The methods employed in this study can be used at other sites to gauge redox conditions and the potential for As mobilization in complex fractured crystalline-rock aquifers where multiple lines of evidence are likely needed to understand As occurrence, mobility, and transport.     

Sources and Processes Affecting Nitrate in a Dam-Controlled Subtropical River,Southwest China

Excess nutrient (N and P) loads are recognized as the major cause of serious water quality problems in China. River systems play a very important role in nitrate (NO₃ ^?) transportation and transformation in the aquatic environment. To understand and clarify the sources and processes affecting NO₃ ^? in river basins, we have examined spatial and temporal variations of concentration and dual-isotopic composition of NO₃ ^? in the dam-controlled Jialing River, a major tributary of the Yangtze River where land use is dominated by agriculture. Water samples were collected in July 2008 and February 2009 from the main channel of the Jialing River and its major tributaries. The δ¹⁵N and δ¹⁸O of NO₃ ^? range from 1.5 to 11.0 ‰ (average 6.2 ‰) and ?5.0 to 11.1 ‰ (average, 1.6 ‰), respectively. NO₃ ^? isotope data and δ¹⁸O of water interpreted in combination with hydrological and chemical data suggest that most of the NO₃ ^? input is from nitrification during the rainy season, and discharge of sewage and manure in the upper course and from cities accounts for much of the NO₃ ^? load during the dry season. The construction of cascade dams has led to retention of Si and a decrease in the Si/N ratio, implying that assimilation and/or denitrification may significantly affect NO₃ ^? in the dam area, as demonstrated by NO₃ ^? and dissolved Si concentrations, and \(\updelta^{ 1 5} {\text{N}}_{{{\text{NO}}_{3} }}\) and \(\updelta^{ 1 8} {\text{O}}_{{{\text{NO}}_{3} }}\) values. This study indicates that dual-isotopic data can be used to identify NO₃ ^? pollution sources and the processes NO₃ ^? has undergone during its retention and transport in the watershed of the dam-controlled Jialing River.     

Removal of nitrates from high-salinity wastewaters from desulphurization process with denitrifying bacteria encapsulated in Lentikats Biocatalyst

Successful elimination of high concentrations of N?CNO _x ^? (up to 250?mg/L) from high salinity wastewaters (up to 35?g/L Cl^??+?17?g/L SO₄ ^2?) originating from desulphurization process within coal power stations was achieved using pure cultures of denitrifying bacteria encapsulated in porous polyvinyl alcohol lenses (so called Lentikats Biocatalyst, LB). Laboratory batch tests revealed inhibitory influence of the raw wastewater on the denitrification activity, which was partially mitigated by the addition of P?CPO₄ ^3?. In following continuous tests, the denitrification activities reached the range 150?C450?mg?N/h/kg LB, i.e., values suitable for industrial scale applications. The higher activities were achieved under a lower salinity, higher N?CNO _x ^? influent concentrations and a prolonged retention time. The effluent N?CNO _x ^? concentrations were below the determination limit of 5?mg/L. After a period of 3?months, a significant decrease of denitrification activity of Lentikats Biocatalyst was observed. Addition of nutrients into the wastewater enabled fast regeneration of the initial activity. The overall results proved the applicability of Lentikats Biocatalysts for the removal of nitrates from high-salinity desulphurization water and other industrial wastewaters of similar character.     

Characterization and origin of two Fe3+ EPR spectra in kaolinite

The electron paramagnetic resonance (EPR) spectra of Fe³⁺ in a well cristallized kaolinite from Decazeville in France are well resolved. It is shown that in this sample there are mainly two slightly different spectra, well separated at low temperature and characterized at -150° C by the constants B ₂ ⁰ = 0.112 cm^?1, B ₂ ² = 0.0688 cm^?1 for one and B ₂ ⁰ = 0.116 cm^?1, B ₂ ² = 0.0766 cm^?1 for the second. These two spectra arise from Fe³⁺ substituted for Al³⁺ at the two octahedral positions in equal amounts. The temperature dependence of EPR spectra was studied and was explained by a modification of the octahedral sites.     

Hydrochemistry and pollution probability of selected sites along the Euphrates River, Western Iraq

The hydrochemistry of Euphrates River in the study area which extended from Hit to Al-Saqlawia was studied in order to determine the physical, chemical, and biological properties in addition to the radiation level. Thirty-one stations along the Euphrates River were chosen, 17 of them represented the Euphrates River itself, whereas the other stations are considered as point pollution sources which all empty their load directly in the Euphrates River with an average total discharge of 32 m³/s. Twenty-eight samples of the Euphrates water of both high- and low-flow periods were analyzed for cations (Ca²⁺, Mg²⁺, Na⁺, and K⁺), anions (SO ₄ ⁼ , Cl^?, CO ₃ ⁼ , HCO ₃ ^? , NO ₃ ^? , PO ₄ ^?3 ), H₂S boron, dissolved oxygen, biological oxygen demand, bacteriological tests, radiation levels in addition to physical parameters such as hydrogen number (pH), total dissolved solid, electrical conductivity, total suspended solid, and temperature. This study showed that the cations and anions during periods of high and low flows are within acceptable limit with exceptional Cl^?. Hydrochemical formula during the high flow was Na-Ca-Mg-Cl-SO₄, then it changed into Na-Ca-Mg-HCO3-SO₄-Cl during the low-flow period. The average output cations and anions at downstream (Saqlawiya area) was relatively higher than those of input at upstream (Hit area); this attributed to the natural and anthropogenic activities originated mainly from agricultural activity and population communities around the river. Radiation level for ²¹²Pb, ²¹⁴Pb, ⁴⁰k, ²²⁰Ac, and ²¹⁴Bi showed that the higher level of radiation is concentrated within sediment rather than in water, but the radiation in both is within acceptable limit.     

Spatial variations of groundwater vulnerability using cluster analysis

An investigation on quality of groundwater has been carried out in the river basin of Varaha located in Visakhapatnam District, Andhra Pradesh to find out the factors that are responsible for spatial variations of water vulnerability. The study area is underlain by the Precambrian rocks of Eastern Ghats over which the Recent Formations occur. Groundwater is a prime source for drinking and irrigation. The quality of groundwater is fresh and brackish with dominance of the latter. Groundwater samples are categorized into two major clusters A and B, using the dendrogram of cluster analyses. Out of these two major clusters, five sub-clusters I to V in the pre-monsoon season and six sub-clusters I to VI in the post-monsoon season are identified. The sub-clusters I to IV of pre-monsoon and I to V of post-monsoon seasons of the cluster A are characterized by less mineralized groundwater compared to those of V of pre-monsoon and VI of post-monsoon seasons of the cluster B, which represent highly mineralized groundwater. The low to high mineral content follows gradually from upstream to the downstream area, being higher in post-monsoon season in both the clusters A and B, depending upon the source, mineral dissolution, and precipitation, solubility and leaching of ions, ion exchange and adsorption processes. Spatial distributions of the sub-clusters give clues to understand the factors that cause variations of groundwater vulnerability at a specific site, vis-a-vis local and regional lithological and non-lithological influences. As a result, the quality of groundwater on a regional scale changes from Na⁺ > Mg²⁺ >Ca²⁺ > K⁺: HCO ₃ ^? > Cl^? > SO ₄ ^2? > NO ₃ ^? > F^? in the cluster A to Na⁺ > Mg²⁺ >Ca²⁺ > K⁺: Cl^? > HCO ₃ ^? > SO ₄ ^2? > NO ₃ ^? > F^? in the cluster B, following the topography. The classification of the area into the zones of relative groundwater vulnerability with respect to drinking water quality of the chemical composition of the sub-clusters helps the planners to identify the specific locations, where the inferior quality of groundwater can occur, for taking the remedial measures.     

Thermodynamics of plagioclase II: Temperature evolution of the spontaneous strain at the I\bar 1 \leftrightarrow P\bar 1 phase transition in anorthite

The temperature dependence of the lattice parameters of pure anorthite with high Al/Si order reveals the predicted tricritical behaviour of the \(I\bar 1 \leftrightarrow P\bar 1\) phase transition at T _c ^* =510 K. The spontaneous strain couples to the order parameter Q° as x _i∝S _xQ ⁱ Q°² with S _xQ ¹ =4.166×10^?3, S _xQ ² =0.771×10^?3, S _xQ ³ =?7.223×10^?3 for the diagonal elements. The temperature dependence of Q° is $$Q^{\text{o}} = \left( {1 - \frac{T}{{510}}} \right)^\beta ,{\text{ }}\beta = \tfrac{{\text{1}}}{{\text{4}}}$$ A strong dependence of T _c ^* , S _xQ ⁱ and β is predicted for Al/Si disordered anorthite.     

Relations of hydrogeologic factors, groundwater reduction-oxidation conditions, and temporal and spatial distributions of nitrate, Central-Eastside San Joaquin Valley, California, USA

In a 2,700-km² area in the eastern San Joaquin Valley, California (USA), data from multiple sources were used to determine interrelations among hydrogeologic factors, reduction-oxidation (redox) conditions, and temporal and spatial distributions of nitrate (NO₃), a widely detected groundwater contaminant. Groundwater is predominantly modern, or mixtures of modern water, with detectable NO₃ and oxic redox conditions, but some zones have anoxic or mixed redox conditions. Anoxic conditions were associated with long residence times that occurred near the valley trough and in areas of historical groundwater discharge with shallow depth to water. Anoxic conditions also were associated with interactions of shallow, modern groundwater with soils. NO₃ concentrations were significantly lower in anoxic than oxic or mixed redox groundwater, primarily because residence times of anoxic waters exceed the duration of increased pumping and fertilizer use associated with modern agriculture. Effects of redox reactions on NO₃ concentrations were relatively minor. Dissolved N₂ gas data indicated that denitrification has eliminated >5 mg/L NO₃–N in about 10% of 39 wells. Increasing NO₃ concentrations over time were slightly less prevalent in anoxic than oxic or mixed redox groundwater. Spatial and temporal trends of NO₃ are primarily controlled by water and NO₃ fluxes of modern land use.     

Electron paramagnetic resonance of PO 3 2− and SO 3 − radicals in anhydrite,celestite and barite: the hyperfine structure and dynamics

Electron paramagnetic resonance (EPR) measurements of natural anhydrite CaSO₄, celestite SrSO₄ and barite BaSO₄ have revealed the presence of PO ₃ ^2? and SO ₃ ^? radicals. Hyperfine structure from³³S has been detected and measured for the first time. Low-symmetry effects, which are manifested in noncoincidence of g and hyperfine axes, were observed for SO ₃ ^? . The dynamics of one of the two SO ₃ ^? types in anhydrite has been investigated. Variations of spin Hamiltonian parameters with temperature have been attributed to thermally induced jumps between the two magnetically inequivalent sites of this center.     

The effect of medium chemistry on the solubility and morphology of brushite crystals

An experimental study of the particulars of the solubility and crystallization of brushite Ca(HPO₄) · 2H₂O from aqueous solution in conditions of a variable pH (6.0–3.0) and the contents of impurity ions (K⁺, Na⁺, NH ₄ ⁺ , Mg²⁺, SO ₄ ^2? , CO ₃ ^2? ) has been conducted. It is established that brushite solubility markedly rises with a decrease in pH from 6 to 3 and slightly rises with an increase in Mg²⁺ and SO ₄ ^2? concentrations. The enrichment in K⁺, Na⁺, and NH ₄ ⁺ does not affect brushite solubility. The changeable chemistry of the medium results in variation of the synthetic crystal habit, from rhombic tabular to thickened prismatic crystals.