Luminescence spectroscopic study of Cr3+ in Brazilian topazes from Ouro Preto

In this paper, the results of investigation of luminescent properties of topazes from Ouro Preto, Brazil are presented. It is established that all photoluminescence characteristics of variously colored topazes are due to three structurally non-equivalent Cr³⁺ centers isomorphically substituting Al³⁺ in the topaz structure and forming [CrO₄F₂]⁷⁻, [CrO₄OH,F]⁷⁻, and [CrO₄(OH)₂]⁷⁻ complexes. Kinetics of thermal annealing indicates different thermal stability of these centers. Less stable [CrO₄OH, F]⁷⁻- and [CrO₄(OH)₂]⁷⁻ complexes diminish in temperature range 950–1,100°C, accompanied by appearance of corundum phase. The most stable [CrO₄F₂]⁷⁻ centers completely decay at 1,250°C and luminescence spectrum of product obtained becomes identical to that of Cr³⁺ in mullite indicating that topaz completely transforms to mullite.

Vibrational states of H<Subscript>2</Subscript>O in beryl: physical aspects

Single-crystal polarized Raman spectra (3,000–4,000 cm⁻¹ at 3 ≤ T ≤ 300 K) were measured for synthetic alkali-free and natural beryl, Be₂Al₃Si₆O₁₈·xH₂O, to determine the behavior of H₂O molecules of both Type I and Type II in the cavities. At low temperature, the H₂O molecules of Type I displace from the center of cavity and give rise to very weak hydrogen bonding with the host lattice. The H₂O Type I translational motion is characterized by substantial anharmonicity and looks like a motion of “a particle in the box” with a frequency of 6.3 cm⁻¹. Water Type II is characterized by a free rotation with respect to the C ₂ molecule axis, and it makes possible the water nuclear isomers (i.e. ortho- and para-) to be observed at low temperature.

Groundwater nitrate contamination and risk assessment in an agricultural area,South Korea

The nitrate of groundwater in the Gimpo agricultural area, South Korea, was characterized by means of nitrate concentration, nitrogen-isotope analysis, and the risk assessment of nitrogen. The groundwaters belonging to Ca–(Cl + NO₃) and Na–(Cl + NO₃) types displayed a higher average NO₃ ⁻ concentration (79.4 mg/L), exceeding the Korean drinking water standard (<44.3 mg/L NO₃ ⁻). The relationship between δ¹⁸O–NO₃ ⁻ values and δ¹⁵N–NO₃ ⁻ values revealed that nearly all groundwater samples with δ¹⁵N–NO₃ ⁻ of +7.57 to +13.5‰ were affected by nitrate from manure/sewage as well as microbial nitrification and negligible denitrification. The risk assessment of nitrate for groundwater in the study area was carried out using the risk-based corrective action model since it was recognized that there is a necessity of a quantitative assessment of health hazard, as well as a simple estimation of nitrate concentration. All the groundwaters of higher nitrate concentration than the Korean drinking water standard (<44.3 mg/L NO₃ ⁻) belonged to the domain of the hazard index <1, indicating no health hazard by nitrate in groundwater in the study area. Further, the human exposure to the nitrate-contaminated soil was below the critical limit of non-carcinogenic risk.     

Sensitivity of high-resolution tropical cyclone intensity forecasts to surface flux parameterization

Surface flux parameterization schemes used in current dynamic models are primarily based upon measurements at low and moderate wind speeds. Recent studies show that these parameterization schemes may be incorrect at high wind speeds (e.g., tropical cyclone forecasts). Five high-resolution numerical model experiments are designed to assess the sensitivity of tropical cyclone intensity forecasts to changes in the surface flux parameterization. The sensitivity experiments are conducted by running 48 h forecasts of the Coupled Ocean/Atmosphere Mesoscale Prediction System (COAMPS) for six selected tropical cyclones with individual modifications to surface flux calculation that include: (1) limiting the surface stress for wind speeds greater than 33 m s⁻¹, or 64 knots (kt); (2) computing the stress at the top of the model bottom grid layer (MBGL) by averaging results from surface layer similarity and turbulence mixing parameterization for wind speeds greater than 33 m s⁻¹; (3) increasing the roughness lengths for heat and moisture transfer by a factor of ten; (4) setting the roughness lengths for heat and moisture transfer to 1/10 of the momentum roughness length; and (5) cooling the sea surface temperature (SST) by a prescribed rate at high winds. Averaged responses for the six storms to these sensitivity tests show that: (i) the limit on surface stress at high winds significantly increases the cyclone intensity in 48 h forecasts; (ii) the averaged surface layer stress at high winds increases the cyclone intensity but to a much lesser degree than limiting the surface stress; (iii) large increases in the roughness lengths for heat and moisture transfer are needed to significantly impact the intensity forecast; (iv) the different roughness length formula for surface transfer coefficients notably increases C _h/C _d ratio from 0.59 to 0.79 for 25 m s⁻¹ and 0.41 to 0.75 for 50 m s⁻¹ that significantly increases the predicted cyclone intensity; and (v) cooling of the SST by −5.8°C in 48 h reduces the maximum surface wind speed by −32 kt, or 16.5 m s⁻¹, at 48 h forecast. These results suggest that a surface flux parameterization scheme suitable for tropical cyclone intensity forecast must correctly model the leveling-off character of surface stress and C _h/C _d ratio at high winds. All modifications to surface flux calculation have little influence on 48 h track forecasts, even though they may significantly impact the intensity forecasts.

Nitrate contamination of groundwater in an agroecosystem in Zhangye Oasis,Northwest China

In order to assess the extent of groundwater contamination by nitrate (NO₃ ⁻–N) and to provide information about the deterioration of the groundwater quality in Zhangye Oasis, Northwest China, a study was conducted in this area. The mean value of NO₃ ⁻–N concentrations in groundwater samples was 10.66 ± 0.19 mg l⁻¹. NO₃ ⁻–N concentrations exceeding 10 mg l⁻¹ (the threshold for drinking water set by the World Health Organization) were found in 32.4% of 71 wells, and were 13, 33.3, 52.4 and 50.0% in the groundwater samples from drinking wells, irrigation wells, hand-pumping wells and groundwater table observation wells, respectively. The result showed that the groundwater samples that had NO₃ ⁻–N concentrations exceeding the threshold for drinking water were mostly collected from a depth of less than 20 m. Groundwater NO₃ ⁻–N concentrations in areas used for the cultivation of vegetables, seed maize and intercropped maize were significantly higher than those in urban or paddy areas. NO₃ ⁻–N contamination of groundwater in areas with sandy soil was more severe than in those with loam soil.     

Calcium diffusivity in alumino-silicate garnets: an experimental and ATEM study

Concentration gradients in calcium are common in metamorphic or magmatic garnets and can be used to determine the timescales of geological processes. However, the kinetics of Ca diffusion in garnet is poorly constrained and experimental studies have to date yielded widely varying diffusion coefficients. In this paper, we describe a new method for generating diffusion profiles in garnet. We incorporated polished and compositionally homogeneous garnet seeds in a finely ground powder of clinopyroxene and garnet. During the experiments (1.3 GPa, 1,050–1,250°C, and ƒO₂ ≤ the graphite-O₂ buffer), the mineral powder partially melted, recrystallized, and formed a 10–50 μm wide overgrowth zone of compositionally distinct garnet around the seeds. Long duration experiments generated measurable relaxation profiles at these seed/overgrowth interfaces. We performed analytical transmission electron microscope traverses across the interfaces in each experiment. Thirteen usable compositional profiles were obtained with characteristic distances of diffusion ranging from 300 to 1,000 nm. From these profiles, Ca–(Fe, Mg) interdiffusion coefficients were retrieved using an analytical solution for the diffusion equation and the data were cast in an Arrhenius relation. Linear regression of the data yields an activation energy Q _{Ca–(Fe, Mg)} equal to 188 ± 48 kJ mol⁻¹ and a frequency factor D ₀ equal to 6.6 × 10⁻¹⁴ m² s⁻¹. Within the compositional range studied, the composition of garnet has no major effect on the Ca–(Fe, Mg) interdiffusion coefficient. The very slow diffusion rate of Ca is in agreement with natural observations indicating that Ca diffuses more slowly than Fe and Mg. The Ca diffusion coefficients derived from this study are not model-dependent and can be used to determine the durations of geological events from Ca relaxation profiles in natural garnets.

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Influence of hydrogen on Fe–Mg interdiffusion in (Mg,Fe)O and implications for Earth’s lower mantle

Interdiffusion of Fe and Mg in (Mg,Fe)O has been investigated experimentally under hydrous conditions. Single crystals of MgO in contact with (Mg_0.73Fe_0.27)O were annealed hydrothermally at 300 MPa between 1,000 and 1,250°C and using a Ni–NiO buffer. After electron microprobe analyses, the dependence of the interdiffusivity on Fe concentration was determined using a Boltzmann–Matano analysis. For a water fugacity of ∼300 MPa, the Fe–Mg interdiffusion coefficient in Fe _x Mg_1−x O with 0.01 ≤ x ≤ 0.25 can be described by with and C = −80 ± 10 kJ mol⁻¹. For x = 0.1 and at 1,000°C, Fe–Mg interdiffusion is a factor of ∼4 faster under hydrous than under anhydrous conditions. This enhanced rate of interdiffusion is attributed to an increased concentration of metal vacancies resulting from the incorporation of hydrogen. Such water-induced enhancement of kinetics may have important implications for the rheological properties of the lower mantle.

Hydroxyl in mantle olivine xenocrysts from the Udachnaya kimberlite pipe

The incorporation of hydrogen in mantle olivine xenocrysts from the Udachnaya kimberlite pipe was investigated by Fourier-transform infrared spectroscopy and secondary ion mass spectrometry (SIMS). IR spectra were collected in the OH stretching region on oriented single crystals using a conventional IR source at ambient conditions and in situ at temperatures down to −180°C as well as with IR synchrotron radiation. The IR spectra of the samples are complex containing more than 20 strongly polarized OH bands in the range 3,730–3,330 cm⁻¹. Bands at high energies (3,730–3,670 cm⁻¹) were assigned to inclusions of serpentine, talc and the 10 Å phase. All other bands are believed to be intrinsic to olivine. The corresponding point defects are (a) associated with vacant Si sites (3,607 cm⁻¹ E || a, 3,597 E || a, 3,571 cm⁻¹ E || c, 3,567 E || c, and 3,556 E || b), and (b) with vacant M1 sites (most of the bands polarized parallel to a). From the pleochroic behavior and position of the OH bands associated with the vacant M1 sites, we propose two types of hydrogen—one bonded to O1 and another to O2, so that both OH vectors are strongly aligned parallel to a. The O2–H groups may be responsible for the OH bands at higher wavenumbers than those for the O1–H groups. The multiplicity of the corresponding OH bands in the spectra can be explained by different chemical environments and by slightly different distortions of the M1 sites in these high-pressure olivines. Four samples were investigated by SIMS. The calculated integral molar absorption coefficient using the IR and SIMS results of 37,500±5,000 L mol H₂O cm⁻² is within the uncertainties slightly higher than the value determined by Bell et al. (J Geophys Res 108(B2):2105–2113, 2003) (28,450±1,830 L mol H₂O cm⁻²). The reason for the difference is the different distributions of the absorption intensity of the spectra of both studies (mean wavenumber 3,548 vs. 3,570 cm⁻¹). Olivine samples with a mean wavenumber of about 3,548 cm⁻¹ should be quantified with the absorption coefficient as determined in this study; those containing more bands at higher wavenumber (mean wavenumber 3,570 cm⁻¹) should be quantified using the value determined by Bell et al. (J Geophys Res 108(B2):2105–2113, 2003).

Optical spectroscopic study of synthetic NaScSi<Subscript>2</Subscript>O<Subscript>6</Subscript>–CaNiSi<Subscript>2</Subscript>O<Subscript>6</Subscript> pyroxenes at normal and high pressures

Six synthetic NaScSi₂O₆–CaNiSi₂O₆ pyroxenes were studied by optical absorption spectroscopy. Five of them of intermediate (Na_1−x , Ca _x )(Sc_1−x , Ni _x )Si₂O₆ compositions show spectra typical of Ni²⁺ in octahedral coordination, more precise Ni²⁺ at the M1 site of the pyroxene structure. The common feature of all spectra is three broad absorption bands with maxima around 8,000, 13,000 and 24,000 cm⁻¹ assigned to ³ A _2g → ³ T _2g, ³ A _2g → ³ T _1g and →³ T _1g (³ P) electronic spin-allowed transitions of ^VINi²⁺. A weak narrow peak at ∼14,400 cm⁻¹ is assigned to the spin-forbidden ³ A _2g → ¹ T _2g (¹ D) transition of Ni²⁺. Under pressure the spin-allowed bands shift to higher energies and change in intensity. The octahedral compression modulus, calculated from the shift of the ³ A _2g → ³ T _2g band in the (Na_0.7Ca_0.3)(Sc_0.7Ni_0.3)Si₂O₆ pyroxene is evaluated as 85±20 GPa. The Racah parameter B of Ni²⁺(M1) is found gradually changing from ∼919 cm⁻¹ at ambient pressure to ∼890 cm⁻¹ at 6.18 GPa. The Ni end-member pyroxene [(Ca_0.93 Ni_0.07)NiSi₂O₆] has a spectrum different from all others. In addition to the above mentioned bands of Ni²⁺(M1) it displays several new relatively intense and broad extra bands, which were attributed to electronic transitions of Ni²⁺ at the M2 site. In difference to CaO₈ polyhedron geometry of an eightfold coordination, Ni²⁺(M2)O₈ polyhedra are assumed to be relatively large distorted octahedra. Due to different distortions and different compressibilities of the M1 and M2 sites the Ni²⁺(M1)- and Ni²⁺(M2)-bands display rather different pressure-induced behaviors, becoming more resolved in the high-pressure spectra than in that measured at atmospheric pressure. The octahedral compression modulus of Ni²⁺(M1) in this end-member pyroxene is evaluated as 150 ± 25 GPa, which is noticeably larger than in Ni_0.3 pyroxene. This is due to a smaller size and, thus, a stiffer character of Ni²⁺(M1)O₆ octahedron in the (Ca_0.93Ni_0.07)NiSi₂O₆ pyroxene compared to (Na_0.7Ca_0.3)(Sc_0.7Ni_0.3)Si₂O₆.

Hydrology of the coastal sabkhas of Abu Dhabi, United Arab Emirates

Water fluxes were estimated and a water budget developed for the land surface and a surficial 10-m-deep section of the coastal sabkhas that extend from the city of Abu Dhabi, United Arab Emirates, west to the border with Saudi Arabia. The fluxes were estimated on the basis of water levels and hydraulic conductivities measured in wells and evaporation rates measured with a humidity chamber. In contrast with conceptual models proposed in earlier studies, groundwater inflow is estimated to be small, whereas the largest components of the water budget are recharge from rainfall and evaporation from the water table. Estimates within a rectilinear volume of sabkha, defined as 1 m wide by 10 km long by 10 m deep, indicate that about 1 m³/year of water enters and exits by lateral groundwater flow; 40–50 m³/year enters by upward leakage; and 640 m³/year enters by recharge from rainfall. Based on the water and solute fluxes estimated for the upward leakage into the sabkha, 7–8 pore volumes of brine have entered the sabkha from below since the time the sabkha became saturated (7,000 years ago) as a result of the last global sea-level rise.

Carbon dioxide,water vapor,and heat fluxes over agricultural crop field in an arid oasis of Northwest China,as determined by eddy covariance

Fluxes of carbon dioxide, water vapor, and heat were measured above crop canopy using the eddy covariance method during the 2008 maize growing season, over an agricultural field within an oasis located in the middle reaches of Heihe River basin, northwest China. The values for friction velocity, the Monin–Obukhov stability parameter, and energy balance closure indicated that the eddy covariance system at this study site provided reliable flux estimates. Results from measurements showed that the mean sensible heat flux was 70 W m⁻² with a maximum value of 164 W m⁻² (May) and a minimum value of 45 W m⁻² (July) during the maize growing season. In contrast, the mean latent heat was 278 W m⁻² with a maximum value of 383 W m⁻² (July) and minimum of 101 W m⁻² (May). The mean downward soil heat flux was 55 W m⁻² with a maximum value of 127 W m⁻² (May) and minimum of 49 W m⁻² (July). The magnitude of mean daytime net CO₂ uptake was −11.50 μmol m⁻² s⁻¹ with a maximum value of −28.32 μmol m⁻² s⁻¹ (18 and 19 July) and a minimum values of −0.32 μmol m⁻² s⁻¹ (18 and 19 May). Correlation was observed between daytime half-hourly carbon dioxide flux and canopy conductance. In addition, the relationship between carbon dioxide flux and photosynthetically active radiation for selected days during different stages of maize growing season indicated the carbon dioxide flux uptake by the canopy was controlled by actual photosynthetic activity related to the variation of green leaf area index for the different growing stages.     

Analysis of the spatial and temporal changes in soil CO<Subscript>2</Subscript> flux in alpine meadow of Qilian Mountain

Field experiments on the CO₂ flux of alpine meadow soil in the Qilian Mountain were conducted along the elevation gradient during the growing season of 2004 and 2005. The soil CO₂ flux was measured using the Li-6400-09 soil respiration chamber attached to the Li-6400 portable photosynthesis system. The effects of water and heat and roots on the soil CO₂ flux were statistically analyzed. The results show that soil CO₂ flux along the elevation gradient gradually decreases. The soil CO₂ flux was low at night, with lowest value occurring between 0200 and 0600 hours, started to rise rapidly during 0700–0830 hours, and then descend during 1600–1830 hours. The peak CO₂ efflux appears during 1100–1600 hours. The diurnal average of soil CO₂ efflux was between 0.56 ± 0.32 and 2.53 ± 0.76 μmol m⁻² s⁻¹. Seasonally, soil CO₂ fluxes are relatively high in summer and autumn and low in spring and winter. The soil CO₂ efflux, from the highest to the lowest in the ranking order, occurred in July and August (4.736 μmol m⁻² s⁻¹), June and September, and May and October, respectively. The soil CO₂ efflux during the growing season is positively correlated with soil temperature, root biomass and soil water content.     

Effects of nitrogen fertilization on soil respiration in temperate grassland in Inner Mongolia,China

Nitrogen addition to soil can play a vital role in influencing the losses of soil carbon by respiration in N-deficient terrestrial ecosystems. The aim of this study was to clarify the effects of different levels of nitrogen fertilization (HN, 200 kg N ha⁻¹ year⁻¹; MN, 100 kg N ha⁻¹ year⁻¹; LN, 50 kg N ha⁻¹ year⁻¹) on soil respiration compared with non-fertilization (CK, 0 kg N ha⁻¹ year⁻¹), from July 2007 to September 2008, in temperate grassland in Inner Mongolia, China. Results showed that N fertilization did not change the seasonal patterns of soil respiration, which were mainly controlled by soil heat-water conditions. However, N fertilization could change the relationships between soil respiration and soil temperature, and water regimes. Soil respiration dependence on soil moisture was increased by N fertilization, and the soil temperature sensitivity was similar in the treatments of HN, LN, and CK treatments (Q ₁₀ varied within 1.70–1.74) but was slightly reduced in MN treatment (Q ₁₀ = 1.63). N fertilization increased soil CO₂ emission in the order MN > HN > LN compared with the CK treatment. The positive effects reached a significant level for HN and MN (P < 0.05) and reached a marginally significant level for LN (P = 0.059 < 0.1) based on the cumulative soil respiration during the 2007 growing season after fertilization (July–September 2007). Furthermore, the differences between the three fertilization treatments and CK reached the very significant level of 0.01 on the basis of the data during the first entire year after fertilization (July 2007–June 2008). The annual total soil respiration was 53, 57, and 24% higher than in the CK plots (465 g m⁻² year⁻¹). However, the positive effects did not reach the significant level for any treatment in the 2008 growing season after the second year fertilization (July–September 2008, P > 0.05). The pairwise differences between the three N-level treatments were not significant in either year (P > 0.05).     

Assessment of groundwater contamination by NO<Subscript>3</Subscript><Superscript>−</Superscript> using geographical information system in the Zhangye Basin,Northwest China

Geographical information system (GIS) technology was used to investigate NO₃ ⁻ concentration of groundwater in the Zhangye Basin, Northwest China. Thematic information and NO₃ ⁻ data of groundwater from the Zhangye Basin were analyzed in a GIS environment to study the extent and variation of NO₃ ⁻ concentration and to establish spatial relationships with corresponding land use types. About 38.8% of groundwater samples showed NO₃ ⁻ concentration above the human affected value (13 mg/l NO₃ ⁻), while more than 10.2% exceeded the maximum acceptable level (50 mg/l NO₃ ⁻) according to WHO regulations. The spatial distribution of NO₃ ⁻ of groundwater in the Zhangye Basin showed an obvious character of zonation; the high NO₃ ⁻ concentration was mainly located in the city seat areas, and Zhangye City was the high-value center. The probability of over 90% for NO₃ ⁻ concentration exceeding 13 mg/l was found in urban seat areas. The spatial analyses indicated that groundwater contamination by NO₃ ⁻ was closely related to one specific land use class, the urban. The NO₃ ⁻ concentration of groundwater under urban was significantly higher than that under irrigation land or sand dune. Most of the unacceptable NO₃ ⁻ levels were found in groundwater samples assigned to urban area, but a few were also found allotted to irrigation land class. Therefore, urban source was considered the principal source of NO₃ ⁻ contamination of groundwater in the Zhangye Basin, while irrigation land source was still a possible source of NO₃ ⁻ contamination.     

Concentration levels of some inorganic contaminants in streams and sediments in areas of pyrometallurgical and hydrometallurgical activities at the Obuasi gold mine,Ghana

This study assessed the levels of selected inorganic contaminants in streams and stream sediments in the effluent areas relating to the pyrometallurgical and hydrometallurgical treatment of gold ores in the Obuasi gold mine, Ghana. Water and stream sediment samples were taken from specific locations during the consecutive rainy and dry seasons, and concentrations of phosphate (PO₄ ³⁻), nitrate (NO₃ ⁻), chloride (Cl⁻), sulphate (SO₄ ²⁻), sodium (Na⁺), potassium (K⁺), calcium (Ca²⁺), magnesium (Mg²⁺), arsenic (As), copper (Cu), iron (Fe), zinc (Zn) and lead (Pb), were determined. Alkalinity, pH, temperature and specific electrical conductivity were also measured. In the water samples, the average pH range for both the seasons is 6.9–7.4, most anions and metals have relatively higher concentrations in the wet season than in the dry season at both the metallurgical sites. Trace metals concentrations were comparatively low (<0.01–5.00 mg/l), higher in the dry season at the pyrometallurgical sites. Irrespective of seasons, SO₄ ²⁻ (0.80–949.50 mg/l) and PO₄ ³⁻ (<0.01–6.30 mg/l) were pronounced at the pyrometallurgical sites, while NO₃ ⁻ (0.01–98.45 mg/l) and Cl⁻ (1.88-49.05 mg/l) were higher at the hydrometallurgical sites. In water samples, Ca²⁺ and SO₄ ²⁺ were the dominant cation and anion, respectively. In the stream sediments, except pH, NO₃ ⁻, Cl⁻, Na⁺ and Mg²⁺, all other parameter values were relatively higher at the hydrometallurgical areas. The average concentrations of Ca²⁺, Mg²⁺, As and Fe are remarkably high at both metallurgical sites (3,217–46,026 mg/kg). Overall, the level of parameters in the water samples are pronounced at pyrometallurgical sites, whereas the levels in sediments are higher at the hydrometallurgical sites.     

Nitrate pollution of groundwater in Toyserkan,western Iran

A total of 95 groundwater samples were collected from Toyserkan, western Iran to assess the chemical composition and nitrate (NO₃ ⁻) status of groundwater. The most prevalent water type is Ca–HCO₃ followed by water types Ca–Mg–HCO₃. In comparison with the World Health Organization (WHO) drinking water guideline of 50 mg l⁻¹ for NO₃ ⁻, a total of nine wells (9.5%) showed higher concentrations. In 36% of samples (34) NO₃ ⁻ concentration was low (<20 mg l⁻¹), and in 53.7% of samples (51), in the range of 20–50 mg l⁻¹. The samples were classified into four groups based on NO₃ ⁻ and chloride (Cl⁻) concentrations. Of the samples, 40% were classified as group 4 and were relatively high in Cl⁻ and NO₃ ⁻ (Cl⁻ > 47 mg l⁻¹, NO₃ ⁻ > 27 mg l⁻¹). The high correlation between NO₃ ⁻ and Cl⁻ (r = 0.86, p < 0.01) is consistent with a manure source, resulting from the practice of adding salt to animal feed. Pollution of groundwaters appeared to be affected by the application of inorganic fertilizer at greater than agronomic rates, Cl-salt inputs, and irrigation practice.     

Correlative and comparative characterization of main ion concentrations in laterite groundwater in semi-arid northern Burkina Faso

About 24 samples from hand-dug wells and boreholes were used to characterize concentrations of the main inorganic ions in a laterite environment under semi-arid climatic conditions in Tikaré, northern Burkina Faso. It was found that the most represented groundwater anion in groundwater was HCO₃ ⁻ with average levels of 49.1 mg/L in the dry season and 33.5 mg/L in the rainy season. The most represented cation was Ca²⁺ with mean concentrations of 13.7 and 9.5 mg/L, respectively. The main processes, which influence the concentrations of these ions, are evaporation (dry season), local enrichment of recharge water in some elements, ion exchange and fixation by clay minerals (in case of K⁺). The best correlations were found between Ca²⁺ and Mg²⁺ (r = 0.95), Cl⁻ and Na⁺ (r = 0.95), HCO₃ ⁻ and Mg²⁺ (r = 0.89), HCO₃ ⁻ and Ca²⁺ (r = 0.89), and between HCO₃ ⁻ and Na⁺ (r = 0.80). In general, the quality of the groundwater from the different wells sampled for this study was good enough to serve as drinking water. However, there were situations where the quality of water was polluted because of anthropogenic contaminants (mainly NO₃ ⁻, K⁺, Cl⁻) from septic tanks and manure pits located in the vicinity of some sampled wells. In addition, application of fertilizers also represents a potential anthropogenic contamination source with regard to SO₄ ²⁻, Ca²⁺, K⁺, Na⁺, and Mg²⁺. Considering the high concentrations of SO₄ ²⁻, Mg²⁺, Na⁺ and Ca²⁺ found in one borehole, the deeper, fractured aquifers were also likely to be enriched in these elements. In contrast, the shallow aquifers are likely to be contaminated with Cl⁻, NO₃ ⁻ and K⁺. Cl⁻ and K⁺ seem to be locally present in recharge water as shown by their relative higher mean concentrations in the rainy season samples.     

Spatial and temporal patterns in sediment and water column nutrients in a eutrophic Southern California estuary

Quarterly field sampling was conducted to characterize variations in water column and sediment nutrients in a eutrophic southern California estuary with a history of frequent macroalgal blooms. Water column and sediment nutrient measures demonstrated that Upper Newport Bay (UNB) is a highly enriched estuary. High nitrate (NO₃ ⁻) loads from the river entered the estuary at all sampling times with a rainy season (winter) maximum estimated at 2,419 mol h⁻¹. This resulted in water NO₃ ⁻ concentration in the estuary near the river mouth at least one order of magnitude above all other sampling locations during every seasons; maximum mean water NO₃ ⁻ concentration was 800 μM during springer 1997. Phosphorus (P)-loading was high year round (5.7–90.4 mol h⁻¹) with no seasonal pattern. Sediment nitrogen (N)-content showed a seasonal pattern with a spring maximum declining through fall. sediment and water nutrients, as well as percent cover of three dominant macroalgae, varied between the main channel and tidal creeks. During all seasons, water column NO₃ ⁻ concentrations were higher in the main channel than in tidal creeks while tidal creeks had higher levels of sediment total Kjeldhal nitrogen (TKN) and P. During each of the four sampling periods, percent cover ofEntermorpha intestinalis andCeramium spp. was higher in tidal creeks than in the main channel, while percent cover ofUlva expansa was always higher in the main channel. Decreases in sediment N in both creek and channel habitats were concurrent with increases in macroalgal cover, possibly reflecting use of stored sediment TKN by macroalgae. Our data suggest a shift in primary nutrient sources for macroalgae in UNB from riverine input during winter and spring to recycling from sediments duirng summer and fall.     

Heat capacity, entropy, and magnetic properties of jarosite-group compounds

Jarosite phases are common minerals in acidic, sulfate-rich environments. Here, we report heat capacities (C _p) and standard entropies (S°) for a number of jarosite samples. Most samples are close to the nominal composition AFe₃(SO₄)₂(OH)₆, where A = K, Na, Rb, and NH₄. One of the samples has a significant number of defects on the Fe sites and is called the defect jarosite; others are referred to as A-jarosite. The samples, their compositions, and the entropies at T = 298.15 K are:

Sulfide Inhibition of Nitrate Removal in Coastal Sediments

Microbial nitrate (NO₃⁻) removal via denitrification (DNF) at high sulfide (H₂S) concentrations was compared in sediment from a coastal freshwater pond in a developed area that receives salt-water influx during storm events, and a saline pond proximal to an undeveloped estuary. Sediments were incubated with added SO₄²⁻ (1,000 μg per gram dry weight basis (gdw)) to determine whether acid volatile sulfides (AVS) were formed. DNF in the sediments was measured with NO₃–N (300 μg gdw⁻¹) alone, and with NO₃–N and H₂S (1,000 μg S²⁻ gdw⁻¹). SO₄²⁻ addition to the freshwater sediments resulted in AVS formation (970 ± 307 μg S gdw⁻¹) similar to the wetland with no added SO₄²⁻ (986 ± 156 μg S gdw⁻¹). DNF rates measured with no added H₂S were greater in the freshwater than the wetland site (10.6 ± 0.6 vs. 6.4 ± 0.1 μg N₂O–N gdw⁻¹ h⁻¹, respectively). High H₂S concentrations retained NH₄–N in the undeveloped wetland and retained NO₃–N in the developed freshwater site, suggesting that potential salt-water influx may reduce the ability of the freshwater sediments to remove NO₃–N.