Airborne gamma-ray spectrometry to quantify chemical erosion processes

Airborne gamma-ray spectrometry data (uranium, potassium and thorium contents) reveal geochemical heterogeneities within the monolithological Hyrôme watershed (ca. 150 km²) in the Armorican massif (western France). Our observations and computations provide important constraints on the spatial distribution and the associated magnitudes of chemical erosion processes at the scale of a small watershed. Two distinct, partially preserved, weathering profiles exhibit a strong correlation between regolith evolution and airborne-derived K/Th ratios, suggesting that the variability is linked to supergene processes. Using both airborne data and laboratory measurements on rock samples, the total net export of potassium has been estimated at 422 ± 50 kg/m² and the chemical weathering rate of potassium at 17 ± 2 kg/km²/a.     

Multi-scale characterisation of coastal sand aquifer media for contaminant transport using X-ray computed tomography

To be able to predict contaminant transport in groundwater, an accurate conceptual and physical understanding of aquifer properties at multiple scales is required. In this study, physical and hydraulic properties of a coastal sand aquifer were derived using micro and macro X-ray computed tomography (XCT) techniques. Qualitative and quantitative data improved conceptualisation of the aquifer structure at micro and macro scale. At the macro scale (50-mm diameter by 1,500-mm long core) XCT images of undisturbed drill core identified coarse grained laminae (not obvious to the naked eye) of increased porosity and permeability, variations in mineral assemblage and particulate organic matter distribution within the core. Micro-XCT analysis (16-mm diameter cores) of the three main aquifer layers provided quantitative micro-scale data on permeability, porosity, grain, pore and throat size distribution statistics, and grain sphericity. Ratios of mean pore to grain diameter were ~0.65–0.75 and ratios of mean throat to mean grain diameter were ~0.2. Multiple permeability and porosity values were derived from micro domains (~4.35 mm³) within each micro-XCT core. Permeability values varied between and within micro-XCT core samples reflecting the heterogeneity at the millimetre core scale in these sediments. Sphericity values were similar for all three layers (average ~0.4) which reflected SEM observations of the semi-spherical nature of the dominant quartz and feldspar grains. The results of this study indicate that models based on the assumptions of homogeneity in depositional structure below centimetre scale may not suitably address factors affecting flow and transport of contaminants.     

Weathering of Fruchtschiefer building stones: mineral dissolution or rock disaggregation?

Building stones manufactured from contact metamorphic slates (Fruchtschiefer slate) from Theuma (Sachsen, Germany) were investigated for mineralogical alterations as well as for changes in porosity and surface roughness due to weathering. After weathering periods of several years to decades, the originally dark gray-colored slates show pale spots of several centimeters in size at the surface of building stones. The dark-colored and light-colored sections of the slate show no differences in mineralogy. Surface weathering did not result in newly precipitated minerals. It was also found that the observed differences in color are not caused by variations in sedimentary organic carbon concentration or in sulfide/sulfate concentrations. Obtained results instead indicate that dark surface sections may show a thin cover of recent organic matter (OM), e.g., living OM, soot, dirt, etc. Microscopic investigations suggested that this cover was exfoliated at light-colored surface sections. The observed disaggregation of the upper 2 mm of the building block material results in an increase in porosity. Porosity of black (unweathered) slate is <2 vol.%. Due to weathering, the slate’s pores with diameters >1 μm show a significant increase in frequency compared to the original pore size distribution. Porosity of weathered rock volumes increased to approx. 8 vol.%. Discolored surface sections show a higher surface roughness (root-mean-square roughness, Rq ~ 1 μm) compared to dark-colored slate surfaces (Rq ~ 200 nm), both data are for cleavage planes. Preferentially, the discolored surface sections are located close to the edges of cut stones. This and the alteration in porosity, pore size, and surface roughness indicate that color changes of the slate are largely influenced by rock disaggregation proceeding from the edges into the center rather than by mineral dissolution/precipitation processes.     

Mineralogical and geochemical alteration of low-grade metamorphic black slates due to oxidative weathering

Low-grade metamorphic black slates of Silurian and Lower Devonian ages (from the Thüringisches Schiefergebirge in Germany) were investigated to identify mineralogical and geochemical alterations that occur during the oxidative weathering black slates.The slates exhibit an intense total organic carbon decrease (>90 wt%) due to oxidative weathering. The organic matter in black slate consists mainly of non-pyrolysable material with only minor portions of pyrolysable material. In contrast to the non-pyrolysable organic matter, the concentration of pyrolysable organic matter is not decreased during weathering. Heating experiments have yielded information about a potential protection of pyrolysable organic matter against weathering, which is probably caused by a structural configuration or the intergrowth of organic matter and illite.The slates consist mainly of illite. Iron oxide (goethite) and phosphate encrustations were formed on slate surfaces as a result of oxidative and acid weathering of both iron sulfide and monazite. Kaolinite often occurs as an older encrustation beneath the iron oxide encrustations. Encrustations of iron oxide and phosphate are major sinks for trace elements, released during oxidative weathering.     

Hydrogeologic and hydrochemical framework of the shallow groundwater system in the southern Voltaian Sedimentary Basin, Ghana

 The southern Voltaian Sedimentary Basin underlies an area of about 5000 km² in east-central Ghana. Groundwater in the basin occurs in fractures in highly consolidated siliciclastic aquifers overlain by a thin unsaturated zone. Aquifer parameters were evaluated from available aquifer-test data on 28 shallow wells in the basin. Hydraulic-conductivity values range from 0.04–3.6 m/d and are about two orders of magnitude greater than the hydraulic conductivity calculated using Darcy's Law and the average groundwater velocity estimated from carbon-14 dating. Linear-regression analysis of the transmissivity and specific-capacity data allowed the establishment of an empirical relationship between log transmissivity and log specific capacity for the underlying aquifers. Groundwater chemistry in the basin is controlled by the weathering of albitic plagioclase feldspar. The weathering rates of various minerals were estimated using ¹⁴C-derived average velocity in the basin. The weathering rate of albite was calculated to be 2.16 μmol L^–1 yr^–1 with the resulting formation of 3.3 μmol L^–1 yr^–1 of kaolinite and 0.047 μmol L^–1 yr^–1 of calcite. The low porosity and permeability of the aquifers in the basin are attributed to the precipitation of secondary minerals on fracture surfaces and interlayer pore spaces. Received, September 1997 Revised, July 1998, August 1998 Accepted, August 1998     

Diffusive transport of water in porous feldspars from granitic saprolites: In situ experiments using FTIR spectroscopy

A novel experimental cell was developed for in situ measurements of transport phenomena in porous media using Fourier-Transform Infrared (FTIR) Spectroscopy. The technique was employed at ambient pressure in the temperatures range of 11–44 °C to study the H₂O → D₂O exchange between water-saturated weathered feldspars (bulk porosity of 5–19 vol% for feldspar) from granitic saprolites and a surrounding aqueous liquid. Such measurements are an important step for understanding internal weathering reactions of feldspars in soils and aquifers. Effective diffusion coefficients D_eff for water in water-saturated porous feldspars were determined assuming one-dimensional diffusion in a quasi-homogeneous medium. The values of D_eff vary from 7.2 × 10⁻¹⁰ to 1.9 × 10⁻¹¹ m²/s and are 1–2 orders of magnitude lower than the diffusion coefficients (D) of protons and molecular H₂O in liquid water. The activation energy for the H₂O → D₂O exchange process in porous feldspars ranges from 7.8 to 18.8 kJ/mol.The results imply that the effective diffusivity of water is mainly controlled by physical properties of the feldspars like porosity, pore connectivity, pore geometry and distribution. Perthitic feldspars with homogeneous pore distribution in the albitic lamellas have diffusional tortuosity factors X = D/D_eff between 3 and 10 while alkali feldspars with inhomogeneously distributed and disconnected pores have much higher X values up to 129. Diffusion anisotropy has been verified for a vein perthite with diffusion perpendicular to the lamellas being faster by 0.3–0.5 log units than within the lamellas. It has to be emphasized that the study is based only on few selected feldspars, including perthitic feldspar, and additional work on samples with different weathering stages is needed to test the importance of the different parameters controlling diffusive transport in the pore system.     

Development of unusual rock weathering features in the Cordillera Blanca,Peru

Mylonite textures in granodiorite boulders are responsible for higher rates of surface denudation of host rocks and the progressive development of unusual rock weathering features, termed weathering posts. These textures are characterized by smaller grain sizes, higher biotite content, and a higher biotite axial ratio in host rocks relative to weathering posts. Elemental concentrations do not show a significant difference between weathering posts and the host rocks in which they are found, and this reflects the absence of a weathering residue on the rock surfaces. Chemical weathering loosens the bonds between mineral grains through the expansion of biotite, and the loosened grains fall off or are blown off the boulder surface and continue their chemical alteration in the surrounding soil. The height of weathering posts on late Quaternary moraines increases at a linear rate of ~ 1.45 ± 0.45 cm (1000 yr)^? 1 until post heights reach the diameter of host rocks. Such a rate of boulder denudation, if unrecognized, would generate significant errors (> 20%) in cosmogenic exposure ages for Pleistocene moraines. Given the paucity of boulders with diameters that significantly exceed 1.5 m, the maximum age of utility of weathering posts as a numeric age indicator is ~ 100 ka.     

Mapping of accumulated nitrogen in the sediment pore water of a eutrophic lake in Iowa, USA

A large pool of nitrogen in the sediment pore fluid of a eutrophic lake in Iowa, USA, was mapped in this study. Previously, the lake had supported fishing and boating, but today it no longer supports its designated uses as a recreational water body. In the top 5 cm of the lake bottom, the pore water nitrogen ranges between 3.1 and 1,250 μg/cm³ of sediments, with an average of 160.3 μg/cm³. Vertically, nitrate concentrations were measured as 153 μg/cm³ at 0–10 cm, 162 μg/cm³ at 10–20 cm, and 32 μg/cm³ at 20–30 cm. Nitrate mass distribution was quantified as 3.67 × 10³ kg (65%) in the bottom sediments, 172 kg (3%) in suspended particulates, and 1.83 × 10³ kg (32%) in the dissolved phase. Soil runoff nutrients arrive at the lake from the heavily fertilized lands in the watershed. Upon sedimentation, a large mass of nitrogen desorbs from mineral particles to the relatively immobile pore fluid. Under favorable conditions, this nitrogen diffuses back into the water column, thereby dramatically limiting the lake’s capability to process incoming nutrients from farmlands. Consequently, a condition of oxygen deficiency disrupts the post-season biological activities in the lake.     

Dissolved Uranium and 234U/238U in the Yamuna and the Chambal Rivers, India

Dissolved uranium concentration and ²³⁴U/²³⁸U activity ratio have been measured in two distinctly different Indian drainage systems: the Yamuna headwaters in the Himalaya and the Chambal river system in the plains to study the weathering and mobility of uranium in these watersheds. The dissolved uranium in the Chambal river system ranges from 0.2 to 1.74 μg L⁻¹ during September (tail end of monsoon), whereas in the Yamuna river system, its concentration varies from 0.1 to 3.18 μg L⁻¹ during October (post-monsoon) and from 0.09 to 3.61 μg L⁻¹ in June (summer). In the Yamuna main stream, uranium is highest at its source and decreases steadily along its course, from 3.18 μg L⁻¹ at Hanuman Chatti to 0.67 μg L⁻¹ at Batamandi, at the base of the Himalaya. This decrease results mainly from mixing of the Yamuna mainstream with its tributaries, which are lower in uranium. The high concentration of uranium at Hanuman Chatti is derived from weathering of the Higher Himalayan Crystalline series (HHC) and associated accessary minerals, which may include uranium-mineralised zones. The ²³⁴U/²³⁸U activity ratios in the samples from the Chambal watershed are in the range of 1.15±0.05 to 1.67±0.04; whereas in the Yamuna the ratios vary from 0.95±0.03 to 1.56±0.07, during post-monsoon and from 0.98±0.01 to 1.30±0.03, during summer. The relatively high ²³⁴U/²³⁸U activity ratios in the Yamuna system are in its tributaries from the lower reaches viz., the Amlawa, Aglar, Bata, Tons and the Giri. It is estimated that ~9×10³ and ~12 × 10³ kg of dissolved uranium are transported annually from the Yamuna at Batamandi and the Chambal at Udi, respectively. This corresponds to uranium weathering rates of 0.9 and 0.09 kg U km⁻² y⁻¹ in the basins of the Yamuna and the Chambal headwaters. This study confirms that uranium weathering rate in the Himalaya is far in excess (by about an order of magnitude) of the global average value of ~0.08 kg U km⁻² y⁻¹.     

Marine Macrophyte Wrack Inputs and Dissolved Nutrients in Beach Sands

We investigated the role of sandy beaches in nearshore nutrient cycling by quantifying macrophyte wrack inputs and examining relationships between wrack accumulation and pore water nutrients during the summer dry season. Macrophyte inputs, primarily giant kelp Macrocystis pyrifera, exceeded 2.3 kg m⁻¹ day⁻¹. Mean wrack biomass varied 100-fold among beaches (range = 0.41 to 46.43 kg m⁻¹). Mean concentrations of dissolved inorganic nitrogen (DIN), primarily NO_x⁻-N, and dissolved organic nitrogen (DON) in intertidal pore water varied significantly among beaches (ranges = 1 to 6,553 μM and 7 to 2,006 μM, respectively). Intertidal DIN and DON concentrations were significantly correlated with wrack biomass. Surf zone concentrations of DIN were also strongly correlated with wrack biomass and with intertidal DIN, suggesting export of nutrients from re-mineralized wrack. Our results suggest beach ecosystems can process and re-mineralize substantial organic inputs and accumulate dissolved nutrients, which are subsequently available to nearshore waters and primary producers.     

Assessing the potential for CO2 adsorption in a subbituminous coal,Huntly Coalfield,New Zealand,using small angle scattering techniques

Small angle scattering techniques (SAXS and SANS) have been used to investigate the microstructural properties of the subbituminous coals (R_max 0.42–0.45%) from the Huntly Coalfield, New Zealand. Samples were collected from the two thick (> 5 m) coal seams in the coalfield and have been analysed for methane and carbon dioxide sorption capacity, petrography, pore size distribution, specific surface area and porosity.Specific surface area (SSA) available for carbon dioxide adsorption, extrapolated to a probe size of 4 Å, ranged from 1.25 × 10⁶ cm^? 1 to 4.26 × 10⁶ cm^? 1 with total porosity varying from 16% to 25%. Porosity was found to be predominantly composed of microporosity, which contributed the majority of the available SSA. Although considerable variation was seen between samples, the results fit well with published rank trends.Gas holding capacity at the reservoir pressure (approximately 4 MPa) ranged from 2.63 to 4.18 m³/t for methane on a dry, ash-free basis (daf) and from 22.00 to 23.72 m³/t daf for carbon dioxide. The resulting ratio of CO₂:CH₄ ranged from 5.7 to 8.6, with an average of 6.7:1.Holding capacities for both methane and carbon dioxide on a dry ash free basis (daf) were found to be correlated with sample microporosity. However, holding capacities for the two gases on an as analysed (aa) basis (that is including mineral matter and moisture), showed no such correlation. Carbon dioxide (aa) does show a negative correlation with both specific surface area and microporosity. As the coals have low inorganic matter content, the reversal is thought to be related to moisture which is likely concentrated in the pore size range 12.5–125 Å. Methane holding capacity, both daf and aa, correlates with macroporosity, thus suggesting that the holding capacity of micropores is diminished by the presence of moisture in the pores.     

Pyritization of trace metals in estuarine sediments and the controlling factors: a case in Jiaojiang Estuary of Zhejiang Province,China

Three undisturbed sediment samples were collected from the intertidal zone of the Jiaojiang Estuary of Zhejiang Province, China. The sediments were found to contain remarkably low concentrations of organic carbon (<0.6%) and acid volatile sulfide (AVS) (<30 μmol g⁻¹). The availability of these two substrates likely constrained sulfate reduction and pyritization of several trace metals, respectively. This was especially true at one station where AVS concentrations in the upper 20 cm averaged less than 0.05 μmol g⁻¹. Although the depth dependence of the degree of trace metal pyritization was generally consistent with expectations based on redox conditions, depth profiles of reactive-metal and pyrite-metal concentrations in several cases revealed more complex behavior and a positive correlation between reactive-metal concentrations and pore water metal concentrations.     

Petrophysical properties, composition and deterioration of the Calatorao biogenic stone: case of the sculptures masonry of the Valley of the Fallen (Madrid, Spain)

The huge sculptures placed outdoors in the Valley of the Fallen Memorial Park (El Escorial, Madrid) made with blocks of Black-Limestone from Calatorao-Zaragoza, Spain (BLCZ) and disposed on a concrete core exhibit weathering traces, flaking, saline efflorescence and falling fragments, currently represent a danger for visitors. Frost action is important in the Valley of the Fallen by the large number of freeze–thaw cycles produced during Sculptures‘live under a temperate Mediterranean climate with severe seasonality. The formation of fissures facilitates the water transport within the rock and the salt- and ice-induced deterioration. Temperate climates with frequent freezing and thawing cycles can be the most effective drivers of the visible physical weathering. In order to propose a suitable weathering model, collected black-limestones from sculptures and Calatorao quarries were analyzed by optical microscopy, environmental scanning electron microscopy with energy dispersive spectrometry (ESEM-EDS), inductively coupled mass spectrometry (ICP-MS) and X-ray diffraction. Mercury intrusion porosimetry (MIP), nitrogen absorption and helium pycnometry techniques were used for pore analyses of the BLCZ micro-blocks (10 × 10 × 10 cm) described in terms of pore size distribution, pore volume and specific surface area. The appreciable amount of organic matter was isolated by solvent extraction, acid treatment, flotation and perborate degradation followed by Gas Chromatography–Mass Spectrometry (GC–MS), Analytical Pyrolysis (Py-GC/MS), Fourier Transformed Infrared Spectroscopy and Raman techniques. Both weathered and fresh BLCZ samples contained more than 90 % calcite shells with circa 10 % of pyrite (fresh samples) or iron hydroxides (weathered samples), quartz grains, claystone and fossil organic matter consisting of a condensed matrix with polyalkyl chains and polycyclic methoxyl-lacking aromatic structures. The petrophysical analyses revealed volumes of pores, sized <0.025 μm obtained by N₂ adsorption, of 3.18 × 10^?3 cm³ g^?1 while the measured porosity by MIP in the pore range from 0.005 to 200 μm was 3.30 × 10^?3 cm³ g^?1. These data could be explained by the existence of clay minerals and organic matter in the pore system less than 50 nm of diameter. Concerning BLCZ deterioration it was found that the porous framework of BLCZ was filled with sulphates formed from artificial cement observed in the sculptures inside trough a testing hole and from its intrinsic pyrite. The results suggested that although biological processes were not major agents in rock deterioration, there was also weak compatibility between sculptures‘constituents, (limestone, concrete and oxidized iron clamps) which under, continental Mediterranean conditions, were continuously releasing weathering compounds accelerating disruption of the cut-stone sculptures.     

Adsorption kinetic control of As(III &; V) mobilization and sequestration by Mangrove sediment

Elevated concentrations of arsenic in the sediment and pore water in the Sundarban wetlands pose an environmental risk. Adsorption and desorption are hypothesized to be the major processes controlling arsenic retention in surface sediment under oxic/suboxic condition. This study aims to investigate sorption kinetics of As(III & V) and its feedback to arsenic mobilization in the mangrove sediment. It ranges from sand to silty clay loam and shows the adsorption of As(III & V) following the Langmuir relation. Estimates of the maximum adsorption capacity are 59.11 ± 13.26 μg g⁻¹ for As(III) and 58.45 ± 8.75 μg g⁻¹ at 30°C for As(V) in the pH range 4 to 8 and salinity 15–30 psu. Extent of adsorption decreases with increasing pH from 4 to 8 and desorption is the rate-limiting step in the reaction of arsenic with sediment. Arsenic in the sediment could be from a Himalayan supply and co-deposited organic matter drives its release from the sediment. Arsenic concentration in the sediment is well below its maximum absorption capacity, suggesting the release of sorbed arsenic in pore water by the microbial oxidation of organic matter in the sediment with less feedback of adsorption.     

Effects of progressive mylonitization on Ar retention in biotites from the Santa Rosa mylonite zone,California, and thermochronologic implications

The Santa Rosa mylonite zone developed predominantly from a granodiorite protolith in the eastern margin of the Peninsular Ranges batholith. A wide variation in K−Ar biotite dates within the zone is shown to reflect the times of cooling through closure temperatures whose variability is chiefly a result of deformation-induced reduction in grain size. We suggest that such variation generally may be exploited to place constraints on the timing of deformation episodes. Previous workers have shown that deformation in the Santa Rosa mylonite zone involved the formation of mylonites and an imbricate series of low-angle faults which divide the area into structural units. Field work, petrographic studies, and TEM analysis of deformation mechanisms in biotite show that the granodiorite mylonite, the lowermost structural unit, formed below the granodiorite solidus. The granodiorite mylonite varies from protomylonite to ultramylonite, with regions of high strain distributed heterogeneously within the zone. Previously reported biotite and hornblende K−Ar dates from the granodiorite protolith below (82–89 Ma) and the Asbestos Mountain granodiorite above (61–68 Ma) the mylonite zone indicate dramatically dissimilar thermal histories for the lowermost and uppermost structural units. Other workers' fission track dates on sphene, zircon, and apatite from the granodiorite mylonite and the Asbestos Mountain granodiorite suggest thermal homogenization and rapid cooling to ∼100° C by ca 60 Ma. Within and adjacent to the mylonite zone, K−Ar dates on 5 samples of biotite from variably deformed granodiorite range from 62–76 Ma; dates are not correlated with structural depth but clearly decrease with degree of deformation and concomitant grain size reduction. ⁴⁰Ar/³⁹Ar incremental heating analyses of biotite from the granodiorite protolith reveals no evidence of excess argon and produces a relatively flat age spectrum. ⁴⁰Ar/³⁹Ar incremental heating analysis of biotite from the granodiorite mylonite discloses discordance consistent with ³⁹Ar recoil loss. K analysis of samples, allowing K−Ar dates to be calculated, is therefore recommended as an adjunct to ⁴⁰Ar/³⁹Ar step heating analysis in rocks that have experienced similar deformation. During mylonitization, biotite grain size reduction through intracrystalline cataclasis results in estimated grain dimensions as small as 0.05 μm locally within porphyroclasts as large as 1 mm. Because biotite compositions are relatively Uniform (Fe/[Fe+Mg+Mn+Ti+Al^VI]=0.47–0.52) and show no systematic variation with grain size, compositional dependence of activation energy and diffusivity can be eliminated as sources of variation in Ar retention. Ar closure temperatures, calculated with appropriate diffusion parameters for the observed grain sizes, are in the range ∼220–280° C and define a cooling curve consistent with a thermal history intermediate between those of the granodiorite protolith below and the Asbestos Mountain granodiorite above the mylonite zone. Changes in the slope of the cooling curve indicate that the main deformation episode initiated at or above ca 330° C (∼80 Ma), above the closure temperature for thermally activated diffusion of argon in biotite, and continued to a minimum of ca 220–260° C (∼62 Ma).     

Microelectrode Study of Oxygen Uptake and Organic Matter Decomposition in The Sediments of Xiamen Western Bay

Sediment cores were sampled from Xiamen Western Bay at five sites during the summer and winter of 2006 and Hg–Au microelectrodes were used to make on board measurements of the concentration gradients of dissolved oxygen, Mn²⁺, and Fe²⁺ within the sediments. The O₂ concentrations decreased sharply from about 200 μmol L⁻¹ in the bottom seawater to zero within a depth of a few millimeters into the sediment. Dissolved Mn²⁺ was detected below the oxic zones with peak concentrations up to 600 μmol L⁻¹, whereas dissolved Fe²⁺ had peak concentrations up to 1,000 μmol L⁻¹ in deeper layers. The elemental contents of organic carbon and nitrogen within the sediments were analyzed and their C/N ratios were in the range of 9.0 to 10.1, indicative of heavy terrestrial origin. Sediments from two sites near municipal wastewater discharge outlets had higher organic contents than those from the other sites. These high organic contents corresponded to shallow O₂ penetration depths, high dissolved Mn²⁺ and Fe²⁺ concentrations, and negative redox potentials within the sediments. This indicated that the high organic matter content had promoted microbial respiration within the sediments. Overall, the organic content did not show any appreciable decrease with increasing sediment depths, so a quadratic polynomial function was used to fit the curve of O₂ profiles within the sediments. Based on the O₂ profiles, O₂ fluxes across the seawater and sediment interface were estimated to be in the range 6.07 to 14.9 mmol m⁻² day⁻¹, and organic carbon consumption rates within the surface sediments were estimated to be in the range 3.3 to 20.8 mgC cm⁻³ a⁻¹. The case demonstrated that biogeochemistry within the sediments of the bay was very sensitive to human activities such as sewage discharge.     

Geo-chemical Behavior of Uranium in the Sambhar Salt Lake, Rajasthan (India): Implications to "Source" of Salt and Uranium "Sink"

Among several salt lakes in the Thar Desert of western India, the Sambhar is the largest lake producing about 2 × 10⁵ tons of salt (NaCl) annually. The “lake system” (lake waters, inflowing river waters, and sub-surface brines) provides a unique setting to study the geo-chemical behavior of uranium isotopes (²³⁸U, ²³⁴U) in conjunction with the evolution of brines over the annual wetting and evaporation cycles. The concentration of ²³⁸U and the total dissolved solids (TDS) in lake water increase from ~8 μg L⁻¹ and ~8 g L⁻¹ in monsoon to ~1,400 μg L⁻¹ and 370 g L⁻¹, respectively, during summer time. The U/TDS ratio (~1 μg g⁻¹ salt) and the ²³⁴U/²³⁸U activity ratio (1.65 ± 0.05), however, remain almost unchanged throughout the year, except when U/TDS ratio approaches to 3.8 at/or beyond halite crystallization. These observations suggest that uranium behaves conservatively in the lake waters during the annual cycle of evaporation. Also, uranium and salt content (TDS) are intimately coupled, which has been used to infer the origin and source of salt in the lake basin. Furthermore, near uniform ratios in evaporating lake waters, when compared to the ratio in seawater (~0.1 μg g⁻¹ salt and 1.14 ± 0.02, respectively), imply that aeolian transport of marine salts is unlikely to be significant source of salt to the lake in the present-day hydrologic conditions. This inference is further consistent with the chemical composition of wet-precipitation occurring in and around the Sambhar lake. The seasonal streams feeding the lake and groundwaters (within the lake’s periphery) have distinctly different ratios of U/TDS (2–69 μg g⁻¹ salt) and ²³⁴U/²³⁸U (1.15–2.26) compared to those in the lake. The average U/TDS ratio of ~1 μg g⁻¹ salt in lake waters and ~19 μg g⁻¹ salt in river waters suggest dilution of the uranium content by the recycled salt and/or removal processes presently operating in the lake during the extraction of salt for commercial use. Based on mass-balance calculations, a conservative estimate of "uranium sink" (in the form of bittern crust) accounts for ~5 tons year⁻¹ from the lake basin, an estimate similar to its input flux from rivers, i.e., 4.4 tons year⁻¹.     

The Contribution of Benthic Nutrient Regeneration to Primary Production in a Shallow Eutrophic Estuary,Weeks Bay,Alabama

Benthic oxygen, dinitrogen, and nutrient fluxes (NH₄⁺, NO₃⁻, and PO₄³⁻) were measured monthly during a 1-year period at two locations in Weeks Bay, a shallow (1.4 m) and eutrophic estuary in Alabama. Gross primary productivity (GPP), ecosystem respiration (R), and net ecosystem metabolism were determined from high-frequency dissolved oxygen measurements. Peak water column NO₃⁻ (55 μM) and chlorophyll a (138 μg/l) concentrations were measured during spring and fall, respectively. Sediments were a net source of NH₄⁺ (102 μmol m⁻² h⁻¹) and PO₄³⁻ (0.9 μmol m⁻² h⁻¹) but a sink for NO₃⁻ (−30 μmol m⁻² h⁻¹). Benthic N₂ fluxes indicated net N fixation (12 μmol N m⁻² h⁻¹). Sediment oxygen demand (0.55 g O₂ m⁻² day⁻¹) accounted for <10% of R (7.3 g O₂ m⁻² day⁻¹). Despite high GPP rates (4.7 g O₂ m⁻² day⁻¹), the estuary was net heterotrophic. Benthic regeneration supplied, on average, 7.5% and 4% of primary productivity N and P demands, respectively. These results contrast with the conventional view that benthic regeneration accounts for a large fraction of phytoplankton nutrient demand in shallow estuaries.     

Anion exclusion effects in compacted bentonites: Towards a better understanding of anion diffusion

Diffusion of ³⁶Cl⁻ in compacted bentonite was studied using through-diffusion, out-diffusion and profile analysis techniques. Both the bulk dry density of the bentonite and the composition of the external solution were varied. Increasing the bulk dry density of the bentonite resulted in a decrease of both the effective diffusion coefficient and the Cl-accessible porosity. Increasing the ionic strength of the external solutions resulted in an increase of both the effective diffusion coefficient and the Cl-accessible porosity. This can be explained by anion exclusion effects (Donnan exclusion). At high ionic strength values (I ? 1 M NaCl) the Cl-accessible porosity approaches the interparticle porosity. This interparticle porosity is the difference between the total and interlayer porosity of the bentonite. The interlayer porosity was found to depend on the degree of compaction. Up to a bulk dry density of 1300 kg m⁻³ the interlayer is built up of 3 water layers. Between 1300 and 1800 kg m⁻³ the interlayer water is reduced from 3 to 2 layers of water. Above 1800 kg m⁻³ evidence for a further decrease to 1 layer of water was found. These findings are in agreement with X-ray data found in the literature showing a decrease of the basal spacing of montmorillonite (the main clay mineral in bentonite) with increasing degree of compaction. The relationship between the effective diffusion coefficient of Cl⁻ and the diffusion-accessible porosity can be described by an empirical relationship analogous to Archie’s law. To predict the effective diffusion coefficient of Cl⁻ in compacted bentonite, the diffusion coefficient of Cl⁻ in water, the bulk dry density and the ionic strength of the pore water have to be known.