Sorption of uranyl and arsenate on SiO2, Al2O3, TiO2 and FeOOH

Migration of uranium and arsenic in aquatic environments is often controlled by sorption on minerals present along the water flow path. To investigate the sorption behaviour, batch experiments were conducted for uranium and arsenic as single components and also solutions containing both uranium and arsenic in the presence of SiO₂, Al₂O₃, TiO₂ and FeOOH at a pH ranging from 3 to 9. In solutions containing only U(VI) or As(V) with the minerals, the sorption of U(VI) was low at acidic pH range and increases with increasing pH, whereas As(V) showed opposite sorption behaviour to Al₂O₃, TiO₂ and FeOOH from acidic pH range to alkaline condition. For the As(V)–SiO₂ system, the sorption was low for almost all pH. Sorption of U(VI) and As(V) on SiO₂ and FeOOH is almost similar in solutions containing either U(VI) or As(V) separately, or both together. In the U(VI)–As(V)–Al₂O₃ system, a significant retardation in uranyl sorption and an enhancement in arsenate sorption on Al₂O₃ were observed for a wide range of pH. The sorption behaviour of U(VI) and As(V) was changed when Al₂O₃ was replaced by TiO₂, where an increase in sorption was observed for both elements. The sorption behaviour of uranyl and arsenate in the U(VI)–As(V)–TiO₂ system gives evidence for the formation of uranyl–arsenate complexes. The change in sorption retardation/enhancement of U(VI) and As(V) could be explained by the formation of uranyl–arsenate complexes or due to the competitive sorption between uranyl and arsenate species.     

Investigation of seawater intrusion in the Dibdibba Aquifer using 2D resistivity imaging in the area between Al-Zubair and Umm Qasr,southern Iraq

Electrical resistivity surveying for delineating seawater intrusion was performed in the Dibdibba aquifer in the area between the cities of Al-Zubair–Safwan and Al-Zubair–Umm Qasr in the vicinity of Khor AL-Zubair Channel, Basrah governorate, southern Iraq. Fourteen 2D resistivity profiles with a total length of 14 km were collected in the study area. The resistivity sections were compared with lithological data extracted from 11 boreholes. Thirty-nine groundwater samples were collected within the area and analyzed for chemical constituents; internal hydrogeological reports and unpublished studies were also evaluated. Results reveal the existence of three major resistivity layers, ranging from 0.1 to 130 Ωm at various depths and locations. The first layer has very low electrical resistivity (0.1–5 Ωm) representing a layer saturated with saltwater intruded from Khor AL-Zubair Channel. The second layer shows resistivity in the range of 5–130 Ωm, attributed to a transition zone and an unaffected zone saturated with brackish groundwater. The last resistivity layer (<?3 Ωm) represents coarse-grain sediments saturated with saline groundwater. Furthermore, a hard clay bed (Jojab) appears with a resistivity of 3–7 Ωm in all 2D imaging lines within a depth of 20–28 m. Electrical conductivity (EC) measurements from seven wells collected in 2014 and 2016 show a positive EC difference increasing landward with an average increase of 1927 µS/cm. In addition, six chemical relationships (Na/Cl, [Ca?+?Mg]/[HCO₃?+?SO₄], SO₄/HCO₃, SO₄/Cl, Mg/Ca and Cl/[HCO₃?+?CO₃]) are used to detect the source of salinity in groundwater. This study proves that extensive use of high-resolution 2D imaging sections, alongside lithological and hydrogeological data, can serve as a useful tool to delineate the boundaries between aquifers, identify hydraulic boundaries between groundwater with different salinities and allocate hard clay layers between the upper and lower Dibdibba aquifer. In general, the combination of 2D imaging and hydrochemistry enables conceptualization of the hydrogeological situation in the subsurface and characterization of the salinity source, here seawater intrusion, in the study area. There have been no studies published so far on the characteristics of saltwater intrusion in the study area, and this study is considered to be important for monitoring and studying the intrusion and regression of seawater.     

Geochemistry of sediments of the Al-Batin alluvial fan,Southern Iraq

The Al-Batin alluvial fan covers a broad area of southern Iraq. It was the main battlefield of two devastating wars in 1991 and 2003, during which huge amounts of depleted uranium (DU) were used. This study aims to assess the geochemistry of this fan sediment including the potential effects of the DU used. Sixty-three samples were collected from sediments including three samples from sediments under tanks attacked by DU ammunition. Major elements were measured by XRF (fusion bead method), whereas ICP-MS was used to measure the trace elements. The results suggest that the most dominant major minerals are in the order of: quartz?>?secondary gypsum?>?calcite?>?feldspar, clay minerals?>?iron oxide, and show abnormal concentrations of Sr, Cr, Ni, and V. This study also determined an area with high concentration of U in the north east part of the fan. Statistical analysis and spatial distribution of important elements suggests that two major factors affect mineral formation. The first factor reflects the influence of minerals in the source area of the sediments (Arabian Shield): quartz, carbonate, clay minerals, feldspars, as well as iron oxides and elevated concentrations of V, Ni, and Cr. The second factor points at authigenic formation of secondary gypsum and celestite and elevated U concentration under the control of a hot arid climate and the specific groundwater situation. However, the origin of the sediments is geogenic, while the anthropogenic impact seems to be minor. Spatial distribution of U and the ^235/238U ratio did not show any peaks in the places where tanks have been destroyed. This is contrary to media speculations and some scientific reports about the permanent risks of DU in the area, which creates public concern about the potential risk of living in this area.     

Identifying sources of salinization using hydrochemical and isotopic techniques, Konarsiah, Iran

Konarsiah salt diapir is situated in the Simply Folded Zone of the Zagros Mountain, south Iran. Eight small permanent brine springs emerge from the Konarsiah salt body, with average total dissolved solids of 326.7 g/L. There are numerous brackish to saline springs emerging from the alluvial and karst aquifers adjacent to the diapir. Concerning emergence of Konarsiah diapir in the study area, halite dissolution is the most probable source of salinity in the adjacent aquifers. However, other sources including evaporation and deep brines through deep Mangerak Fault are possible. The water samples of the study area were classified based on their water-type, salinity, and the trend of the ions concentration curves. The result of this classification is in agreement with the hydrogeological setting of the study area. The hydrochemical and isotopic evaluations show that the groundwater samples are the result of mixing of four end members; Gachsaran sulfate water, Sarvak and Asmari carbonate fresh waters, and diapir brine. The molar ratios of Na/Cl, Li/Cl, Br/Cl, and SO₄/Cl; and isotopic signature of the mixed samples justify a groundwater mixing model for the aquifers adjacent to the salt diapir. The share of brine in each adjacent aquifer was calculated using Cl mass balance. In addition, concentrations of 34 trace elements were determined to characterize the diapir brine and to identify the possible tracers of salinity sources in the mixed water samples. B, Mn, Rb, Sr, Cs, Tl, and Te were identified as trace elements evidencing contact of groundwater with the salt diapir.     

Organic carbon mobilization in a Bangladesh aquifer explained by seasonal monsoon-driven storativity changes

Currently, the most widely accepted hypothesis to explain high As concentrations in Bangladesh groundwaters is that dissolved organic C (DOC) reduces solid Fe (hydr)oxides and mobilizes sorbed arsenate. The nature of the DOC and its release mechanism are still controversial. Based on weekly to biweekly sampling over the course of one monsoon cycle at six monitoring wells of different depths, it is proposed that storativity changes drive natural DOC release from clay–peat layers to the adjacent aquifers. With a decrease in hydraulic heads during the dry season, total mineralization and DOC concentrations increased. With the onset of the rainy season and an increase in hydraulic heads, release of clay–peat derived components stopped and vertical water displacement due to groundwater recharge from rainwater occurred, causing aquifer flushing and a decrease in total mineralization and DOC concentrations. Total As and DOC concentrations correlated over depth. However, at the depth of maximum concentrations, the As peak was observed during the rainy season. At present, the reason for this inverse seasonal trend between As and DOC is unclear. Higher mineralization or DOC concentrations could lead to increased As sorption or the increased arsenite release is a time-lag abiotic or microbial response to the DOC peak. The vulnerability of the Pleistocene aquifer towards increased As concentrations was found to be much higher than previously assumed. Though sorption capacities were determined to be higher than in the Holocene aquifer, probably due to intact Fe (hydr)oxides, long-term continuous As input from overlying clay and peat layers by the proposed seasonal storativity changes has led to increased aqueous As concentrations of 85 μg/L, considerably higher than drinking water standards. Until now, aquifer and especially aquitard and aquiclude hydraulics have not been considered sufficiently when attempting to explain As mobilization in Bangladesh.     

Trace element hydrochemical assessment of the Calabar Coastal Plain Aquifer,southeastern Nigeria using statistical methods

Groundwater samples from 33 locations within the Coastal Plain Sands aquifer of Calabar (Nigeria) were collected and analysed for 43 trace elements by means of ICP-MS. The aim of this study is to determine the natural background levels of trace elements as a guide for future pollution monitoring of the aquifer. Secondly, this article focuses on the pollution vulnerability of the coastal plain sand aquifer. Statistical methods have been used to determine the source(s) of these elements. Results show that the area is characterised by four types of groundwater, including: Na-HCO₃, Na-HCO₃-Cl, Na-Cl and Ca-Na-HCO₃-Cl. Secondly, all the elements considered are below normal averages. In addition, the Spearman correlation shows significant correlation especially among the lanthanide group of elements (p<0.0001). Factors analyses indicate mainly two groups of elements. The first group being due to the natural geochemical process (weathering/leaching of the basement lithology; characteristics of the elements) and the second is due to tidal flushing of the estuary. This indicates that the source of the trace element in the aquifer is due to a geogenic process and not anthropogenic. Thus, the present data set will serve as a reference source for pollution monitoring in the area.     

The transport of bacteria in the sediments of a temperate marsh

The number of bacteria in sediments, interstitial water and overlying tidal water of an oligohaline marsh system are about 10⁹, 10⁶ and 10⁶ cells cm^?3, respectively. Average cell size in the overlying water (about 0·06 μm³), is much smaller than that in sediments and interstitial water (about 0·18 μm³). Most bacterial cells in sediments are bound to sediment particles and less than 1% of the cells were displaced by percolating water through sediment columns. Concentration of bacteria in flooding tidal waters is generally higher than that in ebbing waters. Movement of bacterial biomass does not appear to be a significant mechanism of particulate organic transport in marsh sediments and marsh sediments do not appear to be a source of suspended bacteria for estuaries.     

Equation of state, elasticity, and shear strength of pyrite under high pressure

 Physical properties including the equation of state, elasticity, and shear strength of pyrite have been measured by a series of X-ray diffraction in diamond-anvil cells at pressures up to 50 GPa. A Birch–Murnaghan equation of state fit to the quasihydrostatic pressure–volume data obtained from laboratory X-ray source/film techniques yields a quasihydrostatic bulk modulus K _0T =133.5 (±5.2) GPa and bulk modulus first pressure derivative K ^′ _0T =5.73 (±0.58). The apparent equation of state is found to be strongly dependent on the stress conditions in the sample. The stress dependency of the high-pressure properties is examined with anisotropic elasticity theory from subsequent measurements of energy-dispersive radial diffraction experiments in the diamond-anvil cell. The calculated values of K _0T depend largely upon the angle ψ between the diffracting plane normal and the maximum stress axis. The uniaxial stress component in the sample, t=σ₃−σ₁, varies with pressure as t=−3.11+0.43P between 10 and 30 GPa. The pressure derivatives of the elastic moduli dC ₁₁/dP=5.76 (±0.15), dC ₁₂/dP=1.41 (±0.11) and dC ₄₄/dP=1.92 (±0.06) are obtained from the diffraction data assuming previously reported zero-pressure ultrasonic data (C ₁₁=382 GPa, C ₁₂=31 GPa, and C ₄₄=109 GPa). Received: 21 December 2000 / Accepted: 11 July 2001     

Characterization of a Pleistocene thermal spring in Mozambique

A hydrogeological study was conducted with the objective to investigate the only currently known hot spring of Sofala Province in Mozambique with respect to the origin of the water, the discharge, and its chemical composition. Field investigations comprised a general land use survey, mapping of sediment and water temperatures, discharge measurements and on-site water chemistry as well as sampling for further chemical analyses and groundwater dating. Thermal water discharge occurs along a 100 m long NE–SW zone with water temperatures ranging from 42 to 64.5°C. The thermal water is a low-mineralized sodium-chloride-sulfate water enriched in phosphate, fluorine and nickel. The silica geothermometer, the silica concentration of 43 mg/kg and the ratios of Br/Cl and I/Cl of 2.5?×?10^–3, suggest that the thermal water stems from approximately 5,000 m depth and had a long residence time with silicate rocks. This points towards Gorongosa Mountain as the water source area. ¹⁴C dating suggests a groundwater age of 11,000 years.