Fate of organic matter during aquifer storage and recovery (ASR) of reclaimed water in a carbonate aquifer

Understanding the fate of injected organic matter and the consequences of subsequent redox processes is essential to assess the viability of using reclaimed water in aquifer storage and recovery (ASR). A full-scale field trial was undertaken at Bolivar, South Australia where two ASR cycles injected approximately 3.6 × 10⁵ m³ of reclaimed water into a carbonate aquifer over a 3-a period. Organic C within reclaimed water was predominantly in the dissolved fraction, ranging from 1 to 2 mmol L⁻¹ (10–20 mg L⁻¹), markedly higher than potable supply and stormwater previously reported as source waters for ASR. Between 20% and 24% of the injected dissolved organic C (DOC) was mineralised through reaction with injected O₂ and NO₃. Furthermore, this was achieved mainly within the first 4 m of aquifer passage. Despite the presence of residual DOC, SO₄ reduction was not induced within the bulk of the injected plume. It was only near the ASR well during an extended storage phase where deeply reduced (methanogenic) conditions developed, indicating variable redox zones within the injectant plume. The quality of water recovered from the ASR well indicated that the organic C content of reclaimed water does not restrict its application as a recharge source for ASR.     

Evidence for prolonged El Nino-like conditions in the Pacific during the Late Pleistocene: a 43 ka noble gas record from California groundwaters

Information on the ocean/atmosphere state over the period spanning the Last Glacial Maximum – from the Late Pleistocene to the Holocene – provides crucial constraints on the relationship between orbital forcing and global climate change. The Pacific Ocean is particularly important in this respect because of its dominant role in exporting heat and moisture from the tropics to higher latitudes. Through targeting groundwaters in the Mojave Desert, California, we show that noble gas derived temperatures in California averaged 4.2 ± 1.1 °C cooler in the Late Pleistocene (from ～43 to ～12 ka) compared to the Holocene (from ～10 to ～5 ka). Furthermore, the older groundwaters contain higher concentrations of excess air (entrained air bubbles) and have elevated oxygen-18/oxygen-16 ratios (δ¹⁸O) – indicators of vigorous aquifer recharge, and greater rainfall amounts and/or more intense precipitation events, respectively. Together, these paleoclimate indicators reveal that cooler and wetter conditions prevailed in the Mojave Desert from ～43 to ～12 ka. We suggest that during the Late Pleistocene, the Pacific ocean/atmosphere state was similar to present-day El Nino-like patterns, and was characterized by prolonged periods of weak trade winds, weak upwelling along the eastern Pacific margin, and increased precipitation in the southwestern U.S.     

Glaciations and paleoclimate of Mount Erciyes,central Turkey,since the Last Glacial Maximum,inferred from 36Cl cosmogenic dating and glacier modeling

Forty-four boulders from moraines in two glacial valleys of Mount Erciyes (38.53°N, 35.45°E, 3917 m), central Turkey, dated with cosmogenic chlorine-36 (³⁶Cl), indicate four periods of glacial activity in the past 22 ka (1 ka = 1000 calendar years). Last Glacial Maximum (LGM) glaciers were the most extensive, reaching 6 km in length and descending to an altitude of 2150 m above sea level. These glaciers started retreating 21.3 ± 0.9 ka (1σ) ago. They readvanced and retreated by 14.6 ± 1.2 ka ago (Lateglacial), and again by 9.3 ± 0.5 ka ago (Early Holocene). The latest advance took place 3.8 ± 0.4 ka ago (Late Holocene). Using glacier modeling together with paleoclimate proxy data from the region, we reconstructed the paleoclimate at these four discrete times. The results show that LGM climate was 8–11 °C colder than today and moisture levels were somewhat similar to modern values, with a range between 20% more and 25% less than today. The analysis of Lateglacial advance suggests that the climate was colder by 4.5–6.4 °C based on up to 1.5 times wetter conditions. The Early Holocene was 2.1–4.9 °C colder and up to twice as wet as today, while the Late Holocene was 2.4–3 °C colder and its precipitation amounts approached to similar conditions as today. Our paleoclimate reconstructions show a general trend of warming for the last 22 ka, and an increase of moisture until Early Holocene, and a decrease after that time. The recent glacier terminates at 3450 m on the northwest side of the mountain. It is a remnant from the last advance (possibly during the Little Ice Age). Repeated measurements of glacier length between 1902 and 2008 reveal a retreat rate of 4.2 m per year, which corresponds to a warming rate of 0.9–1.2 °C per century.     

Late-glacial to Holocene transition in northern Spain deduced from land-snail shelly accumulations

Shells of the helicid Cepaea nemoralis were studied using taphonomic, isotopic and morphometric measurements to estimate late glacial–Holocene (~ 12.1–6.3 cal ka BP) environmental conditions in northern Spain. Higher taphonomic alteration among Holocene shells suggests lower sedimentation rates or higher shell-destruction rates than during glacial conditions. Shells preserved the aragonitic composition despite differing degree of skeleton damage. Shell δ¹³C values were ? 10.3 ± 1.1‰, ? 8.2 ± 2.3‰, and ? 7.3 ± 1.6‰ for modern, Holocene and late-glacial individuals, respectively. Higher δ¹³C values during the late-glacial and some Holocene periods imply higher water stress of C₃ plants and/or higher limestone contribution than today. Intrashell δ¹³C values were higher during juvenile stages suggesting higher limestone ingestion to promote shell growth. Shell δ¹⁸O values were ? 1.1 ± 0.7‰, ? 0.9 ± 0.8‰ and ? 0.1 ± 0.7‰ for modern, Holocene and late-glacial specimens, respectively. A snail flux-balance model suggests that during ~ 12.1 ? 10.9 cal ka BP conditions were drier and became wetter at ~ 8.4 ? 6.3 cal ka BP and today. Intrashell δ¹⁸O profiles reveal that glacial individuals experienced more extreme seasonality than interglacial shells, despite possible larger hibernation periods. Shell size correlated positively with δ¹⁸O values, suggesting that growth rates and ultimate adult size of C. nemoralis may respond to climate fluctuation in northern Spain.     

Sources of groundwater nitrate revealed using residence time and isotope methods

Nitrate concentrations approaching and greater than the maximum contaminant level are impairing the viability of many groundwater basins as drinking water sources. Nitrate isotope data are effective in determining contaminant sources, especially when combined with other isotopic tracers such as stable isotopes of water and ³H–He ages to give insight into the routes and timing of NO₃ inputs to the flow system. This combination of techniques is demonstrated in Livermore, CA, where it is determined that low NO₃ reclaimed wastewater predominates in the NW, while two flowpaths with distinct NO₃ sources originate in the SE. Along the eastern flowpath, δ¹⁵N values greater than 10‰ indicate that animal waste is the primary source. Diminishing concentrations over time suggest that contamination results from historical land use practices. The other flowpath begins in an area where rapid recharge, primarily of low-NO₃ imported water (identified by stable isotopes of water and a ³H–He residence time of <1 year), mobilizes a significant local NO₃ source, bringing groundwater concentrations up to 53 mg NO₃ L⁻¹. In this area, artificial recharge of imported water via local arroyos increases the flux of NO₃ to the regional aquifer. The low δ¹⁵N value (3.1‰) in this location implicates synthetic fertilizer. In addition to these anthropogenic sources, natural NO₃ background levels between 15 and 20 mg NO₃ L⁻¹ are found in deep wells with residence times greater than 50 a.     

Determination of slip rate by optical dating of fluvial deposits from the Wangsan fault,SE Korea

The time-integrated slip rate in fault zones can be determined if the deformed deposits are reliably dated. Here, we report optically stimulated luminescence (OSL) ages of Late Pleistocene fluvial deposits cut by the Wangsan fault, southeastern Korea, which displaces a hanging wall block of about 28 m. Five sandy samples of the deformed Quaternary deposits were dated by quartz OSL using the single aliquot regenerative-dose (SAR) protocol. Three samples taken from the footwall block show stratigraphically consistent OSL ages of 54±7, 76±5 and 90±6 ka, from top to bottom. Two samples collected from the same layer in the hanging wall block show reproducible OSL ages of 81±5 and 82±5 ka, which are also in good agreement with the stratigraphic relationships. Our OSL ages yield an average sedimentation rate of the Quaternary deposits as around 0.04 mm a⁻¹, and a minimum value of time-integrated slip rate as 0.52 mm a⁻¹. This minimum slip rate is considerably higher than those reported earlier for Quaternary faults in southeastern Korea. The youngest OSL age (54±7 ka) constrains the maximum value of the recurrence interval of the fault movement.     

Cosmogenic 10Be and 36Cl ages from Late Pleistocene terminal moraine complexes in the Taylor River drainage basin,central Colorado,USA

Cosmogenic surface-exposure ages from boulders on a terminal moraine complex establish the timing of the local last glacial maximum (LGM) in the Taylor River drainage basin, central Colorado. Five zero-erosion ¹⁰Be ages have a mean of 19.5±1.8 ka while that for three ³⁶Cl ages is 20.7±2.3 ka. Corrections for modest rates (∼1 mm ka⁻¹) of boulder surface erosion result in individual and mean ages that are generally within 2% of their zero-erosion values. Both the means and the range in ages of individual boulders are consistent with those reported for late Pleistocene moraines elsewhere in the southern and middle Rocky Mountains, and thus suggest local LGM glacier activity was regionally synchronous. Two anomalously young (?) zero-erosion ¹⁰Be ages (mean 14.4±0.8 ka) from a second terminal moraine are tentatively attributed to the boulders having been melted out during a late phase of ice stagnation.     

Early Holocene fluvial activity from the sedimentology and palaeohydrology of gravel terrace in the semi arid Mahi River Basin,India

Palaeocompetence analysis and palaeodischarge estimation techniques are applied to a late Pleistocene–early Holocene gravel terrace in the Mahi River Basin, western India. Terrace sedimentology, comprising gravels overlain by sand lithofacies suggests a gradual change in palaeohydrological conditions marking a switch from braided to meandering fluvial styles. The discharge values for the gravel bedforms based on the clast size and the cross bed set thickness are estimated between ∼150–180 m³ s⁻¹ comparable with the present day observed values albeit with a much higher competence. Results indicate that fluvial aggradation occurred under low discharge conditions with intermittent high discharge events depositing longitudinal gravel bars. The incision of these gravel bars and the formation of terraces can be attributed to the higher discharge regime post 9.2 ka. The study further indicates that whereas the aggradation of the gravel terrace during the early Holocene was controlled by the large sediment influx, the incision that followed was in response to the increase in the discharge and competence of the river flow.     

A luminescence dating study of the sediment stratigraphy of the Lajia Ruins in the upper Yellow River valley,China

Pedo-sedimentological fieldwork were carried out in the Lajia Ruins within the Guanting Basin along the upper Yellow River valley. In the eolian loess-soil sections on the second river terrace in the Lajia Ruins, we find that the land of the Qijia Culture (4.20–3.95 ka BP) are fractured by several sets of earthquake fissures. A conglomerated red clay covers the ground of the Qijia Culture and also fills in the earthquake fissures. The clay was deposited by enormous mudflows in association with catastrophic earthquakes and rainstorms. The aim of this study is to provide a luminescence chronology of the sediment stratigraphy of the Lajia Ruins. Eight samples were taken from an eolian loess-soil section (Xialajia section) in the ruins for optically stimulated luminescence (OSL) dating. The OSL ages are in stratigraphic order and range from (31.94 ± 1.99) ka to (0.76 ± 0.02) ka. Combined OSL and ¹⁴C ages with additional stratigraphic correlations, a chronological framework is established. We conclude that: (1) the second terrace of the upper part of Yellow River formed 35.00 ka ago, which was followed by the accumulation of the eolian loess-soil section; and (2) the eolian loess-soil section is composed of the Malan Loess of the late last glacial (MIS-2) and Holocene loess-soil sequences.     

Pressure solution of quartz aggregates under low effective stress (0.42–0.61 MPa) at 25–45 °C

Dissolution rates of pressure solution (PS) for quartz aggregates in 0.002 M NaHCO₃ solution were experimentally determined under low effective stress conditions of 0.42–0.61 MPa, and low temperatures of 25–45 °C. At temperatures of 25 °C, 35 °C, and 45 °C, the resultant silicon dissolution rates are 4.2 ± 1.2 × 10⁻¹⁵, 6.0 ± 1.0 × 10⁻¹⁵ and 7.8 ± 1.9 × 10⁻¹⁵ mol/cm²/s, respectively. Ratios between these dissolution rates and those of quartz sand at zero effective stress are 4.1 ± 1.2 at 25 °C, 3.0 ± 0.5 at 35 °C, and 2.4 ± 0.6 at 45 °C. As the uniaxial pressure was increased, the dissolution rate of PS also increased, though gradually decreased when the effective stress was kept constant. After the removal of stress, the dissolution rate was observed to increase once again. The activation energy of our PS experiments was determined to be approximately 24 kJ/mol, lower than the amount required for quartz sand dissolution to commence at zero effective stress. Our results clearly show that, even at such low temperature and effective stress, Si released into solution as a result of PS can be detected. This implies that experimental compaction of quartz aggregates can be measured even under such condition.     

Effects of fluorine on the solubilities of Nb,Ta, Zr and Hf minerals in highly fluxed water-saturated haplogranitic melts

The effect of fluorine on the solubilities of Mn-columbite (MnNb₂O₆), Mn-tantalite (MnTa₂O₆), zircon (ZrSiO₄) and hafnon (HfSiO₄) were determined in highly fluxed, water-saturated haplogranitic melts at 800 to 1000 °C and 2 kbar. The melt composition corresponds to the intersection of the granite minimum with the albite–orthoclase tieline (Ab₇₂Or₂₈) in the quartz–albite–orthoclase system (Q–Ab–Or), which is representative of a highly fluxed melt, from which high field strength element minerals may crystallize. The melt contains 1.7 wt.% P₂O₅, 1.05 wt.% Li₂O and 1.83 wt.% B₂O₃. The main purpose of this study is to examine the effect of F on columbite, tantalite, zircon and hafnon solubility for a melt with this composition. Up to 6 wt.% fluorine was added as AgF in order to keep the aluminum saturation index (ASI, molar Al/[Na + K]) of the melt constant. In an additional experiment F was added as AlF₃ to make a glass peraluminous. The nominal ASI of the melts are close to 1 for the minimum composition and approximately 1.32 in peraluminous glasses, but if Li is considered as an alkali, the molar ratio Al/[Na + K + Li] of the melts are alkaline (0.87) and subaluminous (1.09), respectively.The molar solubility products [MnO] 1 [Nb₂O₅] and [MnO] 1 [Ta₂O₅] are nearly independent of the F content of the melt, at approximately 18.19 ± 1.2 and 43.65 ± 2.5 × 10^− 4 (mol²/kg²), respectively for the minimum composition. By contrast, there is a positive dependence of zircon and hafnon solubilities on the fluorine content in the minimum composition, which increases from 2.03 ± 0.03 × 10^− 4 (mol/kg) ZrO₂ and 4.04 ± 0.2 × 10^− 4 (mol/kg) HfO₂ for melts with 0 wt.% F to 3.81 ± 0.3 × 10^− 4 (mol/kg) ZrO₂ and 6.18 ± 0.04 × 10^− 4 (mol/kg) HfO₂ for melts with 8 wt.% F. Comparison of the data from this work and previous studies indicates that ASI of the melt seems to have a stronger effect than the contents of fluxing elements in the melt and the overall conclusion is that fluorine is less important (relative to melt compositions) than previously thought for the control on the behavior of high field strength elements in highly evolved granitic melts. Moreover, this study confirms that although Nb, Ta, Zr and Hf are all high field strength elements, Nb–Ta and Zr–Hf are complexed differently in the melt.     

Hydrogeochemical evolution of confined groundwater in northeastern Osaka Basin,Japan: estimation of confined groundwater flux based on a cation exchange mass balance method

A confined aquifer system has developed in argillaceous marine and freshwater sediments of Pliocene–Holocene age in the northeastern Osaka Basin (NEOB) in central Japan. The shallow groundwater (<100 m) in the system is recharged in a northern hilly to mountainous area with dominantly Ca-HCO₃ type water, which changes as it flows toward the SW to Mg-HCO₃ type and then to Na-HCO₃ type water. Comparison of the chemical and Sr isotopic compositions of the groundwater with those of the bulk and exchangeable components of the underground sediments indicates that elements leached from the sediments contribute negligibly to the NEOB aquifer system. Moreover, model calculations show that contributions of paleo-seawater in the deep horizon and of river water at the surface are not major factors of chemical change of the groundwater. Instead, the zonal pattern of the HCO₃-dominant groundwater is caused by the loss of Ca²⁺ from the water as it is exchanged for Mg²⁺ in clays, followed by loss of Mg + Ca as they are exchanged for Na + K in clays between the Ca-HCO₃ type recharge water and the exchangeable cations in the clay layers, which were initially enriched in Na⁺. Part of this process was reproduced in a chromatographic experiment in which Na type water with high ⁸⁷Sr/⁸⁶Sr was obtained from Mg type water with low ⁸⁷Sr/⁸⁶Sr by passing it through marine clay packed in a column. The flux of recharge water into the confined aquifer system according to this chromatographic model is estimated to be 0.99 mm/day, which is compatible with the average recharge flux to unconfined groundwater in Japan (1 mm/day).     

Luminescence dating of fluvial and coastal red sediments in the SE coast,India, and implications for paleoenvironmental changes and dune reddening

The Holocene and late Pleistocene environmental history of the teri (‘sandy waste’ in local parlance) red sands in the southeast coastal Tamil Nadu was examined using remote sensing, stratigraphy, and optically stimulated luminescence (OSL) dating. Geomorphological surveys enabled the classification of the teri red sands as, 1) inland fluvial teri, 2) coastal teri and, 3) near-coastal teri dunes. The inland teri sediments have higher clay and silty-sand component than the coastal and near-coastal teri, suggesting that these sediments were deposited by the fluvial process during a stronger winter monsoon around > 15 ka. The coastal teri dunes were deposited prior to 11.4 ± 0.9 ka, and the near-coastal dunes aggraded at around 5.6 ± 0.4 ka. We interpret that the coastal dunes were formed during a period of lower relative sea level and the near-coastal dunes formed during a period of higher sea level. Dune reddening is post deposition occurred after 11.4 ± 0.9 ka for the coastal teri dunes and after 5.6 ± 0.4 ka for the near-coastal teri dunes. Presence of microlithic sites associated with the coastal dunes suggest that the cultures existed in the region during 11.4 ± 0.9 ka and 5.6 ± 0.4 ka.     

Dissolution kinetics of Devonian carbonates at circum-neutral pH, 50 bar pCO2, 105 °C,and 0.4 M: The importance of complex brine chemistry on reaction rates

The dissolution kinetics of carbonate rocks sampled from the Keg River Formation in Northeast British Columbia were measured at 50 bar pCO₂ and 105 °C, in both natural and synthetic brines of 0.4 M ionic strength. Natural brines yielded reaction rates of −12.16 ± 0.11 mol cm⁻² s⁻¹ for Log R_Ca, and −12.64 ± 0.05 for Log R_Mg. Synthetic brine yielded faster rates of reaction than natural brines. Experiments performed on synthetic brines, spiked with 10 mmol of either Sr or Zn, suggest that enhanced reaction rates observed in synthetic brines are due to a lack of trace ion interaction with mineral surfaces. Results were interpreted within the surface complexation model framework, allowing for the discrimination of reactive surface sites, most importantly the hydration of the >MgOH surface site. Dissolution rates extrapolated from experiments predict that CO₂ injected into the Keg River Formation will dissolve a very minor portion of rock in contact with affected formation waters.     

Combining boron isotopes and carbamazepine to trace sewage in salinized groundwater: A case study in Cap Bon,Tunisia

The Korba aquifer on the east coast of Cape Bon has been overexploited since the 1960s with a resultant reversal of the hydraulic gradient and a degradation of the quality due to seawater intrusion. In 2008 the authorities introduced integrated water resources planning based on a managed aquifer recharge with treated wastewater. Water quality monitoring was implemented in order to determine the different system components and trace the effectiveness of the artificial recharge. Groundwater samples taken from recharge control piezometers and surrounding farm wells were analyzed for their chemical contents, for their B isotopes, a proven tracer of groundwater salinization and domestic sewage, and their carbamazepine content, an anti-epileptic known to pass through wastewater treatment and so recognized as a pertinent tracer of wastewater contamination. The system equilibrium was permanently disturbed by the different temporal dynamics of continuous processes such as cation exchange, and by threshold processes linked to oxidation–reduction conditions. The B isotopic compositions significantly shifted back-and-forth due to mixing with end-members of various origin. Under the variable contribution of meteoric recharge, the Plio-Quaternary groundwater (δ¹¹B of 35–40.6‰, a mean B concentration of 30 μmol/L, no carbamazepine, n = 7) was subject to seawater intrusion that induced a high δ¹¹B level (δ¹¹B of 41.5–48.0‰, a mean B concentration of 36 μmol/L, and n = 8). Fresh groundwater (δ¹¹B of 19.89‰, B concentration of 2.8 μmol/L, no carbamazepine) was detected close to the recharge site and may represent the deep Miocene pole which feeds the upper Plio-Quaternary aquifer. The managed recharge water (δ¹¹B of 10.67–13.8‰, n = 3) was brackish and of poor quality with a carbamazepine content showing a large short term variability with an average daily level of 328 ± 61 ng/L. A few piezometers in the vicinity of the recharge site gradually acquired a B isotopic composition close to the wastewater signature and showed an increasing carbamazepine content (from 20 to 910 ng/L). The combination of B isotopic signatures with B and carbamazepine contents is a useful tool to assess sources and mixing of treated wastewaters in groundwaters. Effluent quality needs to be greatly improved before injection to prevent further degradation of groundwater quality.     

Deglaciation and landscape history around Annapurna,Nepal, based on 10Be surface exposure dating

The High Himalaya is a key area for tectonic, geomorphological and climate studies, because of its extreme relief and location at the transition zone between areas with abundant monsoonal precipitation and the arid/semiarid Tibetan Plateau. We present ¹⁰Be surface exposure ages on 22 boulders from the Annapurna area in Nepal. The ages improve understanding of the Late Quaternary landscape history and the geomorphological processes operating in this part of the Himalaya.Although our study is reconnaissance in nature, it highlights the importance of catastrophic events, such as landslides and debris flows, for denudation of high mountains. Holocene exposure ages for the Dhampu–Chooya landslide (～4.1 ± 0.6 ka) and for 600 m of alluviation in Kali Gandaki Valley (～2.1 ± 0.6 ka), for example, indicate the frequent occurrence and extent of catastrophic events and their implications for natural hazards. We also offer an explanation for the differences in Late Quaternary glacial chronologies at closely spaced study sites in the Nepal Himalaya. Topographically controlled and spatially variable precipitation in the Himalaya determines the sensitivity of glaciers to changes in temperature and precipitation. Accordingly, some glaciers advanced in-phase with Northern Hemisphere ice sheets, whereas others reached their maximum extent at times of increased monsoonal precipitation during Marine Isotope Stage 3 and the early Holocene.     

Fluorite solubility in hydrous haplogranitic melts at 100 MPa

Fluorite is the most common fluoride mineral in magmatic silicic systems and its crystallization can moderate or buffer fluorine concentrations in these settings. We have experimentally determined fluorite solubility and speciation mechanisms in haplogranitic melts at 800–950 °C, 100 MPa and aqueous-fluid saturation. The starting haplogranite compositions: peraluminous (alumina saturation index, ASI = 1.2), subaluminous (ASI = 1.0) and peralkaline (ASI = 0.8) were variably doped with CaO or F₂O₋₁ in the form of stoichiometric mineral or glass mixtures. The solubility of fluorite along the fluorite–hydrous haplogranite binaries is low: 1.054 ± 0.085 wt.% CaF₂ (peralkaline), 0.822 ± 0.076 wt.% (subaluminous) and 1.92 ± 0.15 wt.% (peraluminous) at 800 °C, 100 MPa and 10 wt.% H₂O, and exhibits a minimum at ASI ∼ 1. Fluorite saturation isotherms are strongly hyperbolic in the CaO–F₂O₋₁ space, suggesting that fluorite saturation is controlled by the activity product of CaO and F₂O₋₁, i.e., these components are partially decoupled in the melt structure. The form of fluorite liquidus isotherms implies distinct roles of fluorite crystallization: in Ca-dominant systems, fluorite crystallization is controlled by the fluorine concentration in the melt only and remains nearly independent of calcium contents; in F-rich systems, the crystallization of fluorite is determined by CaO contents and it does not buffer fluorine concentration in the melt. The apparent equilibrium constant, K, for the equilibrium CaO + cF₂O₋₁ = CaF₂ (+ associates) is log K= − (2.449 ± 0.085)·Al₂O₃^exc + (4.902 ± 0.066); the reaction-stoichiometry parameter varies as follows: c= − (0.92 ± 0.11)·Al₂O₃^exc + (1.042 ± 0.084) at 800 °C, 100 MPa and fluid saturation where Al₂O₃^exc are molar percent alumina in excess over alkali oxides. The reaction stoichiometry, c, changes at subaluminous composition: in peralkaline melts, competition of other network modifiers for excess fluorine anions leads to the preferential alkali–F short-range order, whereas in peraluminous compositions, excess alumina associates with calcium cations to form calcioaluminate tetrahedra. The temperature dependence of fluorite solubility is described by the binary symmetric Margules parameter, W = 36.0 ± 1.4 kJ (peralkaline), 39.7 ± 0.5 kJ (subaluminous) and 32.8 ± 0.7 kJ (peraluminous). The strong positive deviations from ideal mixing imply the occurrence of CaF₂–granite liquid–liquid immiscibility at temperatures above 1258 °C, which is consistent with previous experimental data. These experimental results suggest very low solubilities of fluorite in Ca-rich melts, consistent with the lack of fluorine enrichment in peralkaline rhyolites and calc-alkaline batholiths. On the other hand, high CaO concentrations necessary to crystallize fluorite in F-rich peraluminous melts are not observed in nature and thus magmatic crystallization of fluorite in topaz-bearing silicic suites is suppressed. A procedure for calculating fluorite solubility and the liquidus isotherms for a whole-rock composition and temperature of interest is provided.     

Activation energies of the self-diffusion of HTO, 22Na+ and 36Cl− in a highly compacted argillaceous rock (Opalinus Clay)

The temperature dependence of the self-diffusion of HTO, ²²Na⁺ and ³⁶Cl⁻ in Opalinus Clay (OPA) was studied using a through-diffusion technique, in which the temperature was gradually increased in the steady state phase of the diffusion. The measurements were done on samples from two different geological locations. The dependence of the effective diffusion coefficient on temperature was found to be of an Arrhenius type in the temperature range between 0 and 70 °C. A slight difference between the two locations could be observed. The average value of the activation energy of the self-diffusion of HTO in OPA was 21.1 ± 1.6 kJ mol⁻¹, and 21.0 ± 3.5 and 19.4 ± 1.5 kJ mol⁻¹ for ²²Na⁺ and ³⁶Cl⁻, respectively. The measured values for HTO are slightly higher than the values found for the bulk liquid water (HTO: 18.8 ± 0.4 kJ mol⁻¹). This indicates that the structure of the confined water in OPA might be slightly different from that of bulk liquid water. Also for Na⁺ and Cl⁻, slightly higher values than in bulk liquid water (Na⁺: 18.4 kJ mol⁻¹; Cl⁻: 17.4 kJ mol⁻¹) were observed.The Stokes–Einstein relationship, based on the temperature dependency of the viscosity of bulk water, could not be used to describe the temperature dependence of the diffusion of HTO in OPA. This additionally indicates the slightly different structure of the pore water in OPA.     

The 8.2 ka event and Early–Mid Holocene forests,fires and flooding in the Central Ebro Desert,NE Spain

The impact of the 8.2 ka cooling event during the Early–Mid Holocene has not been widely observed in Southern Europe, which in contrast to Northern Europe, was already experiencing a cooler than present climate at this time. Multi-proxy analysis of sediment cores from two closed-basin saline lakes in the Central Ebro Desert (NE Spain) has allowed us to investigate the impact of climatic changes around the time of this event in more detail. Long-term changes in climate between the Early and Mid Holocene indicate a shift in winter to a more positive NAO, resulting in declining lake levels in one lake sensitive to winter groundwater recharge, and cooler winter temperatures reconstructed from pollen–climate analysis. Reconstructed summer temperatures also declined over this period while annual precipitation and forest cover increased, interpreted as a result of enhanced convection-driven summer precipitation association with a northward displacement of the sub-tropical high pressure. Around 8.2 ka, a marked increase in fire frequency is shown between ca 8.8 and 8.0 ka BP, along with an expansion of fire-tolerant evergreen oak and peak in water levels in a second storm run-off fed lake. A maximum in fire intensity occurred with the deposition of a charcoal layer at both lake sites dated to 8150±130 and 8285±135 cal BP, respectively. The increase in fire is largely attributed to a temporary return southward of the summer sub-tropical high pressure over the Mediterranean, which not only increased summer aridity, but also caused a contradictory regional warming before Hemispheric cooling set in.     

A conceptual framework of groundwater flow in some crystalline aquifers in Southeastern Ghana

A conceptual groundwater flow model was developed for the crystalline aquifers in southeastern part of the Eastern region, Ghana. The objective was to determine approximate levels of groundwater recharge, estimate aquifer hydraulic parameters, and then test various scenarios of groundwater extraction under the current conditions of recharge. A steady state groundwater flow model has been calibrated against measured water levels of 19 wells in the area. The resulting recharge is estimated to range from 8.97 × 10^?5 m/d to 7.14 × 10^?4 m/d resulting in a basin wide average recharge of about 9.6% of total annual precipitation, which results in a basin wide quantitative recharge of about 2.4 million m³/d in the area. This compares to recharge estimated from the chloride mass balance of 7.6% of precipitation determined in this study. The general groundwater flow in the area has also been determined to conform to the general northeast–southwest structural grain of the country. The implication is that the general hydrogeology is controlled by post genetic structural entities imposed on the rocks to create ingresses for sufficient groundwater storage and transport. Calibrated aquifer hydraulic conductivities range between 0.99 m/d and over 19.4 m/d. There is a significant contribution of groundwater discharge to stream flow in the study area. Increasing groundwater extraction will have an effect on stream flow. This study finds that the current groundwater extraction levels represent only 0.17% of the annual recharge from precipitation, and that groundwater can sustain future increased groundwater demands from population growth and industrialization.