Possible soil tension controls on the isotopic equilibrium fractionation factor for evaporation from soil

The stable isotopes of hydrogen and oxygen (δ²H and δ¹⁸O) are useful conservative tracers for tracking the movement of water in soil. But although the tracking of water infiltrating through the soil profile and its movement as run‐off and groundwater recharge are well developed, water movement through the soil can also include evaporative fractionation. Soil water fractionation factors have, until now, been largely empirical. Unlike open water evaporation where temperature, humidity, and vapour pressure gradient define fractionation, soil water evaporation includes fractionation by soil matrix effects. These effects are still poorly characterized. Here, we present preliminary results from a simple laboratory experiment with four soil admixtures with grain sizes that range from sand to silt and clay. Our results show that soil tension seems to control the isotope fractionation of resident soil water. The relationship between soil tension and equilibrium fractionation appears to be independent of soil texture and appears well supported by thermodynamic theory. Although these results are preliminary, they suggest that future work should go after soil tension effects as a possible explanatory factor of soil water and water vapour fractionation.     

Isotopic composition (δ18O and δD) of precipitation and groundwater in a semi‐arid,mountainous area (Guadiana Menor basin,Southeast Spain)

We characterize the precipitation and groundwater in a mountainous (peaks slightly above 3000 m a.s.l.), semi‐arid river basin in SE Spain in terms of the isotopes ¹⁸O and ²H. This basin, with an extension of about 7000 km², is an ideal site for such a study because fronts from the Atlantic and the Mediterranean converge here. Much of the land is farmed and irrigated both by groundwater and runoff water collected in reservoirs. A total of approximately 100 water samples from precipitation and 300 from groundwater have been analysed. To sample precipitation we set up a network of 39 stations at different altitudes (800–1700 m a.s.l.), with which we were able to collect the rain and snowfall from 29 separate events between July 2005 and April 2007 and take monthly samples during the periods of maximum recharge of the aquifers. To characterize the groundwater we set up a control network of 43 points (23 springs and 20 wells) to sample every 3 months the main aquifers and both the thermal and non‐thermal groundwater. We also sampled two shallow‐water sites (a reservoir and a river). The isotope composition of the precipitation forms a local meteoric water line (LMWL) characterized by the equation δD = 7·72δ¹⁸O + 9·90, with mean values for δ¹⁸O and δD of − 10·28‰ and − 69·33‰, respectively, and 12·9‰ for the d‐excess value. To correlate the isotope composition of the rainfall water with groundwater we calculated the weighted local meteoric water line (WLMWL), characterized by the equation δD = 7·40δ¹⁸O + 7·24, which takes into account the quantity of water precipitated during each event. These values of (dδD/dδ¹⁸O)< 8 and d‐excess (δD–8δ¹⁸O)< 10 in each curve bear witness to the ‘amount effect’, an effect which is more manifest between May and September, when the ground temperature is higher. Other effects noted in the basin were those of altitude and the continental influence. The isotopic compositions of the groundwater are represented by the equation δD = 4·79δ¹⁸O − 18·64. The groundwater is richer in heavy isotopes than the rainfall, with mean values of − 8·48‰ for δ¹⁸O and − 59·27‰ for δD. The isotope enrichment processes detected include a higher rate of evaporation from detrital aquifers than from carbonate ones, the effects of recharging aquifers from irrigation return flow and/or from reservoirs' leakage and enrichment in δ¹⁸O from thermal water. Copyright © 2010 John Wiley & Sons, Ltd.     

Continuous monitoring of stream δ18O and δ2H and stormflow hydrograph separation using laser spectrometry in an agricultural catchment

A portable Wavelength Scanned‐Cavity Ring‐Down Spectrometer (Picarro L2120) fitted with a diffusion sampler (DS‐CRDS) was used for the first time to continuously measure δ¹⁸O and δ²H of stream water. The experiment took place during a storm event in a wet tropical agricultural catchment in north‐eastern Australia. At a temporal resolution of one minute, the DS‐CRDS measured 2160 δ¹⁸O and δ²H values continuously over a period of 36 h with a precision of ±0.08 and 0.5‰ for δ¹⁸O and δ²H, respectively. Four main advantages in using high temporal resolution stream δ¹⁸O and δ²H data during a storm event are highlighted from this study. First, they enabled us to separate components of the hydrograph, which was not possible using high temporal resolution electrical conductivity data that represented changes in solute transfers during the storm event rather than physical hydrological processes. The results from the hydrograph separation confirm fast groundwater contribution to the stream, with the first 5 h of increases in stream discharge comprising over 70% pre‐event water. Second, the high temporal resolution stream δ¹⁸O and δ²H data allowed us to detect a short‐lived reversal in stream isotopic values (δ¹⁸O increase by 0.4‰ over 9 min), which was observed immediately after the heavy rainfall period. Third, δ¹⁸O values were used to calculate a time lag of 20 min between the physical and chemical stream responses during the storm event. Finally, the hydrograph separation highlights the role of event waters in the runoff transfers of herbicides and nutrients from this heavily cultivated catchment to the Great Barrier Reef. Copyright © 2015 John Wiley & Sons, Ltd.     

Sulfur isotopic effects in the disproportionation reaction of sulfur dioxide in hydrothermal fluids: implications for the δS variations of dissolved bisulfate and elemental sulfur from active crater lakes

Sulfur isotope effects during the SO₂ disproportionation reaction to form elemental sulfur (3SO₂+3H₂O→2HSO₄⁻+S+2H⁺) at 200–330°C and saturated water vapor pressures were experimentally determined. Initially, a large kinetic isotopic fractionation takes place between HSO₄⁻ and S, followed by a slow approach to equilibrium. The equilibrium fractionation factors, estimated from the longest run results, are expressed by 1000 ln α_HSO4⁻–S=6.21×10⁶/T²+3.62. The rates at which the initial kinetic fractionation factors approach the equilibrium ones were evaluated at the experimental conditions.δ³⁴S values of HSO₄⁻ and elemental sulfur were examined for active crater lakes including Noboribetsu and Niseko, (Hokkaido, Japan), Khloridnoe, Bannoe and Maly Semiachik (Kamchatka), Poás (Costa Rica), Ruapehu (New Zealand) and Kawah Ijen and Keli Mutu (Indonesia). Δ_HSO4⁻–S values are 28‰ for Keli Mutu, 26‰ for Kawah Ijen, 24‰ for Ruapehu, 23‰ for Poás, 22‰ for Maly Semiachik, 21‰ for Yugama, 13‰ for Bannoe, 9‰ for Niseko, 4‰ for Khloridonoe, and 0‰ for Noboribetsu, in the decreasing order. The SO₂ disproportionation reaction in the magmatic hydrothermal system below crater lakes where magmatic gases condense is responsible for high Δ_HSO4⁻–S values, whereas contribution of HSO₄⁻ produced through bacterial oxidation of reduced sulfur becomes progressively dominant for lakes with lower Δ_HSO4⁻–S values. Currently, Noboribetsu crater lake contains no HSO₄⁻ of magmatic origin. A 40-year period observation of δ³⁴S_HSO4⁻ and δ³⁴S_S values at Yugama indicated that the isotopic variations reflect changes in the supply rate of SO₂ to the magmatic hydrothermal system. This implies a possibility of volcano monitoring by continuous observation of δ³⁴S_HSO4⁻ values. The δ¹⁸O values of HSO₄⁻ and lake water from the studied lakes covary, indicating oxygen isotopic equilibration between them. The covariance gives strong evidence that lake water circulates through the sublimnic zone at temperatures of 140±30°C.     

Origin and type of rainfall for recharge of a karstic aquifer in the western Mediterranean: a case study from the Sierra de Gador–Campo de Dalias (southeast Spain)

Isotope signatures in precipitation from the Global Network for Isotopes in Precipitation around the Mediterranean basin and literature data are compared with isotopic data from a large karstic aquifer in southeast Spain to explain the origin and type of the precipitation events dominating recharge. Analysis of the deuterium excess d at the scale of the Mediterranean basin and at the regional scale allows us to understand the isotopic context of the study area: Campo de Dalias and the Sierra de Gador (Almería province). The origin of precipitation can be determined from its d value. The d value changes as a function of the initial evaporation condition. It depends on the relative humidity and temperature during the evaporation producing the water vapour of the clouds. The water vapour, which dominates the study area, is generated in two areas: the Atlantic Ocean (d = 10‰) and the western Mediterranean basin (d = 15‰). With increasing precipitation volume, the western Mediterranean character dominates. These heavier storms contribute mainly to recharge, as illustrated by the d value of 13·6‰ in deep groundwater of the Campo de Dalias. Weighted d values increase with the volume of precipitation, giving a significant relationship for the southern and eastern coasts of the Iberian Peninsula. This selectivity of d to monthly precipitation was used to estimate the return period of precipitation leading to aquifer recharge at 0·9–4·9 years. Moderate rainfall, which occurs more frequently, still represents ～60–90% of the total precipitation. One of the challenges to meet ever‐growing water demands is to increase recharge from moderate events yielding intermediate quantities per event, but forming the bulk of the annual precipitation. Copyright © 2006 John Wiley & Sons, Ltd.     

Groundwater recharge in the Akaki catchment,central Ethiopia: evidence from environmental isotopes (δ18O, δ2H and 3H) and chloride mass balance

Recharge patterns, possible flow paths and the relative age of groundwater in the Akaki catchment in central Ethiopia have been investigated using stable environmental isotopes δ¹⁸O and δ²H and radioactive tritium (³H) coupled with conservative chloride measurements. Stable isotopic signatures are encoded in the groundwater solely from summer rainfall. Thus, groundwater recharge occurs predominantly in the summer months from late June to early September during the major Ethiopian rainy season. Winter recharge is lost through high evaporation–evapotranspiration within the unsaturated zone after relatively long dry periods of high accumulated soil moisture deficits. Chloride mass balance coupled with the isotope results demonstrates the presence of both preferential and piston flow groundwater recharge mechanisms. The stable and radioactive isotope measurements further revealed that groundwater in the Akaki catchment is found to be compartmentalized into zones. Groundwater mixing following the flow paths and topography is complicated by the lithologic complexity. An uncommon, highly depleted stable isotope and zero‐³H groundwater, observed in a nearly east–west stretch through the central sector of the catchment, is coincident with the Filwoha Fault zone. Here, deep circulating meteoric water has lost its isotopic content through exchange reactions with CO₂ originating at deeper sources or it has been recharged with precipitation from a different rainfall regime with a depleted isotopic content. Copyright © 2006 John Wiley & Sons, Ltd.     

Boron isotopic fractionation in laboratory inorganic carbonate precipitation: evidence for the incorporation of B(OH)<Subscript>3</Subscript> into carbonate

A laboratory inorganic carbonate precipitation experiment at high pH of 8.96 to 9.34 was conducted, and the boron isotopic fractionations of the precipitated carbonate were measured. The data show that boron isotopic fractionation factors (α_carb-3) between carbonate and B(OH)₃ in seawater range 0.937 and 0.965, with an average value of 0.953. Our results together with those reported by Sanyal and collaborators show that the α_carb-3 values between carbonate and B(OH)₃ in solution are not constant but are negatively correlated with the pH of seawater. The measured boron isotopic compositions of carbonate precipitation (δ¹¹B_carb) do not exactly lie on the best-fit theoretical δ¹¹B₄-pH curves and neither do they exactly parallel any theoretical δ¹¹B₄-pH curves. Therefore, it is reasonable to argue that a changeable proportion of B(OH)₃ with pH of seawater should also be incorporated into carbonate except for the dominant incorporation of B(OH)₄ ⁻ in carbonate. Hence, in the reconstruction of the paleo-pH of seawater from boron isotopes in marine biogenic carbonates, the use of theoretical boron isotopic fractionation factor (α₄₋₃) between B(OH)₄ ⁻ and B(OH)₃ is not suitable. Instead, an empirical equation should be established. Supported by National Natural Science Foundation of China (Nos. 40573013 and 40776071), State Key Laboratory of Loess and Quaternary Geology, Institute of Earth Environment, Chinese Academy of Sciences (Grant No SKLLQG0502) and State Key Laboratory of Environmental Geochemistry, Institute of Geochemistry, Chinese Academy of Sciences     

Isotopic composition of precipitation in a topographically steep,seasonally snow‐dominated watershed and implications of variations from the global meteoric water line

The local meteoric water line (LMWL), the functional relationship between locally measured values of δ¹⁸O and δ²H in precipitation, represents the isotopic composition of water entering hydrologic systems. The degree to which the LMWL departs from the global meteoric water line (GMWL), moreover, can reveal important information about meteoric sources of water (e.g. oceanic or terrestrial) and atmospheric conditions during transport. Here we characterize the isotopic composition of precipitation within an experimental watershed in the Western US that is subject to large topographic and seasonal gradients in precipitation. Interpreting the hydrometeorologic and spatial controls on precipitation, we constructed a seasonally weighted LMWL for southwestern Idaho that is expressed by the equation δ²H = 7.40 × δ¹⁸O ? 2.17. A seasonally weighted LMWL that is based on weighting isotopic concentrations by climatic precipitation volumes is novel, and we argue better represents the significant seasonality of precipitation in the region. The developed LMWL is considerably influenced by the semiarid climate experienced in southwest Idaho, yielding a slope and y‐intercept lower than the GMWL (δ²H = 8 × δ¹⁸O + 10). Moderate to strong correlations exist between the isotopic composition of precipitation from individual events and surface meteorologic variables, specifically surface air temperature, relative humidity, and precipitation amount. A strong negative correlation exists between the annual average isotopic composition of precipitation and elevation at individual collection sites, with a lapse rate of ?0.22‰/100 m. Copyright © 2016 John Wiley & Sons, Ltd.     

A tale of two isotopes: differences in hydrograph separation for a runoff event when using δD versus δ18O

It is often assumed that stable water isotopes (δD and δ¹⁸O) provide redundant information for a given sample of water. In this note we illustrate that the choice of isotope used may influence the resultant hydrograph separation. This is especially true in light of the spatial and temporal variability in the isotopic composition of rainfall water at the catchment scale. We present several possible hydrograph separations based on both δD and δ¹⁸O observed in rainfall for a single runoff event occurring in the southwest USA. This study demonstrates the potential of using both stable water isotopes by showing that δD and δ¹⁸O may provide unique information for catchment hydrologists. We also report on the utility of new technology capable of simultaneous measurements of both δD and δ¹⁸O using off‐axis integrated cavity output spectroscopy (OA‐ICOS) methods. This may be of interest to catchment hydrologists seeking to incorporate this type of equipment into their laboratory. Copyright © 2009 John Wiley & Sons, Ltd.     

Characterization of surface and ground water δ18O seasonal variation and its use for estimating groundwater residence times

¹⁸O is an ideal tracer for characterizing hydrological processes because it can be reliably measured in several watershed hydrological compartments. Here, we present multiyear isotopic data, i.e. ¹⁸O variations (δ¹⁸O), for precipitation inputs, surface water and groundwater in the Shingobee River Headwaters Area (SRHA), a well‐instrumented research catchment in north‐central Minnesota. SRHA surface waters exhibit δ¹⁸O seasonal variations similar to those of groundwaters, and seasonal δ¹⁸O variations plotted versus time fit seasonal sine functions. These seasonal δ¹⁸O variations were interpreted to estimate surface water and groundwater mean residence times (MRTs) at sampling locations near topographically closed‐basin lakes. MRT variations of about 1 to 16 years have been estimated over an area covering about 9 km² from the basin boundary to the most downgradient well. Estimated MRT error (±0·3 to ±0·7 years) is small for short MRTs and is much larger (±10 years) for a well with an MRT (16 years) near the limit of the method. Groundwater transit time estimates based on Darcy's law, tritium content, and the seasonal δ¹⁸O amplitude approach appear to be consistent within the limits of each method. The results from this study suggest that use of the δ¹⁸O seasonal variation method to determine MRTs can help assess groundwater recharge areas in small headwaters catchments. Copyright © 2005 John Wiley & Sons, Ltd.     

Numerical studies of vertical Cl−, δ2H and δ18O profiles in the aquifer–aquitard system in the Pearl River Delta,China

Sedimentation may have a significant effect on the transport of solutes and environmental isotopes in sediment. The depth profiles of the Cl^?, δ²H and δ¹⁸O in a borehole in the aquifer–aquitard system in the Pearl River Delta (PRD), China, were obtained by centrifuging the core sediment samples. A one‐dimensional model based on the sedimentation and sea level changes of the PRD during the Holocene was built to investigate numerically the transport mechanisms of Cl^?, δ²H and δ¹⁸O. The sedimentation process was modelled as a moving boundary problem with the moving rate equal to the sedimentation rate. The model was calibrated and the parameters were obtained by comparing simulated and measured data. Very good agreement between all the three observed profiles and the simulated ones demonstrates the reliability of the model and the parameters. Simulation results show that the shapes of the curves are controlled by the combination of sedimentation and upper boundary conditions. Diffusion solely is adequate to reconstruct the observed profiles, which indicates that diffusion is the dominant vertical transport mechanism. The effective diffusion coefficients of the aquitard and the aquifer equal to 5.0 × 10^?11 and 2.0 × 10^?10 m²/s, respectively. The results of this study will help in understanding the transport mechanisms of solutes and environmental tracers in deltas with geology and hydrogeology similar to the PRD. Copyright © 2015 John Wiley & Sons, Ltd.     

Temporal trends in δ18O composition of precipitation in Germany: insights from time series modelling and trend analysis

Temporal and spatial variations of stable oxygen (¹⁸O) and hydrogen (²H) isotope measurements in precipitation act as important proxies for changing hydro‐meteorological and regional and global climate patterns. Temporal trends in time series of the stable isotope composition in precipitation were rarely observed, and they are poorly understood. These might be a result of a lack of proper trend detection tools and effort for exploring trend processes. Here, we investigate temporal trends of δ¹⁸O in precipitation at 17 observation stations in Germany between 1978 and 2009. We test if significant trends in the isotope time series from different models can be observed. Mann–Kendall trend tests are applied on the isotope series, using general multiplicative seasonal autoregressive integrate moving average (ARIMA) models, which account for first and higher order serial correlations. Effects of temperature, precipitation, and geographic parameters on isotope trends are also investigated in the proposed models. To benchmark our proposed approach, the ARIMA results are compared with a trend‐free pre‐whitening procedure, the state of the art method for removing the first order autocorrelation in environmental trend studies. Moreover, we further explore whether higher order serial correlations in isotope series affects our trend results. Overall, three out of the 17 stations show significant changes when higher order autocorrelation are adjusted, and four show a significant trend when temperature and precipitation effects are considered. The significant trends in the isotope time series generally occur only at low elevation stations. Higher order autoregressive processes are shown to be important in the isotope time series analysis. Results suggest that the widely used trend analysis with only the first order autocorrelation adjustment may not adequately take account of the high order autocorrelated processes in the stable isotope series. The investigated time series analysis method including higher autocorrelation and external climate variable adjustments is shown to be a better alternative. Copyright © 2014 John Wiley & Sons, Ltd.     

A stratigraphic network across the Subtropical Front in the central South Atlantic: Multi-parameter correlation of magnetic susceptibility, density, X-ray fluorescence and δO records

Computer aided multi-parameter signal correlation is used to develop a common high-precision age model for eight gravity cores from the subtropical and subantarctic South Atlantic. Since correlations between all pairs of multi-parameter sequences are used, and correlation errors between core pairs (A, B) and (B, C) are controlled by comparison with (A, C), the resulting age model is called a stratigraphic network. Precise inter-core correlation is achieved using high-resolution records of magnetic susceptibility κ, wet bulk density ρ and X-ray fluorescence scans of elemental composition. Additional δ¹⁸O records are available for two cores. The data indicate nearly undisturbed sediment series and the absence of significant hiatuses or turbidites. After establishing a high-precision common depth scale by synchronously correlating four densely measured parameters (Fe, Ca, κ, ρ), the final age model is obtained by simultaneously fitting the aligned δ¹⁸O and κ records of the stratigraphic network to orbitally tuned oxygen isotope [J. Imbrie, J. D. Hays, D. G. Martinson, A. McIntyre, A. C. Mix, J. J. Morley, N. G. Pisias, W. L. Prell, N. J. Shackleton, The orbital theory of Pleistocene climate: support from a revised chronology of the marine δ¹⁸O record, in: A. Berger, J. Imbrie, J. Hays, G. Kukla, B. Saltzman (Eds.), Milankovitch and Climate: Understanding the Response to Orbital Forcing, Reidel Publishing, Dordrecht, 1984, pp. 269-305; D. Martinson, N. Pisias, J. Hays, J. Imbrie, T. C. Moore Jr., N. Shackleton, Age dating and the orbital theory of the Ice Ages: development of a high-resolution 0 to 300.000-Year chronostratigraphy, Quat. Res. 27 (1987) 1-29.] or susceptibility stacks [T. von Dobeneck, F.Schmieder, Using rock magnetic proxy records for orbital tuning and extended time series analyses into the super-and sub-Milankovitch Bands, in: G. Fischer, G. Wefer (Eds.), Use of proxies in paleoceanography: Examples from the South Atlantic, Springer-Verlag, Berlin (1999), pp. 601-633.]. Besides the detection and elimination of errors in single records, the stratigraphic network approach allows to check the intrinsic consistency of the final result by comparing it to the outcome of more restricted alignment procedures. The final South Atlantic stratigraphic network covers the last 400 kyr south and the last 1200 kyr north of the Subtropical Front (STF) and provides a highly precise age model across the STF representing extremely different sedimentary regimes. This allows to detect temporal shifts of the STF by mapping δMn / Fe. It turns out that the apparent STF movements by about 200 km are not directly related to marine oxygen isotope stages.     

Using SPIRAL (Single Pollen Isotope Ratio AnaLysis) to estimate C3- and C4-grass abundance in the paleorecord

C₃ and C₄ grasses differ greatly in their responses to environmental controls and influences on biogeochemical processes (e.g. water, carbon, and nutrient cycling). Difficulties in distinguishing between these two functional groups of grasses have hindered paleoecological studies of grass-dominated ecosystems. Stable carbon isotopic analysis of individual grains of grass pollen using a spooling-wire microcombustion device interfaced with an isotope-ratio mass spectrometer holds promise for improving C₃ and C₄ grass reconstructions. This technique, SPIRAL (Single Pollen Isotope Ratio AnaLysis), has only been evaluated using pollen of known C₃ and C₄ grasses. To test the ability of SPIRAL to reproduce the abundance of C₃ and C₄ grasses on the landscape, we measured δ¹³C values of > 1500 individual grains of grass pollen isolated from the surface sediments of ten lakes in areas that span a large gradient of C₃- and C₄-grass abundance, as determined from vegetation surveys. Results indicate a strong positive correlation between the δ¹³C-based estimates of % C₄-grass pollen and the abundance of C₄ grasses on the landscape. The % C₄-grass pollen slightly underestimates the actual abundance of C₄ grasses at sites with high proportions of C₄ grasses, which can be corrected using regression analysis. Comparison of the % C₄-grass pollen with C/N and δ¹³C measurements of bulk organic matter illustrates the distinct advantages of grass-pollen δ¹³C as a proxy for distinguishing C₃ and C₄ shifts within the grass family. Thus SPIRAL promises to advance our understanding of grassland ecology and evolution.     

Characteristics of δ13CDIC in lakes on the Tibetan Plateau and its implications for the carbon cycle

Dissolved inorganic carbon isotope (δ¹³C_DIC) is an important tool to reveal the carbon cycle in lake systems. However, there are only few studies focusing on the spatial variation of δ¹³C_DIC of closed lakes. Here we analyze the characteristics of δ¹³C_DIC of 24 sampled lakes (mainly closed lakes) across the Qiangtang Plateau (QTP) and identify the driving factors for its spatial variation. The δ¹³C_DIC value of these observed lakes varies in the range of ? 15·0 to 3·2‰, with an average value of ? 1·2‰. The δ¹³C_DIC value of closed lakes is close to the atmospheric isotopic equilibrium value, much higher than that in rivers and freshwater lakes reported before. The high δ¹³C_DIC value of closed lakes is mainly attributed to the significant contribution of carbonate weathering in the catchment and the evasion of dissolved CO₂ induced by the strong evaporation of lake water. The δ¹³C_DIC value of closed lakes has a logarithmic correlation with water chemistry (TDS, DIC and pCO₂), also suggesting that the evapo‐concentration of lake water can influence the δ¹³C_DIC value. The δ¹³C_DIC value shows two opposite logarithmic correlations with lake size depending on the δ¹³C_DIC range. This study suggests that the δ¹³C in carbonates in lacustrine sediments can be taken as an indicator of lake volume variation in closed lakes on QTP. Copyright © 2011 John Wiley & Sons, Ltd.     

Analytical and statistical approach for evaluating the effects of a river barrage on river–aquifer interactions

The construction of a river barrage can increase groundwater levels upstream of the barrage during the rainy season. Analytical and statistical approaches were applied to evaluate the relationship between groundwater and river water at the Changnyeong–Haman river barrage in Korea using time series data of water level and electrical conductivity from June 2011 to September 2014. An artificial neural network based time series model was designed to filter out the effect of rainfall from the groundwater level data in the study area. Aquifer diffusivity and river resistance were estimated from the analytical solution of a one‐dimensional unit step response function by using the filtered groundwater level data. River resistance increased in response to groundwater level fluctuations. Cross‐correlation analyses between the groundwater and the river water showed that the lag time increased during the observation period for both the water level and the electrical conductivity while the cross‐correlation function declined for the same period. The results indicated that a constant river stage maintained at the river barrage can weaken the hydrologic stress and reduce the exchange of material between the river and the adjacent aquifer because of the deposition of fine sediment on the river bottom and walls. Copyright © 2016 John Wiley & Sons, Ltd.     

Origin and evolution of two contrasting thermal groundwaters (CO2-rich and alkaline) in the Jungwon area,South Korea: Hydrochemical and isotopic evidence

In the Jungwon area, South Korea, two contrasting types of deep thermal groundwater (around 20–33 °C) occur together in granite. Compared to shallow groundwater and surface water, thermal groundwaters have significantly lower δ¹⁸O and δD values (> 1‰ lower in δ¹⁸O) and negligible tritium content (mostly < 2 TU), suggesting a relatively high age of these waters (at least pre-thermonuclear period) and relatively long subsurface circulation. However, the hydrochemical evolution yielded two distinct water types. CO₂-rich water (P_CO2 = 0.1 to 2 atm) is characterized by lower pH (5.7–6.4) and higher TDS content (up to 3300 mg/L), whereas alkaline water (P_CO2 = 10^− 4.1–10^− 4.6 atm) has higher pH (9.1–9.5) and lower TDS (< 254 mg/L). Carbon isotope data indicate that the CO₂-rich water is influenced by a local supply of deep CO₂ (potentially, magmatic), which enhanced dissolution of silicate minerals in surrounding rocks and resulted in elevated concentrations of Ca²⁺, Na⁺, Mg²⁺, K⁺, HCO₃⁻ and silica under lower pH conditions. In contrast, the evolution of the alkaline water was characterized by a lesser degree of water–rock (granite) interaction under the negligible inflow of CO₂. The application of chemical thermometers indicates that the alkaline water represents partially equilibrated waters coming from a geothermal reservoir with a temperature of about 40 °C, while the immature characteristics of the CO₂-rich water resulted from the input of CO₂ in Na–HCO₃ waters and subsequent rock leaching.     

Garnet-ilmenite-perovskite transitions in the system Mg4Si4O12-Mg3Al2Si3O12 at high pressures and high temperatures: phase equilibria, calorimetry and implications for mantle structure

Phase relations in the system Mg₄Si₄O₁₂-Mg₃Al₂Si₃O₁₂ were examined at pressures of 19-27 GPa and relatively low temperatures of 800-1000 °C using a multianvil apparatus to clarify phase transitions of pyroxene-garnet assemblages in the mantle. Both of glass and crystalline starting materials were used for the experiments. At 1000 °C, garnet solid solution (s.s.) transforms to aluminous ilmenite s.s. at 20-26 GPa which is stable in the whole compositional range in the system. In Mg₄Si₄O₁₂-rich composition, ilmenite s.s. transforms to a single-phase aluminous perovskite s.s., while Mg₃Al₂Si₃O₁₂-rich ilmenite s.s. dissociates into perovskite s.s. and corundum s.s. These newly determined phase relations at 1000 °C supersede preliminary phase relations determined at about 900 °C in the previous study. The phase relations at 1000 °C are quite different from those reported previously at 1600 °C where garnet s.s. transforms directly to perovskite s.s. and ilmenite is stable only very close to Mg₄Si₄O₁₂. The stability field of Mg₃Al₂Si₃O₁₂ ilmenite was determined at 800-1000 °C and 25-27 GPa by reversed phase boundaries. In ilmenite s.s., the a-axis slightly increases but the c-axis and molar volume decrease substantially with increasing Al₂O₃ content. Enthalpies of ilmenite s.s. were measured by differential drop-solution calorimetry method using a high-temperature calorimeter. The excess enthalpy of mixing of ilmenite s.s. was almost zero within the errors. The measured enthalpies of garnet-ilmenite and ilmenite-perovskite transitions at 298 K were 105.2±10.4 and 168.6±8.2 kJ/mol, respectively, for Mg₄Si₄O₁₂, and 150.2±15.9 and 98.7±27.3 kJ/mol, respectively, for Mg₃Al₂Si₃O₁₂. Thermodynamic calculations using these data give rise to phase relations in the system Mg₄Si₄O₁₂-Mg₃Al₂Si₃O₁₂ at 1000 and 1600 °C that are generally consistent with those determined experimentally, and confirm that the single-phase field of ilmenite expands from Mg₄Si₄O₁₂ to Mg₃Al₂Si₃O₁₂ with decreasing temperature. The earlier mentioned phase relations in the simplified system as well as those in the Mg₂SiO₄-Fe₂SiO₄ system are applied to estimate mineral proportions in pyrolite as a function of depth along two different geotherms: one is a horizontally-averaged temperature distribution in a normal mantle, and the other being 600 °C lower than the former as a possible representative geotherm in subducting slabs. Based on the previously described estimated mineral proportions versus depth along the two geotherms, density and compressional and shear wave velocities are calculated as functions of depth, using available mineral physics data. Along a normal mantle geotherm, jumps of density and velocities at about 660 km corresponding to the post-spinel transition are followed by steep gradients due to the garnet-perovskite transition between 660 and 710 km. In contrast, along a low-temperature geotherm, the first steep gradients of density and velocities are due to the garnet-ilmenite transition between 610 and 690 km. This is followed by abrupt jumps at about 690 km for the post-spinel transition, and steep gradients between 700 and 740 km that correspond to the ilmenite-perovskite transition. In the latter profile along the low-temperature geotherm, density and velocity increases for garnet-ilmenite and ilmenite-perovskite transitions are similar in magnitude to those for the post-spinel transition. The likely presence of ilmenite in cooler regions of subducting slabs is suggested by the fact that the calculated velocity profiles along the low-temperature geotherm are compatible with recent seismic observations indicating three discontinuities or steep velocity gradients at around 600-750 km depth in the regions of subducting slabs.