Spatial variability of N2O concentrations and of denitrification-related factors in the surficial groundwater of a catchment in Northern Germany

N₂O concentrations and denitrification-related factors (NO₃, SO₄, dissolved organic carbon (DOC) and CO₂) were investigated in the surface groundwater of a catchment in northern Germany, the Fuhrberger Feld Aquifer (FFA). We sampled 79 plots that were selected according to the three criteria of land use, historical land use conversion (1954–1995) and groundwater level. We sampled three sites within each plot. The sampling depth was 0.5 m below the groundwater surface.We found no indication for the occurrence of autotrophic denitrification in the surface groundwater. Heterotrophic denitrification was identified as the main process for N₂O accumulation. The variability of N₂O concentrations on the plot-scale was extremely high and was poorly explained by the three sampling criteria. Other denitrification-related variables such as NO₃, SO₄ and DOC were less variable. The selection criteria land use and groundwater level clearly influenced the order of magnitude of N₂O concentrations in the surface groundwater. Under arable land, high NO₃ concentrations resulted in high N₂O concentrations. The surface groundwater under forest and pasture was almost NO₃-free and had also very small N₂O concentrations. Plots where the distance from the soil surface to the groundwater surface was large (>1 m up to 3.4 m) showed higher N₂O concentrations in the surface groundwater than plots where the distance was small (<1 m). A larger distance from the soil surface to the groundwater leads to a longer residence time and more decomposition of DOC in the soil. Consequently the less bioavailable DOC could inhibit the efficiency of the heterotrophic denitrification in the groundwater, yielding more N₂O. Elevated organic carbon levels in plots with historic land use conversion (pasture to arable) were very stable and did not influence N₂O concentrations. The high within plot variability showed that an upscaling of N₂O from the plot-scale to the catchment-scale is possible as long as the groundwater level regime and the land use do not change.     

Assigning land use to supply wells for the statistical characterization of regional groundwater quality: Correlating urban land use and VOC occurrence

Many national and regional groundwater studies have correlated land use “near” a well, often using a 500 m radius circle, with water quality. However, the use of a 500 m circle may seem counterintuitive given that contributing areas are expected to extend up-gradient from wells, and not be circular in shape. The objective of this study was to evaluate if a 500 m circle is adequate for assigning land use to a well for the statistical correlation between urban land use and the occurrence of volatile organic compounds (VOCs). Land use and VOC data came from 277 supply wells in four study areas in California. Land use was computed using ten different-sized circles and wedges (250 m to 10 km in radius), and three different-sized “searchlights” (1–2 km in length). We define these shapes as contributing area surrogates (CASs), recognizing that a simple shape is at best a surrogate for the actual contributing area. The presence or absence of correlation between land use and the occurrence of VOCs was evaluated using Kendall’s tau (τ). Values of τ were within 10% of one another for wedges and circles ranging in size from 500 m to 2 km, with correlations remaining statistically significant (p < 0.05) for all CAS sizes and shapes, suggesting that a 500 m circular CAS is adequate for assigning land use to a well. Additional evaluation indicated that urban land use is autocorrelated at distances ranging from 8 to 36 km. Thus, urban land use in a 500 m CAS is likely to be predictive of urban land use in the actual contributing area.     

Geochemistry and isotopes of fluids from sulphur springs, Valles Caldera, New Mexico

Detailed geochemistry supported by geologic mapping has been used to investigate Sulphur Springs, an acid-sulfate hot spring system that issues from the western flank of the resurgent dome inside Valles Caldera. The most intense activity occurs at the intersection of faults offsetting caldera-fill deposits and post-caldera rhyolites. Three geothermal wells in the area have encountered pressures <1 MPa and temperatures of 200°C at depths of 600 to 1000 m. Hot spring and fumarole fluids may discharge at boiling temperatures with pH 1.0 and SO₄ 8000 mg/l. These conditions cause argillic alterations throughout a large area.Non-condensible gases consist of roughly 99% CO₂ with minor amounts of H₂S, H₂, and CH₄. Empirical gas geothermometry suggests a deep reservoir temperature of 215 to 280°C. Comparison of ¹³C and ¹⁸O between CaCO₃ from well cuttings and CO₂ from fumarole steam indicates a fractionation temperature between 200 and 300°C by decarbonation of hydrothermally altered Paleozoic limestone and vein calcite in the reservoir rocks. Tritium concentrations obtained from steam condensed in a mudpot and deep reservoir fluids (Baca #13, 278°C) are 2.1 and 1.0 T.U. respectively, suggesting the steam originates from a reservoir whose water is mostly >50 yrs old. Deuterium contents of fumarole steam, deep reservoir fluid, and local meteoric water are practically identical even though ¹⁸O contents range through 4‰, thus, precipitation on the resurgent dome of the caldera could recharge the hydrothermal system by slow percolation. From analysis of D and ¹⁸O values between fumarol steam and deep reservoir fluid, steam reaches the surface either (1) by vaporizing relatively shallow groundwater at 200°C or (2) by means of a two-stage boiling process through an intermediate level reservoir at roughly 200°C.Although many characteristics of known vapor-dominated geothermal systems are found at Sulphur Springs, fundamental differences exist in temperature and pressure of our postulated vapor-zone. We propose that the reservoir beneath Sulphur Springs is too small or too poorly confined to sustain a “true” vapor-dominated system and that the Sulphur Springs system may be a “dying” vapor-dominated system that has practically boiled itself dry.     

Infrared surveillance of crater lakes using satellite data

Under optimum circumstances, thermal infrared data recorded from satellites can measure water surface temperatures to accuracies of a few tenths of a degree Celsius. Such techniques are applied here to evaluate volcanic crater lake temperatures. At present, band 6 of the Landsat Thematic Mapper (TM) is the most pertinent sensor in this respect, although its nominal 120 × 120 m “footprint” only permits useful measurements of circular lakes exceeding 340 m in diameter. In addition, the radiative properties of the atmosphere between sensor and target at the instant of observation should be well-characterised in order to make confident measurements of surface temperatures with single-band infrared data.An analysis is presented of three TM band-6 images of the crater lake at Poás volcano, Costa Rica, recorded on February 6, 1986, March 13, 1987, and May 10, 1988. In the February 1986 scene, the band-6-derived water surface temperature is 36°C which is 3°C less than a field measurement made in the same month. Since the satellite measurement was integrated over some 14,400 m² of the lake surface, while the field measurement was obtained at a single point below the surface, the former may be more representative of surface heat losses. Subsequent TM data reveal an increasing discrepancy between contemporaneous field and satellite observations, probably because the lake diameter had decreased to 250 m by March 1987, and to less than 200 m by mid-1988, greatly reducing the likelihood of obtaining a pure “lake” pixel.The Advanced Spaceborne Thermal Emission and Reflection Radiometer (ASTER) which is earmarked for orbit on the first of NASA's Earth Observing System satellite platforms later this decade has five discrete spectral bands in the thermal infrared region and will produce data composed of 90 × 90 m pixels. These specifications could enable the determination of water surface temperatures of > 250 m diameter crater lakes by algorithms that implicitly account for atmospheric effects.     

Noble gas tracers for characterisation of flow dynamics and origin of groundwater: A case study in Switzerland

The Grenchen aquifer system in the Swiss Plateau was extensively investigated in order to determine the extent of groundwater contamination and to assess the natural attenuation capacity. Environmental tracer data were applied to estimate groundwater travel times, mixing ratios, and evaluate groundwater origin. Recharge is basically possible in two distinct topographical areas, the immediate vicinity of the town of Grenchen and the elevated plateau of the first Jura Mountain ridge. Groundwater dating was performed with the ³H/³He dating method and supplemented by ⁸⁵Kr measurements. Stable isotope data (δ¹⁸O, δ²H) and dissolved noble gas concentrations allow the determination of the recharge temperature, which is correlated to the recharge elevation. Noble gas temperatures (NGT) decrease in the direction of groundwater flow and range from 10 to 13 °C in the upstream area of the town to 7–9 °C in the downstream river plain. This trend could suggest the admixture of water from the underlying limestone aquifer recharged under cooler infiltration conditions, e.g. at higher recharge elevations. However, it is shown in this study that the difference in NGT does not require such a recharge. Rather, increasing air temperatures over the last 40 years and the urban heat island effect could possibly explain most of the observed temperature shift. Furthermore, it is concluded that the downstream river plain is hydrologically disconnected from the upstream town area. Consequently most water from the town area is drained by the creek Witibach and recharge in the river plain is higher than previously assumed.     

Chemical geothermometry and fluid–mineral equilibria for the Ömer–Gecek thermal waters, Afyon area, Turkey

Thermal waters of the Ömer–Gecek geothermal field, Turkey, with temperatures ranging from 32 to 92°C vary in chemical composition and TDS contents. They are generally enriched in Na–Cl–HCO₃ and suggest deep water circulation. Silica and cation geothermometers applied to the Ömer–Gecek thermal waters yield reservoir temperatures of 75–155°C. The enthalpy–chloride mixing model, which approximates a reservoir temperature of 125°C for the Ömer–Gecek field, accounts for the diversity in the chemical composition and temperature of the waters by a combination of processes including boiling and conductive cooling of deep thermal water and mixing of the deep thermal water with cold water. It is also determined that the solubility of silica in most of the waters is controlled by the chalcedony phase. Equilibrium states of the Ömer–Gecek thermal waters studied by means of the Na–K–Mg triangular diagram, Na–K–Mg–Ca diagram, K–Mg–Ca geoindicator diagram, activity diagrams in the systems composed of Na₂O–CaO–K₂O–Al₂O₃–SiO₂–CO₂–H₂O phases, log SI diagrams, and finally the alteration mineralogy indicate that most of the spring and low-temperature well waters in the area can be classified as shallow or mixed waters which are likely to be equilibrated with calcite, chalcedony and kaolinite at predicted temperature ranges similar to those calculated from the chemical geothermometers. It was also observed that mineral equilibrium in the Ömer–Gecek waters is largely controlled by CO₂ concentrations.     

Pre-eruptive and syn-eruptive conditions in the Black Butte, California dacite: Insight into crystallization kinetics in a silicic magma system

A series of experiments and petrographic analyses have been run to determine the pre-eruption phase equilibria and ascent dynamics of dacitic lavas composing Black Butte, a dome complex on the flank of Mount Shasta, California. Major and trace element analyses indicate that the Black Butte magma shared a common parent with contemporaneously erupted magmas at the Shasta summit. The Black Butte lava phenocryst phase assemblage (20 v.%) consists of amphibole, plagioclase (core An_77.5), and Fe–Ti oxides in a fine-grained (< 0.5 mm) groundmass of plagioclase, pyroxene, Fe–Ti oxides, amphibole, and cristobalite. The phenocryst assemblage and crystal compositions are reproduced experimentally between 890 °C and 910 °C, ≥ 300 MPa, X_H2O = 1, and oxygen fugacity = NNO + 1. This study has quantified the extent of three crystallization processes occurring in the Black Butte dacite that can be used to discern ascent processes. Magma ascent rate was quantified using the widths of amphibole breakdown rims in natural samples, using an experimental calibration of rim development in a similar magma at relevant conditions. The majority of rims are 34 ± 10 μm thick, suggesting a time-integrated magma ascent rate of 0.004–0.006 m/s among all four dome lobes. This is comparable to values for effusive samples from the 1980 Mount St. Helens eruption and slightly faster than those estimated at Montserrat. A gap between the compositions of plagioclase phenocryst cores and microlites suggests that while phenocryst growth was continuous throughout ascent, microlite formation did not occur until significantly into ascent. The duration of crystallization is estimated using the magma reservoir depth and ascent rate, as determined from phase equilibria and amphibole rim widths, respectively. Textural analysis of the natural plagioclase crystals yields maximum growth rates of plagioclase phenocryst rims and groundmass microlites of 8.7 × 10^− 8 and 2.5 × 10^− 8 mm/s, respectively. These rates are comparable to values determined from time-sequenced samples of dacite erupted effusively from Mount St. Helens during 1980 and indicate that syneruptive crystallization processes were important during the Black Butte eruptive cycle.     

Al–Mg and Pb–Pb systematics of Allende CAIs: Canonical solar initial Al/Al ratio reinstated

The precise knowledge of the initial ²⁶Al/²⁷Al ratio [(²⁶Al/²⁷Al)₀] is crucial if we are to use the very first solid objects formed in our Solar System, calcium–aluminum-rich inclusions (CAIs) as the “time zero” age-anchor and guide future work with other short-lived radio-chronometers in the early Solar System, as well as determining the inventory of heat budgets from radioactivities for early planetary differentiation. New high-precision multi-collector inductively-coupled plasma mass spectrometry (MC-ICP-MS) measurements of ²⁷Al/²⁴Mg ratios and Mg-isotopic compositions of nine whole-rock CAIs (six mineralogically characterized fragments and three micro-drilled inclusions) from the CV carbonaceous chondrite, Allende yield a well-defined ²⁶Al–²⁶Mg fossil isochron with an (²⁶Al/²⁷Al)₀ of (5.23 ± 0.13) × 10^− 5. Internal mineral isochrons obtained for three of these CAIs (A44A, AJEF, and A43) are consistent with the whole-rock CAI isochron. The mineral isochron of AJEF with (²⁶Al/²⁷Al)₀ = (4.96 ± 0.25) × 10^− 5, anchored to our precisely determined absolute ²⁰⁷Pb–²⁰⁶Pb age of 4567.60 ± 0.36 Ma for the same mineral separates, reinstate the “canonical” (²⁶Al/²⁷Al)₀ of 5 × 10^− 5 for the early Solar System. The uncertainty in (²⁶Al/²⁷Al)₀ corresponds to a maximum time span of ± 20 Ka (thousand years), suggesting that the Allende CAI formation events were culminated within this time span. Although all Allende CAIs studied experienced multistage formation history, including melting and evaporation in the solar nebula and post-crystallization alteration likely on the asteroidal parent body, the ²⁶Al–²⁶Mg and U–Pb-isotopic systematics of the mineral separates and bulk CAIs behaved largely as closed-system since their formation. Our data do not support the “supra-canonical” ²⁶Al/²⁷Al ratio of individual minerals or their mixtures in CV CAIs, suggesting that the supra-canonical ²⁶Al/²⁷Al ratio in the CV CAIs may have resulted from post-crystallization inter-mineral redistribution of Mg isotopes within an individual inclusion. This redistribution must be volumetrically minor in order to satisfy the mass balance of the precisely defined bulk CAI and bulk mineral data obtained by MC-ICP-MS.The radiogenic ²⁰⁸Pb/²⁰⁶Pb ratio obtained as a by-product from the Pb–Pb age dating is used to estimate time-integrated ²³²Th/²³⁸U ratio (κ value) of CAIs. Limited κ variations among the minerals within a single CAI, contrasted by much larger variations among the bulk CAIs, suggest Th/U fractionation occurred prior to crystallization of igneous CAIs. If interpreted as primordial heterogeneity, the κ value can be used to calculate the mean age of the interstellar dust from which the CAIs condensed.     

The zonal E×B plasma drift effects on the low latitude ionosphere electron density at solar minimum near equinox

The F2-layer peak density, NmF2, and peak altitude, hmF2, which were observed by 12 ionospheric sounders during the 20 September 1964 geomagnetically quiet time period at solar minimum are compared with those calculated by the three-dimensional time-dependent theoretical model of the Earth's low and middle latitude ionosphere and plasmasphere. The modeled NmF2 are also compared with those measured during the geomagnetically quiet time periods of 12–15, 18–21, and 26 September 1964 to take into account observed day-to-day ionospheric variability. Major features of the data are reproduced by the model if the corrected HWM90 neutral wind is used. The changes in NmF2 due to the zonal E×B plasma drift are found to be less than 20% in the daytime low latitude ionosphere. The model, which does not take into account the zonal E×B plasma drift, underestimates night-time NmF2 up to the maximum factor of 2 at low geomagnetic latitudes. The night-time increase of NmF2 caused by the zonal E×B plasma drift is less pronounced at −20° and 20° geomagnetic latitudes in comparison with that between −10° and 10° geomagnetic latitude. The longitude dependence of the calculated night-time low latitude influence of the zonal E×B plasma drift on NmF2 is explained in terms of the longitudinal asymmetry in B (the eccentric magnetic dipole is displaced from the Earth's center and the Earth's eccentric tilted magnetic dipole moment is inclined with respect to the Earth's rotational axis), and the variations of the wind induced plasma drift and the meridional E×B plasma drift in geomagnetic longitude. The difference between the hmF2 values calculated by including the effect of zonal E×B drift and that obtained when it is excluded does not exceed 19 km in the low latitude ionosphere. Over the geomagnetic equator the zonal E×B plasma drift produces the maximum increase in the electron density by a factor of 1.06–1.48 and 1.05–1.30 at 700 and 1000 km altitude, respectively, and this increase is not significant above about 1500 km. Changes in the vertical electron content, VEC, caused by the zonal E×B plasma do not exceed 16% during the day, while the value of the night-time VEC is increased up to a factor of 1.4 due to this drift. The maximum effects of the zonal E×B plasma drift on the night-time electron density derived from the model results corresponding to solar minimum and maximum are quite comparable.     

Thermal equation of state of magnesite to 32 GPa and 2073 K

Pressure–volume–temperature relations have been measured to 32 GPa and 2073 K for natural magnesite (Mg_0.975Fe_0.015Mn_0.006Ca_0.004CO₃) using synchrotron X-ray diffraction with a multianvil apparatus at the SPring-8 facility. A least-squares fit of the room-temperature compression data to a third-order Birch–Murnaghan equation of state (EOS) yielded K₀ = 97.1 ± 0.5 GPa and K′ = 5.44 ± 0.07, with fixed V₀ = 279.55 ± 0.02 Å³. Further analysis of the high-temperature compression data yielded the temperature derivative of the bulk modulus (∂K_T/∂T)_P = −0.013 ± 0.001 GPa/K and zero-pressure thermal expansion α = a₀ + a₁T with a₀ = 4.03 (7) × 10⁻⁵ K⁻¹ and a₁ = 0.49 (10) × 10⁻⁸ K⁻². The Anderson–Grüneisen parameter is estimated to be δ_T = 3.3. The analysis of axial compressibility and thermal expansivity indicates that the c-axis is over three times more compressible (K_Tc = 47 ± 1 GPa) than the a-axis (K_Tc = 157 ± 1 GPa), whereas the thermal expansion of the c-axis (a₀ = 6.8 (2) × 10⁻⁵ K⁻¹ and a₁ = 2.2 (4) × 10⁻⁸ K⁻²) is greater than that of the a-axis (a₀ = 2.7 (4) × 10⁻⁵ K⁻¹ and a₁ = −0.2 (2) × 10⁻⁸ K⁻²). The present thermal EOS enables us to accurately calculate the density of magnesite to the deep mantle conditions. Decarbonation of a subducting oceanic crust containing 2 wt.% magnesite would result in a 0.6% density reduction at 30 GPa and 1273 K. Using the new EOS parameters we performed thermodynamic calculations for magnesite decarbonation reactions at pressures to 20 GPa. We also estimated stability of magnesite-bearing assemblages in the lower mantle.     

Trace-element geochemistry of thermal water percolating through a karstic environment in the region of Saint Ghislain (Belgium)

Five geothermal waters from the Mons area (southern Belgium) have been studied: one natural hot spring at Stambruges, one stagnant warm water from the “inclined tunnels” at Baudour, and three thermal waters from the drillholes at St. Ghislain, Ghlin and Douvrain, originating from the carbonate/anhydrite-bearing Visean strata, at depths of ca. 2600, 1550 and 1300 m, respectively.Multielement chemical analysis of the filtered water and its suspended matter > 0.4 μm) was carried out by instrumental neutron activation.Temperature in depth, calculated using the silica (chalcedony) chemical geothermometer, ranged from 75 to 88°C, in good agreement with experimentally determined values. Na/K and Na/K/Ca geothermometers yieilded erratic results, as expected from the geological environment in the aquifer.From the analytical data it can be calculated that the thermal waters of St. Ghislain, Ghlin and Douvrain are not only saturated with respect to chalcedony, but also to anhydrite, calcite, fluorite, barite, strontianite, and possibly zinc silicate, iron (III) hydroxide or siderite, albite, microcline, gibbsite and kaolinite. They are oversaturated with respect to muscovite. Data are also presented for the other thermal waters, and a cold spring water (Claire Fontaine, Stambruges).The similar trace-element composition of the thermal waters can be explained by percolation of the water in the same distant recharge zone, from where it descends, becomes heated at depth and rises along collapse breccia, and locally (Baudour, Stambruges) along fissures. The uptake of higher amounts of Ca, Mg, Sr and sulfate in St. Ghislain and Ghlin, as compared to Douvrain and Baudour is correlated with the boundary between the “non-dissolved” and “dissolved” evaporitic zones. This boundary is situated between St. Ghislain and Douvrain, and is roughly parallel with the direction of the groundwater flow (WNW).     

Conservative behavior of arsenic and other oxyanion-forming trace elements in an oxic groundwater flow system

Groundwater samples were collected along a flow path in a shallow, fractured tuffaceous aquifer from the Oasis Valley–Beatty Wash region of southern Nevada, USA, and analyzed for a number of oxyanion-forming trace elements including arsenic (As), antimony (Sb), selenium (Se), molybdenum (Mo), and tungsten (W). In addition, ancillary geochemical parameters, including pH, major solute compositions, dissolved silica, dissolved oxygen, and iron and manganese concentrations were quantified in the groundwaters. Arsenic concentrations range from 70 nmol/kg up to 316 nmol/kg in groundwaters of the Oasis Valley–Beatty Wash flow system, and generally exhibit increasing concentrations with flow down-gradient along the flow path. Antimony, W, and to a lesser extent, Mo, exhibit similar increasing concentration trends with flow down-gradient in the aquifer, albeit, at lower concentrations levels (e.g., mean ± SD for Sb, W, and Mo are 2.3 ± 0.9 nmol/kg, 7.4 ± 3.7 nmol/kg, and 101 ± 19 nmol/kg, respectively). Selenium concentration, which range between 4 and 11 nmol/kg, generally decrease in groundwaters with flow down-gradients in the Oasis Valley–Beatty Wash groundwater flow systems. Inverse modeling of groundwater chemistry evolution from the lower reaches of the Oasis Valley flow path using PHREEQC indicate that the groundwater composition is consistent with mixing of nearly equal proportions of groundwater from upper reaches of Oasis Valley and Beatty Wash groundwater, along with dissolution of volcanic glass, potassium feldspar, and gypsum, followed by calcite precipitation, and formation of secondary zeolites (analcime), clay minerals (Ca-montmorillonite), and cristobalite. The geochemical modeling indicates that the concentrations of As and the other oxyanion-forming trace elements are controlled by dissolution of volcanic glass, water–rock interaction with mineralized zones within the aquifer (i.e., sulfide oxidation), desorption from aquifer surface sites, and mixing of Oasis Valley and Beatty Wash groundwaters.     

Seasonal variations in pCO2 and its controlling factors in surface seawater of the northern East China Sea

Surface partial pressure of CO₂ (pCO₂), temperature, salinity, nutrients, and chlorophyll a were measured in the East China Sea (ECS; 31°30′–34°00′N to 124°00′–127°30′E) in August 2003 (summer), May 2004 (spring), October 2004 (early fall), and November 2005 (fall). The warm and saline Tsushima Warm Current was observed in the eastern part of the survey area during four cruises, and relatively low salinity waters due to outflow from the Changjiang (Yangtze River) were observed over the western part of the survey area. Surface pCO₂ ranged from 236 to 445 μatm in spring and summer, and from 326 to 517 μatm in fall. Large pCO₂ (values >400 μatm) occurred in the western part of the study area in spring and fall, and in the eastern part in summer. A positive linear correlation existed between surface pCO₂ and temperature in the eastern part of the study area, where the Tsushima Warm Current dominates; this correlation suggests that temperature is the major factor controlling surface pCO₂ distribution in that area. In the western part of the study area, however, the main controlling factor is different and seasonally complex. There is large transport in this region of Changjiang Diluted Water in summer, causing low salinity and low pCO₂ values. The relationship between surface pCO₂ and water stability suggests that the amount of mixing and/or upwelling of CO₂-rich water might be the important process controlling surface pCO₂ levels during spring and fall in this shallow region. Sea–air CO₂ flux, based on the application of a Wanninkhof [1992. Relationship between wind speed and gas exchange over the ocean. Journal of Geophysical Research 97, 7373–7382] formula for gas transfer velocity and a set of monthly averaged satellite wind data, were −5.04±1.59, −2.52±1.81, 1.71±2.87, and 0.39±0.18 mmol m⁻² d⁻¹ in spring, summer, early fall, and fall, respectively, in the northern ECS. The ocean in this study area is therefore a carbon sink in spring and summer, but a weak source or in equilibrium with the atmosphere in fall. If the winter flux value is assumed to have been the mean of autumnal and vernal values, then the northern ECS absorbs about 0.013 Pg C annually. That result suggests that the northern ECS is a net sink for atmospheric CO₂, a result consistent with previous studies.     

Groundwater monitoring at the watershed scale: An evaluation of recharge and nonpoint source pollutant loading in the Clear Creek Watershed,Iowa

Determining the groundwater contribution of nonpoint source pollution at a watershed scale is a challenging issue. In this study, we utilized a top‐down approach to characterize representative groundwater response units (GRUs) based on land use and landscape position (e.g., upland, sideslope, or floodplain) in the 275‐km² Clear Creek Watershed, Iowa. Groundwater monitoring wells were then established along downslope transects in representative GRUs. This unique combination of top‐down/bottom‐up approaches allowed us to estimate groundwater pollutant loads at the watershed scale with minimal monitoring. For the 2015 study period, results indicated that more groundwater recharge occurred in the floodplain (404 mm) compared to the uplands or sideslopes (281 and 165 mm, respectively), irrespective of land use. Recharge in the floodplains consisted of 37% of the annual precipitation, whereas upland wells averaged 26% and sideslopes averaged 15% of the annual precipitation. Less recharge was found to occur beneath perennial grass compared to row crop and urbanized areas. Baseflow discharge accounted for 69% of the total NO₃‐N exported from the Clear Creek Watershed, with row crop areas contributing approximately 95% of the annual load. Orthophosphorus (OP) yields were approximately 0.72 kg/ha beneath urban and suburban areas, three times higher than those in row crop or perennial areas. Urban and suburban areas accounted for 21.4% of groundwater orthophosphorus and chloride loads in the watershed compared to only 8.5% of the land area. Overall, the groundwater load allocation model for baseflow nutrient discharge to Clear Creek can be used to target future nonpoint source load reduction strategies at the watershed scale. The use of GRUs can pinpoint better areas of concern for controlling nutrient loads.     

Reassembling the Paleogene–Eocene North Atlantic igneous province: New paleomagnetic constraints from the Isle of Mull, Scotland

The paleomagnetic data sets from the British Tertiary Igneous Province (BTIP) have recently been criticized as being unreliable and discordant with data from elsewhere in the North Atlantic Igneous Province (NAIP) [Riisager et al. Earth Planet. Sci. Lett. 201 (2002) 261–276; Riisager et al. Earth Planet. Sci. Lett. 214 (2003) 409–425]. We offer new paleomagnetic data for the extensive lava flow sequence on the Isle of Mull, Scotland, and can confirm the paleomagnetic pole positions emanating from important earlier studies. Our new north paleomagnetic pole position for Eurasia at 59 ± 0.2 Ma has latitude 73.3°N, longitude 166.2°E (dp/dm = 5.2/7.0).A re-evaluation and an inter-comparison of the paleomagnetic database emanating from the NAIP were carried out to test for sub-province consistency. We find a general agreement between the Eurasian part of NAIP (BTIP and Faeroes) and East Greenland data. However a compilation of West Greenland data displays a large and unexplained dispersion. We speculate on if this is related to different sense of block rotation of the Tertiary West Greenland constituents. Combining all data from the NAIP constituents, give a pole position at 75.0°N, 169.9°E (N = 25, K = 84.3, A₉₅ = 3.2) in Eurasian reference frame.     

Quantitative analysis of the driving factors for groundwater resource changes in arid irrigated areas

How to quantify the impact of climate change and human activities on groundwater is not only a hot topic of current research but also a key point of water resource management in arid irrigated areas. Therefore, this paper analyzes the changes in the trends of land use, climate, and groundwater extraction in the Yanqi Basin in recent years and uses the distributed hydrological model MIKE-SHE to quantitatively analyze the impacts of these three factors on groundwater resources. The results show that: 1. The Nash coefficients of the simulated and observed groundwater levels during the verification period are 0.84, 0.79 and 0.76; the correlation coefficient between the simulated and observed soil moisture is 0.86. Although there are some uncertainties in the simulation, the results prove that the model can be used to simulate arid irrigated areas. 2. The effects of these three factors on groundwater levels are 5, 12.5 and 82.5%, respectively, and have caused the regional average groundwater level to decrease by a maximum of 0.07, 0.23 and 1.79 m, respectively. The effects of these three factors on the interactions between surface water and groundwater were 7.04, 3.63 and 89.33%. Groundwater extraction has become the main influencing factor of regional groundwater resources changes due to its more direct influence. 3. The influence of groundwater extraction has a strong spatial distribution characteristic and 10% of the study area has been greatly impacted by the groundwater extraction. Base on the above results, integrating multidisciplinary knowledge to establish the relationship between ecological environment and groundwater changes can provide strategies for the sustainable development of groundwater.     

Understanding changes in the water budget driven by climate change in cryospheric‐dominated watershed of the northeast Tibetan Plateau,China

Glacial retreat and the thawing of permafrost due to climate warming have altered the hydrological cycle in cryospheric‐dominated watersheds. In this study, we analysed the impacts of climate change on the water budget for the upstream of the Shule River Basin on the northeast Tibetan Plateau. The results showed that temperature and precipitation increased significantly during 1957–2010 in the study area. The hydrological cycle in the study area has intensified and accelerated under recent climate change. The average increasing rate of discharge in the upstream of the Shule River Basin was 7.9 × 10⁶ m³/year during 1957–2010. As the mean annual glacier mass balance lost ?62.4 mm/year, the impact of glacier discharge on river flow has increased, especially after the 2000s. The contribution of glacier melt to discharge was approximately 187.99 × 10⁸ m³ or 33.4% of the total discharge over the study period. The results suggested that the impact of warming overcome the effect of precipitation increase on run‐off increase during the study period. The evapotranspiration (ET) increased during 1957–2010 with a rate of 13.4 mm/10 years. On the basis of water balance and the Gravity Recovery and Climate Experiment and the Global Land Data Assimilation System data, the total water storage change showed a decreasing trend, whereas groundwater increased dramatically after 2006. As permafrost has degraded under climate warming, surface water can infiltrate deep into the ground, thus changing both the watershed storage and the mechanisms of discharge generation. Both the change in terrestrial water storage and changes in groundwater have had a strong control on surface discharge in the upstream of the Shule River Basin. Future trends in run‐off are forecasted based on climate scenarios. It is suggested that the impact of warming will overcome the effect of precipitation increase on run‐off in the study area. Further studies such as this will improve understanding of water balance in cold high‐elevation regions.     

Hydrothermal silica chimney fields in the Galapagos Spreading Center at 86°W

Silica chimneys were discovered in 1985 at 86°W in the rift valley of the Galapagos Spreading Center at 2600 m depth (“Cauliflower Garden”). The inactive chimneys lack any sulfides and consist almost entirely of amorphous silica (up to 96 wt.% SiO₂, opal-A); Fe and Mn oxides are minor constituents. Oxygen isotope data show that formation of the silica chimneys took place at temperatures between 32°C (+29.9‰ δ¹⁸O) and 42°C (+27.8‰ δ¹⁸O).Th/Udating reveals a maximum age of 1440 ± 300y. Amorphous silica solubility relations indicate that the silica chimneys were formed by conductive cooling of pure hydrothermal fluids or by conductive cooling of a fluid/seawater mixture. Assuming equilibrium with quartz at 500 bars, initial fluid temperatures of more than 175°C (i.e., a concentration of > 182 ppm SiO₂) were required to achieve sufficient supersaturation for the deposition of amorphous silica at 40°C and 260 bars. If the silica chimneys originate from the same or a similar fluid as higher-temperature ( < 300°C) sulfide-silica precipitates found nearby (i.e., 2.5 km away), then subsurface deposition of sulfides may have occurred.     

Hydrothermal vent waters at 13°N on the East Pacific Rise: isotopic composition and gas concentration

Gas concentrations and isotopic compositions of water have been measured in hydrothermal waters from 13°N on the East Pacific Rise. In the most Mg-depleted samples ( 5 × 10⁻³ moles/kg) the gas concentrations are: 3–4.5 × 10⁻⁵ cm³ STP/kg helium, 0.62–1.24 cm³ STP/kg CH₄, 10.80–16.71 × 10⁻³ moles/kg CO₂. The samples contain large quantities (95–126 cm³/kg) of H₂ and some carbon monoxide (0.26–0.36 cm³/kg) which result from reaction with the titanium sampling bottles. δ¹³C in methane and CO₂ (−16.6 to −19.5 and −4.1 to −5.5 respectively) indicate temperatures between 475 and 550°C, whereas δ¹³C_CO is compatible with formation by reduction of CO₂ on Ti at 350°C close to the sampling temperature.³He/⁴He are very homogeneous at (7.5 ± 0.1)R_A(³He/⁴He = 1.0 × 10⁻⁵) and very similar to already published data as well as CH₄/³He ratios between 1.4 and 2.1 × 10⁶.¹⁸O and D in water show enrichments from 0.39 to 0.69‰ and from 0.62 to 1.49‰ respectively. These values correspond to W/R ratios of 0.4–7. The distinct¹⁸O enrichments indicate that the isotopic composition of the oceans is not completely buffered by the hydrothermal circulations. The³He-enthalpy relationship is discussed in terms of both hydrothermal heat flux and³He mantle flux.