The use of MRS in the determination of hydraulic transmissivity: The case of alluvial aquifers

Magnetic Resonance Sounding (MRS) is nowadays accepted as a new geophysical method that can be used for a reliable determination of the ground water content distribution in the top 150 m. A great effort has also been made in MRS development to deduce the hydraulic transmissivity, based on empiric relationships of the permeability with a factor F which is calculated with NMR parameters measured at laboratory scale. To use this relationship under field conditions a calibration coefficient C_T = T_pt / F has to be previously established, which demands the knowledge of the transmissivity T_pt evaluated in the pumping test. The transmissivity can then be calculated at any other site of the same aquifer using the relation T_mrs = C_TF. The C_T values reported suggest a certain relationship with the lithology, but with a great dispersion and contradictory results. MRS surveys carried out in alluvial aquifers in Spain have shown that the value of C_T evaluated at one site may not be valid at another place of the same aquifer, because of the great heterogeneity of this kind of geological environment. The demand of a pumping test at each site where a MRS is measured invalidates the method actually used for MRS transmissivity evaluation. More than 50 MRS have been used to propose a new methodology. The aquifers visited cover a great range of transmissivities (from 2 × 10^− 6 to 9 × 10^− 3 m²/s). The MRS signal amplitude varies between 20 and 1400 nV, the signal/noise ratio is in the range from 0.6 to 42, and the value of the decay time constant varies from 200 to 800 ms. It has been demonstrated that when the transmissivity increases, the value of F decreases, and C_T increases, except for certain groups of MRS taken at the same aquifer or part of one aquifer, for which F increases with T_pt, keeping C_T constant. A function C_T(F) of the type C_T = mF^− n has been obtained that allows the transmissivity evaluation without the need of T_pt. Considering that both values of transmissivity, T_pt and T_mrs, are subjected to deviations due to the experimental errors as well as due to evaluation errors, the prediction achieved by the proposed equation is rather good. To perform a better evaluation of the values of the coefficients m and n it is necessary to have a greater number of MR soundings of good quality and with a trustworthy inversion at locations where a really comparable and good performed pumping test is available, covering a sufficient range of transmissivities. Though the data we have used do not always fulfil these conditions, the result is promising. Once a trustable function is available, the forecast of the transmissivity using MRS will not need the existence of any pumping test in the area. The general extension of this methodology demands the availability of MRS taken at all kinds of geological and hydrogeological environments, which is impossible without the existence of a universal MRS data base.     

Characterization of aquifers in the Vientiane Basin,Laos, using Magnetic Resonance Sounding and Vertical Electrical Sounding

The aim of this study is to define and characterize water bearing geological formation and to test the possibility of using geophysical techniques to determine the hydrogeological parameters in three areas in the Vientiane basin, Laos. The investigated areas are part of the Khorat Plateau where halite is naturally occurring at depths as shallow as 50 m in the Thangon Formation. Magnetic Resonance Sounding (MRS) has been used in combination with Vertical Electrical Sounding (VES) in different geological environments. In total, 46 sites have been investigated and the MRS and VES recognized the stratigraphic unit N₂Q_1–3, consisting of alluvial unconsolidated sediments, as the main water bearing unit. The aquifer thickness varies usually between 10 and 40 m and the depth to the main aquifer range from 5 to 15 m. The free water content is here up to 30%, and the decay times vary between 100 and 400 ms, suggesting a mean pore size equivalent to fine sand to gravel. The resistivity is highly variable, but usually around 10–1500 Ω-m, except for some sites in areas 1 and 2, where the aquifer is of low resistivity, probably related to salt water. Hydraulic and storage-related parameters such as transmissivity, hydraulic column, have been estimated from the MRS. The MRS together with VES has been shown to be a useful and important tool for identifying and distinguishing freshwater from possible salt-affected water as well as the salt-related clay layer of the Thangon Formation. This clay layer is characterized by very low free water content and a resistivity lower than 5 Ω-m and can be found in all 3 areas at depths from 15 to 50 m.     

Importance of reversible attachment in predicting E. coli transport in saturated aquifers from column experiments

Drinking water wells indiscriminatingly placed adjacent to fecal contaminated surface water represents a significant but difficult to quantify health risk. Here we seek to understand mechanisms that limit the contamination extent by scaling up bacterial transport results from the laboratory to the field in a well constrained setting. Three pulses of Escherichia coli originating during the early monsoon from a freshly excavated pond receiving latrine effluent in Bangladesh were monitored in 6 wells and modeled with a two-dimensional (2-D) flow and transport model conditioned with measured hydraulic heads. The modeling was performed assuming three different modes of interaction of E. coli with aquifer sands: (1) irreversible attachment only (best-fit k_i = 7.6 day⁻¹); (2) reversible attachment only (k_a = 10.5 and k_d = 0.2 day⁻¹); and (3) a combination of reversible and irreversible modes of attachment (k_a = 60, k_d = 7.6, k_i = 5.2 day⁻¹). Only the third approach adequately reproduced the observed temporal and spatial distribution of E. coli, including a 4-log₁₀ lateral removal distance of ∼9 m. In saturated column experiments, carried out using aquifer sand from the field site, a combination of reversible and irreversible attachment was also required to reproduce the observed breakthrough curves and E. coli retention profiles within the laboratory columns. Applying the laboratory-measured kinetic parameters to the 2-D calibrated flow model of the field site underestimates the observed 4-log₁₀ lateral removal distance by less than a factor of two. This is promising for predicting field scale transport from laboratory experiments.     

Single-crystal elasticity of stishovite: New experimental data obtained using high-frequency resonant ultrasound spectroscopy and a Gingham check structure model

Single-crystal elasticity of stishovite was examined using a new experimental technique and an empirical macroscopic model. Employing high-frequency resonant ultrasound spectroscopy, single-crystal elastic constants of stishovite were determined: C₁₁ = 443(3), C₃₃ = 781(4), C₁₂ = 193(2), C₂₃ = 199(2), C₄₄ = 256(2), and C₃₃ = 316(2) GPa. The frequency range of the resonant ultrasound spectroscopy techniques was 6–20 MHz, which is much lower than the ～10 GHz range of the Brillouin scattering technique. Of the elastic constants, the shear elastic constants C₄₄ and C₆₆ are consistent with the average value of the previously mentioned Brillouin scattering. Conversely, the four elastic constants, C₁₁, C₃₃, C₁₂, and C₂₃, slightly deviate outside the range of previous Brillouin scattering results. The present results, except those for C₁₂, are consistent with recent lattice dynamic analysis of inelastic X-ray scattering data. The adiabatic bulk modulus was calculated as 298 GPa, which is smaller and more consistent with the result of compression experiments than any other Brillouin scattering results (301–312 GPa). The present result shows greater P-wave velocity anisotropy (24.7%) than any preceding work. To understand the unique elastic properties of stishovite, the Gingham check model was proposed and examined. The result shows that the octahedron of 6-coordinated Si in stishovite crystal has stiffness comparable to that of diamond.     

Short- and long-time behavior of aquifer drainage after slow and sudden recharge according to the linearized Laplace equation

During the last 25 years there has been a great interest in deriving aquifer characteristics from outflow data. This analysis has been mainly based of the drainage of a horizontal aquifer after sudden drawdown, using the Boussinesq approximation. Following the general approach of Brutsaert and Lopez [Brutsaert W, Lopez, JP. Basin-scale geohydrologic drought flow features of riparian aquifers in the southern Great Plains. Water Resour Res 1998;34(2):233–40], it was determined that for this geometry the aquifer behavior could be characterized by dQ/dt ∝ Q³ for small t and by dQ/dt ∝ Q^3/2 for large t. It was remarked that dQ/dt ∝ Q for large t is often observed. In practice, it is also difficult to determine if dQ/dt ∝ Q³ for small t because this behavior can only be observed over a very short period.Here, we present a similar analysis of aquifer behavior based on the more fundamental Laplace solution for penetrated aquifers. It has been shown that also when the drain does not fully penetrate the aquifer, the solution still produces good results [Szilagyi, J. Sensitivity analysis of aquifer parameter estimations based on the Laplace equation with linearized boundary conditions. Water Resour Res 2003;39(6)]. The Laplace solution quickly shows that dQ/dt ∝ Q for t → ∞ and dQ/dt ∝ Q^∞ for t → 0, after sudden drawdown. This analysis reconfirms previous findings concerning long-time behavior. More importantly, the analysis shows that the exponent B in dQ/dt ∝ Q^B does not have a fixed limited value for short times for the given geometry. Further analysis, however, shows that under certain conditions the relation dQ/dt ∝ Q³ is retained for 0 ≪ t < 1. Detailed examination of the Laplace solution also shows under which types of recharge dynamics a well-identifiable transition takes place between short- and long-term behavior. As long as such a clear transition exists, the aquifer characterization method proposed earlier by Brutsaert and Lopez [Brutsaert W, Lopez, JP. Basin-scale geohydrologic drought flow features of riparian aquifers in the southern Great Plains. Water Resour Res 1998;34(2):233–40] can be applied. It is shown that for a sharp pulse input, the Laplace solution gives similar results as presented by Brutsaert and Lopez [Brutsaert W, Lopez, JP. Basin-scale geohydrologic drought flow features of riparian aquifers in the southern Great Plains. Water Resour Res 1998;34(2):233–40]. For a smooth pulse, the transition becomes unclear. What is “smooth” and “sharp” depends on input and aquifer characteristics, whereby shallow aquifers give clearer transitions than deep aquifers for the same input. The analysis shows that when rain ceases suddenly after the aquifer has come into equilibrium with a steady rain input, a usable transition in the relation between dQ/dt and Q can be found as well. Researchers can use the present analysis to assess whether specific aquifers and recharge events can be used for the previously suggested characterization method.     

Carbon remineralization in the Amazon–Guianas tropical mobile mudbelt: A sedimentary incinerator

The Amazon River spawns a vast mobile mudbelt extending ∼1600 km from the equator to the Orinoco delta. Deposits along the Amazon–Guianas coastline are characterized by some of the highest C_org remineralization rates reported for estuarine, deltaic, or shelf deposits, however, paradoxically, except where stabilized by mangroves or intertidal algal mats, they are usually suboxic and nonsulfidic. A combination of tides, wind-driven waves, and coastal currents forms massive fluid muds and mobile surface sediment layers ∼0.5–2 m thick which are dynamically refluxed and frequently reoxidized. Overall, the seabed functions as a periodically mixed batch reactor, efficiently remineralizing organic matter in a gigantic sedimentary incinerator of global importance. Amazon River material entering the head of this dynamic dispersal system carries an initial terrestrial sedimentary C_org loading of ∼ 0.7 mg C m⁻² particle surface area. Total C_org loading is lowered to ∼ 0.2 mg C m⁻² in the proximal delta topset, ∼60–70% of which remains of terrestrial origin. Loading decreases further to 0.12–0.14 mg C m⁻² (∼60% terrestrial) in mudbanks ∼600 km downdrift along French Guiana, values comparable to those found in the oligotrophic deepsea. DOC/ΣCO₂ ratios in pore waters of French Guiana mudbanks indicate that >90% of metabolized organic substrates are completely oxidized. Within the Amazon delta topset at the head of the dispersal system, both terrestrial and marine organic matter contribute substantially to early diagenetic remineralization, although reactive marine substrate dominates (∼60–70%). The conditional rate constant for terrestrial C_org in the delta topset is ∼0.2 a⁻¹. As sedimentary C_org is depleted during transit, marine sources become virtually the exclusive substrate for remineralization except very near the mangrove shoreline. The δ¹³C and Δ¹⁴C values of pore water ΣCO₂ in mudbanks demonstrate that the primary source of remineralized organic matter within ∼1 km of shore is a small quantity of bomb signature marine plankton (+80‰). Thus, fresh marine organic material is constantly entrained into mobile deposits and increasingly drives early diagenetic reactions along the transit path. Relatively refractory terrestrial C_org is lost more slowly but steadily during sedimentary refluxing and suboxic diagenesis. Amazon Fan deposits formed during low sea level stand largely bypassed this suboxic sedimentary incinerator and stored material with up to ∼3X the modern high stand inner shelf C_org load (Keil et al., 1997b. Proceedings of the Ocean Drilling Program, Scientific Results. Vol. 155. pp. 531–537). Sedimentary dynamics, including frequency and magnitude of remobilization, and the nature of dispersal systems are clearly key controls on diagenetic processes, biogeochemical cycling, and global C storage along the continental margins.     

The oxidation state of sulfur in magmatic fluids

Sulfur compounds in volcanic gases are responsible for the global cooling after explosive eruptions and they probably controlled the early evolution of the Earth's atmosphere. We have therefore studied the oxidation state of sulfur in aqueous fluids under the pressure and temperature conditions and oxygen fugacities typical for magma chambers (0.5–3 kbar, 650–950 °C, Ni–NiO to Re–ReO₂ buffer conditions). Sulfur speciation was determined by Raman spectroscopy of quenched fluids trapped as inclusions in quartz. Our results show that sulfur in hydrothermal fluids and volcanic gases is much more oxidized than previously thought and in particular, some explosive eruptions may release a significant fraction of sulfur as SO₃ or its hydrated forms. In the pressure range from 500 to 2000 bar, the equilibrium constant K₁ of the reaction 2H₂S + 3O₂ = 2SO₂ + 2H₂O in aqueous fluids can be described by lnK₁ = ?(57.1 ± 7.1) + (173,480 ± 7592)T^? 1, where T is temperature in Kelvin. The equilibrium constant K₂ for the reaction SO₂ + ½O₂ = SO₃ in aqueous fluids, where SO₃ may include hydrated forms, such as H₂SO₄, was found to be strongly pressure dependent, with lnK₂ = ?(5.2 ± 5.7) + (19,243 ± 5993)T^? 1 at 1500 bar; lnK₂ = ?(11.1 ± 1.3) + (25,383 ± 1371)T^? 1 at 2000 bar and lnK₂ = ?(22.1 ± 2.2) + (37,082 ± 2248)T^? 1 at 2500 bar. Our data imply that volcanoes may directly inject hexavalent sulfur in the form of H₂SO₄ into the atmosphere, not only on Earth, but possibly also on Venus and on Mars, when it was still tectonically active. Remote measurements from satellites may have underestimated the sulfur yield of some recent eruptions. Moreover, the mechanisms of the interaction of volcanic gases with the stratosphere need to be reconsidered.     

Tolerance of Brazilian brain coral Mussismilia braziliensis to sediment and organic matter inputs

In Brazil, where reefs occur in markedly turbid environments, the relationship between sedimentation/organic matter and corals is poorly known. Thus, the ex situ effects of sediment with and without organic matter over the ΔF/Fm and physical state of Mussismilia braziliensis were analyzed. The ΔF/Fm and coral physical state, evaluated through the susceptibility index to sedimentation (SI), were measured in seven colonies exposed to sedimentation (0–450 mg cm⁻² day⁻¹) free of organic matter after 45 days of exposure, and in 12 colonies exposed to sedimentation (0–500 mg cm⁻² day⁻¹) with organic matter content (10%), in which case ΔF/Fm was measured after 72 h and SI after 120 h. In both cases there were effects of increasing sedimentation on the SI with no effect on ΔF/Fm. Despite the tolerance to high sedimentation rates shown by this coral, we noted that the presence of organic matter might reduce its tolerance to sedimentation stress.     

Optical signatures of dissolved organic matter in the watershed of a globally large river (Yangtze River,China)

Parallel factor analysis of fluorescence excitation emission matrices of surface water samples of a globally large river (Yangtze River, China) watershed identified three classes of fluorescent dissolved organic matter (FDOM) that had ex/em = 280/330 nm, 305/385 nm and 350/450 nm respectively, resembling “peak T”, “peak M” and “peak C” commonly identified in natural water, respectively. Peak T (a tyrosine/tryptophan-like FDOM) did not show correlations to peak M or C which were humic-like substances, while a positive correlation (r = 0.935, p < 0.001) was present between the natural log-transformed maximum fluorescence intensity (F_max) of peaks T and M indicating a tight link during their production and processing. F_max values (in Raman unit nm^?1) normalized to dissolved organic carbon (DOC) concentration were low, varying in ranges 15.93–85.95, 29.83–83.54 and 19.73–51.05 × 10^?5 nm^?1 (μmol/L)^?1 for peaks T, M and C, respectively, in line with the history of strong photobleaching of the water samples as indicated by fairly high absorption spectral slope ratios (0.75–1.53 with a mean 1.03). Intermediate fluorescence index (FI) (1.46–1.83 with a mean 1.61) and small specific absorption at 254 nm (0.64–1.93 with a mean 1.15 m^?1 mg^?1 L) of the water samples, indicated the presence of both aquatic microbial DOM (e.g. peak T) and soil DOM (e.g. peak C). Peak C could be substantially removed by UV-A (320–400 nm) irradiation, while peak M was slightly increased when a microbe-containing water was exposed to the same UV-A irradiation. Taken together, peak C was attributed to diffuse soil source while peak M was likely attributed to joint effects of microbial activities and solar irradiation on the chromophores in the sample.     

Thermal equation of state of magnesiowüstite (Mg0.6Fe0.4)O

Volume measurements for magnesiowüstite (Mg_0.6Fe_0.4)O, were carried out up to pressures of 10.1 GPa in the temperature range 300–1273 K, using energy-dispersive synchrotron X-ray diffraction. These data allow reliable determination of the temperature dependence of the bulk modulus and good constraint on the thermal expansitivity at ambient pressure which was previously not known for magnesiowüstite. From these data, thermal and elastic parameters were derived from various approaches based on the Birch–Murnaghan equation of state (EOS) and on the relevant thermodynamic relations. The results from three different equations of state are remarkably consistent. With (∂K_T/∂P)_T fixed at 4, we obtained K₀=158(2) GPa, (∂K_T/∂T)_P=−0.029(3) GPa K⁻¹, (∂K_T/∂T)_V=−3.9(±2.3)×10⁻³ GPa K⁻¹, and α_T=3.45(18)×10⁻⁵+1.14(28)×10⁻⁸T. The K₀, (∂K_T/∂T)_P, and (∂K_T/∂T)_V values are in agreement with those of Fei et al. (1992) and are similar to previously determined values for MgO. The zero pressure thermal expansitivity of (Mg_0.6Fe_0.4)O is found to be similar to that for MgO (Suzuki, 1975). These results indicate that, for the compositional range x=0–0.4 in (Mg_1−xFe_x)O, the thermal and elastic properties of magnesiowüstite exhibit a dependence on the iron content that is negligibly small, within uncertainties of the experiments. They are consequently insensitive to the Fe–Mg partitioning between (Mg, Fe)SiO₃ perovskite and magnesiowüstite when applied to compositional models of the lower mantle. With the assumption that (Mg_0.6Fe_0.4)O is a Debye-like solid, a modified equation of heat capacity at constant pressure is proposed and thermodynamic properties of geophysically importance are calculated and tabulated at high temperatures.     

Spatial distribution and ecology of the Recent Ostracoda from Tangra Yumco and adjacent waters on the southern Tibetan Plateau: A key to palaeoenvironmental reconstruction

We elucidate the ecology of Recent Ostracoda from a deep brackish lake, Tangra Yumco (30°45′—31°22′N and 86°23′—86°49′E, 4595 m a.s.l.) and adjacent waters on the southern Tibetan Plateau. Ostracod associations (living and empty valves) in sixty-six sediment samples collected from diverse aquatic habitats (lakes, estuary-like water and lagoon-like water waters, rivers, ponds and springs) were quantitatively assessed.Eleven Recent Ostracoda were found (nine living and two as empty valves only). Cluster analysis established two significant (p < 0.05) habitat specific associations; (i) Leucocytherella sinensis, Limnocythere inopinata, Leucocythere? dorsotuberosa, Fabaeformiscandona gyirongensis and Candona xizangensis are lacustrine fauna. (ii) Tonnacypris gyirongensis, Candona candida, Ilyocypris sp., Heterocypris incongruens and Heterocypris salina are temporary water species.Ostracod distribution and abundance are significantly (p < 0.05) correlated to physico-chemical variables. The first two axes of a canonical correspondence analysis (CCA) explain 30.9% of the variation in the species abundance data. Conductivity and habitat types are the most influential ecological factors explaining the presence and abundance of ostracods. Spearman correlation analysis reveals that: (i) Two species, L.? dorsotuberosa (r = 0.25) and L. inopinata (r = 0.36) have a significant positive correlation with conductivity while one species, T. gyirongensis (r = −0.68) displays a significant negative correlation with conductivity. Limnocythere inopinata correlates significantly positive (r = 0.37) with alkalinity. Fabaeformiscandona gyirongensis correlates significantly positive (r = 0.28) with water depth.Key indicator living assemblages are: (i) L. sinensis dominates Ca-depleted brackish waters although ubiquitously distributed; (ii) L.? dorsotuberosa dwells in fresh to brackish waters; (iii) L. inopinata predominates in mesohaline to polyhaline waters; (iv) F. gyirongensis inhabits exclusively brackish-lacustrine deeper waters; (v) C. candida populates freshwaters; (vi) T. gyirongensis and Ilyocypris sp. are restricted to shallow temporary waters; (vii) H. incongruens occurs in ponds.Water depth indicators are F. gyirongensis and L.? dorsotuberosa, useful in ostracod assemblages for palaeo-water depth reconstruction.Our results expand the knowledge of the ecological significance of Recent Tibetan Ostracoda ecology. This is a new insight on habitat chacteristics of both living assemblages and sub-Recent associations of ostracods in mountain aquatic ecosystems. The new modern ostracod dataset can be used for the quantitative reconstruction of past environmental variables (e.g., conductivity) and types of water environment. The key indicator ostracods are relevant in palaeolimnological and climate research on the Tibetan Plateau.     

Timescales of seawater intrusion and retreat

Quantifying the timescales associated with moving freshwater–seawater interfaces is critical for effective management of coastal groundwater resources. In this study, timescales of interface movement in response to both inland and coastal water level variations are investigated. We first assume that seawater intrusion (SWI) and retreat (SWR) are driven by an instantaneous freshwater-level variation at the inland boundary. Numerical modelling results reveal that logarithmic timescales of SWI (lnT_i) and SWR (lnT_r) can be described respectively by various simple linear equations. For example, SWI timescales are described by lnT_i = a + blnh′_f–s, where a and b are linear regression coefficients and h′_f–s is the boundary head difference after an instantaneous drop of inland freshwater head. For SWR cases with the same initial conditions, but with different increases in freshwater head, lnT_r = c + dΔX_T, where c and d are regression coefficients and ΔX_T is the distance of toe response that can be estimated by a steady-state, sharp-interface analytical solution. For SWR cases with the same freshwater head increase, but with different initial conditions, in contrast, lnT_r = e + flnΔX_T, where e and f are regression coefficients. The timescale of toe response caused by an instantaneous variation of sea level is almost equivalent to that induced by an instantaneous inland head variation with the same magnitude of water level change, but opposite in direction. Accordingly, the empirical equations of this study are also applicable for sea-level variations in head-controlled systems or for simultaneous variations of both inland and coastal water levels. Despite the idealised conceptual models adopted in this study, the results imply that for a particular coastal aquifer, SWI timescales are controlled by the boundary water levels after variations, whereas SWR timescales are dominated by the distance of toe response.     

High-precision 40Ar/39Ar age of the Jänisjärvi impact structure (Russia)

The ～ 14 km diameter Jänisjärvi impact structure is located in Svecofennian Proterozoic terrain in the southeastern part of the Baltic shield, Karelia, Russia. Previous radioisotopic dating attempts gave K/Ar and ⁴⁰Ar/³⁹Ar ages of 700 ± 5 Ma and 698 ± 22 Ma, respectively, with both results being difficult to interpret. Recent paleomagnetic results have challenged these ages and proposed instead ages of either 500 Ma or 850–900 Ma. In order to better constrain the age of the Jänisjärvi impact structure, we present new ⁴⁰Ar/³⁹Ar data for the Jänisjärvi impact melt rock. We obtained five concordant isochron ages that yield a combined isochron age of 682 ± 4 Ma (2σ) with a MSWD of 1.2, P = 0.14, and ⁴⁰Ar/³⁶Ar intercept of 475 ± 3. We suggest that this date indicates the age of the impact and therefore can be used in conjunction with existing paleomagnetic results to define the position of the Baltica paleocontinent at that time. Argon isotopic results imply that melt homogenization was achieved at the hundred-micrometer scale certainly, because of the low-silica content of the molten target rock that allows fast ⁴⁰Ar^? diffusion in the melt. However, the large range of F(⁴⁰Ar^?_inherited) (4.1% to 11.0%) observed for seven grains shows that complete isotopic homogenization was not reached at the centimeter and perhaps the millimeter scale. The F(⁴⁰Ar^?_inherited) results are also in good agreement with previous Rb and Sr isotopic data.     

Mercury emissions and stable isotopic compositions at Vulcano Island (Italy)

Sampling and analyses methods for determining the stable isotopic compositions of Hg in an active volcanic system were tested and optimized at the volcanic complex of Vulcano (Aeolian Islands, Italy). Condensed gaseous fumarole Hg_(fum)^T, plume gaseous elemental Hg_(g)⁰ and plume particulate Hg_(p)^II were obtained at fumaroles F0, F5, F11, and FA. The average total Hg emissions, based on Hg^T/SO₂ in condensed fumarolic gases and plumes, range from 2.5 to 10.1 kg y^? 1, in agreement with published values [Ferrara, R., Mazzolai, B., Lanzillotta, E., Nucaro, E., Pirrone, N., 2000. Volcanoes as emission sources of atmospheric mercury in the Mediterranean Basin. Sci. Total Environ. 259(1–3), 115–121; Aiuppa, A., Bagnato, E., Witt, M.L.I., Mather, T.A., Parello, F., Pyle, D.M., Martin, R.S., 2007. Real-time simultaneous detection of volcanic Hg and SO₂ at La Fossa Crater, Vulcano (Aeolian Islands, Sicily). Geophys. Res. Lett. 34(L21307).]. Plume Hg_(p)^II increases with distance from the fumarole vent, at the expense of Hg_(g)⁰ and indicates significant in-plume oxidation and condensation of fumarole Hg_(fum)^T.Relative to the NIST SRM 3133 Hg standard, the stable isotopic compositions of Hg are δ²⁰²Hg_(fum)^T = ? 0.74‰ ± 0.18 (2SD, n = 4) for condensed gaseous fumarole Hg_(fum)^T, δ²⁰²Hg_(g)⁰ = ? 1.74‰ ± 0.36 (2SD, n = 1) for plume gaseous elemental Hg_(g)⁰ at the F0 fumarole, and δ²⁰²Hg_(p)^II = ? 0.11‰ ± 0.18 (2SD, n = 4) for plume particulate Hg_(p)^II. The enrichment of Hg_(p)^II in the heavy isotopes and Hg_(g)⁰ in the light isotopes relative to the total condensed fumarolic Hg_(fum)^T gas complements the speciation data and demonstrates a gas-particle fractionation occurring after the gas expulsion in ambient T° atmosphere. A first order Rayleigh equilibrium condensation isotope fractionation model yields a fractionation factor α_cond-gas of 1.00135 ± 0.00058.     

The Himalayan foreland basin crust and upper mantle

Modeling of multimode surface wave group velocity dispersion data sampling the eastern and the western Ganga basins, reveals a three layer crust with an average V_s of 3.7 km s^?1, draped by ～2.5 km foreland sediments. The Moho is at a depth of 43 ± 2 km and 41 ± 2 km beneath the eastern and the western Ganga basins respectively. Crustal V_p/V_s shows a felsic upper and middle crust beneath the eastern Ganga basin (1.70) compared to a more mafic western Ganga basin crust (1.77). Due to higher radiogenic heat production in felsic than mafic rocks, a lateral thermal heterogeneity will be present in the foreland basin crust. This heterogeneity had been previously observed in the north Indian Shield immediately south of the foreland basin and must also continue northward below the Himalaya. The high heat producing felsic crust, underthrust below the Himalayas could be an important cause for melting of midcrustal rocks and emplacement of leucogranites. This is a plausible explanation for abundance of leucogranites in the east-central Himalaya compared to the west. The uppermost mantle V_s is also significantly lower beneath the eastern Ganga basin (4.30 km s^?1) compared to the west (4.44 km s^?1).     

Seasonal variability of primary production in a fjord ecosystem of the Chilean Patagonia: Implications for the transfer of carbon within pelagic food webs

We characterized the seasonal cycle of productivity in Reloncaví Fjord (41°30′S), Chilean Patagonia. Seasonal surveys that included measurements of gross primary production, community respiration, bacterioplankton secondary production, and sedimentation rates along the fjord were combined with continuous records of water-column temperature variability and wind forcing, as well as satellite-derived data on regional patterns of wind stress, sea surface temperatures, and surface chlorophyll concentrations. The hydrography and perhaps fjord productivity respond to the timing and intensity of wind forcing over a larger region. Seasonal changes in the direction and intensity of winds, along with a late-winter improvement in light conditions, may determine the timing of phytoplankton blooms and potentially modulate productivity cycles in the region.Depth-integrated gross primary production estimates were higher (0.4–3.8 g C m^?2 d^?1) in the productive season (October, February, and May), and lower (0.1–0.2 g C m^?2 d^?1) in the non-productive season (August). These seasonal changes were also reflected in community respiration and bacterioplankton production rates, which ranged, respectively, from 0.3 to 4.8 g C m^?2 d^?1 and 0.05 to 0.4 g C m^?2 d^?1 during the productive and non-productive seasons and from 0.05 to 0.6 g C m^?2 d^?1 and 0.05 to 0.2 g C m^?2 d^?1 during the same two periods. We found a strong, significant correlation between gross primary production and community respiration (Spearman, r=0.95; p<0.001; n=12), which suggests a high degree of coupling between the synthesis of organic matter and its usage by the planktonic community. Similarly, strong correlations were found between bacterioplankton secondary production and both gross primary production (Spearman, r=0.7, p<0.05, n=9) and community respiration (Spearman, r=0.8, p<0.05, n=9), indicating that bacterioplankton may be processing an important fraction (8–59%) of the organic matter produced by phytoplankton in Reloncaví Fjord. In winter, bacterial carbon utilization as a percentage of gross primary production was >100%, suggesting the use of allochthonous carbon sources by bacterioplankton when the levels of gross primary production are low. Low primary production rates were associated with a greater contribution of small cells to autotrophic biomass, highlighting the importance of small-sized plankton and bacteria for carbon cycling and fluxes during the less productive winter months. Fecal pellet sedimentation was minimal during this period, also suggesting that most of the locally produced organic carbon is recycled within the microbial loop. During the productive season, on the other hand, the area exhibited a great potential to export organic matter, be it to higher trophic levels or vertically towards the bottom.     

Magnesium isotopes constraints on the origin of Mg-rich olivines from the Allende chondrite: Nebular versus planetary?

High precision Mg isotope measurements by multi-collector ion microprobe show that refractory olivines from the Allende chondrite, either olivines isolated in the matrix (2 samples studied) or olivines in type I chondrules (6 samples studied), have variable δ²⁶Mg* enrichments and deficits (calculated in permil as the ²⁶Mg deviation from the instrumental mass fractionation line) relative to the Earth. Most average δ²⁶Mg* (noted δ²⁶Mg*_av) values (between 10 and 20 analyses per chondrule) are negative but the total range is from ?0.029 (± 0.010) ‰ (2 sigma errors) to + 0.011 (± 0.011) ‰ with an exception of one olivine at + 0.043 (± 0.023) ‰. These variations in δ²⁶Mg*_av reflect the formation of the olivines from reservoirs enriched in various amounts of ²⁶Mg by the decay of short-lived ²⁶Al (T_1/2 = 0.73 Ma). Similarly, 30 analyses of olivines from the Eagle Station pallasite show a δ²⁶Mg*_av value of ?0.033 ± 0.008‰, as negative as some olivines from Allende chondrules and the Solar system initial δ²⁶Mg* value of ?0.038 ± 0.004‰ (defined at the time of formation of type B Ca–Al-rich inclusions – CAIs – when ²⁶Al/²⁷Al = 5.23 × 10^?5, Jacobsen et al., 2008).Because olivines are Al-poor and because their Mg isotopic compositions are not reset during the chondrule forming events, their δ²⁶Mg*_av can be used to calculate model crystallization ages relative to various theoretical Mg isotope growth curves. The two end-member scenarios considered are (i) a “nebular” growth in which the Al/Mg ratio remains chondritic and (ii) a “planetary” growth in which a significant increase of the Al/Mg ratio can be due to, for instance, olivine magmatic fractionation. The low δ²⁶Mg*_av value of olivines from the Eagle Station pallasite demonstrate that metal-silicate differentiation occurred as early as ~ 0. 15_- 0. 23^+ 0. 29 Ma after CAIs in either of the growth scenarios. Similarly the variable δ²⁶Mg*_av values of refractory olivines can be understood if they were formed in planetesimals which started to differentiate as early as the Eagle Station parent body. Accretion of these planetesimals must have been coeval to the formation of CAIs and their disruption could explain why their fragments (Mg-rich olivines) were distributed in the chondrule forming regions of the disk.     

Latitudinal patterns of export production recorded in surface sediments of the Chilean Patagonian fjords (41–55°S) as a response to water column productivity

The Chilean Patagonian fjords region (41–56°S) is characterized by highly complex geomorphology and hydrographic conditions, and strong seasonal and latitudinal patterns in precipitation, freshwater discharge, glacier coverage, and light regime; all of these directly affect biological production in the water column. In this study, we compiled published and new information on water column properties (primary production, nutrients) and surface sediment characteristics (biogenic opal, organic carbon, molar C/N, bulk sedimentary δ¹³C_org) from the Chilean Patagonian fjords between 41°S and 55°S, describing herein the latitudinal pattern of water column productivity and its imprint in the underlying sediments. Based on information collected at 188 water column and 118 sediment sampling sites, we grouped the Chilean fjords into four main zones: Inner Sea of Chiloé (41° to ～44°S), Northern Patagonia (44° to ～47°S), Central Patagonia (48–51°S), and Southern Patagonia (Magellan Strait region between 52° and 55°S). Primary production in the Chilean Patagonian fjords was the highest in spring–summer, reflecting the seasonal pattern of water column productivity. A clear north–south latitudinal pattern in primary production was observed, with the highest average spring and summer estimates in the Inner Sea of Chiloé (2427 and 5860 mg C m^?2 d^?1) and Northern Patagonia (1667 and 2616 mg C m^?2 d^?1). This pattern was closely related to the higher availability of nutrients, greater solar radiation, and extended photoperiod during the productive season in these two zones. The lowest spring value was found in Caleta Tortel, Central Patagonia (91 mg C m^?2 d^?1), a site heavily influenced by glacier meltwater and river discharge loaded with glacial sediments. Biogenic opal, an important constituent of the Chilean fjord surface sediments (Si_OPAL ～1–13%), reproduced the general north–south pattern of primary production and was directly related to water column silicic acid concentrations. Surface sediments were also rich in organic carbon content and the highest values corresponded to locations far away from glacier influence, sites within fjords, and/or semi-enclosed and protected basins, reflecting both autochthonous (water column productivity) and allochthonous sources (contribution of terrestrial organic matter from fluvial input to the fjords). A gradient was observed from the more oceanic sites to the fjord heads (west–east) in terms of bulk sedimentary δ¹³C_org and C/N ratios; the more depleted (δ¹³C_org ?26‰) and higher C/N (23) values corresponded to areas close to rivers and glaciers. A comparison of the Chilean Patagonian fjords with other fjord systems in the world revealed high variability in primary production for all fjord systems as well as similar surface sediment geochemistry due to the mixing of marine and terrestrial organic carbon.     

Balancing the global oceanic neodymium budget: Evaluating the role of groundwater

The distinctly different, ε_Nd(0) values of the Atlantic, Indian, and Pacific Oceans requires that the residence time of Nd in the ocean (i.e., τ_Nd) be on the order of, or less than, the ocean mixing time of ∼ 500–1500 yr. However, estimates of τ_Nd, based on river influxes, range from 4000 to 15,000 yr, thus exceeding the ocean mixing time. In order to reconcile the oceanic Nd budget and lower the residence time by roughly a factor of 10, an additional, as yet unidentified, and hence “missing Nd flux” to the ocean is necessary. Dissolution of materials deposited on continental margins has previously been proposed as a source of the missing flux. In this contribution, submarine groundwater discharge (SGD) is examined as a possible source of the missing Nd flux. Neodymium concentrations (n = 730) and ε_Nd(0) values (n = 58) for groundwaters were obtained from the literature in order to establish representative groundwater values. Mean groundwater Nd concentrations and ε_Nd(0) values were used along with recent estimates of the terrestrial (freshwater) component of SGD (6% of river discharge on a global basis) to test whether groundwater discharge to the coastal oceans could account for the missing flux. Employing mean Nd concentrations of the compiled data base (i.e., 31.8 nmol/kg for all 730 analyses and 11.3 nmol/kg for 141 groundwater samples from a coastal aquifer), the global, terrestrial-derived SGD flux of Nd is estimated to range between 2.9 × 10⁷ and 8.1 × 10⁷ mol/yr. These estimates are of the same order of magnitude, and within a factor of 2, of the missing Nd flux (i.e., 5.4 × 10⁷ mol/yr). Applying the SGD Nd flux estimates, the global average ε_Nd(0) of SGD is predicted to be − 9.1, which is similar to our estimate for the missing Nd flux (− 9.2), and in agreement with the mean (± S.D.) ε_Nd(0) measured in groundwaters (i.e., ε_Nd(0) = −8.9 ± 4.2). The similarities in the estimated SGD Nd flux and corresponding ε_Nd(0) values to the magnitude and isotope composition of the missing Nd flux are compelling, and suggest that discharge of groundwater to the oceans could account for the missing Nd flux. Future investigations should focus on quantifying the Nd concentrations and isotope compositions of groundwater from coastal aquifers from a variety of coastal settings, as well as the important geochemical reactions that effect Nd concentrations in subterranean estuaries in order to better constrain contributions of SGD to the oceanic Nd budget.     

Elasticity of antigorite,seismic detection of serpentinites,and anisotropy in subduction zones

Serpentinization of the mantle wedge is an important process that influences the seismic and mechanical properties in subduction zones. Seismic detection of serpentines relies on the knowledge of elastic properties of serpentinites, which thus far has not been possible in the absence of single-crystal elastic properties of antigorite. The elastic constants of antigorite, the dominant serpentine at high-pressure in subduction zones, were measured using Brillouin spectroscopy under ambient conditions. In addition, antigorite lattice preferred orientations (LPO) were determined using an electron back-scattering diffraction (EBSD) technique. Isotropic aggregate velocities are significantly lower than those of peridotites to allow seismic detection of serpentinites from tomography. The isotropic V_P/V_S ratio is 1.76 in the Voigt–Reuss–Hill average, not very different from that of 1.73 in peridotite, but may vary between 1.70 and 1.86 between the Voigt and Reuss bonds. Antigorite and deformed serpentinites have a very high seismic anisotropy and remarkably low velocities along particular directions. V_P varies between 8.9 km s^? 1 and 5.6 km s^? 1 (46% anisotropy), and 8.3 km s^? 1 and 5.8 km s^? 1 (37%), and V_S between 5.1 km s^? 1 and 2.5 km s^? 1 (66%), and 4.7 km s^? 1 and 2.9 km s^? 1 (50%) for the single-crystal and aggregate, respectively. The V_P/V_S ratio and shear wave splitting also vary with orientation between 1.2 and 3.4, and 1.3 and 2.8 for the single-crystal and aggregate, respectively. Thus deformed serpentinites can present seismic velocities similar to peridotites for wave propagation parallel to the foliation or lower than crustal rocks for wave propagation perpendicular to the foliation. These properties can be used to detect serpentinite, quantify the amount of serpentinization, and to discuss relationships between seismic anisotropy and deformation in the mantle wedge. Regions of high V_P/V_S ratios and extremely low velocities in the mantle wedge of subduction zones (down to about 6 and 3 km.s^?1 for V_P and V_S, respectively) are difficult to explain without strong preferred orientation of serpentine. Local variations of anisotropy may result from kilometer-scale folding of serpentinites. Shear wave splittings up to 1–1.5 s can be explained with moderately thick (10–20 km) serpentinite bodies.