Sulfur speciation in natural hydrothermal waters, Iceland

The speciation of aqueous dissolved sulfur was determined in hydrothermal waters in Iceland. The waters sampled included hot springs, acid-sulfate pools and mud pots, sub-boiling well discharges and two-phase wells. The water temperatures ranged from 4 to 210 °C, the pH_T was between 2.20 and 9.30 at the discharge temperature and the SO₄ and Cl concentrations were 0.020-52.7 and <0.01-10.0 mmol kg⁻¹, respectively. The analyses were carried out on-site within ∼10 min of sampling using ion chromatography (IC) for sulfate (SO₄²⁻), thiosulfate (S₂O₃²⁻) and polythionates (S_xO₆²⁻) and titration and/or colorimetry for total dissolved sulfide (S²⁻). Sulfite (SO₃²⁻) could also be determined in a few cases using IC. Alternatively, for few samples in remote locations the sulfur oxyanions were stabilized on a resin on site following elution and analysis by IC in the laboratory. Dissolved sulfate and with few exceptions also S²⁻ were detected in all samples with concentrations of 0.02-52.7 mmol kg⁻¹ and <1-4100 μmol kg⁻¹, respectively. Thiosulfate was detected in 49 samples of the 73 analyzed with concentrations in the range of <1-394 μmol kg⁻¹ (S-equivalents). Sulfite was detected in few samples with concentrations in the range of <1-3 μmol kg⁻¹. Thiosulfate and SO₃²⁻ were not detected in <100 °C well waters and S₂O₃²⁻ was observed only at low concentrations (<1-8 μmol kg⁻¹) in ∼200 °C well waters. In alkaline and neutral pH hot springs, S₂O₃²⁻ was present in significant concentrations sometimes corresponding to up to 23% of total dissolved sulfur (S_TOT). In steam-heated acid-sulfate waters, S₂O₃²⁻ was not a significant sulfur species. The results demonstrate that S₂O₃²⁻ and SO₃²⁻ do not occur in the deeper parts of <150 °C hydrothermal systems and only in trace concentrations in ∼200-300 °C systems. Upon ascent to the surface and mixing with oxygenated ground and surface waters and/or dissolution of atmospheric O₂, S²⁻ is degassed and oxidized to SO₃²⁻ and S₂O₃²⁻ and eventually to SO₄²⁻ at pH >8. In near-neutral hydrothermal waters the oxidation of S²⁻ and the interaction of S²⁻ and S⁰ resulting in the formation of S_x²⁻ are considered important. At lower pH values the reactions seemed to proceed relatively rapidly to SO₄²⁻ and the sulfur chemistry of acid-sulfate pools was dominated by SO₄²⁻, which corresponded to >99% of S_TOT. The results suggest that the aqueous speciation of sulfur in natural hydrothermal waters is dynamic and both kinetically and source-controlled and cannot be estimated from thermodynamic speciation calculations.     

Sodium and potassium coprecipitation in aragonite

The coprecipitation of Na and K was experimentally investigated in aragonite. The distribution functions were determined at pH 6.8 and 8.8 over aqueous Na and K concentrations of between 5 × 10^?4and 2.0 M and temperatures of between 25 and 75°C.The mole fractions of Na and K in aragonite are related to the aqueous ratios of Na and Ca by a function of the form

$\text{log}\text{X}{}_{\mathrm{Na}}{}_2\text{CO}{}_3\text{,K}{}_2\text{CO}{}_3\text{= C}{}_0\text{+ C}{}_1\text{log}\text{a}{}^2{}_{\mathrm{Na}}\text{? ,K}{}^{\mathrm{?}}\text{a}{}_{\mathrm{Ca}}{}^{\mathrm{2+}}$

where C₀ and C₁ are constants at a given temperature. This equation was derived by a statistical model assuming a heterogeneous energy distribution for the sites of incorporation. The independence of the coprecipitation process from aqueous anion activities suggests that carbonate is the only anionic species in the solid solution.     

Polymetamorphism in the NE Shackleton Range, Antarctica: Constraints from Petrology and U-Pb, Sm-Nd, Rb-Sr TIMS and in situ U-Pb LA-PIMMS Dating

Metapelitic rock samples from the NE Shackleton Range, Antarctica,include garnet with contrasting zonation patterns and two agespectra. Garnet porphyroblasts in K-rich kyanite–sillimanite–staurolite–garnet–muscovite–biotite schistsfrom Lord Nunatak show prograde growth zonation, and give Sm–Ndgarnet, U–Pb monazite and Rb–Sr muscovite ages of518 ± 5, 514 ± 1 and 499 ± 12 Ma, respectively.Geothermobarometry and P–T pseudo-section calculationsin the model system CaO–Na₂O–K₂O– TiO₂–MnO–FeO–MgO–Al₂O₃–SiO₂–H₂Oare consistent with garnet growth during prograde heating from540°C/7 kbar to 650°C/7·5 kbar, and partial resorptionduring a subsequent P–T decrease to <650°C at <6kbar. All data indicate that rocks from Lord Nunatak were affectedby a single orogenic cycle. In contrast, garnet porphyroblastsin K-poor kyanite–sillimanite– staurolite–garnet–cordierite–biotite-schistsfrom Meade Nunatak show two growth stages and diffusion-controlledzonation. Two distinct age groups were obtained. Laser ablationplasma ionization multicollector mass spectrometry in situ analysesof monazite, completely enclosed by a first garnet generation,yield ages of c. 1700 Ma, whereas monazite grains in open garnetfractures and in most matrix domains give c. 500 Ma. Both agegroups are also obtained by U–Pb thermal ionization massspectrometry analyses of matrix monazite and zircon, which fallon a discordia with lower and upper intercepts at 502 ±1 and 1686 ± 2 Ma, respectively. Sm–Nd garnet datingyields an age of 1571 ± 40 Ma and Rb–Sr biotiteanalyses give an age of 504 ± 1 Ma. Integrated geochronologicaland petrological data provide evidence that rocks from MeadeNunatak underwent a polymetamorphic Barrovian-type metamorphism:(1) garnet 1 growth and subsequent diffusive garnet annealingbetween 1700 and 1570 Ma; (2) garnet 2 growth during the RossOrogeny at c. 500 Ma. During the final orogenic event the rocksexperienced peak P–T conditions of about 650°C/7·0kbar and a retrograde stage at c. 575°C/4·0 kbar. KEY WORDS: garnet microtexture; P–T pseudosection; geochronology; polymetamorphism; Shackleton Range; Antarctica     

Atmospheric mercury near Salmon Falls Creek Reservoir in southern Idaho

Gaseous elemental mercury (GEM) and reactive gaseous mercury (RGM) were measured over 2-week seasonal field campaigns near Salmon Falls Creek Reservoir in south-central Idaho from the summer of 2005 through the fall of 2006 and over the entire summer of 2006 using automated Tekran Hg analyzers. GEM, RGM, and particulate Hg (HgP) were also measured at a secondary site 90 km to the west in southwestern Idaho during the summer of 2006. The study was performed to characterize Hg air concentrations in the southern Idaho area for the first time, estimate Hg dry deposition rates, and investigate the source of observed elevated concentrations. High seasonal variability was observed with the highest GEM (1.91 ± 0.9 ng m⁻³) and RGM (8.1 ± 5.6 pg m⁻³) concentrations occurring in the summer and lower values in the winter (1.32 ± 0.3 ng m⁻³, 3.2 ± 2.9 pg m⁻³ for GEM, RGM, respectively). The summer-average HgP concentrations were generally below detection limit (0.6 ± 1 pg m⁻³). Seasonally averaged deposition velocities calculated using a resistance model were 0.034 ± 0.032, 0.043 ± 0.040, 0.00084 ± 0.0017 and 0.00036 ± 0.0011 cm s⁻¹ for GEM (spring, summer, fall and winter, respectively) and 0.50 ± 0.39, 0.40 ± 0.31, 0.51 ± 0.43 and 0.76 ± 0.57 cm s⁻¹ for RGM. The total annual RGM + GEM dry deposition estimate was calculated to be 11.9 ± 3.3 μg m⁻², or about 2/3 of the total (wet + dry) deposition estimate for the area. Periodic elevated short-term GEM (2.2–12 ng m⁻³) and RGM (50–150 pg m⁻³) events were observed primarily during the warm seasons. Back-trajectory modeling and PSCF analysis indicate predominant source directions to the SE (western Utah, northeastern Nevada) and SW (north-central Nevada) with fewer inputs from the NW (southeastern Oregon and southwestern Idaho).     

Carbonate equilibria in hydrothermal systems: First ionization of carbonic acid in NaCl media to 300°C

The ionization quotients of aqueous carbon dioxide (carbonic acid) have been precisely determined in NaCl media to 5 m and from 50° to 300°C using potentiometric apparatus previously developed at Oak Ridge National Laboratory. The pressure coefficient was also determined to 250°C in the same media. These results have been combined with selected information in the literature and modeled in two ways to arrive at the best fits and to derive the thermodynamic parameters for the ionization reaction, including the equilibrium constant, activity coefficient quotients, and pressure coefficients. The variation with temperature of the two fundamental quantities $\text{Δ}\text{V}\text{?}{}^{\mathrm{o}}$ and $\text{Δ}\text{C}\text{?}{}^{\mathrm{o}}{}_{\mathrm{p}}$ were examined along the saturation vapor pressure curve and at constant density. The results demonstrated again that for reactions with minimal electrostriction changes the magnitudes and variations of $\text{Δ}\text{C}\text{?}{}^{\mathrm{o}}{}_{\mathrm{p}}$ and $\text{Δ}\text{V}\text{?}{}^{\mathrm{o}}$ with temperature are small and, in addition, $\text{Δ}\text{C}\text{?}{}_{\mathrm{p}}$ and $\text{Δ}\text{V}\text{?}$ are approximately independent of salt concentration.The results have also been applied to an examination of the solubility of calcite as a function of pH (in a given NaCl medium) for the neutral to acidic region both for systems with fixed CO₂ pressure and systems where the calcium ion concentration equals the concentration of carbon. The pH of saturated solutions of calcite with P_CO2 of 12 bars increases from 5.1 to 5.5 between 100° and 300°C.     

Evolution and REE geochemistry of Huangsha-Tieshanlong ore-bearing granite

Our studies show that the granite bodies (γ ₅ ^{2 − 1} and γ ₅ ³ ) which constitute the Huangsha-Tieshanlong composite granitic intrusion in Jiangxi are characterized by their similarities in mineral assemblage, petrochemistry, trace element and REE distribution pattern. The values of ΣREE, ΣLREE, ΣHREE, ΣCe/ΣY, δEu and La/Yb apparently decrease from γ ₅ ^{2 − 1a} to γ ₅ ^{2 − 1b} , γ ₅ ³ and γ ₅ ³ . It is shown that the early Yenshanian W(Ta, Nb)-bearing granite (γ ₅ ^{2 − 1} ) and late Yenshanian Ta, Nb-bearing granite (γ ₅ ³ ) may have been derived from the differentiation and evolution of granitic magmas due to repeated remelting of the crust and their earlier and later intrusion. Although the earlier (γ ₅ ^{2 − 1b} and later (γ ₅ ³ ) albitized Ta, Nb-bearing granites show some obvious differences in REE content, their δEu values and La/Yb ratios are similar to each other. Therefore, it may be concluded that the early and late Ta, Nb-bearing granites were derived from a congenetic magma.     

Adsorption of NO, SO2 and light hydrocarbons on activated Greek brown coals

Twenty-eight samples of peat, peaty lignites and lignites (of both matrix and xylite-rich lithotypes) and subbituminous coals have been physically activated by pyrolysis. The results show that the surface area of the activated coal samples increases substantially and the higher the carbon content of the samples the higher the surface area.The adsorption capacity of the activated coals for NO, SO₂, C₃H₆ and a mixture of light hydrocarbons (CH₄, C₂H₆, C₃H₈ and C₄H₁₀) at various temperatures was measured on selected samples. The result shows a positive correlation between the surface area and the gas adsorption. In contrast, the gas adsorption is inversely correlated with the temperature. The maximum recorded adsorption values are: NO = 8.22 × 10^− 5 mol/g at 35 °C; SO₂ = 38.65 × 10^− 5 mol/g at 60 °C; C₃H₆ = 38.9 × 10^− 5 mol/g at 35 °C; and light hydrocarbons = 19.24 × 10^− 5 mol/g at 35 °C. Adsorption of C₃H₆ cannot be correlated with either NO or SO₂. However, there is a significant positive correlation between NO and SO₂ adsorptions. The long chain hydrocarbons are preferentially adsorbed on activated lignites as compared to the short chain hydrocarbons.The results also suggest a positive correlation between surface area and the content of telohuminite maceral sub-group above the level of 45%.     

Molecular biomarker evidence of origins and transport of organic matter in sediments of the Pearl River estuary and adjacent South China Sea

Surface sediments from the subtropical Pearl River estuary and adjacent South China Sea were investigated by molecular organic geochemical methods to determine the composition, distribution and origin of extractable lipids (n-alkanes, n-alkanols and sterols). The absolute and organic C normalized concentrations of total alkane, n-alkanol, and sterol ranged from 0.16 to 2.67 μg g⁻¹ and 0.9 to 12.3 μg g⁻¹ OC, 24.4 to 427.3 ng g⁻¹ and 63.2 to 1966.7 ng g⁻¹ OC, and 9.0 to 493.5 ng g⁻¹ and 58.4 to 1042.4 ng g⁻¹ OC, respectively. The spatial distributions of these biomarkers indicated that terrestrial-derived molecular biomarkers such as long-chain n-alkanes, n-alkanols and plant-derived sterols were higher at the river mouth and along the coastline, suggesting that a higher proportion of terrestrial particulate organic matter was deposited there. Relatively lower amounts of marine-derived biomarkers such as short-chain n-alkanes, algal sterols at the river mouth reflected the lower primary productivity due to high turbidity. The spatial patterns of these biomarkers were partially related to the estuarine processes and conditions, evidencing an increased terrestrial signal from the Pearl River mouth to the inner estuary, and enhanced marine conditions further offshore.     

Calculated Phase Relations in the System NCKFMASH (Na2O-CaO-K2O-FeO-MgO-Al2O3-SiO2-H2O) for High-Pressure Metapelites

Petrogenetic grids in the system NCKFMASH (Na₂O–CaO–K₂O–FeO–MgO–Al₂O₃–SiO₂–H₂O)and the subsystems NCKMASH and NCKFASH calculated with the softwareTHERMOCALC 3.1 are presented for the P–T range 7–30kbar and 450–680°C, for assemblages involving garnet,chloritoid, biotite, carpholite, talc, chlorite, kyanite, staurolite,paragonite, glaucophane, jadeite, omphacite, diopsidic pyroxene,plagioclase, zoisite and lawsonite, with phengite, quartz/coesiteand H₂O in excess. These grids, together with calculated compatibilitydiagrams and P–T and T–X_Ca and P–X_Ca pseudosectionsfor different bulk-rock compositions, show that incorporationof Ca into the NKFMASH system leads to many of the NKFMASH invariantequilibria moving to lower pressure and/or lower temperature,which results, in most cases, in the stability of jadeite andgarnet being enlarged, but in the reduction of stability ofglaucophane, plagioclase and AFM phases. The effect of Ca onthe stability of paragonite is dependent on mineral assemblageat different P–T conditions. The calculated NCKFMASH diagramsare powerful in delineating the phase equilibria and P–Tconditions of natural pelitic assemblages. Moreover, contoursof the calculated phengite Si isopleths in P–T and P–X_Capseudosections confirm that phengite barometry in NCKFMASH isstrongly dependent on mineral assemblage. KEY WORDS: phase relations; metapelites; NCKFMASH; THERMOCALC; phengite geobarometry     

The Partitioning of Tungsten bwtween Aqueous Fluids and Silicate Melts

An experimental study has been carried out to determine the partition coefficients of tungsten between aqueous fluids and granitic melts at 800 °C and 1.5 kb with natural granite as the starting material. The effects of the solutions on the partition coefficients of tungsten show a sequence of P > CO ₃ ²⁻ > B > H₂O. The effects are limited (generallyK _D < 0.3) and the tungsten shows a preferential trend toward the melt over the aqueous fluid. The value ofK _D increases with increasing concentration of phosphorus; theK _D increases first and then reduces with the concentration of CO ₃ ²⁻ when temperature decreases, theK _D between the solution of CO ₃ ²⁻ and the silicate melt increases, and that between the solution of B₄O ₇ ²⁻ and the silicate melt decreases. The partition coefficients of phosphorus and sodium between fluids and silicate melts have been calculated from the concentrations of the elements in the melts. TheK _D value for phosphorus is 0.38 and that for sodium is 0.56. Evidence shows that the elements tend to become richer and richer in the melts.     

Analysis of terrestrial naturally occurring radionuclides in soil samples from some areas of Sirsa district of Haryana,India using gamma ray spectrometry

The activity concentration and the gamma-absorbed dose rates of the terrestrial naturally occurring radionuclides (²³²Th, ²²⁶Ra and ⁴⁰K) were determined in soil samples collected from ten different locations of Sirsa district of Haryana, using HPGe detector based on high-resolution gamma spectrometry system. The range of activity concentrations of ²²⁶Ra, ²³²Th and ⁴⁰K in the soil samples from the studied areas varies from 19.18 Bq kg⁻¹ (Moriwala) to 40.31 Bq kg⁻¹ (Rori), 59.43 Bq kg⁻¹ (Pipli) to 89.54 Bq kg⁻¹ (Fatehpur) and 223.22 Bq kg⁻¹ (Moriwala) to 313.32 Bq kg⁻¹ (SamatKhera) with overall mean values of 27.94, 72.75 and 286.73 Bq kg⁻¹ respectively. The absorbed dose rate calculated from activity concentration of ²²⁶Ra, ²³²Th and ⁴⁰K ranges between 8.84 and 18.58, 37.02 and 55.78, and 9.24 and 12.97 nGy h⁻¹, respectively. The total absorbed dose in the study area ranges from 60.40 to 82.15 nGy h⁻¹ with an average value of 70.12 nGy h⁻¹. The calculated values of external hazard index (H _ex) for the soil samples of the study area range from 0.36 to 0.49 with an average value of 0.42.     

Respiration and Calcification of <Emphasis Type="Italic">Crassostrea gigas</Emphasis>: Contribution of an Intertidal Invasive Species to Coastal Ecosystem CO<Subscript>2</Subscript> Fluxes

Respiration and calcification rates of the Pacific oyster Crassostrea gigas were measured in a laboratory experiment in the air and underwater, accounting for seasonal variations and individual size, to estimate the effects of this exotic species on annual carbon budgets in the Bay of Brest, France. Respiration and calcification rates changed significantly with season and size. Mean underwater respiration rates, deducted from changes in dissolved inorganic carbon (DIC), were 11.4 μmol DIC g⁻¹ ash-free dry weight (AFDW) h⁻¹ (standard deviation (SD), 4.6) and 32.3 μmol DIC g⁻¹ AFDW h⁻¹ (SD 4.1) for adults (80–110 mm shell length) and juveniles (30–60 mm), respectively. The mean daily contribution of C. gigas underwater respiration (with 14 h per day of immersion on average) to DIC averaged over the Bay of Brest population was 7.0 mmol DIC m⁻² day⁻¹ (SD 8.1). Mean aerial CO₂ respiration rate, estimated using an infrared gas analyzer, was 0.7 μmol CO₂ g⁻¹ AFDW h⁻¹ (SD 0.1) for adults and 1.1 μmol CO₂ g⁻¹ AFDW h⁻¹ (SD 0.2) for juveniles, corresponding to a mean daily contribution of 0.4 mmol CO₂ m⁻² day⁻¹ (SD 0.50) averaged over the Bay of Brest population (with 10 h per day of emersion on average). Mean CaCO₃ uptake rates for adults and juveniles were 4.5 μmol CaCO₃ g⁻¹ AFDW h⁻¹ (SD 1.7) and 46.9 μmol CaCO₃ g⁻¹ AFDW h⁻¹ (SD 29.2), respectively. The mean daily contribution of net calcification in the Bay of Brest C. gigas population to CO₂ fluxes during immersion was estimated to be 2.5 mmol CO₂ m⁻² day⁻¹ (SD 2.9). Total carbon release by this C. gigas population was 39 g C m⁻² year⁻¹ and reached 334 g C m⁻² year⁻¹ for densely colonized areas with relative contributions by underwater respiration, net calcification, and aerial respiration of 71%, 25%, and 4%, respectively. These observations emphasize the substantial influence of this invasive species on the carbon cycle, including biogenic carbonate production, in coastal ecosystems.     

Hydrochemical characteristics and quality assessment of shallow groundwater in a coastal area of Southwest Bangladesh

In this study, the hydrochemical characteristics of shallow groundwater in a coastal region (Khulna) of southwest Bangladesh have been evaluated based on different indices for drinking and irrigation uses. Water samples were collected from 26 boreholes and analyzed for major cations and anions. Other physico-chemical parameters like pH, electrical conductivity (EC), and total dissolved solids were also measured. Most groundwater is slightly alkaline and largely varies in chemical composition, e.g. EC ranges from 962 to 9,370 μs/cm. The abundance of the major ions is as follows: Na⁺ > Ca²⁺ > Mg²⁺ > K⁺ = Cl⁻ > HCO₃ ⁻ > SO₄ ²⁻ > NO₃ ⁻. Interpretation of analytical data shows two major hydrochemical facies (Na⁺–K⁺–Cl⁻–SO₄ ²⁻ and Na⁺–K⁺–HCO₃ ⁻) in the study area. Salinity, total hardness, and sodium percentage (Na%) indicate that most of the groundwater samples are not suitable for irrigation as well as for domestic purposes and far from drinking water standard. Results suggest that the brackish nature in most of the groundwaters is due to the seawater influence and hydrogeochemical processes.     

Effect of plant life form on relationship between δD values of leaf wax n-alkanes and altitude along Mount Taibai, China

We present δD_wax values from different forms of plants and soils, and δD_sw values from soil water along the northern slope of Mount Taibai, China. The results show a highly negative linear correlation of the δD_wax values for soils with altitude (R² 0.74) and we observed the same correlation for δD_sw values of soil water with altitude (R² 0.68). The δD_wax of living plants behaves like the soil, but does not exhibit a significant linear correlation with altitude (R² 0.11). The δD_wax values of woody plants and grasses also show a similar trend with respect to altitude with significant and no linear correlation, respectively (R² 0.50 for woody plants and 0.17 for grass), which suggest that the “altitude effect” can not be well documented for the δD_wax values of living plants, which may be due to differences in plant type and/or evapotranspiration controlled by the plant microclimate. The ε_wax-sw values of woody plants, grasses and soil show minor fluctuations with altitude. However, the ε_wax-sw and δD_wax values of woody plants are roughly 51‰ and 50‰ more positive, respectively, than those of grasses, suggesting that an “altitude effect” could be documented in the δD_wax of woody plants and grasses, with each responding independently to changes in precipitation along the altitude transect. Additionally, the ε_wax-sw values of soil are relatively constant with altitude, suggesting that the altitudinal change in the proportions between woody plant and grass input to soils will likely change the relationship between the δD_wax values of soil n-alkanes and altitude.     

Molecular H2O in armenite, BaCa2Al6Si9O30·2H2O, and epididymite, Na2Be2Si6O15·H2O: Heat capacity, entropy and local-bonding behavior of confined H2O in microporous silicates

Armenite, ideal formula BaCa₂Al₆Si₉O₃₀·2H₂O, and its dehydrated analog BaCa₂Al₆Si₉O₃₀ and epididymite, ideal formula Na₂Be₂Si₆O₁₅·H₂O, and its dehydrated analog Na₂Be₂Si₆O₁₅ were studied by low-temperature relaxation calorimetry between 5 and 300 K to determine the heat capacity, C_p, behavior of their confined H₂O. Differential thermal analysis and thermogravimetry measurements, FTIR spectroscopy, electron microprobe analysis and powder Rietveld refinements were undertaken to characterize the phases and the local environment around the H₂O molecule.The determined structural formula for armenite is Ba_0.88(0.01)Ca_1.99(0.02)Na_0.04(0.01)Al_5.89(0.03)Si_9.12(0.02)O₃₀·2H₂O and for epididymite Na_1.88(0.03)K_0.05(0.004)Na_0.01(0.004)Be_2.02(0.008)Si_6.00(0.01)O₁₅·H₂O. The infrared (IR) spectra give information on the nature of the H₂O molecules in the natural phases via their H₂O stretching and bending vibrations, which in the case of epididymite only could be assigned. The powder X-ray diffraction data show that armenite and its dehydrated analog have similar structures, whereas in the case of epididymite there are structural differences between the natural and dehydrated phases. This is also reflected in the lattice IR mode behavior, as observed for the natural phases and the H₂O-free phases. The standard entropy at 298 K for armenite is S° = 795.7 ± 6.2 J/mol K and its dehydrated analog is S° = 737.0 ± 6.2 J/mol K. For epididymite S° = 425.7 ± 4.1 J/mol K was obtained and its dehydrated analog has S° = 372.5 ± 5.0 J/mol K. The heat capacity and entropy of dehydration at 298 K are Δ = 3.4 J/mol K and ΔS^rxn = 319.1 J/mol K and Δ = −14.3 J/mol K and ΔS^rxn = 135.7 J/mol K for armenite and epididymite, respectively. The H₂O molecules in both phases appear to be ordered. They are held in place via an ion-dipole interaction between the H₂O molecule and a Ca cation in the case of armenite and a Na cation in epididymite and through hydrogen-bonding between the H₂O molecule and oxygen atoms of the respective silicate frameworks. Of the three different H₂O phases ice, liquid water and steam, the C_p behavior of confined H₂O in both armenite and epididymite is most similar to that of ice, but there are differences between the two silicates and from the C_p behavior of ice. Hydrogen-bonding behavior and its relation to the entropy of confined H₂O at 298 K is analyzed for various microporous silicates.The entropy of confined H₂O at 298 K in various silicates increases approximately linearly with increasing average wavenumber of the OH-stretching vibrations. The interpretation is that decreased hydrogen-bonding strength between a H₂O molecule and the silicate framework, as well as weak ion-dipole interactions, results in increased entropy of H₂O. This results in increased amplitudes of external H₂O vibrations, especially translations of the molecule, and they contribute strongly to the entropy of confined H₂O at T < 298 K.     

Background concentrations of elements in surface soils and their changes as affected by agriculture use in the desert-oasis ecotone in the middle of Heihe River Basin,North-west China

The concentrations of twenty four chemical elements in the surface layer of natural desert soils and the cultivated farmland soils were measured at a desert-oasis ecotone in the middle of Heihe river basin, north-west China. Background values were estimated for (a) major elements (Si 335.3 g kg^− 1, Al 49.4 g kg^− 1, Fe 19.1 g kg^− 1, Ca 29.4 g kg^− 1, Mg 8.9 g kg^− 1, K 20.1 g kg^− 1, Na 17.5 g kg^− 1 and P 0.338 g kg^− 1), (b) heavy metals and non-metals (Cr 55.8 mg kg^− 1, Mn 404.8 mg kg^− 1, Ni 17.7 mg kg^− 1, Cu 5.1 mg kg^− 1, Zn 33.7 mg kg^− 1, Pb 15.5 mg kg^− 1 and As 5.2 mg kg^− 1) and (c) other trace elements (Ti 2.0 mg kg^− 1, V 55.3 mg kg^− 1, Co 5.7 mg kg^− 1, Rb 82.4 mg kg^− 1, Sr 232.9 mg kg^− 1, Y 14.7 mg kg^− 1, Zr 194.9 mg kg^− 1, Nb 7.8 mg kg^− 1 and Ba 720.6 mg kg^− 1). After natural desert soil was cultivated for agricultural use, significant changes in element concentrations occurred under tillage, irrigation and fertilisation management. Compared to natural soil, the for the levels of Si, K, Na, Sr, Zr and Ba decreased, and no changes were observed for Rb, while the values of the other 17 elements increase in agricultural soil from 1.2 to 3.5 times. However, their absolute concentrations are still low, suggesting that the arable soil in this region remains comparatively a clean soil. The increased silt, clay and organic carbon content, under long-term irrigation, enriched the fine-grained materials, and application of fertilisers and manure contributed to the accumulation of most elements in arable soil. The accumulation of elements in agricultural soil increased with increasing cultivation years and extent of soil development.     

Does reactive surface area depend on grain size? Results from pH 3, 25 °C far-from-equilibrium flow-through dissolution experiments on anorthite and biotite

Laboratory determined mineral weathering rates need to be normalised to allow their extrapolation to natural systems. The principle normalisation terms used in the literature are mass, and geometric- and BET specific surface area (SSA). The purpose of this study was to determine how dissolution rates normalised to these terms vary with grain size. Different size fractions of anorthite and biotite ranging from 180-150 to 20-10 μm were dissolved in pH 3, HCl at 25 °C in flow through reactors under far from equilibrium conditions. Steady state dissolution rates after 5376 h (anorthite) and 4992 h (biotite) were calculated from Si concentrations and were normalised to initial- and final- mass and geometric-, geometric edge- (biotite), and BET SSA. For anorthite, rates normalised to initial- and final-BET SSA ranged from 0.33 to 2.77 × 10⁻¹⁰ mol_feldspar m⁻² s⁻¹, rates normalised to initial- and final-geometric SSA ranged from 5.74 to 8.88 × 10⁻¹⁰ mol_feldspar m⁻² s⁻¹ and rates normalised to initial- and final-mass ranged from 0.11 to 1.65 mol_feldspar g⁻¹ s⁻¹. For biotite, rates normalised to initial- and final-BET SSA ranged from 1.02 to 2.03 × 10⁻¹² mol_biotite m⁻² s⁻¹, rates normalised to initial- and final-geometric SSA ranged from 3.26 to 16.21 × 10⁻¹² mol_biotite m⁻² s⁻¹, rates normalised to initial- and final-geometric edge SSA ranged from 59.46 to 111.32 × 10⁻¹² mol_biotite m⁻² s⁻¹ and rates normalised to initial- and final-mass ranged from 0.81 to 6.93 × 10⁻¹² mol_biotite g⁻¹ s⁻¹. For all normalising terms rates varied significantly (p ? 0.05) with grain size. The normalising terms which gave least variation in dissolution rate between grain sizes for anorthite were initial BET SSA and initial- and final-geometric SSA. This is consistent with: (1) dissolution being dominated by the slower dissolving but area dominant non-etched surfaces of the grains and, (2) the walls of etch pits and other dissolution features being relatively unreactive. These steady state normalised dissolution rates are likely to be constant with time. Normalisation to final BET SSA did not give constant ratios across grain size due to a non-uniform distribution of dissolution features. After dissolution coarser grains had a greater density of dissolution features with BET-measurable but unreactive wall surface area than the finer grains. The normalising term which gave the least variation in dissolution rates between grain sizes for biotite was initial BET SSA. Initial- and final-geometric edge SSA and final BET SSA gave the next least varied rates. The basal surfaces dissolved sufficiently rapidly to influence bulk dissolution rate and prevent geometric edge SSA normalised dissolution rates showing the least variation. Simple modelling indicated that biotite grain edges dissolved 71-132 times faster than basal surfaces. In this experiment, initial BET SSA best integrated the different areas and reactivities of the edge and basal surfaces of biotite. Steady state dissolution rates are likely to vary with time as dissolution alters the ratio of edge to basal surface area. Therefore they would be more properly termed pseudo-steady state rates, only appearing constant because the time period over which they were measured (1512 h) was less than the time period over which they would change significantly.     

Basaltic and Solution Reference Materials for Iron,Copper and Zinc Isotope Measurements

Iron, Cu and Zn stable isotope systems are applied in constraining a variety of geochemical and environmental processes. Secondary reference materials have been developed by the Institute of Geology, Chinese Academy of Geological Sciences (CAGS), in collaboration with other participating laboratories, comprising three solutions (CAGS‐Fe, CAGS‐Cu and CAGS‐Zn) and one basalt (CAGS‐Basalt). These materials exhibit sufficient homogeneity and stability for application in Fe, Cu and Zn isotopic ratio determinations. Reference values were determined by inter‐laboratory analytical comparisons involving up to eight participating laboratories employing MC‐ICP‐MS techniques, based on the unweighted means of submitted results. Isotopic compositions are reported in per mil notation, based on reference materials IRMM‐014 for Fe, NIST SRM 976 for Cu and IRMM‐3702 for Zn. Respective reference values of CAGS‐Fe, CAGS‐Cu and CAGS‐Zn solutions are as follows: δ⁵⁶Fe = 0.83 ± 0.07 and δ⁵⁷Fe = 1.20 ± 0.13, δ⁶⁵Cu = 0.57 ± 0.06, and δ⁶⁶Zn = ?0.79 ± 0.12 and δ⁶⁸Zn = ?1.65 ± 0.24, respectively. Those of CAGS‐Basalt are δ⁵⁶Fe = 0.15 ± 0.07, δ⁵⁷Fe = 0.22 ± 0.10, δ⁶⁵Cu = 0.12 ± 0.08, δ⁶⁶Zn = 0.17 ± 0.13, and δ⁶⁸Zn = 0.34 ± 0.26 (2s).     

Partitioning of Ru, Rh, Pd, Re, Ir, and Au between Cr-bearing spinel, olivine, pyroxene and silicate melts

A series of high temperature experiments was undertaken to study partitioning of several highly siderophile elements (HSE; Ru, Rh, Pd, Re, Os, Ir, Pt and Au) between Cr-rich spinel, olivine, pyroxene and silicate melt. Runs were carried out on a Hawaiian ankaramite, a synthetic eucrite basalt, and a DiAn eutectic melt, at one bar, 19 kbar, and 20 kbar, respectively, in the temperature range of 1200 to 1300°C, at oxygen fugacities between the nickel-nickel oxide (NNO) and hematite-magnetite (HM) oxygen buffers. High oxygen fugacities were used to suppress the formation of HSE-rich “nuggets” in the silicate melts. The resulting oxide and silicate crystals (<100 μm) were analyzed using both SIMS and LA-ICP-MS, with a spatial resolution of 15 to 50 μm. Rhenium, Au and Pd were all found to be incompatible in Cr-rich spinel (D_Re^sp/melt = 0.0012-0.21, D_Au^sp/melt = 0.076, D_Pd^sp/melt = 0.14), whereas Rh, Ru and Ir were all found to be highly compatible (D_Rh^sp/melt = 41-530, D_Ru^sp/melt = 76-1143, D_Ir^sp/melt = 5-22000). Rhenium, Pd, Au and Ru were all found to be incompatible in olivine (D_Re^oliv/melt = 0.017-0.073, D_Pd^oliv/melt = 0.12, D_Au^oliv/melt = 0.12, D_Ru^oliv/melt = 0.23), Re is incompatible in orthopyroxene and clinopyroxene (D_Re^opx/melt = 0.013, D_Re^cpx/melt = 0.18-0.21), and Pt is compatible in clinopyroxene (D_Pt^cpx/melt = 1.5). The results are compared to and combined with previous work on HSE partitioning among spinel-structured oxides, and applied to some natural magmatic suites to demonstrate consistency.     

Transport and Storage of Potassium in the Earths Upper Mantle and Transition Zone: an Experimental Study to 23 GPa in Simplified and Natural Bulk Compositions

We have investigated the stability and composition of potassiumamphibole and its high-pressure breakdown product phase X insynthetic peralkaline and subalkaline KNCMASH (K₂O–Na₂O–CaO–MgO–Al₂O₃–SiO₂–H₂O)and natural KLB-1 peridotite bulk compositions between 10 and23 GPa at 800–1800°C. In the KNCMASH system, potassiumamphibole reaches its upper pressure stability limit at 13–15GPa at