Compositional differences of chromophoric dissolved organic matter derived from phytoplankton and macrophytes

Chromophoric dissolved organic matter (CDOM) is an important component in the aquatic environment and plays a key role in light attenuation and in carbon biogeochemical cycles. We examined CDOM production in each of two laboratory experiments in which phytoplankton and macrophyte degradation were monitored using absorption and excitation–emission matrix fluorescence spectroscopy (EEMs). During the incubation period, CDOM was produced from phytoplankton and macrophytes, and partly decomposed by microorganisms. The absorption spectra of the phytoplankton derived and the macrophyte derived CDOM were distinct and characterized by peaks and shoulders in the UV bands. Production of CDOM absorption at 350 nm, a(350), was 0.0125 m²/g per unit of chlorophyll a from phytoplankton CDOM from 0–3 d. Meanwhile a(350) production was 2.708 × 10⁻⁴ m²/g per unit of wet biomass from macrophytes CDOM from 1–7 d. Despite the high production of CDOM by phytoplankton and macrophytes, extrapolation of these values to the field indicated that about 15% of total CDOM was produced from phytoplankton during algal blooms in Meiliang Bay in summer and about 8% of total CDOM was produced from macrophytes in the macrophyte dominated littorals. The mean value of the spectral slope (S) describing the exponential decrease of the absorption spectrum, which was strongly correlated to an optical index of molecular size, for the phytoplankton derived CDOM was 10.26 ± 2.05 μm⁻¹, which was significantly lower than the mean S of 14.47 ± 2.88 μm⁻¹ for the macrophyte derived CDOM (t-test, p < 0.001). The mean value of the spectral slope ratio (S_R) for the phytoplankton derived CDOM was 1.79 ± 0.52, which was significantly higher than that of 0.35 ± 0.58 for the macrophyte derived CDOM (t-test, p < 0.001). Three fluorescent components were validated in parallel factor analysis (PARAFAC) models calculated separately for phytoplankton derived and macrophyte derived CDOM, each CDOM source resulting in distinct excitation and emission maxima for each component. The significant differences in CDOM absorption spectra, S, S_R and PARAFAC fluorescence component characteristics, all showed that phytoplankton derived CDOM was compositionally distinct from macrophyte derived CDOM. Overall both sources were important to the CDOM pool in the shallow temperate lake.     

Rock interface strength influences fluid-filled fracture propagation pathways in the crust

Rock interface strengths have often been assumed to be zero in numerical and analogue models of fracture propagation and magma intrusion in the crust. Rock strength tests were performed to explore the role that rock interfaces have on the geometry and propagation dynamics of fluid-filled fractures in the crust. We used a 1 kN test machine to study 5 mm thick cuboidal specimens cut from a sandstone-siltstone rock core, where the strata were known to host magma intrusions and the rock interface between the units was intact. By measuring the load required to grow a crack running along the lithological contact between the layers we calculate its fracture toughness K_c. The siltstone had an average K_c of 0.56 ± 0.03 MPa m^1/2 compared to the sandstone at 0.42 ± 0.02 MPa m^1/2. The rock interface had intermediate average fracture toughness to the parent units at 0.45 ± 0.03 MPa m^1/2. These results have important implications on fracture propagation pathways through rocks, as well as for the geometry and propagation dynamics of magma intrusions in the crust.     

Assessment of carbonaceous aerosol over Delhi in the Indo-Gangetic Basin: characterization, sources and temporal variability

Semi-continuous measurements of organic carbon (OC) and elemental carbon (EC) and continuous measurements of black carbon (BC) and PM_2.5 aerosols were conducted simultaneously during the winter period of 2010–2011 at Delhi, one of the polluted urban megacities in western part of the Indo-Gangetic Basin region. The average mass concentrations of OC, EC, BC and PM_2.5 were about 54 ± 39, 10 ± 5, 12 ± 5 and 210 ± 146 μg m^?3, respectively. Contribution of total carbonaceous aerosol mass to PM_2.5 mass was found to be ~46 %. Average OC/EC ratio was found to be 5 ± 2 during the study period, suggesting the presence of secondary organic aerosols in the atmosphere over Delhi. Estimated mean secondary organic aerosol mass concentration was found to be 25 μg m^?3 and varied between 14.6 (February) and 37.0 μg m^?3 (December). A diurnal variation of OC and EC shows lower values during the day time and higher during the morning and night, which are highly associated with the corresponding variability in mixing layer heights. OC and EC were also found to be significantly correlated (r = 0.71) to each other, indicating their common sources. Concentrations of OC and EC were about 45 and 13 % higher during weekdays than weekends, respectively. Higher OC (67 %) and EC (53 %) were observed in the late evening during weekdays than those on weekends, which could be due to different emission sources during these two periods. The night/day ratio of EC and OC was found to be larger than 1.0, suggesting the relative accumulation of EC and OC near the surface at night hours.     

Interannual Variation in Photosynthetically Significant Optical Properties and Water Quality in a Coastal Blackwater River Plume

Surface water optical characteristics, nutrients, and planktonic chlorophyll a concentrations were analyzed in the Cape Fear River (CFR) plume over a 2-year period. CFR discharge during the dry year (109 ± 105 m³s⁻¹) was only 25% of the wet year discharge (429 ± 337 m³s⁻¹). Partitioning the contributions of phytoplankton pigments, non-pigmented particles, and colored dissolved organic matter (CDOM) to the absorption of photosynthetically active radiation (PAR) indicated that CDOM was the dominant contributor to PAR absorption. Particulate absorption was relatively greater during the dry year. Pigment absorption was minor and varied little among stations or between years. Chlorophyll a concentrations were reduced at the most plume-influenced stations during the wet year, despite lower turbidity and higher nitrate concentrations. Ammonium and orthophosphate concentrations were not different between years. CDOM absorption [a _CDOM (412)] ranged from 0.05 to 8.25 m⁻¹ with highest values occurring near the CFR mouth. Our results suggest that for coastal ecosystems with significant blackwater river inputs, CDOM may exert a major limiting influence over near-shore primary production.     

Benthic fluxes and the cycling of biogenic silica and carbon in two southern California borderland basins

Benthic fluxes in two southern California borderland basins have been estimated by modeling water column property gradients, by modeling pore water gradients and by measuring changes in concentration in a benthic chamber. Results have been used to compare the different methods, to establish budgets for biogenic silica and carbon and to estimate rate constants for models of CaCO₃ dissolution. In San Pedro Basin, a low oxygen, high sedimentation rate area, fluxes of radon-222 (86 ± 8 atoms m⁻² s⁻¹), SiO₂ (0.7 ± 0.1 mmol m⁻² d⁻¹), alkalinity (1.7 ± 0.3 meq m⁻² d⁻¹), TCO₂ (1.9 ± 0.3 mmol m⁻² d⁻¹) and nitrate (−0.8 ± 0.1 mmol m⁻² d⁻¹) measured in a benthic chamber agree within the measurement uncertainty with fluxes estimated from modeling profiles of nutrients and radon obtained in the water column. The diffusive fluxes of radon, SiO₂ and TCO₂ determined from modeling the sediment and pore water also agree with the other approaches. Approximately 33 ± 13% of the organic carbon and 37 ± 47% of the CaCO₃ arriving at the sea floor are recycled. In San Nicolas Basin, which has larger oxygen concentrations and lower sedimentation rates than San Pedro, the fluxes of radon (490 ± 16 atoms m⁻² s⁻¹), SiO₂ (0.7 ± 0.1 mmol m⁻² d⁻¹), alkalinity (1.7 ± 0.3 meq m⁻² d⁻¹), TCO₂ (1.7 ± 0.2 mmol m⁻² d⁻¹), oxygen (−0.7 ± 0.1 mmol m⁻² d⁻¹) and nitrate (-0.4 ± 0.1 mmol m⁻² d⁻¹) determined from chamber measurements agree with the water column estimates given the uncertainty of the measurements and model estimates. Diffusion from the sediments matches the lander-measured SiO₂ and PO₄³⁻ (0.017 ± 0.002 mmol m⁻² d⁻¹) fluxes, but is not sufficient to supply the radon or TCO₂ fluxes observed with the lander. In San Nicolas Basin 38 ± 9% of the organic carbon and 43 ± 22% of the CaCO₃ are recycled. Approximately 90% of the biogenic silica arriving at the sea floor in each basin is recycled. The rates of CaCO₃ dissolution determined from chamber flux measurements and material balances for protons and electrons are compared to those predicted by previously published models of CaCO₃ dissolution and this comparison indicates that in situ rates are comparable to those observed in laboratory studies of bulk sediments, but orders of magnitude less than those observed in experiments done with suspended sediments.     

Stable isotopic signatures of the modern land snail Eremina desertorum from a low-latitude (hot) dry desert—A study from the Petrified Forest,New Cairo,Egypt

This study was conducted on recent desert samples—including (1) soils, (2) plants, (3) the shell, and (4) organic matter from modern specimens of the land snail Eremina desertorum—which were collected at several altitudes (316–360 m above sea level) from a site in the New Cairo Petrified Forest. The soils and shell_{E. desertorum} were analyzed for carbonate composition and isotopic composition (δ¹⁸O, δ¹³C). The plants and organic matter_{E. desertorum} were analyzed for organic carbon content and δ¹³C. The soil carbonate, consisting of calcite plus minor dolomite, has δ¹⁸O values from −3.19 to −1.78‰ and δ¹³C values −1.79 to −0.27‰; covariance between the two values accords with arid climatic conditions. The local plants include C3 and C4 types, with the latter being dominant. Each type has distinctive bulk organic carbon δ¹³C values: −26.51 to −25.36‰ for C3-type, and −13.74 to −12.43‰ for C4-type plants.The carbonate of the shell_{E. desertorum} is composed of aragonite plus minor calcite, with relatively homogenous isotopic compositions (δ¹⁸O_mean = −0.28 ± 0.22‰; δ¹³C_mean = −4.46 ± 0.58‰). Most of the δ¹⁸O values (based on a model for oxygen isotope fractionation in an aragonite-water system) are consistent with evaporated water signatures. The organic matter_{E. desertorum} varies only slightly in bulk organic carbon δ¹³C values (−21.78 ± 1.20‰) and these values suggest that the snail consumed more of C3-type than C4-type plants. The overall offset in δ¹³C values (−17.32‰) observed between shell_{E. desertorum} carbonate and organic matter_{E. desertorum} exceeds the value expected for vegetation input, and implies that 30% of carbon in the shell_{E. desertorum} carbonate comes from the consumption of limestone material.     

Dynamics of carbon fluxes with responses to vegetation,meteorological and terrain factors in the south-eastern Tibetan Plateau

Tibetan Plateau (TP) is the highest and most extensive plateau in the world and has been known as the roof of the world, and it is sensitive to climate change. The researches of CO₂ fluxes (F _C) in the TP region play a significant role in understanding regional and global carbon balance and climate change. Eddy covariance flux measurements were conducted at three sites of south-eastern TP comprising Dali (DL, cropland ecosystem), LinZhi (LZ, alpine meadow ecosystem) and Wenjiang (WJ, cropland ecosystem); amongst those DL and LZ are located in plateau region, while WJ is in plain region. Dynamics of F _C and influences of vegetation, meteorological (air temperature, photosynthetically active radiation, soil temperature and soil water content) and terrain factors (altitude) were analysed on the basis of data taken during 2008. The results showed that, in the cool sub-season (March, April, October and December), carbon sink appeared even in December with fluxes of (?0.021 to ?0.05) mg CO₂ m^?2 s^?1 and carbon source only in October (0.03 ± 0.0048) mg CO₂ m^?2 s^?1 in DL and WJ site. In LZ site, carbon sink was observed in April: (?0.036 ± 0.0023) mg CO₂ m^?2 s^?1 and carbon sources in December and March (0.008–0.010 mg CO₂ m^?2 s^?1). In the hot sub-season (May–August), carbon source was observed only in May with (0.011 ± 0.0022), (0.104 ± 0.0029) and (0.036 ± 0.0017) fluxes in LZ, DL and WJ site, respectively, while carbon sinks with (?0.021 ± 0.0041), (?0.213 ± 0.0007) and (?0.110 ± 0.0015) mg CO₂ m^?2 s^?1 fluxes in LZ, DL, and WJ, respectively. Comparing with plain region (WJ), carbon sinks in plateau region (DL and LZ) lasted for a longer time, and the absorption sum was large and up to (–357.718 ± 0.0054) and (?371.111 ± 0.0039) g C m^?2 year^?1, respectively. The LZ site had the weakest carbon sink with (?178.547 ± 0.0070) g C m^?2 year^?1. Multivariate analysis of covariance showed that altitude (AL) as an independent factor explained 39.5 % of F _C (P < 0.026). F _C had a quadratic relationship with Normalized difference vegetation index (NDVI) (R ² ranges from 0.485 to 0.640 for three sites), an exponential relationship with soil temperature at 5-cm depth (ST ₅) at night time and a quadratic relationship with air temperature (T _a) at day time. Path analysis indicated that photosynthetically active radiation (PAR), sensible heat fluxes (H) and other factors all had direct or indirect effects on F _C in all of the three tested sites around the south-eastern TP.     

Diel Aquatic CO<Subscript>2</Subscript> System Dynamics of a Bermudian Mangrove Environment

Mangrove ecosystems play an important, but understudied, role in the cycling of carbon in tropical and subtropical coastal ocean environments. In the present study, we examined the diel dynamics of seawater carbon dioxide (CO₂) and dissolved oxygen (DO) for a mangrove-dominated marine ecosystem (Mangrove Bay) and an adjacent intracoastal waterway (Ferry Reach) on the island of Bermuda. Spatial and temporal trends in seawater carbonate chemistry and associated variables were assessed from direct measurements of dissolved inorganic carbon, total alkalinity, dissolved oxygen (DO), temperature, and salinity. Diel pCO₂ variability was interpolated across hourly wind speed measurements to determine variability in daily CO₂ fluxes for the month of October 2007 in Bermuda. From these observations, we estimated rates of net sea to air CO₂ exchange for these two coastal ecosystems at 59.8 ± 17.3 in Mangrove Bay and 5.5 ± 1.3 mmol m⁻² d⁻¹ in Ferry Reach. These results highlight the potential for large differences in carbonate system functioning and sea-air CO₂ flux in adjacent coastal environments. In addition, observation of large diel variability in CO₂ system parameters (e.g., mean pCO₂: 390–2,841 μatm; mean pH_T: 8.05–7.34) underscores the need for careful consideration of diel cycles in long-term sampling regimes and flux estimates.     

Fe(III) mobilisation by carbonate in low temperature environments: Study of the solubility of ferrihydrite in carbonate media and the formation of Fe(III) carbonate complexes

The linkage between the iron and the carbon cycles is of paramount importance to understand and quantify the effect of increased CO₂ concentrations in natural waters on the mobility of iron and associated trace elements. In this context, we have quantified the thermodynamic stability of mixed Fe(III) hydroxo-carbonate complexes and their effect on the solubility of Fe(III) oxihydroxides. We present the results of carefully performed solubility measurements of 2-line ferrihydrite in the slightly acidic to neutral–alkaline pH ranges (3.8–8.7) under constant pCO₂ varying between (0.982–98.154 kPa) at 25 °C.The outcome of the work indicates the predominance of two Fe(III) hydroxo carbonate complexes FeOHCO₃ and Fe(CO₃)₃³⁻, with formation constants log^*β°_1,1,1 = 10.76 ± 0.38 and log β°_1,0,3 = 24.24 ± 0.42, respectively.The solubility constant for the ferrihydrite used in this study was determined in acid conditions (pH: 1.8–3.2) in the absence of CO₂ and at T = (25 ± 1) °C, as log^*K_s,0 = 1.19 ± 0.41.The relative stability of the Fe(III)-carbonate complexes in alkaline pH conditions has implications for the solubility of Fe(III) in CO₂-rich environments and the subsequent mobilisation of associated trace metals that will be explored in subsequent papers.     

Change in carbonate budget and composition during subduction below metal saturation boundary

It is generally accepted that carbonates can be subducted to the mantle depths, where they are reduced with iron metal to produce a diamond. In this work, we found that this is not always the case. The mantle carbonates from inclusions in diamonds show a wide range of cation compositions (Mg, Fe, Ca, Na, and K). Here we studied the reaction kinetics of these carbonates with iron metal at 6–6.5 GPa and 1000–1500 °C. We found that the reduction of carbonate with Fe produces C-bearing species (Fe, Fe-C melt, Fe₃C, Fe₇C₃, C) and wüstite containing Na₂O, CaO, and MgO. The reaction rate constants (k = Δx²/2t) are log-linear relative to 1/T and their temperature dependences are determined to bek_MgCO3 (m²/s) = 4.37 × 10^?3 exp [?251 (kJ/mol)/RT]k_CaMg(CO3)2 (m²/s) = 1.48 × 10^?3 exp [?264 (kJ/mol)/RT]k_CaCO3 (m²/s) = 3.06 × 10^?5 exp [?245 (kJ/mol)/RT] andk_Na2CO3 (m²/s) = 1.88 × 10^?10 exp [?155 (kJ/mol)/RT].According to obtained results at least, 45–70 vol% of carbonates preserve during subduction down to the 660-km discontinuity if no melting occurs. The slab stagnation and warming, subsequent carbonate melting, and infiltration into the mantle saturated with iron metal are accompanied by a reduction of carbonate melt with Fe. The established sequence of reactivity of carbonates: FeCO₃ ≥ MgCO₃ > CaMg(CO₃)₂ > CaCO₃ ? Na₂CO₃, where K₂CO₃ does not react at all with iron metal, implies that during reduction carbonate melt with Fe evolves toward alkali-rich. The above conclusions are consistent with the findings of carbonates in inclusions in diamonds from the lower mantle and high concentrations of alkalis, particularly K, in mantle carbonatite melts entrapped by diamonds from kimberlites and placers worldwide.     

Measuring the effective diffusion coefficient of dissolved hydrogen in saturated Boom Clay

Boom Clay is studied as a potential host formation for the disposal of high-and intermediate level long-lived radioactive waste in Belgium. In such a geological repository, generation of gases (mainly H₂ from anaerobic corrosion) will be unavoidable. In order to make a good evaluation of the balance between gas generation vs. gas dissipation for a particular waste form and/or disposal concept, good estimates for gas diffusion coefficients of dissolved gases are essential. In order to obtain an accurate diffusion coefficient for dissolved hydrogen in saturated Boom Clay, diffusion experiments were performed with a recently developed through-diffusion set-up for dissolved gases. Due to microbial activity in the test set-up, conversion of hydrogen into methane was observed within several experiments. A complex sterilisation procedure was therefore developed in order to eliminate microbiological disturbances. Only by a combination of heat sterilisation, gamma irradiation and the use of a microbial inhibitor, reliable, reproducible and accurate H₂(g) diffusion coefficients (measured at 21 °C) for samples oriented parallel (D_eff = 7.25 × 10⁻¹⁰ m²/s and D_eff = 5.51 × 10⁻¹⁰ m²/s) and perpendicular (D_eff = 2.64 × 10⁻¹⁰ m²/s) to the bedding plane were obtained.     

Geochemistry and U–Pb zircon geochronology of the Alvand plutonic complex in Sanandaj–Sirjan Zone (Iran): New evidence for Jurassic magmatism

This paper presents geochemical, Sr–Nd isotopic, and U–Pb zircon geochronological data on the Alvand plutonic complex in Sanandaj–Sirjan zone (SSZ), Western Iran. The gabbroic rocks show a trend of a calc-alkaline magma suite and are characterized by low initial ⁸⁷Sr/⁸⁶Sr ratios (0.7023–0.7037) and positive εNd(t) values (2.9–3.3), which suggest derivation from a moderately depleted mantle source. Geochemical features of the granites illustrate a high-K calc-alkaline magma series, whereas the leucocratic granitoids form part of a low-K series. Granites have intermediate ⁸⁷Sr/⁸⁶Sr ratios (0.707–0.719) and negative εNd_(t) values (−1.0 to −3.4), while leucocratic granitoids have higher initial ⁸⁷Sr/⁸⁶Sr ratio (0.713–0.714) and more negative εNd_(t) values (−3.5 to −4.5). Potential basement source lithologies for the granites are Proterozoic granites and orthogneisses, and those for the leucocratic granites are plagioclase-rich sources such as meta-arkoses or tonalites. The U–Pb dating results demonstrate that all granitoids were exclusively emplaced during the Jurassic instead of being Cretaceous or younger in age as suggested previously. The pluton was assembled incrementally over c. 10 Ma. Gabbros formed at 166.5 ± 1.8 Ma, granites between 163.9 ± 0.9 Ma and 161.7 ± 0.6 Ma, and leucocratic granitoids between 154.4 ± 1.3 and 153.3 ± 2.7 Ma. Granites and leucocratic granitoids show some A-type affinity. It is concluded that the Alvand plutonic complex was generated in a continental-arc-related extensional regime during subduction of Neo-Tethyan oceanic crust beneath the SSZ. The U/Pb zircon age data, recently corroborated by similar results in the central and southern SSZ, indicate that Jurassic granitoids are more areally extensive in this belt than previously thought.     

Use of mineral/solution equilibrium calculations to assess the potential for carnotite precipitation from groundwater in the Texas Panhandle,USA

This study investigated the potential for the uranium mineral carnotite (K₂(UO₂)₂(VO₄)₂·3H₂O) to precipitate from evaporating groundwater in the Texas Panhandle region of the United States. The evolution of groundwater chemistry during evaporation was modeled with the USGS geochemical code PHREEQC using water-quality data from 100 groundwater wells downloaded from the USGS National Water Information System (NWIS) database. While most modeled groundwater compositions precipitated calcite upon evaporation, not all groundwater became saturated with respect to carnotite with the system open to CO₂. Thus, the formation of calcite is not a necessary condition for carnotite to form. Rather, the determining factor in achieving carnotite saturation was the evolution of groundwater chemistry during evaporation following calcite precipitation. Modeling in this study showed that if the initial major-ion groundwater composition was dominated by calcium-magnesium-sulfate (>70 precent Ca + Mg and >50 percent SO₄ + Cl) or calcium-magnesium-bicarbonate (>70 percent Ca + Mg and <70 percent HCO₃ + CO₃) and following the precipitation of calcite, the concentration of calcium was greater than the carbonate alkalinity (2mCa⁺² > mHCO₃⁻ + 2mCO₃⁻²) carnotite saturation was achieved. If, however, the initial major-ion groundwater composition is sodium-bicarbonate (varying amounts of Na, 40–100 percent Na), calcium-sodium-sulfate, or calcium-magnesium-bicarbonate composition (>70 percent HCO₃ + CO₃) and following the precipitation of calcite, the concentration of calcium was less than the carbonate alkalinity (2mCa⁺² < mHCO₃^- + 2mCO₃⁻²) carnotite saturation was not achieved. In systems open to CO_2, carnotite saturation occurred in most samples in evaporation amounts ranging from 95 percent to 99 percent with the partial pressure of CO₂ ranging from 10^−3.5 to 10^−2.5 atm. Carnotite saturation occurred in a few samples in evaporation amounts ranging from 98 percent to 99 percent with the partial pressure of CO₂ equal to 10^−2.0 atm. Carnotite saturation did not occur in any groundwater with the system closed to CO₂.     

pH effect on Re(VII) and Se(IV) diffusion in compacted GMZ bentonite

In a high-level radioactive waste (HLW) repository, pH has an impact on the solubility, migration, and adsorption of radionuclides. Thus, understanding the effects of pH on the diffusion of radionuclides is essential for long-term disposal of HLW. In this work, the diffusion behaviors of Re(VII) and Se(IV) in compacted Gaomiaozi (GMZ) bentonite at different pH have been investigated by a through-diffusion method. The effective diffusion coefficient, i.e., D_e values of Re(VII) and Se(IV) were in the range of (1.0–2.4) × 10⁻¹¹ m²/s at pH 3.0–10.0 and (0.38–2.3) × 10⁻¹¹ m²/s at pH 3.0–9.0. In the case of Re(VII), the D_e values remained almost unchanged probably because ReO₄⁻ was the dominant species in the pH range of 3.0–10.0. In the case of Se(IV), whose predominant species were HSeO₃⁻ at pH < 9.0 and SeO₃²⁻ at pH ≥ 9.0, the D_e values decreased by a factor of 3–6 at pH 9.0, i.e., D_e (pH < 9.0)/D_e (pH 9.0) ≈ 3–6, implying that the species with a higher valence state had a stronger anion exclusion effect. The decrease in D_e values can be explained by the diffusion species of Se(IV). Additionally, the rock capacity factor α decreased with the increase of pH. HSeO₃⁻ was absorbed on GMZ bentonite with distribution coefficient K_d values in the range of (1.0–2.5) × 10⁻⁴ m³/kg at pH ≤ 8.0, whereas SeO₃²⁻ was negligibly sorbed at pH > 8.0.     

Solubility of Ca6[Al(OH)6]2(CrO4)3·26H2O,the chromate analog of ettringite; 5–75°C

Ca₆[Al(OH)₆]₂(CrO₄)₃·26H₂O, the chromate analog of the sulfate mineral ettringite, was synthesized and characterized by X-ray diffraction, Fourier transform infra-red spectroscopy, thermogravimetric analyses, energy dispersive X-ray spectrometry, and bulk chemical analyses. The solubility of the synthesized solid was measured in a series of dissolution and precipitation experiments conducted at 5–75°C and at initial pH values between 10.5 and 12.5. The ion activity product (IAP) for the reaction Ca₆[Al(OH)₆]₂(CrO₄)₃·26H₂O⇌6Ca²⁺+2Al(OH)⁻₄+3CrO²⁻₄+4OH⁻+26H₂O varies with pH unless a CaCrO_4(aq) complex is included in the speciation model. The log K for the formation of this complex by the reaction Ca²⁺+CrO²⁻₄=CaCrO_4(aq) was obtained by minimizing the variance in the IAP for Ca₆[Al(OH)₆]₂(CrO₄)₃·26H₂O. There is no significant trend in the formation constant with temperature and the average log K is 2.77±0.16 over the temperature range 5–75°C. The log solubility product (log K_SP) of Ca₆[Al(OH)₆]₂(CrO₄)₃·26H₂O at 25°C is −41.46±0.30. The temperature dependence of the log K_SP is log K_SP=A−B/T+D log(T) where A=498.94±48.99, B=27,499±2257, and D=−181.11±16.74. The values of ΔG⁰_r,298 and ΔH⁰_r,298 for the dissolution reaction are 236.6±3.9 and 77.5±2.4 kJ mol⁻¹. the values of ΔC⁰_P,r,298 and ΔS⁰_r,298 are −1506±140 and −534±83 J mol⁻¹ K⁻¹. Using these values and published standard state partial molal quantities for constituent ions, ΔG⁰_f,298=−15,131±19 kJ mol⁻¹, ΔH⁰_f,298=−17,330±8.6 kJ mol⁻¹, ΔS⁰₂₉₈=2.19±0.10 kJ mol⁻¹ K⁻¹, and ΔC⁰_Pf,298=2.12±0.53 kJ mol⁻¹ K⁻¹, were calculated.     

H2O Content Measurement in Phengite by Secondary Ion Mass Spectrometry: A New Set of Reference Materials

Five new natural white mica reference materials (RMs) were developed for in situ H₂O content analyses by secondary ion mass spectrometry at the SwissSIMS laboratory of Lausanne University, Switzerland. The white mica reference materials cover a large part of the natural muscovite–phengite compositional range and are therefore suitable as reference materials for the analysis of natural rocks as well as individual minerals. The independent H₂O content of the reference materials UNIL_WM1 to UNIL_WM5 was obtained by thermal conversion elemental analyser and corresponds to 4.35 ± 0.02, 4.33 ± 0.03, 4.30 ± 0.07, 4.50 ± 0.02 and 4.42 ± 0.11 (% m/m, ± 1s), respectively. SIMS determinations of H₂O content revealed a matrix effect correlated to the FeO content of white mica. The compositional range in FeO of the reference materials that were calibrated for H₂O determination is from 1.13% to 3.67% m/m. No crystallographic orientation dependency was observed at the level of homogeneity of these reference materials. An analytical precision of 0.02% to 0.08% m/m (1SE) is expected for the final uncertainty on measurements of unknown white micas in natural samples.     

Spatial variability of initial 230Th/232Th in modern Porites from the inshore region of the Great Barrier Reef

The main limiting factor in obtaining precise and accurate uranium-series (U-series) ages of corals that lived during the last few hundred years is the ability to constrain and correct for initial thorium-230 (²³⁰Th₀), which is proportionally much higher in younger samples. This is becoming particularly important in palaeoecological research where accurate chronologies, based on the ²³⁰Th chronometer, are required to pinpoint changes in coral community structure and the timing of mortality events in recent time (e.g. since European settlement of northern Australia in the 1850s). In this study, thermal ionisation mass spectrometry (TIMS) U-series dating of 43 samples of known ages collected from living Porites spp. from the far northern, central and southern inshore regions of the Great Barrier Reef (GBR) was performed to spatially constrain initial ²³⁰Th/²³²Th (²³⁰Th/²³²Th₀) variability. In these living Porites corals, the majority of ²³⁰Th/²³²Th₀ values fell within error of the conservative bulk Earth ²³⁰Th/²³²Th atomic value of 4.3 ± 4.3 × 10^?6 (2σ) generally assumed for ²³⁰Th₀ corrections where the primary source is terrestrially derived. However, the results of this study demonstrate that the accuracy of ²³⁰Th ages can be further improved by using locally determined ²³⁰Th/²³²Th₀ values for correction, supporting the conclusion made by Shen et al. (2008) for the Western Pacific. Despite samples being taken from regions adjacent to contrasting levels of land modification, no significant differences were found in ²³⁰Th/²³²Th₀ between regions exposed to varying levels of sediment during river runoff events. Overall, 39 of the total 43 ²³⁰Th/²³²Th₀ atomic values measured in samples from inshore reefs across the entire region show a normal distribution ranging from 3.5 ± 1.1 to 8.1 ± 1.1 × 10^?6, with a weighted mean of 5.76 ± 0.34 × 10^?6 (2σ, MSWD = 8.1). Considering the scatter of the data, the weighted mean value with a more conservative assigned error of 25% (i.e. 5.8 ± 1.4 × 10^?6) that encompasses the full variation of the 39 ²³⁰Th/²³²Th₀ measurements is recommended as a more appropriate value for initial ²³⁰Th corrections for U-series dating of most Porites samples from inshore regions of the GBR. This will result in significant improvement in both the precision and accuracy of the corrected ²³⁰Th ages related to those based on the assumed bulk Earth ²³⁰Th/²³²Th₀ value of 4.3 ± 4.3 × 10^?6. However, several anomalously high ²³⁰Th/²³²Th₀ values reaching up to 28.0 ± 1.6 × 10^?6 occasionally found in some coral annual bands coinciding with El Niño years imply high ²³⁰Th/²³²Th₀ sources and highlight the complexities of understanding ²³⁰Th/²³²Th₀ variability. For U-series dating of young coral samples from such sites where anomalous ²³⁰Th/²³²Th₀ values occur, we suggest replicate dating of multiple growth bands with known age difference to verify age accuracy.     

Complex formation of Cm(III) with formate studied by time-resolved laser fluorescence spectroscopy

Pore waters of natural clays, which are investigated as potential host rock formations for high-level nuclear waste, are known to contain large amounts of low-molecular weight organic compounds. These small organic ligands might impact the aqueous geochemistry of the stored radionuclides and, thus, their migration behavior. In the present work, the complexation of Cm(III) with formate in aqueous NaCl solution is investigated by time-resolved laser fluorescence spectroscopy (TRLFS) as a function of the ionic strength (0.5–3.0 mol/kg), the ligand concentration (0–0.2 mol/kg) and the temperature (20–90 °C). The Cm(III) speciation is determined by deconvolution of the emission spectra. The obtained distribution of Cm(III) species is used to calculate the conditional stability constants (log K′(T)) at a given temperature and ionic strength which are extrapolated to zero ionic strength by using the specific ion interaction theory (SIT). Thus, the thermodynamic log K⁰_n(T) values for the formation of [Cm(Form)_n]⁽³⁻ⁿ⁾⁺ (n = 1, 2) and the ion interaction coefficients (ε(i,k)) for [Cm(Form)_n]⁽³⁻ⁿ⁾⁺ (n = 1, 2) with Cl⁻ are obtained. The log K⁰₁(T) (2.11 (20 °C)–2.49 (90 °C)) and log K⁰₂(T) values (1.17 (30 °C–2.01 (90 °C)) increase continuously with increasing temperature. The log K⁰_n(T) values are used to derive the standard reaction enthalpies and entropies (Δ_rH⁰_m, Δ_rS⁰_m) of the respective complexation reactions according to the Van’t Hoff equation. In all cases, positive Δ_rH⁰_m and Δ_rS⁰_m values are obtained. Thus, both complexation steps are endothermic and entropy-driven.     

Radon emanation of heterogeneous basin deposits in Kathmandu Valley,Nepal

Effective radium-226 concentration (EC_Ra) has been measured in soil samples from seven horizontal and vertical profiles of terrace scarps in the northern part of Kathmandu Valley, Nepal. The samples belong to the Thimi, Gokarna, and Tokha Formations, dated from 50 to 14 ky BP, and represent a diverse fluvio-deltaic sedimentary facies mainly consisting of gravelly to coarse sands, black, orange and brown clays. EC_Ra was measured in the laboratory by radon-222 emanation. The samples (n = 177) are placed in air-tight glass containers, from which, after an accumulation time varying from 3 to 18 days, the concentration of radon-222, radioactive decay product of radium-226 and radioactive gas with a half-life of 3.8 days, is measured using scintillation flasks. The EC_Ra values from the seven different profiles of the terrace deposits vary from 0.4 to 43 Bq kg^?1, with profile averages ranging from 12 ± 1 to 27 ± 2 Bq kg^?1. The values have a remarkable consistency along a particular horizon of sediment layers, clearly demonstrating that these values can be used for long distance correlations of the sediment horizons. Widely separated sediment profiles, representing similar stratigraphic positions, exhibit consistent EC_Ra values in corresponding stratigraphic sediment layers. EC_Ra measurements therefore appear particularly useful for lithologic and stratigraphic discriminations. For comparison, EC_Ra values of soils from different localities having various sources of origin were also obtained: 9.2 ± 0.4 Bq kg^?1 in soils of Syabru–Bensi (Central Nepal), 23 ± 1 Bq kg^?1 in red residual soils of the Bhattar-Trisuli Bazar terrace (North of Kathmandu), 17.1 ± 0.3 Bq kg^?1 in red residual soils of terrace of Kalikasthan (North of Trisuli Bazar) and 10 ± 1 Bq kg^?1 in red residual soils of a site near Nagarkot (East of Kathmandu). The knowledge of EC_Ra values for these various soils is important for modelling radon exhalation at the ground surface, in particular in the vicinity of active faults. Importantly, the study also reveals that, above numerous sediments of Kathmandu Valley, radon concentration in dwellings can potentially exceed the level of 300 Bq m^?3 for residential areas; a fact that should be seriously taken into account by the governmental and non-governmental agencies as well as building authorities.     

Petrogenesis and tectonic settings of the Late Carboniferous Jiamantieliek and Baogutu ore-bearing porphyry intrusions in the southern West Junggar,NW China

Porphyry Cu deposits occurred in the southern West Junggar of Xinjiang, NW China and are represented by the Baogutu and newly-discovered Jiamantieliek porphyry Cu deposits. Petrographical and geochemical studies show that both Jiamantieliek and Baogutu ore-bearing intrusions comprise main-stage diorite stock and minor late-stage diorite porphyry dikes and are the calc-alkaline intermediate intrusions. Based on U–Pb zircon SHRIMP analyses, the Jiamantieliek intrusion formed in 313 ± 4 Ma and 310 ± 5 Ma, while, based on U–Pb zircon SIMS analyses, the Baogutu intrusion formed in 313 ± 2 Ma and 312 ± 2 Ma. Rocks in the Jiamantieliek intrusion are enriched in light rare earth elements (LREE) and large ion lithophile elements (LILE) with negative Nb anomaly. Their isotopic compositions (ε_Nd(t) = +1.6 to +3.4, (⁸⁷Sr/⁸⁶Sr)_i = 0.70369–0.70401, (²⁰⁷Pb/²⁰⁴Pb)_i = 15.31–5.41) suggest a mixing origin from depleted to enriched mantle sources. In the Baogutu intrusion, the rocks are similar to those of the Jiamantieliek intrusion. Their Sr-Nd-Pb isotopic composition (ε_Nd(t) = +4.4 to +6.0, (⁸⁷Sr/⁸⁶Sr)_i = 0.70368–0.70385, (²⁰⁷Pb/²⁰⁴Pb)_i = 15.34–5.42) shows a more depleted mantle source. These features suggest generation in an island arc. The Jiamantieliek and Baogutu intrusions have similar characteristics, indicating that a relatively uniform and integrated source region has existed in the southern West Junggar since the Palaeozoic. A larger contribution of calc-alkaline magma would be required to generate the Jiamantieliek intrusion, which may reflect the development of magma arc maturation towards the western section of the southern West Junggar.