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1.

Background

The interaction between Ca-HAP and Pb2+ solution can result in the formation of a hydroxyapatite–hydroxypyromorphite solid solution [(PbxCa1?x)5(PO4)3(OH)], which can greatly affect the transport and distribution of toxic Pb in water, rock and soil. Therefore, it’s necessary to know the physicochemical properties of (PbxCa1?x)5(PO4)3(OH), predominantly its thermodynamic solubility and stability in aqueous solution. Nevertheless, no experiment on the dissolution and related thermodynamic data has been reported.

Results

Dissolution of the hydroxypyromorphite–hydroxyapatite solid solution [(PbxCa1?x)5(PO4)3(OH)] in aqueous solution at 25 °C was experimentally studied. The aqueous concentrations were greatly affected by the Pb/(Pb + Ca) molar ratios (XPb) of the solids. For the solids with high XPb [(Pb0.89Ca0.11)5(PO4)3OH], the aqueous Pb2+ concentrations increased rapidly with time and reached a peak value after 240–720 h dissolution, and then decreased gradually and reached a stable state after 5040 h dissolution. For the solids with low XPb (0.00–0.80), the aqueous Pb2+ concentrations increased quickly with time and reached a peak value after 1–12 h dissolution, and then decreased gradually and attained a stable state after 720–2160 h dissolution.

Conclusions

The dissolution process of the solids with high XPb (0.89–1.00) was different from that of the solids with low XPb (0.00–0.80). The average K sp values were estimated to be 10?80.77±0.20 (10?80.57–10?80.96) for hydroxypyromorphite [Pb5(PO4)3OH] and 10?58.38±0.07 (10?58.31–10?58.46) for calcium hydroxyapatite [Ca5(PO4)3OH]. The Gibbs free energies of formation (ΔG f o ) were determined to be ?3796.71 and ?6314.63 kJ/mol, respectively. The solubility decreased with the increasing Pb/(Pb + Ca) molar ratios (XPb) of (PbxCa1?x)5(PO4)3(OH). For the dissolution at 25 °C with an initial pH of 2.00, the experimental data plotted on the Lippmann diagram showed that the solid solution (PbxCa1?x)5(PO4)3(OH) dissolved stoichiometrically at the early stage of dissolution and moved gradually up to the Lippmann solutus curve and the saturation curve for Pb5(PO4)3OH, and then the data points moved along the Lippmann solutus curve from right to left. The Pb-rich (PbxCa1?x)5(PO4)3(OH) was in equilibrium with the Ca-rich aqueous solution.
Graphical abstractLippmann diagrams for dissolution of the hydroxypyromorphite–hydroxyapatite solid solution [(PbxCa1?x)5(PO4)3OH] at 25??C and an initial pH of 2.00.
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2.
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3.
The paper presents the results of a thermochemical and thermal study of cancrinite, (Na6.93Ca0.545K0.01)Σ7.485[(Si6.47Al5.48Fe0.05)Σ12O24](CO3)1.25 · 2.30 H2O, and cancrisilite, (Na7.17 Ca0.01)Σ7.18[(Si7.26Al4.70Fe0.04)Σ12O24][(CO3)1.05(OH)0.21(PO4)0.04(SO4)0.01] · 2.635 H2O, from the Khibina-Lovozero Complex, Kola Peninsula, Russia. Stages of the thermal decomposition of these minerals were studied using IR spectroscopy. The enthalpies of formation of the minerals from elements were determined by melt drop solution calorimetry: Δ f H el 0 (298.15 K) = ?14 490 ± 16 kJ/mol for cancrinite and ?14302 ± 17 kJ/mol for cancrisilite. The values of Δ f H el 0 (298.15 K), S o(298.15 K), and Δ f H el 0 (298.15 K) are determined for cancrinite and cancrisilite of theoretical composition.  相似文献   

4.
Hydrotalcite-like solid solutions have been synthesized by coprecipitation in basic solutions with variable SO 4 2? /CO 3 2? ratios. Chemical determination of CO 3 2? in the interlayer was impossible because of the presence of minor hydromagnesite. SO 4 2? was determined both by chemical analysis and X-ray photoelectron spectroscopy (XPS), the two methods giving similar results. A Raman spectrometry gave additional data on the SO 4 2? /CO 3 2? ratio. Then, the stoichiometry of the anionic interlayers, X s , X c , and X OH were determined, and the influence of X s on the c′ parameter (increasing from c′=7.97 Å to c′=8.63 Å between X s =0 and X s =1) was characterized. In addition, a partitioning curve of SO 4 2? and CO 3 2? between aqueous solutions and hydrotalcite-like compounds was established. Its general shape strongly suggests a miscibility gap between a sulfate-rich end and a carbonate-rich solid solution (maximum SO 4 2? /CO 3 2? about 0.2). This result explains why most of the hydrotalcites synthesized during experimental alteration of basaltic glasses by sea-water (a sulfate-rich solution) are CO 3 2? -rich solid solutions.  相似文献   

5.
The crystal structures of two new compounds (H3O)2[(UO2)(SeO4)2(H2O)](H2O)2 (1, orthorhombic, Pnma, a = 14.0328(18), b = 11.6412(13), c = 8.2146(13) Å, V = 134.9(3) Å3) and (H3O)2[(UO2)(SeO4)2(H2O)](H2O) (2, monoclinic, P21/c, a = 7.8670(12), b = 7.5357(7), c = 21.386(3) Å, β = 101.484(12)°, V = 1242.5(3) Å3) have been solved by direct methods and refined to R 1 = 0.076 and 0.080, respectively. The structures of both compounds contain sheet complexes [(UO2)(SeO4)2]2? formed by cornershared [(UO2)O4(H2O)] bipyramids and SeO4 tetrahedrons. The sheets are parallel to the (100) plane in structure 1 and to (?102) in structure 2. The [(UO2)(SeO4)2(H2O)]2? layers are linked by hydrogen bonds via interlayer groups H2O and H3O+. The sheet topologies in structures 1 and 2 are different and correspond to the topologies of octahedral and tetrahedral complexes in rhomboclase (H2O2)+[Fe(SO4)2(H2O)2] and goldichite K[Fe(SO4)2(H2O)2](H2O)2, respectively.  相似文献   

6.
A new mineral, tatarinovite, ideally Са3Аl(SO4)[В(ОН)4](ОН)6 · 12Н2O, has been found in cavities of rhodingites at the Bazhenovskoe chrysotile asbestos deposit, Middle Urals, Russia. It occurs (1) colorless, with vitreous luster, bipyramidal crystals up to 1 mm across in cavities within massive diopside, in association with xonotlite, clinochlore, pectolite and calcite, and (2) as white granular aggregates up to 5 mm in size on grossular with pectolite, diopside, calcite, and xonotlite. The Mohs hardness is 3; perfect cleavage on (100) is observed. D meas = 1.79(1), D calc = 1.777 g/cm3. Tatarinovite is optically uniaxial (+), ω = 1.475(2), ε = 1.496(2). The IR spectrum contains characteristic bands of SO4 2?, CO3 2?, B(OH)4 ?, B(OH)3, Al(OH)6 3-, Si(OH)6 2-, OH–, and H2O. The chemical composition of tatarinovite (wt %; ICP-AES; H2O was determined by the Alimarin method; CO2 was determined by selective sorption on askarite) is as follows: 27.40 CaO, 4.06 B2O3, 6.34 A12O3, 0.03 Fe2O3, 2.43 SiO2, 8.48 SO3, 4.2 CO2, 46.1 H2O, total is 99.04. The empirical formula (calculated on the basis of 3Ca apfu) is H31.41Ca3.00(Al0.76Si0.25)Σ1.01 · (B0.72S0.65C0.59)Σ1.96O24.55. Tatarinovite is hexagonal, space gr. P63, a = 11.1110(4) Å, c = 10.6294(6) Å, V = 1136.44(9) A3, Z = 2. Its crystal chemical formula is Са3(Аl0.70Si0.30) · {[SO4]0.34[В(ОН)4]0.33[СO3]0.24}{[SO4]0.30[В(ОН)4]0.34[СО3]0.30[В(ОН)3]0.06}(ОН5·73О0.27) · 12Н2O. The strongest reflections of the powder X-ray diffraction pattern [d, Å (I, %) (hkl)] are 9.63 (100) (100), 5.556 (30) (110), 4.654 (14) (102), 3.841 (21) (112), 3.441 (12) (211), 2.746 (10) (302), 2.538 (12) (213). Tatarinovite was named in memory of the Russian geologist and petrologist Pavel Mikhailovich Tatarinov (1895–1976), a well-known specialist in chrysotile asbestos deposits. Type specimens have been deposited at the Fersman Mineralogical Museum of the Russian Academy of Sciences, Moscow.  相似文献   

7.
Recent improvements to experiments and modelling of batch dissolution in a turbulent reactor, based upon the shrinking object model, are extended to middle loadings of gypsum, that is, in the region between low and high loadings, which lead, respectively, to high under-saturation or saturation with a great excess of solid left undissolved. Dissolved calcium sulphate concentration was monitored by change in electrical conductivity. This investigation uses an improved, ion-pair model for CaSO 4 0 to allow for the presence of calcium or sulphate added as common ions. The study demonstrates that the full dissolution curve for 5.82 mM loadings of 106-μm particles of gypsum (~1.00 g L?1) in de-ionised water barely changed in the presence of either 4.64 or 8.09 mM calcium chloride, or 4.39 mM sodium sulphate. However, this masked a doubling of dissolution rate imposed by comparable increases in ionic strength from sodium chloride. The results are consistent with the ion pair, CaSO 4 0 , being the key species in the rate-determining step of the back-reaction, and perhaps all salt dissolutions, including calcium carbonate. In this case, the rate equation is as follows: \( {\frac{{{\text{d}}c}}{{{\text{d}}t}}} = \frac{S}{V} \cdot (k_{1} - k_{2}^{\prime } \cdot [{\text{CaSO}}_{ 4}^{0} ]) \), where k 1 and k 2′ are rate constants. The reported observations are interpreted as effects of ionic strength and common ion concentrations upon the formation equilibrium for the ion pair. This rate equation readily transforms mathematically to one involving the product of [Ca2+] and [SO4 2?] in the back-reaction. The parallel of this with the well-known PWP equation used in calcium carbonate dissolution is discussed, with the CaHCO3 + ion pair of the equation being replaced by that of CaCO 3 0 . Meanwhile, the earlier use of the product, [Ca2+]½ × [CO3 2?]½, in the back-reaction term of another dissolution rate equation for calcite is shown to be incorrect. Finally, it is argued that the shrinking object model should be repositioned as a logical derivative of the hydrodynamical approach to dissolution.  相似文献   

8.
The crystal structures of synthetic K-dravite [XKYMg 3 Z Al 6 T Si6O18(BO3) 3 V (OH) 3 W (OH)], dravite [XNaYMg 3 Z Al 6 T Si6O18(BO3) 3 V (OH) 3 W (OH)], oxy-uvite [XCaYMg 3 Z Al 6 T Si6O18(BO3) 3 V (OH) 3 W O], and magnesio-foitite [X?Y(Mg2Al)ZAl 6 T Si6O18(BO3) 3 V (OH) 3 W (OH)] are investigated by polarized Raman spectroscopy, single-crystal structure refinement (SREF), and powder X-ray diffraction. The use of compositionally simple tourmalines characterized by electron microprobe analysis facilitates the determination of site occupancy in the SREF and band assignment in the Raman spectra. The synthesized K-dravite, oxy-uvite, and magnesio-foitite have significant Mg–Al disorder between their octahedral sites indicated by their respective average 〈Y–O〉 and 〈Z–O〉 bond lengths. The Y- and Z-site compositions of oxy-uvite (YMg1.52Al1.48(10) and ZAl4.90Mg1.10(15)) and magnesio-foitite (YAl1.62Mg1.38(18) and ZAl4.92Mg1.08(24)) are refined from the electron densities at each site. The Mg–Al ratio of the Y and Z sites is also determined from the relative integrated peak intensities of the Raman bands in the O–H stretching vibrational range (3250–3850 cm?1), producing values in good agreement with the SREF data. The unit cell volume of tourmaline increases from magnesio-foitite (1558.4(3) Å3) to dravite (1569.5(4)–1571.7(3) Å3) to oxy-uvite (1572.4(2) Å3) to K-dravite (1588.1(2) Å3), mainly due to lengthening of the crystallographic c-axis. The increase in the size of the X-site coordination polyhedron from dravite (Na) to K-dravite (K) is accommodated locally in the crystal structure, resulting in the shortening of the neighboring O1–H1 bond. In oxy-uvite, Ca2+ is locally associated with a deprotonated W (O1) site, whereas vacant X sites are neighbored by protonated W (O1) sites. Increasing the size of the X-site-occupying ion does not detectably affect bonding between the other sites; however, the higher charge of Ca and the deprotonated W (O1) site in oxy-uvite are correlated to changes in the lattice vibration Raman spectrum (100–1200 cm?1), particularly for bands assigned to the T 6O18 ring. The Raman spectrum of magnesio-foitite shows significant deviations from those of K-dravite, dravite, and oxy-uvite in both the lattice and O–H stretching vibrational ranges (100–1200 and 3250–3850 cm?1, respectively). The vacant X site is correlated with long- and short-range changes in the crystal structure, i.e., deformation of the T 6O18 ring and lengthening of the O1–H1 and O3–H3 bonds. However, X-site vacancies in K-dravite, dravite, and oxy-uvite result only in the lengthening of the neighboring O1–H1 bond and do not result in identifiable changes in the lattice-bonding environment.  相似文献   

9.
The density and compressibility of seawater solutions from 0 to 95 °C have been examined using the Pitzer equations. The apparent molal volumes (X = V) and compressibilities (X = κ) are in the form $$ X_{\phi } = \bar{X}^{0} + A_{X} I/(1.2 \, m)\ln (1 + 1.2 \, I^{0.5} ) + \, 2{\text{RT }}m \, (\beta^{(0)X} + \beta^{(1)X} g(y) + C^{X} m) $$ where $ \bar{X}^{0} $ is the partial molal volume or compressibility, I is the ionic strength, m is the molality of sea salt, AX is the Debye–Hückel slope for volume (X = V) or adiabatic compressibility (X = κ s), and g(y) = (2/y 2)[1 ? (1 + y) exp(?y)] where y = 2I 0.5. The values of the partial molal volume and compressibility ( $ \bar{X}^{0} $ ) and Pitzer parameters (β (0)X , β (1)X and C X ) are functions of temperature in the form $$ Y^{X} = \sum_{i} a_{i} (T-T_{\text{R}} )^{i} $$ where a i are adjustable parameters, T is the absolute temperature in Kelvin, and T R = 298.15 K is the reference temperature. The standard errors of the seawater fits for the specific volumes and adiabatic compressibilities are 5.35E?06 cm3 g?1 and 1.0E?09 bar?1, respectively. These equations can be combined with similar equations for the osmotic coefficient, enthalpy and heat capacity to define the thermodynamic properties of sea salt to high temperatures at one atm. The Pitzer equations for the major components of seawater have been used to estimate the density and compressibility of seawater to 95 °C. The results are in reasonable agreement with the measured values (0.010E?03 g cm?3 for density and 0.050E?06 bar?1 for compressibility) from 0 to 80 °C and salinities from 0 to 45 g kg?1. The results make it possible to estimate the density and compressibility of all natural waters of known composition over a wide range of temperature and salinity.  相似文献   

10.
The thermal stability of sideronatrite, ideally Na2Fe3+(SO4)2(OH)·3(H2O), and its decomposition products were investigated by combining thermogravimetric and differential thermal analysis, in situ high-temperature X-ray powder diffraction (HT-XRPD) and Fourier transform infrared spectroscopy (HT-FTIR). The data show that for increasing temperature there are four main dehydration/transformation steps in sideronatrite: (a) between 30 and 40 °C sideronatrite transforms into metasideronatrite after the loss of two water molecules; both XRD and FTIR suggest that this transformation occurs via minor adjustments in the building block. (b) between 120 and 300 °C metasideronatrite transforms into metasideronatrite II, a still poorly characterized phase with possible orthorhombic symmetry, consequently to the loss of an additional water molecule; X-ray diffraction data suggest that metasideronatrite disappears from the assemblage above 175 °C. (c) between 315 and 415 °C metasideronatrite II transforms into the anhydrous Na3Fe(SO4)3 compound. This step occurs via the loss of hydroxyl groups that involves the breakdown of the [Fe3+(SO4)2(OH)] ∞ 2? chains and the formation of an intermediate transient amorphous phase precursor of Na3Fe(SO4)3. (d) for T > 500 °C, the Na3Fe(SO4)3 compound is replaced by the Na-sulfate thenardite, Na2SO4, plus Fe-oxides, according to the Na3Fe3+(SO4)3 → 3/2 Na2(SO4) + 1/2 Fe2O3 + SOx reaction products. The Na–Fe sulfate disappears around 540 °C. For higher temperatures, the Na-sulfates decomposes and only hematite survives in the final product. The understanding of the thermal behavior of minerals such as sideronatrite and related sulfates is important both from an environmental point of view, due to the presence of these phases in evaporitic deposits, soils and sediments including extraterrestrial occurrences, and from the technological point of view, due to the use of these materials in many industrial applications.  相似文献   

11.
Na–H3O jarosite was synthesized hydrothermally at 413 K for 8 days and investigated using single-crystal X-ray diffraction (XRD) and electron microprobe analysis (EMPA). The chemical composition of the studied crystal is [Na0.57(3) (H3O)0.36 (H2O)0.07]A Fe2.93(3) (SO4)2 (OH)5.70 (H2O)0.30, and Fe deficiency was confirmed by both EMPA and XRD analysis. The single-crystal XRD data were collected at 298 and 102 K, and crystal structures were refined in space group \( R\overline{3}m\). The room-temperature data match structural trends of the jarosite group, which vary linearly with the c axis. The low-temperature structure at 102 K shows an anisotropic decrease in the unit cell parameters, with c and a decreasing by 0.45 and 0.03 %, respectively. Structural changes are mainly confined to the A site environment. Only minor changes occur in FeO6 and SO4 polyhedra. The structure responds upon cooling by increasing bond length distortion and by decreasing quadratic elongation of the large AO12 polyhedra. The structural parameters at low temperature follow very similar patterns to structural changes that correspond to compositional variation in the jarosite group, which is characterised by the flexibility of AO12 polyhedra and rigidity of Fe(OH)4O2–SO4 layers. The most flexible areas in the jarosite structure are localized at AO12 edges that are not shared with neighbouring FeO6 octahedra. Importantly, for the application of XRD in planetary settings, the temperature-related changes in jarosite can mimic compositional change.  相似文献   

12.
The present study attempts to model the spatial variability of three groundwater qualitative parameters in Guilan Province, northern Iran, using artificial neural networks (ANNs) and support vector machines (SVMs). Data collected from 140 observation wells for the years 2002–2014 were used. Five variables, X and Y coordinates of the observation well, distance of the observation well from the shoreline, areal average 6-month rainfall depth, and groundwater level at the day of water quality sampling, were considered as primary input variables. In addition, nine qualitative variables were also considered as auxiliary input variables. Electrical conductivity (EC), sodium concentration (Na+), and sulfate concentration (SO4 2?) of the groundwater in the region were estimated using ANNs and SVMs with different input combinations. The results showed that both ANNs and SVMs work well when the only primary input variable is the well location. The ANN yielded an RMSE of 1.03 mEq/l for SO4 2?, 1.05 mEq/l for Na+, and 203.17 μS/cm for EC, using the X and Y coordinates of the observation wells in the study area. In the case of SVM, these values were, respectively, 0.87, 0.87, and 176.68. Considering the auxiliary input variables (pH, EC, and the concentrations of Na+, K+, Ca2+, Mg2+, Cl?, SO4 2?, and HCO3 ?) resulted in a significant decrease in the RMSE of both ANNs (0.22, 0.30, and 33.04) and SVMs (0.26, 0.34, and 36.23). Comparing these RMSE values with those of cokriging interpolation technique (0.59, 0.98, and 177.59) indicated that ANNs and SVMs produced more accurate estimates of the three qualitative parameters. The relative importance of auxiliary input variables was also determined using Gamma test. The output uncertainty of ANNs and SVMs were determined using p-factor and d-factor. The results showed that SVMs have less uncertainty than ANNs.  相似文献   

13.
The crystal chemistry and the elastic behavior under isothermal conditions up to 9 GPa of a natural, and extremely rare, 3T-phlogopite from Traversella (Valchiusella, Turin, Western Alps) [(K0.99Na0.05Ba0.01)(Mg2.60Al0.20Fe 0.21 2+ )[Si2.71Al1.29O10](OH)2, space group P3112, with a = 5.3167(4), c = 30.440(2) Å, and V = 745.16(9) ų] have been investigated by electron microprobe analysis in wavelength dispersion mode, single-crystal X-ray diffraction at 100 K, and in situ high-pressure synchrotron radiation powder diffraction (at room temperature) with a diamond anvil cell. The single-crystal refinement confirms the general structure features expected for trioctahedral micas, with the inter-layer site partially occupied by potassium and sodium, iron almost homogeneously distributed over the three independent octahedral sites, and the average bond distances of the two unique tetrahedra suggesting a disordered Si/Al-distribution (i.e., 〈T1-O〉 ~ 1.658 and 〈T2-O〉 ~ 1.656 Å). The location of the H-site confirms the orientation of the O–H vector nearly perpendicular to (0001). The refinement converged with R 1(F) = 0.0382, 846 unique reflections with F O > 4σ(F O) and 61 refined parameters, and not significant residuals in the final difference-Fourier map of the electron density (+0.77/?0.37 e ?/Å3). The high-pressure experiments showed no phase transition within the pressure range investigated. The P–V data were fitted with a Murnaghan (M-EoS) and a third-order Birch-Murnaghan equation of state (BM-EoS), yielding: (1) M-EoS, V 0 = 747.0(3) Å3, K T0 = 44.5(24) GPa, and K′ = 8.0(9); (2) BM-EoS, V 0 = 747.0(3) Å3, K T0 = 42.8(29) GPa, and K′ = 9.9(17). A comparison between the elastic behavior in response to pressure observed in 1M- and 3T-phlogopite is made.  相似文献   

14.
Zusammenfassung Röntgenographische Untersuchungen an Einkristallen von Arsenbrackebuschit, Pb2(Fe, Zn)(OH, OH2) (AsO4)2 (mit FeZn21), ergaben die RaumgruppeP21/m mita 0=7,763(1) Å,b 0=6.046(1) Å,c 0=9.022(1)Å, =112,5(1)°,V=391,2(1) Å3,Z=2 und x =6,54 g/cm3. Dreidimensionale Fouriersynthesen und Verfeinerungen nach der Methode der kleinsten Quadrate bis zu einemR-Wert von 0,073 zeigten, daß das neue Mineral strukturell einer Gruppe von Blei-Mineralen der allgemeinen Formel Pb2 Me(Z) (XO4) (YO4) — mitMe=Cu2+, Mn2+, Zn2+, Fe3+;X=S, Cr, V, As;Y=P, As, V;Z=OH, OH2 — zuzuordnen ist. Vertreter dieser Gruppe sind z. B. Tsumebit Pb2Cu(OH) (SO4) (PO4), Vauquelinit Pb2Cu(OH) (CrO4) (PO4) und auch Brackebuschit Pb2(Mn, Fe) (OH2) (VO4)2. Strukturelle Verwandtschaft besteht mit Tsumcorit Pb(Zn, Fe)2(OH, OH2)2(AsO4)2, einem weiteren Blei-Arsenat der gleichen Lagerstätte.
Structural investigation of arsenbrackebuschite
Summary X-ray single crystal work on arsenbrackebuschite, Pb2(Fe, Zn) (OH, OH2) (AsO4)2 (with FeZn21), gave space groupP21/m witha 0=7.763(1),b 0=6.046(1),c 0=9.022(1) Å, =112.5(1)°,V=391.2(1) Å3,Z=2 and x =6,54 g/cm3. 3-dimensional Fourier syntheses and least-squares refinement (finalR=0.073) showed that the new mineral belongs to a group of lead minerals with the general formula Pb2 Me(Z) (XO4) (YO4)Me=Cu2+, Mn2+, Zn2+, Fe2+, Fe3+;X=S, Cr, V, As; Y=P, As, V;Z=OH, OH2. Members of this group, are for example tsumebite, Pb2Cu(OH) (SO4)(PO4), vauquelinite, Pb2Cu(OH) (CrO4) (PO4), and brackebuschite, Pb2 (Mn, Fe) (OH2) (VO4)2. A structural relationship exists to tsumcorite, Pb(Zn, Fe)2(OH, OH2)2 (AsO4)2, another lead-arsenate from Tsumeb.

Mit 2 Abbildungen  相似文献   

15.
A 4-week laboratory experiment investigated the behaviour (survival and bioirrigation) and impact of the invasive polychaetes Marenzelleria viridis, M. neglecta and M. arctia on sediment-water solutes exchange, porewater chemistry, and Fe and P interactions in high-salinity sandy sediment (HSS) and low-salinity muddy sediment (LSM) from the Baltic Sea. M. viridis showed deep burrowing with efficient bioirrigation (11 L m?2 day?1) and high survival (71%) in HSS, while M. arctia exhibited shallow burrowing with high bioirrigation (12 L m?2 day?1) and survival (88%) in LSM. M. neglecta behaved poorly in both ecological settings (bioirrigation, 5–6 L m?2 day?1; survival, 21–44%). The deep M. viridis bioirrigation enhanced total microbial CO2 (TCO2) production in HSS by 175% with a net efflux of NH4+ and PO43?, at rates 3- to 27-fold higher than for the other species. Although the shallow and intense bioirrigation of M. arctia in LSM stimulated microbial TCO2 production to some extent (61% enhancement), the nutrient fluxes close to zero indicate that it effectively prevented the P release. Porewater Fe:PO43? ratios revealed that the oxidizing effect of M. arctia bioirrigation increased the PO43? adsorption capacity of LSM twofold relative to defaunated controls while no buffering of PO43? was detected in M. viridis HSS treatment. Therefore, the different behaviour of the three species in various environments and the sharp contrast between M. viridis and M. arctia effects on C, N and P cycling must be considered carefully when the ecological role of Marenzelleria species in the Baltic Sea is evaluated.  相似文献   

16.
Thaumasite, Ca3Si(OH)6(CO3)(SO4)12H2O, occurs as a low-temperature secondary alteration phase in mafic igneous and metamorphic rocks, and is recognized as a product and indicator of sulfate attack in Portland cement. It is also the only mineral known to contain silicon in six-coordination with hydroxyl (OH)? that is stable at ambient P–T conditions. Thermal expansion of the various components of this unusual structure has been determined from single-crystal X-ray structure refinements of natural thaumasite at 130 and 298 K. No phase transitions were observed over this temperature range. Cell parameters at room temperature are: a= 11.0538(6) Å, c=10.4111(8) Å and V=1101.67(10) Å3, and were measured at intervals of about 50 K between 130 and 298 K, resulting in mean axial and volumetric coefficients of thermal expansion (×10?5K?1); α a =1.7(1), α c =2.1(2), and α V =5.6(2). Although the unit cell and VIIICaO8 polyhedra show significant positive thermal expansion over this temperature range, the silicate octahedron, sulfate tetrahedron, and carbonate group show zero or negative thermal expansion, with α V (VISiO6) = ?0.6 ± 1.1, α V (IVSO4)=?5.8 ± 1.4, and α R (C–O)= 0.0 ± 1.8 (×10?5 K?1). Most of the thermal expansion is accommodated by lengthening of the R(O...O) hydrogen bond distances by on average 5σ, although the hydrogen bonds involving hydroxyl sites on VISi expand twice as much as those on molecular water, causing the [Ca3Si(OH)6(H2O)12]4+ columns to expand in diameter more than they move apart over this temperature range. The average Si–OH bond length of the six-coordinated Si atom 〈R(VISi–OH)〉 in thaumasite is 1.783(1) Å, being about 0.02 Å (?20σ) shorter than VISi–OH in the dense hydrous magnesium silicate, phase D, MgSi2H2O6.  相似文献   

17.
The paper reports original thermochemical data on six natural amphibole samples of different composition. The data were obtained by high-temperature melt solution calorimetry in a Tian–Calvet microcalorometer and include the enthalpies of formation from elements for actinolite Ca1.95(Mg4.4Fe 0.5 2+ Al01)[Si8.0O22](OH)2(–12024 ± 13 kJ/mol) and Ca2.0(Mg2.9Fe 1.9 2+ Fe 0.2 3+ )[Si7.8Al0.2O22](OH)2, (–11462 ± 18 kJ/mol), and Na0.1Ca2.0(Mg3.2Fe 1.6 2+ Fe 0.2 3+ )[Si7.7Al0.3O22](OH)2 (–11588 ± 14 kJ/mol); for pargasite Na0.5K0.5Ca2.0-(Mg3.4Fe 1.8 2+ Al0.8)[Si6.2Al1.8O22](OH)2 (–12316 ± 10 kJ/mol) and Na0.8K0.2Ca2.0(Mg2.8Fe 1.3 3+ Al0.9) [Si6.1Al1.9O22](OH)2 (–12 223 ± 9 kJ/mol); and for hastingsite Na0.3K0.2Ca2.0(Mg0.4Fe 1.3 2+ Fe 0.9 3+ Al0.2) [Si6.4Al1.6O22](OH)2 (?10909 ± 11 kJ/mol). The standard entropy, enthalpy, and Gibbs free energy of formation are estimated for amphiboles of theoretical composition: end members and intermediate members of the isomorphic series tremolite–ferroactinolite, edenite–ferroedenite, pargasite–ferropargasite, and hastingsite.  相似文献   

18.
We have performed experiments to determine the effects of pressure, temperature and oxygen fugacity on the CO2 contents in nominally anhydrous andesitic melts at graphite saturation. The andesite composition was specifically chosen to match a low-degree partial melt composition that is generated from MORB-like eclogite in the convective, oceanic upper mantle. Experiments were performed at 1–3 GPa, 1375–1550?°C, and fO2 of FMQ ?3.2 to FMQ ?2.3 and the resulting experimental glasses were analyzed for CO2 and H2O contents using FTIR and SIMS. Experimental results were used to develop a thermodynamic model to predict CO2 content of nominally anhydrous andesitic melts at graphite saturation. Fitting of experimental data returned thermodynamic parameters for dissolution of CO2 as molecular CO2: ln(K 0) = ?21.79?±?0.04, ΔV 0?=?32.91?±?0.65 cm3mol?1, ΔH 0?=?107?±?21 kJ mol?1, and dissolution of CO2 as CO3 2?: ln(K 0 ) = ?21.38?±?0.08, ΔV 0?=?30.66?±?1.33 cm3 mol?1, ΔH 0?=?42?±?37 kJ mol?1, where K 0 is the equilibrium constant at some reference pressure and temperature, ΔV 0 is the volume change of reaction, and ΔH 0 is the enthalpy change of reaction. The thermodynamic model was used along with trace element partition coefficients to calculate the CO2 contents and CO2/Nb ratios resulting from the mixing of a depleted MORB and the partial melt of a graphite-saturated eclogite. Comparison with natural MORB and OIB data suggests that the CO2 contents and CO2/Nb ratios of CO2-enriched oceanic basalts cannot be produced by mixing with partial melts of graphite-saturated eclogite. Instead, they must be produced by melting of a source containing carbonate. This result places a lower bound on the oxygen fugacity for the source region of these CO2-enriched basalts, and suggests that fO2 measurements made on cratonic xenoliths may not be applicable to the convecting upper mantle. CO2-depleted basalts, on the other hand, are consistent with mixing between depleted MORB and partial melts of a graphite-saturated eclogite. Furthermore, calculations suggest that eclogite can remain saturated in graphite in the convecting upper mantle, acting as a reservoir for C.  相似文献   

19.
Zinclipscombite, a new mineral species, has been found together with apophyllite, quartz, barite, jarosite, plumbojarosite, turquoise, and calcite at the Silver Coin mine, Edna Mountains, Valmy, Humboldt County, Nevada, United States. The new mineral forms spheroidal, fibrous segregations; the thickness of the fibers, which extend along the c axis, reaches 20 μm, and the diameter of spherulites is up to 2.5 mm. The color is dark green to brown with a light green to beige streak and a vitreous luster. The mineral is translucent. The Mohs hardness is 5. Zinclipscombite is brittle; cleavage is not observed; fracture is uneven. The density is 3.65(4) g/cm3 measured by hydrostatic weighing and 3.727 g/cm3 calculated from X-ray powder data. The frequencies of absorption bands in the infrared spectrum of zinclipscombite are (cm?1; the frequencies of the strongest bands are underlined; sh, shoulder; w, weak band) 3535, 3330sh, 3260, 1625w, 1530w, 1068, 1047, 1022, 970sh, 768w, 684w, 609, 502, and 460. The Mössbauer spectrum of zinclipscombite contains only a doublet corresponding to Fe3+ with sixfold coordination and a quadrupole splitting of 0.562 mm/s; Fe2+ is absent. The mineral is optically uniaxial and positive, ω = 1.755(5), ? = 1.795(5). Zinclipscombite is pleochroic, from bright green to blue-green on X and light greenish brown on Z (X > Z). Chemical composition (electron microprobe, average of five point analyses, wt %): CaO 0.30, ZnO 15.90, Al2O3 4.77, Fe2O3 35.14, P2O5 33.86, As2O5 4.05, H2O (determined by the Penfield method) 4.94, total 98.96. The empirical formula calculated on the basis of (PO4,AsO4)2 is (Zn0.76Ca0.02)Σ0.78(Fe 1.72 3+ Al0.36)Σ2.08[(PO4)1.86(AsO4)0.14]Σ2.00(OH)1. 80 · 0.17H2O. The simplified formula is ZnFe 2 3+ (PO4)2(OH)2. Zinclipscombite is tetragonal, space group P43212 or P41212; a = 7.242(2) Å, c = 13.125(5) Å, V = 688.4(5) Å3, Z = 4. The strongest reflections in the X-ray powder diffraction pattern (d, (I, %) ((hkl)) are 4.79(80)(111), 3.32(100)(113), 3.21(60)(210), 2.602(45)(213), 2.299(40)(214), 2.049(40)(106), 1.663(45)(226), 1.605(50)(421, 108). Zinclipscombite is an analogue of lipscombite, Fe2+Fe 2 3+ (PO4)2(OH)2 (tetragonal), with Zn instead of Fe2+. The mineral is named for its chemical composition, the Zn-dominant analogue of lipscombite. The type material of zinclipscombite is deposited in the Mineralogical Collection of the Technische Universität Bergakademie Freiberg, Germany.  相似文献   

20.
Thermochemical properties have been either measured or estimated for synthetic monazite, LaPO4, and dissakisite, CaLaMgAl2(SiO4)3OH, the Mg-equivalent of allanite. A dissakisite formation enthalpy of ?6,976.5 ± 10.0 kJ mol?1 was derived from high-temperature drop-solution measurements in lead borate at 975 K. A third-law entropy value of 104.9 ± 1.6 J mol?1 K?1 was retrieved from low-temperature heat capacity (C p) measured on synthetic LaPO4 with an adiabatic calorimeter in the 30–300 K range. The C p values of lanthanum phases were measured in the 143–723 K range by differential scanning calorimetry. In this study, La(OH)3 appeared as suitable for drop solution in lead borate and represents an attractive alternative to La2O3. Pseudo-sections were calculated with the THERIAK-DOMINO software using the thermochemical data retrieved here for a simplified metapelitic composition (La = ∑REE + Y) and considering monazite and Fe-free epidotes along the dissakisite-clinozoïsite join, as the only REE-bearing minerals. Calculation shows a stability window for dissakisite-clinozoïsite epidotes (T between 250 and 550°C and P between 1 and 16 kbar), included in a wide monazite field. The P–T extension of this stability window depends on the bulk-rock Ca-content. Assuming that synthetic LaPO4 and dissakisite-(La) are good analogues of natural monazite and allanite, these results are consistent with the REE-mineralogy sequence observed in metapelites, where (1) monazite is found to be stable below 250°C, (2) around 250–450°C, depending on the pressure, allanite forms at the expense of monazite and (3) towards amphibolite conditions, monazite reappears at the expense of allanite.  相似文献   

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