Wien effect of Cd/Zn on soil clay fraction and their interaction

Background

The coexistence of Cd²⁺ and Zn²⁺ ions in nature has a significant influence on their environmental behaviors in soils and bioavailability for plants. While many studies have been done on the mutual toxicity of Cd²⁺ and Zn²⁺, few studies can be found in the literature focused on the interaction of Cd²⁺ and Zn²⁺ on soil clay fractions especially in terms of energy relationship.

Results

The binding energies of Cd²⁺ on boggy soil (Histosols) particles and Zn²⁺ on yellow brown soil (Haplic Luvisols) particles were the highest, while those of Cd²⁺ and Zn²⁺ on paddy soil (Inceptisols) particles were the lowest. These results indicated that Cd²⁺ and Zn²⁺ have a strong capacity to adsorb in the solid phase at the soil–water interface of boggy soil and yellow brown soil, respectively. However, both Cd²⁺ and Zn²⁺ adsorbed on paddy soil particles easily release into the solution of the soil suspension. Unlike the binding energy, the higher adsorption energies of ions in boggy and yellow brown soils showed a weak binding force of ions in boggy soil and yellow brown soil. A 1:1 ratio of Cd²⁺ to Zn²⁺ promotes the mutual inhibition of their retentions. Cd²⁺ and Zn²⁺ have high mobility and bioavailability in paddy soil and yellow drab soil (Ustalfs), whereas they have high potential mobility and bioavailability in boggy soil and yellow brown soil.

Conclusion

In the combined system, Zn²⁺ had preferential adsorption than Cd²⁺ on soil clay fractions. Boggy soil and yellow brown soil have a low environmental risk with lower mobility and bioavailability of Cd²⁺ and Zn²⁺ while paddy soil and yellow drab soil present a substantial environmental risk. In the combined system, Cd²⁺ and Zn²⁺ restrain each other, resulting in the weaker binding force between ions and soil particles at a 1:1 ratio of Cd²⁺–Zn²⁺.

     

Cell parameters of thermally treated anorthite. Al,Si configurations in the average structures of the high temperature calcic plagioclases

Thermal treatments of anorthite carried out at up to 1,547° C show that the unit cell parameter changes as a function of the treatment temperature. The best fit curve found by non-linear least squares analysis is: =91.419-(0.327·10^-6)T ²+(0.199·10^-12)T ⁴-(0.391·10)T ⁶. The results obtained support significant Al,Si disorder (Al0.10, where Al=t ₁(0)-1/3 [t ₁(m)+t ₂(0)+t ₂(m)], Ribbe 1975), in anorthite equilibrated near the melting point and confirm a high temperature series differentiated from the low temperature series for calcic plagioclases in the An₈₅–An₁₀₀ range also. In the plot vs. An-content the high and low temperature curves intersect at An₈₅ composition and progressively diverge in the An₈₅–An₁₀₀ range. The trends of the high and low temperature curves in this range are interpretable on the basis of the degree of Al, Si order in the average structures of calcic plagioclases.     

Oxygen isotopes in mantle related and geothermally altered magmatites of the Transhimalayan (Gangdese) ranges

In closed magma systems SiO₂ approximately measures differentiation progress and oxygen isotopes can seem to obey Rayleigh fractionation only as a consequence of the behaviour of SiO₂. The main role of ¹⁸O is as a sensitive indicator of contamination, either at the start of differentiation ( ¹⁸O_init) or as a proportion of fractionation in AFC. Plots of ¹⁸O vs SiO₂-allow to determine initial ¹⁸O values for different sequences for source comparison. For NBS-28=9.60, the ¹⁸O at 48% SiO₂-varies between a high 6.4 for Kiglapait (Kalamarides 1984), 5.9 for Transhimalaya, 5.8 for Hachijo-Jima (Matsuhisa 1979), 5.6 for Koloula (Chivas et al. 1982) and a low 5.3 for the Darran Complex, New Zealand. The Transhimalayan batholiths (Gangdese belt) were emplaced in the Ladakh-Lhasa terrane, between the present-day Banggong-Nujiang, and Indus-Yarlung Tsangbo suture zones, after its accretion to Eurasia. The gradient of the least contaminated continuous ( ¹⁸O vs SiO₂-igneous trend line is similar to that of Koloula, and AFC calculations suggest a low secondary assimilation rate of less than 0.05 times the rate of crystallisation. Outliers enriched in ¹⁸O are frequent in the Lhasa, and apparently rare in the Ladakh transsect. Low- ¹⁸O (5.0–0) granitoids and andesites on the Lhasa-Yangbajain axis are the result of present day or recent near-surface geothermal activity; their quartzes still trace the granitoids to the Transhimalaya ¹⁸O trend line, but the distribution of low total rock or feldspar ¹⁸O values could be a guide to more recent heat flow and thermally marked tectonic lineaments. Two ignimbrites from Maqiang show hardly any ¹⁸O-contamination by crustal material.     

An enriched mantle source for potassic basanites: evidence from Karisimbi volcano,Virunga volcanic province,Rwanda

Lavas from Karisimbi, the largest volcano in the Virunga province in the Western Branch of the African rift on the Zaire-Rwandan border, constitute a suite of mafic potassic basanites and more evolved potassic derivatives. All of the lavas are potassic with K₂O/Na₂O1, and enriched in incompatible elements, with chondrite normalised (La/Yb)_n>18 and Nb/Zr>0.25. The ⁸⁷Sr/⁸⁶Sr and ¹⁴³Nd/¹⁴⁴Nd ratios reflect these enriched compositions, varying from 0.7052 and 0.51258 respectively in the K-basanites to 0.7132 and 0.51226 in the most evolved K-trachyte, although at MgO abundances >4% there is no systematic variation of isotope ratios with fractionation. At >4% MgO, lava compositions were controlled by assimilation and fractional crystallization in a sub-volcanic magma chamber. Trace-element and isotope variations in the more mafic lavas appear to reflect mixing between a primitive K-basanite (PKB) magma and a Sr-rich end-member, similar to melilite nephelinites from the neighbouring volcano, Nyiragongo. Both endmembers are mantle-derived and isotopically distinct, with the PKB being characterised by ⁸⁷Sr/⁸⁶Sr up to 0.707 and ¹⁴³Nd/¹⁴⁴Nd as low as 0.51236. Alternatively, isotope variations may be the time-integrated response to trace-element fractionations in a variably enriched mantle source. The Pb isotope variations within Karisimbi are complex. In the more evolved lavas all three ratios increase coherently with fractionation, whereas in the mafic varieties ²⁰⁶Pb/²⁰⁴Pb remains roughly constant at 19.2 while ²⁰⁷Pb/²⁰⁴Pb and ²⁰⁸Pb/²⁰⁴Pb vary from 15.67 to 15.78 and 39.49 to 40.80 respectively, defining sub-vertical trends, consistent with PKB-nephelinite magma mixing. The Nd and Sr isotopes indicate trace-element fractionation in the PKB source at 1 Ga, similar to ages derived from the overlying crust and suggesting a lithospheric origin. Elevated ²⁰⁸Pb/²⁰⁴Pb and ²⁰⁸Pb^*/²⁰⁶Pb^* values of the PKB are also consistent with Th/U fractionation at a similar time. However, this 1Ga age contrasts with that derived from the elevated ²⁰⁷Pb/²⁰⁴Pb ratios which indicate U/Pb fractionation during the Archaean. Crustal contamination can be excluded as the major control of Pb isotope variation in the PKB because their high Ce/Pb ratios (27) are similar to those typical of oceanic basalts. Parent/daughter trace-element fractionation and the high Ti, Nb and Ta abundances of the PKB lavas are all consistent with enrichment of a lithospheric source region by small-degree silicate melts at 1Ga. Comparison between measured and time-integrated trace-element ratios suggests that the degree of melting associated with recent magmatism was 5%. These data show that significant Th/U and Rb/Sr fractionation can be produced by intra-mantle melting processes and that high ²⁰⁸Pb/²⁰⁴Pb and ²⁰⁸Pb^*/²⁰⁶Pb^* values can evolve within the upper mantle and do not necessarily require the recycling of crustal material. Comparable isotope features in continental flood basalts and DUPAL ocean island basalts may be explained in a similar way.     

Hydrogen and carbon isotope studies on the graphite-bearing metapelites in the northern Kiso district of central Japan

Measurements were made of the hydrogen isotope ratios of hydrous silicates (mica and amphibole) and whole rocks, and the carbon isotope ratios of graphite and carbonaceous matter in the metamorphic rocks from the northern Kiso district in central Japan.D values of hydrous silicates in the graphite-bearing metapelites are always higher than those in graphite-free schists, even though the sample localities of the two rock-types are very close. Hydrogen isotopic equilibrium has been attained between the coexisting minerals.D/H ratios of water in the metamorphic fluids seem to depend strongly on the presence or absence of graphite and seem to be not constant throughout the district. The district is divided into three areas of low (metamorphic zones I, II), medium (zones IIIa–V) and high ¹³C_gr value (zones VIa–VII) areas. In the high ¹³C_gr values area, the carbon contents of the graphite-bearing rocks decrease slightly from zones VIa to VII, whereas the ¹³C_gr values increase sharply from the upper part of zone VIa to VIb. TheD values of biotite in these graphite-bearing rocks are higher than those in the medium ¹³C_gr area. This suggests that methane enriched inH and¹²C is produced and liberated by the devolatilization reactions between muscovite, graphite and water. The fluid produced is composed of water, methane and a subordinate amount of carbon dioxide, and its logfO₂ value is deduced to be about 1.2 lower than that defined by the FMQ buffer. In the medium ¹³C_gr area, the ¹³C values of graphite are nearly constant (–20.8), while the Fe₂O₃/(Fe₂O₃ + FeO) ratio of the graphite-bearing rocks apparently decreases with increasing metamorphic grade.D differences in hydrous silicates between graphite-bearing and graphite-free rocks are observed. These facts are interpreted to mean that methane was produced in addition to water and carbon dioxide, and that its generation ( ratio of the fluid was about 2) had practically no isotope effect on the graphite. In the low ¹³C_gr area, the carbon contents of the rocks decrease clearly from zones I to IIIa. TheD and ¹³C_gr values of the non-metamorphosed shales are much lower than those of the low grade graphite-bearing metapelites. This suggests that methane is produced and liberated from the rocks even at the incipient stage of metamorphism.     

A study on the dissolution rates of K-Cr(VI)-jarosites: kinetic analysis and implications

Background

The presence of natural and industrial jarosite type-compounds in the environment could have important implications in the mobility of potentially toxic elements such as lead, mercury, arsenic, chromium, among others. Understanding the dissolution reactions of jarosite-type compounds is notably important for an environmental assessment (for water and soil), since some of these elements could either return to the environment or work as temporary deposits of these species, thus would reduce their immediate environmental impact.

Results

This work reports the effects of temperature, pH, particle diameter and Cr(VI) content on the initial dissolution rates of K-Cr(VI)-jarosites (KFe₃[(SO₄)_2 ? X(CrO₄)_X](OH)₆). Temperature (T) was the variable with the strongest effect, followed by pH in acid/alkaline medium (H₃O⁺/OH^?). It was found that the substitution of CrO₄ ^2?in Y-site and the substitution of H₃O⁺ in M-site do not modify the dissolution rates. The model that describes the dissolution process is the unreacted core kinetic model, with the chemical reaction on the unreacted core surface. The dissolution in acid medium was congruent, while in alkaline media was incongruent. In both reaction media, there is a release of K⁺, SO₄ ^2? and CrO₄ ^2? from the KFe₃[(SO₄)_2 ? X(CrO₄)_X](OH)₆ structure, although the latter is rapidly absorbed by the solid residues of Fe(OH)₃ in alkaline medium dissolutions. The dissolution of KFe₃[(SO₄)_2 ? X(CrO₄)_X](OH)₆ exhibited good stability in a wide range of pH and T conditions corresponding to the calculated parameters of reaction order n, activation energy E _A and dissolution rate constants for each kinetic stages of induction and progressive conversion.

Conclusions

The kinetic analysis related to the reaction orders and calculated activation energies confirmed that extreme pH and T conditions are necessary to obtain considerably high dissolution rates. Extreme pH conditions (acidic or alkaline) cause the preferential release of K⁺, SO₄ ^2? and CrO₄ ^2? from the KFe₃[(SO₄)_2 ? X(CrO₄)_X](OH)₆ structure, although CrO₄ ^2? is quickly adsorbed by Fe(OH)₃ solid residues. The precipitation of phases such as KFe₃[(SO₄)_2 ? X(CrO₄)_X](OH)₆, and the absorption of Cr(VI) after dissolution can play an important role as retention mechanisms of Cr(VI) in nature.

     

The crystal structures of CuSO4 · H2O and CuSeO4 · H2O,and their relationships to kieserite

Summary The crystal structures of hydrothermally grown CuSO₄ · H₂O and CuSeO₄ · H₂O were determined by single crystal X-ray methods [Space group ,a = 5.037 (1), 5.129 (1) Å,b = 5.170(1), 5.527(1)Å,c = 7.578(2), 7.469(2)Å, = 108.62(1), 103.98(1)°, = 108.39(1), 106.52(1)°, = 90.93(1), 97.19(1)°; Z = 2; R_w = 0.026, 0.030 for 2065, 2235 reflections with sin / 0.90 Å^–1]. The Cu atoms are [4 + 2]-coordinated to O atoms. These elongated octahedra are corner connected via the H₂O molecule to form chains. The formal units ¹ [Cu₂O₈(H₂O)2]^12- are interconnected by [XO₄]^2- groups (X=S,Se) and hydrogen bonds (bond lengths 2.72–2.83 Å). The crystal structures show pseudomonoclinic symmetry and are strongly related to the structure type of kieserite.[/p]

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Die Kristallstrukturen von CuSO₄ · H₂O und CuSeO₄ · H₂O und ihre Beziehungen zum Kieserit

Zusammenfassung Die Kristallstrukturen von hydrothermal gezüchtetem CUSO₄ · H₂O und CuSeO₄. H₂O wurden an Einkristallen mittels Röntgenbeugung bestimmt [Raumgruppe ;a = 5.037(1), 5.129(1)Å,b = 5.170(1), 5.527(1)Å,c = 7.578(2), 7.469 (2) Å, = 108.62(1), 103.98(1)°, = 108.39(1), 106.52(1)°, = 90.93(1), 97.19(1)°; Z = 2; R_W = 0.026, 0.030 für 2065, 2235 Reflexe mit sin / 0.90)Å^–1]. Die Cu-Atome werden durch O-Atome [4+2]-koordiniert. Diese gestreckten /lOktaeder sind miteinander über Ecken durch die H₂O-Moleküle zu Ketten verknüpft. Die formalen Einheiten ¹ [CU₂O₈(H₂O)₂]^12– werden durch [XO₄]^2–-Gruppen (X = S, Se) und Wasserstoffbrücken (Bindungslängen 2.72–2.83Å) miteinander verbunden. Die Kristallstrukturen zeigen pseudomonokline Symmetrie und sind sehr nahe mit dem Strukturtyp des Kieserits verwandt.

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With 1 Figure     

Zwei Seladonite ungewöhnlicher chemiseher Zusammensetzung

Zusammenfassung Die optische, röntgenographische and chemische Untersuchung.zweier Seladonite aus einem Al₂0₃-reichen basaltischen Gestein and einem Porphyr ergab, daß dieses Mineral anscheinend doch häufiger als angenommen eine glaukonitähnliche Zusammensetzung haben and daß sein Chemismus auch von dem Ausgangsgestein abhängen kann. Im Rahmen dieser Untersuchung erhebt sich die Frage, ob es nicht sinnvoll ist, den Begriff Glaukonit auch auf Minerale nicht sedimentärer Herkunft aber der entsprechenden chemischen Zusammensetzung auszudehnen.

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Untill now the term celadonite was used for micaceous minerals which as well occured in igneous rocks as had the chemical composition (K, Na, Ca, H₃O) _<1 (Al, Fe³⁺)₁ (Fe²⁺, Mg)₁ [(OH)₂A_l>0Si_<4O₁₀], while the term glaucontte was restricted to micaceous minerals with the composition (K, Na, Ca, H₃0⁺)_<1 (Al, Fe³⁺, Fe²⁺; Mg)₂[(OH)₂Al_<1Si_>3O₁₀] formed in sedimentary rocks, mainly of marine origin. The few micas with glauconitic composition found in igneous rocks were called celadonites. Based on the analysis of two celadonites of such a kind from one rhyolite and one altered basaltic rock it is discussed, whether the term glaucontte should be extended to micaceous minerals of non-sedimentary origin but glauconitic composition.

     

The formation and development of debris flows in large watersheds after the 2008 Wenchuan Earthquake

The Wenchuan earthquake has caused abundance of loose materials supplies for debris flows. Many debris flows have occurred in watersheds in area beyond 20 km², presenting characteristics differing from those in small watersheds. The debris flows yearly frequency decreases exponentially, and the average debris flow magnitude increases linearly with watershed size. The rainfall thresholds for debris flows in large watersheds were expressed as I?=?14.7 D ^?0.79 (2 h?<?D?<?56 h), which is considerably higher than those in small watersheds as I?=?4.4 D ^?0.70 (2 h?<?D?<?37 h). A case study is conducted in Ergou, 39.4 km² in area, to illustrate the formation and development processes of debris flows in large watersheds. A debris flow develops in a large watershed only when the rainfall was high enough to trigger the wide-spread failures and erosions on slope and realize the confluence in the watershed. The debris flow was supplied by the widely distributed failures dominated by rill erosions (14 in 22 sources in this case). The intermittent supplying increased the size and duration of debris flow. While the landslide dam failures provided most amounts for debris flows (57 % of the total amount), and amplified the discharge suddenly. During these processes, the debris flow velocity and density increased as well. The similar processes were observed in other large watersheds, indicating this case is representative.     

Koritnigit,Zn[H2O|HOAsO3], ein neues Mineral aus Tsumeb,Südwestafrika

Zusammenfassung Das neue Mineral Koritnigit ist ein wasserhaltiges Zinkhydrogenarsenat der Formel Zn[H₂O|HOAsO₃]. Die chemische Analyse (Elektronenmikrosonde und T.G.A.) ergab: As₂O₅ 51,75%, ZnO 35,97% und H₂O 12,3%, Summe 100,0%. Die HOAsO₃-Ionen wurden IR-spektroskopisch nachgewiesen. Koritnigit ist löslich in kalter, verdünnter HCl und HNO₃.Die Gitterkonstanten sind:a ₀=7,948(2),b ₀=15,829(5),c ₀=6,668(2) Å, =90,86(2), =96,56(2), =90,05(2)^o,V=833,2(4)ų,V=8. Die Raumgruppe ist . Die stärksten Linien des Pulverdiagramms sind: 7,90(10) (020,100), 3,83(7) ( ), 3,16(9) ( ) 2,926(4) (150), 2,679(4) ( ), 2,461(6) ( ), 2,186(5) ( ), 1,969(4) (400), 1,649(3) (004).Koritnigit ist wasserklar bis durchscheinend weiß. Idiomorphe Kristalle sind nicht bekannt. Die Spaltbarkeit nach {010} ist ausgezeichnet und auf {010} sind Spaltspuren nach [001] und nach [100] erkennbar. Härte 2.G=3,54 g·cm^–3,D _x =3,56 g·cm^–3. Koritnigit ist optisch zweiachsig positiv, 2V70(5)^o. Die Werte der Lichtbrechung sind:n =1,632(5),n =1,652(3) undn =1,693(3).Koritnigit wurde auf der 31. Sohle der Tsumeb-Mine, Südwestafrika gefunden. Er kommt als Sekundärmineral in Paragenese mit Cu-Adamin, Stranskiit und drei weiteren, vorerst nicht identifizierten mineralen in Zersetzungshohlräumen von Tennantit vor.

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Koritnigite, Zn[H₂O|HOAsO₃], a new mineral from Tsumeb, South West Africa

Summary The new mineral koritnigite is a hydrated zinc hydrogen arsenate with the formula Zn[H₂O|HOAsO₃]. Chemical analysis (electron microprobe and t.g.a.) gave: As₂O₅ 51.75%, ZnO 35.97%, and H₂O 12.3%, total 100.0%. The HOAsO₃ ions were determined by IR spectroscopy. Koritnigite is soluble in cold diluted HCl and HNO₃. The unit cell dimensions are:a ₀=7.948(2),b ₀=15.829(5),c ₀=6.668(2)Å, =90.86(2), =96.56(2), =90.05(2)^o,V=833.2(4) ų,Z=8. The space group is . The strongest lines of the powder pattern are: 7.90(10) (020, 100), 3.83(7) ( ), 3.16(9) ( ), 2.926(4) (150), 2.679(4) ( ), 2.461(6) ( ), 2.186(5) ( ), 1.969(4)(400), 1.649(3) (004).

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Mit 2 Abbildungen

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Herrn Univ. Prof. Dr.H. Meixner zum 70. Geburtstag gewidmet.     

Weakly bound water structure,bond valence saturation and water dynamics at the goethite (100) surface/aqueous interface: ab initio dynamical simulations

Background

Many important geochemical and biogeochemical reactions occur in the mineral/formation water interface of the highly abundant mineral, goethite [α-Fe(OOH)]. Ab initio molecular dynamics (AIMD) simulations of the goethite α-FeOOH (100) surface and the structure, water bond formation and dynamics of water molecules in the mineral/aqueous interface are presented. Several exchange correlation functionals were employed (PBE96, PBE96 + Grimme, and PBE0) in the simulations of a (3 × 2) goethite surface with 65 absorbed water molecules in a 3D-periodic supercell (a = 30 Å, FeOOH slab ~12 Å thick, solvation layer ~18 Å thick).

Results

The lowest energy goethite (100) surface termination model was determined to have an exposed surface Fe³⁺ that was loosely capped by a water molecule and a shared hydroxide with a neighboring surface Fe³⁺. The water molecules capping surface Fe³⁺ ions were found to be loosely bound at all DFT levels with and without Grimme corrections, indicative that each surface Fe³⁺ was coordinated with only five neighbors. These long bonds were supported by bond valence theory calculations, which showed that the bond valence of the surface Fe³⁺ was saturated and surface has a neutral charge. The polarization of the water layer adjacent to the surface was found to be small and affected only the nearest water. Analysis by density difference plots and localized Boys orbitals identified three types of water molecules: those loosely bound to the surface Fe³⁺, those hydrogen bonded to the surface hydroxyl, and bulk water with tetrahedral coordination. Boys orbital analysis showed that the spin down lone pair orbital of the weakly absorbed water interact more strongly with the spin up Fe³⁺ ion. These weakly bound surface water molecules were found to rapidly exchange with the second water layer (~0.025 exchanges/ps) using a dissociative mechanism.

Conclusions

Water molecules adjacent to the surface were found to only weakly interact with the surface and as a result were readily able to exchange with the bulk water. To account for the large surface Fe–OH₂ distances in the DFT calculations it was proposed that the surface Fe³⁺ atoms, which already have their bond valence fully satisfied with only five neighbors, are under-coordinated with respect to the bulk coordination.

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Graphical abstract All first principle calculations, at all practically achievable levels, for the goethite 100 aqueous interface support a long bond and weak interaction between the exposed surface Fe³⁺ and water molecules capping the surface. This result is supported by bond valence theory calculations and is indicative that each surface Fe³⁺ is coordinated with only 5 neighbors.

     

Clinopyroxenes from plagioclase peridotites (Zabargad Island,Red Sea) and comparison between high- and low-pressure mantle clinopyroxenes

Summary A detailed crystal-chemical study of clinopyroxenes from the peridotite-pyroxenite association from Zabargad Island (Red Sea) has been carried out to decline the intercrystalline relationships in mantle-derived clinopyroxenes equilibrated at low pressure conditions (plagioclase facies:Pl-Cpx).Pl-Cpx typically show larger cell volume (>437 °A3) compared with those from spinel and garnet-spinel peridotite nodules (Sp-Cpx). The larger cell volume is mainly achieved through higher Mgm, and louver Al^VI occupancies, which strongly increase the M l volume. Concurrently, overcharging on the O3 oxygens due te, the high Ca_M2 ( 0.828 atoms per formula unit, a.f.u.) and low Na_M2 (< 0.037 a.f.u.) occupancies requires lengthening of T-0 distances and increase of the T volume. Consequently: i) for the saine M 1 volume,Pl-Cpx have larger cell volume compared withSp-Cpx; ii) for a given trivalent cations (R³⁺) content in M1, Al^IV is higher inPl-Cpx than inSp-Cpx. Plots of cell volume vs Ml volume and of M1-O2 vs T-O_nbr bond lengths are a simple way to illustrate the complex intracrystalline relationships which control (Ca Na)_M2, (Si Al^IV)_T and (Mg R³⁺)_M1 substitutions, and thus permit sensitive qualitative discrimination of the pressure regimes of equilibration of mantle clinopyroxenes.

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Klinopyroxene aus Plagioklas-Peridotiten der Insel Zabargad (Rotes Meer) und Verqleich zwischen Hoch- und Tiefdruck-Klinopyroxenen des Mantels

Zusammenfassung Klinopyroxene aus der Peridotit-Pyroxenit-Assoziation der Insel Zabargad (Rotes Meer) wurden eingehend kristallchemisch untersucht, um die inter-kristallinen Bezie-hungen in aus dem Mantel stammenden Klinopyroxenen zu definieren, die unter niedrigem Druck (Plagioklas-Fazies,PI-Cpx) equilibriert wurden.PI-Cpx zeigen typisch ein größeres Zellvolumen (>437 ų) im Vergleich zu jenen aus Knollen von Spinell- und Granat-Spinell-Peridotiten (Sp-Cpx). Das größere Zellvolumen wird hauptsächlich durch größere Mg_M1- und kleinere Al^VI-Besetzungen erreicht, welche das M1-Volumen stark erhöhen. Gleichlaufend verlangt ein Ladungsüberschuß an den O3-Sauerstoffen durch hohe Ca_M2-Besetzungen (> 0,828 Atome pro Formeleinheit) und niedrige Na_M2-Besetzungen ( 0,037 Atome pro Formeleinheit) eine Verlängerung der T-O-Abstände und ein Anwachsen des T-Volumens. Folglich haben für das gleiche M1-Volumen diePl-Cpx ein größeres Zellvolumen gegenüber denSp-Cpx, und ferner ist für einen gegebenen Gehalt an dreiwertigen Kationen (R³⁺) auf M1 das Al^IV inPI-Cpx höher als inSp-Cpx. Diagramme von Zellvolumen gegen Volumen von M1, sowie von M1-O2 gegen T-O_nbr sind ein einfaches Mittel, um die komplexen interkristallinen Beziehungen aufzuzeigen, welche die Substitutionen (Ca Na)_M2, (Si AI_IV)_T und (Mg R³⁺)_M1 beherrschen, sie erlauben eine empfindliche qualitative Unterscheidung der Druckverhältnisse bei der Equilibrierung von Klinopyroxenen aus dem Mantel.

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With 6 Figures     

Characterization,dissolution and solubility of the hydroxypyromorphite–hydroxyapatite solid solution [(Pb<Subscript>x</Subscript>Ca<Subscript>1−x</Subscript>)<Subscript>5</Subscript>(PO<Subscript>4</Subscript>)<Subscript>3</Subscript>OH] at 25 °C and pH 2–9

Background

The interaction between Ca-HAP and Pb²⁺ solution can result in the formation of a hydroxyapatite–hydroxypyromorphite solid solution [(Pb_xCa_1?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 (Pb_xCa_1?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 [(Pb_xCa_1?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 (X_Pb) of the solids. For the solids with high X_Pb [(Pb_0.89Ca_0.11)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 X_Pb (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 X_Pb (0.89–1.00) was different from that of the solids with low X_Pb (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 (X_Pb) of (Pb_xCa_1?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 (Pb_xCa_1?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 (Pb_xCa_1?x)₅(PO₄)₃(OH) was in equilibrium with the Ca-rich aqueous solution.

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Graphical abstractLippmann diagrams for dissolution of the hydroxypyromorphite–hydroxyapatite solid solution [(Pb_xCa_1?x)₅(PO₄)₃OH] at 25??C and an initial pH of 2.00.

     

The pleochroism of a gem-quality enstatite in the region of the OH stretching frequency,with a stereochemical interpretation

Summary The pleochroic behaviour of a gem-quality enstatite from Tanzania was investigated in the region =2500 to 4000 cm^–1. Two sharp absorption bands at =3410 cm^–1 and =3510 cm^–1 are interpreted to be caused by OH stretching vibrations. As their absorption coefficients are considerably larger parallel to [001] (=direction of the silicate chains) than perpendicular to this direction, the OH dipoles have to be oriented approximately parallel to [001]. On this basis, a stereochemical interpretation of the incorporation of the OH groups into the structure is given.

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Der Pleochroismus eines Enstatits von Edelsteinqualität im Gebiet der OH-Streckfrequenz und seine kristallchemische Interpretation

Zusammenfassung Das pleochroitische Verhalten eines Enstatits von Edelsteinqualität aus Tansania wurde im Bereich =2500 bis 4000 cm^–1 untersucht. Von zwei scharfen Banden bei =3410 cm^–1 und 3510 cm^–1 wird angenommen, daß sie durch OH-Streckschwingungen herrühren. Da ihre Absorptionskoeffizienten parallel zu [001] (=Richtung der Silikatketten) beträchtlich größer sind als senkrecht dazu, müssen die OH-Dipole ungefähr parallel zu [001] liegen. Auf dieser Basis wird der Einbau der OH-Gruppen in die Struktur diskutiert.

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Carbon dioxide emissions from the Three Gorges Reservoir,China

Carbon dioxide (CO₂) emission from the river-type reservoir is an hotspot of carbon cycle within inland waters. However, related studies on the different types of reservoirs are still inadequate. Therefore, we sampled the Three Gorges Reservoir (TGR), a typical river-type reservoir having both river and lake characteristics, using an online system (HydroCTM/CO₂) and YSI-6600v2 meter to determine the partial pressure of carbon dioxide (pCO₂) and physical chemical parameters in 2013. The results showed that the CO₂ flux from the mainstream ranged from 26.1 to 92.2 mg CO₂/m² h with average CO₂ fluxes of 50.0 mg/m² h. The CO₂ fluxes from the tributary ranged from ?10.91 to 53.95 mg CO₂/m² h with area-weighted average CO₂ fluxes of 11.4 mg/m² h. The main stream emits CO₂ to the atmosphere the whole year; however, the surface water of the tributary can sometimes act as a sink of CO₂ for the atmosphere. As the operation of the TGR, the tributary became more favorable to photosynthetic uptake of CO₂ especially in summer. The total CO₂ flux was estimated to be 0.34 and 0.03 Tg CO₂/year from the mainstream and the tributaries, respectively. Our emission rates are lower than previous estimates, but they are in agreement with the average CO₂ flux from temperate reservoirs estimated by Barros et al. (Nat Geosci 4(9):593–596, 2011).     

Oxygen,sulfur, and strontium isotope and fluid inclusion studies of barite deposits from the Iglesiente-Sulcis mining district,Southwestern Sardinia,Italy

This paper deals with barite from stratiform, karst, and vein deposits hosted within Lower Paleozoic rocks of the Iglesiente-Sulcis mining district in southwestern Sardinia. For comparison sulfates from mine waters are studied. Stratiform barite displays ³⁴S=28.8–32.1, ¹⁸O=12.7–15.6, and ⁸⁷Sr/⁸⁶Sr=0.7087, in keeping with an essentially Cambrian marine origin of both sulfate and strontium. Epigenetic barite from post-Hercynian karst and vein deposits is indistinguishable for both sulfur and oxygen isotopes with ³⁴S=15.3–26.4 and ¹⁸O=6.6–12.5; ⁸⁷Sr/⁸⁶Sr ratios vary 0.7094–0.7140. These results and the microthermometric and salinity data from fluid inclusions concur in suggesting that barite formed at the site of mineralization by oxidation of reduced sulfur from Cambrian-Ordovician sulfide ores in warm, sometimes hot solutions consisting of dilute water and saline brine with different ¹⁸O values. The relative proportion of the two types of water may have largely varied within a given deposit during the mineralization. In the karst barite Sr was essentially provided by carbonate host rocks, whereas both carbonate and Lower Paleozoic shale host rocks should have been important sources for Sr of the vein barite. Finally, ³⁴S data of dissolved sulfate provide further support for the mixed seawater-meteoric water composition of mine waters from the Iglesiente area.     

Carbon and oxygen isotopic covariations in hydrothermal calcites

Isotopic covariations of carbon and oxygen in hydrothermal calcites are quantitatively modeled in terms of the following three mixing processes: (1) mixing between two different fluids which leads to the precipitation of calcite; (2) mixing between fluid and rock: (a) calcite precipitation due to fluid/rock interaction, (b) secondary alteration of primary calcite by interaction with a subsequent fluid. The models are derived from mass balance equations. A distinction among the three mixing processes can be made on a ¹³C vs ¹⁸O diagram, which places important constraints on the genesis of hydrothermal mineralization. The variables which control the ultimate isotopic composition of hydrothermal calcites include the composition of the initial fluid and the wallrock, temperature, and dissolved carbon species. Owing to significant temperature-dependent fractionation effects during equilibrium precipitation of calcite from a hydrothermal fluid, the mixing processes may be distinguished by telltale patterns of isotopic data in ¹³C vs ¹⁸O space. In particular, caution must be exercised in postulating the fluid mixing as the cause for mineral deposition. This is demonstrated for hydrothermal Pb-Zn deposits in the western Harz Mountains, Germany. A positive correlation between ¹³C and ¹⁸O values is observed for calcites from the Bad Grund deposit in the Upper Harz. Two sample profiles through calcite veins show similar correlations with the lowest -values at the center of the veins and the highest -values at the vein margins. Because the correlation array has a greater slope than for calcite precipitation at equilibrium in a closed system and because fluid mixing may not proceed perpendicular to the vein strike, it is assumed that a fluid/rock interaction is responsible for the observed correlation and thus for the precipitation of calcite. A deep-seated fluid is inferred with a ¹³C value of — 7% and a ¹⁸O value of +10%., as well as H₂CO₃ as the dominant dissolved carbon species; precipitation temperatures of the calcites are estimated to be about 280 170°C. Quite different isotopic distributions are observed for calcites from the St. Andreasberg deposit in the Middle Harz. An alteration model is suggested based mainly on the isotopic distribution through a calcite vein. In addition to a primary fluid which has the same isotopic composition as that in the Bad Grund deposit and thus seems to be responsible for the precipitation of calcite associated with sulfides, an evolved, HCO ₃ ^- -dominant subsurface fluid with ¹³C about -20 — 15% and ¹⁸O 0% is deduced to alter the primary calcite at low temperatures of 70 40°C.     

The hydraulic retention time on the particle removal efficiency by <Emphasis Type="Italic">Daphnia magna</Emphasis> filtration on treated wastewater

The study of low-cost techniques for the tertiary treatment of wastewater is of global interest; above all low-energy techniques that do not require the use of chemicals. In this study, a wastewater treatment technology based on the filtration by a zooplanktonic population (Daphnia magna) is studied in controlled laboratory and mesocosm experiments for different hydraulic retention times (HRT). The efficiency of the treatment is evaluated in terms of particle removal efficiency. From laboratory experiments, HRT over 12 h and Daphnia concentrations above 50 individuals l^?1 guarantee a particle removal efficiency greater than 30 %. However, low HRT of 6 h would require Daphnia concentrations above 70 individuals l^?1 in order to obtain a particle removal efficiency of 20 %. The minimum removal efficiency of 2 % was for HRT = 3 h, independent of the Daphnia concentration. In the mesocosm, the growth of Daphnia individuals enhanced Daphnia magna filtering rates and higher removal efficiencies than those in the laboratory for the same HRT range. In the mesocosm experiments E. coli concentrations were reduced to a maximum of 2 logarithmic units. A balance equation model is proposed to predict particle removal efficiencies for varying HRT.     

Synthesis and properties of Mn-bearing yoderite and of Mn-bearing kornerupine as by-product

Summary Yoderite with compositions close to those of the natural purple variety were synthesized from gels at high water pressures (15–16 kbar) and temperatures (650, 800°C) at the oxygen fugacities of the Mn₂O₃/MnO₂-buffer with yields up to 95%. Chemical formulae based on microprobe data and water analyses are Mg_1.90(Al_6.01Fe³⁺ _0.28Mn³⁺ _0.11)_=6.40Si_3.8O_18.21(OH)_1.79 and Mg_1.86(Al_5.77Fe³⁺ _0.36Mn³⁺ _0.04)_=6.17Si₄O_18.20(OH)_1.80. Manganiferous, but iron-free yoderite with the formula Mg_1.85(Al_6.26Mn³⁺ _0.10)_=6.36Si_3.91O_18.15(OH)_1.85 was also obtained and proves that Mn³⁺ alone may stabilize the yoderite structure, although this does not necessarily imply thermodynamic-stability. All these synthetic yoderites exhibit the typical purple color known from the natural mineral with pleochroism of dark blue b to colorless b, which confirms the earlier spectroscopic conclusion that Mn is responsible for the purple color of yoderite. Compared to ferric iron, Mn³⁺ is incorporated into yoderite in much smaller amounts, although the maximum attained here (0.11 p.f.u.) is still below the 0.15 found in new analyses of natural yoderite from Tanzania.In some runs yoderite coexisted with kornerupine containing Mn and Fe as well and showing spectacular pleochroism from dark green b to light red c. Relative to yoderite Mn is fractionated into kornerupine. The analytical data suggest that most of the manganese is incorporated as Mn²⁺, although some Mn³⁺ may be the reason for the color. Coexisting braunite contains high amounts of Mg and Al substituting for Mn²⁺ and Mn³⁺, respectively. Garnet obtained from the Fe-free gel contains only Mn²⁺ and has the end member composition Pyrope₇₉Spessartine₂₁ despite high oxygen fugacity.

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Synthese und Eigenschaften von Mn-haltigem Yoderit und Mn-haltigem Kornerupin als Nebenprodukt

Zusammenfassung Die Synthese von Yoderiten mit chemischen Zusammensetzungen nahe denjenigen der natürlichen, blau gefärbten Varietät gelang in Ausbeuten bis zu 95% aus Gelen bei hohen Versuchsdrücken (15, 16 kbar) und Temperaturen von 650 bzw. 800°C. Die Sauerstoffugazität wurde durch den Puffer Mn₂O₃/MnO₂ kontrolliert. Aus Mikrosondenanalysen und Wasserbestimmungen wurden folgende chemische Formeln von Yoderit bestimmt: Mg_1.90(Al_6.01Fe³⁺ _0.28Mn³⁺ _0.11)_=6.40Si_3.80O_18.21(OH)1.79 and Mg_1.86(Al_5.77Fe³⁺ _0.36Mn³⁺ _0.04)_=6.17Si₄O_18.20(OH)_1.80. Die Stabilisierung der Yoderitstruktur allein durch Mangan wurde durch die Synthese manganhaltigen, aber eisenfreien Yoderits, Mg_1.85(Al_6.26Mn³⁺ _0.10)_=6.36Si_3.91O_18.15(OH)_1.85 belegt. Sämtliche synthetisierten Yoderite besitzen die typische dunkelblaue Farbe, wie sie vom natürlichen Mineral bekannt ist, und zeigen einen Pleochroismus von dunkelblau b zu farblos b. Dies unterstützt die ursprüngliche auf spektroskopischen Untersuchungen basierende Vermutung, daß Mangan für die blaue Farbe von Yoderit verantwortlich ist. Im Vergleich zu Eisen wird Mn³⁺ in geringerem Ausmaß in die Yoderit-struktur eingebaut, wobei die hier erreichte maximale Menge von 0.11 Mn³⁺ p.F.E. unter derjenigen der natürlichen Yoderite von Mautia Hill, Tansania, liegt (dort 0.15 Mn³⁺ p.F.E.).In einigen Versuchsprodukten koexistierte mit Yoderit auch Fe-Mn haltiger Kornerupin, der einen ausgeprägten Pleochroismus von dunkelgrün b zu hellrot c besitzt. Kornerupin enthält im Vergleich zu Yoderit mehr Mangan. Chemische Analysen dieser Phase belegen den Einbau von zweiwertigem Mangan, obwohl wahrscheinlich Spuren von Mn³⁺ die Farbe von Kornerupin verursachen. Mit Yoderit koexistierender Braunit besitzt Mg und Al, die für Mn²⁺ bzw. Mn³⁺ substituiert wurden. Trotz hoher Sauerstoffugazität enthält Granat, der aus einem Fe-freien Gel erhalten wurde, ausschließlich zweiwertiges Mangan und stellt einen Mischkristall zwischen Pyrop und Spessartin dar (Py₇₉Spess₂₁).

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Redox states of lithospheric and asthenospheric upper mantle

The oxidation state of lithospheric upper mantle is heterogeneous on a scale of at least four log units. Oxygen fugacities ( ) relative to the FMQ buffer using the olivine-orthopyroxene-spinel equilibrium range from about FMQ-3 to FMQ+1. Isolated samples from cratonic Archaean lithosphere may plot as low as FMQ-5. In shallow Proterozoic and Phanerozoic lithosphere, the relative is predominantly controlled by sliding Fe³⁺-Fe²⁺ equilibria. Spinel peridotite xenoliths in continental basalts follow a trend of increasing with increasing refractoriness, to a relative well above graphite stability. This suggests that any relative reduction in lithospheric upper mantle that may occur as a result of stripping lithosphere of its basaltic component is overprinted by later metasomatism and relative oxidation. With increasing pressure and depth in lithosphere, elemental carbon becomes progressively refractory and carbon-bearing equilibria more important for control. The solubility of carbon in H₂O-rich fluid (and presumably in H₂O-rich small-degree melts) under the P,T conditions of Archaean lithosphere is about an order of magnitude lower than in shallow modern lithosphere, indicating that high-pressure metasomatism may take place under carbon-saturated conditions. The maximum in deep Archaen lithosphere must be constrained by equilibria such as EMOG/D. If the marked chemical depletion and the orthopyroxene-rich nature of Archaean lithospheric xenoliths is caused by carbonatite (as opposed to komatiite) melt segregation, as suggested here, then a realistic lower limit may be given by the H₂O +C=CH₄+O₂ (C-H₂O) equilibrium. Below C –H₂O a fluid becomes CH₄ rather than CO₂-bearing and carbonatitic melt presumably unstable. The actual in deep Archaean lithosphere is then a function of the activities of CO₂ and MgCO₃. Basaltic melts are more oxidized than samples from lithospheric upper mantle. Mid-ocean ridge (MORB) and ocean-island basalts (OIB) range between FMQ-1 (N-MORB) and about FMQ +2 (OIB). The most oxidized basaltic melts are primitive island-arc basalts (IAB) that may fall above FMQ+3. If basalts are accurate probes of their mantle sources, then asthenospheric upper mantle is more oxidized than lithosphere. However, there is a wide range of processes that may alter melt relative to that of the mantle source. These include partial melting, melt segregation, shifts in Fe³⁺/Fe²⁺ melt ratios upon decompression, oxygen exchange with ambient mantle during ascent, and low-pressure volatile degassing. Degassing is not very effective in causing large-scale and uniform shifts, while the elimination of buffering equilibria during partial melting is. Upwelling graphite-bearing asthenosphere will decompress along -pressure paths approximately parallel to the graphite saturation surface, involving reduction relative to FMQ. The relative will be constrained to below the CCO equilibrium and will be a function of . Upwelling asthenosphere whose graphite content has been exhausted by partial melting, or melts that have segregated and chemically decoupled from a graphite-bearing residuum will decompress along -decompression paths controlled by continuous Fe³⁺-Fe²⁺ solid-melt equilibria. These equilibria will involve increases in relative to the graphite saturation surface and relative to FMQ. Melts that finally segregate from that source and erupt on the earth's surface may then be significantly more oxidized than their mantle sources at depth prior to partial melting. The extent of melt oxidation relative to the mantle source may be directly proportional to the depth of graphite exhaustion in the mantle source.