Arsenic mobility in the ambient sulfidic environment: Sorption of arsenic(V) and arsenic(III) onto disordered mackinawite

Arsenate, As(V), sorption onto synthetic iron(II) monosulfide, disordered mackinawite (FeS), is fast. As(V) sorption decreases above the point of zero surface charge of FeS and follows the pH-dependent concentration of positively charged surface species. No redox reaction is observed between the As(V) ions and the mineral surface over the time span of the experiments. This observation shows that As(V) dominantly forms an outer-sphere complex at the surface of mackinawite. Arsenite, As(III), sorption is not strongly pH-dependent and can be expressed by a Freundlich isotherm. Sorption is fast, although slower than that of As(V). As(III) also forms an outer-sphere complex at the surface of mackinawite. In agreement with previous spectroscopic studies, complexation at low As(V) and As(III) concentration occurs preferentially at the mono-coordinated sulfide edge sites. The K_d (L g⁻¹) values obtained from linear fits to the isotherm data are ∼9 for As(V) and ∼2 for As(III). Stronger sorption of As(V) than As(III), and thus a higher As(III) mobility, may be reflected in natural anoxic sulfidic waters when disordered mackinawite controls arsenic mobility.     

Constraints on the timing of granite emplacement, deformation and metamorphism in the Shamva area, Zimbabwe

In order to constrain the temporal relationship between granite (sensu lato) emplacement and metamorphism, isotope work was carried out on the minerals zircon and apatite (U-Pb), garnet (Pb-Pb) and hornblende (Ar-Ar) from wall rock samples in the Shamva area in Zimbabwe. The area, encompassing parts of the Chinamora and Murehwa batholiths and a wedge-shaped greenstone belt segment in between, is commonly quoted in the literature as an example illustrating pluton emplacement processes and deformational models for the Archean. New U-Pb dating of apatite from a boudinaged pegmatite within mafic schists in the batholith-greenstone contact zone has yielded an age of 2619 +28/-24 Ma. This age is interpreted as the best estimation of the intrusion age of this unit, depending on the assumed closure temperature, and provides an upper age limit for the syntectonic emplacement of the now gneissic granites. Pb-Pb dating of late kinematic garnets in cordierite-bearing rocks within the greenstone belt wall rocks gives an age of 2623NJ Ma. Together, this timing of relatively late, syntectonic plutonism and metamorphic mineral growth at ca. 2.62 Ga compares well with existing zircon crystallization ages for felsic volcanics (2645dž Ma, 2643NJ Ma) and post-tectonic porphyritic monzogranites (2601ᆢ Ma). Ar-Ar hornblende ages for mafic schists from different areas within the greenstone belt wall rocks range between 2621 and 2498 Ma and have been interpreted to indicate mixing between metamorphic ages and cooling ages. The data support a geological model whereby volcanism and sedimentation are associated with an early phase of regional deformation at ca. 2.64 Ga, which may have started earlier and lasted longer, and evolves into the voluminous emplacement of granites (now gneissic granites) in the batholiths at approximately 2.62 Ga. Emplacement of post-tectonic tabular monzogranites takes place at ca. 2.60 Ga.     

Effect of Fe on garnet–melt trace element partitioning: experiments in FCMAS and quantification of crystal-chemical controls in natural systems

Garnet–melt trace element partitioning experiments were performed in the system FeO–CaO–MgO–Al₂O₃–SiO₂ (FCMAS) at 3 GPa and 1540°C, aimed specifically at studying the effect of garnet Fe²⁺ content on partition coefficients (D^Grt/Melt). D^Grt/Melt, measured by SIMS, for trivalent elements entering the garnet X-site show a small but significant dependence on garnet almandine content. This dependence is rationalised using the lattice strain model of Blundy and Wood [Blundy, J.D., Wood, B.J., 1994. Prediction of crystal–melt partition coefficients from elastic moduli. Nature 372, 452–454], which describes partitioning of an element i with radius r_i and valency Z in terms of three parameters: the effective radius of the site r₀(Z), the strain-free partition coefficient D₀(Z) for a cation with radius r₀(Z), and the apparent compressibility of the garnet X-site given by its Young's modulus E_X(Z). Combination of these results with data in Fe-free systems [Van Westrenen, W., Blundy, J.D., Wood, B.J., 1999. Crystal-chemical controls on trace element partitioning between garnet and anhydrous silicate melt. Am. Mineral. 84, 838–847] and crystal structure data for spessartine, andradite, and uvarovite, leads to the following equations for r₀(3+) and E_X(3+) as a function of garnet composition (X) and pressure (P):

r₀(3+) [Å]=0.930X_Py+0.993X_Gr+0.916X_Alm+0.946X_Spes+1.05(X_And+X_Uv)−0.005(P [GPa]−3.0)(±0.005 Å)

E_X(3+) [GPa]=3.5×10¹²(1.38+r₀(3+) [Å])^−26.7(±30 GPa)

Accuracy of these equations is shown by application to the existing garnet–melt partitioning database, covering a wide range of P and T conditions (1.8 GPa<P<5.0 GPa; 975°C<T<1640°C). D^Grt/Melt for all 3+ elements entering the X-site (REE, Sc and Y) are predicted to within 10–40% at given P, T, and X, when D^Grt/Melt for just one of these elements is known. In the absence of such knowledge, relative element fractionation (e.g. D_Sm^Grt/Melt/D_Nd^Grt/Melt) can be predicted. As an example, we predict that during partial melting of garnet peridotite, group A eclogite, and garnet pyroxenite, r₀(3+) for garnets ranges from 0.939±0.005 to 0.953±0.009 Å. These values are consistently smaller than the ionic radius of the heaviest REE, Lu. The above equations quantify the crystal-chemical controls on garnet–melt partitioning for the REE, Y and Sc. As such, they represent a major advance en route to predicting D^Grt/Melt for these elements as a function of P, T and X.     

Deep mantle storage of the Earth’s missing niobium in late-stage residual melts from a magma ocean

The origin of the observed niobium deficit in the bulk silicate Earth (BSE) compared to chondritic meteorites constitutes a long-standing problem in geochemistry. The deficit requires a large-scale process fractionating niobium from tantalum, and a super-chondritic Nb/Ta reservoir hidden in the deep silicate Earth and/or in the metallic core. The only voluminous super-chondritic Nb/Ta silicate reservoir analysed to date is found in lunar basalts that assimilated highly evolved Fe-rich rocks associated with anorthosites in the lunar crust. These Fe-rich rocks, enriched in incompatible elements, are thought to represent the last fractions of melt remaining at the end of lunar magma ocean crystallization. Here we report high-precision Nb-Ta data for a Fe-rich, late-stage rock suite associated with a terrestrial anorthosite from the Proterozoic Bolangir complex in India. The geochemical characteristics of this rock suite resemble those expected for late-stage residual melts from a terrestrial magma ocean. Samples show extreme, super-chondritic Nb/Ta up to 31.1 and highly elevated Nb concentrations up to 338 ppm. We argue that formation of an early enriched crustal reservoir (EECR) with these characteristics (high Fe, high Nb, superchondritic Nb/Ta) is likely in the course of Hadean late-stage terrestrial magma ocean solidification. Subduction and subsequent permanent deep mantle storage in the D′′ layer of a minor amount (∼0.5% of the BSE mass) of this EECR can readily explain the terrestrial Nb deficit, without the need to invoke core Nb storage. Our model is consistent with short-lived ¹⁴²Nd and long-lived ¹⁷⁶Hf-¹⁴³Nd isotope models for early differentiation of the Earth’s crust. In addition, the inferred Lu/Hf of this EECR implies that this reservoir can also balance the offset of terrestrial Hf isotope ratios compared to the chondritic reservoir. As such, late-stage magma ocean residual melts may constitute the enigmatic parental reservoir of Hadean zircons with low time-integrated Hf isotope compositions.     

Lower crustal melting and the role of open-system processes in the genesis of syn-orogenic quartz diorite–granite–leucogranite associations: constraints from Sr–Nd–O isotopes from the Bandombaai Complex, Namibia

The Bandombaai Complex (southern Kaoko Belt, Namibia) consists of three main intrusive rock types including metaluminous hornblende- and sphene-bearing quartz diorites, allanite-bearing granodiorites and granites, and peraluminous garnet- and muscovite-bearing leucogranites. Intrusion of the quartz diorites is constrained by a U–Pb zircon age of 540±3 Ma.

Quartz diorites, granodiorites and granites display heterogeneous initial Nd- and O isotope compositions (_{Nd (540 Ma)}=−6.3 to −19.8; δ¹⁸O=9.0–11.6‰) but rather low and uniform initial Sr isotope compositions (⁸⁷Sr/⁸⁶Sr_initial=0.70794–0.70982). Two leucogranites and one aplite have higher initial ⁸⁷Sr/⁸⁶Sr ratios (0.70828–0.71559), but similar initial _Nd (−11.9 to −15.8) and oxygen isotope values (10.5–12.9‰). The geochemical and isotopic characteristics of the Bandombaai Complex are distinct from other granitoids of the Kaoko Belt and the Central Zone of the Damara orogen. Our study suggests that the quartz diorites of the Bandombaai Complex are generated by melting of heterogeneous mafic lower crust. Based on a comparison with results from amphibolite-dehydration melting experiments, a lower crustal garnet- and amphibole-bearing metabasalt, probably enriched in K₂O, is a likely source rock for the quartz diorites. The granodiorites/granites show low Rb/Sr (<0.6) ratios and are probably generated by partial melting of meta-igneous (intermediate) lower crustal sources by amphibole-dehydration melting. Most of the leucogranites display higher Rb/Sr ratios (>1) and are most likely generated by biotite-dehydration melting of heterogeneous felsic lower crust. All segments of the lower crust underwent partial melting during the Pan-African orogeny at a time (540 Ma) when the middle crust of the central Damara orogen also underwent high T, medium P regional metamorphism and melting. Geochemical and isotope data from the Bandombaai Complex suggest that the Pan-African orogeny in this part of the orogen was not a major crust-forming episode. Instead, even the most primitive rock types of the region, the quartz diorites, represent recycled lower crustal material.     

Fluids in granulites of the Southern Marginal Zone of the Limpopo Belt, South Africa

The Southern Marginal Zone of the Limpopo Belt in South Africa is characterised by a granulite and retrograde hydrated granulite terrane. The Southern Marginal Zone is, therefore, perfectly suitable to study fluids during and after granulite facies metamorphism by means of fluid inclusions and equilibrium calculations. Isolated and clustered high-salinity aqueous and CO₂(-CH₄) fluid inclusions within quartz inclusions in garnet in metapelites demonstrate that these immiscible low H₂O activity fluids were present under peak metamorphic conditions (800-850 °C, 7.5-8.5 kbar). The absence of widespread high-temperature metasomatic alteration indicates that the brine fluid was probably only locally present in small quantities. Thermocalc calculations demonstrate that the peak metamorphic mineral assemblage in mafic granulites was in equilibrium with a fluid with a low H₂O activity (0.2-0.3). The absence of water in CO₂-rich fluid inclusions is due to either observation difficulties or selective water leakage. The density of CO₂ inclusions in trails suggests a retrograde P-T path dominated by decompression at T<600 °C. Re-evaluation of previously published data demonstrates that retrograde hydration of the granulites at 600 °C occurred in the presence of H₂O and CO₂-rich fluids under P-T conditions of 5-6 kbar and ~600 °C. The different compositions of the hydrating fluid suggest more than one fluid source.     

Swimming upstream: addressing fossil fuel supply under the UNFCCC

Reducing fossil fuel supply is necessary to meet the Paris Agreement goal to keep warming ‘well below 2°C’, yet the Agreement is silent on the topic of fossil fuels. This article outlines reasons why it is important that Parties to the Agreement find ways to more explicitly address the phasing out of fossil fuel production under the UNFCCC. It describes how countries aiming to keep fossil fuel supply in line with Paris goals could articulate and report their actions within the current architecture of the Agreement. It also outlines specific mechanisms of the Paris Agreement through which issues related to the curtailment of fossil fuel supply can be addressed. Mapping out a transition away from fossil fuels – and facilitating this transition under the auspices of the UNFCCC process – can enhance the ambition and effectiveness of national and international climate mitigation efforts.

Key policy insights

• The international commitment to limit global average temperature increases to ‘well below 2°C’ provides a strong rationale for Parties to the Paris Agreement and the UNFCCC to pursue a phase-down in fossil fuel production, not just consumption.

• Several countries have already made commitments to address fossil fuel supply, by agreeing to phase down coal or oil exploration and production.

• Integrating these commitments into the UNFCCC process would link them to global climate goals, and ensure they form part of a broader global effort to transition away from fossil fuels.

• The Paris Agreement provides a number of new opportunities for Parties to address fossil fuel production.

     

全球贸易自由化对中国和世界经济的影响

全球贸易自由化是当前和未来世界经济发展不可避免的趋势,2001年开始的多哈回合贸易自由化多边谈判和最近刚刚取消的“多种纤维协定”（MFA）将在全球贸易自由化进程中发挥重要的作用。本研究的目的是通过一些案例分析,揭示贸易自由化对中国和世界经济的影响。采用全球贸易模型,我们分析了MFA和在多哈回合初期欧盟、美国和凯恩斯集团分别提出的贸易自由化提案。研究结果表明,虽然取消MFA对一些国家纺织部门带来冲击,但它极大地促进了大多数国家经济的发展,改善了全球福利;多哈谈判过程中提出的各种贸易自由化提案都在不同程度上促进世界经济的发展,但其影响大小依次为凯恩斯提案、美国提案和欧盟提案;贸易自由化对经济的影响在不同部门和不同国家间存在显著差别;更大程度的贸易自由化不但符合全球共同利益,也符合中国国家利益;中国在推动全球贸易自由化过程中应发挥更积极和更大的作用。