Nanoparticles in natural systems II: The natural oxide fraction at interaction with natural organic matter and phosphate

Information on the particle size and reactive surface area of natural samples and its interaction with natural organic matter (NOM) is essential for the understanding bioavailability, toxicity, and transport of elements in the natural environment. In part I of this series (Hiemstra et al., 2010), a method is presented that allows the determination of the effective reactive surface area (A, m²/g soil) of the oxide particles of natural samples which uses a native probe ion (phosphate) and a model oxide (goethite) as proxy. In soils, the natural oxide particles are generally embedded in a matrix of natural organic matter (NOM) and this will affect the ion binding properties of the oxide fraction. A remarkably high variation in the natural phosphate loading of the oxide surfaces (Γ, μmol/m²) is observed in our soils and the present paper shows that it is due to surface complexation of NOM, acting as a competitor via site competition and electrostatic interaction. The competitive interaction of NOM can be described with the charge distribution (CD) model by defining a ≡NOM surface species. The interfacial charge distribution of this ≡NOM surface species can be rationalized based on calculations done with an evolved surface complexation model, known as the ligand and charge distribution (LCD) model. An adequate choice is the presence of a charge of −1 v.u. at the 1-plane and −0.5 v.u. at the 2-plane of the electrical double layer used (Extended Stern layer model).The effective interfacial NOM adsorption can be quantified by comparing the experimental phosphate concentration, measured under standardized field conditions (e.g. 0.01 M CaCl₂), with a prediction that uses the experimentally derived surface area (A) and the reversibly bound phosphate loading (Γ, μmol/m²) of the sample (part I) as input in the CD model. Ignoring the competitive action of adsorbed NOM leads to a severe under-prediction of the phosphate concentration by a factor ∼10 to 1000. The calculated effective loading of NOM is low at a high phosphate loading (Γ) and vice versa, showing the mutual competition of both constituents. Both constituents in combination usually dominate the surface loading of natural oxide fraction of samples and form the backbone in modeling the fate of other (minor) ions in the natural environment.Empirically, the effective NOM adsorption is found to correlate well to the organic carbon content (OC) of the samples. The effective NOM adsorption can also be linked to DOC. For this, a Non-Ideal Competitive adsorption (NICA) model is used. DOC is found to be a major explaining factor for the interfacial loading of NOM as well as phosphate. The empirical NOM-OC relation or the parameterized NICA model can be used as an alternative for estimating the effective NOM adsorption to be implemented in the CD model for calculation of the surface complexation of field samples. The biogeochemical impact of the NOM-PO₄ interaction is discussed.     

Leaching and differential recrystallization of metamict zircon under experimental hydrothermal conditions

We report results of hydrothermal experiments on four alluvial zircons from Sri Lanka, which cover a wide range of radiation damage, at 450 °C and 1.3 kbar for 744 h with 2 M CaCl₂ solution as reactive fluid. After the hydrothermal treatment, the most metamict samples show micrometer-thick reaction rims, which surround apparently unreacted zircon, as revealed by cathodoluminescence (CL) and Nomarski differential interference contrast (NDIC) images. These rims have sharp, curved, and transgressive boundaries with unreacted zircon and are, in some cases, spread out along cracks. The thickness of reaction rims increases with increasing cumulated !-dosage of the starting materials. The reaction rims are strongly enriched in Ca (up to 7000 ppm) and a water species and depleted in radiogenic Pb, Zr, and Si, as revealed by electron microprobe analyses. A significant Th loss from the reaction rims was detected in the case of the most metamict sample, whereas U remained in the structure. FT-infrared spectrometry and X-ray diffraction measurements revealed that the bulk run products were recrystallized. Using micro-Raman spectrometry, we were able to demonstrate that differential recrystallization took place. The reaction rims are strongly recrystallized, whereas the unreacted grain interiors underwent only minor recrystallization. Recrystallization of the rims is accompanied by an enhancement of the integral CL intensity. It is suggested that recrystallization in the reaction rims was catalyzed by water infiltration and ion exchange and prevented significant congruent zircon dissolution under the given experimental conditions. Previous zircon studies have shown that (1) a transgressive morphology, (2) a reduced Th-U ratio, and (3) an enhanced CL emission are also characteristics of rims in zircons from high-grade metamorphic rocks. Based on these similarities between natural and experimentally produced rims, it is suggested that leaching-catalyzed recrystallization is an important alteration process in zircon under wet geological conditions and can account for many complex core-rim structures found in natural zircons. Furthermore, the strong enrichment of Ca in the reaction rims supports previous assumptions that high Ca concentrations in natural zircons are of secondary origin. It is suggested that lower U-Pb concordia intercept ages obtained from single-phase zircons with high Ca contents date a leaching event.     

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.     

Transient release of Ni,Mn and Fe from mixed metal sulphides under oxidising and reducing conditions

The potential release of metals from anoxic sediments exposed to oxygen was investigated by using a synthetic preparation of metal sulphides dominated by solid phase FeS. The technique of DGT (diffusive gradients in thin-films) was used to measure sulphide and Fe, Mn and Ni in the anoxic metal-sulphide slurry, which had a pH of 6.4. Speciation calculations based on these data showed there was moderate supersaturation with respect to amorphous FeS in the solution phase. Measurements made using DGT with a range of diffusion layer thicknesses showed that when Fe, Mn and Ni are removed from solution there is fairly rapid (minutes) release from the solid phase, that is reasonably well sustained. This presumed desorptive release will be responsible for elevated concentrations of some metals in solution when sediments are resuspended. Oxidation of the slurry by bubbling with air rapidly (hours) removed Fe, Mn and Ni from the pore water solution. While Fe concentrations in solution remained low after the removal, Mn and Ni were transiently released. These results were consistent with initial rapid oxidation of Fe(II) to oxyhydroxides, which remove Mn(II) and Ni by adsorption. The slower oxidation of FeS then releases Mn and Ni, but these too are eventually removed by adsorption to iron oxyhydroxides. These data suggest that oxidation of metal sulphides will contribute to the release of metals from sediment disturbed by dredging or remedial aeration, but it is likely to be short lived, with complete removal within a day.     

Hydrological response to climate change in a glacierized catchment in the Himalayas

The analysis of climate change impact on the hydrology of high altitude glacierized catchments in the Himalayas is complex due to the high variability in climate, lack of data, large uncertainties in climate change projection and uncertainty about the response of glaciers. Therefore a high resolution combined cryospheric hydrological model was developed and calibrated that explicitly simulates glacier evolution and all major hydrological processes. The model was used to assess the future development of the glaciers and the runoff using an ensemble of downscaled climate model data in the Langtang catchment in Nepal. The analysis shows that both temperature and precipitation are projected to increase which results in a steady decline of the glacier area. The river flow is projected to increase significantly due to the increased precipitation and ice melt and the transition towards a rain river. Rain runoff and base flow will increase at the expense of glacier runoff. However, as the melt water peak coincides with the monsoon peak, no shifts in the hydrograph are expected.     

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。     

Concentration profiles of particles settling in the neutral and stratified atmospheric boundary layer

An expression for the vertical equilibrium concentration profile of heavy particles, including the effects of canopy on the eddy diffusivity as well as corrections for atmospheric stability, is proposed. This expression is validated against measurements of vertical concentration profiles of corn pollen above a corn field. The fitted theoretical profiles show that particle settling is correctly accounted for. The sensitivity to variations in the turbulent Schmidt number, settling velocity and stability corrections are explicitly characterized. The importance of independent measurements of the surface flux of pollen in future experiments is noted.     

The Summer Surface Energy Balance of the High Antarctic Plateau

The summertime surface energy balance (SEB) at Kohnen station, situated on the high Antarctic plateau (75°00′ S, 0°04′ E, 2892m above sea level) is presented for the period of 8 January to 9 February 2002. Shortwave and longwave radiation fluxes were measured directly; the former was corrected for problems associated with the cosine response of the instrument. Sensible and latent heat fluxes were calculated using the bulk method, and eddy-correlation measurements and the modified Bowen ratio method were used to verify these calculated fluxes. The calculated sub-surface heat flux was checked by comparing calculated to measured snow temperatures. Uncertainties in the measurements and energy-balance calculations are discussed. The general meteorological conditions were not extraordinary during the period of the experiment, with a mean 2-m air temperature of −27.5°C, specific humidity of 0.52×10⁻³kg kg⁻¹ and wind speed of 4.1ms⁻¹. The experiment covered the transition period from Antarctic summer (positive net radiation) to winter (negative net radiation), and as a result the period mean net radiation, sensible heat, latent heat and sub-surface heat fluxes were small with values of −1.1, 0.0, −1.0 and 0.7 Wm⁻², respectively. Daily mean net radiation peaked on cloudy days (16 Wm⁻²) and was negative on clear-sky days (minimum of −19 W m⁻²). Daily mean sensible heat flux ranged from −8 to +10 Wm⁻², latent heat flux from −4 to 0 Wm⁻² and sub-surface heat flux from −8 to +7 Wm⁻².