Isotopic fractionation and reaction kinetics between Cr(III) and Cr(VI) in aqueous media

The redox-sensitive stable isotope geochemistry of chromium bears the potential to monitor the attenuation of chromate pollution and to investigate changes in environmental conditions in the present and the past. The use of stable Cr isotope data as a geo-environmental tracer, however, necessitates an understanding of the reaction kinetics and Cr fractionation behaviour during redox transition and isotope exchange. Here, we report stable chromium isotope fractionation data for Cr(VI) reduction, Cr(III) oxidation and isotopic exchange between soluble Cr(III) and Cr(VI) in aqueous media. The reduction of Cr(VI) to Cr(III) with H₂O₂ under strongly acidic conditions shows a near-equilibrium isotope fractionation of Δ^53/52Cr_{(Cr(III)-Cr(VI))} of −3.54 ± 0.35‰. At pH neutrality, however, the reduction experiments show a kinetic isotope fractionation Δ^53/52Cr_{(Cr(III)-Cr(VI))} of −5‰ for the extent of reduction of up to 85% of the chromium. The oxidation of Cr(III) to Cr(VI) in alkaline media, using H₂O₂ as the oxidant, cannot be explained by a single, unidirectional reaction. Our experiments indicate that the involvement of the unstable intermediates Cr(IV) and Cr(V) and their disproportionation during redox reactions between Cr(III) and Cr(VI) influence the overall fractionation factor, depending on the prevailing pH conditions and the reaction rates. No detectable isotope exchange between soluble Cr(VI) and Cr(III) species at pH values of 5.5 and 7 was revealed over a timescale of days to weeks. This means that, at least within such a time frame, the isotopic composition of Cr(VI) in a natural system will not be influenced by equilibration with any Cr(III) and thus reveal the true extent of reduction, given that the Cr isotope composition of the source Cr(VI) and the fractionation factor for the prevailing conditions are known.     

Additionality revisited: guarding the integrity of market mechanisms under the Paris Agreement

ABSTRACT

The Paris Agreement requires mitigation contributions from all Parties. Therefore, the determination of additionality of activities under the market mechanisms of its Article 6 will need to be revisited. This paper provides recommendations on how to operationalize additionality under Article 6. We first review generic definitions of additionality and current approaches for testing of additionality before discussing under which conditions additionality testing of specific activities or policies is still necessary under the new context of the Paris Agreement, that is, in order to prevent increases of global emissions. We argue that the possibility of ‘hot air’ generation under nationally-determined contributions (NDCs) requires an independent check of the NDC’s ambition. If the NDC of the transferring country does contain ‘hot air’, or if the transferred emission reductions are not covered by the NDC, a dedicated additionality test should be required. While additionality tests of projects and programmes could continue to be done through investment analysis, for policy instruments new approaches are required. They should be differentiated according to type of policy instrument. For regulation, we suggest calculating the resulting pay-back period for technology users. If the regulation generates investments exceeding a payback period threshold, it could be deemed additional. Similarly, carbon pricing policies that generate a carbon price exceeding a threshold could qualify; for trading schemes an absence of over-allocation needs to be shown. The threshold should be differentiated according to country categories and rise over time.

Key policy insights

• Without additionality testing, market mechanisms under the Paris Agreements might lead to an international diffusion of ‘hot air’. To avoid this, an independent assessment of NDC ambition is in order. Otherwise, activities under the mechanisms need to undergo specific additionality tests.

• Additionality testing of projects and programmes should build on the experience developed under the Kyoto Protocol mechanisms.

• Bold approaches are needed for assessing additionality of policies. To avoid cumbersome assessment of all activities triggered by such policies, highly aggregated approaches are suggested, ranging from payback period thresholds for technologies mandated by regulation to minimum price levels triggered by carbon pricing policies. Over time, the stringency of threshold values should increase.

     

The effect of fluid saturation in an anisotropic multi-scale equant porosity model

It is recognised that exchange of fluid between fractures and the rock matrix can have a strong impact on a rock's anisotropic elastic properties. A recent theoretical advance considers the effect of the scale length of the fractures. We show that under certain circumstances, this model can be simplified. The simplified model matches laboratory data. A prediction of the model is that frequency-dependent effects are important for fluid substitution in the anisotropic case.     

How hydrofractures become arrested

Fluids in the earth's crust are commonly transported by hydrofractures, such as dykes and mineral veins, many of which become arrested at various crustal depths. Hydrofractures are commonly arrested – some showing blunt tips – at contacts between soft (low Young's modulus) and stiff (high Young's modulus) layers. For example, many dyke tips are arrested at contacts between soft pyroclastic rocks and stiff basaltic lava flows, and vein tips at contacts between soft marl and stiff limestone. Theoretical models indicate that overpressured, buoyant hydrofractures in homogeneous, isotropic host rocks should normally reach the surface. In layered host rocks, however, abrupt changes in Young's moduli, horizontal discontinuities, and layers with unusually high fracture-perpendicular stresses encourage hydrofracture arrest. It is proposed that for layer-parallel loading, stiff layers favour hydrofracture arrest during active compression but soft layers during extension. It is concluded that for hydrofracture propagation to occur, the stress field along its potential pathway must be essentially homogenous.     

The scientific basis of marine pollution control

The author examines the scientific basis of the work of the Joint Group of Experts on the Scientific Aspects of Marine Pollution (GESAMP). Problems of definition and methodology are discussed, and the work of GESAMP working groups on, among others, Marine Waste Disposal, Coastal Water Quality Criteria and the Impact of Oil on the Marine Environment are reported. The author concludes that marine pollution control at the international level has not been able to make much practical headway because political expectations have outstripped scientific and administrative possibilities.     

Continuous 60-year stable isotopic and earth-alkali element records in a modern laminated tufa (Jaruga,river Krka,Croatia): Implications for climate reconstruction

A continuous 60-year record (1938–1998) of stable isotope compositions of carbon and oxygen, as well as trace metal (Mg, Sr, Ba) concentrations in a laminated calcite crust precipitated in a short artificial tunnel on a non-equilibrium groundwater-fed karstic river is presented. Chemical and isotopic records have been compared to hydrometeorological data, available for the last 48 years. An attempt is made to relate isotopic and geochemical variations in the crust to environmental parameters, such as temperature, precipitation and changes in vegetation cover, as well as to postdepositional recrystallisation of the older crust material. Isotopic composition of the crust is largely influenced by non-equilibrium precipitation, which favours the incorporation of isotopically depleted C and O into the carbonate. Furthermore, because of the complicated hydrological situation, there is no observable correlation between the stable oxygen isotope composition of water and temperature. The result is that the ¹⁸O isotopic thermometers overestimate the measured precipitation temperatures. Temperatures calculated from Mg/Ca ratios of water and the carbonate match the δ¹⁸O palaeotemperatures within ± 2.4 °C in the older part of the crust, precipitated before the onset of industrial pollution of the river. It was demonstrated that the application of Mg palaeothermometry in natural systems, where the Mg/Ca ratio of water is influenced not only by temperature, but also by other environmental parameters such as precipitation, surface runoff, groundwater retention time and anthropogenic influences, is subject to a large uncertainty, up to 10 °C.     

Magma chamber evolution prior to the Campanian Ignimbrite and Neapolitan Yellow Tuff eruptions (Campi Flegrei,Italy)

The Campi Flegrei (Campanian Region, Italy) experienced two cataclysmic caldera-forming eruptions which produced the Campanian Ignimbrite (39 ka, CI) and the Neapolitan Yellow Tuff (15 ka, NYT). We studied the minor eruptions before both these large events to understand magma chamber evolution leading towards such catastrophic eruptions. Major, trace element, and Sr and Nd isotope compositions of pre-Campanian Ignimbrite and pre-Neapolitan Yellow Tuff products define distinct geochemical groups, which are here interpreted as distinct magma batches. These batches do not show any transitional trend towards the CI and NYT eruptions. The CI and NYT systems are decoupled geochemically and isotopically. At least one of the pre-CI and one of the pre-NYT erupted magma batches qualifies as mixing endmembers for the large CI and NYT eruptions, and thus, must have been stored in reservoirs for some time to remain available for the CI and NYT eruptions. The least evolved, isotopically distinct magma compositions that are typical of the last phases of the NYT and CI eruptions did not occur before caldera-forming events. Based on the new data, we propose the following scenario: Multiple magma chambers with distinct compositions existed below the Campi Flegrei before the CI and NYT eruptions and remained generally separated for some time unless new magma was recharged. In each case, one of the residing magma reservoirs was recharged by a new large-volume magma input of intermediate composition from a deeper differentiating magma reservoir. This may have triggered the coalescence of the previously separated reservoirs into one large chamber which fed the cataclysmic caldera-forming eruption. Large magma chambers in the Campi Flegrei may therefore be ephemeral features, interrupted by periods of evolution in individual, separated magma reservoirs.