Iron isotope compositions of carbonatites record melt generation, crystallization, and late-stage volatile-transport processes

Carbonatites define the largest range in Fe isotope compositions yet measured for igneous rocks, recording significant isotopic fractionations between carbonate, oxide, and silicate minerals during generation in the mantle and subsequent differentiation. In contrast to the relatively restricted range in δ⁵⁶Fe values for mantle-derived basaltic magmas (δ⁵⁶Fe?=?0.0?±?0.1‰), calcite from carbonatites have δ⁵⁶Fe values between ?1.0 and +0.8‰, similar to the range defined by whole-rock samples of carbonatites. Based on expected carbonate-silicate fractionation factors at igneous or mantle temperatures, carbonatite magmas that have modestly negative δ⁵⁶Fe values of ~ ?0.3‰ or lower can be explained by equilibrium with a silicate mantle. More negative δ⁵⁶Fe values were probably produced by differentiation processes, including crystal fractionation and liquid immiscibility. Positive δ⁵⁶Fe values for carbonatites are, however, unexpected, and such values seem to likely reflect interaction between low-Fe carbonates and Fe³⁺-rich fluids at igneous or near-igneous temperatures; the expected δ⁵⁶Fe values for Fe²⁺-bearing fluids are too low to produced the observed positive δ⁵⁶Fe values of some carbonatites, indicating that Fe isotopes may be a valuable tracer of redox conditions in carbonatite complexes. Further evidence for fluid-rock or fluid-magma interactions comes from the common occurrence of Fe isotope disequilibrium among carbonate, oxide, silicate, and sulfide minerals in the majority of the carbonatites studied. The common occurrence of Fe isotope disequilibrium among minerals in carbonatites may also indicate mixing of phenocyrsts from distinct magmas. Expulsion of Fe³⁺-rich brines into metasomatic aureols that surround carbonatite complexes are expected to produce high-δ⁵⁶Fe fenites, but this has yet to be tested.     

An experimental study of the effects of melt composition on plagioclase-melt equilibria at 5 and 10 kbar: implications for the origin of magmatic high-An plagioclase

An experimental investigation of plagioclase crystallization in broadly basaltic/andesitic melts of variable Ca# (Ca/(Ca+Na)*100) and Al# (Al/(Al+Si)*100) values and H₂O contents has been carried out at high pressures (5 and 10 kbar) in a solid media piston-cylinder apparatus. The H₂O contents of glasses coexisting with liquidus or near-liquidus plagioclases in each experiment were determined via an FTIR spectroscopic technique. This study has shown that melt Ca# and Al#, H₂O content and crystallization pressure all control the composition of liquidus plagioclase. Increasing melt Ca# and Al# increase An content of plagioclase, whereas the effect of increasing pressure is the opposite. However, the importance of the role played by each of these factors during crystallization of natural magmas varies. Melt Ca# has the strongest control on plagioclase An content, but melt Al# also exerts a significant control. H₂O content can notably increase the An content of plagioclase, up to 10 mol % for H₂O-undersaturated melts, and 20 mol % for H₂O-saturated melts. Exceptionally calcic plagioclases (up to An₁₀₀) in some primitive subduction-related boninitic and related rocks cannot be attributed to the presence of the demonstrated amounts of H₂O (up to 3 wt %). Rather, they must be due to the involvement of extremely refractory (CaO/Na₂O>18) magmas in the petrogenesis of these rocks. Despite the refractory nature of some primitive MORB glasses, none are in equilibrium with the most calcic plagioclase (An₉₄) found in MORB. These plagioclases were likely produced from more refractory melts with CaO/Na₂O = 12–15, or from melts with exceptionally high Al₂O₃(>18%). Magmas of appropriate compositions to crystallize these most calcic plagioclases are sometimes found as melt inclusions in near liquidus phenocrysts from these rocks, but are not known among wholerock or glass compositions. The fact that such melts are not erupted as discrete magma batches indicates that they are effectively mixed and homogenized with volumetrically dominant, less refractory magmas. The high H₂O contents (∼ 6 wt%) in some high-Al basaltic arc magmas may be responsible for the existence of plagioclases up to An₉₅ in arc lavas. However, an alternative possibility is that petrogenesis involving melts with abnormally high CaO/Na₂O values (> 8) may account for the presence of highly anorthitic plagioclases in these rocks. Received: 31 August 1993 / Accepted: 20 May 1994     

On the role of Mn(IV) vacancies in the photoreductive dissolution of hexagonal birnessite

Photoreductive dissolution of layer type Mn(IV) oxides (birnessite) under sunlight illumination to form soluble Mn(II) has been observed in both field and laboratory settings, leading to a consensus that this process is a key driver of the biogeochemical cycling of Mn in the euphotic zones of marine and freshwater ecosystems. However, the underlying mechanisms for the process remain unknown, although they have been linked to the semiconducting characteristics of hexagonal birnessite, the ubiquitous Mn(IV) oxide produced mainly by bacterial oxidation of soluble Mn(II). One of the universal properties of this biogenic mineral is the presence of Mn(IV) vacancies, long-identified as strong adsorption sites for metal cations. In this paper, the possible role of Mn vacancies in photoreductive dissolution is investigated theoretically using quantum mechanical calculations based on spin-polarized density functional theory (DFT). Our DFT study demonstrates unequivocally that Mn vacancies significantly reduce the band-gap energy for hexagonal birnessite relative to a hypothetical vacancy-free MnO₂ and thus would increase the concentration of photo-induced electrons available for Mn(IV) reduction upon illumination of the mineral by sunlight. Calculations of the charge distribution in the presence of vacancies, although not fully conclusive, show a clear separation of photo-induced electrons and holes, implying a slow recombination of these charge-carriers that facilitates the two-electron reduction of Mn(IV) to Mn(II).     

Adaptation, Spatial Heterogeneity, and the Vulnerability of Agricultural Systems to Climate Change and CO2 Fertilization: An Integrated Assessment Approach

In this paper we develop economic measures of vulnerability to climate change with and without adaptation in agricultural production systems. We implement these measures using coupled, site-specific ecosystem and economic simulation models. This modeling approach has two key features needed to study the response of agricultural production systems to climate change: it represents adaptation as an endogenous, non-marginal economic response to climate change; and it provides the capability to represent the spatial variability in bio-physical and economic conditions that interact with adaptive responses. We apply this approach to the dryland grain production systems of the Northern Plains region of the United States. The results support the hypothesis that the most adverse impacts on net returns distributions tend to occur in the areas with the poorest resource endowments and when mitigating effects of CO₂ fertilization and adaptation are absent. We find that relative and absolute measures of vulnerability depend on complex interactions between climate change, CO₂ level, adaptation, and economic conditions such as relativeoutput prices. The relationship between relative vulnerability and resource endowments varies with assumptions about climate change, adaptation, and economic conditions. Vulnerability measured with respect to an absolute threshold is inversely related to resource endowments in all cases investigated.     

A comparison of a GCM response to historical anthropogenic land cover change and model sensitivity to uncertainty in present-day land cover representations

This study assesses the sensitivity of the fully coupled NCAR-DOE PCM to three different representations of present-day land cover, based on IPCC SRES land cover information. We conclude that there is significant model sensitivity to current land cover characterization, with an observed average global temperature range of 0.21 K between the simulations. Much larger contrasts (up to 5 K) are found on the regional scale; however, these changes are largely offsetting on the global scale. These results show that significant biases can be introduced when outside data sources are used to conduct anthropogenic land cover change experiments in GCMs that have been calibrated to their own representation of present-day land cover. We conclude that hybrid systems that combine the natural vegetation from the native GCM datasets combined with human land cover information from other sources are best for simulating such impacts. We also performed a prehuman simulation, which had a 0.39 K ~higher average global temperature and, perhaps of greater importance, temperature changes regionally of about 2 K. In this study, the larger regional changes coincide with large-scale agricultural areas. The initial cooling from energy balance changes appear to create feedbacks that intensify mid-latitude circulation features and weaken the summer monsoon circulation over Asia, leading to further cooling. From these results, we conclude that land cover change plays a significant role in anthropogenically forced climate change. Because these changes coincide with regions of the highest human population this climate impact could have a disproportionate impact on human systems. Therefore, it is important that land cover change be included in past and future climate change simulations.     

Expert judgements on the response of the Atlantic meridional overturning circulation to climate change

We present results from detailed interviews with 12 leading climate scientists about the possible effects of global climate change on the Atlantic Meridional Overturning Circulation (AMOC). The elicitation sought to examine the range of opinions within the climatic research community about the physical processes that determine the current strength of the AMOC, its future evolution in a changing climate and the consequences of potential AMOC changes. Experts assign different relative importance to physical processes which determine the present-day strength of the AMOC as well as to forcing factors which determine its future evolution under climate change. Many processes and factors deemed important are assessed as poorly known and insufficiently represented in state-of-the-art climate models. All experts anticipate a weakening of the AMOC under scenarios of increase of greenhouse gas concentrations. Two experts expect a permanent collapse of the AMOC as the most likely response under a 4×CO₂ scenario. Assuming a global mean temperature increase in the year 2100 of 4 K, eight experts assess the probability of triggering an AMOC collapse as significantly different from zero, three of them as larger than 40%. Elicited consequences of AMOC reduction include strong changes in temperature, precipitation distribution and sea level in the North Atlantic area. It is expected that an appropriately designed research program, with emphasis on long-term observations and coupled climate modeling, would contribute to substantially reduce uncertainty about the future evolution of the AMOC.     

Middle Pleistocene environments,landscapes and tephrostratigraphy of the Armenian Highlands: evidence from Bird Farm 1, Hrazdan Valley

The significance of the southern Caucasus in understanding Pleistocene hominin expansions is well established. However, the palaeoenvironments in which Palaeolithic occupation of the region took place are presently poorly defined. The Hrazdan river valley, Armenian Highlands, contains a rich Palaeolithic record alongside Middle Pleistocene volcanic, fluvial and lacustrine strata, and thus offer exciting potential for palaeoenvironmental reconstruction. We present the first results of sedimentological, geochemical, tephrostratigraphical and biological (diatoms) study of the sequence of Bird Farm 1, located in the central part of the valley. These data show six phases of landscape development during the interval 440–200 ka. The sequence represents the first quantitative Pleistocene diatom record from the Armenian Highlands and the southern Caucasus, and indicates the persistence of a deep, stratified lacustrine system, with evidence for changing lake productivity that is tentatively linked to climate. Furthermore, major element chemical characterization of visible and crypto-tephra horizons in the sequence enables the first stages of the development of a regional tephrostratigraphy. Together, the evidence from Bird Farm 1 demonstrates the importance of lacustrine archives in the region for palaeoenvironmental reconstruction and highlights the potential for linkages between archives on both a local and regional scale.