The isotopic effects of electron transfer: An explanation for Fe isotope fractionation in nature

Isotope fractionation of electroplated Fe was measured as a function of applied electrochemical potential. As plating voltage was varied from −0.9 V to 2.0 V, the isotopic signature of the electroplated iron became depleted in heavy Fe, with δ⁵⁶Fe values (relative to IRMM-14) ranging from −0.18(±0.02) to −2.290(±0.006) ‰, and corresponding δ⁵⁷Fe values of −0.247(±0.014) and −3.354(±0.019) ‰. This study demonstrates that there is a voltage-dependent isotope fractionation associated with the reduction of iron. We show that Marcus’s theory for the kinetics of electron transfer can be extended to include the isotope effects of electron transfer, and that the extended theory accounts for the voltage dependence of Fe isotope fractionation. The magnitude of the electrochemically-induced fractionation is similar to that of Fe reduction by certain bacteria, suggesting that similar electrochemical processes may be responsible for biogeochemical Fe isotope effects. Charge transfer is a fundamental physicochemical process involving Fe as well as other transition metals with multiple isotopes. Partitioning of isotopes among elements with varying redox states holds promise as a tool in a wide range of the Earth and environmental sciences, biology, and industry.     

Classifying coastal waters: Current necessity and historical perspective

Coastal ecosystems are ecologically and commercially valuable, productive habitats that are experiencing escalating compromises of their structural and functional integrity. The Clean Water Act (USC 1972) requires identification of impaired water bodies and determination of the causes of impairment. Classification simplifies these determinations, because estuaries within a class are more likely to respond similarly to particular stressors. We reviewed existing classification systems for their applicability to grouping coastal marine and Great Lakes water bodies based on their responses to aquatic stressors, including nutrients, toxic substances, suspended sediments, habitat alteration, and combinations of stressors. Classification research historically addressed terrestrial and freshwater habitats rather than coastal habitats. Few efforts focused on stressor response, although many well-researched classification frameworks provide information pertinent to stressor response. Early coastal classifications relied on physical and hydrological properties, including geomorphology, general circulation patterns, and salinity. More recent classifications sort ecosystems into a few broad types and may integrate physical and biological factors. Among current efforts are those designed for conservation of sensitive habitats based on ecological processes that support patterns of biological diversity. Physical factors, including freshwater inflow, residence time, and flushing rates, affect sensitivity to stressors. Biological factors, such as primary production, grazing rates, and mineral cycling, also need to be considered in classification. We evaluate each existing classification system with respect to objectives, defining factors, extent of spatial and temporal applicability, existing sources of data, and relevance to aquatic stressors. We also consider classification methods in a generic sense and discuss their strengths and weaknesses for our purposes. Although few existing classifications are based on responses to stressors, may well-researched paradigms provide important information for improving our capabilities for classification, as an investigative and predictive management tool.     

Heat-producing elements in the lunar mantle: Insights from ion microprobe analyses of lunar pyroclastic glasses

We provide new estimates for the abundance of heat-producing elements in the lunar mantle by using SIMS techniques to measure the concentrations of thorium and samarium in lunar pyroclastic glasses. Lunar pyroclastic glasses are utilized in this study because they represent quenched products of near-primary melts from the lunar mantle and as such, they provide compositional information about the mantle itself. Thorium and samarium were measured because: (1) Th is not significantly fractionated from Sm during partial melting of the pyroclastic glass source regions, which are dominated by olivine and pyroxene. Therefore, the Th/Sm ratios that we measure in the pyroclastic glasses reflect the Th/Sm ratio of the pyroclastic glass source regions. (2) Strong correlations between Th, U, and K on the Moon allow us to use measured Th concentrations to estimate the concentrations of U and K in the pyroclastic glasses. (3) Th, Sm, U, and K are radioactive elements and as such, their concentrations can be used to investigate heat production in the lunar mantle.The results from this study show that the lunar mantle is heterogeneous with respect to heat-producing elements and that there is evidence for mixing of a KREEP component into the source regions of some of the pyroclastic glasses. Because the source regions for many of the glasses are deep (?400 km), we propose that a KREEP component was transported to the deep lunar mantle. KREEP enriched sources produce 138% more heat than sources that do not contain KREEP and therefore, could have provided a source of heat for extended periods of nearside basaltic magmatism. Data from this study, in conjunction with models for the fractional crystallization of a lunar magma ocean, are used to show that the average lunar mantle contains 0.15 ppm Th, 0.54 ppm Sm, 0.039 ppm U, and 212 ppm K. This is a greater enrichment in radiogenic elements than some earlier estimates, suggesting a more prolonged impact of radiogenic heat on nearside basaltic volcanism.     

Freeze thaw cycles in Toronto, Canada in a changing climate

Summary Freeze thaw cycles are examined in Toronto Canada. Using data from 1960 to 1989 for three Toronto area weather stations, trends in freeze thaw activity, the relationship to mean monthly temperature and projections of freeze thaw activity are examined. For downtown Toronto the annual frequency of freeze thaw cycles is decreasing significantly, most notably in the shoulder months of October and April. At the Pearson International Airport and the Toronto Island Airport similar annual trends were not found, however there was evidence of decreased freeze thaw activity in April and October. Polynomial curve fitting provided functional relationships between mean monthly temperature and freeze thaw activity. These relationships enabled the assessment of freeze thaw activity under synthetic warming conditions. The results of this analysis show that the warming of the magnitude typically projected for the rest of this century will not likely generate a significant change in the freeze thaw activity although there are indications that the freeze thaw season will contract.     

Storm track response to ocean fronts in a global high-resolution climate model

Synoptic atmospheric eddies are affected by lower tropospheric air-temperature gradients and by turbulent heat fluxes from the surface. In this study we examine how ocean fronts affect these quantities and hence the storm tracks. We focus on two midlatitude regions where ocean fronts lie close to the storm tracks: the north-west Atlantic and the Southern Ocean. An atmospheric climate model of reasonably high resolution (~50 km) is applied in a climate-length (60 year) simulation in order to obtain stable statistics. Simulations with frontal structure in the sea surface temperature (SST) in one of the regions are compared against simulations with globally smoothed SST. We show that in both regions the ocean fronts have a strong influence on the transient eddy heat and moisture fluxes, not just in the boundary layer, but also in the free troposphere. Local differences in these quantities between the simulations reach 20–40 % of the maximum values in the simulation with smoothed SST. Averaged over the entire region of the storm track over the ocean the corresponding differences are 10–20 %. The effect on the transient eddy meridional wind variance is strong in the boundary layer but relatively weak above that. The potential mechanisms by which the ocean fronts influence the storm tracks are discussed, and our results are compared against previous studies with regional models, Aquaplanet models, and coarse resolution coupled models.     

Real-time multi-model decadal climate predictions

We present the first climate prediction of the coming decade made with multiple models, initialized with prior observations. This prediction accrues from an international activity to exchange decadal predictions in near real-time, in order to assess differences and similarities, provide a consensus view to prevent over-confidence in forecasts from any single model, and establish current collective capability. We stress that the forecast is experimental, since the skill of the multi-model system is as yet unknown. Nevertheless, the forecast systems used here are based on models that have undergone rigorous evaluation and individually have been evaluated for forecast skill. Moreover, it is important to publish forecasts to enable open evaluation, and to provide a focus on climate change in the coming decade. Initialized forecasts of the year 2011 agree well with observations, with a pattern correlation of 0.62 compared to 0.31 for uninitialized projections. In particular, the forecast correctly predicted La Niña in the Pacific, and warm conditions in the north Atlantic and USA. A similar pattern is predicted for 2012 but with a weaker La Niña. Indices of Atlantic multi-decadal variability and Pacific decadal variability show no signal beyond climatology after 2015, while temperature in the Niño3 region is predicted to warm slightly by about 0.5 °C over the coming decade. However, uncertainties are large for individual years and initialization has little impact beyond the first 4 years in most regions. Relative to uninitialized forecasts, initialized forecasts are significantly warmer in the north Atlantic sub-polar gyre and cooler in the north Pacific throughout the decade. They are also significantly cooler in the global average and over most land and ocean regions out to several years ahead. However, in the absence of volcanic eruptions, global temperature is predicted to continue to rise, with each year from 2013 onwards having a 50 % chance of exceeding the current observed record. Verification of these forecasts will provide an important opportunity to test the performance of models and our understanding and knowledge of the drivers of climate change.     

Impact of vegetation feedback on the temperature and its diurnal range over the Northern Hemisphere during summer in a 2 × CO2 climate

This study examines the potential impact of vegetation feedback on the changes in the diurnal temperature range (DTR) due to the doubling of atmospheric CO₂ concentrations during summer over the Northern Hemisphere using a global climate model equipped with a dynamic vegetation model. Results show that CO₂ doubling induces significant increases in the daily mean temperature and decreases in DTR regardless of the presence of the vegetation feedback effect. In the presence of vegetation feedback, increase in vegetation productivity related to warm and humid climate lead to (1) an increase in vegetation greenness in the mid-latitude and (2) a greening and the expansion of grasslands and boreal forests into the tundra region in the high latitudes. The greening via vegetation feedback induces contrasting effects on the temperature fields between the mid- and high-latitude regions. In the mid-latitudes, the greening further limits the increase in T _max more than T _min, resulting in further decreases in DTR because the greening amplifies evapotranspiration and thus cools daytime temperature. The greening in high-latitudes, however, it reinforces the warming by increasing T _max more than T _min to result in a further increase in DTR from the values obtained without vegetation feedback. This effect on T _max and DTR in the high latitude is mainly attributed to the reduction in surface albedo and the subsequent increase in the absorbed insolation. Present study indicates that vegetation feedback can alter the response of the temperature field to increases in CO₂ mainly by affecting the T _max and that its effect varies with the regional climate characteristics as a function of latitudes.     

Potential impacts of northeastern Eurasian snow cover on generation of dust storms in northwestern China during spring

The effects of the northeastern Eurasian snow cover on the frequency of spring dust storms in northwestern China have been examined for the period 1979–2007. Averaged over all 43 stations in northwestern China, a statistically significant relationship has been found between dust-storm frequency (DSF) and Eurasian snow-water equivalent (SWE) during spring: mean DSF of 7.4 and 3.3 days for years of high- and low SWE, respectively. Further analyses reveal that positive SWE anomalies enhance the meridional gradients of the lower tropospheric temperatures and geopotential heights, thereby strengthening westerly jets and zonal wind shear over northwestern China and western Inner Mongolia of China, the regions of major dust sources. The anomalous atmospheric circulation corresponding to the Eurasian SWE anomalies either reinforces or weakens atmospheric baroclinicity and cyclogenesis, according to the sign of the anomaly, to affect the spring DSF. This study suggests that Eurasian SWE anomalies can be an influential factor of spring DSF in northwestern China and western Inner Mongolia of China.