Natural attenuation processes of chlorinated solvents in soils and groundwaters are increasingly considered as options to manage contaminated sites. Under anoxic conditions, reactions with ferrous iron sorbed at iron(hyro)xides may dominate the overall transformation of carbon tetrachloride (CCl4) and other chlorinated aliphatic hydrocarbons. We investigated mechanisms and product formation of CCl4 reduction by Fe(II) sorbed to goethite, which may lead to completely dehalogenated products or to chloroform (CHCl3), a toxic product which is fairly persistent under anoxic conditions. A simultaneous transfer of two electrons and cleavage of two C-Cl bonds of CCl4 would completely circumvent chloroform production. To distinguish between initial one- or two-bond cleavage, 13C-isotope fractionation of CCl4 was studied for reactions with Fe(II)/ goethite (isotopic enrichment factor epsilon = -26.5% percent per thousand) and with model systems for one C-Cl bond cleavage and either single-electron transfer (Fe(II) porphyrin, epsilon = -26.1 percent per thousand) or partial two-electron transfer (polysulfide, epsilon = -22.2 percent per thousand). These epsilon values differ significantlyfrom calculations for simultaneous cleavage of two C-Cl bonds (epsilon approximately equal to -50 percent per thousand), indicating that only one C-Cl bond is broken in the critical first step of the reaction. At pH 7, reduction of CCl4 by Fe(II)/ goethite produced approximately 33% CHCl3, 20% carbon monoxide (CO), and up to 40% formate (HCOO-). Addition of 2-propanol-d8 resulted in 33% CDCl3 and only 4% CO, indicating that both products were generated from trichloromethyl radicals (*CCl3), chloroform by reaction with hydrogen radical donors and CO by an alternative pathway likely to involve surface-bound intermediates. Hydrolysis of CO to HCOO-was surface-catalyzed by goethite butwastoo slow to account for the measured formate concentrations. Chloroform yields slightly increased with pH at constant Fe(II) sorption density, suggesting that pH-dependent surface processes direct product branching ratios. Surface-stabilized intermediates may thus facilitate abiotic mineralization of CCl4, whereas the presence of H radical donors, such as natural organic matter, enhances formation of toxic CHCl3.

We present a reconstruction of tropical South American temperature anomalies over the last ∼1600 years. The reconstruction is based on a highly resolved and carefully dated ammonium record from an ice core that was drilled in 1999 on Nevado Illimani in the eastern Bolivian Andes. Concerning the relevant processes governing the observed correlation between ammonium concentrations and temperature anomalies, we discuss anthropogenic emissions, biomass burning, and precipitation changes but clearly favor a temperature‐dependent source strength of the vegetation in the Amazon Basin. That given, the reconstruction reveals that Medieval Warm Period– and Little Ice Age–type episodes are distinguishable in tropical South America, a region for which until now only very limited temperature proxy data have been available. For the time period from about 1050 to 1300 AD, our reconstruction shows relatively warm conditions that are followed by cooler conditions from the 15th to the 18th century, when temperatures dropped by up to 0.6°C below the 1961–1990 average. The last decades of the past millennium are characterized again by warm temperatures that seem to be unprecedented in the context of the last ∼1600 years.

The energy imbalance at the top of the atmosphere determines the temporal evolution of the global climate, and vice versa changes in the climate system can alter the planetary energy fluxes. This interplay is fundamental to our understanding of Earth’s heat budget and the climate system. However, even today, the direct measurement of global radiative fluxes is difficult, such that most assessments are based on changes in the total energy content of the climate system. We apply the same approach to estimate the long-term evolution of Earth’s radiative imbalance in the past. New measurements of noble gas-derived mean ocean temperature from the European Project for Ice Coring in Antarctica Dome C ice core covering the last 40,000 y, combined with recent results from the West Antarctic Ice Sheet Divide ice core and the sea-level record, allow us to quantitatively reconstruct the history of the climate system energy budget. The temporal derivative of this quantity must be equal to the planetary radiative imbalance. During the deglaciation, a positive imbalance of typically +0.2 W⋅m−2 is maintained for ∼10,000 y, however, with two distinct peaks that reach up to 0.4 W⋅m−2 during times of substantially reduced Atlantic Meridional Overturning Circulation. We conclude that these peaks are related to net changes in ocean heat uptake, likely due to rapid changes in North Atlantic deep-water formation and their impact on the global radiative balance, while changes in cloud coverage, albeit uncertain, may also factor into the picture.

ABSTRACT. A recently developed dating method for glacier ice, based on the analysis of radiocarbon in carbonaceous aerosol particles, is thoroughly investigated. We discuss the potential of this method to achieve a reliable dating using examples from a mid-and a low-latitude ice core. Two series of samples from Colle Gnifetti (4450 m a.s.l., Swiss Alps) and Nevado Illimani (6300 m a.s.l., Bolivian Andes) demonstrate that the 14 C ages deduced from the water-insoluble organic carbon fraction represent the age of the ice. Sample sizes ranged between 7 and 100 m mg carbon. For validation we compare our results with those from independent dating. This new method is thought to have major implications for dating non-polar ice cores in the future, as it provides complementary age information for time periods not accessible with common dating techniques.