Pleistocene loess records of the Khovaling Loess Plateau (KLP) in Tajikistan provide rich collections of lithic artifacts demonstrating past human presence in the region. To understand the timing of human activity and environmental conditions prevailing at that time U-Th dating and clumped/stable C/O isotope measurements have been applied to modern and Pleistocene soil carbonates (SCs) collected at several sites on the KLP and surroundings. U-Th ages were corrected by two methods: 1) assuming an initial [Th-230/Th-232] activity ratio of 0.85 +/- 0.25 based on gamma spectrometry of loess/paleosol samples, and 2) the isochron technique using leachates and fully dissolved subsamples. Diagenetic alteration and potential U/Th mobilization and related isotope fractionation due to alpha-recoil was also modelled and found to be minor in the studied soil carbonates. Compared to model ages as references, uncorrected 230 Th ages are only acceptable if measured [Th-230/Th-232] activity ratios of leachates are high (>30), while Th-230 ages derived using method 1 are mostly overcorrected. It appears that SCs can be reliably dated by the U-series disequilibrium method in this sedimentary setting, but isochron dating cannot be spared. Application of the isochron method is required to derive (230)Thmodel ages, which ensures that the non-zero initial (230) Th and possible U-Th gain/loss due to alpha-recoil can be simultaneously corrected and reliable U-Th ages obtained. U-Th ages of Pleistocene SCs clearly demonstrate postpedogenic ingrowth of multiple, non-contemporaneous populations of SCs within loess/paleosol units, and that SC formation happened in many cases under cold, presumably dry glacial climate conditions. Considering that U-Th ages of SCs provide minimum ages of the sediment in which they form, these ages can be useful in developing loess stratigraphic models and for correlation of paleosols with marine isotope stages. This implies that the age of a given paleosol and any lithic artifacts it may contain, indicating human activity, cannot be younger than the age of SCs formed in that paleosol. This is due to the nature of soil carbonates, which can be the product of both syn- and post-depositional processes. Clumped isotope thermometry of SCs collected from modern soils at three sites in Tajikistan provide evidence for SCs dominantly recording summer season soil temperatures, while the calculated soil water oxygen isotope signatures reflect annual signals and carbonate precipitation from source waters incorporating rainfall from prior to and during SC formation. In contrast, some Pleistocene SCs record soil temperatures and stable isotope compositions more appropriate to glacial conditions, confirming the findings of U-Th ages, and highlighting the primary role of aridity-driven soil moisture changes in SC precipitation in this setting. Considering the interpretative complexities of SC stable isotope compositions, involving issues such as SC formation depth within a soil/paleosol profile, seasonality of SC growth and violation of the law of superposition, SC stable isotope proxy records of past climates cannot be considered as a set of clearly sequential data through time. This implies that such SC-based stable isotope records must be accompanied by U-Th dating of carbonates to be meaningful.

The clumped and stable isotope (Delta(47), delta O-18, and delta C-13) composition of pedogenic (soil) carbonates from cold, arid environments may be a valuable paleoclimate archive for climate change-sensitive areas at high latitudes or elevations. However, previous work suggests that the isotopic composition of cold-climate soil carbonates is susceptible to kinetic isotope effects (KIE). To evaluate the conditions under which KIE occur in cold-climate soil carbonates, we examine the Delta(47), delta O-18, and delta C-13 composition of soil carbonate pendants from Antarctica (Dry Valleys, 77 degrees S), the High Arctic (Svalbard 79 degrees N), the Chilean and Argentinian Andes, and the Tibetan plateau (3800-4800 m), and compare the results to local climate and water delta O-18 records. At each site we calculate the expected equilibrium soil carbonate Delta(47) and delta O-18 values and estimate carbonate Delta(47) and delta O-18 anomalies (observed Delta(47) or delta O-18 minus the expected equilibrium Delta(47) or delta O-18). Additionally, we compare the measured carbonate delta C-13 to the expected range of equilibrium soil carbonate delta C-13 values. To provide context for interpreting the Delta(47) and delta O-18 anomalies, the soil carbonate results are compared to results for sub-glacial carbonates from two different sites, which exhibit large Delta(47) anomalies (up to -0.29 parts per thousand). The Antarctic and 4700 masl Chilean Andes samples have negative Delta(47) anomalies and positive delta O-18 anomalies consistent with KIE due to rapid bicarbonate dehydration during cryogenic carbonate formation. In contrast, the lower elevation Chilean Andes, Argentinian Andes, Tibetan Plateau and High Arctic results are consistent with equilibrium, summer carbonate formation. We attribute the differences in Delta(47) and delta O-18 anomalies to variations in inter-cobble matrix grain size and its effects on the effective soil pore space, permeability (hydraulic conductivity), moisture, and bicarbonate dehydration rate. The Antarctic and 4700 masl Chilean Andean soils have coarse-grained matrices that facilitate rapid bicarbonate dehydration. In contrast, the lower elevation Chilean Andes, Argentinian Andes, High Arctic and Tibetan Plateau soils have finer-grained matrices that decrease the soil pore space, soil permeability and CO2 gas flux, promoting equilibrium carbonate formation. The sub-glacial carbonate samples yield highly variable Delta(47) and delta O-18 anomalies, and we propose that the differences between the two glacier sites may be due to variations in local sub-glacial drainage conditions, pCO(2), and pH. Our findings suggest that carbonates from soils with coarse-grained matrices may exhibit KIE in cold climates, making them poor paleoclimate proxies. Soils with fine-grained matrices are more likely to yield equilibrium carbonates suitable for paleoclimate reconstructions regardless of climate. Paleosol matrix grain size should therefore be taken into account in the evaluation of carbonate stable and clumped isotope values in paleoclimate studies. (C) 2018 Elsevier Ltd. All rights reserved.