Sizeable net export of base cations from a Carpathian flysch catchment indicates their geogenic origin while the 26Mg/24Mg, 44Ca/40Ca and 87Sr/86Sr isotope ratios in runoff are indistinguishable from atmospheric input.

Nutrient imbalances may negatively affect the health status of forests exposed to multiple stress factors, including drought and bark beetle calamities. We studied the origin of base cations in runoff from a small Carpathian catchment underlain by base-poor flysch turbidites using magnesium (Mg), calcium (Ca) and strontium (Sr) isotope composition of 10 ecosystem compartments. Our objective was to constrain conclusions drawn from long-term hydrochemical monitoring of inputs and outputs. Annual export of Mg, Ca and Sr exceeds 5-to-15 times their atmospheric input. Mass budgets per se thus indicate sizeable net leaching of Mg, Ca and Sr from bedrock sandstones and claystones. Surprisingly, δ26Mg, δ44Ca and 87Sr/86Sr isotope ratios of runoff were practically identical to those of atmospheric deposition and soil water but significantly different from bedrock isotope ratios. We did not find any carbonates in the studied area as a hypothetical, easily dissolvable source of base cations whose isotope composition might corroborate the predominance of geogenic base cations in the runoff. Marine carbonates typically have lower δ26 Mg and 87Sr/86Sr ratios, and silicate sediments often have higher δ26Mg and 87Sr/86Sr ratios than runoff at the study site. Mixing of these two sources, if confirmed, could reconcile the flux and isotope data.

Were there royal herds? Understanding herd management and mobility using isotopic characterizations of cattle tooth enamel from Early Dynastic Ur.

During the third millennium BC, Mesopotamia (the land between the Tigris and Euphrates Rivers, in modern Iraq-Syria), was dominated by the world's earliest cities and states, which were ruled by powerful elites. Ur, in present-day southern Iraq, was one of the largest and most important of these cities, and irrigation-based agriculture and large herds of domesticated animals were the twin mainstays of the economy and diet. Texts suggest that the societies of the Mesopotamian city-states were extremely hierarchical and underpinned by institutionalised and heavily-managed farming systems. Prevailing narratives suggest that the animal management strategies within these farming systems in the third millennium BC were homogenous. There have been few systematic science-based studies of human and animal diets, mobility, or other forms of human-animal interaction in Mesopotamia, but such approaches can inform understanding of past economies, including animal management, social hierarchies, diet and migration. Oxygen, carbon and strontium isotopic analysis of animal tooth enamel from both royal and private/non-royal burial contexts at Early Dynastic Ur (2900-2350 BC) indicate that a variety of herd management strategies and habitats were exploited. These data also suggest that there is no correlation between animal-management practices and the cattle found in royal or private/non-royal burial contexts. The results demonstrate considerable divergence between agro-pastoral models promoted by the state and the realities of day-to-day management practices. The data from Ur suggest that the animals exploited different plant and water sources, and that animals reared in similar ways ended up in different depositional contexts.

Cr Isotopes and the Engineered Attenuation of Cr(VI)-Rich Runoff.

The leaching of lateritic soils can result in drainage waters with high concentrations of Cr(VI). Such Cr(VI)-rich waters have developed in streams that drain lateritic soils in Central Sulawesi Island, Indonesia. Chromium in this lateritic drainage system is removed by reduction of Cr(VI) to Cr(III) through two faucets delivering an FeSO4 solution to the drainage waters. Cr stable isotope compositions from both water and sediment samples along the drainage path were used to evaluate the efficacy of this remediation strategy. Overall, dissolved [Cr(VI)] decreased moving downstream, but there was an increase in [Cr(VI)] after the first faucet that was effectively removed at the second faucet. This intermittent increase in [Cr(VI)] was the likely result of oxidative remobilization of sediment Cr(III) through reaction with Mn oxides. Cr isotope distributions reflect near quantitative reduction associated with the FeSO4 faucets but also reveal that Cr isotope fractionation is imparted due to Cr redox cycling, downstream. During this redox cycling, fractionation appeared to accompany oxidation, with the product Cr(VI) becoming enriched in 53Cr relative to the reactant Cr(III) with an apparent fractionation factor of 0.7 ± 0.3‰. This study suggests that while FeSO4 effectively removes Cr(VI) from the drainage, the presence of Mn oxides can confound attenuation and improvements to Cr(VI) remediation should consider means of preventing the back reaction of Cr(III) with Mn oxides.

Cr isotopic insights into ca. 1.9 Ga oxidative weathering of the continents using the Beaverlodge Lake paleosol, Northwest Territories, Canada.

The ca. 1.9 Ga Beaverlodge Lake paleosol was studied using redox-sensitive Cr isotopes in order to determine the isotopic response to paleoweathering of a rhyodacite parent rock 500 million years after the Great Oxidation Event. Redox reactions occurring in modern weathering environments produce Cr(VI) that is enriched in heavy Cr isotopes compared to the igneous inventory. Cr(VI) species are soluble and easily leached from soils into streams and rivers, thus, leaving particle-reactive and isotopically light Cr(III) species to build up in soils. The Beaverlodge Lake paleosol and two other published weathering profiles of similar age, the Flin Flon and Schreiber Beach paleosols, are not as isotopically light as modern soils, indicating that rivers were not as isotopically heavy at that time. Considering that the global average δ53 Cr value for the oxidative weathering flux of Cr to the oceans today is just 0.27 ± 0.30‰ (1σ) based on a steady-state analysis of the modern ocean Cr cycle, the oxidative weathering flux of Cr to the oceans at ca. 1.9 Ga would have likely been shifted to lower δ53 Cr values, and possibly lower than the igneous inventory (-0.12 ± 0.10‰, 2σ). Mn oxides are the main oxidant of Cr(III) in modern soils, but there is no evidence that they formed in the studied paleosols. Cr(VI) may have formed by direct oxidation of Cr(III) using molecular oxygen or H2 O2 , but neither pathway is as efficient as Mn oxides for producing Cr(VI). The picture that emerges from this and other studies of Cr isotope variation in ca. 1.9 Ga paleosols is of atmospheric oxygen concentrations that are high enough to oxidize iron, but too low to oxidize Mn, resulting in low Cr(VI) inventories in Earth surface environments.

Two millennia of North Atlantic seasonality and implications for Norse colonies.

delta(18)O values of mollusks recovered from near-shore marine cores in northwest Iceland quantify significant variation in seasonal temperature over the period from approximately 360 B.C. to approximately A.D. 1660. Twenty-six aragonitic bivalve specimens were selected to represent intervals of climatic interest by using core sedimentological characteristics. Carbonate powder was sequentially micromilled from shell surfaces concordant with growth banding and analyzed for stable oxygen (delta(18)O) and carbon (delta(13)C) isotope values. Because delta(18)O values record subseasonal temperature variation over the lifetime of the bivalves, these data provide the first 2,000-year secular record of North Atlantic seasonality from ca. 360 cal yr B.C. to cal yr A.D. 1660. Notable cold periods (360 B.C. to 240 B.C.; A.D. 410; and A.D. 1380 to 1420) and warm periods (230 B.C. to A.D. 140 and A.D. 640 to 760) are resolved in terms of contrast between summer and winter temperatures and seasonal temperature variability. Literature from the Viking Age (ca. 790 to 1070) during the establishment of Norse colonies (and later) in Iceland and Greenland permits comparisons between the delta(18)O temperature record and historical records, thereby demonstrating the impact of seasonal climatic extremes on the establishment, development, and, in some cases, collapse of societies in the North Atlantic.