Lithium isotopic constraints on the evolution of continental clay mineral factory and marine oxygenation in the earliest Paleozoic Era.

The evolution of oxygen cycles on Earth's surface has been regulated by the balance between molecular oxygen production and consumption. The Neoproterozoic-Paleozoic transition likely marks the second rise in atmospheric and oceanic oxygen levels, widely attributed to enhanced burial of organic carbon. However, it remains disputed how marine organic carbon production and burial respond to global environmental changes and whether these feedbacks trigger global oxygenation during this interval. Here, we report a large lithium isotopic and elemental dataset from marine mudstones spanning the upper Neoproterozoic to middle Cambrian [~660 million years ago (Ma) to 500 Ma]. These data indicate a dramatic increase in continental clay formation after ~525 Ma, likely linked to secular changes in global climate and compositions of the continental crust. Using a global biogeochemical model, we suggest that intensified continental weathering and clay delivery to the oceans could have notably increased the burial efficiency of organic carbon and facilitated greater oxygen accumulation in the earliest Paleozoic oceans.

Initial Validation of a Soil-Based Mass-Balance Approach for Empirical Monitoring of Enhanced Rock Weathering Rates.

Enhanced rock weathering (ERW) is a promising scalable and cost-effective carbon dioxide removal (CDR) strategy with significant environmental and agronomic co-benefits. A major barrier to large-scale implementation of ERW is a robust monitoring, reporting, and verification (MRV) framework. To successfully quantify the amount of carbon dioxide removed by ERW, MRV must be accurate, precise, and cost-effective. Here, we outline a mass-balance-based method in which analysis of the chemical composition of soil samples is used to track in situ silicate rock weathering. We show that signal-to-noise issues of in situ soil analysis can be mitigated by using isotope-dilution mass spectrometry to reduce analytical error. We implement a proof-of-concept experiment demonstrating the method in controlled mesocosms. In our experiment, a basalt rock feedstock is added to soil columns containing the cereal crop Sorghum bicolor at a rate equivalent to 50 t ha-1. Using our approach, we calculate rock weathering corresponding to an average initial CDR value of 1.44 ± 0.27 tCO2eq ha-1 from our experiments after 235 days, within error of an independent estimate calculated using conventional elemental budgeting of reaction products. Our method provides a robust time-integrated estimate of initial CDR, to feed into models that track and validate large-scale carbon removal through ERW.

A lithium-isotope perspective on the evolution of carbon and silicon cycles.

The evolution of the global carbon and silicon cycles is thought to have contributed to the long-term stability of Earth's climate1-3. Many questions remain, however, regarding the feedback mechanisms at play, and there are limited quantitative constraints on the sources and sinks of these elements in Earth's surface environments4-12. Here we argue that the lithium-isotope record can be used to track the processes controlling the long-term carbon and silicon cycles. By analysing more than 600 shallow-water marine carbonate samples from more than 100 stratigraphic units, we construct a new carbonate-based lithium-isotope record spanning the past 3 billion years. The data suggest an increase in the carbonate lithium-isotope values over time, which we propose was driven by long-term changes in the lithium-isotopic conditions of sea water, rather than by changes in the sedimentary alterations of older samples. Using a mass-balance modelling approach, we propose that the observed trend in lithium-isotope values reflects a transition from Precambrian carbon and silicon cycles to those characteristic of the modern. We speculate that this transition was linked to a gradual shift to a biologically controlled marine silicon cycle and the evolutionary radiation of land plants13,14.

European atmospheric pollution imported by cooler air masses to the Eastern Mediterranean during the summer.

In this study we combine Pb isotopes, Pb, Ni, Cu, Zn, and several major metal concentrations, identification of the aerosol particles, and synoptic and back trajectory analyses to obtain direct evidence for the extent and nature of mixing between Middle Eastern and European sources emissions of metals and aerosols. During the summer months aerosols collected in Israel are highly polluted by metals (EF(Ni) = 120, EF(Cu) = 320, EF(Zn) = 30, EF(Pb) = 540; average values). The fraction of European Pb of mostly industrial sources is 61 +/- 21% in Jerusalem, and the fraction of European Cu, Zn, Ni, and aerosols should be on the same order. Whenever a steep pressure gradient is built between the barometric trough originating from the Persian Gulf and the subtropical ridge along the African coast, stronger westerly winds and cooler temperatures (deep Persian Trough) prevail overthe Middle East, and higher amounts of European pollution are observed in the atmosphere (74 +/- 13%). On the other hand, when the Persian Trough is in its shallow mode, the proportion of European pollution is lower (45 +/- 18%, based on Pb isotopes). This study demonstrates that atmospheric pollution over the East Mediterranean region during the summer is influenced not only by local atmospheric dispersion conditions but also by the ability of the atmosphere to inherit a significant proportion of pollutants from European sources.