The use of the trace element content of sedimentary pyrite as a proxy for the trace element composition of past oceans has recently emerged. The pyrite proxy has several potential advantages over bulk sample analysis: preservation through metamorphism; little dilution during analysis (samples are ablated not dissolved, allowing for the less abundant elements commonly held in the sulfide fraction to be investigated as proxies); accurate measurement of several elements simultaneously; the ability to screen sediments for hydrothermal overprint; and the technique can give information regarding trace element availably at multiple stages of diagenesis. Because of these multiple strengths, the pyrite trace element proxy is a valuable potential addition to the paleo-ocean chemistry tool kit.

Paleosols formed in direct contact with the Earth's atmosphere, so they can record the composition of the atmosphere through weathering processes and products. Herein we critically review a variety of different approaches for reconstructing atmospheric O2 and CO2 over the past three billion years. Paleosols indicate relatively low CO2 over that time, requiring additional greenhouse forcing to overcome the 'faint young Sun' paradox in the Archean and Mesoproterozoic, as well as low O2 levels until the Neoproterozoic. Emerging techniques will revise the history of Earth's atmosphere further and may provide a window into atmospheric evolution on other planets.

Diverse and abundant lipid biomarker assemblages have been reported from a variety of Proterozoic marine environments from the careful analysis of well-preserved rocks and oils. These molecular biosignatures have provided unique insights into the communities and the environmental conditions which characterized the Proterozoic marine biosphere. We summarize some of the major temporal patterns evident in Proterozoic lipid biomarkers found to date, whilst emphasizing the scale of local heterogeneity found within Neoproterozoic oceans from region to region, and their relationship with the evolving ecological, climatic and ocean/atmospheric redox conditions. Short commentaries on a selection of papers published from the last 15 years of biomarker literature are given. The focus here is on key studies, highlighted for further reading, which have helped to better constrain the timing of the ecological expansion of eukaryotes in Proterozoic oceans or which have impacted on our knowledge of the biological sources of Proterozoic biomarkers.

Ce anomalies track changes in oxygen availability due to the anomalous redox-sensitivity of Ce compared with the other rare earth elements. The proxy systematics have been calibrated experimentally as well as in modern anoxic water bodies. Ce anomalies are unique because they track intermediate manganous conditions, rather than fully anoxic conditions. In addition, they are sensitive to local–regional redox conditions, and can be analysed in chemical sediments such as carbonate rocks. This makes them especially useful as a tool to track local oxygen distribution in shallow shelf environments, where biodiversity is highest. This review focusses on the systematics of the Ce anomaly proxy, the preservation and extraction of the signal in sedimentary rocks, and the potential applications of the proxy.

This book brings together the essential theory required to understand the behaviour of trace elements in magmas and magma-derived rocks.

Vanadium isotope ratios (51V/50V) have potential to provide information about changes in past ocean oxygen contents. In particular, V isotopes may find utility in tracing variations at non-zero oxygen concentrations because the redox couple that controls V elemental and isotopic abundances in seawater (vanadate-vanadyl) appears to operate around 10M O2. This characteristic sets V isotopes apart from many other metal isotope redox proxies that require more reducing conditions to register significant changes in their isotope budgets. The oxygen abundance sensitivity range of V isotopes suggests that this paleoproxy could be particularly useful in tracing marine oxygenation changes throughout the Phanerozoic and potentially beyond.

Reconstruction of ocean paleoproductivity and paleochemistry is paramount to understanding global biogeochemical cycles such as the carbon, oxygen and sulfur cycles and the responses of these cycles to changes in climate and tectonics. Paleo-reconstruction involves the application of various tracers that record seawater compositions, which in turn may be used to infer oceanic processes. Several important tracers are incorporated into pelagic barite, an authigenic mineral that forms in the water column. Here we summarize the utility of pelagic barite for the reconstruction of export production and as a recorder of seawater S, O, Sr, Ca and Ba.

In one form or another, iron speciation has had a long history as a paleoredox proxy. The technique has been refined considerably over the years, and the most recent scheme is unique in its potential to distinguish three major oceanic redox states - oxygenated, ferruginous and euxinic. This Element covers the theory behind the proxy, methods involved in applying the technique, and potential complications in interpreting Fe speciation data. A series of case studies are also provided, which highlight how more advanced consideration of the data, often in concert with other techniques, can provide unprecedented insight into the redox state of ancient oceans.

In the modern marine environment, barium isotope (δ138Ba) variations are primarily driven by barite cycling—barite incorporates 'light' Ba isotopes from solution, rendering the residual Ba reservoir enriched in 'heavy' Ba isotopes by a complementary amount. Since the processes of barite precipitation and dissolution are vertically segregated and spatially heterogeneous, barite cycling drives systematic variations in the barium isotope composition of seawater and sediments. This Element examines these variations; evaluates their global, regional, local, and geological controls; and, explores how δ138Ba can be exploited to constrain the origin of enigmatic sedimentary sulfates and to study marine biogeochemistry over Earth's history.

Vanadium isotope ratios (51V/50V) have potential to provide information about changes in past ocean oxygen contents. In particular, V isotopes may find utility in tracing variations at non-zero oxygen concentrations because the redox couple that controls V elemental and isotopic abundances in seawater (vanadate-vanadyl) appears to operate around 10M O2. This characteristic sets V isotopes apart from many other metal isotope redox proxies that require more reducing conditions to register significant changes in their isotope budgets. The oxygen abundance sensitivity range of V isotopes suggests that this paleoproxy could be particularly useful in tracing marine oxygenation changes throughout the Phanerozoic and potentially beyond.