Silicon Isotope Geochemistry: Fractionation Linked to Silicon Complexations and Its Geological Applications.

The fundamental advances in silicon isotope geochemistry have been systematically demonstrated in this work. Firstly, the continuous modifications in analytical approaches and the silicon isotope variations in major reservoirs and geological processes have been briefly introduced. Secondly, the silicon isotope fractionation linked to silicon complexation/coordination and thermodynamic conditions have been extensively stressed, including silicate minerals with variable structures and chemical compositions, silica precipitation and diagenesis, chemical weathering of crustal surface silicate rocks, biological uptake, global oceanic Si cycle, etc. Finally, the relevant geological implications for meteorites and planetary core formation, ore deposits formation, hydrothermal fluids activities, and silicon cycling in hydrosphere have been summarized. Compared to the thermodynamic isotope fractionation of silicon associated with high-temperature processes, that in low-temperature geological processes is much more significant (e.g., chemical weathering, biogenic/non-biogenic precipitation, biological uptake, adsorption, etc.). The equilibrium silicon isotope fractionation during the mantle-core differentiation resulted in the observed heavy isotope composition of the bulk silicate Earth (BSE). The equilibrium fractionation of silicon isotopes among silicate minerals are sensitive to the Si-O bond length, Si coordination numbers (CN), the polymerization degrees of silicate unites, and the electronegativity of cations in minerals. The preferential enrichment of different speciation of dissoluble Si (DSi) (e.g., silicic acid H4SiO4° (H4) and H3SiO4- (H3)) in silica precipitation and diagenesis, and chemical weathering, lead to predominately positive Si isotope signatures in continental surface waters, in which the dynamic fractionation of silicon isotope could be well described by the Rayleigh fractionation model. The role of complexation in biological fractionations of silicon isotopes is more complicated, likely involving several enzymatic processes and active transport proteins. The integrated understanding greatly strengthens the potential of δ30Si proxy for reconstructing the paleo terrestrial and oceanic environments, and exploring the meteorites and planetary core formation, as well as constraining ore deposits and hydrothermal fluid activity.

Learning Atom Probe Tomography time-of-flight peaks for mass-to-charge ratio spectrometry.

In laser-assisted atom probe tomography, an important goal is to reconstruct the mass-to-charge ratio, (m/z), spectrum due to various ion species. In general, the probability mass function (pmf) associated with the time-of-flight (TOF) spectrum produced by each ion species is unknown and varies from species-to-species. Moreover, measuring pmfs for distinct ion species in calibration experiments is not practical. Here, we present a mixture model method to determine TOF pmfs that can vary from peak-to-peak. In this approach, we determine weights of candidate pmfs with a maximum likelihood method. In a proof-of-principle study, we apply our method to a TOF spectrum acquired from a silicon sample and determine intensity estimates of singly charged isotopes of silicon.

Isotopic analyses of Ordovician-Silurian siliceous skeletons indicate silica-depleted Paleozoic oceans.

The Phanerozoic Eon marked a major transition from marine silica deposition exclusively via abiotic pathways to a system dominated by biogenic silica sedimentation. For decades, prevailing ideas predicted this abiotic-to-biogenic transition were marked by a significant decrease in the concentration of dissolved silica in seawater; however, due to the lower perceived abundance and uptake affinity of sponges and radiolarians relative to diatoms, marine dissolved silica is thought to have remained elevated above modern values until the Cenozoic radiation of diatoms. Studies of modern marine silica biomineralizers demonstrated that the Si isotope ratios (δ30 Si) of sponge spicules and planktonic silica biominerals produced by diatoms or radiolarians can be applied as quantitative proxies for past seawater dissolved silica concentrations due to differences in Si isotope fractionations among these organisms. We undertook 446 ion microprobe analyses of δ30 Si and δ18 O of sponge spicules and radiolarians from Ordovician-Silurian chert deposits of the Mount Hare Formation in Yukon, Canada. These isotopic data showed that sponges living in marine slope and basinal environments displayed small Si isotope fractionations relative to coeval radiolarians. By constructing a mathematical model of the major fluxes and reservoirs in the marine silica cycle and the physiology of silica biomineralization, we found that the concentration of dissolved silica in seawater was less than ~150 µM during early Paleozoic time-a value that is significantly lower than previous estimates. We posit that the topology of the early Paleozoic marine silica cycle resembled that of modern oceans much more closely than previously assumed.

Identification of organosiloxanes in ambient fine particulate matters using an untargeted strategy via gas chromatography and time-of-flight mass spectrometry.

Organosilicons are widely used in consumer products and are ubiquitous in living environments. However, there is little systemic information on this group of pollutants in ambient particles. This study proposes a novel untargeted strategy based mainly on the mass difference of three silicon isotopes to screen organosilicon compounds from 2-year PM2.5 samples of Beijing using gas chromatography and high-resolution time-of-flight mass spectrometry. 61 organosilicons were filtered from 1019 peaks, and 35 ones were identified as organosiloxanes including 17 methylsiloxanes and 18 phenylmethylsiloxanes, of which 6 and 3 species were confirmed using reference standards, respectively. These organosiloxanes could be clustered into three groups: low-silicon-number methylsiloxanes, high-silicon-number methylsiloxanes, and phenylmethylsiloxanes. Low-silicon-number methylsiloxanes showed high abundance in the heating season but low abundance in the non-heating season, whereas high-silicon-number methylsiloxanes showed the opposite seasonal variation. This study provides a promising strategy for screening organosilicon compounds through an untargeted approach and gives insights for further investigation of the sources and health risks of organosiloxanes.

Utilizing sponge spicules in taxonomic, ecological and environmental reconstructions: a review.

Most sponges produce skeletons formed by spicules, structural elements that develop in a wide variety of sizes and tridimensional shapes. The morphologies of spicules are often unique to clade- or even species-level taxa which makes them particularly useful in taxonomic assignments. When dead sponge bodies disintegrate, spicules become incorporated into sediments and sometimes accumulate into enormous agglomerations called spicule mats or beds, or fossilize to form special type of rocks called the spiculites. The record of fossil and subfossil sponge spicules is extraordinarily rich and often serves as a basis for far-reaching reconstructions of sponge communities, though spicules are also bearers of significant ecological and environmental information. Specific requirements and preferences of sponges can be used to interpret the environment in which they lived, and reconstruct oscillations in water depths, pH, temperatures, and other parameters, providing snapshots of past climate conditions. In turn, the silicon isotope compositions in spicules (δ30Si) are being increasingly often used to estimate the level of silicic acid in the marine settings throughout the geological history, which enables to reconstruct the past silica cycle and ocean circulation. This contribution provides a review of the use of sponge spicules in reconstructions of sponge communities, their ecology, and environments, and aims to detect the pertinent gaps in their utilization. Even though spicules are well known for their significance as bearers of taxonomic, ecological, and environmental data, their potential remains to be fully exploited.

Silicon isotopes in Arctic and sub-Arctic glacial meltwaters: the role of subglacial weathering in the silicon cycle.

Glacial environments play an important role in high-latitude marine nutrient cycling, potentially contributing significant fluxes of silicon (Si) to the polar oceans, either as dissolved silicon (DSi) or as dissolvable amorphous silica (ASi). Silicon is a key nutrient in promoting marine primary productivity, contributing to atmospheric CO2 removal. We present the current understanding of Si cycling in glacial systems, focusing on the Si isotope (δ30Si) composition of glacial meltwaters. We combine existing glacial δ30Si data with new measurements from 20 sub-Arctic glaciers, showing that glacial meltwaters consistently export isotopically light DSi compared with non-glacial rivers (+0.16‰ versus +1.38‰). Glacial δ30SiASi composition ranges from -0.05‰ to -0.86‰ but exhibits low seasonal variability. Silicon fluxes and δ30Si composition from glacial systems are not commonly included in global Si budgets and isotopic mass balance calculations at present. We discuss outstanding questions, including the formation mechanism of ASi and the export of glacial nutrients from fjords. Finally, we provide a contextual framework for the recent advances in our understanding of subglacial Si cycling and highlight critical research avenues for assessing potential future changes in these environments.

Coupled Si and O isotope measurements of meteoritic material by laser fluorination isotope ratio mass spectrometry.

We present a procedure for the determination of the isotopic ratios of silicon and oxygen from the same aliquot of anhydrous silicate material. The sample is placed in a bromine pentafluoride atmosphere as it is heated with a CO2 laser system releasing silicon tetrafluoride and oxygen gasses. The oxygen gas is then purified to remove other reaction by-products through several liquid nitrogen traps before being captured onto a molecular sieve and transferred to an isotope ratio mass spectrometer. The silicon tetrafluoride gas is then purified using a supplementary line by repeatedly freezing to -196°C with liquid nitrogen and then thawing with an ethanol slurry at -110°C through a series of metal and Pyrex traps. The purified gas is then condensed into a Pyrex sample tube before it is transferred to an isotope ratio mass spectrometer for silicon isotope ratio measurements. This system has silicon yields of greater than 90% for pure quartz, olivine, and garnet standards and has a reproducibility of ±0.1‰ (2σ) for pure quartz for both oxygen and silicon isotope measurements. Meteoritic samples were also successfully analyzed to demonstrate this system's ability to measure the isotopic ratio composition of bulk powders with precision. This unique technique allows for the fluorination of planetary material without the need for wet chemistry. Though designed to analyze small aliquots of meteoritic material (1.5 to 3 mg), this approach can also be used to investigate refractory terrestrial samples where traditional fluorination is not suitable.