Using the silica isotope composition of biogenic materials in marine sediments to reconstruct ocean chemistry

Author(s):  
Daniel Conley ◽  
Katherine Hendry

<div><span>The silicon isotopic composition of sedimentary biogenic opal can be used to track shifts in the balance between silicon inputs to the ocean and outputs by burial. In addition to biosilicification and opal burial, the global cycles of climate (hydrology, weathering, glaciation, etc.), tectonics (volcanoes, LIPs, mountain building, etc.) and geochemistry (reverse weathering, inorganic Si precipitation, etc.) have driven variations in the global Si cycle over geologic time. Prior to the start of the Phanerozoic it is thought that burial in the global oceans was controlled inorganically through chert formation. The evolution of the Si depositing organisms, radiolarians and sponges, reduced oceanic dissolved Si, but the largest reductions occurred with the evolution of the diatoms bringing dissolved Si to the low concentrations (relative to saturating concentrations) observed today. However, the timing of the depletion of dissolved Si by diatoms is currently under debate.</span></div><div><span> </span></div><div><span>Our understanding of the biological components of the Si cycle has grown enormously. In the last decade, silicon isotope ratios (expressed as δ30Si) in marine microfossils are becoming increasingly recognised for their ability to provide insight into silicon cycling. In particular, the δ30Si of deep-sea sponge spicules has been demonstrated to be a useful proxy for past dissolved Si concentrations. However, more recent studies find anomalies in the isotopic fractionation of sponge spicules that relate to skeletal morphology: reliable reconstructions of past dissolved Si can only be obtained using silicon isotope ratios derived from sponges with certain spicule types. We are applying δ30Si proxies from biosiliceous material contained in sediments to generate robust estimates of the timing and magnitude of dissolved Si drawdown. We will provide fundamental new insights into the drawdown of dissolved Si and other key events, which reorganized the distribution of carbon and nutrients in seawater, with implications for productivity of the biological communities within the ancient oceans. </span></div>

2018 ◽  
Author(s):  
Lucie Cassarino ◽  
Christopher D. Coath ◽  
Joana R. Xavier ◽  
Katharine R. Hendry

Abstract. The silicon isotope composition of deep-sea sponges skeletal element – spicules – reflects the silicic acid (DSi) concentration of their surrounding water, and can be used as natural archives of bottom water nutrients. In order to reconstruct the past silica cycle robustly, it is essential to better constrain the mechanisms of biosilicification, which are not yet well understood. Here, we show that the apparent isotopic fractionation (∆30Si) during spicule formation in deep–sea sponges from the equatorial Atlantic range from −6.74 ‰ to −1.50 ‰ in relatively low DSi concentrations (15 to 35 μM). The wide range in isotopic composition highlights the potential difference in silicification mechanism between the two major classes, Demospongiae and Hexactinellida. We find the anomalies in the isotopic fractionation correlates with skeletal morphology, whereby fused framework structures, characterised by secondary silicification, exhibit extremely light δ30Si signatures. Our results provide insights into the process involved during silica deposition, and indicate that reliable reconstructions of past DSi can only be obtained using silicon isotopes ratios derived from sponges with certain spicule types.


2006 ◽  
Vol 361 (1474) ◽  
pp. 1715-1720 ◽  
Author(s):  
M Anand ◽  
S.S Russell ◽  
R.L Blackhurst ◽  
M.M Grady

Recent spacecraft and lander missions to Mars have reinforced previous interpretations that Mars was a wet and warm planet in the geological past. The role of liquid water in shaping many of the surface features on Mars has long been recognized. Since the presence of liquid water is essential for survival of life, conditions on early Mars might have been more favourable for the emergence and evolution of life. Until a sample return mission to Mars, one of the ways of studying the past environmental conditions on Mars is through chemical and isotopic studies of Martian meteorites. Over 35 individual meteorite samples, believed to have originated on Mars, are now available for lab-based studies. Fe is a key element that is present in both primary and secondary minerals in the Martian meteorites. Fe-isotope ratios can be fractionated by low-temperature processes which includes biological activity. Experimental investigations of Fe reduction and oxidation by bacteria have produced large fractionation in Fe-isotope ratios. Hence, it is considered likely that if there is/were any form of life present on Mars then it might be possible to detect its signature by Fe-isotope studies of Martian meteorites. In the present study, we have analysed a number of Martian meteorites for their bulk-Fe-isotope composition. In addition, a set of terrestrial analogue material has also been analysed to compare the results and draw inferences. So far, our studies have not found any measurable Fe-isotopic fractionation in bulk Martian meteorites that can be ascribed to any low-temperature process operative on Mars.


2018 ◽  
Vol 15 (22) ◽  
pp. 6959-6977 ◽  
Author(s):  
Lucie Cassarino ◽  
Christopher D. Coath ◽  
Joana R. Xavier ◽  
Katharine R. Hendry

Abstract. The silicon isotopic composition (δ30Si) of deep sea sponges' skeletal element – spicules – reflects the silicic acid (DSi) concentration of their surrounding water and can be used as natural archives of bottom water nutrients. In order to reconstruct the past silica cycle robustly, it is essential to better constrain the mechanisms of biosilicification, which are not yet well understood. Here, we show that the apparent isotopic fractionation (δ30Si) during spicule formation in deep sea sponges from the equatorial Atlantic ranges from −6.74 ‰ to −1.50 ‰ in relatively low DSi concentrations (15 to 35 µM). The wide range in isotopic composition highlights the potential difference in silicification mechanism between the two major classes, Demospongiae and Hexactinellida. We find the anomalies in the isotopic fractionation correlate with skeletal morphology, whereby fused framework structures, characterised by secondary silicification, exhibit extremely light δ30Si signatures compared with previous studies. Our results provide insight into the processes involved during silica deposition and indicate that reliable reconstructions of past DSi can only be obtained using silicon isotope ratios derived from sponges with certain spicule types.


2013 ◽  
Vol 109 ◽  
pp. 384-399 ◽  
Author(s):  
Paul S. Savage ◽  
R. Bastian Georg ◽  
Helen M. Williams ◽  
Alex N. Halliday

2003 ◽  
Vol 69 (8) ◽  
pp. 4997-5000 ◽  
Author(s):  
Max L. Coleman ◽  
Magali Ader ◽  
Swades Chaudhuri ◽  
John D. Coates

ABSTRACT Perchlorate contamination can be microbially respired to innocuous chloride and thus can be treated effectively. However, monitoring a bioremediative strategy is often difficult due to the complexities of environmental samples. Here we demonstrate that microbial respiration of perchlorate results in a significant fractionation (∼−15‰) of the chlorine stable isotope composition of perchlorate. This can be used to quantify the extent of biotic degradation and to separate biotic from abiotic attenuation of this contaminant.


2014 ◽  
Vol 14 (23) ◽  
pp. 31813-31841
Author(s):  
S. J. Allin ◽  
J. C. Laube ◽  
E. Witrant ◽  
J. Kaiser ◽  
E. McKenna ◽  
...  

Abstract. The stratospheric degradation of chlorofluorocarbons (CFCs) releases chlorine, which is a major contributor to the destruction of stratospheric ozone (O3). A recent study reported strong chlorine isotope fractionation during the breakdown of the most abundant CFC (CFC-12, CCl2F2), similar to effects seen in nitrous oxide (N2O). Using air archives to obtain a long-term record of chlorine isotope ratios in CFCs could help to identify and quantify their sources and sinks. We analyse the three most abundant CFCs and show that CFC-11 (CCl3F) and CFC-113 (CClF2CCl2F) exhibit significant stratospheric chlorine isotope fractionation, in common with CFC-12. The apparent isotope fractionation (ϵapp) for mid- and high-latitude stratospheric samples are (−2.4 ± 0.5) and (−2.3 ± 0.4)‰ for CFC-11, (−12.2 ± 1.6) and (−6.8 ± 0.8)‰ for CFC-12 and (−3.5 ± 1.5) and (−3.3 ± 1.2)‰ for CFC-113, respectively. Assuming a constant source isotope composition, we estimate the expected trends in the tropospheric isotope signature of these gases due to their stratospheric 37Cl enrichment and stratosphere–troposphere exchange. We compare these model results to the long-term δ(37Cl) trends of all three CFCs, measured on background tropospheric samples from the Cape Grim air archive (Tasmania, 1978–2010) and tropospheric firn air samples from Greenland (NEEM site) and Antarctica (Fletcher Promontory site). Model trends agree with tropospheric measurements within analytical uncertainties. From 1970 to the present-day, we find no evidence for variations in chlorine isotope ratios associated with changes in CFC manufacturing processes. Our study increases the suite of trace gases amenable to direct isotope ratio measurements in small air volumes, using a single-detector gas chromatography-mass spectrometry system.


PeerJ ◽  
2019 ◽  
Vol 7 ◽  
pp. e7890 ◽  
Author(s):  
Hideyuki Doi ◽  
Eisuke Kikuchi ◽  
Shigeto Takagi ◽  
Shuichi Shikano

Analysis of aquatic food webs is typically undertaken using carbon and nitrogen stable isotope composition of consumer and producer species. However, the trophic consequences of spatio-temporal variation in the isotope composition of consumers have not been well evaluated. Lake Katanuma, Japan, is highly acidic and has only one dominant species of benthic alga and one planktonic microalga, making it a prime system for studying trophic relationships between primary consumers and producers. In this simple lake food web, we conducted a field survey to evaluate spatial and temporal variation in the carbon and nitrogen stable isotope composition of a chironomid larvae in association with a single benthic and planktonic alga. We found a significant correlation between carbon stable isotope ratios of the chironomid larvae and the benthic diatom species in the lake. Thus, chironomid larvae may represent a reliable isotopic baseline for estimating isotope values in benthic diatoms. However, although the correlation held in shallow water, at four m depths, there was no significant relationship between the isotope ratios of chironomids and benthic diatoms, probably because deep-water larvae spend part of their life cycle migrating from the lake shore to deeper water. The differing isotope ratios of deeper chironomid tissues likely reflect the feeding history of individuals during this migration.


2017 ◽  
Vol 32 (3) ◽  
pp. 562-578 ◽  
Author(s):  
Patricia Grasse ◽  
Mark A. Brzezinski ◽  
Damien Cardinal ◽  
Gregory F. de Souza ◽  
Per Andersson ◽  
...  

The first inter-calibration study of the stable silicon isotope composition of dissolved silicic acid in seawater, δ30Si(OH)4, is presented as a contribution to the international GEOTRACES program.


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