Stoll
Heather M.
Stoll
Heather M.
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ArticleInsights on coccolith chemistry from a new ion probe method for analysis of individually picked coccoliths(American Geophysical Union, 2007-06-30) Stoll, Heather M. ; Shimizu, Nobumichi ; Arevalos, Alicia ; Matell, Nora ; Banasiak, Adam ; Zeren, SethThe elemental chemistry of calcareous nannofossils may provide valuable information on past ocean conditions and coccolithophorid physiology, but artifacts from noncoccolith particles and from changing nannofossil assemblages may bias geochemical records from coccolith size fractions. We describe the first method for picking individual coccoliths using a tungsten needle in micromanipulator. Epoxy-mounted individuals and populations of coccoliths can be analyzed by secondary ion mass spectrometry (SIMS). For Paleocene sediments the technique distinguishes the high Sr/Ca ratios of coccoliths (0.3 to 2.8 mmol/mol) from low ratios in abiogenic calcite blades (0.1 mmol/mol). The large heterogeneity of Sr/Ca ratios among different genera suggests that primary geochemical differences have not been homogenized by diagenetic overgrowth and the thick massive coccoliths of the late Paleocene are a primary feature of biomineralization. Sr/Ca ratios for modern genera are on average higher than those of Paleogene genera but exhibit a comparable level of variability.
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ArticleB content and Si/C ratios from cultured diatoms (Thalassiosira pseudonana and Thalassiosira weissflogii) : relationship to seawater pH and diatom carbon acquisition(Elsevier, 2013-06-18) Mejia, Luz Maria ; Isensee, Kirsten ; Mendez-Vicente, Ana ; Pisonero, Jorge ; Shimizu, Nobumichi ; Gonzalez, Cristina ; Monteleone, Brian D. ; Stoll, Heather M.Despite the importance of diatoms in regulating climate and the existence of large opal-containing sediments in key air-ocean exchange areas, most geochemical proxy records are based on carbonates. Among them, Boron (B) content and isotopic composition have been widely used to reconstruct pH from foraminifera and coral fossils. We assessed the possibility of a pH/CO2 seawater concentration control on B content in diatom opal to determine whether or not frustule B concentrations could be used as a pH proxy or to clarify algae physiological responses to acidifying pH. We cultured two well-studied diatom species, Thalassiosira pseudonana and Thalassiosira weissflogii at varying pH conditions and determined Si and C quotas. Frustule B content was measured by both laser-ablation inductively coupled mass spectrometry (LA-ICPMS) and secondary ion mass spectrometry (SIMS/ion probe). For both species, frustules grown at higher pH have higher B contents and higher Si requirements per fixed C. If this trend is representative of diatom silicification in a future more acidic ocean, it could contribute to changes in the efficiency of diatom ballasting and C export, as well as changes in the contribution of diatoms relative to other phytoplankton groups in Si-limited regions. If B enters the cell through the same transporter employed for HCO3− uptake, an increased HCO3− requirement with decreasing CO2 concentrations (higher pH), and higher B(OH)4/HCO3− ratios would explain the observed increase in frustule B content with increasing pH. The mechanism of B transport from the site of uptake to the site of silica deposition is unknown, but may occur via silicon transport vesicles, in which B(OH)4− may be imported for B detoxification and/or as part of a pH regulation strategy either though Na-dependent B(OH)4−/Cl− antiport or B(OH)4−/H+ antiport. B deposition in the silica matrix may occur via substitution of a B(OH)4− for a negatively charged SiO− formed during silicification. With the current analytical precision, B content of frustules is unlikely to resolve ocean pH with a precision of paleoceanographic interest. However, if frustule B content was controlled mainly by HCO3− uptake for photosynthesis, which appears to show a threshold behavior, then measurements of B content might reveal the varying importance of active HCO3− acquisition mechanisms of diatoms in the past.
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ArticleProductivity response of calcareous nannoplankton to Eocene Thermal Maximum 2 (ETM2)(Copernicus Publications on behalf of the European Geosciences Union, 2012-05-31) Dedert, M. ; Stoll, Heather M. ; Kroon, Dick ; Shimizu, Nobumichi ; Kanamaru, K. ; Ziveri, PatriziaThe Early Eocene Thermal Maximum 2 (ETM2) at ~53.7 Ma is one of multiple hyperthermal events that followed the Paleocene-Eocene Thermal Maximum (PETM, ~56 Ma). The negative carbon excursion and deep ocean carbonate dissolution which occurred during the event imply that a substantial amount (103 Gt) of carbon (C) was added to the ocean-atmosphere system, consequently increasing atmospheric CO2(pCO2). This makes the event relevant to the current scenario of anthropogenic CO2 additions and global change. Resulting changes in ocean stratification and pH, as well as changes in exogenic cycles which supply nutrients to the ocean, may have affected the productivity of marine phytoplankton, especially calcifying phytoplankton. Changes in productivity, in turn, may affect the rate of sequestration of excess CO2 in the deep ocean and sediments. In order to reconstruct the productivity response by calcareous nannoplankton to ETM2 in the South Atlantic (Site 1265) and North Pacific (Site 1209), we employ the coccolith Sr/Ca productivity proxy with analysis of well-preserved picked monogeneric populations by ion probe supplemented by analysis of various size fractions of nannofossil sediments by ICP-AES. The former technique of measuring Sr/Ca in selected nannofossil populations using the ion probe circumvents possible contamination with secondary calcite. Avoiding such contamination is important for an accurate interpretation of the nannoplankton productivity record, since diagenetic processes can bias the productivity signal, as we demonstrate for Sr/Ca measurements in the fine (<20 μm) and other size fractions obtained from bulk sediments from Site 1265. At this site, the paleoproductivity signal as reconstructed from the Sr/Ca appears to be governed by cyclic changes, possibly orbital forcing, resulting in a 20–30% variability in Sr/Ca in dominant genera as obtained by ion probe. The ~13 to 21% increase in Sr/Ca above the cyclic background conditions as measured by ion probe in dominating genera may result from a slightly elevated productivity during ETM2. This high productivity phase is probably the result of enhanced nutrient supply either from land or from upwelling. The ion probe results show that calcareous nannoplankton productivity was not reduced by environmental conditions accompanying ETM2 at Site 1265, but imply an overall sustained productivity and potentially a small productivity increase during the extreme climatic conditions of ETM2 in this portion of the South Atlantic. However, in the open oceanic setting of Site 1209, a significant decrease in dominant genera Sr/Ca is observed, indicating reduced productivity.
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ArticleDecrease in coccolithophore calcification and CO2 since the middle Miocene(Nature Publishing Group, 2016-01-14) Bolton, Clara T. ; Hernandez-Sanchez, Maria T. ; Fuertes, Miguel-Ángel ; Gonzalez-Lemos, Saul ; Abrevaya, Lorena ; Mendez-Vicente, Ana ; Flores, Jose-Abel ; Probert, Ian ; Giosan, Liviu ; Johnson, Joel E. ; Stoll, Heather M.Marine algae are instrumental in carbon cycling and atmospheric carbon dioxide (CO2) regulation. One group, coccolithophores, uses carbon to photosynthesize and to calcify, covering their cells with chalk platelets (coccoliths). How ocean acidification influences coccolithophore calcification is strongly debated, and the effects of carbonate chemistry changes in the geological past are poorly understood. This paper relates degree of coccolith calcification to cellular calcification, and presents the first records of size-normalized coccolith thickness spanning the last 14 Myr from tropical oceans. Degree of calcification was highest in the low-pH, high-CO2 Miocene ocean, but decreased significantly between 6 and 4 Myr ago. Based on this and concurrent trends in a new alkenone εp record, we propose that decreasing CO2 partly drove the observed trend via reduced cellular bicarbonate allocation to calcification. This trend reversed in the late Pleistocene despite low CO2, suggesting an additional regulator of calcification such as alkalinity.