Geochemistry Commons^™

Paleoenvironmental Reconstruction Using Coral Microatolls (Sp. Siderastrea Siderea) From The Gulf Of Gonâve, Haiti, Gilman Reno Ouellette Jr.

LSU Doctoral Dissertations

Natural and anthropogenic climate changes present unique and serious risks to society. In order to plan and implement adaptation and mitigation strategies successfully, regional manifestations of broad-scale climate changes must be understood robustly. The Caribbean region contains part of the Western Hemisphere Warm Pool (WHWP), a major sea surface temperature (SST) feature that plays a key role in North Atlantic climate. Climate variability in the Caribbean is captured poorly by climate models, due in part to a lack of continuous, multidecadal instrumental climate records from the region. I explored three research questions in this dissertation: Does non-systematic bias exist in …

Selenium Distribution And Cycling In The Eastern Equatorial Pacific Ocean, Zoe Wambaugh

OES Theses and Dissertations

Oxygen minimum zones in oceanic waters have become increasingly important to the marine environment and society. Low oxygen waters affect not only the distribution and abundance of marine organisms, but also impact the solubility and transport of trace elements that are of biological importance, with the chemical speciation and solubility depending on the actual redox poise of the waters. One redox sensitive trace element of interest is selenium, which can be both toxic and essential for organisms, depending on its chemical speciation. In 2013, the US GEOTRACES program completed the GP16 transect from Peru to Tahiti, going through the oxygen …

Actively Forming Kuroko-Type Volcanic-Hosted Massive Sulfide (Vhms) Mineralization At Iheya North, Okinawa Trough, Japan, Christopher J. Yeats, Steven P. Hollis, Angela Halfpenny, Juan-Carlos Corona, Crystal Laflamme, Gordon Southam, Marco Fiorentini, Richard J. Herrington, John Spratt

All Faculty Scholarship for the College of the Sciences

Modern seafloor hydrothermal systems provide important insights into the formation and discovery of ancient volcanic-hosted massive sulfide (VHMS) deposits. In 2010, Integrated Ocean Drilling Program (IODP) Expedition 331 drilled five sites in the Iheya North hydrothermal field in the middle Okinawa Trough back-arc basin, Japan. Hydrothermal alteration and sulfide mineralization is hosted in a geologically complex, mixed sequence of coarse pumiceous volcaniclastic and fine hemipelagic sediments, overlying a dacitic to rhyolitic volcanic substrate. At site C0016, located adjacent to the foot of the actively venting North Big Chimney massive sulfide mound, massive sphalerite-(pyrite-chalcopyrite ± galena)-rich sulfides were intersected (to 30.2% …

Spatial Patterns Of Sea Level Variability Associated With Natural Internal Climate Modes, Weiqing Han, Gerald A. Meehl, Detlef Stammer, Aixue Hu, Benjamin Hamlington, Jessica Kenigson, Hindumathi Palanisamy, Philip Thompson

OES Faculty Publications

Sea level rise (SLR) can exert significant stress on highly populated coastal societies and low-lying island countries around the world. Because of this, there is huge societal demand for improved decadal predictions and future projections of SLR, particularly on a local scale along coastlines. Regionally, sea level variations can deviate considerably from the global mean due to various geophysical processes. These include changes of ocean circulations, which partially can be attributed to natural, internal modes of variability in the complex Earth's climate system. Anthropogenic influence may also contribute to regional sea level variations. Separating the effects of natural climate modes …

Community Production Modulates Coral Reef Ph And The Sensitivity Of Ecosystem Calcification To Ocean Acidification, Thomas M. Decarlo, Anne L. Cohen, George T. F. Wong, Fuh-Kwo Shiah, Steven J. Lentz, Kristen A. Davis, Kathryn E. F. Shamberger, Pat Lohmann

OES Faculty Publications

Coral reefs are built of calcium carbonate (CaCO₃) produced biogenically by a diversity of calcifying plants, animals, and microbes. As the ocean warms and acidifies, there is mounting concern that declining calcification rates could shift coral reef CaCO3 budgets from net accretion to net dissolution. We quantified net ecosystem calcification (NEC) and production (NEP) on Dongsha Atoll, northern South China Sea, over a 2 week period that included a transient bleaching event. Peak daytime pH on the wide, shallow reef flat during the nonbleaching period was ~8.5, significantly elevated above that of the surrounding open ocean (~8.0-8.1) as …

A Tribute To Thomas M. Church: Exploring Chemical Oceanography In The Coastal Zone-The History And Future, Gregory A. Cutter, David J. Burdige

OES Faculty Publications

(First paragraph) One can find different historical perspectives on the development of studying the chemistry of oceans as well as names for this study—marine chemistry, chemistry of the sea, marine aquatic chemistry, marine biogeochemistry, or chemical oceanography. It could be argued that chemical oceanography is the most inclusive for an earth science since oceanography itself is an integrated discipline that links the biology, chemistry, geology, and physics together. Regardless of the name, perhaps the first intensive, modern/post-nineteenth century study of the ocean’s chemistry was the GEOSECS Program from ca. 1970–1978. The significance of GEOSECS was that it examined the chemistry …

Iron Sources And Dissolved-Particulate Interactions In The Seawater Of The Western Equatorial Pacific, Iron Isotope Perspectives, M. Labatut, F. Lacan, C. Pradoux, J. Chmeleff, A. Radic, J. W. Murray, F. Poitrasson, Anne M. Johansen, F. Thil

All Faculty Scholarship for the College of the Sciences

This work presents iron isotope data in the western equatorial Pacific. Marine aerosols and top core margin sediments display a slightly heavy Fe isotopic composition (δ⁵⁶Fe) of 0.33 ± 0.11‰ (2SD) and 0.14 ± 0.07‰, respectively. Samples reflecting the influence of Papua New Guinea runoff (Sepik River and Rabaul volcano water) are characterized by crustal values. In seawater, Fe is mainly supplied in the particulate form and is found with a δ⁵⁶Fe between −0.49 and 0.34 ± 0.07‰. The particulate Fe seems to be brought mainly by runoff and transported across continental shelves and slopes. …

Molecular Characterization And Photochemical Transformation Of Dissolved Organic Matter From Land To Ocean, Hongmei Chen

Chemistry & Biochemistry Theses & Dissertations

Molecular characterization and photochemical transformation of dissolved organic matter (DOM) in both rivers and the ocean is the main research focus of this dissertation. Chemical characterization of DOM is hampered by the limited application of advanced techniques to desalt, concentrate, isolate and then molecularly characterize DOM. An affordable, commercially available mini-electrodialysis (mini-ED) system has been evaluated and recommended for the efficient desalting of small volume samples of seawater prior to analysis by electrospray Fourier transform ion cyclotron resonance mass spectrometry (ESI FTICR-MS).

A high-recovery technique of DOM isolation – reverse osmosis coupled with electrodialysis (RO/ED) – was used to isolate …

Glacial Shortcut Of Arctic Sea-Ice Transport, Michael Stärz, Xun Gong, Rüdiger Stein, Dennis A. Darby, Frank Kauker, Gerrit Lohmann

OES Faculty Publications

Due to the lack of data, the extent, thickness and drift patterns of sea ice and icebergs in the glacial Arctic remains poorly constrained. Earlier studies are contradictory proposing either a cessation of the marine cryosphere or an ice drift system operating like present-day. Here we examine the marine Arctic cryosphere during the Last Glacial Maximum (LGM) using a high-resolution, regional ocean-sea ice model. Whereas modern sea ice in the western Arctic Basin can circulate in the Beaufort Gyre for decades, our model studies present an extreme shortcut of glacial ice drift. In more detail, our results show a clockwise …

A New Phase Speciation Leaching Procedure For The Determination Of Metals In Oxic And Anoxic Sediments, Brandon R. Gipson

OES Theses and Dissertations

Toxic trace elements such as cadmium, lead, chromium, and arsenic released by human activities can accumulate in marine and estuarine sediments, where these metals are often sequestered until local environmental changes (e.g., redox, salinity, and/or pH) allow these elements to be reintroduced into the food web. In order to assess the extent of toxic trace element contamination in sediment, numerous leaching schemes have been developed that separate sediment-bound trace metals into operationally defined geochemical phases. These "phase speciation" leaching schemes are typically designed with the purpose of being used on either oxic or anoxic sediments. However, natural sediments often contain …

Early Season Depletion Of Dissolved Iron In The Ross Sea Polynya: Implications For Iron Dynamics On The Antarctic Continental Shelf, Peter N. Sedwick, C. M. Marsay, B. M. Sohst, A. M. Aguilar-Islas, M. C. Lohan, M. C. Long, K. R. Arrigo, R. B. Dunbar, M. A. Saito, W. O. Smith, G. R. Ditullio

OES Faculty Publications

The Ross Sea polynya is among the most productive regions in the Southern Ocean and may constitute a significant oceanic CO₂sink. Based on results from several field studies, this region has been considered seasonally iron limited, whereby a "winter reserve" of dissolved iron (dFe) is progressively depleted during the growing season to low concentrations (~ 0.1 nM) that limit phytoplankton growth in the austral summer (December-February). Here we report new iron data for the Ross Sea polynya during austral summer 2005-2006 (27 December-22 January) and the following austral spring 2006 (16 November-3 December). The summer 2005-2006 data show …

Trace Metal Biogeochemistry In The Western North Pacific, Peter Lynn Morton

OES Theses and Dissertations

Dissolved and suspended particulate samples collected during the Intergovernmental Oceanographic Commission 2002 Contaminant Baseline Survey were analyzed to determine the surface and vertical distributions of Cd, Co, Cu, Mn, Ni Zn and Pb across the western and central North Pacific.

Dissolved trace metal concentrations were measured using a novel isotope dilution-ICP-MS method after extraction over an 8-hydroxyquinoline resin column and validated through the use of the SAFe consensus reference materials. Filtered suspended particulate matter was digested using an HCl/HNO3/HF mixture and analyzed by HR-ICP-MS to obtain total particulate concentrations for the trace metals and other tracer elements such as Al, …

A Seasonal Study Of Dissolved Cobalt In The Ross Sea, Antarctica: Micronutrient Behavior, Absence Of Scavenging, And Relationships With Zd, Cd, And P., M. A. Saito, T. J. Goepfert, A. E. Noble, E. M. Bertrand, Peter N. Sedwick, Giacomo R. Ditullio

OES Faculty Publications

We report the distribution of cobalt (Co) in the Ross Sea polynya during austral summer 2005-2006 and the following austral spring 2006. The vertical distribution of total dissolved Co (dCo) was similar to soluble reactive phosphate (PO(4)(3-)), with dCo and PO(4)(3-) showing a significant correlation throughout the water column (r(2) = 0.87, 164 samples). A strong seasonal signal for dCo was observed, with most spring samples having concentrations ranging from similar to ~ 45-85 pM, whereas summer dCo values were depleted below these levels by biological activity. Surface transect data from the summer cruise revealed concentrations at the low range …

Anthropogenic Osmium In Rain And Snow Reveals Global-Scale Atmospheric Contamination, Cynthia Chen, Peter N. Sedwick, Mukul Sharma

Dartmouth Scholarship

Osmium is one of the rarer elements in seawater, with typical concentration of approximately 10 x 10(-15) g g(-1) (5.3 x 10(-14) mol kg(-1)). The osmium isotope composition ((187)Os/(188)Os ratio) of deep oceans is 1.05, reflecting a balance between inputs from continental crust (approximately 1.3) and mantle/cosmic dust (approximately 0.13). Here, we show that the (187)Os/(188)Os ratios measured in rain and snow collected around the world range from 0.16 to 0.48, much lower than expected (>1), but similar to the isotope composition of ores (approximately 0.2) that are processed to extract platinum and other metals to be used primarily …

Export Of Terrestrial Dissolved Organic Matter Along A River To Ocean Transect Of The Lower Chesapeake Bay Investigated By Advanced Analytical Techniques, Rachel Leigh Sleighter

Chemistry & Biochemistry Theses & Dissertations

Ultrahigh resolution electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry (ESI-FTICR-MS) has proved essential for the complete separation of the thousands of peaks present in natural organic matter (NOM), a complex assemblage of organic molecules present in water, soils, and sediments. An improved understanding of its composition is crucial to understand how pollutants interact with NOM and how NOM cycles through global carbon cycles.

Optimizing the acquisition and handling of the FTICR mass spectra is the first step to obtaining high quality data. A simple method to internally calibrate the peaks in the complex spectra, using naturally present fatty …

Biogenic Tracers Through The Holocene On The Alaskan Shelf, Carie A. Curry

OES Theses and Dissertations

Dramatic environmental changes in the Arctic Ocean have been observed for the last two decades including changing the amount of sea ice thickness and extent, and increased river discharge. In order to put these and other current day observations into historical context and perhaps reveal mechanisms controlling them, a suite of paleo-proxies were used to analyze two high resolution cores collected on the 2005 HOTRAX expedition. The goals of this research were: (1) develop an analytical method for determining biogenic calcite, (2) identify the major sources of biogenic matter into the system over the Holocene, and (3) assemble the history …

Arctic Perennial Ice Cover Over The Last 14 Million Years, Dennis A. Darby

OES Faculty Publications

Knowledge of the long-term history of the perennial ice is an important issue that has eluded study because the Cenozoic core material needed has been unavailable until the recent Arctic Coring Expedition (ACEX). Detrital Fe oxide mineral grains analyzed by microprobe from the last 14 Ma (164 m) of the ACEX composite core on the Lomonosov Ridge were matched to circum-Arctic sources with the same mineral and 12-element composition. These precise source determinations and estimates of drift rates were used to determine that these sand grains could not be rafted to the ACEX core site in less than a year. …

Impact Of Anthropogenic Combustion Emissions On The Fractional Solubility Of Aeroosol Iron: Evidence From The Sargasso Sea, Peter N. Sedwick, Edward R. Sholkovitz, Thomas M. Church

OES Faculty Publications

We report empirical estimates of the fractional solubility of aerosol iron over the Sargasso Sea during periods characterized by high concentrations of Saharan dust (summer 2003) and by low concentrations of aerosols in North American/maritime North Atlantic air masses (spring 2004 and early summer 2004). We observed a strong inverse relationship between the operational solubility of aerosol iron (defined using a flow-through deionized-water leaching protocol) and the total concentration of aerosol iron, whereby the operational solubility of aerosol iron was elevated when total aerosol iron loadings were low. This relationship is consistent with source-dependent differences in the solubility characteristics of …

Interdecadal-Decadal Climate Variability From Multi-Coral Oxygen Isotope Records In The South Pacific Convergence Zone Region Since 1650ad, Peipei Zhang

Geology Theses and Dissertations

Annual average oxygen isotope (δ18O) time series from five coral cores collected from Fiji and Tonga are used to construct a Fiji-Tonga Interdecadal-Decadal Pacific Oscillation (F-TIDPO) index of low frequency (>9yr and <55yr) climate variability in this area back to 1650 A.D. Presently, both Fiji and Tonga are located in the South Pacific Convergence Zone (SPCZ) salinity front region where the Interdecadal Pacific Oscillation (IPO) variation is most pronounced. We first demonstrate the consistency between this F-T IDPO index and a MSL pressure-based SPCZ Position Index (SPI) (1891-2000), thus verifying the ability of coral δ18O to record past interdecadal-decadal climatic variations in this region back to 1891. The F-T IDPO index is then shown to be synchronous with the IPO index (1856-2000), suggesting that this coral-based index effectively represents the interdecadal-decadal scale climate variance back to 1650. The consistently anti-phase spectrums of the F-T five-coral composite and the interdecadal-decadal components in equatorial Pacific coral δ18O series from Maiana [Urban et al., 2000] and Palmyra [Cobb et al., 2001] suggest that the simultaneous eastern expansion (western contraction) of the eastern salinity front of Western Pacific Warm Pool (WPWP) occurs at the same time as the northeast (southwest) movement of the SPCZ during a positive IPO (negative IPO) phase.

Western Caribbean Sea Surface Temperatures During The Late Quaternary, Matthew W. Schmidt, Maryline J. Vautravers, Howard J. Spero

OES Faculty Publications

[1] Mg/Ca ratios in the planktonic foraminifera Globigerinoides ruber from Colombian Basin core ODP 999A suggest that Caribbean sea surface temperatures ( SSTs) were from 2.1 to 2.7°C colder than the present during the last three glacial maximums. In comparison, faunal derived SSTs ( SIMMAX method) show that August SSTs in the Caribbean varied < 2° over the past 360 kyr, whereas February SSTs varied between 21.0°C and 26.5°C. Changes in the Mg/Ca-SST record contain a strong 23 kyr periodicity, suggesting the Mg/Ca-SST record reflects a warm season weighted SST average rather than an annual mean SST. Combining several dissolution indices, we identify brief periods of decreased carbonate preservation in our record and show that MIS 11 stands out as the most intensive dissolution cycle in the Caribbean over the last 460 kyr. Comparison of Caribbean SST change with a similar estimate of tropical SST variability in the western Pacific over the past 360 kyr reveals shifts in the east-west tropical SST gradient that are coeval with glacial-interglacial climate change and consistent both with a southward migration of the glacial ITCZ and with a glacial El Niño-like mode of tropical circulation.

Assessing The Paleoceanographic Potential Of The Coral Montipora Venosa At Fanning Atoll, Central Equatorial Pacific, Alexa Stolorow

Geology Theses and Dissertations

As interest in global climate change increases, so does the need for better and more extensive climate proxies. The central equatorial Pacific has been established as the region with the largest ENSO-related sea surface temperature (SST) and precipitation (PPT) anomalies, which are known to impact global interannual climate variability. To date, the coral genus Porites has been most commonly utilized for coral-based paleo-reconstructions of ENSO and lower frequency phenomena. However, due to questions of biological artifacts in coral, to more fully understand coral-based reconstruction, different coral genera need to be analyzed.
In this study, oxygen (δ18O) and carbon (δ13C) isotopic …

Relating Water And Otolith Chemistry In Chesapeake Bay, And Their Potential To Identify Essential Seagrass Habitats For Juveniles Of An Estuarine-Dependent Fish, Spotted Seatrout (Cynoscion Nebulosus), Emmanis Dorval

Biological Sciences Theses & Dissertations

A quantitative understanding of habitat use of estuarine-dependent fishes is critical to the conservation of their most essential habitats. Because recruitment and fitness may be influenced by the quality of juvenile habitats, developing methods to quantify habitat-specific survivorship is pivotal to such understanding. An initial step to quantify survivorship is to validate the habitat-specific natural tags contained in otoliths. To this aim I investigated the variability in the chemistry of surface waters and otoliths of juvenile spotted seatrout, Cynoscion nebulosus, in five seagrass habitats of Chesapeake Bay, namely: Potomac, Rappahannock, York, Island, and Eastern Shore. I measured Mg, Ca, …

Methods And Models For Estimating Advective Pore Water Exchange In Tidal Flats, Timothy J. Shaw

Faculty Publications

No abstract provided.

Nitrate Anomaly In The Upper Nutricline In The Northern South China Sea - Evidence For Nitrogen Fixation, George T. F. Wong, Shi-Wei Chung, Fuh-Kwo Shiah, Chung-Chi Chen, Liang-Saw Wen, Kon-Kee Liu

OES Faculty Publications

[1] Up to 2 μM of nitrate anomaly, N*, were found in the upper nutricline at the South East Asia Time-series Study (SEATS) site in the northern South China Sea (SCS). These concentrations were among the higher values reported in the Pacific and indicate the significant contribution of the remineralization of nitrogen-rich organic matter formed by nitrogen fixation to the nutrient dynamics of the area. The concentrations were systematically higher, by up to 2.5 μM, in the Fall through the early Spring, during the northeast monsoon, than in the Summer, suggesting that the impact of nitrogen fixation was higher during …

Intra-Annual Variation In The Stable Oxygen And Carbon And Trace Element Composition Of Sclerosponges, P. K. Swart, S. Thorrold, B. Rosenheim, A. Eisenhauer, C. G. A. Harriason, M. Grammer, C. Latkoczy

Biological Sciences Faculty Publications

This paper presents data to support the presence of (1) intra-annual signals in the chemical composition (δ¹⁸O and Sr/Ca) of the skeletons ofsclerosponges from the Bahamas and (2) variable rates of skeletal accretion. These conclusions are based on data obtained by using a microsampling method for the stable oxygen and carbon isotopes in which material was extracted at a resolution of one sample every 34 μm and a laser microprobe which obtained trace element data every 20 μm (Sr, Mg, and Pb). An age model was established using a combination of changes in the concentration of Pb, the …

Identification Of Past Climate Variability Of The Eastern Pacific Ocean Using Both D13c And D18o Records In Corals From Clipperton Atoll (1994-1906), Lei Ren

Geology Theses and Dissertations

The ENSO (El Nino and the Southern Oscillation) is a fundamental ocean-atmosphere phenomenon that dominates interannual global climate variability. Reconstructing past ENSO events is therefore important for documenting and understanding the past behavior of the global climate system and enabling us to predict future climate change. However, the present understanding of ENSO events has been mainly based on the instrumental record of Pacific climate which provides detailed data only for the past few decades. Recent studies have shown that the stable isotope record in coral skeletons can be used as a valuable indicator of paleoclimatic changes in tropical regions, and …

The Implications Of Turbidite-Driven Redox Changes In Sediments Of The Iberia Abyssal Plain, Timothy J. Shaw, P. A. Meyers

Faculty Publications

No abstract provided.

Organic Matter Accumulation, Sulfate Reduction, And Methanogenesis In Pliocene–Pleistocene Turbidites On The Iberia Abyssal Plain, P. A. Meyers, Timothy J. Shaw

Faculty Publications

No abstract provided.

Identification And Quantitation Of Volatile Amines In Chesapeake Bay Sediments, Neeraja Y. Krishna

Chemistry & Biochemistry Theses & Dissertations

Sediments from different parts of the Chesapeake Bay were analyzed to determine the presence of volatile amines. A HF-HCl extraction method was used to extract both exchangeable and fixed amines from the sediments and a purge-and-trap technique was used to concentrate the amines. Following derivatization with heptafluorobutyric anhydride (HFBA), the HFBA-amines were analyzed by gas chromatography with electron capture detection and with mass spectrometric detection. One primary amine, i-amylamine with a concentration ranging from 0. 78 nmoles/g dry weight to < 0.05 nmoles/g dry weight was found in a total of twenty seven samples collected on three different dates in 1993. Another primary amine, 2-methylbutylamine with a concentration ranging from 0.18 nmoles/g dry weight to < 0.05 nmoles/g dry weight was found in a total of twenty three samples collected on three different dates in 1993. A secondary amine, diethylamine was detected but could not be quantified in a total of seven samples collected in September 1993. The concentrations of these amines varied with location in the Bay, depth in the sediment, and time of year the sediments were collected. The origin of i-amylamine and 2-methylbutylamine might be from the biological decarboxylation of amino acids leucine and isoleucine, respectively. The origin of diethylamine is unknown.

Trace Metals And Pyrite In Sediments Of Chesapeake Bay, Robert S. Kluckhohn

OES Theses and Dissertations

The formation and cycling of iron sulfides within anoxic sediments can affect the cycling of trace metals. The sediments at station CB-27 (near Annapolis, Maryland) in Chesapeake Bay were rich in FeS (39% of TS), low in greigite (3.6% of TS), and has a relatively constant pyrite concentration (50 - 60% of TS) with depth. The percent composition of total metals in pyrite were 25.7% cu, 11.8% Zn, 15.8% Fe, and non-detectable to 2.1% Cd. At Station CB- 28 (near the Choptank River), the sediments were low in FeS (1.7% of TS), richer in greigite (up to 14% of TS), …