Physical Sciences and Mathematics Commons^™

Exploring Indicator Displacement Assays For Phosphate Detection In Seawater, Francis Radics

Chemistry & Biochemistry Student Scholarship

Francis Radics ’22
Major: Biochemistry
Faculty Mentor: Dr. John Breen, Chemistry and Biochemistry

Indicator displacement assays are based on the optical signal modulation of a noncovalently bound indicator upon dissociation by an analyte species. Our work has focused on exploring the lower detection limits for luminescent displacement assays for inorganic phosphate in seawater using complex ions containing two di(2-picolyl)amine ligands (also called DPA or bis(2-pyridylmethyl)amine), each coordinating a zinc cation. Following the work of B.D. Smith and coworkers, we have prepared three ligands by covalently attaching two DPA moieties, 2,6-bis(chloromethyl) benzene, and 2,6-bis(chloromethyl)-4-methylphenol, and 1,2-phenylenedimethylamine, for assays with 6,7-dihydroxy-4-methanesulfonic acid …

Insights Into The Deglacial Variability Of Phytoplankton Community Structure In The Eastern Equatorial Pacific Ocean Using [231Pa/230Th]Xs And Opal-Carbonate Fluxes, Danielle Schimmenti, Franco Marcantonio, Christopher T. Hayes, Jennifer Hertzberg, Matthew Schmidt, John Sarao

OES Faculty Publications

Fully and accurately reconstructing changes in oceanic productivity and carbon export and their controls is critical to determining the efficiency of the biological pump and its role in the global carbon cycle through time, particularly in modern CO₂ source regions like the eastern equatorial Pacific (EEP). Here we present new high-resolution records of sedimentary ²³⁰Th-normalized opal and nannofossil carbonate fluxes and [²³¹Pa/²³⁰Th]xs ratios from site MV1014-02-17JC in the Panama Basin. We find that, across the last deglaciation, phytoplankton community structure is driven by changing patterns of nutrient (nitrate, iron, and silica) availability which, in …

Iron Speciation In Pm2.5 From Urban, Agriculture, And Mixed Environments In Colorado, Usa, Joseph R. Salazar, David J. Pfotenhauer, Frank Leresche, Fernando L. Rosario-Ortiz, Michael P. Hannigan, Sirine C. Fakra, Brian Majestic

Chemistry and Biochemistry: Faculty Scholarship

Atmospheric iron solubility varies depending on whether the particles are collected in rural or urban areas, with urban areas showing increased iron solubility. In this study, we investigate if the iron species present in different environments affects its ultimate solubility. Field data are presented from the Platte River Air Pollution and Photochemistry Experiment (PRAPPE), aimed at understanding the interactions between organic carbon and trace elements in atmospheric particulate matter (PM). 24-hr PM2.5 samples were collected during the summer and winter (2016–2017), at three different sites on the Eastern Colorado plains: an urban, agricultural, and a mixed site. Downtown Denver had …

Molecular Fossils From Phytoplankton Reveal Secular Pco2 Trend Over The Phanerozoic, Caitlyn R. Witkowski, Johan W. H. Weijers, Brian S. Blais, Stefan Schouten, Jaap S. Sinninghe Damsté

Science and Technology Department Faculty Journal Articles

Past changes in the atmospheric concentration of carbon dioxide (PCO2) have had a major impact on earth system dynamics; yet, reconstructing secular trends of past PCO2 remains a prevalent challenge in paleoclimate studies. The current long-term PCO2reconstructions rely largely on the compilation of many different proxies, often with discrepancies among proxies, particularly for periods older than 100 million years (Ma). Here, we reconstructed Phanerozoic PCO2 from a single proxy: the stable carbon isotopic fractionation associated with photosynthesis (Ɛp) that increases as PCO2 increases. This concept has been widely applied to alkenones, but here, we …

Perspectives On Chemical Oceanography In The 21st Century: Participants Of The Come Aboard Meeting Examine Aspects Of The Field In The Context Of 40 Years Of Disco, Andrea J. Fassbender, Hilary I. Palevsky, Todd R. Martz, Anitra E. Ingalls, Martha Gledhill, Sarah E. Fawcett, Jay A. Brandes, Lihini I. Aluwihare, The Participants Of Come Aboard, Disco Xxv

OES Faculty Publications

The questions that chemical oceanographers prioritize over the coming decades, and the methods we use to address these questions, will define our field's contribution to 21st century science. In recognition of this, the U.S. National Science Foundation and National Oceanic and Atmospheric Administration galvanized a community effort (the Chemical Oceanography MEeting: A BOttom-up Approach to Research Directions, or COME ABOARD) to synthesize bottom-up perspectives on selected areas of research in Chemical Oceanography. Representing only a small subset of the community, COME ABOARD participants did not attempt to identify targeted research directions for the field. Instead, we focused on how best …

Phytoplankton Plastid Proteomics: Cracking Open Diatoms To Understand Plastid Biochemistry Under Iron Limitation, Skyler J. Nunn, Phoebe Dreux Chappell, Kristofer Gomes, Anasthasia Bonderenko, Bethany D. Jenkins, Brook L. Nunn

OES Faculty Publications

Diatoms, such as Thalassiosira pseudonana, are important oceanic primary producers, as they sequester carbon dioxide (CO₂) out of the atmosphere, die, and precipitate to the ocean floor. In many areas of the world’s oceans, phytoplankton, such as diatoms, are limited in growth by the availability of iron (Fe). Fe is an essential nutrient for phytoplankton, as it is central in the electron transport chain component of photosynthesis. Through this study, we examined if Fe-limitation makes a significant difference in the proteins expressed within the chloroplast, the power source for diatoms. Here, we utilized a new plastid isolation technique specific …

Measurement Of Antioxidant Activity Toward Superoxide In Natural Waters, D. Whitney King, Emma Berger, Zachary Helm, Eleanor Irish, Kenneth Mopper

Chemistry & Biochemistry Faculty Publications

Antioxidants are a class of molecules that provide a protective function against reactive oxygen species (ROS) in biological systems by out competing physiologically important molecules for ROS oxidation. In natural waters, the reactivity of antioxidants gives an estimate of oxidative stress, and may determine the reactivity and distribution of reactive oxidants. We present an analytical method to measure antioxidant activity in natural waters through the competition between ascorbic acid, an antioxidant, and MCLA, a chemiluminescent probe for superoxide. A numerical kinetic model of the analytical method has been developed to optimize analytical performance. Measurements of antioxidant concentrations in pure and …

The Role Of Blowing Snow In The Activation Of Bromine Over First-Year Antarctic Sea Ice, R. M. Lieb-Lappen, R. W. Obbard

Dartmouth Scholarship

It is well known that during polar springtime halide sea salt ions, in particular Br^-, are photochemically activated into reactive halogen species (e.g., Br and BrO), where they break down tropospheric ozone. This research investigated the role of blowing snow in transporting salts from the sea ice/snow surface into reactive bromine species in the air. At two different locations over first-year ice in the Ross Sea, Antarctica, collection baskets captured blowing snow at different heights. In addition, sea ice cores and surface snow samples were collected throughout the month-long campaign. Over this time, sea ice and surface snow …

Technical Note: Swift - A Fast Semi-Empirical Model For Polar Stratospheric Ozone Loss, M. Rex, S. Kremser, P. Huck, G. Bodeker, I. Wohltmann, M. L. Santee, P. F. Bernath

Chemistry & Biochemistry Faculty Publications

An extremely fast model to estimate the degree of stratospheric ozone depletion during polar winters is described. It is based on a set of coupled differential equations that simulate the seasonal evolution of vortex-averaged hydrogen chloride (HCl), nitric acid (HNO3), chlorine nitrate (ClONO₂), active forms of chlorine (ClO_x = Cl+ClO+2ClOOCl) and ozone (O₃) on isentropic levels within the polar vortices. Terms in these equations account for the chemical and physical processes driving the time rate of change of these species. Eight empirical fit coefficients associated with these terms are derived by iteratively fitting the equations …

Middle Atmospheric Changes Caused By The January And March 2012 Solar Proton Events, C. H. Jackman, C. E. Randall, V. L. Harvey, S. Wang, E. L. Fleming, M. López-Puertas, B. Funke, P. F. Bernath

Chemistry & Biochemistry Faculty Publications

The recent 23-30 January and 7-11 March 2012 solar proton event (SPE) periods were substantial and caused significant impacts on the middle atmosphere. These were the two largest SPE periods of solar cycle 24 so far. The highly energetic solar protons produced considerable ionization of the neutral atmosphere as well as HOx (H, OH, HO2) and NOx (N, NO, NO2). We compute a NOx production of 1.9 and 2.1 Gigamoles due to these SPE periods in January and March 2012, respectively, which places these SPE periods among the 12 largest in the past 50 yr. Aura Microwave Limb Sounder (MLS) …

Kinetic Fractionation Of Gases By Deep Air Convection In Polar Firn, K. Kawamura, J. P. Severinghaus, M. R. Albert, Z. R. Courville

Dartmouth Scholarship

A previously unrecognized type of gas fractiona- tion occurs in firn air columns subjected to intense convec- tion. It is a form of kinetic fractionation that depends on the fact that different gases have different molecular diffusivi- ties. Convective mixing continually disturbs diffusive equi- librium, and gases diffuse back toward diffusive equilibrium under the influence of gravity and thermal gradients. In near- surface firn where convection and diffusion compete as gas transport mechanisms, slow-diffusing gases such as krypton (Kr) and xenon (Xe) are more heavily impacted by convec- tion than fast diffusing gases such as nitrogen (N2) and ar- gon …

Process-Evaluation Of Tropospheric Humidity Simulated By General Circulation Models Using Water Vapor Isotopologues: 1. Comparison Between Models And Observations, Camille Risi, David Noone, John Worden, Christian Frankenberg, Gabriele Stiller, Michael Kiefer, Bernd Funke, Kaley Walker, Peter Bernath, Matthias Schneider, Debra Wunch, Vanessa Sherlock, Nicholas Deutscher, David Griffith, Paul O. Wennberg, Kimberly Strong, Dan Smale, Emmanuel Mahieu, Sabine Barthlott, Frank Hase, Omaira García, Justus Notholt, Thorsten Warneke, Geoffrey Toon, David Sayres, Sandrine Bony, Jeonghoon Lee, Derek Brown, Ryu Uemura, Christophe Sturm

Chemistry & Biochemistry Faculty Publications

The goal of this study is to determine how H₂O and HDO measurements in water vapor can be used to detect and diagnose biases in the representation of processes controlling tropospheric humidity in atmospheric general circulation models (GCMs). We analyze a large number of isotopic data sets (four satellite, sixteen ground-based remote-sensing, five surface in situ and three aircraft data sets) that are sensitive to different altitudes throughout the free troposphere. Despite significant differences between data sets, we identify some observed HDO/H₂O characteristics that are robust across data sets and that can be used to evaluate …

Chemistry–Climate Model Simulations Of Twenty-First Century Stratospheric Climate And Circulation Changes, Neal Butchart, I. Cionni, V. Eyring, T. G. Shepherd, D. W. Waugh, H. Akiyoshi, J. Austin, C. Brühl, M. P. Chipperfield, Eugene C. Cordero, M. Dameris, R. Deckert, S. Dhomse, S. M. Frith, R. R. Garcia, A. Gettelman, M. A. Giorgetta, D. E. Kinnison, F. Li, E. Mancini, S. Pawson, G. Pitari, D. A. Plummer, E. Rozanov, F. Sassi, J. F. Scinocca, K. Shibata, B. Steil, W. Tian

Faculty Publications, Meteorology and Climate Science

The response of stratospheric climate and circulation to increasing amounts of greenhouse gases (GHGs) and ozone recovery in the twenty-first century is analyzed in simulations of 11 chemistry–climate models using near-identical forcings and experimental setup. In addition to an overall global cooling of the stratosphere in the simulations (0.59 ± 0.07 K decade⁻¹ at 10 hPa), ozone recovery causes a warming of the Southern Hemisphere polar lower stratosphere in summer with enhanced cooling above. The rate of warming correlates with the rate of ozone recovery projected by the models and, on average, changes from 0.8 to 0.48 K decade …

Abnormal Vapor Densities, Minnie Elizabeth Rice

Student and Lippitt Prize Essays

This essay questions Italian chemist Avogadro’s hypothesis about vapor densities, ultimately coming to the conclusion that Avogadro’s law is open to objection.