Environmental Chemistry Commons^™

Fossil And Contemporary Aerosol Particulate Organic Carbon In The Eastern United States: Implications For Deposition And Inputs To Watersheds, Andrew S. Wozniak, James E. Bauer, Rebecca M. Dickhut

Chemistry & Biochemistry Faculty Publications

Atmospheric particulate matter samples were collected from mid-Atlantic and northeastern U. S. (Virginia and New York, respectively) sites to assess the fossil versus contemporary sources contributing to aerosol organic carbon (OC) and the implications for its deposition to watersheds. Mean particulate matter total OC (TOC) deposition rates (wet + dry deposition) were calculated to be 1.6 and 2.4 mg C m^-2 d^-1 for the Virginia and New York sites, respectively. Wet deposition of particulate TOC was determined to be the dominant depositional mode, accounting for >65% (Virginia) and >80% (New York) of total aerosol TOC deposition. Isotopic mass …

Post-Coring Entrapment Of Modern Air In Some Shallow Ice Cores Collected Near The Firn-Ice Transition: Evidence From Cfc-12 Measurements In Antarctic Firn Air And Ice Cores, Murat Aydin, S. A. Montzka, M. O. Battle, M. B. Williams, Warren J. De Bruyn, J. H. Butler, K. R. Verhulst, C. Tatum, B. K. Gun, D. A. Plotkin, B. D. Hall, Eric S. Saltzman

Biology, Chemistry, and Environmental Sciences Faculty Articles and Research

In this study, we report measurements of CFC-12 (CCl2F2) in firn air and in air extracted from shallow ice cores from three Antarctic sites. The firn air data are consistent with the known atmospheric history of CFC-12. In contrast, some of the ice core samples collected near the firn-ice transition exhibit anomalously high CFC-12 levels. Together, the ice core and firn air data provide evidence for the presence of modern air entrapped in the shallow ice core samples that likely contained open pores at the time of collection. We propose that this is due to closure of the open pores …

A Chemical Ionization Mass Spectrometer For Continuous Underway Shipboard Analysis Of Dimethylsulfide In Near-Surface Seawater, Eric S. Saltzman, Warren J. De Bruyn, M. J. Lawler, Christa Marandino, C. A. Mccormick

Biology, Chemistry, and Environmental Sciences Faculty Articles and Research

A compact, low-cost atmospheric pressure, chemical ionization mass spectrometer ('mini-CIMS') has been developed for continuous underway shipboard measurements of dimethylsulfide (DMS) in seawater. The instrument was used to analyze DMS in air equilibrated with flowing seawater across a porous Teflon membrane equilibrator. The equilibrated gas stream was diluted with air containing an isotopically-labeled internal standard. DMS is ionized at atmospheric pressure via proton transfer from water vapor, then declustered, mass filtered via quadrupole mass spectrometry, and detected with an electron multiplier. The instrument described here is based on a low-cost residual gas analyzer (Stanford Research Systems), which has been modified …

Air-Sea Gas Exchange Of Co2 And Dms In The North Atlantic By Eddy Covariance, Scott Miller, Christa Marandino, Warren J. De Bruyn, Eric S. Saltzman

Biology, Chemistry, and Environmental Sciences Faculty Articles and Research

We report the first simultaneous eddy covariance flux measurements of CO2 and dimethylsulfide (DMS) over the open ocean for two North Atlantic cruises. After normalization for Schmidt number, the two gases give essentially identical gas transfer coefficients and wind speed dependences for the wind speed range 2-10 ms(-1). The data indicate a linear relationship between the gas transfer coefficient and mean wind speed, with measured gas transfer coefficients slightly above the Wanninkhof (1992) parameterization, particularly at low wind speeds. Citation: Miller, S., C. Marandino, W. de Bruyn, and E. S. Saltzman (2009), Air-sea gas exchange of CO2 and DMS in …

Open Ocean Dms Air/Sea Fluxes Over The Eastern South Pacific Ocean, C. A. Marandino, Warren J. De Bruyn, S. D. Miller, E. S. Saltzman

Biology, Chemistry, and Environmental Sciences Faculty Articles and Research

Air/sea fluxes of dimethylsulfide (DMS) were measured by eddy correlation over the Eastern South Pacific Ocean during January 2006. The cruise track extended from Manzanillo, Mexico, along 110 degrees W, to Punta Arenas, Chile. Bulk air and surface ocean DMS levels were also measured and gas transfer coefficients (k(DMS)) were computed. Air and seawater DMS measurements were made using chemical ionization mass spectrometry (API-CIMS) and a gas/liquid membrane equilibrator. Mean surface seawater DMS concentrations were 3.8 +/- 2.2 nM and atmospheric mixing ratios were 340 +/- 370 ppt. The air/sea flux of DMS was uniformly out of the ocean, with …

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

OES Faculty Publications

Osmium is one of the rarer elements in seawater, with typical concentration of ≈10 x 10^-15 g g^-1 ( 5.3 x 10^-14 mol kg^-1. The osmium isotope composition (¹⁸⁷Os/¹⁸⁸Os ratio) of deep oceans is 1.05, reflecting a balance between inputs from continental crust (≈ 1.3) and mantle/cosmic dust (≈ 0.13). Here, we show that the ¹⁸⁷Os/¹⁸⁸Os 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 (approximate to 0.2) …

Dms Air/Sea Flux And Gas Transfer Coefficients From The North Atlantic Summertime Coccolithophore Bloom, Christa Marandino, Warren J. De Bruyn, Scott Miller, Eric S. Saltzman

Biology, Chemistry, and Environmental Sciences Faculty Articles and Research

Dimethylsulfide (DMS) atmospheric and oceanic concentrations and eddy covariance air/sea fluxes were measured over the N. Atlantic Ocean during July 2007 from Iceland to Woods Hole, MA, USA. Seawater DMS levels north of 55 degrees N ranged from 3 to 17 nM, with variability related to the satellite-derived distributions of coccoliths and to a lesser extent, chlorophyll. For the most intense bloom region southwest of Iceland, DMS air/sea fluxes were as high as 300 mu mol m(-2) d(-1), larger than current model estimates. The observations imply that gas exchange coefficients in this region are significantly greater than those estimated using …

Origin And Paleoclimatic Significance Of Late Quaternary Loess In Nebraska: Evidence From Stratigraphy, Chronology, Sedimentology, And Geochemistry, Daniel R. Muhs, E. Arthur Bettis Iii, John N. Aleinikoff, John P. Mcgeehin, Jossh Beann, Gary Skipp, Brian D. Marshall, Helen M. Roberts, William C. Johnson, Rachel Benton

United States Geological Survey: Staff Publications

Loess is one of the most extensive surficial geologic deposits in mid-continental North America, particularly in the central Great Plains region of Nebraska. Last-glacial-age loess (Peoria Loess) reaches its greatest known thickness in the world in this area. New stratigraphic, geochronologic, mineralogic, and geochemical data yield information about the age and provenance of Peoria Loess, as well as evaluation of recent climate models.

Salt Marshes As A Source Of Chromophoric Dissolved Organic Matter (Cdom) To Southern California Coastal Waters, Catherine D. Clark, Liannea P. Litz, Stanley B. Grant

Biology, Chemistry, and Environmental Sciences Faculty Articles and Research

To determine chromophoric dissolved organic matter (CDOM) sources in Southern California coastal waters, optical properties of a river outlet and adjacent tidally flushed salt marshes were monitored (dry season; June July 2001). Average absorption coefficients doubled at ebb vs. flood tides (4.8 +/- 1.5 vs. 2.1 +/- 0.9 m(-1); 300 nm), suggesting significant salt marsh CDOM inputs into coastal waters. Average spectral slopes were not statistically different for any sites or tides (0.010 +/- 0.002 nm(-1)), consistent with salt marsh CDOM dominating coastal waters. Three-dimensional fluorescence excitation-emission matrices (EEMs) at ebb tide showed contributions from terrestrial, protein, and marine humic-like …

Investigating The Spring Bloom In San Francisco Bay: Links Between Water Chemistry, Metal Cycling, Mercury Speciation, And Phytoplankton Community Composition, Allison C. Luengen

Environmental Science

Investigating the spring bloom in San Francisco Bay: Links between water chemistry, metal cycling, mercury speciation, and phytoplankton community composition This dissertation addresses the relationship between two problems facing estuaries nationwide: nutrient enrichment and metal contamination. The focus is on the southern reach of San Francisco Bay, where high nutrient concentrations can control the magnitude of the predictably occurring spring phytoplankton bloom. The bloom in this study, in spring 2003, was one of the largest blooms on record, exceeding 150 μg L ^-1 of chlorophyll α. As the bloom grew, diatoms (e.g. Thalassiosira punctigera ) depleted dissolved nutrients from the …

Eddy Correlation Measurements Of The Air/Sea Flux Of Dimethylsulfide Over The North Pacific Ocean, Christa A. Marandino, Warren J. De Bruyn, Scott D. Miller, Eric S. Saltzman

Biology, Chemistry, and Environmental Sciences Faculty Articles and Research

Shipboard measurements of air/sea fluxes and sea surface concentrations of dimethylsulfide (DMS) were made over the tropical and midlatitude North Pacific Ocean. Atmospheric pressure chemical ionization mass spectrometry was used to measure DMS levels in ambient air and in air equilibrated with surface seawater drawn from a depth of 5 m. Air/sea fluxes were obtained using eddy covariance. Corrections and uncertainties involved in the calculation of fluxes from shipboard data are discussed. The surface ocean DMS concentrations measured during this study ranged from 1 to 10 nM, and atmospheric mixing ratios ranged from 20 to 1000 ppt. Air/sea fluxes ranged …

Isotope Sourcing Of Prehistoric Willow And Tule Textiles Recovered From Western Great Basin Rock Shelters And Caves: Proof Of Concept, Larry V. Benson, E. M. Hattori, H. E. Taylor, S. R. Poulson, E. A. Jolie

United States Geological Survey: Staff Publications

Isotope and trace-metal analyses were used to determine the origin of plants used to manufacture prehistoric textiles (basketry and matting) from archaeological sites in the western Great Basin. Research focused on strontium (⁸⁷Sr/⁸⁶Sr) and oxygen (¹⁸O/¹⁶O) isotope ratios of willow (Salix sp.) and tule (Schoenoplectus sp.), the dominant raw materials in Great Basin textiles. The oxygen-isotope data indicated that the willow and tule used to produce the textiles were harvested from the banks of rivers or in marshes characterized by flowing water and not from lakes or sinks. The strontium-isotope …

Open-Ocean Carbon Monoxide Photoproduction, Aron Stubbins, Günther Uher, Cliff S. Law, Kenneth Mopper, Carol Robinson, Robert C. Upstill-Goddard

Chemistry & Biochemistry Faculty Publications

Sunlight-initiated photolysis of chromophoric dissolved organic matter (CDOM) is the dominant source of carbon monoxide (CO) in the open-ocean. A modelling study was conducted to constrain this source. Spectral solar irradiance was obtained from two models (GCSOLAR and SMARTS2). Water-column CDOM and total light absorption were modelled using spectra collected along a Meridional transect of the Atlantic ocean using a 200-cm pathlength liquid waveguide UV-visible spectrophotometer. Apparent quantum yields for the production of CO (AQY_CO) from CDOM were obtained from a parameterisation describing the relationship between CDOM light absorption coefficient and AQY_CO and the CDOM spectra collected. …

The Composition Of Coexisting Jarosite-Group Minerals And Water From The Richmond Mine, Iron Mountain, California, Heather E. Jamieson, Clare Robinson, Charles N. Alpers, D. Kirk Nordstrom, Alexei Poustovetov, Heather A. Lowers

United States Geological Survey: Staff Publications

Jarosite-group minerals accumulate in the form of stalactites and fine-grained mud on massive pyrite in the D drift of the Richmond mine, Iron Mountain, California. Water samples were collected by placing beakers under the dripping stalactites and by extracting pore water from the mud using a centrifuge. The water is rich in Fe³⁺ and SO₄^2–, with a pH of approximately 2.1, which is significantly higher than the extremely acidic waters found elsewhere in the mine. Electron-microprobe analysis and X-ray mapping indicate that the small crystals (<10 > μm in diameter) are compositionally zoned with respect to Na …

Oceanic Uptake And The Global Atmospheric Acetone Budget, Christa Marandino, Warren J. De Bruyn, Scott Miller, M. J. Prather, Eric S. Saltzman

Biology, Chemistry, and Environmental Sciences Faculty Articles and Research

In this study, direct measurements of the air/ sea flux of acetone were made over the North Pacific Ocean. The results demonstrate that the net flux of acetone is into, rather than out of the oceans. The extrapolated global ocean uptake of 48 Tg yr(-1) requires a major revision of the atmospheric acetone budget. This result is consistent with a recent reevaluation of acetone photodissociation quantum yields.

Atmospheric Variability Of Methyl Chloride During The Last 300 Years From An Antarctic Ice Core And Firn Air, M. Aydin, Eric S. Saltzman, Warren J. De Bruyn, S. A. Montzka, J. H. Butler, M. Battle

Biology, Chemistry, and Environmental Sciences Faculty Articles and Research

Measurements of methyl chloride (CH3Cl) in Antarctic polar ice and firn air are used to describe the variability of atmospheric CH3Cl during the past 300 years. Firn air results from South Pole and Siple Dome suggest that the atmospheric abundance of CH3Cl increased by about 10% in the 50 years prior to 1990. Ice core measurements from Siple Dome provide evidence for a cyclic natural variability on the order of 10%, with a period of about 110 years in phase with the 20th century rise inferred from firn air. Thus, the CH3Cl increase measured in firn air may largely be …

The Aqueous Phase Yield Of Alkyl Nitrates From Roo+No: Implications For Photochemical Production In Seawater, Elizabeth E. Dahl, Eric S. Saltzman, Warren J. De Bruyn

Biology, Chemistry, and Environmental Sciences Faculty Articles and Research

Alkyl nitrates have been observed in remote oceanic regions of the troposphere and in the surface ocean. The mechanism for their production in the oceans is not known. A likely source is the reaction of ROO + NO (where R is an alkyl group). Steady-state laboratory experiments show that alkyl nitrates are produced in the aqueous phase via this reaction, with branching ratios of 0.23 +/- 0.04, 0.67 +/- 0.03, and 0.71 +/- 0.04 for methyl, ethyl, and propyl nitrate respectively. The branching ratios in aqueous solution are significantly higher than in the gas phase. Irradiation of surface seawaters yield …

Organic Geochemical Analysis Of Late-Glacial And Early-Holocene Ecosystem Changes: A Case Study From Northern New England Lakes, Michael A. Kruge, Andrea Lini

Department of Earth and Environmental Studies Faculty Scholarship and Creative Works

The lacustrine sedimentary archive of organic remains provides important evidence for the reconstruction of the environmental histories of lakes and their watersheds, recording the response of the Earth's biota to changes on scales varying from the local to the global. The last Glacial-Interglacial transition presents an opportunity to investigate how, and at what rates, watershed and lake ecosystems were established on once glaciated, carbon and nutrient-poor landscapes. The small lakes of northern Vermont (USA) provide an appropriate setting in which to investigate such changes.

As part of a multidisciplinary study of three Vermont lake sediment cores, samples ranging in age …

Strontium Isotopic Signatures Of The Streams And Lakes Of Taylor Valley, Southern Victoria Land, Antarctica: Chemical Weathering In A Polar Climate, W. B. Lyons, Carmen A. Nezat, Larry V. Benson, Thomas D. Bullen, Elizabeth Y. Graham, Jesicca Kidd, Kathleen A. Welch, James M. Thomas

United States Geological Survey: Staff Publications

We have collected and analyzed a series of water samples from three closed-basin lakes (Lakes Bonney, Fryxell, and Hoare) in Taylor Valley, Antarctica, and the streams that flow into them. In all three lakes, the hypolimnetic waters have different ⁸⁷Sr/⁸⁶Sr ratios than the surface waters, with the deep water of Lakes Fryxell and Hoare being less radiogenic than the surface waters. The opposite occurs in Lake Bonney. The Lake Fryxell isotopic ratios are lower than modern-day ocean water and most of the whole-rock ratios of the surrounding geologic materials. A conceivable source of Sr to the system …

Empirical Model For The Variarion In Concentration Of Metal Ions During A Precipitation Event, David M. Chittenden Ii, Julie D. Chittenden

Journal of the Arkansas Academy of Science

The concentration of a pollutant in an air mass and the concentration of that pollutant in a series of rain water samples from a single event within that air mass, fluctuate during the course of the event. This the result of scavenging, diffusion, and advection processes. A simple mathematical model, containing only a scavenging term has had limited success in describing changes of concentration in rain water. To date, no attempt has been made to include diffusion or advection terms in the model. In this study, a two factor model was developed after determining that (1) the exponential scavenging term …

Moisture Determination By Thermal Titrimetry Using The Enthalpy Of Reaction Of 2,2-Dimethoxypropane With Water, Edmond W. Wilson Jr., Reagan Baber

Journal of the Arkansas Academy of Science

Assays for water content can be readily and simply carried out using the technique of thermal titrations. The method is based on measuring the endothermic heat of reaction exhibited when 2,2-dimethoxypropane is brought into contact with water in the presence of an acid catalyst. The apparatus is simple, requiring a constant delivery rate buret, a recording thermistor thermometer, and a stirred, thermally insulated reaction container. The 2,2-dimethoxypropane reagent used for the water assays is environmentally friendly ("green"). It is stable, pleasant smelling and economical. Working curves in three solvents, acetonitrile, tetrahydrofuran and 1,4-dioxane, show excellent precision and linearity with increasing …

Interagency Lake Mead And Las Vegas Wash Monitoring Program: Standard Operating Procedures Manual, Bureau Of Reclamation, City Of Henderson Water Reclamation Facility, City Of Las Vegas Water Pollution Control Facility, Clark County Sanitation District, Nevada, Southern Nevada Water Authority

Publications (WR)

A number of agencies sample Lake Mead and the Las Vegas Wash on a routine basis at several locations. In order to share and properly interpret the data, the Bureau of Reclamation, Southern Nevada Water Authority and the three Wastewater Treatment Facilities (City of Las Vegas, Clark County Sanitation District and City of Henderson) formed a committee to examine sampling and analytical protocols and to share information with the goal of maximizing the data quality. The group first met in April 1997. It was agreed that an effort should be made to discuss and compare specific sampling and analytical techniques …

Estimation Of Groundwater Velocities From Yucca Flat To The Amargosa Desert Using Geochemistry And Environmental Isotopes, Ronald L. Hershey, Steve Y. Acheampong

Publications (WR)

Geochemical modeling techniques were applied to groundwater flowpaths from Yucca Flat on the Nevada Test Site (NTS) to the Amargosa Desert, south of the NTS to estimate groundwater flow velocities for independent comparison to velocities calculated by other methods. The groundwater flowpaths examined considered flow in the carbonate aquifer beneath Yucca and Frenchman flats mixing with flow from carbonate aquifers east and southeast of the NTS and discharging at wells south of the NTS border. The approach used the computer codes WATEQ4F and NETPATH to calculate chemical speciation, determine the saturation state of mineral phases, and simulate mixing and the …

Nutrient Limitation In A Southwestern Desert Reservoir: Eutrophication Of Las Vegas Bay, Lake Mead, Nevada, Davine M. Lieberman

Publications (WR)

Algal bioassay tests were conducted with Selenastrum capricornutum and natural algae on inner Las Vegas Bay, Lake Mead, Nevada, from December 1992 through September 1993, to identify any nutrient limitation in an area of the reservoir that has experienced problems associated with severe nutrient enrichment. Three areas were sampled based on a gradient of water quality conditions that existed in Las Vegas Bay (LVB). Disodium ethylenedinitrilotetraacetate (EDTA) significantly stimulated algal growth compared to non-EDTA treatment. Algal bioassays indicated that phosphorus (P) was the primary limiting nutrient at all stations for most of the test dates. Chl a response with EDTA …

Baseline Water Quality Data Inventory And Analysis: Lake Mead National Recreation Area, Volume Ii Of Ii, National Park Service

Publications (WR)

This document presents the results of surface-water-quality data retrievals for Lake Mead National Recreation Area (LAME) from five of the United States Environmental Protection Agency's (EPA) national databases: (1) Storage and Retrieval (STORET) database management system; (2) River Reach File (RF3); (3) Industrial Facilities Discharge (IFD); (4) Drinking Water Supplies (DRINKS); and (5) Flow Gages (GAGES). This document is one product resulting from a cooperative contractual endeavor between the National Park Service's Servicewide Inventory and Monitoring Program, the National Park Service's Water Resources Division (WRD), and Horizon Systems Corporation to retrieve, format, and analyze water quality data for all units …

Baseline Water Quality Data Inventory And Analysis: Lake Mead National Recreation Area, Volume I Of Ii, National Park Service

Publications (WR)

This document presents the results of surface-water-quality data retrievals for Lake Mead National Recreation Area (LAME) from five of the United States Environmental Protection Agency's (EPA) national databases: (1) Storage and Retrieval (STORET) database management system; (2) River Reach File (RF3); (3) Industrial Facilities Discharge (IFD); (4) Drinking Water Supplies (DRINKS); and (5) Flow Gages (GAGES). This document is one product resulting from a cooperative contractual endeavor between the National Park Service's Servicewide Inventory and Monitoring Program, the National Park Service's Water Resources Division (WRD), and Horizon Systems Corporation to retrieve, format, and analyze water quality data for all units …

Surface Flow Structure Of The Gulf Stream From Composite Imagery And Satellite-Tracked Drifters, C. P. Mullen, A. D. Kirwan Jr.

CCPO Publications

A unique set of coutemporaneous satellite-tracked drifters and five-day composite Advanced Very High Resolution Radionmeter (AVHRR) satellite imagery of the North Atlantic has been analyzed to examine the surface flow structure of the Gulf Stream. The study region was divided into two sections, greater than 37 degrees N and less than 37 degrees N, in order to answer the question of geographic variability. Fractal and spectral analyses methods were applied to the data. Fractal analysis of the Lagrangian trajectories showed a fractal dimension of 1.21 +/- 0.02 with a scaling range of 83 - 343 km. The fractal dimension of …

Analytical Modeling And Simulation For Investigation Of A Digital Gas Filter Correlation Radiometer, Catherine P. Mcgowan

Electrical & Computer Engineering Theses & Dissertations

This thesis investigates a digital gas filter correlation radiometer called the Tropospheric Radiometer for Atmospheric Chemistry and Environmental Research (TRACER), which will be used to remotely measure carbon monoxide at three levels in the troposphere. The nadir-viewing radiometer measures the differential absorption of radiation through the atmosphere at 4.67@m and 2.33pm wavelengths. This thesis develops an analytical model of the TRACER measurement process to evaluate the effect of varying certain system parameters on the measurement. The independent sampling criterion and the response of linear systems to random signals are explained. A parametric simulation model is also developed to evaluate the …

Total Maximum Daily Loads And Waste Load Allocations For Las Vegas Bay: Rationale And Calulations, State Of Nevada: Division Of Environmental Protection

Publications (WR)

In September 1987 the Nevada Division of Environmental Protection revised Water Quality Standards for Las Vegas Wash (LVW) and Lake Mead. Standards were set for chlorophyll-a and unionized ammonia in Las Vegas Bay (LVB) (NDEP 1987). The 1986 and 1987 LVB data showed non-achievement of both the chlorophyll-a and unionized ammonia standard which triggered an analysis of total phosphorus and total ammonia Total Maximum Daily Loads and Waste Load Allocations which are presented in this report. This report is separated into three sections: 1. 1987 Las Vegas Bay Water Quality Conditions and Seasonal Periodicity. 2. Concentration Estimates at Northshore Road …

Permanganate Colorimetric Rapid Method For Chemical Oxygen Demand In Seawater, Myung Zoon Czae, Taekee Hong, Myung Hoon Kim

Chemistry & Biochemistry Faculty Publications

No abstract provided.