Contaminants in Chesapeake Bay: The Regional Perspective

Industrial and municipal point sources of contaminants are scattered along the shores of Chesapeake Bay and its tributaries, but reach especially high density at Norfolk, Va., and Baltimore, Md. Sedimentation and various chemical processes in many cases conspire to restrict the water-borne transport of contaminant away from point source . Kepone, residual chlorine, volatile halogenated hydrocarbons, and anthropogenic trace metals are well-studied example of point-source contaminants. For the most part, their concentration in water and sediment drop to nearly immeasurable values within a distance of a few kilometers, or sometimes a few tens of kilometers, from their source . On the other hand, certain contaminants have now been shown to be truly regionally dispersed. Included are polychlorinated biphenyls, phthalate esters, anthropogenic trace metal (Cu, Zn, Pb), polycyclic aromatic hydrocarbons, herbicides and weapon derived radionuclides. Most of these enter the Bay in significant amount from the atmosphere. Thus their dispersion throughout the Bay is not dependent on aquatic tranport processes. Although it is tempting to link the existence of this regional contamination with well publicized regional biological problem , no link has yet been proven.https://scholarworks.wm.edu/vimsbooks/1058/thumbnail.jp

Toward an understanding of disequilibrium dihedral angles in mafic rocks

[1] The median dihedral angle at clinopyroxene-plagioclase-plagioclase junctions in mafic rocks, Θcpp, is generally lower than equilibrium (109° ± 2°). Observation of a wide range of mafic bodies demonstrates that previous work on systematic variations of Θcpp is incorrect in several important respects. First, the spatial distribution of plagioclase compositional zoning demonstrates that the final geometry of three-grain junctions, and hence Θcpp, is formed during solidification (the igneous process): sub-solidus textural modification in most dolerites and gabbros, previously thought to be the dominant control on Θcpp, is insignificant. Θcpp is governed by mass transport constraints, the inhibiting effects of small pore size on crystallization, and variation in relative growth rates of pyroxene and plagioclase. During rapid cooling, pyroxene preferentially fills wider pores while the narrower pores remain melt-filled, resulting in an initial value of Θcpp of 78°, rather than 60° which would be expected if all melt-filled pores were filled with pyroxene. Lower cooling rates create a higher initial Θcpp due to changes in relative growth rates of the two minerals at the nascent three-grain junction. Low Θcpp (associated with cuspate clinopyroxene grains at triple junctions) can also be diagnostic of infiltration of previously melt-free rocks by late-stage evolved liquids (the metasomatic process). Modification of Θcpp by sub-solidus textural equilibration (the metamorphic process) is only important for fine-grained mafic rocks such as chilled margins and intraplutonic chill zones. In coarse-grained gabbros from shallow crustal intrusions the metamorphic process occurs only in the centers of oikocrysts, associated with rounding of chadacrysts

A report on the concentration, distribution and impact of certain trace metals from sewage treatment plants on the Chesapeake Bay

Population densities are ever increasing on the shores of the Chesapeake Bay and hence the flow of goods and services is being shifted to supply these people. This self perpetuating system demanismore and more of the surrounding envirorunent f or recreation, work and waste disposal. This is the case f or the Chesapeake and its sub- estuaries. According to Brush (1974), of the total fresh water input into the Chesapeake Bay, between 1 and 2 percent is treated sewage. Toxic components on these waters may be of paramount importance in the Bay ecosystem and ma;y have disastrous effects on the biota. It is essential then that the magnitude of the exist ing problem be determined and understood, and results and recommendations be made available to decision makers so that in the future we can control the inputs, properly select sewage outfall locations and preserve the Chesapeake Bey for future generations . This document is a first attempt at this

A model for uranium, rhenium, and molybdenum diagenesis in marine sediments based on results from coastal locations

Author Posting. © The Author(s), 2009. This is the author's version of the work. It is posted here by permission of Elsevier B.V. for personal use, not for redistribution. The definitive version was published in Geochimica et Cosmochimica Acta 73 (2009): 2938-2960, doi:10.1016/j.gca.2009.02.029.The purpose of this research is to characterize the mobilization and immobilization processes that control the authigenic accumulation of uranium (U), rhenium (Re) and molybdenum (Mo) in marine sediments. We analyzed these redox– sensitive metals (RSM) in benthic chamber, pore water and solid phase samples at a site in Buzzards Bay, Massachusetts, U.S.A., which has high bottom water oxygen concentrations (230–300 mol/L) and high organic matter oxidation rates (390 mol C/cm2/y). The oxygen penetration depth varies from 2–9 mm below the sediment–water interface, but pore water sulfide is below detection (< 2M). The RSM pore water profiles are modeled with a steady–state diagenetic model that includes irrigation, which extends 10–20 cm below the sediment–water interface. To present a consistent description of trace metal diagenesis in marine sediments, RSM results from sediments in Buzzards Bay are compared with previous research from sulfidic sediments (Morford et al., GCA 71). Release of RSM to pore waters during the remineralization of solid phases occurs near the sediment–water interface at depths above the zone of authigenic RSM formation. This release occurs consistently for Mo at both sites, but only in the winter for Re in Buzzards Bay and intermittently for U. At the Buzzards Bay site, Re removal to the solid phase extends to the bottom of the profile, while the zone of removal is restricted to ~2–9 cm for U and Mo. Authigenic Re formation is independent of the anoxic remineralization rate, which is consistent with an abiotic removal mechanism. The rate of authigenic U formation and its modeled removal rate constant increase with increasing anoxic remineralization rates, and is consistent with U reduction being microbially mediated. Authigenic Mo formation is related to the formation of sulfidic microenvironments. The depth and extent of Mo removal from pore water is closely associated with the balance between iron and sulfate reduction and the consumption of pore water sulfide via iron sulfide formation. Pore water RSM reach constant asymptotic concentrations in sulfidic sediments, but only pore water Re is constant at depth in Buzzards Bay. The increases in pore water U at the Buzzards Bay site are consistent with addition via irrigation and subsequent upward diffusion to the removal zone. Deep pore water Mo concentrations exceed its bottom water concentration due to irrigation–induced oxidation and remobilization from the solid phase. In sulfidic sediments, there is no evidence for higher pore water U or Mo concentrations at depth due to the absence of irrigation and/or the presence of more stable authigenic RSM phases. There are good correlations between benthic fluxes and authigenic accumulation rates for U and Mo in sulfidic sediments. However, results from Buzzards Bay suggest irrigation ultimately results in the partial loss of U and Mo from the solid phase, with accumulation rates that are 20–30% of the modeled flux. Irrigation can augment (Re, possibly U) or compromise (U, Mo) authigenic accumulation in sediments, and is important when determining burial rates in continental margin sediments.The authors also acknowledge financial support from the National Science Foundation (JLM, WRM: OCE–0220892), Research Corporation (JLM, CMC), Franklin & Marshall College, and the Hackman Summer Research Program at F&M

Calculation of the visible-UV absorption spectra of hydrogen sulfide, bisulfide, polysulfides, and As and Sb sulfides, in aqueous solution

Recently we showed that visible-UV spectra in aqueous solution can be accurately calculated for arsenic (III) bisulfides, such as As(SH)(3), As(SH)(2)S(- )and their oligomers. The calculated lowest energy transitions for these species were diagnostic of their protonation and oligomerization state. We here extend these studies to As and Sb oxidation state III and v sulfides and to polysulfides S(n)(2-), n = 2–6, the bisulfide anion, SH(-), hydrogen sulfide, H(2)S and the sulfanes, S(n)H(2), n = 2–5. Many of these calculations are more difficult than those performed for the As(iii) bisulfides, since the As and Sb(v) species are more acidic and therefore exist as highly charged anions in neutral and basic solutions. In general, small and/or highly charged anions are more difficult to describe computationally than larger, monovalent anions or neutral molecules. We have used both Hartree-Fock based (CI Singles and Time-Dependent HF) and density functional based (TD B3LYP) techniques for the calculations of absorption energy and intensity and have used both explicit water molecules and a polarizable continuum to describe the effects of hydration. We correctly reproduce the general trends observed experimentally, with absorption energies increasing from polysulfides to As, Sb sulfides to SH(- )to H(2)S. As and Sb(v) species, both monomers and dimers, also absorb at characteristically higher energies than do the analogous As and Sb(III)species. There is also a small reduction in absorption energy from monomeric to dimeric species, for both As and Sb III and v. The polysufides, on the other hand, show no simple systematic changes in UV spectra with chain length, n, or with protonation state. Our results indicate that for the As and Sb sulfides, the oxidation state, degree of protonation and degree of oligomerization can all be determined from the visible-UV absorption spectrum. We have also calculated the aqueous phase energetics for the reaction of S(8 )with SH(- )to produce the polysulfides, S(n)H(-), n = 2–6. Our results are in excellent agreement with available experimental data, and support the existence of a S(6 )species

A Raman spectroscopic study of arsenite and thioarsenite species in aqueous solution at 25°C

The Raman spectra of thioarsenite and arsenite species in aqueous solution were obtained at room temperature. Solutions at constant ΣAs + ΣS of 0.1 and 0.5 mol kg(-1 )were prepared with various ΣS/ΣAs ratios (0.1–9.0) and pH values (~7–13.2). Our data suggest that the speciation of As under the conditions investigated is more complicated than previously thought. The Raman measurements offer evidence for at least six separate S-bearing As species whose principal bands are centered near 365, 385, 390, 400, 415 and 420 cm(-1). The data suggest that at least two different species may give rise to bands at 385 cm(-1), bringing the probable minimum number of species to seven. Several additional species are possible but could not be resolved definitively. In general, the relative proportions of these species are dependent on total As concentration, ΣS/ΣAs ratio and pH. At very low ΣS/ΣAs ratios we also observe Raman bands attributable to the dissociation products of H(3)AsO(3)(aq). Although we were unable to assign precise stoichiometries for the various thioarsenite species, we were able to map out general pH and ΣS/ΣAs conditions under which the various thioarsenite and arsenite species are predominant. This study provides a basis for more detailed Raman spectroscopic and other types of investigations of the nature of thioarsenite species

Insights on geochemical cycling of U, Re and Mo from seasonal sampling in Boston Harbor, Massachusetts, USA

Author Posting. © The Author(s), 2006. This is the author's version of the work. It is posted here by permission of Elsevier B.V. for personal use, not for redistribution. The definitive version was published in Geochimica et Cosmochimica Acta 71 (2007): 895-917, doi:10.1016/j.gca.2006.10.016.This study examined the removal of U, Mo, and Re from seawater by sedimentary processes at a shallow-water site with near-saturation bottom water O2 levels (240-380 μmol O2/L), very high organic matter oxidation rates (annually averaged rate is 870 μmol C/cm2/y), and shallow oxygen penetration depths (4 mm or less throughout the year). Under these conditions, U, Mo, and Re were removed rapidly to asymptotic pore water concentrations of 2.2–3.3 nmol/kg (U), 7–13 nmol/kg (Mo), and 11–14 pmol/kg (Re). The order in which the three metals were removed, determined by fitting a diffusion-reaction model to measured profiles, was Re < U < Mo. Model fits also suggest that the Mo profiles clearly showed the presence of a near-interface layer in which Mo was added to pore waters by remineralization of a solid phase. The importance of this solid phase source of pore water Mo increased from January to October as the organic matter oxidation rate increased, bottom water O2 decreased, and the O2 penetration depth decreased. Experiments with in situ benthic flux chambers generally showed fluxes of U and Mo into the sediments. However, when the overlying water O2 concentration in the chambers was allowed to drop to very low levels, Mn and Fe were released to the overlying water along with the simultaneous release of Mo and U. These experiments suggest that remineralization of Mn and/or Fe oxides may be a source of Mo and perhaps U to pore waters, and may complicate the accumulation of U and Mo in bioturbated sediments with high organic matter oxidation rates and shallow O2 penetration depths. Benthic chamber experiments including the nonreactive solute tracer, Br-, indicated that sediment irrigation was very important to solute exchange at the study site. The enhancement of sediment-seawater exchange due to irrigation was determined for the nonreactive tracer (Br-), TCO2, NH4 +, U and Mo. The comparisons between these solutes showed that reactions within and around the burrows were very important for modulating the Mo flux, but less important for U. The effect of these reactions on Mo exchange was highly variable, enhancing Mo (and, to a lesser extent, U) uptake at times of relatively modest irrigation, but inhibiting exchange when irrigation rates were faster. These results reinforce the observation that Mo can be released to and removed from pore waters via sedimentary reactions. The removal rate of U and Mo from seawater by sedimentary reactions was found to agree with the rate of accumulation of authigenic U and Mo in the solid phase. The fluxes of U and Mo determined by in situ benthic flux chamber measurements were the largest that have been measured to date. These results confirm that removal of redoxsensitive metals from continental margin sediments underlying oxic bottom water is important, and suggest that continental margin sediments play a key role in the marine budgets of these metals.We appreciate the financial support from the National Science Foundation (OCE-0220892). Funding for this work was also provided to JLM by the Postdoctoral Scholar Program at WHOI courtesy of the Cabot Marine Environmental Science Fund and the J. Seward Johnson Fund. Financial support to IMK was given by The Swedish Foundation for International Cooperation in Research and Higher Education

Marine oxygen production and open water supported an active nitrogen cycle during the Marinoan Snowball Earth

The Neoproterozoic Earth was punctuated by two low-latitude Snowball Earth glaciations. Models permit oceans with either total ice cover or substantial areas of open water. Total ice cover would make an anoxic ocean likely, and would be a formidable barrier to biologic survival. However, there are no direct data constraining either the redox state of the ocean or marine biological productivity during the glacials. Here we present iron-speciation, redox-sensitive trace element, and nitrogen isotope data from a Neoproterozoic (Marinoan) glacial episode. Iron-speciation indicates deeper waters were anoxic and Fe-rich, while trace element concentrations indicate surface waters were in contact with an oxygenated atmosphere. Furthermore, synglacial sedimentary nitrogen is isotopically heavier than the modern atmosphere, requiring a biologic cycle with nitrogen fixation, nitrification and denitrification. Our results indicate significant regions of open marine water and active biologic productivity throughout one of the harshest glaciations in Earth history

Speciation of arsenic in sulfidic waters

Formation constants for thioarsenite species have been determined in dilute solutions at 25°C, ΣH(2)S from 10(-7.5 )to 10(-3.0 )M, ΣAs from 10(-5.6 )to 10(-4.8 )M, and pH 7 and 10. The principal inorganic arsenic species in anoxic aquatic systems are arsenite, As(OH)(3)(0), and a mononuclear thioarsenite with an S/As ratio of 3:1. Thioarsenic species with S/As ratios of 1 : 1,2 : 1, and 4 : 1 are lesser components in sulfidic solutions that might be encountered in natural aquatic environments. Thioarsenites dominate arsenic speciation at sulfide concentrations > 10(-4.3 )M at neutral pH. Conversion from neutral As(OH)(3)(0 )to anionic thioarsenite species may regulate the transport and fate of arsenic in sulfate-reducing environments by governing sorption and mineral precipitation reactions