Martin William R.
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PreprintA model for uranium, rhenium, and molybdenum diagenesis in marine sediments based on results from coastal locations( 2008-12-31) Morford, Jennifer L. ; Martin, William R. ; Francois, Roger ; Carney, Caitlin M.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.
PreprintThe radiocarbon age of organic carbon in marine surface sediments( 2010-08) Griffith, David R. ; Martin, William R. ; Eglinton, Timothy I.Long-term carbon cycling and climate change are strongly dependent on organic carbon (OC) burial in marine sediments. Radiocarbon (14C) has been widely used to constrain the sources, sinks, and processing of sedimentary OC. To elucidate the dominant controls on the radiocarbon content of total organic carbon (14CTOC) accumulating in surface sediments we construct a box model that predicts 14CTOC in the sediment mixed layer (measured as fraction modern, Fm). Our model defines three distinct OC pools (“degradable,” “semi-labile,” and “refractory”) and assumes that 14CTOC flux to sediments is exclusively derived from surface ocean primary productivity, and hence follows a “generic” surface ocean dissolved inorganic carbon (DIC) bomb curve. Model predictions are compared to a set of 75 surface sediment samples, which span a wide geographic range and reflect diverse water column and depositional conditions, and for which sedimentation rate and mixed layer depth are well characterized. Our model overestimates the Fm value for a majority (65%) of these sites, especially at shallow water depths and for sites characterized by depleted δ13CTOC values. The model is most sensitive to sedimentation rate and mixed-layer depth. Therefore, slight changes to these parameters can lead to a match between modeled and measured Fm values at many sites. Because of model sensitivity, slight changes in sedimentation rate and mixed layer depth can allow predictions to match measured Fm at many sites. Yet, in some cases, we find that measured Fm values cannot be simulated without large and unrealistic changes to sedimentation rate and mixed layer depth. These results point to sources of pre-aged OC to surface sediments and implicate soil-derived terrestrial OC, reworked marine OC, and/or anthropogenic carbon as important components of the organic matter present in surface sediments. This approach provides a valuable framework within which to explore controls on sedimentary organic matter composition and carbon burial over a range of spatial and temporal scales.
PreprintUranium diagenesis in sediments underlying bottom waters with high oxygen content( 2009-01-23) Morford, Jennifer L. ; Martin, William R. ; Carney, Caitlin M.We measured U in sediments (both pore waters and solid phase) from three locations on the middle Atlantic Bight (MAB) from the eastern margin of the United States: a northern location on the continental shelf off Massachusetts (OC426, 75 m water depth), and two southern locations off North Carolina (EN433-1, 647 m water depth and EN433-2, 2648 m water depth). These sediments underlie high oxygen bottom waters (250-270 μM), but become reducing below the sediment-water interface due to the relatively high organic carbon oxidation rates in sediments (EN433-1: 212 μmol C/cm2/y; OC426: 120±10 μmol C/cm2/y; EN433-2: 33 μmol C/cm2/y). Pore water oxygen goes to zero by 1.4-1.5 cm at EN433-1 and OC426 and slightly deeper oxygen penetration depths were measured at EN433-2 (~4 cm). All of the pore water profiles show removal of U from pore waters. Calculated pore water fluxes are greatest at EN433-1 (0.66±0.08 nmol/cm2/y) and less at EN433-2 and OC426 (0.24±0.05 and 0.13±0.05 nmol/cm2/y, respectively). Solid phase profiles show authigenic U enrichment in sediments from all three locations. The average authigenic U concentrations are greater at EN433-1 and OC426 (5.8±0.7 nmol/g and 5.4±0.2 nmol/g, respectively) relative to EN433-2 (4.1±0.8 nmol/g). This progression is consistent with their relative ordering of ‘reduction intensity’, with greatest reducing conditions in sediments from EN433-1, less at OC426 and least at EN433-2. The authigenic U accumulation rate is largest at EN433-1 (0.47±0.05 nmol/cm2/y), but the average among the three sites on the MAB is ~0.2 nmol/cm2/y. Pore water profiles suggest diffusive fluxes across the sediment-water interface that are 1.4-1.7 times greater than authigenic accumulation rates at EN433-1 and EN433-2. These differences are consistent with oxidation and loss of U from the solid phase via irrigation and/or bioturbation, which may compromise the sequestration of U in continental margin sediments that underlie bottom waters with high oxygen concentrations. Previous literature compilations that include data exclusively from locations where [O2]bw < 150 μM suggest compelling correlations between authigenic U accumulation and organic carbon flux to sediments or organic carbon burial rate. Sediments that underlie waters with high [O2]bw have lower authigenic U accumulation rates than would be predicted from relationships developed from results that include locations where [O2]bw < 150 μM.
PreprintInsights on geochemical cycling of U, Re and Mo from seasonal sampling in Boston Harbor, Massachusetts, USA( 2006-10-23) Morford, Jennifer L. ; Martin, William R. ; Kalnejais, Linda H. ; Francois, Roger ; Bothner, Michael H. ; Karle, Ida-MajaThis 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.
ThesisTransport of trace metals in nearshore sediments(Massachusetts Institute of Technology and Woods Hole Oceanographic Institution, 1985-04) Martin, William R.The focus of this thesis is on rates of transport of metals both across the sediment/water interface and within the sediment column of nearshore sediments. The early diagenesis of several first-row transition metals exhibiting a variety of behaviors in the ocean -- Mn, Fe, Co, Ni, and Cu -- has been studied intensively at a site in Buzzards Bay, Mass. By limiting the study to a single site, independent measurements over the seasonal cycle of the concentrations of the metals in pore water, of the pore water constituents important to metal cycling, and of particle and solute transport rates could be made at the same site. In addition, a direct, in situ study of the interaction of chemical and transport processes was undertaken using radiotracer techniques. Thus, the study emphasizes the mechanisms of metal cycling near the interface of nearshore sediments. Transport rates were estimated using excess 234Th distributions for particle transport, and pore water 222Rn deficit distributions for solute transport. Particle transport rates, modeled by analogy to Fickian diffusion, ranged from 7-80x10-8 cmz/sec, with excess 234Th reaching to 2-2.5 cm below the interface. There was a significant seasonal variation in rates, with a warm-season average of 40x10-8 cm2/sec and a cold-season average of 20x10-8 cm 2/sec. 234Th-derived mixing rates were applied to Mn distributions through a mass balance model of Mn cycling. It was found that a particulate flux due to bioturbation, from the net dissolved Mn removal layer to a net dissolved Mn production layer adjacent to the interface, was as large as 38% of net dissolved Mn production. Mixing of particulate Fe sulfides may have a similar importance for Fe cycling. Solute transport was estimated using measured 222Rn/ 226 Ra disequilibrium. The pore water 222Rn deficit could be explained using a model including vertical molecular diffusion and exchange with overlying seawater via exchange of pore water with bottom water in rapidly flushed burrows. Cores taken in all seasons could be split into three groups: (1) December through March: the 222Rn deficit was explained by vertical molecular diffusion alone; (2) early summer (June): irrigation affected the 222Rn profile to a depth of at least 20cm; (3) late summer/fall: irrigation was still important near the interface, affecting 222Rn profiles to depths of 10-12 cm. 222Rn deficits were adequately explained by an exchange parameter (a) which decreased exponentially with depth below the interface, but not by a constant-α model. Previous studies have explained irrigation using a constant exchange parameter throughout the irrigated layer. For comparative purposes, an α averaged over the upper 20 cm of the sediment column was calculated at the Buzzards Bay site: the range of depth-averaged α values found, 4-12x10-7 sec-1, is in agreement with values reported previously for a variety of nearshore sediments, using pore water Si02 as a tracer, of 1-20x10-7 sec-1. 222Rn-derived irrigation rates were applied to pore water Mn and Fe distributions. It was estimated that irrigation may contribute 20-40% of the dissolved Mn flux across the interface and about 20% of the dissolved Fe flux. Study of pore water metal chemistry at the Buzzards Bay site included measurements of pore water Mn and Fe during all seasons, and measurements of Co, Cu, and Ni in two cores: one under late winter conditions when the interface is most oxidizing; one when sulfate reduction was very important in the upper centimeter of the sediments. Fe regeneration sufficient to produce enrichments on water column particles was observed only during periods of summer and fall when the interface was reducing; otherwise, oxidation of Fe to insoluble Fe(III) limited Fe fluxes. Mn, Co, Cu, and Ni fluxes varied inversely to Fe fluxes; the primary control on fluxes of these elements was their limited solubility in reducing marine systems. The control was least important for Mn and Co; fluxes of Ni and Cu were significantly greater than zero only when sulfate reduction was unimportant in the upper centimeter of the sediment column. Fluxes of Mn were sufficient to affect the water column Mn distribution, with enrichments on water column particulates of up to 10,000 ppm inferred from calculated fluxes. Tentative estimates of the turnover time of dissolved Co, Cu, and Ni in the water column relative to the benthic flux indicated that the flux may be a significant contributor to the coastal Co cycle (turnover time = 1 yr), but is less likely to be important to Cu and Ni cycles (turnover times greater than 2 yrs). In situ radiotracer migration experiments were carried out at the Buzzards Bay site. 54Mn, 59Fe, 60Co, and 63Ni were released into the sediments at depths ranging from 2.5 to 7 cm below the interface. The order of mobilities was Mn»Fe>Co,Ni, which is similar to the solubility trend for these metals in reducing marine systems. 63Ni and 60Co were essentially particle-bound in these experiments; apparent diffusion coefficients calculated from their dispersion rates agreed with particle mixing rates from excess 234Th distributions. Solid:solution distribution coefficients were calculated from 54Mn dispersion and found to agree with directly measured values. The coefficient was approximately 15 (dpm/gm solid ÷ dpm/gm pore water) in the upper 0.5 cm and below 5 cm, and 5-10 from 0.5 to 5 cm. Distribution coefficients for 59Fe were approximately 120 below 0.5 cm. Although the trend of the distribution coefficients is clear, the quantitative results from these experiments are preliminary, in that the model used to explain metal ion dispersion, when applied to the nonreactive tracer, 36Cl, could only explain a portion of the 36Cl distribution. The agreement between calculated and directly measured s4Mn distribution coefficients, as well as the way the distributions of tracers varied as a function of apparent diffusion coefficient and time, provides evidence in favor of the adequacy of the model used.