The supply and accumulation of silica in the marine environment

Rivers and submarine hydrothermal emanations supply 6.1 × 10¹⁴g SiO₂/yr to the marine environment. Approximately two-thirds of the silica supplied to the marine environment can be accounted for in continental margin and deep-sea deposits. Siliceous deep-sea sediments located beneath the Antarctic Polar Front (Convergence) account for over a fourth (1.6 × 10¹⁴g SiO₂/yr) of the silica supplied to the oceans. Deep-sea sediment accumulation rates beneath the Polar Front are highest in the South Atlantic with values as large as 53cm/kyr during the last 18.000 yr. Siliceous sediments in the Bering Sea, Sea of Okhotsk, and Subarctic North Pacific accumulate 0.6 × 10¹⁴g SiO₂/yr or 10% of the dissolved silica input to the oceans. The accumulation of biogenic silica in estuarine deposits removes a maximum of 0.8 × 10¹⁴g SiO₂/yr. Although estuarine silica versus salinity plots indicate extensive removal of riverine silica from surface waters, the removal rates must be considered as maximum values because of dissolution of siliceous material in estuarine sediments and bottom waters. Siliceous sediments from continental margin upwelling areas (e.g. Gulf of California, Walvis Bay, or Peru-Chile coast) have the highest biogenic silica accumulation rates in the marine environment (69 g SiO₂ cm²/kyr). Despite the rapid accumulation of biogenic silica, upwelling areas account for less than 5% of the silica supplied to the marine environment because they are confined laterally to such small areas.     

Sediment flux distribution in the Southern Brazil Basin during the late Quaternary: the role of deep-sea currents

Detailed sedimentological and stratigraphic analyses were carried out on seven Kullenberg cores collected across the Brazilian continental margin during the French cruises Byblos and Apsara III, in order to highlight the factors controlling the sediment flux distribution in the Southern Brazil Basin during the late Quaternary. On the continental slope and upper continental rise above 3000 m depth, sediment fluxes are important and highly variable (4·2–14·2 g cm^?2 10^?3 yr). The sediments show a pelagic or turbiditic character, depending on the width of the shelf and proximity of canyons. The material is characterized by high kaolinite contents, and originates from the coastal rivers draining the South American continent north of Rio de Janeiro. On the middle continental rise between 3000 and 4000 m depth, sediment fluxes are the lowest observed in the area (0·9 g cm^?2 10^?3 yr), because terrigenous input is trapped at shallower depths on the São Paulo Plateau. Pelagic settling is the dominant process. In the deep domains, below 4000 m depth, contouritic accumulations are developed on the path of the northwards moving Antarctic bottom water (AABW) currents. The deposits consist of fine-grained silty-clayey muds with very low carbonate contents. The sediment fluxes (1·45 g cm^?2 10^?3 yr) are higher than on the middle continental rise, as a consequence of fine-grained terrigenous supply derived from higher latitudes (Argentine Basin and Southern Ocean), and transported in the basin through the Vema Channel by the AABW currents. This material is characterized by high smectite and chlorite contents. These data reveal large sediment flux variations which are linked to distinct depth-related domains. Such a distribution is the consequence of the presence of two available sources of terrigenous sediments: (1) the Brazilian continental areas with a downslope material transport and a sediment distribution controlled by the morphology of the margin, and (2) the Argentine Basin with an alongslope material transport by deep-sea currents which dominate the sedimentation in the abyssal domains.     

Rate of mercury loss from contaminated estuarine sediments

The concentration of mercury in contaminated estuarine sediments of Bellingham Bay, Washington was found to decrease with a half-time of about 1.3 yr after the primary anthropogenic source of mercury was removed. In situ measurements of the mercury flux from sediments, in both dissolved and volatile forms, could not account for this decrease. This result suggests that the removal of mercury is associated with sediment particles transported out of the study area. This decrease was modeled using a steady-state mixing model.Mercury concentrations in anoxic interstitial waters reached 3.5 μg/l, 126 times higher than observed in the overlying seawater. Mercury fluxes from these sediments ranged from 1.2 to 2.8 × 10^?5 ng/cm²/sec, all in a soluble form. In general, higher Hg fluxes were associated with low oxygen or reducing conditions in the overlying seawater. In contrast, no flux was measurable from oxidizing interstitial water having mercury concentrations of 0.01-0.06 μ/l.     

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

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 880 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 depth 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, , 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 redox-sensitive 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.     

Remobilization of authigenic uranium in marine sediments by bioturbation

Uranium behaves as a nearly conservative element in oxygenated seawater, but it is precipitated under chemically reducing conditions that occur in sediments underlying low-oxygen bottom water or in sediments receiving high fluxes of particulate organic carbon. Sites characterized by a range of bottom-water oxygen (BWO) and organic carbon flux (OCF) were studied to better understand the conditions that determine formation and preservation of authigenic U in marine sediments. Our study areas are located in the mid latitudes of the northeast Pacific and the northwest Atlantic Oceans, and all sites receive moderate (0.5 g/cm² kyr) to high (2.8 g/cm² kyr) OCF to the sediments. BWO concentrations vary substantially among the sites, ranging from <3 to ∼270 μM. A mass balance approach was used to evaluate authigenic U remobilization at each site. Within each region studied, the supply of particulate nonlithogenic U associated with sinking particles was evaluated by means of sediment traps. The diffusive flux of U into sediments was calculated from pore-water U concentration profiles. These combined sources were compared with the burial rate of authigenic U to assess the efficiency of its preservation. A large fraction (one-third to two-thirds) of the authigenic U precipitated in these sediments via diffusion supply is later regenerated, even under very low BWO concentrations (∼15 μM). Bioturbating organisms periodically mix authigenic U-containing sediment upward toward the sediment-water interface, where more oxidizing conditions lead to the remobilization of authigenic U and its loss to bottom waters.     

Biogenic-silica accumulation in the Ross Sea and the importance of Antarctic continental-shelf deposits in the marine silica budget

Thirty-five box cores were collected from the continental shelf in the Ross Sea during cruises in January and February, 1983. Pb-210 and Pu-239, 240 geochronologies coupled with biogenic-silica measurements were used to calculate accumulation rates of biogenic silica. Sediment in the southern Ross Sea accumulates at rates ranging from ≤0.6 to 2.7 mm/y, with the highest values occurring in the southwestern Ross Sea. Biogenic-silica content in surface sediments ranges from 2% (by weight) in Sulzberger Bay and the eastern Ross Sea to 41% in the southwestern Ross Sea. Biogenic-silica accumulation in the southwestern Ross Sea averages 2.7 × 10⁻² g/cm²/y and is comparable to accumulation rates in high-productivity, upwelling environments from low-latitude continental margins (e.g., Gulf of California, coast of Peru). The total rate of biogenic-silica accumulation in the southern Ross Sea is approximately 0.2 × 10¹⁴ g/y, with most of the accumulation occurring in basins (500–1000 m water depth). If biogenic-silica accumulation in the southern Ross Sea continental shelf is typical of other basins on the Antarctic continental shelf, as much as 1.2 × 10¹⁴ g/y of silica could be accumulating in these deposits. Biogenic-silica accumulation on the Antarctic continental shelf may account for as much as a fourth of the dissolved silica supplied to the world ocean by rivers and hydrothermal vents.     

Sedimentary record of heavy metal pollution in Lake Erie

Three cores, one kilometer apart, from each of seven locations along Lake Erie were analyzed for heavy metals and dated by ²¹⁰Pb techniques. The sedimentary record of anthropogenic inputs of heavy metals parallels the increasing intensity of cultural activity in the lake basin. On the average, pollution sources annually contribute 0.4 μg of Cd, 12 μg of Cu, 12 μg of Pb and 36 μg of Zn deposited per each cm² of the Eastern Basin sediments: 0.5, 8.8, 11 and 31 μg of Cd, Cu, Pb and Zn, respectively, deposited per cm² of Western Basin sediments and 0.7, 1.4, 2.0 and 5.6 μg of Cd, Cu, Pb and Zn, respectively, deposited per cm² of fine-grained sediments in the Central Basin. These anthropogenic flux rates exceed the pre-colonial data by 80–600%. The mean flux rates for ²¹⁰Pb into the Eastern. Central and Western Basins are 0.45, 0.07 and 0.15dpm cm^?2 yr^?1. respectively. From an inventory of sources and sinks of the metals, it is shown that about 2500 × 10³ kg of Cu. 1900 × 10³ kg of Pb and 6750 × 10³kg of Zn are delivered annually into the lake. The calculated retention in the lake sediments of 45%, 65% and 35% of the total annual inputs of Cu. Pb and Zn, respectively, agrees closely with the accumulation of data derived from sediment analyses. Sewage discharges, direct and indirect, are shown to be an important source of metal in the lake. The mean residence times in the water column are inferred to be 104 days for Cu. 180 days for Pb and 152 days for Zn.     

Pollution records from sediments of three lakes in New York State

Sediment core segments from Sylvan Lake, Lake Champlain and Lake Canadarago were dated radiometrically with ²¹⁰Pb and ¹³⁷Cs. Their respective sedimentation rates were determined to be 0.11, 0.14 and 0.52 g cm^?2 yr^?1. For the two lakes of lower sedimentation the variations of selected elemental abundances as function of depth were analyzed. Two groupings were found: Al, K, Ti, Rb and Zr were correlated among themselves but reflected different variations in the input of terrigenous erosion material to the lakes. The Cu, Zn and Pb correlated among themselves showed similar depth dependence with increasing concentrations toward the top which can be attributed to cultural pollution. Recent ‘excess’ fluxes to the sediments above the natural contribution by clastic material were derived for the location of the cores, which for Cu, Zn and Pb amounted to 3.8, 24 and 16 μg cm^?2 yr^?1 respectively for Sylvan Lake and 4.9, 20 and 16 μg cm^?2 yr^?1 for Lake Champlain. The corresponding ²¹⁰Pb flux was 3.3 and 2.3 dpm cm^?2 yr^?1, respectively for the two lakes.Approximate residence times in the water column were obtained for trace metals at the Lake Champlain location. Short residence times estimated for Pb (< 0.15 yr) and Cu (< 0.4 yr) indicate fast removal, whereas those for Zn (1.0 ± 0.3 yr) and Cr (2.0 ± 0.5 yr) appeared to be dominated by the water residence time.     

Uranium diagenesis in sediments underlying bottom waters with high oxygen content

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.     

Diagenesis of oxyanions (V, U, Re, and Mo) in pore waters and sediments from a continental margin

This research tests the hypothesis that trace metals respond to the extent of reducing conditions in a predictable way. We describe pore water and sediment measurements of iron (Fe), manganese (Mn), vanadium (V), uranium (U), rhenium (Re), and molybdenum (Mo) along a transect off Washington State (USA). Sediments become less reducing away from the continent, and the stations have a range of oxygen penetration depths (depth to unmeasurable O₂ concentration) varying from a few millimeters to five centimeters. When oxygen penetrates ∼1 cm or less, Fe is reduced in the pore waters but reoxidized near the sediment-water interface, preventing a flux of Fe²⁺ to overlying waters, whereas Mn oxides are reduced and Mn²⁺ diffuses to overlying waters. Both Re and U authigenically accumulate in sediments. Only at the most reducing location, where the oxygen penetrates 0.3 cm below the sediment-water interface, does the surface 30 cm of sediments become reducing enough to authigenically accumulate Mo.Stations in close proximity to the Juan de Fuca Ridge crest are enriched in Mn and Fe from hydrothermal plume processes. Both V and Mo clearly associate with Mn cycling, whereas U may be associating with either Mn oxides and/or Fe oxyhydroxides. Rhenium is uncomplicated by adsorption to Mn oxides and/or Fe oxyhydroxides, and Re accumulation in sediments appears to be due solely to the extent of reducing conditions. Therefore, authigenic sediment Re enrichment appears to be the best indicator for intermediate reducing conditions, where oxygen penetrates less than ∼1 cm below the sediment-water interface, when coupled with negligible authigenic Mo enrichment.     

Biogeochemical cycling in an organic rich coastal marine basin—II. Nutrient sediment-water exchange processes

The release of remineralized N and P from the organic-rich anoxic sediments of Cape Lookout Bight is controlled by processes occurring within the sediment column and at the sediment-water interface. The relatively rapid rates of temperature dependent microbial degradation of organic matter support seasonally varying nutrient fluxes ranging from 20 to 1200 μmol·m^?2·hr^?1 for dissolved ammonium and from ? 20 to 120 μmol·m^?2·hr^?1 for total dissolved phosphate (measured in situ over the period October, 1976 to October, 1978). Molecular diffusion along steep vertical pore water concentration gradients measured simultaneously cannot explain the high fluxes observed during warmer months. Gradients for ammonium and phosphate ranged from 0.33 to 1.10 and from 0 to 0.29 μmol·cm^?3_pw·cm^?1_s respectively. These high summertime fluxes appear to result from increased sediment-water transport associated with bubble tubes created and maintained by low-tide methane gas bubble ebullition. When these tubes are present, apparent bulk sediment diffusivities calculated from concurrent studies of methane and radon-222 sediment-water exchange are 1.0–3.1 times greater than molecular diffusivities. Nutrient fluxes calculated via Fick's first law taking into account this enhanced transport and the differential diffusive mobilities of dissolved ammonium, phosphate and phosphate ion pairs indicate that removal by aerobic adsorption and/or biological uptake at the sediment-water interface plays an important role in controlling nutrient exchange in these sediments.     

Accumulation rates of Th-230, Pa-231, and some transition metals on the Bermuda Rise

Measurements of ²³⁸U, ²³⁴U, ²³⁰Th, ²³²Th, ²³¹Pa, Mn, Fe, Co, Ni, Cu, and Zn were made on 23 samples from core GPC-5, a 29-m giant piston core from a water depth of 4583 m on the northeastern Bermuda Rise (33°41.2′N, 57°36.9′W). This area is characterized by rapid deposition of sediment transported by abyssal currents. Unsupported ²³⁰Th and ²³¹Pa are present throughout the core but, because of large variations in the sedimentation rate, show marked departures from exponential decay with depth. The trend with depth of the ${}^{231}\text{Pa}{}_{\mathrm{ex}}{}^{230}\text{Th}{}_{\mathrm{ex}}$ ratio is consistent with the average accumulation rate of 36 cm/1000 y reported earlier on the basis of radiocarbon dating and CaCO₃ stratigraphy. When expressed on a carbonate-free basis, concentrations of Mn, Co, Ni, Cu, Zn, ²³⁰Th_ex, and ²³¹Pa_ex all show cyclic variations positively correlated with those of CaCO₃. The correlations can be explained by a model in which all of these constituents, including CaCO₃, are supplied to the sediments from the water column at a constant rate. Concentration variations are controlled mainly by varying inputs of terrigenous detritus, with low inputs occurring during interglacials and high inputs during glacials. Relationships between the metal and ²³⁰Th_ex concentrations permit estimates of the rates at which the metals are removed to the sediment by scavenging from the water column. The results, in μg/cm²-1000 y, are: 4300 ± 1100 for Mn, 46 ± 16 for Ni and 76 ± 26 for Cu. These rates are somewhat larger than ocean-wide averages estimated by other methods, and the absolute rate of ²³⁰Th accumulation in GPC-5 averages about nine times higher than production in the overlying water column. This part of the Bermuda Rise and similar bottom-current deposits may act as important accumulators of elements scavenged from seawater.     

Anthropogenic contributions to atmospheric Hg, Pb and As accumulation recorded by peat cores from southern Greenland and Denmark dated using the C “bomb pulse curve”

Mercury concentrations are clearly elevated in the surface and sub-surface layers of peat cores collected from a minerotrophic (“groundwater-fed”) fen in southern Greenland (GL) and an ombrotrophic (“rainwater-fed”) bog in Denmark (DK). Using ¹⁴C to precisely date samples since ca. AD 1950 using the “atmospheric bomb pulse,” the chronology of Hg accumulation in GL is remarkably similar to the bog in DK where Hg was supplied only by atmospheric deposition: this suggests not only that Hg has been supplied to the surface layers of the minerotrophic core (GL) primarily by atmospheric inputs, but also that the peat cores have preserved a consistent record of the changing rates of atmospheric Hg accumulation. The lowest Hg fluxes in the GL core (0.3 to 0.5 μg/m²/yr) were found in peats dating from AD 550 to AD 975, compared to the maximum of 164 μg/m²/yr in AD 1953. Atmospheric Hg accumulation rates have since declined, with the value for 1995 (14 μg/m²/yr) comparable to the value for 1995 obtained by published studies of atmospheric transport modelling (12 μg/m²/yr).The greatest rates of atmospheric Hg accumulation in the DK core are also found in the sample dating from AD 1953 and are comparable in magnitude (184 μg/m²/yr) to the GL core; again, the fluxes have since gone into strong decline. The accumulation rates recorded by the peat core for AD 1994 (14 μg/m²/yr) are also comparable to the value for 1995 obtained by atmospheric transport modelling (18 μg/m²/yr). Comparing the Pb/Ti and As/Ti ratios of the DK samples with the corresponding crustal ratios (or “natural background values” for preanthropogenic peat) shows that the samples dating from 1953 also contain the maximum concentration of “excess” Pb and As. The synchroneity of the enrichments of all three elements (Hg, Pb, and As) suggests a common source, with coal-burning the most likely candidate. Independent support for this interpretation was obtained from the Pb isotope data (²⁰⁶Pb/²⁰⁷Pb = 1.1481 ± 0.0002 in the leached fraction and 1.1505 ± 0.0002 in the residual fraction) which is too radiogenic to be explained in terms of gasoline lead alone, but compares well with values for U.K. coals. In contrast, the lowest values for ²⁰⁶Pb/²⁰⁷Pb in the DK profile (1.1370 ± 0.0003 in the leached fraction and 1.1408 ± 0.0003 in the residual fraction) are found in the sample dating from AD 1979: this shows that the maximum contribution of leaded gasoline occurred approximately 25 yr after the zenith in total anthropogenic Pb deposition.     

Changes of lead and barium with time in California off-shore basin sediments

During ancient times the natural deposition fluxes of lead which can be leached with dilute acid from sediments in Santa Barbara, Santa Monica and San Pedro basins offshore from the Los Angeles Urban complex, were about 0.7, 0.1 and 0.2 μg Pb/cm² yr respectively. Since there was little difference in biological productivity in surface waters of these basins, it is proposed that clay is a major transport vehicle for sequestered soluble lead, which then explains why the lead deposition flux within the Santa Barbara basin was so much larger compared to the other basins. The fluxes of silicate mud in the basins in ancient times were about 92, 19 and 30 mg/cm² yr in Santa Barbara, Santa Monica and San Pedro basins respectively. Today deposition fluxes of acid soluble lead within these three basins are 3- to 9-fold greater, being about 2.1, 1.1 and 1.8 μg Pb/cm² yr respectively, partly in the form of directly deposited large sewage particles, which account for none, $\text{2}\text{3}$ and $\text{3}\text{4}$ of the total industrial lead deposition fluxes in the respective basins. Concentrations of leachable lead in varve dated sediment layers increase with time and isotopic compositions of these leads change in accordance with corresponding known changes of isotopic compositions of industrial lead in the Los Angeles atmosphere. Lead remaining in acid leached sediment residues originates from igneous and clay minerals, exhibiting no change in concentration or isotopic composition since pre-industrial times.Deposition fluxes of total barium in sediments among the three basins were proportional to mass deposition fluxes before 1950 in the same manner as for lead. Afterwards, there are barium concentration maxima with time in both Santa Monica and San Pedro Basin sediments which are attributable to industrial sewage rather than to episodic erosion from barium-rich sedimentary evaporite strata exposed locally along the shore. An increase of barium concentrations in present day Santa Barbara basin sediments may reflect dispersal of barium-rich drilling mud from local drilling operations.     

Polycyclic aromatic hydrocarbon fingerprints in the Pichavaram mangrove–estuarine sediments,southeastern India

The sources and historical deposition of 16 polycyclic aromatic hydrocarbons (PAHs) were investigated in dated sediment cores from the Pichavaram mangrove–estuarine complex. The ΣPAH flux in mangrove and estuarine sediments was 0.064 ± 0.031 μg/cm²/yr and 0.043 ± 0.020 μg/cm²/yr, respectively. The PAH flux in sediments increased up-core, coinciding with rapid urbanization since the 1970s. The flux showed a decrease in recent years (since 1990), coinciding with less riverine discharge, and perhaps more effective implementation of environmental regulations. The sediments were dominated by low molecular weight PAHs, suggesting anthropogenic input. Ratios of specific PAH isomer pairs suggested a greater input of petrogenic vs. pyrogenic derived PAHs. Notably, the deposition of high molecular weight PAHs increase in mangrove surface sediments was due to lignite and firewood combustion. Because of their overall low concentration in sediments it is unlikely these PAHs pose an immediate ecological hazard.     

Accumulation rates and predominant atmospheric sources of natural and anthropogenic Hg and Pb on the Faroe Islands

A monolith representing 5420 ¹⁴C yr of peat accumulation was collected from a blanket bog at Myrarnar, Faroe Islands. The maximum Hg concentration (498 ng/g at a depth of 4.5 cm) coincides with the maximum concentration of anthropogenic Pb (111 μg/g). Age dating of recent peat accumulation using ²¹⁰Pb (CRS model) shows that the maxima in Hg and Pb concentrations occur at AD 1954 ± 2. These results, combined with the isotopic composition of Pb in that sample (²⁰⁶Pb/²⁰⁷Pb = 1.1720 ± 0.0017), suggest that coal burning was the dominant source of both elements. From the onset of peat accumulation (ca. 4286 BC) until AD 1385, the ratios Hg/Br and Hg/Se were constant (2.2 ± 0.5 × 10^-4 and 8.5 ± 1.8 × 10^-3, respectively). Since then, Hg/Br and Hg/Se values have increased, also reaching their maxima in AD 1954. The age date of the maximum concentrations of anthropogenic Hg and Pb in the Faroe Islands is consistent with a previous study of peat cores from Greenland and Denmark (dated using the atmospheric bomb pulse curve of ¹⁴C), which showed maximum concentrations in AD 1953.The average rate of atmospheric Hg accumulation from 1520 BC to AD 1385 was 1.27 ± 0.38 μg/m²/yr. The Br and Se concentrations and the background Hg/Br and Hg/Se ratios were used to calculate the average rate of natural Hg accumulation for the same period, 1.32 ± 0.36 μg/m²/yr and 1.34 ± 0.29 μg/m²/yr, respectively. These fluxes are similar to the preanthropogenic rates obtained using peat cores from Switzerland, southern Greenland, southern Ontario, Canada, and the northeastern United States. Episodic volcanic emissions and the continual supply of marine aerosols to the Faroe Islands, therefore, have not contributed significantly to the Hg inventory or the Hg accumulation rates, relative to these other areas. The maximum rate of Hg accumulation was 34 μg/m²/yr. The greatest fluxes of anthropogenic Hg accumulation calculated using Br and Se, respectively, were 26 and 31 μg/m²/yr. The rate of atmospheric Hg accumulation in 1998 (16 μg/m²/yr) is comparable to the values recently obtained by atmospheric transport modeling for Denmark, the Faroe Islands, and Greenland.     

Rates of silicate dissolution in deep-sea sediment: In situ measurement using U/U of pore fluids

Bulk dissolution rates for sediment from ODP Site 984A in the North Atlantic are determined using the ²³⁴U/²³⁸U activity ratios of pore water, bulk sediment, and leachates. Site 984A is one of only several sites where closely spaced pore water samples were obtained from the upper 60 meters of the core; the sedimentation rate is high (11-15 cm/ka), hence the sediments in the upper 60 meters are less than 500 ka old. The sediment is clayey silt and composed mostly of detritus derived from Iceland with a significant component of biogenic carbonate (up to 30%).The pore water ²³⁴U/²³⁸U activity ratios are higher than seawater values, in the range of 1.2 to 1.6, while the bulk sediment ²³⁴U/²³⁸U activity ratios are close to 1.0. The ²³⁴U/²³⁸U of the pore water reflects a balance between the mineral dissolution rate and the supply rate of excess ²³⁴U to the pore fluid by α-recoil injection of ²³⁴Th. The fraction of ²³⁸U decays that result in α-recoil injection of ²³⁴U to pore fluid is estimated to be 0.10 to 0.20 based on the ²³⁴U/²³⁸U of insoluble residue fractions. The calculated bulk dissolution rates, in units of g/g/yr are in the range of 4 × 10⁻⁷ to 2 × 10⁻⁶ yr⁻¹. There is significant down-hole variability in pore water ²³⁴U/²³⁸U activity ratios (and hence dissolution rates) on a scale of ca. 10 m. The inferred bulk dissolution rate constants are 100 to 10⁴ times slower than laboratory-determined rates, 100 times faster than rates inferred for older sediments based on Sr isotopes, and similar to weathering rates determined for terrestrial soils of similar age. The results of this study suggest that U isotopes can be used to measure in situ dissolution rates in fine-grained clastic materials.The rate estimates for sediments from ODP Site 984 confirm the strong dependence of reactivity on the age of the solid material: the bulk dissolution rate (R_d) of soils and deep-sea sediments can be approximately described by the expression R_d ≈ 0.1 Age⁻¹ for ages spanning 1000 to 5 × 10⁸ yr. The age of the material, which encompasses the grain size, surface area, and other chemical factors that contribute to the rate of dissolution, appears to be a much stronger determinant of dissolution rate than any single physical or chemical property of the system.     

Organo-sulfur compounds in sediments of the Puget Sound basin

Sediment samples from a variety of different environments were analyzed for organo-sulfur compounds (OSC) to provide the first characterization of the amounts and types of these compounds in sediments of the greater Puget Sound basin. A gas Chromatograph equipped with a sulfur specific flame photometric detector was used to quantify individual OSC. Compositions of OSC mixtures were essentially constant throughout the study area. Dibenzothiophene (DBT), its alkylated homologs, and an unknown compound were the predominant OSC in most samples. Concentrations of total OSC and DBT ranged from 4 to 60 and 0.4 to 2 μg/g organic carbon, respectively. The flux of OSC to the sediments at a station in central Puget Sound west of Seattle was approximately 140 ng/cm²/yr. The profile of total OSC concentration with depth showed three organic sulfur compounds that are apparently created in situ in the vicinity of where hydrogen sulfide production begins. The concentrations of the aromatic OSC were relatively constant with depth. Although several anthropogenic sources of OSC were identified, there was no evidence that OSC from these sources were accumulating in the sediments. The major source of the aromatic OSC in the sediments is apparently atmospheric input from natural sources such as forest fires.