Kinetic studies of the rate of dissolution of silica and diatom tests in sea water

Kinetic studies have been carried out on the dissolution of 10μm beads of silica and of the siliceous tests of two species of diatoms (Thalassiosira fluviatus andSkeletonema costatum) in sea water at 10–50°C and over the pH range 6–9. At all temperatures dissolution of the biogenous silica occurred most rapidly at pH 8 and most slowly at pH 6. First order kinetics were closely followed when the silica was present in a considerable excess over that required for saturation, the rate being proportional to the area of the silica. Apparent deviation from this type of kinetics occurred when there was insufficient silica to bring about saturation. This was undoubtedly due to the progressive decrease in the surface area which takes place as the particle dissolves. Application of the rather simplistic model developed by Kamataniet al. (1980), which makes allowance for this decrease, gave a close correspondence with the data until ∼ 90% of the silica had dissolved.     

Dissolution kinetics of biogenic silica collected from the water column and sediments of three Southern California borderland basins

Understanding biogenic silica (bSi) dissolution kinetics in margin environments is important in assessing the global silicon cycle, a cycle closely linked to the global carbon cycle. This understanding is also essential to answer the question of whether bSi content in marine sediment is a valid indicator of productivity in the overlying surface ocean. In this study, plankton tow, sediment trap, and sediment samples were collected at sites in three Southern California borderland basins. Batch dissolution experiments with plankton tow and sediment trap materials (conducted in the laboratory at 22 °C) showed linear dissolution kinetics, from which mean dissolution rate constants of 0.05 d^? 1 for plankton tow samples and 0.07 d^? 1 for sediment trap samples could be calculated. The dissolution rate constants for both types of samples showed seasonal variability but not the same seasonal patterns. Faster dissolution was observed with sediment trap samples collected at 800 m than at 550 m. With sediment multi-core samples, non-linear dissolution kinetics was observed, which complicates the direct comparison of dissolution rates. Nonetheless, dissolution appeared to be slower for the sediments samples than for samples collected from the water column and to decrease with depth in the sediments. Rate constants for surface sediment (0–0.5 cm) were at least 3–5 times less, and sediments at depths > 2 cm had rate constants at least 6–13 times less than those for material sinking to the sediment surface at these sites. Dissolution experiments conducted with Santa Barbara Basin surface sediment samples amended with dissolved aluminum (Al) and San Pedro Basin trap samples amended with enriched detrital materials (obtained by leaching bSi from sediment samples) suggested that dissolution was inhibited by Al and that the sediments from the different basins varied in the extent of Al release.     

Detection of rapid deposition of sea ice-rafted material to the Arctic Ocean benthos using the cosmogenic tracer Be

During three icebreaker cruises in the Arctic Ocean under different sea-ice conditions in 2002, undisturbed benthic surface sediments were collected and assayed for the presence of a short-lived (t_1/2=53 d), particle-reactive cosmogenic radionuclide, ⁷Be, that is solely derived from atmospheric deposition. Under largely ice-covered conditions in May–June 2002, we did not detect this radionuclide in benthic surface sediments, despite significant inventories present in ice-rafted snow on the overlying sea ice (mean=86.8 Bq m⁻²±32.0 SD; n=9). During the July–August 2002 Shelf–Basin Interactions (SBI) cruise aboard the USCGC Healy and during a simultaneous cruise of the CCGS Sir Wilfrid Laurier on the Bering and Chukchi Shelf, which occupied the same general region following retreat and dissolution of Arctic ice cover, the ⁷Be present in this snow as well as surface deposition on to the sea ice-free water surface was detected in many benthic surface sediments, including some as deep as 945 m in Barrow Canyon. Inventories of ⁷Be in sediments were as high (60 Bq m⁻²) as the entire decay-corrected inventory present earlier in some snow samples collected on the sea-ice cover. Other deposition indicators such as the inventories of sediment chlorophyll, sediment oxygen respiration rates and ²³⁴Th-derived export fluxes also showed post-ice melt particle deposition and vertical transport, but in most cases the ⁷Be deposition was not tightly correlated with these other indicators, suggesting that ⁷Be sedimentation may not be controlled by the same processes. Our observations indicate that materials in sea ice, including contaminants, particulate organic, and mineral matter originating from atmospheric deposition or entrained in continental shelf sediments and rafted onto sea ice, can be rapidly transported to depth. The re-distribution of these materials as sea-ice drifts and eventually melts has the potential for impacting Arctic Ocean biogeochemical cycles and contaminant concentrations in areas of the Arctic remote from the original point of deposition.     

Rates of oxygen transfer from air bubbles to aqueous NaCl solutions at various temperatures

Experiments have been conducted to investigate the effects of temperature on the interfacial surface area and on the rate of oxygen transfer from air bubbles dispersed in aqueous NaCl solutions. Tests were also conducted to estimate the effects of salt concentration on the size of the bubbles. In addition to NaCl solutions, seawater was used in some tests. The temperature effects were investigated at 5, 10, 15, 20, 25, and 30°C. The results showed a pronounced effect of the salt on the size of the bubbles, which first decreased sharply with increasing concentration, but showed no further drop when the concentration was increased beyond 0.6 M. Both in seawater and in the 0.6 M solution, the mass transfer rate, K_LA, increased almost linearly when temperature was increased within the range from 5 to 25°C. The salt solution, as well as the seawater, showed an increase of K_LA of 60–70% over that in pure water at the same temperatures. This effect was the result of increased surface area of bubbles because of decreased coalescence. The increase in surface area was strongly temperature dependent, especially between 15 and 20°C. Contrary to this behavior the surface area in pure water showed, practically, no temperature dependence. The results are explained and discussed on the basis of ion-water interactions.     

Tidal deposits. A casebook of recent examples and fossil counterparts: R.N. Ginsburg (editor). Springer,Berlin, 1975, 428 pp., US $ 34.80

Pollen and foraminifera were analyzed from identical samples in two marine cores taken from the upper and lower continental rise between Cape Hatteras and Chesapeake Bay. Down-core variations in percent abundance of pollen taxa permit the identification of three floral events. These floral events are comparable to and isochronous with changes in polleniferous sediments from the adjacent continental United States through the last 20,000 y, the time interval represented in these cores.A transfer function was used to obtain sea surface paleotemperature estimates from planktonic foraminifera. These estimates indicate that surface waters were relatively warm at the site of both cores from 8,000 y BP to present. Between 12,400 and 8,000 y BP the nearshore core continued to record warm temperatures whereas the offshore core, which should be closer to warm Gulf Stream waters, seems to have recorded significantly colder temperatures. These temperature discrepancies appear to result from severe carbonate dissolution in the offshore core. Temperature estimates are lowered by dissolution of the less resistant tropical species leaving resistant transitional and subpolar forms. This dissolution event coincides with the maximum upslope movement of the Western Boundary Undercurrent as indicated by changes in sedimentation rate.As shown by the nearshore core, in which dissolution was not severe, surface temperatures in this area increased abruptly about 12,000 y BP and remained relatively warm until 4,000 y BP when they decreased slightly. These changes in sea surface temperature appear to be related to the position of the Gulf Stream as indicated by percent abundance of Globigerinoides sacculifer. The Gulf Stream moved into this area about 12,000 y BP and attained its maximum northward penetration about 8,000 y BP.Marine and terrestrial paleoclimatic changes in this area are not synchronous. Sea surface temperatures increased about 12,000 y BP whereas the change from a glacial to an interglacial forest occurred several thousand years later, about 10,000 y BP.     

Shell preservation of Limacina inflata (Pteropoda) in surface sediments from the Central and South Atlantic Ocean: a new proxy to determine the aragonite saturation state of water masses

Over 300 surface sediment samples from the Central and South Atlantic Ocean and the Caribbean Sea were investigated for the preservation state of the aragonitic test of Limacina inflata. Results are displayed in spatial distribution maps and are plotted against cross-sections of vertical water mass configurations, illustrating the relationship between preservation state, saturation state of the overlying waters, and overall water mass distribution. The microscopic investigation of L. inflata (adults) yielded the Limacina dissolution index (LDX), and revealed three regional dissolution patterns. In the western Atlantic Ocean, sedimentary preservation states correspond to saturation states in the overlying waters. Poor preservation is found within intermediate water masses of southern origin (i.e. Antarctic intermediate water (AAIW), upper circumpolar water (UCDW)), which are distinctly aragonite-corrosive, whereas good preservation is observed within the surface waters above and within the upper North Atlantic deep water (UNADW) beneath the AAIW. In the eastern Atlantic Ocean, in particular along the African continental margin, the LDX fails in most cases (i.e. less than 10 tests of L. inflata per sample were found). This is most probably due to extensive “metabolic” aragonite dissolution at the sediment-water interface combined with a reduced abundance of L. inflata in the surface waters. In the Caribbean Sea, a more complex preservation pattern is observed because of the interaction between different water masses, which invade the Caribbean basins through several channels, and varying input of bank-derived fine aragonite and magnesian calcite material. The solubility of aragonite increases with increasing pressure, but aragonite dissolution in the sediments does not simply increase with water depth. Worse preservation is found in intermediate water depths following an S-shaped curve. As a result, two aragonite lysoclines are observed, one above the other. In four depth transects, we show that the western Atlantic and Caribbean LDX records resemble surficial calcium carbonate data and δ¹³C and carbonate ion concentration profiles in the water column. Moreover, preservation of L. inflata within AAIW and UCDW improves significantly to the north, whereas carbonate corrosiveness diminishes due to increased mixing of AAIW and UNADW. The close relationship between LDX values and aragonite contents in the sediments shows much promise for the quantification of the aragonite loss under the influence of different water masses. LDX failure and uncertainties may be attributed to (1) aragonite dissolution due to bottom water corrosiveness, (2) aragonite dissolution due to additional CO₂ release into the bottom water by the degradation of organic matter based on an enhanced supply of organic matter into the sediment, (3) variations in the distribution of L. inflata and hence a lack of supply into the sediment, (4) dilution of the sediments and hence a lack of tests of L. inflata, or (5) redeposition of sediment particles.     

A comparative study of three methods for the determination of iodate in seawater

A comparative study of three methods for the determination of iodate-iodine in seawater is described. In one method the iodate is determined polarographically while in the others the iodate is determined colorimetrically as iodonium ions. In one of the colorimetric methods each sample is pre-treated with excess iodine-water in an attempt to eliminate suspected interference from naturally occurring reducing agents. The tests were conducted on a selection of open-ocean and near-shore waters with iodate concentrations ranging from 0 to 60 μg 1^?1-I. The tests indicated that the polarographic method and the colorimetric method without iodine-water give the more reliable measurement of iodate concentration. Also, the method with iodine water was found to be in error especially at low iodate concentrations. Reducing agents, if present, were found not to interfere significantly.     

Bacterial kinetics and environmental capacity in he Western Xiamen Harbour

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Dissolved silica concentrations and reactions in pore waters from continental slope sediments offshore from Cape Hatteras, North Carolina, USA

The pore water concentrations of dissolved silica in sediment cores from the continental slope offshore from Cape Hatteras, North Carolina, varied from 150 to almost 700 μ,M with depth in the top 40 cm of sediment. Sediment cores from 630 to 2010 m depth had very similar profiles of dissolved silica in their pore waters, even though these cores came from regions greatly different in slope, topography, sedimentation rate, and abundance of benthic macrofauna. Cores from 474 to 525 m were more variable, both with respect to pore water dissolved silica profiles, and with respect to sediment texture. Experiments indicate that both the rate of dissolution of silica and the saturation concentration decrease as sediment depth below the sediment-seawater interface increases. These data are consistent with depletion of a reactive silica phase in surface sediment, which may be radiolarian tests, or the alteration of biogenic silica to a less reactive form over time. Experimental results suggest that the pore water dissolved silica concentration in sediments below the top few centimeters may be higher than the sediments could now achieve. The flux of dissolved silica out of these sediments is estimated to be 15 μmoles cm⁻² yr⁻¹.     

Vertical and seasonal differences in biogenic silica dissolution in natural seawater in Suruga Bay, Japan: Effects of temperature and organic matter

Vertical and seasonal characteristics of biogenic silica (BSi) dissolution in seawater were investigated by multiple dissolution experiments using seawater collected from surface and mesopelagic layers in Suruga Bay during the period 2002–2004. The dissolution rate coefficients calculated based on temporal changes of BSi concentration varied with the season of sample collection. They ranged from 0.023–0.057 day^− 1 for surface samples and 0.0018–0.0025 day^− 1 for mesopelagic samples for temperatures approaching in situ conditions. Experiments at various temperatures confirmed that BSi dissolution depends on temperature in natural seawater. Dissolution rate coefficient (day^− 1) of BSi correlated significantly with temperature (°C), and Q₁₀ was 2.6. Addition of bioavailable organic matter to low-bioactivity seawater enhanced the protease activity and abundance of bacteria, and increased BSi dissolution rate by a factor of 1.4–2.0. There is clear evidence that BSi dissolution is accelerated by bacterial activity and potentially limited by bioavailable organic matter in natural seawater. Dissolution rates and total decreases of BSi concentration were lower during experiments using mesopelagic samples than in those using surface samples. This suggests that dissolution of BSi varies with depth and that BSi in the mesopelagic water is more resistant to the dissolution than that in the surface water. This lower dissolution rate was caused by lower temperature and lower bacterial activity due to less bioavailable organic matter in mesopelagic water. Our results provide a mechanistic understanding of variations in silica cycling within the seasonally and vertically differing marine environment.     

Microbial mediation of benthic biogenic silica dissolution

Pore water profiles from 24 stations in the South Atlantic (located in the Guinea, Angola, Cape, Guyana, and Argentine basins) show good correlations of oxygen and silicon, suggesting microbially mediated dissolution of biogenic silica. We used simple analytical transport and reaction models to show the tight coupling of the reconstructed process kinetics of aerobic respiration and silicon regeneration. A generic transport and reaction model successfully reproduced the majority of Si pore water profiles from aerobic respiration rates, confirming that the dissolution of biogenic silica (BSi) occurs proportionally to O₂ consumption. Possibly limited to well-oxygenated sediments poor in BSi, benthic Si fluxes can be inferred from O₂ uptake with satisfactory accuracy. Compared to aerobic respiration kinetics, the solubility of BSi emerged as a less influential parameter for silicon regeneration. Understanding the role of bacteria for silicon regeneration requires further investigations, some of which are outlined. The proposed aerobic respiration control of benthic silicon cycling is suitable for benthic–pelagic models. The empirical relation of BSi dissolution to aerobic respiration can be used for regionalization assessments and estimates of the silicon budget to increase the understanding of global primary and export production patterns.     

Spring distribution of dissolved organic matter in a system encompassing the Northeast Water Polynya: Implications for early-season sources and sinks

This study addresses sources and diagenetic state of early-season dissolved organic matter (DOM) in the Northeast Water Polynya (NEWP) area northeast of Greenland from distributions of humic substance fluorescence (HSfl), dissolved organic carbon (DOC), and dissolved organic nitrogen (DON) in the water column inside and outside the NEWP area. The water masses of the polynya area had acquired their spring/summer temperature–salinity characteristics at the time of sampling, and also had individual, different DOM signatures. DOC concentrations were variable within and among water masses in the polynya area, indicating patchy local sources and sinks of DOC. PySW and polynya intermediate water (PyIW) had higher average DON concentrations and average lower C:N ratios than polynya bottom water (PyBW), indicating a larger fraction of fresh DOM in PySW and PyIW than in PyBW. Ice-covered, polynya area surface waters (PySW) had higher DOC concentrations (113±14 μM, n=68) than surface water (SW) outside the polynya area (96±18 μM, n=6). The DOM C:N ratios in a low-salinity, ice-melt subgroup of PySW samples indicate labile material, and these low-salinity surface waters appeared to have a local DOC and DON source. In contrast, HSfl was significantly lower inside than outside the NEWP area. Despite the lower HSfl values within the NEWP area, the PySW values were high when compared to open-ocean water. There were no local terrestrial sources for HSfl to the NEWP area and the East Greenland Current is therefore proposed as a likely source of allochtonous HSfl. When HSfl was used as a conservative tracer, up to 70% of the water in PySW and PyIW was found to be derived from SW, which contains a high fraction of water from the East Greenland Current. Similarly, a mixing model based on HSfl indicated that 80% of early-season DOC and 90–100% of early-season DON in PySW and PyIW were derived from SW, indicating a potentially high fraction of terrestrially-derived, relatively refractory DOM in the early-season NEWP area.     

The spatial distribution of surface <Emphasis Type="Italic">f</Emphasis>CO<Subscript>2</Subscript> in the Southwestern East Sea/Japan sea during summer 2005

Fugacity of CO₂ (fCO₂), temperature, salinity, nutrients, and chlorophyll-a were measured in the surface waters of southwestern East Sea/Japan Sea in July 2005. Surface waters were divided into three waters based on hydrographic characteristics: the water with moderate sea surface temperature (SST) and high sea surface salinity (SSS) located east of the front (East water); the water with high SST and moderate SSS located west of the front (West water); and the water with low SST and SSS located in the middle part of the study area (Middle water). High fCO₂ larger than 420 μatm were found in the West water. In the Middle water, CO₂ was undersaturated with respect to the atmosphere, with values between 246 and 380 μatm. Moderate fCO₂ values ranging from 370 to 420 μatm were observed in the East water. For the East and West waters, estimates of temperature dependency of fCO₂ (12.6 and 15.1 μatm °C⁻¹, respectively) were rather similar to a theoretical value, indicating that SST is likely to be a major factor controlling the surface fCO₂ distribution in these two regions. In the Middle water, however, the estimated temperature dependence was somewhat lower than the theoretical value, and relatively high concentrations of surface chlorophyll-a coincided with the low surface fCO₂, implying that biological uptake may considerably affect the fCO₂ distribution. The net sea-to-air CO₂ flux of the study area was estimated to be 0.30±4.81 mmol m⁻² day⁻¹ in summer, 2005.     

Interactions of phytoplankton, zooplankton and microorganisms

We present evidence that there are significant interactions between heterotrophic microorganisms, doliolids and Fritillaria within intrusions of nutrient-rich Gulf Stream water stranding on the continental shelf. During the summer of 1981 cold, nutrient-rich water from below the surface of the Gulf Stream was repeatedly intruded and stranded on the continental shelf off northeastern Florida. On August 6 old, stranded Gulf Stream water depleted of nitrate occupied the lower layer on the outer shelf. The upper water was continental shelf water, older but of undefined age. On August 6 free-living bacteria were >10⁶ml⁻¹ everywhere at all depths, an order of magnitude greater than normal bacterial numbers on the northeastern Florida continental shelf. Over 10 days the numbers of free bacteria doubled while bacteria attached to particles increased by a factor of four. The adenylate/chlorophyll ratio showed that phytoplankton dominated the lower layers of intruded water, while the surface water became increasingly dominated by heterotrophic microorganisms (bacteria and protozoa) over 10 days. There were significant, negative correlations between bacteria and doliolids and between bacteria and Fritillaria. Regions of maximum bacterial numbers did not coincide with locations of salp swarms. The increased numbers of bacteria at all depths in a highly stratified system in which most phytoplankton are in the lower layer suggests a diverse source of bacterial growth substrates, some of which involve zooplankton as intermediaries. Production of autotrophs is more than twice that of microheterotrophs on average, but because of their differential distribution, microheterotrophs are the dominant biomass in much of the surface water and may be significant in energy flux to metazoan consumers as well as competitors for mutually useable sources of nutrition.     

Spring–summer cycling of DOC, DON and inorganic N in a highly seasonal system encompassing the Northeast Water Polynya, 1993

Dissolved organic nitrogen (DON), dissolved organic carbon (DOC) and inorganic nutrient concentrations were determined in samples from an area encompassing the Northeast Water Polynya from June to August 1993. In June, still ice-covered polynya area surface waters (PySW) had significantly higher (p<0.05) DOC concentrations (110 μM, n=68) than surface water outside the polynya area (96 μM, n=6). Melting ice and ice algae are suggested as DOC sources. DOC concentrations found in this study are consistent with other studies showing higher DOC concentrations in the Arctic than in other ocean areas. As the productive season progressed, DOC concentrations in Polynya surface water (PySW) decreased (p<0.05) from 110 to 105 μM, while DON concentrations increased (p<0.05) from 5.6 to 6.1 μM, causing a significant decrease (p<0.05) in the C : N ratios of DOM from spring (C : N ratio 20) to summer (C : N ratio 17). We found a significant (p<0.05) decrease in the DOM C : N ratio in all water masses within the polynya area as the productive season progressed. DON was the largest fraction of total dissolved nitrogen (TDN) in PySW and surface waters outside the polynya area. TDN was calculated as the sum of DON, nitrate, nitrite and ammonium concentrations. DON increased (p<0.05) from 62% to 73% of TDN in PySW from spring to summer, a result of increasing DON concentrations and decreasing inorganic nitrogen concentrations over the productive season. The seasonal accumulation of DON and the corresponding decrease in nitrate concentrations in waters with primary production indicate that it is important to take the DON pool into account when estimating export production from nitrate concentration decreases in surface waters. PySW TDN concentrations decreased (p<0.05) from 9.1 (n=61) to 8.6 μM (n=60) from spring (May 25 through June 19) to summer (July 1 through July 27). The seasonal decrease in surface water TDN concentrations corresponded to increases in TDN concentrations in deeper water masses within the Polynya. Most of the TDN increase in deep water was in the form of DON. A possible explanation is that PON was dissolved (partially remineralized) in the water column at mid depths, causing increases in the DON concentration. Transfer of N from PySW (with a short residence time in the polynya area) to Polynya Intermediate Water and deep waters of the Norske and Westwind Trough with multi-year residence times keeps N from leaving the polynya area. In spring, nutrients from degradation of OM in PyIW could support primary production. The role of PyIW as an OM trap could be important in supporting primary production in the polynya area.     

Methane hydrate dissolution rates in undersaturated seawater under controlled hydrodynamic forcing

The dissolution of in-situ generated methane hydrate in undersaturated, synthetic seawater (S = 35) was investigated in a series of laboratory-based experiments at P-/T-conditions within the hydrate stability field. A controlled flow field was generated across the smooth hydrate surface to test if, in addition to thermodynamic variables, the dissolution rate is influenced by changing hydrodynamic conditions. The dissolution rate was found to be strongly dependent on the friction velocity, showing that hydrate dissolution in undersaturated seawater is a diffusion-controlled process. The experimental data was used to obtain diffusional mass transfer coefficients k_d, which were found to correlate linearly with the friction velocity, u. The resulting k_d/u-correlation allows predicting the flux of methane from natural gas hydrate exposures at the sediment/seawater interface into the bulk water for a variety of natural P, T and flow conditions. It also is a tool for estimating the rate of hydrate regrowth at locations where natural hydrate outcrops at the seafloor persist in contact with undersaturated seawater.     

2001/2002年夏季南极普里兹湾及其邻近海域的浮游植物

报道了 2 0 0 1 /2 0 0 2年夏季南极普里兹湾邻近海域 3 7个大面测站浮游植物的调查结果。经初步鉴定共有浮游植物 3门 3 7属 86种 ,其中硅藻在种类和细胞丰度上占绝对优势 ,其次为甲藻。主要优势种为克格伦拟脆杆藻 (Fragilariopsiskerguelensis)、细条伪菱形藻 (Pseu do nitzschialineola)、短拟脆杆藻 (Fragilariopsiscurta)和赖氏束盒藻 (Trichotoxonreinboldii)等南极特有种类和常见种类。调查区浮游植物分为两个群集 ,分布在 6 7°S以南的普里兹湾内的群集主要以克格伦拟脆杆藻、短拟脆杆藻、胡克星脐藻 (Asteromphalushookeri)和南极弯角藻 (Eu campiaantarctica)等南极特有种类和常见种类为主 ;分布在 6 7°S以北的大洋海域的群集主要以细条伪菱形藻、赖氏束盒藻、拟膨胀伪菱形藻 (Pseudo nitzschiaturgiduloides)和羽状环毛藻(Corethronpennatum)等南极常见种为主。调查区浮游植物的平均细胞丰度为 (8796± 2 92 85 )ind/L ,细胞多分布于海水的表层 ,密集区分布在 6 7°S以南的普里兹湾内 ,浮游植物的细胞丰度同硝酸盐的浓度密切相关。调查区浮游植物的多样性程度是低的。     

Pyrite formation under conditions approximating those in anoxic sediments: II. Influence of precursor iron minerals and organic matter

In the paper (Wang and Morse, 1996) that preceded this study, we presented results of experiments performed using a silica gel crystal growth technique to produce pyrite under conditions approximating those commonly occurring in anoxic marine sediments. The primary focus of that study was on the chemical pathways that pyrite formation follows and how differing conditions influenced reaction kinetics and morphology of pyrite crystals. In this paper, we present results of further long-term (up to 1 y) studies of pyrite formation, using the silica gel experimental technique, in which we investigated the role that different precursor iron (hydr)oxide minerals and marine organic matter play in pyrite formation. The minerals studied were akaganeite (β-FeOOH), ferrihydrite (Fe₅HO₈ · 4H₂O), goethite (α-FeOOH), hematite (α-Fe₂O₃), lepidocrocite (γ-FeOOH), and magnetite (Fe₃O₄). Marine organic matter used in this study was freeze-dried plankton collected from near-surface water in the Gulf of Mexico. The influence of precursor iron (hydr)oxide mineralogy, although important for initial iron sulfidization rates, was relatively minor compared to other variables, such as solution pH and sulfide concentration, in controlling the rate of pyrite formation. Consequently, major variations in the observed rate of pyritization of different iron (hydr)oxide minerals in sediments (e.g., Canfield and Berner, 1987) may reflect large differences in surface areas of the minerals rather than their intrinsic reactivity and is a confirmation of the estimates of Canfield et al. (1992) that most iron oxides have similar reactivity. The presence of marine organic matter (freeze-dried plankton) caused an increase in the sulfidization rate of goethite and a major (about 20 ×) decrease in the rate of pyrite formation. This can be interpreted as indicating that organic matter-iron interactions are important in both iron (hydr)oxide dissolution, and pyrite nucleation and growth. A possible explanation for this behavior is that dissolved organic matter produced during the long experiments (up to 1 year) increased the rate of goethite dissolution while inhibiting pyrite nucleation and growth by complexing iron. The lessons learned in the study of other mineral reaction kinetics (e.g., calcite and aragonite), that rates determined in pure inorganic systems, may not always be reliably applied to natural systems where organic matter can significantly influence mineral dissolution and growth rates, are, alas, repeated here for pyrite.     

Overrunning of shelf water in the southern Mid-Atlantic Bight

Analyses of two years (1992 and 1993) of high-resolution sea surface temperature satellite images of the southern Mid Atlantic Bight (MAB), showed that unusually extensive overhang of shelf water occurs episodically, and coherently over along shelf distances of several 100 km. These episodes are dubbed overrunning of the Slope Sea by shelf water. The overrunning volume has a “face” and a “back” (southern and northern limit). It transports substantial quantities of shelf water southward, and does not retreat onto the shelf, but eventually joins the western edge of the Gulf Stream in the vicinity of Chesapeake Bay. The combined analyses of satellite imagery and various in situ data further demonstrated that the shelf waters overrunning the Slope Sea were not mere surface features but reached depths between 40 and 60 m. Results confirm previous concepts on shelf circulation, shelf–slope exchange and fate of shelf water. They also shed new light on shelf water budget: overrunning of the Slope Sea and southwest transport by upper slope current constitutes an important conduit for shelf water transport. Winter storms move the shelf–slope front, and with it shelf water, offshore to distances 10–40 km. The offshore displacement of shelf water can be related to the onshore veering of the Gulf Stream near Cape Hatteras, producing a blocking effect on the shelf circulation. Such a blocking effect of the southwestward flow of shelf water in the MAB appeared to be the reason for the overrunning of shelf water off New Jersey. In addition, the excess fresh water discharge from the St. Lawerence was also observed to be related to the overflow of shelf water off New Jersey.