Chesapeake Bay nutrient and plankton dynamics: III. The annual cycle of dissolved silicon

Silicic acid (H₄SiO₄) flux from the sediment, H₄SiO₄ concentration and river flow were used to obtain an annual dissolved silicon budget for Chesapeake Bay. H₄SiO₄ concentrations vary seasonally in the estuary: for a 12-year period, mean H₄SiO₄ concentrations in the mesohaline region were high both in spring and in late summer to early fall, and were low in late spring—occasionally approaching levels potentially limiting to diatom growth. Most of the annual allochthonous H₄SiO₄ supply to the estuary derives from the three major rivers, but regenerative H₄SiO₄ flux from the sediment to the water column exceeds the total riverine input by a factor of at least five. Sediment H₄SiO₄ efflux exhibits seasonality and averages approximately 2–3 mol Si m^?2 yr^?1. The high rates of sediment dissolution and efflux appear to maintain high levels of H₄SiO₄ in the mesohaline region, and Si-limitation of diatom growth there seems unlikely. The relative rates of biogenic silica formation and dissolution do not vary synchronously: seasonal variations in diatom productivity, sedimentary release of H₄SiO₄ and river flow all contribute to the observed late winter and late summer seasonal maxima and late spring minimum in water column H₄SiO₄ concentrations. If the only source of Si to support sedimentary H₄SiO₄ efflux is biogenic particulate silica recently deposited from the water column and this silica in turn was produced by diatoms in a ratio of 8C:1 Si, the minimum annual primary production by diatoms is at least 260 g C m^?2, approximately half of annual total plankton primary production. This estimate would be revised upwards according to the amount of particulate biogenic silica dissolving in the water column. Burial of biogenic silica amounts to from 2 to 84% of the sediment efflux of H₄SiO₄, depending on location in the bay. On an annual basis, burial represents from 60 to 100% of fluvial H₄SiO₄-Si inputs.     

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

Methane produced in anoxic organic-rich sediments of Cape Lookout Bight, North Carolina, enters the water column via two seasonally dependent mechanisms: diffusion and bubble ebullition. Diffusive transport measured in situ with benthic chambers averages 49 and 163 μmol · m ^?2 · hr ^?1 during November–May and June–October respectively. High summer sediment methane production causes saturation concentrations and formation of bubbles near the sediment-water interface. Subsequent bubble ebullition is triggered by low-tide hydrostatic pressure release. June–October sediment-water gas fluxes at the surface average 411 ml (377 ml STP: 16.8 mmol) · m^?2 per low tide. Bubbling maintains open bubble tubes which apparently enhance diffusive transport. When tubes are present, apparent sediment diffusivities are 1.2–3.1-fold higher than theoretical molecular values reaching a peak value of 5.2 × 10^?5 cm² · sec^?1. Dissolution of 15% of the rising bubble flux containing 86% methane supplies 170μmol · m^?2 · hr^?1 of methane to the bight water column during summer months; the remainder is lost to the troposphere. Bottom water methane concentration increases observed during bubbling can be predicted using a 5–15 μm stagnant boundary layer dissolution model. Advective transport to surrounding waters is the major dissolved methane sink: aerobic oxidation and diffusive atmospheric evasion losses are minor within the bight.     

Mechanisms controlling silicon isotope distribution in the Eastern Equatorial Pacific

The distribution of silicon isotopes along a meridional transect at 140°W longitude in the Eastern Equatorial Pacific was used to test the hypothesis that δ³⁰Si of silicic acid in surface waters should correlate with net silica production rates (gross silica production minus silica dissolution) rather than rates of gross silica production due to the opposing Si isotope fractionations associated with silica production and silica dissolution. Variations in δ³⁰Si appeared significantly correlated with net silica production rates in equatorial surface waters and not with gross production rates. Around the Equator, values of δ³⁰Si as low as deep water values occurred in the upper mesopelagic in a zone of net silica dissolution and high detrital biogenic silica content, where the release of low δ³⁰Si silicic acid from opal dissolution would be expected to decrease δ³⁰Si. The δ³⁰Si of the deep water at 140°W appears constant for depths >2000 m and is similar to the deep water at 110°W. This study brings to light the importance of considering Si fractionation during diatom silica dissolution, the biological fractionation during silica production and physical factors such as currents and mixing with adjacent water masses when interpreting silicon isotope distributions.     

Dissolution of silica and the development of concentration profiles in freshwater sediments

The dissolution of silica and diffusion of reactive dissolved Si in the porewaters of river sediments are investigated using sediments of different physical and chemical properties. Three sediments are considered: (a) from sectioned cores taken from a river-bed, (b) fine organic-rich surface sediment (<5 cm depth) installed in a fluvarium channel and, (c) coarse river sediment of low organic matter content also installed in a fluvarium channel. Dissolution rates of silica are measured at 10°C using batches of suspended material. The derived dissolution rate constants show large differences between the sediments. The river bed-sediment cores had vertical concentration profiles of dissolved Si that are consistent with the diffusion and dissolution of biogenic silica. Experiments in a fluvarium channel enabled Si fluxes to be calculated from a mass-balance of the overlying solution. The results are consistent with the attainment of a steady-state concentration profile of dissolved Si in the sediment. There are no discernible effects of water velocity over the sediment between 5 and 11 cm s⁻¹. However, at 20 cm s⁻¹, the flux increases as a result of either entrainment of fine particles at the surface or advective effects in the surface sediment. A fluvarium experiment with the fine sediment (<125 μm) over 61 days, produced a concentration profile with the highest concentration of 1025 μmol dm⁻³ at a depth of 4–5 cm in the sediment. A FORTRAN program is used to model the results of the increase in dissolved Si in the overlying water and development of a concentration profile in the porewater. This leads to a sediment diffusion coefficient of 1.21×10⁻⁹ m² s⁻¹ at 8.8°C at the beginning of the experiment and rate constant k=13.1×10⁻⁷ s⁻¹ at pH=7.82 and average temperature of 7.6°C for the entire experiment. Fluxes measured at the sediment–surface interface and calculated assuming steady-state profiles had developed are typically 0.01–0.04 μmol m⁻² (of river bed) s⁻¹. The approach enables the efflux of dissolved Si from bottom-sediments to be estimated from dissolution rates measured using suspensions of bed-sediment.     

Silica distribution in interstitial waters and sediments from the southeastern pacific

Analyses for silica in the interstitial water of five cores from the southeast Pacific are presented. Silica is enriched in these interstitial waters resulting in a vertical flux of silica of between 10 and 50 μmol cm^?2 yr^?1 from the sediment into the overlaying seawater. This flux is generated by the dissolution of biogenic silica, the dissolution of which is increased in areas of bottom water turbulence. The Si, Al and calculated opal (Leinen, 1977) contents of the bulk sediment of these cores are also presented. Small scale variations over depth intervals of tens of centimetres are present as a result of chaning conditions of sedimentation.     

Vertical Carbon Flux of Biogenic Matter in a Coastal Area of the Aegean Sea: The Importance of Appendicularians

This work focuses on the direct measurement of the vertical flux of appendicularian houses in order to assess their importance as a component of vertical carbon flux in coastal areas. For this purpose, arrays of cylindrical sediment traps were deployed for 5 to 8 days at two depths in a coastal area of the northern Aegean Sea (inner Thermaikos Gulf) during spring. The data support the contention that resuspension was minimal. Fecal pellet (FP) production and grazing experiments with the dominant copepods (Acartia clausi) were conducted to provide additional information on the potential FP contribution to the total carbon flux. The magnitude of the vertical flux of particulate organic carbon (POC) ranged between 310 and 724 mg C m^?2 day^?1. The proportion of phytoplankton carbon in the POC vertical flux was up to 45 %. The contribution of zooplankton FPs to the total carbon never exceeded 5 %. On the contrary, appendicularian houses were an essential component of the biogenic carbon flux contributing up to 55.3 % of the total vertical carbon flux. Consequently, both phytoplankton and appendicularian houses contributed equally to the biogenic carbon flux exceeding 80 % of the total sinking POC. Taking into account the sinking speed of the particles and the environment in the area, all this carbon probably reaches the seafloor, thus indicating a strong pelagic–benthic coupling.     

Loading, Transformation, and Retention of Nitrogen and Phosphorus in the Tidal Freshwater James River (Virginia)

A nutrient mass balance for the tidal freshwater segment of the James River was used to assess sources of nutrients supporting phytoplankton production and the importance of the tidal freshwater zone in mitigating nutrient transport to marine waters. Monthly mass balances for 2007–2010 were based on riverine inputs, local point sources (including sewer overflow events), ungauged inputs, riverine outputs, and tidal exchange. The tidal freshwater James River received exceptionally high areal loads (446 mg TN m^?2 day^?1 and 55 mg TP m^?2 day^?1) compared to other estuaries in the region and elsewhere. P inputs were principally from riverine sources (84 %) whereas point sources contributed appreciably (54 %) to high N loads. Despite high loading rates and short water residence time, areal mass retention was high (143 mg TN m^?2 day^?1 and 33 mg TP m^?2 day^?1). Retention of particulate fractions occurred during high discharge, whereas dissolved inorganic fractions were retained during low discharge when chlorophyll-a concentrations were high. On an annualized basis, P was retained more effectively (59 %) than N (32 %). P was retained by abiotic mechanisms via trapping of particulate forms, whereas N was retained through biological assimilation of dissolved inorganic forms. Results from a limited suite of stable isotope determinations suggest that DIN from point sources was preferentially retained. Combined inputs from diffuse and point sources accounted for only 20 % and 36 % (respectively) of estimated algal N and P demand, indicating that internal nutrient recycling was important to sustaining high rates of phytoplankton production in the tidal freshwater zone.     

Temperature Dependence of Oxygen Dynamics and Community Metabolism in a Shallow Mediterranean Macroalgal Meadow (Caulerpa prolifera)

Hypoxia is emerging as a major threat to marine coastal biota. Predicting its occurrence and elucidating the driving factors are essential to set successful management targets to avoid its occurrence. This study aims to elucidate the effects of warming on the likelihood of hypoxia. High-frequency dissolved oxygen measurements have been used to estimate gross primary production (GPP), net ecosystem production (NEP) and community respiration (CR) in a shallow macroalgae (Caulerpa prolifera) ecosystem in a highly human-influenced closed Mediterranean bay. Daily averaged GPP and CR ranged from 0 to 1,240.9 and 51.4 to 1,297.3?mmol?O₂?m^?2?day^?1, respectively. The higher GPP and CR were calculated for the same day, when daily averaged water temperature was 28.3?°C, and resulted in a negative NEP of ?56.4?mmol?O₂?m^?2?day^?1. The ecosystem was net heterotrophic during the studied period, probably subsidized by allochthonous organic inputs from ground waters and from the surrounding town and boating activity. Oxygen dynamics and metabolic rates strongly depend on water temperature, with lower oxygen content at higher temperatures. The probability of hypoxic conditions increased at a rate of 0.39?% °C^?1 (±0.14?% °C^?1). Global warming will increase the likelihood of hypoxia in the bay studied, as well as in other semi-enclosed bays.     

Community Oxygen and Nutrient Fluxes in Seagrass Beds of Florida Bay, USA

We used clear, acrylic chambers to measure in situ community oxygen and nutrient fluxes under day and night conditions in seagrass beds at five sites across Florida Bay five times between September 1997 and March 1999. Underlying sediments are biogenic carbonate with porosities of 0.7–0.9 and with low organic content (<1.6%). The seagrass communities always removed oxygen from the water column during the night and produced oxygen during daylight, and sampling date and site significantly affected both night and daytime oxygen fluxes. Net daily average fluxes of oxygen (?4.9 to 49 mmol m^?2 day^?1) ranged from net autotrophy to heterotrophy across the bay and during the 18-month sampling period. However, the Rabbit Key Basin site, located in the west-central bay and covered with a dense Thalassia testudinum bed, was always autotrophic with net average oxygen production ranging from 4.8 to 49 mmol m^?2 day^?1. In November 1998, three of the five sites were strongly heterotrophic and oxygen production was least at Rabbit, suggesting the possibility of hypoxic conditions in fall. Average ammonium (NH₄) concentrations in the water column varied widely across the bay, ranging from a mean of 6.9 μmol l^?1 at Calusa in the eastern bay to a mean of 0.6 μmol l^?1 at Rabbit Key for the period of study. However, average NH₄ fluxes by site and date (?240 to 110 μmol m^?2 h^?1) were not correlated with water column concentrations and did not vary in a consistent diel, seasonal, or spatial pattern. Concentrations of dissolved organic nitrogen (DON) in the water column, averaged by site (15–25 μmol l^?1), were greater than mean NH₄ concentrations, and the range of day and night DON fluxes (?920 to 1,300 μmol m^?2 h^?1), averaged by site and date, was greater than the range of mean NH₄ fluxes. Average DON fluxes did not vary consistently from day to night, seasonally or spatially. Mean silicate fluxes ranged from ?590 to 860 μmol m^?2 h^?1 across all sites and dates, but mean net daily fluxes were less variable and most of the time contributed small amounts of silicate to the water column. Mean concentrations of filterable reactive phosphorus (FRP) in the water column across the bay were very low (0.021–0.075 μmol l^?1); but site average concentrations of dissolved organic phosphorus (DOP) were higher (0.04–0.15 μmol l^?1) and showed a gradient of increasing concentration from east to west in the bay. A pronounced gradient in average surficial sediment total phosphorus (1.1–12 μmol g DW^?1) along an east-to-west gradient was not reflected in fluxes of phosphorus. FRP fluxes, averaged by site and date, were low (?5.2 to 52 μmol m^?2 h^?1), highly variable, and did not vary consistently from day to night or across season or location. Mean DOP fluxes varied over a smaller range (?8.7 to 7.4 μmol m^?2 h^?1), but also showed no consistent spatial or temporal patterns. These small DOP fluxes were in sharp contrast to the predominately organic phosphorus pool in surficial sediments (site means?=?0.66–7.4 μmol g DW^?1). Significant correlations of nutrient fluxes with parameters related to seagrass abundance suggest that the seagrass community may play a major role in nutrient recycling. Integrated means of net daily fluxes over the area of Florida Bay, though highly variable, suggest that seagrass communities might be a source of DOP and NH₄ to Florida Bay and might remove small amounts of FRP and potentially large amounts of DON from the waters of the bay.     

Kinetics of zircon dissolution and zirconium diffusion in granitic melts of variable water content

The experimental dissolution of zircon into a zircon-undersaturated felsic melt of variable water content at high pressure in the temperature range 1,020° to 1,500° C provides information related to 1) the solubility of zircon, 2) the diffusion kinetics of Zr in an obsidian melt, and 3) the rate of zircon dissolution. Zirconium concentration profiles observed by electron microprobe in the obsidian glass adjacent to a large, polished zircon face provide sufficient information to calculate model diffusion coefficients. Results of dissolution experiments conducted in the virtual absence of water (<0.2% H₂O) yield an activation energy (E) for Zr transport in a melt ofM=1.3 [whereM is the cation ratio (Na+K+2Ca)/(Al·Si)] of 97.7±2.8 kcal-mol^?1, and a frequency factor (D ₀) of 980 _?580 ^+1,390 cm²-sec^?1. Hydrothermal experiments provide an E=47.3±1.9 kcal-mol^?1 andD ₀=0.030 _?0.015 ^+0.030 cm²-sec^?1. Both of these results plot close to a previously defined diffusion compensation line for cations in obsidian. The diffusivity of Zr at 1,200° C increases by a factor of 100 over the first 2% of water introduced into the melt, but subsequently rises by only a factor of five to an apparent plateau value of ～2×10^?9 cm²-sec^?1 by ～6% total water content. The remarkable contrast between the wet and dry diffusivities, which limits the rate of zircon dissolution into granitic melt, indicates that a 50 μm diameter zircon crystal would dissolve in a 3 to 6% water-bearing melt at 750° C in about 100 years, but would require in excess of 200 Ma to dissolve in an equivalent dry system. From this calculation we conclude that zircon dissolution proceeds geologically instantaneously in an undersaturated, water-bearing granite. Estimates of zircon solubility in the obsidian melt in the temperature range of 1,020° C to 1,500° C confirm and extend an existing model of zircon solubility to these higher temperatures in hydrous melts. However, this model does not well describe zircon saturation behavior in systems with less than about 2% water.     

Biological uptake and accumulation of silica on the Amazon continental shelf

Water column and seabed samples were obtained from 92 stations on the Amazon continental shelf during October of 1979. Uptake of silica near and southeast of the river mouth began at a salinity of 8%. and accounted for 17% of the riverine silica flux to this region. Uptake northwest of the river mouth began at a salinity of 20%. and resulted in 33% removal of the riverine silica flux. Examination of filtered suspended solids revealed abundant diatoms in the surface waters, including Coscinodiscus. Skeletonema, Synedra. and Thalassiosira. The biological uptake of silica appears to be dependent on three factors: turbidity, turbulence, and nutrient availability. There was no evidence of abiological removal of silica in the Amazon estuary. 75 to 88% of the silica removed from surface waters by diatoms dissolves prior to accumulation in the seabed. Based on the mean biogenic silica content of shelf sediment (0.25%) and estimates of rates of sediment accumulation, the biogenic silica accumulation rate on the shelf is 2 × 10¹² g/yr, which represents only 4% of the dissolved silica supplied by the Amazon River. Biological uptake of silica in estuarine surface waters may not accurately reflect permanent removal of biogenic silica to the seabed because of dissolution which occurs in bottom waters and near the sediment-water interface.     

An XPS study of the dissolution kinetics of chrysotile in 0.1 N oxalic acid at different temperatures

The dissolution of chrysotile is studied in regard to the surfaces analysis by photoelectron spectrometry. After leaching of chrysotile (Provenance: Thetford; about 200 mg of fibers of 1 cm length) in nonstirred 0.1 N oxalic conditions, the composition of the mineral surfaces is determined by XPS; kinetic curves of dissolution are given in the range 22–80°C. Two conditions for the rate-limiting step are involved for the explanation of the dissolution: diffusion of Mg²⁺ through the fibrous gel or dissociation of chrysotile. By the former, some values of the diffusion coefficient are proposed: D varies from 5·10^?19 cm²s^?1 to 5·10^?16 cm²s^?1, in the range 22–80°C. By the second model, the leaching rate is estimated from 3 Å (22°C) per h to 250 Å (80°C) per h. For the 2 models, the activation heat energy is in the range 15–20 Kcal.     

The dissolution kinetics of shallow marine carbonates in seawater: A laboratory study

The dissolution kinetics of shallow water marine carbonates (low-Mg calcite, aragonite and Mg-calcites) were investigated in seawater (S = 35) at 25°C and a P_CO2 of 10^?2.5 atm. using the pH-stat method. Carbonate dissoluton rates (μmoles g^?1 hr^?1) fit the empirical kinetic expression, R = k(1 - Ω)ⁿ, where R = dissolution rate, k = rate constant, Ω = saturation state, and n = order of reaction. Reaction orders were near 2.9 for low-Mg calcites, 2.5 for aragonites and 3.4 for Mg-calcites.The rate constant, k, expressed as μmoles g^?1 hr^?1, varied by nearly a factor of ten for the different samples, reflecting differences in amount of reactive surface area. Reactive surface area of the biogenic phases ranged from 0.3% to 66% of the total surface area determined by the BET gas adsorption method. The discrepancy between reactive and total surface area was greatest for samples with high BET surface areas (> 1 m² g^?1) and delicate microstructures.Relative dissolution rates of the various biogenic carbonates as a function of seawater calcium carbonate ion molal product (IMP) were related to both mineral stability and grain microstructure. In seawater undersaturated with respect to aragonite, finely crystalline aragonites dissolved more rapidly than thermodynamically less stable high Mg-calcites (15–18 mole% MgCO₃) with lower reactive surface areas. Therefore, under certain conditions, differences in grain microstructural complexity can override thermodynamic constraints and lead to selective dissolution of a thermodynamically more stable mineral phase.     

Benthic fluxes and the cycling of biogenic silica and carbon in two southern California borderland basins

Benthic fluxes in two southern California borderland basins have been estimated by modeling water column property gradients, by modeling pore water gradients and by measuring changes in concentration in a benthic chamber. Results have been used to compare the different methods, to establish budgets for biogenic silica and carbon and to estimate rate constants for models of CaCO₃ dissolution. In San Pedro Basin, a low oxygen, high sedimentation rate area, fluxes of radon-222 (86 ± 8 atoms m⁻² s⁻¹), SiO₂ (0.7 ± 0.1 mmol m⁻² d⁻¹), alkalinity (1.7 ± 0.3 meq m⁻² d⁻¹), TCO₂ (1.9 ± 0.3 mmol m⁻² d⁻¹) and nitrate (−0.8 ± 0.1 mmol m⁻² d⁻¹) measured in a benthic chamber agree within the measurement uncertainty with fluxes estimated from modeling profiles of nutrients and radon obtained in the water column. The diffusive fluxes of radon, SiO₂ and TCO₂ determined from modeling the sediment and pore water also agree with the other approaches. Approximately 33 ± 13% of the organic carbon and 37 ± 47% of the CaCO₃ arriving at the sea floor are recycled. In San Nicolas Basin, which has larger oxygen concentrations and lower sedimentation rates than San Pedro, the fluxes of radon (490 ± 16 atoms m⁻² s⁻¹), SiO₂ (0.7 ± 0.1 mmol m⁻² d⁻¹), alkalinity (1.7 ± 0.3 meq m⁻² d⁻¹), TCO₂ (1.7 ± 0.2 mmol m⁻² d⁻¹), oxygen (−0.7 ± 0.1 mmol m⁻² d⁻¹) and nitrate (-0.4 ± 0.1 mmol m⁻² d⁻¹) determined from chamber measurements agree with the water column estimates given the uncertainty of the measurements and model estimates. Diffusion from the sediments matches the lander-measured SiO₂ and PO₄³⁻ (0.017 ± 0.002 mmol m⁻² d⁻¹) fluxes, but is not sufficient to supply the radon or TCO₂ fluxes observed with the lander. In San Nicolas Basin 38 ± 9% of the organic carbon and 43 ± 22% of the CaCO₃ are recycled. Approximately 90% of the biogenic silica arriving at the sea floor in each basin is recycled. The rates of CaCO₃ dissolution determined from chamber flux measurements and material balances for protons and electrons are compared to those predicted by previously published models of CaCO₃ dissolution and this comparison indicates that in situ rates are comparable to those observed in laboratory studies of bulk sediments, but orders of magnitude less than those observed in experiments done with suspended sediments.     

Extent of diagenetic transformations in severely altered biogenic silica deposits from Tunisia: new insights from mineralogy and geochemistry

Sedimentary biogenic silica from Redeyef in Gafsa basin (southern Tunisia) was analysed for its ²⁹Si and ²⁷Al magic angle spinning nuclear magnetic resonance (MAS NMR) spectra and complemented by X-ray diffraction and SEM observations. The ²⁹Si MAS NMR spectrum is characterized by the abundance of hydroxylated silicon, displayed in resonance intensities and reflects a clear tendency towards dissolution of diatomaceous amorphous silica and the occurrence of the hydrated silica, which is the main component that ensures the diagenetic transition via the mechanism of dissolution–precipitation to other more crystalline silica phases, after the lost of its hydroxyls groups (water) by heating (burial). ²⁷Al MAS NMR reveals two coordinations of Al; the octahedrally coordinated Al suggests the presence of clay relics trapped during crystal growth or a microcrystalline zeolite (clinoptilolite detected by SEM observations), while the tetrahedrally coordinated Al suggests the presence of minor quantities of minerals with tetrahedral Al, such as an Al-rich fluid and/or minerals such as feldspars.     

Fluid production rate during the regional metamorphism of a pelitic schist

Phase equilibria modeling of the pressure–temperature (P–T) path of regional metamorphism and associated fluid expulsion, combined with constraints on the timescale of garnet growth by Sm–Nd geochronology, elucidates the fluid production rate and fluid flux during Barrovian metamorphism of pelitic rocks from Townshend Dam, VT, USA. This modeling builds on a published companion study that utilized Sm–Nd geochronology of concentric growth zones in multiple garnet grains, to constrain the duration of garnet growth in a large sample of schist at Townshend Dam to 3.8?±?2.2 million years (Gatewood et al., Chem Geol 401:151–168, 2015). P–T pseudosections combined with observed mineral compositions constrain garnet growth conditions, and were utilized to construct P–T path-dependent thermodynamic forward models. These models determine that garnet growth was initiated at ~?0.6 GPa and ~?525 °C, with a roughly linear loading and heating P–T trajectory to >?0.8 GPa and ~?610 °C. Loading and heating rates of 2.4 km·Myear^?1 (with a range of 1.6 to 5.8 km·million year^?1) and 23 °C·million year^?1 (with a range of 14 to 54 °C·million year^?1), respectively, are consistent with model estimates and chronologic constraints for tectono-metamorphic rates during orogenesis. Phase equilibria modeling also constrains the amount of water release during garnet growth to be ~?0.7 wt% (or >?2 vol%), largely resulting from the complete consumption of chlorite. Coupling this estimate with calculated garnet growth durations provides a fluid production rate of 5.2 kg·m^?3·million year^?1 (with a range of 3.2 to 12.2 kg·m^?3·million year^?1) and when integrated over the overlying crustal column, a regional-scale fluid flux of 0.07–0.37 kg·m^?2·million year^?1. This range of values is consistent with those derived by numerical models and theory for regional-scale, pervasive fluid flow. This study signifies the first derivation of a fluid production rate and fluid flux in regional metamorphism using a direct chronology of water-producing (garnet-forming) reactions and can provide a framework for future studies on elucidating the nature and timescales of fluid release.     

Estimation of authigenic alteration of biogenic and reactive silica in Pearl River estuarine sediments using wet-chemical digestion methods

The extent of authigenic alteration of biogenic and reactive silica in Pearl River estuarine sediments has been estimated using wet-chemical digestion methods. Results show relatively constant distributions of biogenic and reactive Si horizontally and vertically. Based on three core measurements, the biogenic and total reactive Si average 77.91 and 264.77 μmol Si g⁻¹, respectively. Their extents of authigenic alteration are correspondingly estimated as ~55.6 and ~70.6%. The average biogenic Si accumulation rate is calculated as 1.91 × 10⁹ mol Si year⁻¹, which translates into storage of ~7.15% of the annual riverine dissolved silica input. By contrast, the total reactive Si accumulation rate is as high as 6.49 × 10⁹ mol Si year⁻¹, improving annual riverine silicic acid storage to ~24.19%. Detailed investigation is required for a good understanding of early diagenetic process of biogenic and reactive silica in this subtropical area.     

Isolation and chemical characterization of dissolved and particulate polysaccharides in Mikawa Bay

Isolation and chemical elucidation of dissolved and particulate polysaccharides in seawater were conducted. The water samples were collected in Mikawa Bay, Japan during a red tide bloom of the dinoflagellate, Prorocentrum minimum.Dissolved polysaccharides were concentrated from 5–101 of seawater with dialysis followed by separation by gel flitration, and isolation by ethanol precipitation. A heteropolysaccharide consisting of glucose, galactose, mannose, xylose, arabinose, fucose and rhamnose and a glucan were isolated from the polysaccharide component having a molecular weight more than 4,000 Dalton and were characterized by several chemical analyses. The heteropolysaccharide is a mucilaginous polysaccharide having a highly branched structure and a molecular weight of 10⁴?5 × 10⁶ Daltons and probably contains a sulfate half ester: the glucan is a polysaccharide with β-1,3- and 1,6-linkages (chrysolaminaran type). Concentrations of these were respectively ca. 20 and 67 μg l^?1 at 1 m, and 2 and 26 μg l^?1 at 6 m.A similar heteropolysaccharide was found in the boiling water extract of the particulate matter, while β-glucan was isolated in a much less purified form than the seawater β-glucan. In addition, a large amount of β-1,4 glucan was found in the strong alkali extract of the particulate matter, indicating that this glucan must be a cell wall polysaccharide derived from phytoplankton. These results strongly suggest that the heteropolysaccharide and chrysolaminaran type polysaccharide dissolved in seawater were derived from water soluble carbohydrates of phytoplankton through extracellular release or cell lysis.     

The kinetics of the oxidation of ferrous iron in synthetic and natural waters

The rate of oxidation of ferrous iron in a seasonally anoxic lake was measured on 39 occasions with respect to both depth and time. Sample disturbance was minimal as only oxygen had to be introduced to initiate the reaction. The data were consistent with the simple rate law for homogeneous chemical kinetics previously established for synthetic solutions. The rate constant for the oxidation reaction in lake water was indistinguishable from that measured in synthetic samples. It did not appear to be influenced by changes in the microbial populations or by changes in any particulate or soluble components in the water, including iron and manganese. Analysis of the errors inherent in the kinetic measurements showed that the estimation of pH was the major source of inaccuracy and that values of the rate constant determined by different workers could easily differ by a factor of six.The present data, together with a comprehensive survey of the literature, are used to suggest a ‘universal’ rate constant of ca. 2 × 10¹³ M^?2 atm^?1 min^?1 (range 1.5–3 × 10¹³) in the rate law $\text{?d[Fe II]}\text{dt}\text{= k[Fe II]pO}{}_2\text{(OH?)}{}^2$ for natural freshwaters in the pH range 6.5–7.4. Discrepancies in the effects of ionic strength and interfering substances reported in the literature are highlighted. Generally substances have only been found to interfere at concentrations which far exceed those in most natural waters.     

Silicate mineral dissolution at pH 4 and near standard temperature and pressure

The dissolution of labradorite, microcline, enstatite, augite and forsterite in acidified deionized water was investigated at near standard temperature and pressure and constant pH of 4.00 to determine the kinetics of the release of silica, and cations. Saturation indices and mass balance calculations suggest that after 700 hours, the release of silica from forsterite and augite was controlled by the precipitation of a solid silica phase, whereas silica mass transfer from the feldspars and enstatite was essentially as silicic acid. Iron release from the pyroxenes and olivine was probably controlled by the precipitation of iron oxyhydroxide phases. Linear-rate constants calculated after 700 hours for release of magnesium ranged from 10^?15.2 to 10^?14.4 M · cm^?2 s^?1 for augite and forsterite respectively. Linear-rate constants for the release of cations from feldspars ranged from 10^?15.8 to 10^?15.3 M · cm^?2 s^?1.