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.     

Natural enrichment of arsenic in Loch Lomond sediments

Concentrations of arsenic in surface or near-surface sediment in 12 of 13 cores from the three major basins of Loch Lomond are substantially enhanced, up to 675 mg/kg compared with background values of 15–50 mg/kg. Sedimentary As profiles are attributed to post-depositional enrichment processes since there are no recent significant sources of environmental As contamination, anthropogenic or natural, in the Loch Lomond area. The enrichments can be interpreted in terms of post-depositional diagenetic remobilization processes in sediment reducing zones, followed by upward migration of As through interstitial waters and oxidation/adsorption/precipitation reactions in near-surface oxidizing layers. Confirmation of the diagenetic/adsorption hypothesis is provided directly by the analysis of As species (1.5–81 μg/l) in pore water and indirectly via comparison with sedimentary phosphorus.     

The occurrence of Greigite in sediments from Loch Lomond

Greigite has been identified in the sediments of Loch Lomond using X-ray diffraction. Greigite is the dominant magnetic mineral in the oldest sediments recovered, while magnetite predominates in the younger sediments which had previously been used for palaeomagnetic secular variation studies. A layer of sediment in between these two magnetic mineral regimes has very low magnetic concentrations, probably as a consequence of magnetite dissolution associated with sulphide rich pore-waters produced at the time of a marine incursion. The greigite largely oxidises once the sediment is exposed to air, but if freeze dried the greigite becomes surprisingly stable. Following freeze drying the greigite can be heated to 280°C in air before it alters and loses its strong ferrimagnetic properties.     

Particulate metal speciation in surficial sediments from Loch Dee, southwest Scotland, U.K.

The geochemical partitioning of ten elements in stratified Holocene sediments from Loch Dee, southwest Scotland, has been established by use of a five-stage sequential extraction procedure. Samples from below 15 cm sediment depth show minimal evidence of modification by anthropogenic contamination or active diagenesis and hold Fe, Mg, Cu, Cd, Co, Pb, and Ni primarily in detrital silicates or organic complexes, while Mn, Ca, and Zn reside largely in adsorbed and reducible oxide phases. In the uppermost ca 15 cm of sediment, enhanced total concentrations of Zn, Cu, and Pb reflect increased atmospheric deposition during the postindustrial period. Of these metals, only Pb displays any notable adjustment of partitioning in the enriched zone, showing disproportionate accumulation in labile oxides and organic-Pb phases. The lack of Pb and Zn carbonates in the contaminated horizon may reflect inherent thermodynamic instability under the acid surface and pore-water conditions of Loch Dee. Increments to total Mn and Co in the surficial ca 5 cm of sediment are attributable to the accumulation of secondary oxides and adsorbed species, consistent with precipitation from the interstitial pore-waters across a sedimentary redox front. The presence of metals such as Zn and Cd in soluble or acid-volatile phases in the interfacial sediment has implications for the future management of the Loch Dee basin, with leaching into the overlying waters likely, given the continuation of current trends of lake acidification.     

Diagenetic mobilization of manganese in Peru Basin sediments

The Mn contents and sedimentation rates of two cores from different areas of the Peru Basin have been determined. The southern core is associated with Mn nodules of conventional slow accretion rates (~ mm/10⁶ yr) while the northern one accompanies nodules with very high growth rates (~10² mm/10⁶ yr). The depletion of Mn observed within the top 40 cm of the cores is interpreted as resulting from a diagenetic remobilization of Mn⁺² due to the oxidative characteristics of the sedimentary column. In both cores, the calculated flux of Mn provided by the sediment is higher than the total Mn recovered in the overlying nodules. This indicates that the Mn content of the Peru Basin nodules can be supplied by diagenetic processes from the sediment, not only for the slowly growing nodules but also for the extremely fast growing concretions found in the north of the basin.     

Industrialization affects heavy metal and carbon isotope concentrations in recent Baltic Sea sediments

Recent sediment cores of the western Baltic Sea were analyzed for heavy metal and carbon isotope contents. The sedimentation rate was determined from radiocarbon dates to be 1.4 mm/yr. The ‘recent age’ of the sediment was about 850 yr. Within the upper 20 cm of sediment, certain heavy metals became increasingly enriched towards the surface; Cd, Pb, Zn and Cu increased 7-, 4-, 3- and 2-fold, respectively, whereas Fe, Mn, Ni and Co remained unchanged. Simultaneously, the radiocarbon content decreased by about 14 per cent. The enrichment in heavy metals as well as the decrease in the ¹⁴C-concentration during the last 130 ± 30yr parallels industrial growth as reflected in European fossil fuel consumption within that same period of time. The near-surface sediments are affected by residues released from fossil fuels at the rate of about 30 g/m² yr for the past two decades. The residues have a pronounced effect on the heavy metal and carbon isotope composition of the most Recent sediments allowing estimates to be made for sedimentation, erosion and heavy metal pollution.     

Diagenetic migration of sulfides in sediments accumulated in different sedimentation settings

Migration and accumulation of sulfides at the contact of lithologically and geochemically different layers are considered. The possible mechanisms (gravitational, diffusion, elision, and electrogeochemical) for sulfide transportation during diagenesis are discussed. Data are presented to explain the localization of sulfide minerals at the boundary of reduced and oxidized sediments. The paper considers examples of stratiform sulfide concentrations of not only ore grade, but also lower grade, which, however, are of great significance for understanding the formation conditions of some geochemical anomalies. Link between the diagenetic migration of sulfides and the formation of iridium anomaly is substantiated.     

A recent history of metal accumulation in the sediments of the Thames Estuary, United Kingdom

Sediment cores were collected from the Tilbury Tidal Basin in the Thames Estuary to determine the depositional history of metals in the estuary. Profiles of metals in sediments deposited in the lower Thames Estuary show a 30–50% decrease in concentration for Ag, Cd, Cu, Pb, and Zn, and a 70% decrease for Hg in recent decades. Historic depth soundings data showed the decreases in metal concentrations occurred between 1944 and 1966. The decline in sediment metal concentrations has been attributed to reduced inputs to the estuary, following updating of the major sewage treatment works in 1959 and 1963. This is indicated by the through-core distribution of Mn which implies that prior to 1960 the sediments were deposited in anoxic conditions, which subsequently improved. An increase in Mn concentrations observed in one of the cores has been attributed to increases in the dissolved oxygen of the estuarine waters resulting from the increased efficiency of the sewage treatment works.     

Diagenetic cycling of arsenic in the sediments of eutrophic Baldeggersee,Switzerland

Sedimentation and benthic release of As was determined in Baldeggersee, a eutrophic lake in central Switzerland. Sediment traps recorded As sedimentation during 1994, including a flood event in spring. Diagenetic processes were studied using porewater profiles at the sediment–water interface and in deeper sediment strata deposited in the mesotrophic lake (before 1885). Sediment cores were used to calculate the accumulation and to construct the balance of sedimentation and remobilisation. The results showed that the lake sediment acts as an efficient sink for As. Only 22% of the particulate As flux reaching the sediment surface was remobilised at the sediment–water interface. The As accumulation in the recent varved section of the eutrophic lake was 40 mg As m⁻² a⁻¹. Iron reduction in older sediment caused a remobilisation of 1.2 mg As m⁻² a⁻¹. This upward flux from the deeper sediment was quantitatively immobilised in the recent sulfidic sediments. The flood event in spring contributed about 34% of the yearly sediment load and led to distinct peak profiles of dissolved As in the porewater. This evidence for rapid remobilisation disappeared within months.     

Nutrient and metal accumulation in a freshwater tidal marsh

Stratigraphic records from sediment cores collected in a freshwater tidal marsh and in the estuary upstream and downstream from the marsh were used to determine the accumulation of nutrients and trace metals over long time periods. Analysis of pollen and seeds show that the high marsh has formed only within the past 100 yr, following increased sedimentation rates in the area. Variations in nutrient and trace metal accumulations over several decades show that pollutants from agricultural runoff and wastewater discharge are stored to a greater extent in high-marsh than in low-marsh sediments. Greater accumulation rates in the high marsh are probably related to its greater sedimentary organic carbon concentration.     

Early diagenesis of fatty acids in lacustrine sediments—I. Identification and distribution of fatty acids in recent sediment from a freshwater lake

Fatty acids have been isolated and quantitatively determined from a 1.5 m sediment core of Lake Suwa, a eutrophic lake in the central districts of Japan.The fatty acids identified by combined gas chromatography-mass spectrometry were straight-chain saturated (C₁₂ to C₃₄), monounsaturated with even carbon number (C₁₆ to C₂₄) and branched-chain (iso, anteiso, 10-methyloctadecanoic) acids. The concentrations of the higher molecular weight (? C₂₀) saturated fatty acids remained nearly constant throughout the core, suggesting a high degree of preservation of those acids, whereas the monounsaturated and the lower molecular weight saturated fatty acids indicated a great decrease in concentration with depth to an approximately 20cm level. It is suggested that the microbial activity in sediments causes a significant reconstruction of the fatty acid distribution during early diagenesis.     

Early diagenetic behaviour of selenium in freshwater sediments

The vertical distributions of dissolved Se species [Se(IV), Se(VI) and organic Se] and diagenetic constituents [Fe(II) and Mn(II)] were obtained in porewater samples of two Sudbury area lakes (Clearwater and McFarlane). The sedimentary concentration profiles of total Se, Se species bound to Fe–Mn oxyhydroxides and to organic matter, and of elemental Se were also determined along with the concentrations of Fe, Mn and S in different extractable fractions. Results indicated that the concentrations of total dissolved Se in porewater samples were very low, varying from around 2.0 nM to a maximum level of 6.5 nM, while the concentrations of total Se species in the solid phase varied between 2 and 150 nmol/g on a dry weight basis. The two lakes showed striking differences in the presence of Se(IV) and Se(VI) at the sediment–water interface (SWI). In Clearwater Lake, Se(VI) was present at this interface and Se(IV) was not detectable, whereas the opposite was found in McFarlane Lake. This suggests that reducing conditions might have existed near the SWI of McFarlane Lake at the sampling time; this hypothesis was confirmed by several other measured chemical parameters. The profiles of total dissolved Se of both lakes suggest upward and downward diffusion of dissolved Se species along the concentration gradients. Assuming that no precipitation occurred at the SWI, the fluxes of dissolved Se species across the SWI in Clearwater and McFarlane lakes were estimated to be 0.108 and 0.034 nmol cm⁻² a⁻¹, respectively. These values do not include the possible losses of volatile Se species due to microbial methylation. In the reducing sediments of both lakes, the formation of elemental Se and pyritic Se were found to be important mechanisms for controlling the solubility of Se in this environment. The main geochemical processes involving Se identified in this study are: the adsorption of Se onto Fe–Mn oxyhydroxides at or near the SWI, the release of adsorbed Se by the reduction of the same oxyhydroxides and the mineralization of organic matter, and the removal of Se from porewaters to form elemental Se and a S mineral phase such as Se–pyrite or pure ferroselite.     

Diagenetic processes in Holocene carbonate sediments: Florida Bay mudbanks and islands

The sedimentology, mineralogy and pore fluid chemistry of seven cores from the Holocene sediments of Florida Bay were studied to determine the physical processes and diagenetic reactions affecting the sediments. The cores were taken in a transect from a shallow mudbank onto a small adjacent island, Jimmy Key. Steady state models of pore fluid chemistry are used to estimate the rates of various reactions. In the mudbank sediments, little carbonate mineral diagenesis is taking place. No change in sediment mineralogy is detectable and pore water profiles of Ca²⁺, Mg²⁺ and Sr²⁺ show only minor variation. Chloride concentrations indicate substantial biological mixing of seawater from the bay into the sediments in one of the cores. Pore water analyses of sulphate and alkalinity show only a low degree of sulphate depletion and a decreasing extent of sulphate reduction downcore. Models of sulphate reduction in the mudbank show that there is substantial chemical exchange between the sediment pore fluids and water from the bay probably as a result of bio-irrigation. The sulphate and alkalinity data also suggest that the underlying Pleistocene rocks contain water of near normal seawater composition. Stratigraphic analysis and δ¹³C analyses of the organic carbon in the sediments of the island cores show that the sediments were primarily deposited in a subtidal mudbank setting; only the upper 20–30 cm is supratidal in origin. Nevertheless, island formation had a significant effect on pore fluid chemistry and the types of diagenetic reactions throughout the sediment column. Chloride in the sediment pore fluids is more than twice the normal seawater concentrations over most of the depth of the cores. The constant, elevated chloride concentrations indicate that hypersaline fluids which formed in ponds on the island are advected downward through the sediments. Models of the chloride profiles yield an estimate of 2·5 cm yr^?1 as a minimum advective velocity. Changes in pore water chemistry with depth are interpreted as indicating the following sequence of reactions: (1) minor high-Mg calcite dissolution and low-Mg calcite precipitation, from 0 to 35 cm; (2) Ca- or Mg-sulphate dissolution and low-Mg calcite precipitation, from 5 to 35 cm; (3) dolomite or magnesite precipitation together with sulphate reduction, from 35 to 55 cm; and (4) little reaction below 55 cm. In addition, one or more as yet unidentified reactions must be taking place from 5 to 55 cm depth as an imbalance in possible sources and sinks of alkalinity is observed. The imbalance could be explained if chloride is not completely conservative. Despite the pore fluid chemical evidence for diagenetic reactions involving carbonate minerals, no changes in sediment mineralogy were detected in X-ray diffraction analyses, probably because of the comparatively young age of the island.     

Bacterial wax esters in recent fluvial sediments

We investigated the molecular inventory of River Danube sediments and identified wax esters with 28–36 carbons, with C₃₀, C₃₁ and C₃₂ homologs the most abundant. They consist of various combinations of n-, iso- and anteiso-aliphatic acid and alcohol moieties, with different isomer distributions for the esters with odd and even carbon numbers. The short chain length (C₂₈–C₃₆), high proportion of methyl moieties and presence of monounsaturated esters together suggest a bacterial origin for the wax esters. The concentration in surface sediments varied from 0 to 741 μg/kg, being significantly enriched at locations with high nutrient concentration and high primary productivity. Cluster analysis of denaturing gradient gel electrophoresis (DGGE) band patterns revealed different bacterial communities in surface sediments from the stream and surface sediments from the reservoir. The concentration in a 70 cm core of rapidly deposited sediments decreased significantly with depth, following first order kinetics, suggesting a loss of the esters within ca. 3 years following burial and hence a low probability for preservation in the geological record. Wax esters in rivers have rarely been investigated; our results suggest that they represent a bacterial response to enhanced primary production, triggered by higher nutrient supply.     

Long-chain unsaturated ketones in recent lacustrine sediments

C₃₇–C₃₉ ketones containing 2–4 double bonds and similarly-unsaturated C₃₈–C₄₀ ethyl ketones have been detected for the first time in lacustrine sediments. Tetra-unsaturated compounds are relatively more abundant than in marine sediments. The similar molecular composition of methyl ketones and cooccurring ethyl ketones containing one additional carbon atom indicates that the two classes are biosynthetically related.No source of these potential biological markers in lacustrine sediments has been identified. The abundance and unsaturation pattern of alkenones in lacustrine sediments may reflect the relative input and species composition, respectively, of algae presumed to belong to the Phylum Chrysophyta, by analogy with the marine source.     

Nitrogen and phosphorus in the sediments of a tidal,freshwater marsh in Massachusetts

Total organic nitrogen (TON) and phosphorus (TOP) were measured as a function of depth in 14 cores taken from a New England, tidal, freshwater marsh. TON and TOP ranged from 1.56 to 1.97% and 0.11 to 0.30% of dry weight sediments, respectively. The variation in both pool sizes over time was small and TON varied inconsistently with depth; however, TOP decreased regularly down to 20 cm. Consequently, the TON: TOP ratio increased linearly from 14∶1 at the surface to 32∶1 at 20 cm, then was nearly constant to 70 cm. This pattern may be a general feature of marsh sediments and may indicate 1) that phosphorus is recycled less efficiently than nitrogen, 2) that over time proportionately more introgen than phosphorus is incorporated into recalcitrant compounds, or 3) that phosphorus is more mobile than nitrogen in these marsh sediments. The total inorganic nitrogen pool was measured in this marsh also and was dominated by ammonium (97% of total). The annual average free ammonium concentration was 3.70±0.64 mg N per 1 at the surface and decreased to 0.92±0.18 mg N per 1 at 20 to 22 cm in the sediments. Sorptiondesorption studies showed that, on a fresh sediment volume basis, sediment sorbed ammonium was roughly equivalent to free porewater ammonium (K=0.8). The relationship between free and sorbed ammonium was linear between 0.4 and 24.0 mg NH₄·N per 1 of pore water. The depth distribution of ammonium in these sediments is probably maintained by a dynamic balance between net microbial mineralization of litter, plant uptake, transpiration, diffusion, and porewater advection.     

Diagenetic alteration of smectite in argillaceous sediments of the Rhinegraben (SW Germany)

Clay minerals of about 600 samples from drill cores in the Tertiary shales of the Rhinegraben, were analysed by X-ray diffraction methods. It was found that the abundance of smectite decreases with increasing amounts of mixed layer clays and illites, suggesting a diagenetic alteration of smectite with increasing temperatures of the sediments as was also observed in other sedimentary basins. As for the relation between smectite alteration and temperatures as measured in sample depths, in the marine Graue Schichtenfolge (Middle Oligocene) when temperatures reach 70°C and over, smectite no longer is to be found. In the limnic Bunte Niederröderner Schichten (Upper Oligocene) the maximum temperature of smectite occurrence is about 80°C. These temperatures also fit the results of former field studies of the thermal stability of smectite. In the brackish to limnic Obere and Untere Hydrobienschichten (Lower Miocene) however, smectite seems to have disappeared already at a temperature of over 30°C. Although the smectite distribution in the latter formations may depend partly on its inhomogenous deposition there is also evidence for the diagenetic alteration of smectite in these formations. The rapid disappearance of smectite in these formations was possibly caused by a greater availability of potassium ions since high permeability of these strata provide extraordinarily good mobility of the pore solutions. In the older Lymnäenmergel formation (Upper Eocene) a more advanced stage of smectite alteration is found as compared to the other formations at corresponding temperatures. This is considered to be the consequence of the longer duration of diagenesis and the rock salt inclusions of this saline formation which might have enriched the pore solutions with potassium ions.     

海湾水库蓄水初期底质与淡水盐分交换的试验研究

在现场调查和钻探的基础上,采集了沐官岛水库库区3种典型底质(粉质粘土、泥质粉沙和中细砂)的原状/扰动土样和地表水样,然后分别采用静水土柱和动水水槽试验测定盐分的时-空变化规律,最后定量计算出不同底质盐分的释放通量,从而为该海湾水库蓄水初期水质的评价和预测提供了科学依据.土柱试验表明,在分子扩散作用下高盐分区主要集中在水-沉积物界面之上7.5 cm的范围内,7.5 cm之上的水体盐分较为均一,底质盐分释放通量按粉质粘土、中细砂、泥质粉沙的顺序递减,盐分释放通量符合负的幂指数形式,而且抽排界面之上高浓度水体对降低水体盐分含量效果显著.根据水槽模拟试验,风的吹拂会影响到界面之上水体盐分的分层,有利于海湾水库中盐分的混合作用.     

Biological diagenesis: dicarboxylic acids in recent sediments

A series of even carbon numbered α, ω-dicarboxylic acids ranging from C₁₆ to C₂₄ has been identified in recent sediments from various environments and sampling localities. A lacustrine sediment did not show detectable quantities of diacids. Consideration of quantitative relationships involving the diacids leads us to propose a dual origin for these diacids: deposition by mangroves is their main source in mangal areas while in situ production by sedimentary organisms is the only important source of diacids in a non-mangal marine environment. A fresh water lagoon shows an intermediate situation between these extremes.     

Diagenetic control on arsenic partitioning in sediments of the Meghna River delta,Bangladesh

A stratigraphic profile of solid phase As was measured to investigate the diagenetic cycling of arsenic and related elements in fluvial sediments of the Meghna River delta plain. The distributions of Fe, Mn, and Al are typically characterized by surficial solid phase enrichment, and As is distributed down to 36.6 m showing similar alternate layers of maxima and minima with Fe, Mn and TOC, which reflects the diagenetic remobilization and periodical differences in source materials of As. Lithological characteristics and geochemical data suggest that elevated levels of As are found in organic-matter-rich clay and silty sand rather than sand samples, with occasionally enriched As content in iron-oxyhydroxide-coated sand grains. Arsenic demonstrates a positive and significant co-variation with total organic carbon in sediments, which suggests the important role of particulate and colloidal organic matter and biological activity in controlling the distribution of arsenic in the Bengal delta. However, the concentrations of Fe and Mn weakly correlate with As contents, whereas Al contents show no relationship with As. The results of this study suggest that reactive oxides or hydroxides of Fe and Mn, rather than Fe and Mn with other minerals, might control arsenic distribution.