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1.
To ascertain the influence of hydrological boundary conditions on acidity fluxes in lakes influenced by acid mine drainage, acidity budgets were developed for two sediments in areas of differential groundwater inflow (approx. 1 L m?2 d?1 and 10 L m?2 d?1). In both sediments iron was deposited as schwertmannite leading to iron(III) enriched sediments (3.9…6.2 mmol g?1, referred to dry weight). Compared to the surface water, the inflowing groundwater had higher pH (4.5 vs. 3), ferrous iron (6…20 mmol L?1 vs. 0.8…2.0 mmol L?1), and sulfate (5…60 mmol L?1 vs. 8…13 mmol L?1) concentrations. The inflow changed the sediment pore water chemistry and triggered a further increase in pH to above 5.5. In both sediments acidity generation in the surface water (10…30 mol m?2 a?1) strongly prevailed over acidity consumption in the sediments (> ?0.6 mol m?2 a?1). With advective groundwater inflow, however, more acidity was consumed due to TRIS formation (?0.12 mol m?2 a?1 vs. ?0.017 mol m?2 a?1), iron carbonate burial (upper estimate: ?0.14 mol m?2 a?1 vs. ?0.022 mol m?2 a?1), and unspecific ferrous iron retention (?0.39 mol m?2 a?1 vs. ?0.08 mol m?2 a?1). Also, less acidity was generated due to schwertmannite transformation (?2.4 mol m?2 a?1 vs. ?0.11 mol m?2 a?1). The acidity balance of internal processes in the sediment with groundwater inflow was negative, whereas it was positive in the other sediment. The study demonstrates that in acidic and iron rich lakes the hydrological boundary conditions strongly affect geochemical processes as subsumed in acidity fluxes.  相似文献   

2.
3.
Processes controlling the nitrogen (N) exchange between water and sediment in eutrophic Lake Sempach were studied using three different independent methods: benthic flux chambers, interstitial water data and hypolimnetic mass balances. The sediments released NH 4 + (1.1–16.1 mmoles m–2 d–1), NO 2 - (0.1–0.4 mmoles m–2 d–1) and dissolved organic N (<0.25 mmoles m–2 d–1). A net NO 3 - consumption (2.4–11.1 mmoles m–2 d–1) related to the NO 3 - concentrations in the overlying water was observed in all benthic chamber experiments. The flux of the reactive species NO 3 - and NH 4 + was found to depend on hydrodynamic conditions in the water overlying the sediment. For this reason, benthic chambers overestimated the fluxes of inorganic N compared to the other methods. Thus, in short-term flux chamber experiments the sediment may either become a sink or a source for inorganic N depending on the O2 concentration in the water overlying the sediment and the stirring rate. As demonstrated with a15NO 3 - experiment, nitrate-ammonification accounted for less than 12% of the total NO 3 - consumption. After six years of artificial oxygenation in Lake Sempach, a decrease in hypolimnetic total inorganic nitrogen (TIN) was observed in the last two years. The occurrence of dense mats of H2S-oxidizingBeggiatoa sp. indicated micro-aerobic conditions at the sediment surface. Under these conditions, a shorter distance between the ecological niches of nitrifying and denitrifying bacteria, and therefore a faster NO 3 - -transport, can possibly explain the lowering of TIN by enhanced net denitrification.  相似文献   

4.
A critical evaluation of literature values for the solubility products, K sp NBS = [Fe2+][HS] Fe2+ HS (H NBS + )–1, of various iron sulphide phases results in consensus values for the pKs of 2.95 ± 0.1 for amorphous ferrous sulphide, 3.6 ± 0.2 for mackinawite, 4.4 ± 0.1 for greigite, 5.1 ± 0.1 for pyrrhotite, 5.25 ± 0.2 for troilite and 16.4 ± 1.2 for pyrite.Where the analogous ion activity products have been measured in anoxic freshwaters in which there is evidence for the presence of solid phase FeS, the values lie within the range of 2.6–3.22, indicating that amorphous iron sulphide is the controlling phase. The single value for a groundwater of 2.65 (2.98 considering carbonate complexation) agrees. In seawater four values range between 3.85 to 4.2, indicating that mackinawite or greigite may be the controlling phase. The single low value of 2.94 is in a situation where particularly high fluxes of Fe (II) and S (–II) may result in the preferential precipitation of amorphous iron sulphide. Formation of framboidal pyrite in these sulphidic environments may occur in micro-niches and does not appear to influence bulk concentrations. Calculations show that the formation of Fe2S2 species probably accounts for very little of the iron or sulphide in most natural waters. Previously reported stability constants for the formation of Fe (HS)2 and (Fe (HS)3) are shown to be suspect, and these species are also thought to be negligible in natural waters. In completely anoxic pore waters polysulphides also have a negligible effect on speciation, but in tidal sediments they may reach appreciable concentrations and lead to the direct formation of pyrite. Concentrations of iron and sulphide in pore waters can be controlled by the more soluble iron sulphide phase. The change in the IAP with depth within the sediment may reflect ageing of the solid phase or a greater flux of Fe (II) and S (–II) nearer the sediment surface. This possible kinetic influence on the value of IAPs has implications for their use in geochemical studies involving phase formation.  相似文献   

5.
The influence of a further developed inlake restoration method on the P-immobilisation and microbial activities, especially under anoxic conditions was investigated. The impact of nitrate and iron dosing with a newly developed nitrate storage compound (Depox®Fe) was tested in enclosures in the eutrophic dimictic Lake Dagowsee, Germany. Additions of 50 g m−2 of NO3–N and 66 g m−2 of Fe3+ ensured availability of nitrate at the sediment surface during a 2-months period.As a result the phosphate release from the anoxic sediments was completely suppressed even 1 year after the application. The hypolimnetic deoxygenation was unaffected by the Depox®Fe addition. However, sulfur reduction and methanogenesis were inhibited and the phosphatase activity increased.  相似文献   

6.
The flow of carbon and nitrogen in sediments of the far northern and northern sections of the Great Barrier Reef continental shelf was examined. Most of the organic carbon (81–94%) and total nitrogen (74–92%) depositing to the seabed was mineralized, with burial of carbon (6–19%) and nitrogen (8–20%) being proportionally less on this tropical shelf compared with other non-deltaic shelves. Differences in carbon and nitrogen mineralization among stations related best to water depth and proximity to river basins, with rates of mineralization based on net ∑CO2 production ranging from 17 to 39 ( mean=23) mmol C m−2 d−1. The overall ratio of O2:CO2 flux was 1.3, close to the Redfield ratio, implying that most organic matter mineralized was algal. Sulfate reduction was estimated to account for ≈30% (range: 6–62%), and denitrification for ≈5% (range: 2–13%), of total C mineralization; there was no measurable CH4 production. Discrepancies between ∑CO2 production across the sediment–water interface and sediment incubations suggest that as much as 5 mmol m−2 d−1 (≈25% of ∑CO2 flux) was involved in carbonate mineral formation. Most microbial activity was in the upper 20 cm of sediment. Rates of net NH4+ production ranged from 1.6 to 2.7 mmol N m−2 d−1, with highly variable N2 fixation rates contributing little to total N input. Ammonification and nitrification rates were sufficient to support rapid rates of denitrification (range: 0.1–12.4 mmol N m−2 d−1). On average, nearly 50% of total N input to the shelf sediment was denitrified. The average rates of sedimentation, mineralization, and burial of C and N were greater in the northern section of the shelf than in the far northern section, presumably due to higher rainfall and river discharge, as plankton production was similar between regions. The relative proportion of plankton primary production remineralized at the seafloor was in the range of 30–50% which is at the high end of the range found on other shelves. The highly reactive nature of these sediments is attributed to the deposition of high-quality organic material as well as to the shallowness of the shelf, warm temperatures year-round, and a variety of physical disturbances (cyclones, trawling) fostering physicochemical conditions favorable for maintaining rapid rates of microbial metabolism. The rapid and highly efficient recycling of nutrients on the inner and middle shelf may help to explain why the coral reefs on the outer shelf have remained unscathed from increased sediment delivery since European settlement.  相似文献   

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8.
Exchange of groundwater and lake water with typically quite different chemical composition is an important driver for biogeochemical processes at the groundwater‐lake interface, which can affect the water quality of lakes. This is of particular relevance in mine lakes where anoxic and slightly acidic groundwater mixes with oxic and acidic lake water (pH < 3). To identify links between groundwater‐lake exchange rates and acid neutralization processes in the sediments, exchange rates were quantified and related to pore‐water pH, sulfate and iron concentrations as well as sulfate reduction rates within the sediment. Seepage rates measured with seepage meters (?2.5 to 5.8 L m‐2 d‐1) were in reasonable agreement with rates inverted from modeled chloride profiles (?1.8 to 8.1 L m‐2 d‐1). Large‐scale exchange patterns were defined by the (hydro)geologic setting but superimposed by smaller scale variations caused by variability in sediment texture. Sites characterized by groundwater upwelling (flow into the lake) and sites where flow alternated between upwelling and downwelling were identified. Observed chloride profiles at the alternating sites reflected the transient flow regime. Seepage direction, as well as seepage rate, were found to influence pH, sulfate and iron profiles and the associated sulfate reduction rates. Under alternating conditions proton‐consuming processes, for example, sulfate reduction, were slowed. In the uppermost layer of the sediment (max. 5 cm), sulfate reduction rates were significantly higher at upwelling (>330 nmol g‐1 d‐1) compared to alternating sites (<220 nmol g‐1 d‐1). Although differences in sulfate reduction rates could not be explained solely by different flux rates, they were clearly related to the prevailing groundwater‐lake exchange patterns and the associated pH conditions. Our findings strongly suggest that groundwater‐lake exchange has significant effects on the biogeochemical processes that are coupled to sulfate reduction such as acidity retention and precipitation of iron sulfides. Copyright © 2012 John Wiley & Sons, Ltd.  相似文献   

9.
Tropical mobile mud belts represent a major class of biogeochemical and diagenetic systems characterized by extensive and frequent physical reworking of fine-grained, organic-rich deposits underlying oxygenated waters. Large regions of the Gulf of Papua, Papua New Guinea deltaic complex are dominated by such conditions. A reworked mud belt lies within the inner shelf between 10 and 20 m depth on a sedimentary clinoform derived from coalescing deltas. Deposits across the topset are typically suboxic, nonsulfidic over the upper 0.5–1 m, and have low to moderate maximum pore water concentrations of dissolved Fe(II) and Mn(II) (100–200, but up to 800 μM). Sediments are reactive, with surficial ΣCO2 production 0.1–0.3 mM d−1 and benthic O2 fluxes 23±15 mmol m−2 d−1 (upper 20 cm). The highest rates occur within inner topset deposits (10–20 m) and near the high accumulation rollover region of the topset–foreset beds (40–50 m). Lower rates are found inshore along intertidal channels—mangrove fringe and within scoured or exposed consolidated deposits of the middle topset region. Remineralization rate patterns are independent of relative dominance by terrestrial or marine carbon in sediments. Dissolved O2 usually penetrates 2–5 mm into surface sediments when macrofaunal burrows are absent. More than 75% of the highly reactive sedimentary Fe(III) pool (350–400 μmol g−1) is typically diagenetically reduced in the upper 0.5 m. Pore water can be measureably depleted at depths >0.5 m, but dissolved H2S generally remains below detection over the upper 1–2 m. As in other deltaic topset regions, concentration gradients often indicate that compared to many marine deposits of similar sediment accumulation rates, relatively refractory Corg is supplied to the SO4 reducing zone. Sedimentary C/S ratios are 4–6 within the suboxic topset regions but decrease to <3 in offshore foreset beds where sulfidic diagenesis dominates. Only 15–20% of the diagenetically reduced Fe(II) is pyritic and a maximum of 10–25% is carbonate, implying that most Fe(II) is associated with authigenic or lithogenic silicates or oxides. The dominance of suboxic, nonsulfidic diagenetic processes reflect coupling between delivery of oxide-rich terrestrial debris, remobilization and reoxidation of deposits, and repetitive entrainment/remineralization of both labile and refractory organics. Distinct sedimentary indicators of reactive, suboxic mobile mud belts within tropical climatic zones are: abundant total highly reactive Fe (ΣFeR )>300 μmol g−1; most reactive Fe is diagenetically reduced (ΣFe(II)/ΣFeR0.7–0.8); the proportion of diagenetically reduced Fe present as pyrite is low (Py–Fe(II)<0.2); C/S 4–8; and Corg/particle surface area <0.4 (mg C m−2). These depositional environments must be most common in tropical climates during high sea stand.  相似文献   

10.
The effects of temperature, diffusive boundary-layer thickness, and sediment composition on fluxes of inorganic N and P were estimated for sediment cores with oxidized surfaces from nearshore waters (2?C10?m) of a montane oligotrophic lake. Fluxes of N and P were not affected by diffusive boundary-layer thickness but were strongly affected by temperature. Below 16?°C, sediments sequestered small amounts of P and released small amounts of N. Above 16?°C, the seasonal maximum water temperature, sediments were substantial sources of N (NH4 +?CN?=?2?C24?mg?m?2 d?1; NO3 ??+?NO2 ??CN?=?2?C5?mg?m?2 d?1) and P (0.1?C0.4?mg?m?2 d?1), indicating potential responsiveness of sediment?Cwater nutrient exchange, and of corresponding phytoplankton growth, to synoptic warming.  相似文献   

11.
A vacuum microbalance technique has been used to determine the specific surface areas and porosities of suspended solids and sediments from two turbid estuaries. In the Tamar Estuary, the suspended solids had specific surface areas in the range 8–20 m2 g−1 whereas the sediments were in the range 5–15 m2 g−1. Sediments from the iron-rich system of Restronguet Creek were in the range 5–26 m2 g−1. The specific surface areas and porosities of the particles were influenced by the carbon and non-detrital iron contents. The results are relevant to sorption behaviour of dissolved trace constituents in the presence of natural particles.  相似文献   

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13.
The influence of riverine inputs on biogeochemical cycling and organic matter recycling in sediments on the continental shelf off the Rhône River mouth (NW Mediterranean Sea) was investigated by measuring sediment oxygen uptake rates using a combination of in situ and laboratory techniques. Four stations were investigated during two cruises in June 2001 and June 2002, with depths ranging from 9 to 192 m and over a distance to the Rhône River mouth ranging from 4 to 36 km. Diffusive oxygen uptake (DOU) rates were determined using an in situ sediment microprofiler and total oxygen uptake (TOU) rates were measured using sediment core incubations. There was good agreement between these two techniques which indicates that the non-diffusive fraction of the oxygen flux was minimal at the investigated stations. DOU rates ranged from 3.7±0.4 mmol O2 m−2 d−1 at the continental shelf break to 19.3±0.5 mmol O2 m−2 d−1 in front of the Rhône River mouth. Sediment oxygen uptake rates mostly decreased with increasing depth and with distance from the Rhône mouth. The highest oxygen uptake rate was observed at 63 m on the Rhône prodelta, corresponding to intense remineralization of organic matter. This oxygen uptake rate was much larger than expected for the increasing bathymetry, which indicates that biogeochemical cycles and benthic deposition are largely influenced by the Rhône River inputs. This functioning was also supported by the detailed spatial distribution of total organic carbon (TOC), total nitrogen (TN) and C/N atomic ratio in surficial sediments. Sediments of the Rhône prodelta are enriched in organic carbon (2–2.2%) relative to the continental shelf sediments (<1%) and showed C/N ratios exceeding Redfield stoichiometry for fresh marine organic matter. A positive exponential correlation was found between DOU and TOC contents (r2=0.98, n=4). South-westward of the Rhône River mouth, sediments contained highly degraded organic matter of both terrestrial and marine origin, due to direct inputs from the Rhône River, sedimentation of marine organic matter and organic material redeposition after resuspension events.  相似文献   

14.
The occurrence of submarine groundwater discharge (SGD) as well as its supply of many nutrients and metals to coastal seawaters is now generally known. However, previous studies have focused on the chemical and radiological analysis of groundwater, surface seawater, shallow marine sediments and their pore waters, as well as the measurement of upward flow through the marine sediments, as end members of the discharge process. In this study, chemical and isotopic analysis results of marine subsurface waters are reported. These were obtained from deep boreholes of an undersea liquefied petroleum gas (LPG) storage cavern, located about 8 km off the western coast of Korea. The cavern is about 130–150 m below the sea bottom, which is covered by a 4.8–19.5 m silty clay stratum. An isotopic composition (δ2H and δ18O) of the marine subsurface waters falls on a mixing line between terrestrial groundwater and seawater. Vertical EC profiling at the cavern boreholes revealed the existence of a fresh water zone. An increase in the contents of ferrous iron and manganese and a decrease in levels of nitrate, bicarbonate and cavern seepage were recorded in August 2006, indicating a decreased submarine groundwater flux originating from land, mainly caused by an elevated cavern gas pressure. It is suggested in this study that the main source of fresh waters in the man-made undersea cavern is the submarine groundwater discharge mainly originating from the land.  相似文献   

15.
The significance of organic matter origin for carbon oxidation via sulfate and iron reduction in the sediments of three acid mine lakes is analyzed. Carbon reactivity was estimated by fitting first‐order expressions to measured rates. Carbon oxidation rates via sulfate and ferric iron reduction ranged from 3.4 to 4.7 mmol m–2 d–1 and resembled those reported for freshwater lakes. The estimated reaction constants increased from about 10–3 a–1 at the interface to the former mine grounds to 0.05 to 0.2 a–1 at the current sediment‐water interface. Aquatic organic matter accounted for an estimated 45...75% of total carbon oxidation rates while it amounted only to about 5...14% of the total organic matter that had been deposited. The results of this study suggest that in highly acidic mine lakes the reactivity of the deposited organic matter can rapidly increase after flooding, enhancing carbon oxidation and internal neutralization rates in the sediments.  相似文献   

16.
The biogeochemistry of methane in the sediments of Lake Caviahue was examined by geochemical analysis, microbial activity assays and isotopic analysis. The pH in the water column was 2.6 and increased up to a pH of 6 in the deeper sediment pore waters. The carbon isotope composition of CH4 was between − 65 and − 70‰ which is indicative for the biological origin of the methane. The enrichment factor ε increased from − 46‰ in the upper sediment column to more than − 80 in the deeper sediment section suggesting a transition from acetoclastic methanogenesis to CO2 reduction with depth. In the most acidic surface layer of the sediment (pH < 4) methanogenesis is inhibited as suggested by a linear CH4 concentration profile, activity assays and MPN analysis. The CH4 activity assays and the CH4 profile indicate that methanogenesis in the sediment of Lake Caviahue was active below 40 cm depth. At that depth the pH was above 4 and sulfate reduction was sulfate limited. Methane was diffusing with a flux of 0.9 mmol m− 2 d− 1 to the sediment surface where it was probably oxidized. Methanogenesis contributed little to the sediments carbon budget and had no significant impact on lake water quality. The high biomass content of the sediment, which was probably caused by the last eruption of Copahue Volcano, supported high rates of sulfate reduction which probably raised the pH and created favorable conditions for methanogens in deeper sediment layers.  相似文献   

17.
The kinetics of conversion of iron(III) (hydr)oxides to ferrous iron mediated by fulvic acid have been investigated in order to improve the understanding of the redox cycling of iron at the oxic-anoxic boundary in natural waters. Under the conditions similar to natural waters, fulvic acid is able to reduce the iron(III) (hydr)oxide. The kinetics of the reaction depend on the reactivity of iron(III) (hydr)oxides and the reducing power of the fulvic acid. The rate of reaction is 60 nm/h obtained under following conditions: total concentration of Fe(III) 1.0 × 10–4 M, pH 7.5, fulvic acid 5 mg/L. The rate is considered as a net result of reduction and oxidation in the > FeIII-OH/Fe(II) wheel coupled with fulvic acid. In a real natural water system, reductants other than fulvic acid may be of importance. The results obtained in the laboratory, however, provide evidence that the Fe(OH)3(s)/Fe(II) redox couple is able to act as an electron-transfer mediator for the oxidation of natural organic substances, such as fulvic acid by molecular oxygen either in the absence of microorganisms or as a supplement to microbial activity.  相似文献   

18.
δ87Sr values and Ca/Sr ratios were employed to quantify solute inputs from atmospheric and lithogenic sources to a catchment in NW Germany. The aquifer consists primarily of unconsolidated Pleistocene eolian and fluviatile deposits predominated by >90% quartz sand. Accessory minerals include feldspar, glauconite, and mica, as well as disperse calcium carbonate in deeper levels. Decalcification of near-surface sediment induces groundwater pH values up to 4.4 that lead to enhanced silicate weathering. Consequently, low mineralized Ca–Na–Cl- and Ca–Cl-groundwater types are common in shallow depths, while in deeper located calcareous sediment Ca–HCO3-type groundwater prevails. δ87Sr values and Ca/Sr ratios of the dissolved pool range from 7.3 to −2.6 and 88 to 493, respectively. Positive δ87Sr values and low Ca/Sr ratios indicate enhanced feldspar dissolution in shallow depths of less than 20 m below soil surface (BSS), while equilibrium with calcite governs negative δ87Sr values and elevated Ca/Sr ratios in deep groundwater (>30 m BSS). Both positive and negative δ87Sr values are evolved in intermediate depths (20–30 m BSS). For groundwater that is undersaturated with respect to calcite, atmospheric supplies range from 4% to 20%, while feldspar-weathering accounts for 8–26% and calcium carbonate for 62–90% of dissolved Sr2+. In contrast, more than 95% of Sr2+ is derived by calcium carbonate and less than 5% by feldspar dissolution in Ca–HCO3-type groundwater. The surprisingly high content of carbonate-derived Sr2+ in groundwater of the decalcified portion of the aquifer may account for considerable contributions from Ca-containing fertilizers. Complementary tritium analyses show that equilibrium with calcite is restricted to old groundwater sources.  相似文献   

19.
Sediment samples were collected from three seawater aquaculture ponds, and soil characteristics, sediment oxygen consumption (SOC), dissolved organic carbon (DOC) and nutrient fluxes were measured using chamber incubations at laboratory. The three ponds were each representing a specific monoculture or polyculture model of sea cucumber. Total organic carbon (TOC) and total nitrogen (TN) contents in the dry sediment ranged from 0.14 to 0.26% and 0.022 to 0.037%, respectively. Total phosphorus (TP) contents in the sediment were more spatially and temporally variable. SOC ranged from 15.29 to 45.86 mmol m–2 d–1 and showed significant differences among the three ponds (p < 0.05). TOC, total carbon (TC) contents, and SOC of the sediment in the pond polycultured with jellyfish increased with culture time, indicating that jellyfish farming enhanced the accumulation of organic matter in the sediments to some extent. Sediment showed net nitrate and ammonium uptake in most ponds and months, and significant differences were found among months (p < 0.05). Dissolved inorganic phosphate (DIP) was released from the sediments in all ponds with low flux rates. DOC was released from the sediment in all ponds and ranged from 0.67 to 1.74 g DOC m–2 d–1. The results suggested that non‐artificial‐feeding sea cucumber culture ponds could not only yield valuable seafood products, but also effectively remove nutrients from the aquaculture systems and consequently alleviate nutrient loadings of the nearby coast.  相似文献   

20.
The study of the fine structure of the phosphorus and silicon distribution in near-bottom layers and in the interstitial water of the sediments has been carried out in the different Baltic Sea regions (Gulf of Finland, Bornholm, Gotland). The data of this study are used to calculate the flows and effective transport coefficients for mineral phosphorus and silicon exchange processes between sediment and near-bottom layer. The values of nutrient flows varied depending on sediment type from 9.8 to 632 μg-at. m−2 year−1 for phosphorus and from 232.4 to 1881.1 μg-at. m−2 year−1 for silicon. The dependence of the effective transport coefficients versus the distance from the bottom (h) is expressed by empirically-derived equation: Keff = Ah−b. The values of constants “A” and “b” depend on the hydrochemical conditions, sediment type and hydrophysical conditions in the near-bottom layers. Calculated constants for regions are discussed.  相似文献   

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