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1.
Iron and manganese solubility at the sediment/water interface has been studied at a water depth of 20 m in Kiel Bight, Western Baltic. By means of an in situ bell jar system enclosing 3.14 m2 sediment surface and 2094 l water a complete redox turn-over in the bottom water was simulated in an experiment lasting 99 days. The concentration of dissolved Fe in the bell jar water never exceeded 0.041 μmol · dm?3during the first 50 days of the experiment and then rose abruptly as the Eh fell from +600 to ?200 mV. The concentration of dissolved Fe under oxic and anoxic conditions seems to be limited by equilibria with solid Fe-phases (hydroxides and amorphous sulphide, respectively). In contrast to Fe, manganese was released continuously from the bottom during the first 50 days of the experiment leading to exponentially increasing manganese concentrations in the bell jar water. During this time dissolved O2 had become ready depleted and pH had dropped from 8.3 to 7.5. Contrary to iron, manganese being solubilized in reduced sediment layers can penetrate oxic strata in metastable form due to slow oxidation kinetics; when the redoxcline moves upwards Mn2+ is enriched in bottom waters. The maximum concentration of dissolved Mn under anoxic conditions is controlled by a solid phase with solubility properties similar to MnCO3 (rhodochrosite). Bottom water enrichment in dissolved Mn2+ could be traced to originate from excess solid manganese within the top 3 cm of the sediment.  相似文献   

2.
Vertical and horizontal distributions of dissolved and suspended particulate Fe and Mn, and vertical fluxes of these metals (obtained with sediment traps) were determined throughout the Pacific Ocean. In general, dissolved Fe is low in surface and deep waters (0.1 to 0.7 nmol/kg), with maxima associated with the intermediate depth oxygen minimum zone (2.0 to 6.6 nmol/kg). Vertical distributions of dissolved Mn are similar to previous reports, exhibiting a surface maximum, a subsurface minimum, a Mn maximum layer coincident with the oxygen minimum zone, and lowest values in deep waters.Near-shore removal processes are more intense for dissolved Fe than for dissolved Mn. Dissolved Mn in the surface mixed layer remains elevated much farther offshore than dissolved Fe. Elevated near-surface dissolved Mn concentrations occur in the North Pacific Equatorial Current, suggesting transport from the eastern boundary. Near-surface mixed-layer dissolved Mn concentrations are higher in the North Pacific gyre reflecting enhanced northern hemisphere aeolian sources.Residence time estimates for the settling of refractory paniculate Fe and Mn from the upper water column are 62–220 days (Fe), and 105–235 days (Mn). In contrast, residence times for the scavenging of dissolved Fe and Mn are 2–13 years (Fe) and 3–74 years (Mn). Scavenging residence times for dissolved Mn based on horizontal mixing in the surface mixed layer of the northeast Pacific are 0.4 years (nearshore) to 19 years (1000 km offshore).There is no evidence for in situ Fe redox dissolution within sub-oxic waters in the eastern tropical North Pacific. Dissolved Fe appeared to be controlled by dissolution from sub-oxic sediments, with oxidative scavenging in the water column or upper sediment layers. However, in situ Mn dissolution within the oxygen minimum zone was evident.  相似文献   

3.
Particulate Fe and Mn may be important trace metal scavengers in the water column as well as being probable indicators of biologically mediated redox processes. A study has been made of suspended particulate composition in the Santa Barbara Basin, a shallow near-shore basin off southern California with sub-oxic conditions below sill depth. Observations have revealed several interesting phenomena relating to the geochemistry of Fe and Mn. Most striking is a profound enrichment of particulate Fe in samples from the bottom two hundred meters. These particulates have a constant Fe/P mole ratio of about three and may originate at the sediment-water interface or may be transported to the basin from local marshes. For particulate Mn, enrichments are observed both in the sub-sill waters and near the base of the euphotic zone. A consideration of particle removal rates suggests that the sub-photic zone enrichment has a biogenic origin. In the sub-sill waters, enrichment in Mn is apparently due to the precipitation of dissolved Mn diffusing from the anoxic basin sediments. A simple mass balance suggests that most of the Mn lost from the sediments is transported from the Santa Barbara Basin in dissolved form.  相似文献   

4.
Trace metal dynamics in a seasonally anoxic lake   总被引：1，自引：0，他引：1  
Selected results are presented from a detailed 12-month study of trace metals in a seasonally anoxic lake. Dissolved concentrations of Fe, Mn, organic carbon, Cd, Cu, Pb, Zn, and pH were determined in the water column and the interstitial waters on 39 occasions. Trace metal concentrations remained low throughout the year in both water column and pore waters. There was evidence for some remobilization at the sediment-water interface but sediments deeper than 3 cm acted as a sink throughout the year. Variations in the water concentrations were largely associated with increased loading during periods of heavy rainfall. During the summer, concentrations of Cu and Zn in the waters overlying the sediments were enhanced by release from decomposing algal material. Similarly, enhanced concentrations of Cd, Cu, Pb, and Zn were observed during periods of much reduced mixing during ice-cover. Although there were large seasonal variations in the concentrations of dissolved and particulate Fe and Mn, there were no comparable changes in the concentrations of trace metals.  相似文献   

5.
Mn(II) oxidation in the suboxic zone of the water column was studied at four stations in the western Black Sea. We measured Mn(II) oxidation rates using 54Mn tracer and tested the hypothesis of alternative oxidants for Mn(II) other than dissolved oxygen. In anoxic incubation experiments with water from different depths of the chemocline, Mn(II) was not oxidized by nitrite, nitrate, or iodate. In the presence of light, Mn(II) also was not oxidized under anoxic conditions as well. Anaerobic Mn(II) oxidizing microorganisms could not be enriched. In oxic incubation experiments, the addition of alternative oxidants did not significantly increase the Mn(II) oxidation rate. The lack of an anaerobic Mn(II) oxidation in our experiments does not unambiguously prove the absence of anaerobic Mn(II) oxidation in the Black Sea but suggests that dissolved oxygen is the only oxidant for biologically catalyzed Mn(II) oxidation. Lateral intrusions of modified Bosphorus water were shown to be the main mechanism providing dissolved oxygen in the suboxic and the upper anoxic zones and explaining observed Mn(II) oxidation rates. Maximum in situ Mn(II) oxidation rates in the suboxic zone were 1.1 nM Mn(II) per h in the central Black Sea, 25 nM Mn(II) per h on the Romanian continental slope and 60 nM Mn(II) per h on the Anatolian continental slope. These rates correlate with the amount of particulate Mn and the number of Mn-oxide particles and are in agreement with rates measured 13 yr before. Our study highlights the importance of lateral intrusions of oxygen for the ventilation of the suboxic zone and the anoxic interior and for the regulation of different oxidation-reduction processes in the chemocline, including Mn(II) oxidation, which may be significant for other anoxic basins as well.  相似文献   

6.
Pore water and solid phase data for redox-sensitive metals (Mn, Fe, V, Mo and U) were collected on a transect across the Peru upwelling area (11°S) at water depths between 78 and 2025 m and bottom water oxygen concentrations ranging from ∼0 to 93 μM. By comparing authigenic mass accumulation rates and diffusive benthic fluxes, we evaluate the respective mechanisms of trace metal accumulation, retention and remobilization across the oxygen minimum zone (OMZ) and with respect to oxygen fluctuations in the water column related to the El Niño Southern Oscillation (ENSO).Sediments within the permanent OMZ are characterized by diffusive uptake and authigenic fixation of U, V and Mo as well as diffusive loss of Mn and Fe across the benthic boundary. Some of the dissolved Mn and Fe in the water column re-precipitate at the oxycline and shuttle particle-reactive trace metals to the sediment surface at the lower and upper boundary of the OMZ. At the lower boundary, pore waters are not sufficiently sulfidic as to enable an efficient authigenic V and Mo fixation. As a consequence, sediments below the OMZ are preferentially enriched in U which is delivered via both in situ precipitation and lateral supply of U-rich phosphorites from further upslope. Trace metal cycling on the Peruvian shelf is strongly affected by ENSO-related oxygen fluctuations in bottom water. During periods of shelf oxygenation, surface sediments receive particulate V and Mo with metal (oxyhydr)oxides that derive from both terrigenous sources and precipitation at the retreating oxycline. After the recurrence of anoxic conditions, metal (oxyhydr)oxides are reductively dissolved and the hereby liberated V and Mo are authigenically removed. This alternation between supply of particle-reactive trace metals during oxic periods and fixation during anoxic periods leads to a preferential accumulation of V and Mo compared to U on the Peruvian shelf. The decoupling of V, Mo and U accumulation is further accentuated by the varying susceptibility to re-oxidation of the different authigenic metal phases. While authigenic U and V are readily re-oxidized and recycled during periods of shelf oxygenation, the sequestration of Mo by authigenic pyrite is favored by the transient occurrence of oxidizing conditions.Our findings reveal that redox-sensitive trace metals respond in specific manner to short-term oxygen fluctuations in the water column. The relative enrichment patterns identified might be useful for the reconstruction of past OMZ extension and large-scale redox oscillations in the geological record.  相似文献   

7.
New data are presented on the contents of Fe, Mn, Zn, Cu, Pb, Cd, and Ni in dissolved and particulate modes of occurrence in unpolluted or anthropogenically contaminated major rivers of Primorye. The background contents of dissolved metals are as follows: 0.1–0.5 μg/l for Zn and Ni, 0.3–0.7 μg/l for Cu, 0.01–0.04 μg/l for Pb and Cd, and 2–20 μg/l for Fe and Mn. Common anthropogenic loading (communal wastewaters) notably increases the dissolved Fe and Mn concentrations Industrial wastes lead to a local increase in the contents of dissolved metals in river waters by one to three orders of magnitude. The effect of hydrological regime is expressed most clearly in the areas of anthropogenic impact. The metal contents in the particulate matter are controlled mainly by its granulometric composition. Original Russian Text ? V.M. Shulkin, N.N. Bogdanov, V.I. Kiselev, 2007, published in Geokhimiya, 2007, No. 1, pp. 79–88.  相似文献   

8.
The geochemical processes operating on metals in anoxic marine waters influence metal mobility and mode of transport to the sediments in a manner different from that observed in oxic regimes. In order to better understand these processes, dissolved and particulate Mn, Fe, Co, Ni, Cu, Zn, and Cd concentrations were determined in the water column of a permanently anoxic basin, Framvaren Fjord, Norway. Class specific behavior determines the degree to which these metals are involved in the processes of redox cycling at the O2H2S interface and metal sulfide precipitation in the sulfidic water. Metal sulfide precipitation influences the magnitude of metal enrichment in the sediments. The transition metals, Mn, Fe, and Co, show active involvement in redox cycling, characterized by dissolved maxima just below the O2H2S interface. Nickel concentrations appear unaffected by processes influencing the profiles of the other metals. The metals, Cu, Zn, and Cd, display a dramatic solubility decrease across the interface, are not involved in redox cycling, and are enriched in the sediments relative to a lithogenic component by factors of 11, 105, and 420, respectively. Ion activity products of the metals and sulfide provide evidence that chemical equilibria with a pure metal sulfide solid phase is not the dominant process controlling dissolved metal concentrations in the sulfide containing waters.  相似文献   

9.
Trace metal clean techniques were used to sample Hawaii Ocean Time-series (HOT) station ALOHA on seven occasions between November 1998 and October 2002. On three occasions, full water-column profile samples were obtained; on the other four occasions, surface and near-surface euphotic zone profiles were obtained. Together with three other published samplings, this site may have been monitored for “dissolved” (≤0.4 or ≤0.2 μm) Fe more frequently than any other open ocean site in the world.Low Fe concentrations (<0.1 nmol kg−1) are seen in the lower euphotic zone, and Fe concentrations increase to a maximum in intermediate waters. In the deepwaters (>2500 m), the concentrations we observe (0.4-0.5 nmol kg−1) are significantly lower than some other deep North Pacific stations but are similar to values that have been reported for a station 350 miles to the northeast. We attribute these low deepwater values to transport of low-Fe Antarctic Bottom Water into the basin and a balance between Fe regeneration and scavenging in the deep water. Near-surface waters have higher Fe levels than observed in the lower euphotic zone. Significant temporal variability is seen in near-surface Fe concentrations (ranging from 0.2-0.7 nmol kg−1); we attribute these surface Fe fluctuations to variable dust deposition, biological uptake, and changes in the mixed layer depth. This variability could occur only if the surface layer Fe residence time is less than a few years, and based on that constraint, it appears that a higher percentage of the total Fe must be released from North Pacific aerosols compared to North Atlantic aerosols. Surprisingly, significant temporal variability and high particulate Fe concentrations are observed for intermediate waters (1000-1500 m). These features are seen in the depth interval where high δ3He from the nearby Loihi Seamount hydrothermal fields has been observed; the total Fe/3He ratio implies that the hydrothermal vents are the source of the high and variable Fe.The vertical profile of Mn at ALOHA qualitatively resembles other North Pacific Mn profiles with surface and intermediate water maxima, but there are some significant quantitative differences from other reported profiles. The ≤0.4 μm Mn concentration is highest near the surface, decreases sharply in the upper 500 m, then shows an intermediate water maximum at 800 m and then decreases in the deepest waters; these concentrations are higher than observed at a station 350 miles to the northeast that shows similar vertical variations. It appears that there is a significant Mn gradient (throughout the water column) from HOT towards the northeast.Compared to the first valid oceanic Pb data for samples collected in 1976, Pb at ALOHA in 1997-1999 shows decreases in surface waters and waters shallower than 200 m. Pb concentrations in central North Pacific surface waters have decreased by a factor of 2 during the past 25 yr (from ∼65 to ∼30 pmol kg−1); surface water Pb concentrations in the central North Atlantic and central North Pacific are now comparable. We attribute the surface water Pb decrease to the elimination of leaded gasoline in Japan and to some extent by the U.S. and Canada. We attribute most of the remaining Pb in Pacific surface waters to Asian emissions, more likely due to high-temperature industrial activities such as coal burning rather than to leaded gasoline consumption. A 3-year mixed-layer time series from the nearby HALE-ALOHA mooring site (1997-1999) shows that there is an annual cycle in Pb with concentrations ∼20% higher in winter months; this rise may be created by downward mixing of the winter mixed layer into the steep gradient of higher Pb in the upper thermocline (Pb concentrations double between the surface and 200 m). From 200 m to the bottom, Pb concentrations decrease to levels of 5-9 pmol kg−1 near the bottom; for most of the water column, thermocline and deepwater Pb concentrations do not appear to have changed significantly during the 23-yr interval.  相似文献   

10.
《Applied Geochemistry》2003,18(7):1095-1110
The exchange of 226Ra and trace metals across the tailings-water interface and the mechanisms governing their mobility were assessed via sub-centimetre resolution profiling of dissolved constituents across the tailings–water interface in Cell 14 of the Quirke Waste Management Area at Rio Algom's Quirke Mine, near Elliot Lake, Ontario, Canada. Shallow zones (<1.5 m water depth) are characterized by sparse filamentous vegetation, well-mixed water columns and fully oxygenated bottom waters. Profiles of dissolved O2, Fe and Mn indicate that the tailings deposits in these areas are sub-oxic below tailings depths of ∼3 cm. These zones exhibit minor remobilization of Ra in the upper 5 cm of the tailings deposit; 226Ra fluxes at these sites are relatively small, and contribute negligibly to the water column activity of 226Ra. The shallow areas also exhibit minor remobilization of Ni, As, Mo and U. The release of these elements to the water cover is, however, limited by scavenging mechanisms in the interfacial oxic horizons. The presence of thick vegetation (Chara sp.) in the deeper areas (>2 m water depth) fosters stagnant bottom waters and permits the development of anoxia above the benthic boundary. These anoxic tailings are characterized by substantial remobilization of 226Ra, resulting in a relatively large flux of 226Ra from the tailings to the water column. The strong correlation between the porewater profiles of 226Ra and Ba (r2=0.99), as well as solubility calculations, indicate that the mobility of Ra is controlled by saturation with respect to a poorly ordered and/or impure barite phase [(Ra,Ba)SO4]. In the anoxic zones, severe undersaturation with respect to barite is sustained by microbial SO4 reduction. Flux calculations suggest that the increase in 226Ra activity in the water cover since 1995 (from <0.5 to 2.5 Bq l−1) can be attributed to an increase in the spatial distribution of anoxic bottom waters caused by increased density of benthic flora. The anoxic, vegetated areas also exhibit minor remobilization with respect to dissolved As, Ni and Zn. The removal of trace metals in the anoxic bottom waters appears to be limited by the availability of free sulphide. Collectively, the data demonstrate that while the water cover over the U mill tailings minimizes sulphide oxidation and metal mobility, anoxic conditions which have developed in deeper areas have led to increased mobility of 226Ra.  相似文献   

11.
Microorganisms play important roles in mediating biogeochemical reactions in deep-sea hydrothermal plumes, but little is known regarding the mechanisms that underpin these transformations. At Guaymas Basin (GB) in the Gulf of California, hydrothermal vents inject fluids laden with dissolved Mn(II) (dMn) into the deep waters of the basin where it is oxidized and precipitated as particulate Mn(III/IV) oxides, forming turbid hydrothermal “clouds”. Previous studies have predicted extremely short residence times for dMn at GB and suggested they are the result of microbially-mediated Mn(II) oxidation and precipitation. Here we present biogeochemical results that support a central role for microorganisms in driving Mn(II) oxidation in the GB hydrothermal plume, with enzymes being the primary catalytic agent. dMn removal rates at GB are remarkably fast for a deep-sea hydrothermal plume (up to 2 nM/h). These rapid rates were only observed within the plume, not in background deep-sea water above the GB plume or at GB plume depths (∼1750-2000 m) in the neighboring Carmen Basin, where there is no known venting. dMn removal is dramatically inhibited under anoxic conditions and by the presence of the biological poison, sodium azide. A conspicuous temperature optimum of dMn removal rates (∼40 °C) and a saturation-like (i.e. Michaelis-Menten) response to O2 concentration were observed, indicating an enzymatic mechanism. dMn removal was resistant to heat treatment used to select for spore-forming organisms, but very sensitive to low concentrations of added Cu, a cofactor required by the putative Mn(II)-oxidizing enzyme. Extended X-ray absorption fine structure spectroscopy (EXAFS) and synchrotron radiation-based X-ray diffraction (SR-XRD) revealed the Mn oxides to have a hexagonal birnessite or δ-MnO2-like mineral structure, indicating that these freshly formed deep-sea Mn oxides are strikingly similar to primary biogenic Mn oxides produced by laboratory cultures of bacteria. Overall, these results reveal a vigorous Mn biogeochemical cycle in the GB hydrothermal plume, where a distinct microbial community enzymatically catalyzes rapid Mn(II) oxidation and the production of Mn biooxides.  相似文献   

12.
The effects of freshwater infaunal invertebrates on sediment geochemical properties were studied through an experimental approach using indoor microcosms during a 56-day experiment. The bioturbating organisms were tubificid worms, which consume sediment at depth and deposit undigested material at the sediment?Cwater interface. Bioturbation intensity was determined using fluorescent tracers, and the distribution of redox-sensitive compounds was studied from replicate experimental units handled 7, 14, 21, 28 and 56?days after tubificid colonization. Worm activity transferred reduced particles and pore water at the sediment surface at a rate of 0.14?cm?day?1. Compared to control experimental units, this recycled material represented at the end a several centimetre-thick layer enriched in water content, dissolved nitrate and sulphate, and depleted in oxygen, ammonium and dissolved Mn(II). Tubificids consumed O2 in bottom water, so that the sediment was anoxic, allowing a direct flux of dissolved reduced species into overlying water. Lower ammonium and Mn(II) concentrations and fluxes in anoxic sediment possibly resulted from a decrease in anaerobic microbial metabolism due to competition for labile organic carbon with tubificids. Higher sulphate concentration resulted from burial of surface waters with particle at the sediment surface, but not from bio-irrigation of burrows. Nitrate was produced in anoxic condition, as observed in almost every mixed modern sediments.  相似文献   

13.
The biogeochemistry of iron sulfide minerals in the water column of the Cariaco Basin was investigated in November 2007 (non-upwelling season) and May 2008 (upwelling season) as part of the on-going CARIACO (CArbon Retention In A Colored Ocean) time series project. The concentrations of particulate sulfur species, specifically acid volatile sulfur (AVS), greigite, pyrite, and particulate elemental sulfur, were determined at high resolution near the O2/H2S interface. In November 2007, AVS was low throughout the water column, with the highest concentration at the depth where sulfide was first detected (260 m) and with a second peak at 500 m. Greigite, pyrite, and particulate elemental sulfur showed distinct concentration maxima near the interface. In May 2008, AVS was not detected in the water column. Maxima for greigite, pyrite, and particulate elemental sulfur were again observed near the interface. We also studied the iron sulfide flux using sediment trap materials collected at the Cariaco station. Pyrite comprised 0.2-0.4% of the total particulate flux in the anoxic water column, with a flux of 0.5-1.6 mg S m−2 d−1.Consistent with the water column concentration profiles for iron sulfide minerals, the sulfur isotope composition of particulate sulfur found in deep anoxic traps was similar to that of dissolved sulfide near the O2/H2S interface. We conclude that pyrite is formed mainly within the redoxcline where sulfur cycling imparts a distinct isotopic signature compared to dissolved sulfide in the deep anoxic water. This conclusion is consistent with our previous study of sulfur species and chemoautotrophic production, which suggests that reaction of sulfide with reactive iron is an important pathway for sulfide oxidation and sulfur intermediate formation near the interface. Pyrite and elemental sulfur distributions favor a pathway of pyrite formation via the reaction of FeS with polysulfides or particulate elemental sulfur near the interface. A comparison of thermodynamic predictions with actual concentration profiles for iron sulfides leads us to argue that microbes may mediate this precipitation.  相似文献   

14.
Montmorillonite, kaolinite, goethite, and particulate and soluble natural organic materials influence the rate of Mn(II) oxidation. While surfaces accelerate the reaction, apparently by bonding Mn2+ in a manner which fulfills the requirements of the transition state, soluble organic materials retard the reaction by complexing the oxidizable species. It is doubtful whether particulate matter would influence the oxidation process under natural loading conditions since 50–500 mg l?1quantities are required to produce measurable changes in the reaction rate. Complexation by humic materials, however, might be expected to reduce the rate of oxidation by an amount proportional to the dissolved organic carbon concentration. Oxidation followed by precipitation is predicted to be an important mechanism for Mn2+ removal in oceanic waters. The situation is less predictable in lake waters.  相似文献   

15.
《Applied Geochemistry》1995,10(2):237-250
The geochemistry of metal-rich mine waters and mineral precipitates from the Levant mine, Cornwall, has been examined. Sulphide oxidation at Levant mine has produced a wide range of secondary sulphides, oxides, chlorides, sulphates and carbonates in a gossan environment. The mine waters display a wide variation in alkalinity, pH, chloride, sulphate, sodium, potassium and heavy metal content which can be explained by variable degrees of mixing between acidic, metal-rich, rock drainage waters and neutral to alkaline sea waters. Transition metals are soluble in the acidic mine waters with concentrations up to 665 mg/l Cu, 41 mg/l Zn, 76 mg/l Mn, 6 mg/l Co and >2500 mg/l total Fe. The production of acid rock drainage and leaching of metals can be related to sulphide oxidation. Where these metal-rich acidic waters mix with infiltrated sea water, neutralization occurs and some metals are precipitated (principally Cu). Where pools of mine drainage are stagnant native copper and cuprite are precipitated, frequently observed replacing iron pipes and rail tracks and wooden shaft supports, due to electrode potential differences. In these solutions, dissolved copper species are also reduced by interaction with wood-derived organic species. Precipitation of iron oxyhydroxides, caused by a pH increase, also occurs and leads. to coprecipitation of other metals, including Cd, Co, Ph, Mn, Ag and Zn, thus limiting the release of dissolved metals in solution from the mine. However, the release of suspended metal-rich ochres in mine discharge waters (with high Ph, Zn, Cd, Mn, Ni, Sn, Sb, As, Bi, Cu, Co and Ag) will still present a potential environmental hazard.  相似文献   

16.
Naturally-occurring radionuclides (uranium, radium, and radon), major dissolved constituents, and trace elements were investigated in fresh groundwater in 117 wells in fractured crystalline rocks from the Piedmont region (North Carolina, USA). Chemical variations show a general transition between two water types: (1) slightly acidic (pH 5.0–6.0), oxic, low-total dissolved solids (TDS) waters, and (2) near neutral, oxic to anoxic, higher-TDS waters. The uranium, radium, and radon levels in groundwater associated with granite (Rolesville Granite) are systematically higher than other rock types (gneiss, metasedimentary, and metavolcanic rocks). Water chemistry plays a secondary role on radium and radon distributions as the 222Rn/226Ra activity ratio is correlated with redox-sensitive solutes such as dissolved oxygen and Mn concentrations, as well as overall dissolved solids content including major divalent cations and Ba. Since 224Ra/228Ra activity ratios in groundwater are close to 1, we suggest that mobilization of Ra and Rn is controlled by alpha recoil processes from parent nuclides on fracture surfaces, ruling out Ra sources from mineral dissolution or significant long-distance Ra transport. Alpha recoil is balanced by Ra adsorption that is influenced by redox conditions and/or ion concentrations, resulting in an approximately one order of magnitude decrease (~ 20,000 to ~ 2000) in the apparent Ra distribution coefficient between oxygen-saturated and anoxic conditions and also across the range of dissolved ion concentrations (up to ~ 7 mM). Thus, the U and Th content of rocks is the primary control on observed Ra and Rn activities in groundwater in fractured crystalline rocks, and in addition, linked dissolved solids concentrations and redox conditions impart a secondary control.  相似文献   

17.
Trace metals (Mn, Fe, Mo, U, Cr, V) were studied in pore waters of an intertidal flat located in the German Wadden Sea. The study system is an example of a permeable tidal flat system where pore water exchange is affected by tidal driven pressure gradients besides diffusion. Permanently installed in situ samplers were used to extract pore waters down to 5 m depth throughout one year. The samplers were either located close to the tidal flat margin or in central parts of the tidal flat. Despite dynamic sedimentological and hydrological conditions, the general trends with depth in deep tidal flat pore waters are remarkably similar to those observed in deep sea environments. Rates of trace metal cycling must be comparably large in order to maintain the observed pore water profiles. Trace metals further show similar general trends with depth close to the margin and in central parts of the tidal flat. Seasonal sampling revealed that V and Cr vary concurrent with seasonal changes in dissolved organic carbon (DOC) concentration. This effect is most notable close to the tidal flat margin where sulphate, DOC, and nutrients vary with season down to some metres depth. Seasonal variations of Mn, Fe, Mo, and U are by contrast limited to the upper decimetres of the sediment. Their seasonal patterns depend on organic matter supply, redox stratification, and particulate matter deposited on sediment surfaces. Pore water sampling within one tidal cycle provides evidence for pore water advection in margin sediments. During low tide pore water flow towards the creekbank is generated by a hydraulic gradient suggesting that deep pore waters may be seeping out of creekbank sediments. Owing to the enrichment of specific elements like Mn in pore water compared to sea water, seeping pore waters may have an impact on the chemistry of the open water column. Mass balance calculations reveal that the impact of deep pore waters on the Mn budget in the open water column is below 4%. Mn deep pore water discharge of the whole Wadden Sea is estimated to be about 9% of the total dissolved riverine Mn input into the Southern North Sea.  相似文献   

18.
The Riogrande II reservoir in Colombia has a total storage capacity of 240 million m3 and lies 2,270 m above sea level. The reservoir is used for power generation, water supply and environmental improvement. Dissolved manganese (Mn) is removed from reservoir water dedicated to domestic use by purification processes. Removal of Mn, however, poses a major challenge to purification processes and warrants the study of ways to naturally reduce dissolved Mn levels in the reservoir. The source of Mn within the reservoir is not well understood, however, presumably arises from sediment mobilization initiated by variation in pH, redox potential (ORP or Eh), dissolved oxygen (O2) and ionic strength conditions. This study investigated conditions within the reservoir to further understand Mn transfer from the sediment into the water column. O2, pH, oxidation–reduction potential (ORP or Eh), organic matter content and electric conductivity were measured in water samples and sediment from the reservoir. Sequential extraction (SE) procedures were used to test the specific effects exerted by each of these conditions on Mn mobilization from the sediments. The European Community Bureau of Reference (BCR) sequential extraction procedure was used to quantify metals in sediment (referred to as the BCR extraction below). Statistical analysis of geochemical data from water samples (both water column and sediment pore water) and sediments demonstrated the conditions under which Mn can be released from sediments into the water column. The results indicated a primarily oxic water column and anoxic reducing conditions in the sediment (ORP or Eh ≤ ?80 mV). The pH of water in contact with bottom sediments varied from 7.6 to 6.8. The pH of sedimentary pore water varied from 6.8 to 4.7. The sediments contained significant amounts of organic matter (20 %). Chemical extractions showed that the exchangeable fraction contained over 50 % of the total Mn within sediments. Microscopic analysis using scanning electron microscopy–energy dispersive spectroscopy (SEM–EDS) indicated that Mn does not occur within well-crystallized mineral phases in the Riogrande II sediments. A large proportion of Mn exists instead as material adsorbed onto the surfaces of recently deposited sediment particles. Bacterial oxidation of organic matter may cause the observed anoxic conditions at the bottom of the reservoir. Mineralization of organic matter therefore contributes to reducing conditions within the sediments. Mobilization of Mn from the sediment into the water column may result from reductive dissolution of this fraction. Manganese release by this mechanism diminishes the water quality of the Riogrande II reservoir and warrants further study.  相似文献   

19.
The distributions of particulate elements (Al, P, Mn, Fe, Co, Cu, Zn, Cd, and Pb), dissolved trace metals (Mn, Fe, Co, Cu, Zn, and Cd), and dissolved nutrients (nitrate, phosphate, and silicic acid) were investigated in the Gulf of the Farallones, a region of high productivity that is driven by the dynamic mixing of the San Francisco Bay plume, upwelled waters, and California coastal surface waters. Particulate metals were separated into >10 and 0.4-10 μm size-fractions and further fractionated into leachable (operationally defined with a 25% acetic acid leach) and refractory particulate concentrations. Dissolved metals (< 0.4 μm pore-size filtrate) were separated into colloidal (0.03-0.4 μm) and soluble (<0.03 μm) fractions. The percent leachable particulate fractions ranged from 2% to 99% of the total particulate concentration for these metals with Mn and Cd being predominantly leachable and Fe and Al being predominantly refractory. The leachable particulate Pb concentration was associated primarily with suspended sediments from San Francisco Bay and was a tracer of the plume in coastal waters. The particulate trace metal data suggest that the leachable fraction was an available source of trace metal micronutrients to the primary productivity in coastal waters. The dissolved trace metals in the San Francisco Bay plume and freshly upwelled surface waters were similar in concentration, with the exception of Cu and Co, which exhibited relatively high concentrations in plume waters and served as tracers of this water mass. The dissolved data and estimates of the plume dynamics suggest that the impact of anthropogenic inputs of nutrients and trace metals in the San Francisco Bay plume contributes substantially to the concentrations found in the Gulf of the Farallones (10-50% of estimated upwelled flux values), but does not greatly disrupt the natural stoichiometric balance of trace metal and nutrient elements within coastal waters given the similarity in concentrations to sources in upwelled water. In all, the data from this study demonstrate that the flux of dissolved nutrients and bioactive trace metals from the San Francisco Bay plume contribute to the high and relatively constant phytoplankton biomass observed in the Gulf of the Farallones.  相似文献   

20.
Two laboratory microcosm experiments were conducted to mimic an annual spring diatom bloom in South San Francisco Bay by isolating the phytoplankton community from the benthic grazing pressure to induce a phytoplankton bloom. The purpose of these experiments was to isolate the impact of a spring diatom bloom on the nutrient and trace metal geochemical cycling. Microcosms were created in 2.5 L incubation bottles and subjected to one of 4 treatments (control, copper [Cu] addition, manganese [Mn] addition, and both Cu and Mn addition) to investigate the toxicity of Cu on the resident plankton and the potential antagonistic effects of Mn on reducing Cu toxicity. Dissolved macronutrient (nitrate + nitrite, phosphate, and silicate), and dissolved and particulate trace metal (Cu, Ni, Mn) concentrations were monitored in the grow-out incubations on a daily basis. Chlorophylla concentrations were also monitored over the course of the experiment and used to calculate diatom-specific growth rates. In the experiments containing ambient South San Francisco Bay surface waters, average specific growth rates were on the order of 1.1 d?1. The induced diatom blooms resulted in significant removal of macronutrients from the microcosms over the course of the experiments. Our research supports previous suggestions that dissolved Ni and Cu concentrations in South San Francisco Bay have a very low biological availability as a result of organic chelation. Ni(EDTA)2? has been found to be the dominant dissolved Ni species by other researchers and Cu speciation analyses from this study and others indicate that > 99% of the dissolved Cu in South San Francisco Bay is strongly chelated as CuL1. The free cupric ion concentration was on the order of 10?12 M. Marked removal of dissolved Mn was observed in the control treatments, well exceeding expected dissolved Mn removal by diatom uptake. Additions of 375 nM Cu resulted in the complete titration of the chelating ligand (L1) concentrations. The elevated [Cu2+] (≈10?8MM) appeared to have a toxic effect on the diatom community observed in the significant decreases in their specific growth rates (μ=0.4 d?1). The suppression of dissolved Mn removal from solution was also observed in treatments spiked with high levels of dissolved Cu, providing support that Mn precipitation was due to biologically mediated oxidation not phytoplankton assimilation. The observed geochemical behavior in the concurrent Cu and Mn addition treatments provide evidence in support of Mn alleviation of Cu toxicity. The biological role in the ambient short-term biogeochemical cycling of Cu and Ni in South San Francisco Bay appears to be minimal due to the inert character of the organic ligand-metal complexes. A significant portion of the annual macronutrient and Mn cycling occurs as a result of spring diatom blooms in South San Francisco Bay.  相似文献   

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