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1.
《Applied Geochemistry》1996,11(4):601-603
An equation is presented for predicting solid/liquid distribution coefficients of radiocaesium on soils and sediments (freshwater and marine). The equation is based on the value of the radiocaesium interception potential of the illitic frayed edge sites of the system and liquid phase composition (K, NH4 and Na). The predictive potential of the equation is tested for some 130 combinations of soil/sediment and water composition covering a three-order-of-magnitude range in KD137Cs values. On average, experimental KD137Cs values exceed predicted values by a factor of 1.62 ± 0.75.  相似文献   

2.
The desorption of 137Cs+ was investigated on sediments from the United States Hanford site. Pristine sediments and ones that were contaminated by the accidental release of alkaline 137Cs+-containing high level nuclear wastes (HLW, 2 × 106 to 6 × 107 pCi 137Cs+/g) were studied. The desorption of 137Cs+ was measured in Na+, K+, Rb+, and NH4+electrolytes of variable concentration and pH, and in presence of a strong Cs+-specific sorbent (self-assembled monolayer on a mesoporous support, SAMMS). 137Cs+ desorption from the HLW-contaminated Hanford sediments exhibited two distinct phases: an initial instantaneous release followed by a slow kinetic process. The extent of 137Cs+ desorption increased with increasing electrolyte concentration and followed a trend of Rb+ ≥ K+ > Na+ at circumneutral pH. This trend followed the respective selectivities of these cations for the sediment. The extent and rate of 137Cs+ desorption was influenced by surface armoring, intraparticle diffusion, and the collapse of edge-interlayer sites in solutions containing K+, Rb+, or NH4+. Scanning electron microscopic analysis revealed HLW-induced precipitation of secondary aluminosilicates on the edges and basal planes of micaceous minerals that were primary Cs+ sorbents. The removal of these precipitates by acidified ammonium oxalate extraction significantly increased the long-term desorption rate and extent. X-ray microprobe analyses of Cs+-sorbed micas showed that the 137Cs+ distributed not only on mica edges, but also within internal channels parallel to the basal plane, implying intraparticle diffusive migration of 137Cs+. Controlled desorption experiments using Cs+-spiked pristine sediment indicated that the 137Cs+ diffusion rate was fast in Na+-electrolyte, but much slower in the presence of K+ or Rb+, suggesting an effect of edge-interlayer collapse. An intraparticle diffusion model coupled with a two-site cation exchange model was used to interpret the experimental results. Model simulations suggested that about 40% of total sorbed 137Cs+ was exchangeable, including equilibrium and kinetic desorbable pools. At pH 3, this ratio increased to 60-80%. The remainder of the sorbed 137Cs+ was fixed or desorbed at much slower rate than our experiments could detect.  相似文献   

3.
We examined the effects of seasonal salinity changes on sediment ammonium (NH4 +) adsorption and exchange across the sediment–water interface in the Parker River Estuary, by means of seasonal field sampling, laboratory adsorption experiments, and modeling. The fraction of dissolved NH4 + relative to adsorbed NH4 + in oligohaline sediments rose significantly with increased pore water salinity over the season. Laboratory experiments demonstrated that small (∼3) increases in salinity from freshwater conditions had the greatest effect on NH4 + adsorption by reducing the exchangeable pool from 69% to 14% of the total NH4 + in the upper estuary sediments that experience large (0–20) seasonal salinity shifts. NH4 + dynamics did not appear to be significantly affected by salinity in sediments of the lower estuary where salinities under 10 were not measured. We further assessed the importance of salinity-mediated desorption by constructing a simple mechanistic numerical model for pore water chloride and NH4 + diffusion for sediments of the upper estuary. The model predicted pore water salinity and NH4 + profiles that fit measured profiles very well and described a seasonal pattern of NH4 + flux from the sediment that was significantly affected by salinity. The model demonstrated that changes in salinity on several timescales (tidally, seasonally, and annually) can significantly alter the magnitude and timing of NH4 + release from the sediments. Salinity-mediated desorption and fluxes of NH4 + from sediments in the upper estuary can be of similar magnitude to rates of organic nitrogen mineralization and may therefore be important in supporting estuarine productivity when watershed inputs of N are low.  相似文献   

4.
《Applied Geochemistry》1998,13(2):155-164
Two issues are addressed in this paper: the solid/liquid distribution behaviour of radiocaesium (137Cs and 134Cs) and radiostrontium (90Sr) in sapropels, and the potential effectiveness of sapropels as amendments to remediate soils contaminated with these radionuclides. It is shown that the solid/liquid partitioning of radiocaesium and radiostrontium in sapropels is governed by the same processes as in soils. Experimental KD values measured in a representative solution vary between 300 and 5000 dm3 kg−1 for radiocaesium and between 15 and 50 dm kg−1 for radiostrontium. These KD values can be interpreted quantitatively on the basis of the main factors which govern the solid/liquid partitioning of these radionuclides.This quantitative approach also allows predictions to be made on the potential effectiveness of sapropel amendments in contaminated soils. These predictions agree very well with experimental results from simple laboratory experiments aimed at investigating the amendment effect. Addition of 1–4 wt.% doses of 2 sapropel samples with different radiocaesium retention characteristics had no significant effect on the radiocaesium distribution coefficient in sandy soils. It is therefore expected that the addition of such sapropels will not result in a decrease of the radiocaesium soil-to-plant transfer, at least not from the point of view of the increase of the radiocaesium retention in the amended soil. Addition of 1–4 wt.% doses of a high CEC sapropel to low CEC sandy soils increased the radiostrontium distribution coefficient up to 3.5 times. It can thus be expected that addition of such high CEC sapropel will increase the radiostrontium retention in the amended soil, and thus decrease the radiostrontium soil-to-plant transfer.  相似文献   

5.
Sorption of Cs to micaceous subsurface sediments from the Hanford site, USA   总被引：1，自引：0，他引：1  
The sorption of Cs+ was investigated over a large concentration range (10−9−10−2 mol/L) on subsurface sediments from a United States nuclear materials site (Hanford) where high-level nuclear wastes (HLW) have been accidentally released to the vadose zone. The sediment sorbs large amounts of radiocesium, but expedited migration has been observed when HLW (a NaNO3 brine) is the carrier. Cs+ sorption was measured on homoionic sediments (Na+, K+, Ca2+) with electrolyte concentrations ranging from 0.01 to 1.0 mol/L. In Na+ electrolyte, concentrations were extended to near saturation with NaNO3(s) (7.0 mol/L). The sediment contained nonexpansible (biotite, muscovite) and expansible (vermiculite, smectite) phyllosilicates. The sorption data were interpreted according to the frayed edge-planar site conceptual model. A four-parameter, two-site (high- and low-affinity) numeric ion exchange model was effective in describing the sorption data. The high-affinity sites were ascribed to wedge zones on the micas where particle edges have partially expanded due to the removal of interlayer cations during weathering, and the low-affinity ones to planar sites on the expansible clays. The electrolyte cations competed with Cs+ for both high- and low-affinity sites according to the trend K+ >> Na+ ≥ Ca2+. At high salt concentration, Cs+ adsorption occurred only on high-affinity sites. Na+ was an effective competitor for the high-affinity sites at high salt concentrations. In select experiments, silver-thiourea (AgTU) was used as a blocking agent to further isolate and characterize the high-affinity sites, but the method was found to be problematic. Mica particles were handpicked from the sediment, contacted with Cs+(aq), and analyzed by electron microprobe to identify phases and features important to Cs+ sorption. The microprobe study implied that biotite was the primary contributor of high-affinity sites because of its weathered periphery. The poly-phase sediment exhibited close similarity in ion selectivity to illite, which has been well studied, although its proportion of high-affinity sites relative to the cation exchange capacity (CEC) was lower than that of illite. Important insights are provided on how Na+ in HLW and indigenous K+ displaced from the sediments may act to expedite the migration of strongly sorbing Cs+ in subsurface environments.  相似文献   

6.
Cs migration in the environment is mainly controlled by sorption onto mineral surfaces, in particular on clay minerals. With the objective of designing a geochemical reactive barrier to treat 137Cs accidental pollution in an industrial waste repository, different natural clayrocks were studied to analyse their capacity to retain Cs.The simple semi-empiric Kd-approach for experimental data analysis, is unsatisfactory to describe the variability of sorption upon chemical changes. Indeed, due to the high salinity of the site, the effects of competitive ions must be evaluated and quantified. Thus, the development of sorption models, capable of reproducing experimental data obtained under conditions representative of the contaminated site, and applicable to reactive transport studies, is needed.In this study, a model for Cs sorption, which takes into account the main mineralogy of the sorbent, the composition of the natural water (and ion competition) was successfully applied to interpret the non-linear Cs sorption under natural conditions.The selectivity coefficients of Cs with respect to the most important cations present in the site water (Na, K, NH4, Ca) were derived by means of experiments in single clay minerals and synthetic mono-component solutions. Then, these parameters were tested in systems of increasing complexity.Considering the mineralogical composition of raw materials, it was shown that the principal contribution to Cs sorption is given by the mineral illite, while smectite starts to be relevant only at very high Cs loadings. Kaolinite, even in concentrations around 10 wt% of the clayey fraction, played only a minor role.With respect to the solution composition, the model was able to predict Cs sorption in electrolyte concentrations up to twice than that of seawater and up to 500 mg/L NH4+. The effect of highly competing ions, especially NH4+ and K+, on Cs retention is more important at low ionic strengths and low Cs loadings, where adsorption is dominated by illite selective frayed edge sites, FES. Divalent cations are not especially relevant as competing cations for Cs.  相似文献   

7.
The composition of river water, sediments, and pore waters (down to 30 cm below the bed) of Las Catonas Stream was studied to analyze the distribution of trace elements in a peri-urban site. The Las Catonas Stream is one of the main tributaries of Reconquista River, a highly polluted water course in the Buenos Aires Province, Argentina. The semi-consolidated Quaternary sediments of the Luján Formation are the main source of sediments for Las Catonas Stream. The coarse-grained fraction in the sediments is mainly composed of tosca (calcretes), intraclasts, bone fragments, glass shards, quartz, and aggregates of fine-grained sediments together with considerably amounts of vegetal remains. The clay minerals are illite, illite–smectite, smectite, and kaolinite. For the clay-sized fraction, the external surface area values are mostly between 70 and 110 m2g?1, although the fraction at 15 cm below the bottom of the river shows a lower surface area of 12 m2g?1. The N2 adsorption–desorption isotherms at 77 K for this sample display a behavior indicative of non-porous or macroporous material, whereas the samples above and below present a typical behavior of mesoporous materials with pores between parallel plates (slit-shaped). As, Cr, Cu, and Cd concentrations increase down to 15 cm depth in the sediments, where the highest trace element and total organic carbon (TOC) concentrations were found, and then decrease toward the bottom of the core. Except for As, the levels of the other heavy metals show higher concentration in surficial waters than in pore waters. Distribution coefficients between the sediments, pore water, and surficial water phases indicate that As is released from the sediments to the pore and surficial waters. Cu content strongly correlates with TOC (mainly from vegetal remains), suggesting that this element is mainly bound to the organic phase.  相似文献   

8.
The content and distribution of NH4-bearing micas in micaschists and paragneisses of the Alpujárride complex (Betic Cordillera, Spain) are interpreted on the basis of textures, metamorphic history and crystal-chemical constraints. NH4 is present in important amounts in early micas, recording their older diagenetic-to-metamorphic history. NH4 was inherited by micas formed in successive metamorphic events. At similar metamorphic grade, annite is enriched in NH4 relative to muscovite with a fractionation of 4:1. Maximum NH4 contents were estimated in golden annite from medium-grade schists and in retrogressive annite-chlorite mixed-layers (~1.0?wt.%). A Ti-NH4 avoidance gives rise to associated chemical changes, such as the enrichment in Mg and in VIAl. These data suggest that NH4 can be a decisive factor in chemical equilibrium and element partitioning between coexisting phases, thus affecting to the commonly used thermobarometers. Estimation of the P-T conditions from texturally different muscovite-annite pairs reveals the superposition of several stages of mica growth, under different geothermal gradients.  相似文献   

9.
Fixed-ammonium in clays associated with crude oils   总被引：3，自引：0，他引：3  
The association of ammonium (NH4+) silicates with organic-rich sedimentary environments has stimulated interest in the chemical cycle of N, and its possible application as an indicator of in situ organic maturation reactions or crude oil migration. Fixed-NH4 in clay minerals was determined from three hydrocarbon occurrences of similar depositional environment but different ages, depth and thermal maturity, to determine whether anomalously high NH4-substitution occurs near mature hydrocarbons. Results show higher fixed-NH4 concentrations in marginally mature mudstones than in immature sediments. The highest fixed-NH4 concentrations were found in clays from sandstone reservoirs containing migrated crude oil.Fixed-NH4 in clays from Holocene oil seep sediments in the Gulf of Mexico continental slope, offshore Louisiana, averages 0.08 wt % and increases with depth in shallow cores (420 cm), reflecting an early diagenetic trend that is apparently not influenced by migrating crude oil. Programmed pyrolysis shows that the sediments are thermally immature (av.Tmax = 419°C). High Hydrogen Index values (av.= 359mg/g) are the result of biodegraded crude oil, and a high Oxygen Index (av.= 182mg/g) reflects the presence of authigenic carbonate.Fixed-NH4 averages 0.16 wt % in Wilcox Group (Eocene) mudstones enclosing two sandstone reservoirs at Fordoche Field, onshore Louisiana. In comparison to these mudstones, anomalously high NH4-fixation appears to occur in reservoir clay minerals. Pyrolysis shows that the sediments are marginally mature for crude oil generation (av.Tmax = 432°C). Average Hydrogen Index (187 mg/g) and Oxygen Index values (75 mg/g) are consistent with oil-prone Type II and Type III kerogen. Increased pyrolysis Production Index values and solvent extraction shows the presence of migrated crude oil. This suggests that a reaction which releases NH3 during crude oil generation or migration is recorded byNH4+ substitution in clays.Fixed-NH4 and total organic carbon (TOC) at Fordoche Field show no statistically significant correlation, suggesting that NH4+ substitution in clay minerals is not simply related to the amount of organic matter in the section, but is also influenced by the presence of crude oil. Once NH4+ has been fixed in clays, it is a more stable hydrocarbon proximity indicator than pore fluid tracers, because it is less influenced by later chemical or geological changes.  相似文献   

10.
Sediment-water oxygen and nutrient (NH4 +, NO3 ?+NO2 ?, DON, PO4 3?, and DSi) fluxes were measured in three distinct regions of Chesapeake Bay at monthly intervals during 1 yr and for portions of several additional years. Examination of these data revealed strong spatial and temporal patterns. Most fluxes were greatest in the central bay (station MB), moderate in the high salinity lower bay (station SB) and reduced in the oligohaline upper bay (station NB). Sediment oxygen consumption (SOC) rates generally increased with increasing temperature until bottom water concentrations of dissolved oxygen (DO) fell below 2.5 mg l?1, apparently limiting SOC rates. Fluxes of NH4 + were elevated at temperatures >15°C and, when coupled with low bottom water DO concentrations (<5 mg l?1), very large releases (>500 μmol N m?2 h?1) were observed. Nitrate + nitrite (NO3 ?+NO2 ?) exchanges were directed into sediments in areas where bottom water NO3 ?+NO2 ? concentrations were high (>18 μM N); sediment efflux of NO3 ?+NO2 ? occurred only in areas where bottom water NO3 ?+NO2 ? concentrations were relatively low (<11 μM N) and bottom waters well oxygenated. Phosphate fluxes were small except in areas of hypoxic and anoxic bottom waters; in those cases releases were high (50–150 μmol P m?2 h?1) but of short duration (2 mo). Dissolved silicate (DSi) fluxes were directed out of the sediments at all stations and appeared to be proportional to primary production in overlying waters. Dissolved organic nitrogen (DON) was released from the sediments at stations NB and SB and taken up by the sediments at station MB in summer months; DON fluxes were either small or noninterpretable during cooler months of the year. It appears that the amount and quality of organic matter reaching the sediments is of primary importance in determining the spatial variability and interannual differences in sediment nutrient fluxes along the axis of the bay. Surficial sediment chlorophyll-a, used as an indicator of labile sediment organic matter, was highly correlated with NH4 ?, PO4 3?, and DSi fluxes but only after a temporal lag of about 1 mo was added between deposition events and sediment nutrient releases. Sediment O:N flux ratios indicated that substantial sediment nitrification-denitrification probably occurred at all sites during winter-spring but not summer-fall; N:P flux ratios were high in spring but much less than expected during summer, particularly at hypoxic and anoxic sites. Finally, a comparison of seasonal N and P demand by phytoplankton with sediment nutrient releases indicated that the sediments provide a substantial fraction of nutrients required by phytoplankton in summer, but not winter, especially in the mid bay region.  相似文献   

11.
Eutrophication of lakes and reservoirs has become a worldwide environmental problem, and nitrogen (N) has been recognized as one of the key factors responsible for eutrophication. Nitrogen adsorbed on sediments may be released via chemical and biological processes under changing environmental conditions. Spatial distributions of concentrations of ammonia nitrogen (NH4 +–N), nitrate nitrogen (NO3 ?–N) and total nitrogen (TN) were investigated in sediments and overlying water of Dongting Lake, the second largest freshwater lake in China. The concentration of TN in the sediments exhibited strong spatial variation with relatively high values in the eastern part and relatively low values in the southern part of the lake. The TN concentration in the water of different regions of Dongting Lake was affected by the internal load of sediment N. The vertical distribution of TN in sediment cores showed a decreasing trend with an increase in depth. Concentrations of NH4 +–N in the sediment cores decreased with the depth increase until 6–8 cm and then increased slowly. However, concentrations of NO3 ?–N in the sediment cores showed an opposite trend from those of NH4 +–N. A kinetic release experiment of NH4 +–N showed that the maximum release rate occurred in the first 5 min and the amount of NH4 +–N release reached 77.93–86.34 % of the total amount in 0–10 min. The release of NH4 +–N in the surface sediments of Dongting Lake fits a first-order kinetics function.  相似文献   

12.
The ammonium contents of biotites in Precambrian rocks from Finland have been determined, to examine the possibility that ammonium in biotites represents a chemical fossil. If biologic activity existed in Precambrian sedimentary environments, biotites formed from the sediments should contain distinctly larger quantities of NH4+ than biotites from igneous rocks.Biotites from Svecokarelidic metasediments, which were originally products of sedimentation about 2400-1900 Ma ago, have high NH4+ contents (hundreds of ppm), while biotites from Svecokarelidic plutonic rocks of 1800–1900 Ma old and Postsvecokarelian rapakivi granites of 1650–1700 Ma old have low NH4+ contents (tens of ppm). The results may indicate that biologic activity was plentiful during sedimentation of the Svecokarelian strata. This agrees with evidence for ancient life found in dolomites and greywacke-slates of the Svecokarelides. Biotites from Presvecokarelidic schists of more than 2600–2800 Ma old have only tens of ppm of NH4+. This value is at the same level as those of biotites from the rapakivi granites and the Svecokarelidic plutonic rocks. Considering the rarity of fossils in Presvecokarelidic rocks, the low NH4+ content of biotite from a Presvecokarelidic pelitic schist may indicate less biologic activity during the sedimentation of the original sediments.These data emphasize that ammonium in biotites of Precambrian metasediments may be a useful chemical fossil for identifying the geologic sites of ancient life.  相似文献   

13.
Benthic nitrogen (N) cycling was investigated at six stations along a transect traversing the Peruvian oxygen minimum zone (OMZ) at 11°S. An extensive dataset including porewater concentration profiles and in situ benthic fluxes of nitrate (NO3−), nitrite (NO2−) and ammonium (NH4+) was used to constrain a 1-D reaction-transport model designed to simulate and interpret the measured data at each station. Simulated rates of nitrification, denitrification, anammox and dissimilatory nitrate reduction to ammonium (DNRA) by filamentous large sulfur bacteria (e.g. Beggiatoa and Thioploca) were highly variable throughout the OMZ yet clear trends were discernible. On the shelf and upper slope (80-260 m water depth) where extensive areas of bacterial mats were present, DNRA dominated total N turnover (?2.9 mmol N m−2 d−1) and accounted for ?65% of NO3− + NO2− uptake by the sediments from the bottom water. Nonetheless, these sediments did not represent a major sink for dissolved inorganic nitrogen (DIN = NO3− + NO2− + NH4+) since DNRA reduces NO3− and, potentially NO2−, to NH4+. Consequently, the shelf and upper slope sediments were recycling sites for DIN due to relatively low rates of denitrification and high rates of ammonium release from DNRA and ammonification of organic matter. This finding contrasts with the current opinion that sediments underlying OMZs are a strong sink for DIN. Only at greater water depths (300-1000 m) did the sediments become a net sink for DIN. Here, denitrification was the major process (?2 mmol N m−2 d−1) and removed 55-73% of NO3− and NO2− taken up by the sediments, with DNRA and anammox accounting for the remaining fraction. Anammox was of minor importance on the shelf and upper slope yet contributed up to 62% to total N2 production at the 1000 m station. The results indicate that the partitioning of oxidized N (NO3−, NO2−) into DNRA or denitrification is a key factor determining the role of marine sediments as DIN sinks or recycling sites. Consequently, high measured benthic uptake rates of oxidized N within OMZs do not necessarily indicate a loss of fixed N from the marine environment.  相似文献   

14.
《Geochimica et cosmochimica acta》1999,63(19-20):3217-3227
A natural illite (illite du Puy) was purified and converted to the homo-ionic Na form. The conditioned Na–illite was characterised in terms of its mineralogy, chemical inventory, and surface properties. The structural formula was determined from EDS analyses (SEM/TEM) and bulk chemistry. A cation exchange capacity of 127 mEq/kg was determined by the Na isotope dilution method at neutral pH.The sorption of Cs was measured as a function of NaClO4 background electrolyte concentration (1.0, 0.1 and 0.01 M), Cs concentration and pH in the range ≈3 to ≈10. Before obtaining these measurements the kinetics of Cs uptake were determined at initial concentrations of 2 × 10−8 M and 7 × 10−5 M, representing the extremes of the range investigated, and was found to be concentration dependent. The supernatant solutions after centrifugation were analysed for major cations in all of the sorption tests.A two-site cation exchange model was developed to describe the sorption of Cs over the whole range of experimental conditions. The two-site types were termed frayed edge sites, FES (high affinity/low capacity) and type II sites (low affinity/high capacity). At low NaClO4 concentrations, Cs sorption decreased at pH values less than neutral. This was interpreted in terms of competitive effects from H, and K released by the partial dissolution of illite, which cannot be avoided at low and high pH values. Selectivity coefficient values for Cs–Na, Cs–K, K–Na, and H–Na exchange equilibria on the FES sites, and Cs–Na exchange on the type II sites are given for illite together with the corresponding site capacities.  相似文献   

15.
《Applied Geochemistry》1996,11(4):589-594
A comparative study is presented on the quantitative characterisation procedures of soils and sediments in terms of specific radiocaesium sorption potentials obtained during elaborate procedures, which include masking techniques, and a simplified protocol relying on a single KD137Csmeasurement. The elaborate and simple procedures were compared for some 120 soils and sediments of widely different origin, covering some three orders of magnitude in specific sorption capacities. The excellent agreement between both procedures provides the basis for a new and simple characterisation procedure which can be used in routine application.  相似文献   

16.
During a semi-lunar tidal cycle from full moon till new moon, tide is characterized by the periodic change in spring and neap tide. Under the in situ conditions of light and temperature, the influence of a semi-lunar spring and neap tidal cycle on nutrient cycling in intertidal flat of the Yangtze estuary was simulated in the laboratory in July 2002. Lab experiments showed that NH4+ and PO43– were always released into overlying waters, while NO3– was directed into sediments in the permanently waterlogged systems, suggesting that the long-term waterlogged sediment acts as a significant source for NH4+ and PO43–, and a sink for NO3– in water columns. In contrast, reflooding of intertidal sediments after long-term desiccation promoted the considerable effluxes of NH4+, NO3– and PO43– into overlying waters, reflecting that the long-term exposed sediment is an important source for nutrients in overlying waters. In addition, the semi-lunar tidal cycle led to the intricate depth distribution patterns of nutrients in intertidal sediments. During long-term exposure, NH4+ in sediments was quickly transformed into NO2– and NO3–, while organic P pool might be converted to slightly adsorbed and iron-bound P. Therefore, it is considered that the semi-lunar tidal circulation has the significant influence on the biogeochemical cycle of nutrients in intertidal systems.  相似文献   

17.
Size fractions <5 μm of Fithian illite were treated with 1 N HCl, H+- from cation-exchange resin, and 5% NH4-EDTA-solution, and analyzed for their Rb-Sr isotopic composition. In comparison to the effects of HCl, the ion-exchange resin leached the same amount of Sr, but significantly less Rb and radiogenic 87Sr from poorly-crystallized 1 M illite.An age of 284 ± 8 Ma (I.R. 0.7109 ± 6 is more or less in agreement with the Missourian (Stephanian) age of deposition. The agreement is fortuitous because of the presence of small amounts of detrital 2 M illite and kaolinite, thus the true age of diagenesis might be somewhat less.87Sr86Sr ratio measurements of Tithonian Solnhofen limestone demonstrate that, even though the silicate component constitutes less than 5% of the total, the majority of the radiogenic 87Sr is leached from “broken-bond” surfaces of the nearly pure kaolinite-residues during the HCl treatment. Ion-exchange and EDTA treatment can be useful in this situation to obtain a precise separation of environmental Sr (in carbonate) from radiogenic 87Sr (in silicates), and an adequate spread of RbSr values from argillaceous fine fractions in the construction of isochrons.  相似文献   

18.
The thermal decomposition of ammonium-exchanged natural analcime is characterized by gas chromatography, IR spectroscopy and X-ray diffraction. The de-ammoniation and dehydroxylation proceed in parallel throughout the decomposition, which evidences the instability of the protonated analcime framework. The mechanism of degassing of NH4-analcime changes throughout its decomposition. At the initial step, the mechanism of de-ammoniation consists in thermal dissociation of NH4+ molecule onto NH3 and proton (framework OH group) and diffusion of NH3 out of the structure. Subsequent decomposition and removal of the OH groups lead to a progressive loss of crystallinity. At this step, an apparent activation energy for NH3 desorption is estimated to be 145(±13) kJ mol–1. This value is within the upper limit of the activation energy characteristic for the NH3 desorption from proton centres in large-pore zeolites. At the final step, the adsorption of NH3 and protons onto the defect centres in the amorphosed aluminosilicate framework results in a significant increase of an apparent activation energy for the de-ammoniation and dehydroxylation up to 270(±20) kJ mol–1.  相似文献   

19.
Benthic metabolism and nutrient exchange across the sediment-water interface were examined over an annual cycle at four sites along a freshwater to marine transect in the Parker River-Plum Island Sound estuary in northeastern Massachusetts, U.S. Sediment organic carbon content was highest at the freshwater site (10.3%) and decreased along the salinity gradient to 0.2% in the sandy sediments at the marine end of the estuary. C:N ratios were highest in the mid estuary (23:1) and lowest near the sea (11:1). Chlorophyll a in the surface sediments was high along the entire length of the estuary (39–57 mg chlorophyll a m−2) but especially so in the sandy marine sediments (172 mg chlorophyll a m−2). Chlorophyll a to phaeophytin ratios suggested most chlorophyll is detrital, except at the sandy marine site. Porewater sulfide values varied seasonally and between sites, reflecting both changes in sulfate availability as overlying water salinity changed and sediment metabolism. Patterns of sediment redox potential followed those of sulfide. Porewater profiles of inorganic N and P reflected strong seasonal patterns in remineralization, accumulation, and release. Highest porewater NH4 + values were found in upper and mid estuarine sediments, occasionally exceeding 1 mM N. Porewater nitrate was frequently absent, except in the sandy marine sediments where concentrations of 8 μM were often observed. Annual average respiration was lowest at the marine site (13 mmol O2 m−2 d−1 and 21 mmol TCO2 m−2 d−1) and highest in the mid estuary (130 mmol O2 m−2 d−1 and 170 mmol TCO2 m−2 d−1) where clam densities were also high. N2O and CH4 fluxes were low at all stations throughout the year: Over the course, of a year, sediments varied from being sources to sinks of dissolved organic C and N, with the overall spatial pattern related closely to sediment organic content. There was little correlation between PO4 3− flux and metabolism, which we attribute to geochemical processes. At the two sites having the lowest salinities, PO4 3− flux was directed into the sediments. On average, between 22% and 32% of total system metabolism was attributable to the benthos. The mid estuary site was an exception, as benthic metabolism accounted for 95% of the total, which is attributable to high densities of filter-feeding clams. Benthic remineralization supplied from less than 1% to over 190% of the N requirements and 0% to 21% of the P requirements of primary producers in this system. Estimates of denitrification calculated from stoichiometry of C and N fluxes ranged from 0% for the upper and mid estuary site to 35% for the freshwater site to 100% of sediment organic N remineralization at the marine site. We hypothesize that low values in the upper and mid estuary are attributable to enhanced NH4 + fluxes during summer due to desorption of exchangeable ammonium from rising porewater salinity. NH4 + desorption during summer may be a mechanism that maintains high rates of pelagic primary production at a time of low inorganic N inputs from the watershed.  相似文献   

20.
A simple, reliable, and high-performance method has been proposed for direct determination of the isotopic composition of authigenic uranium in silica lacustrine sediments. The method is based on studying the kinetics of the selective extraction of authigenic uranium from sediments with weak solutions of ammonium hydrocarbonate followed by the ICP-MS analysis of the nuclides. To estimate the contamination of authigenic uranium by terrigenous one, the contents of 232Th and some other clastogenic elements in the extracts were measured simultaneously. The selectivity of extraction of authigenic uranium from the sediments treated with a 1% NH4HCO3 solution appeared to be no worse than 99%. The method was used to analyze the isotopic composition of authigenic uranium at several key horizons of a core dated before. The measurements directly prove that the 234U/238U values in Baikal water varied depending on climate, which contradicts the previous statements. The measured 234U/238U ratios in paleo-Baikal water match the values reconstructed from isotopic data for total uranium in the sediments on the supposition that the U/Th ratio is constant in the terrigenous part of the sediment. Direct experimental determination of total and authigenic nuclides in sediments enhances the potentiality of the method for absolute 234U-230Th dating of carbonate-barren lacustrine sediments, including those from Lake Baikal, within the intervals corresponding to the periods of glaciation, where the sediments contain a large fraction of terrigenous component. Given the fractions of terrigenous and authigenic uranium are accurately determined, we have an opportunity to study the variability of the sources of terrigenous matter and to refine the previous model for reconstructing the climate humidity in East Siberia.  相似文献   

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