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1.
Depth profiles of the naturally-occurring radionuclides 238U, 234U, 226Ra, 228Ra and 228Th were obtained in two diverse anoxic marine environments; the permanently anoxic Framvaren Fjord in southern Norway and the intermittently anoxic Saanich Inlet in British Columbia. Concentrations of total H2S were over three orders of magnitude greater in the anoxic bottom waters of Framvaren Fjord compared to those in Saanich Inlet.In Framvaren Fjord, the O2/H2S interface was located at 17 m. While dissolved 238U behaved conservatively throughout the oxic and anoxic water columns, concentrations based on the 238U/salinity ratio in oxic oceanic waters were almost 30% lower. Dissolved 226Ra displayed a sharp maximum just below the O2/H2S interface, coinciding with dissolved Mn (II) and Fe (II) maxima in this zone. It is suggested that reductive dissolution of Fe-Mn oxyhydroxides remobilizes 226Ra in this region.In Saanich Inlet, the O2/H2S interface was located at 175 m. Dissolved 238U displayed a strongly nonconservative distribution. The depth profiles of dissolved 226Ra and 228Th correlated well with the distribution of dissolved Mn (II) in the suboxic waters above the O2/H2S interface, suggesting that reduction of particulate Mn regulates the behavior of 226Ra and 228Th in this region.Removal residence times for dissolved 228Th in the surface oxic waters of both systems are longer than those generally reported for particle-reactive radionuclides in coastal marine environments. In the anoxic waters of Framvaren Fjord and Saanich Inlet, however, the dissolved 228Th removal residence times are quite similar to values reported for dissolved 210Pb in the anoxic waters of the Cariaco Trench and the Orca Basin. This implies that the geochemistries of Th and Pb may be similar in anoxic marine waters.  相似文献   

2.
The content and the oxidation state of arsenic and antimony in coastal seawater were determined coupled with chemical separation and neutron activation method. The contents of arsenic and antimony in coastal seawater were estimated to be 1.56–2.73g As/l, 0.25–0.57g Sb/l. Most parts of these elements exist as soluble ionic species, passing through 0.45 pore-size membrane filter, and at surface, 80–97% of arsenic occurs as arsenate and 70–94 % of antimony may occurs as antimonate. The vertical distribution of arsenite and arsenate is almost constant from the surface to 1,200 m depth. However the distribution of Sb(III) and Sb(V) is much more complicated with depth.  相似文献   

3.
The concentrations of arsenic species in continental-shelf waters of the southeastern U.S. are controlled mainly by simple physical mixing of shelf waters and Gulf Stream intrusions. The biota mediate redox reactions which result in a disequilibrium of arsenic species; up to 20% of the total arsenic (averaging 1.1 μg/l) occurs as unstable arsenite [As (III)] and dimethylarsenic, the remainder consists of thermodynamically favored arsenate [As (V)]. Uptake of arsenic by the biota has a minor effect on arsenic distribution in offshore waters, producing a deep-water arsenate maximum, and minima for arsenite and dimethylarsenic. Riverine and atmospheric arsenic inputs to the shelf waters are relatively insignificant. Southeastern rivers contain only about 0.3 μg/l dissolved arsenic, and the atmosphere adjacent to continental shelf waters contains about 1.7 ng/m3 of As (V), exclusively associated with the particulate fraction.  相似文献   

4.
《Marine Chemistry》2001,73(1):37-51
Vertical profiles of 14C-uptake were acquired monthly from the mouths and landward stations of periodically anoxic Saanich Inlet and oxygenated Jervis Inlet, British Columbia, Canada from August 1985 to October 1989. Saanich Inlet (490 g C m−2 year−1) was 1.7 times more productive than Jervis Inlet (290 g C m−2 year−1) and primary production toward the mouths of both inlets was 1.4 times higher than at the landward stations. The elevated rates of primary production in Saanich Inlet may have been due to exchange with the nutrient-rich surface waters of the passages leading to the Pacific Ocean and the up-inlet gradients in both fjords also may have reflected relative nutrient supply. Sediment-trap results show enhanced fluxes of biogenic silica to the deep waters of Saanich Inlet; associated organic matter is likely to have caused a large oxygen demand. Combined with the high primary production and export flux, low rates of vertical mixing and particle-entrapment within the fjord, factors associated with weak estuarine circulation as well as weak winds and tides in Saanich Inlet, may also stimulate anoxia.Although in Jervis Inlet there is more stagnant water behind the sill and deep-water renewals appear to be less frequent than in Saanich Inlet, the deep sill allows degradation of a significant fraction of the sinking organic matter before the stagnant waters are reached, reducing the chances of oxygen depletion in the bottom waters.  相似文献   

5.
Cytochrome c and ferricyanide reducing activities are measured in a Desulfovibrio desulfuricans (strain ATCC No. 17990) that indicate that the APS reductase activity is constitutive. This enzymatic activity is also measured in a Saanich Inlet isolate identified as Desulfovibrio salexigens (Saanich). Successful measurement of the Cytochrome c reducing activity was also made in the sediment extracts from Saanich Inlet, and this activity was found to be present in sediments as deep as 50 cm. Bacterial biomass distributions were estimated using measurements of ATP in the Saanich Inlet sediments. ETS activity measurements correlated well with the in situ [35S]-SO42? reduction rate measurements; both of the methods showing a subsurface maximum in activity at a depth of about 10 cm. However, some differences between the results obtained from these two procedures were also found, e.g., the in situ [35S]-SO42? reduction activity approximated zero values at or near 25 cm depth, while 5–10% of the surface ETS activity was present at a depth of as much as 50 cm. The hypothesis presented is that the subsurface maximum may be due to the anaerobic oxidation of methane by [35S]-SO42? ions as mediated by the sulfate-reducing bacteria. A discussion of the strong interactive relationships between a variety of organisms in an ecosystems context, so necessary in bringing about organic matter diagenesis in anoxic marine environments, is also presented.  相似文献   

6.
Anodic stripping voltammetry and gel filtration chromatography were used to examine the speciation and organic complexation of copper and lead in seawater. The extent of metal complexation in biologically different water types, the molecular weight ranges of the dissolved organic matter involved in metal-organic associations, and the metal uptake kinetics of these naturally occurring organic species were examined. Analyses of samples from Saanich and Narrows inlets, British Columbia, suggest organic complexation throughout the water column, including anoxic waters of Saanich Inlet. Several fractions of organic material from sedimentary interstitial water in the molecular weight range 500–10,000 were found to complex copper and lead, the concentration of complexing ligands decreasing with depth in the core. Rates of uptake of metals by organic material are slow, of the order of tens of minutes or longer.  相似文献   

7.
Arsenic compounds in the marine polychaete Arenicola marina collected from Odense Fjord, Denmark were determined by HPLC-ICPMS. In contrast to most other marine animals, A. marina contained most of its water soluble arsenic as inorganic forms, arsenite (58%) and arsenate (16%), and arsenobetaine was present as a minor constituent (6%) only. Other arsenic compounds detected in A. marina were dimethylarsinate (4%), two arsenosugars (1 and 3%), tetramethylarsonium ion (1.5%), and arsenocholine (<1%). A new arsenobetaine -trimethylarsoniopropionate-previously only reported in fish, was also present at trace levels (<1%), and an unknown anionic arsenical (approximately 10%) remains unidentified. When A. marina was exposed in laboratory experiments to different concentrations of arsenate in seawater (10, 50. 100, 500 and 1000 microg As 1(-1)) the polychaetes accumulated arsenic in a dose dependent. non-linear manner. Most of the accumulated arsenic was biotransformed to arsenite and dimethylarsinate. with the remainder being accumulated as unchanged arsenate. None of the other arsenic compounds naturally present in A. marina increased in concentration following arsenate exposure.  相似文献   

8.
A series of high resolution (10 cm) vertical profiles of iron were determined across the oxic/anoxic boundary in the Lower Pond of the Pettaquamscutt Estuary. Selective chemical treatments and multiple analytical methods were used to detemine the oxidation state and lability of iron across the oxic/anoxic boundary. The vertical distributions of dissolved and total iron were determined by atomic absorption spectroscopy, and dissolved Fe(II) and reducible iron were determined using a modified Ferrozine spectrophotometric method. Well-developed maxima of total dissolved iron ≈7·5 μM occurred within the oxic/anoxic transition zone. Analysis of Fe(II) by the FZ method indicates that more than 95% of the dissolved iron determined by atomic absorption spectroscopy within the maximum is in the form of Fe(II). The concentration of dissolved Fe(II) ranged from <4 nM in oxygenated surface waters to between 7 and 8 μM at the total dissolved iron maximum.Both dissolved and total iron samples were treated with ascorbic acid to quantify the fraction of iron that was reducible in this system. Dissolved iron is quantitatively reduced to Fe(II) by 3·5 m depth, and particulate iron was almost completely dissolved by 6 m. Thermodynamic speciation calculations indicate that the dominant species of Fe(II) in the anoxic waters is the Fe(HS)+complex. In addition, the concentration of Fe(II) in the anoxic zone appears to be controlled by precipitation of a sulfide phase, the ion activity product for waters below 7 m is in good agreement with the solubility product of mackinawite.The vertical distribution of oxidation states of the metals indicates non-equilibrium conditions due to microbiological and chemical processes occurring in the redox transition zone. A one-dimensional vertical, eddy diffusion model is presented that incorporates redox reactions of iron, sulfide and oxygen. The modeling suggests the maximum in Fe(II) can be achieved through inorganic oxidation and reduction reactions, however the depth at which the maximum occurs is sensitive to sulfide oxidation, which appears to be dominated by biological oxidation. The magnitude of the Fe(II) maximum depends on the flux of iron into the basin, and reductive dissolution of particulate iron.  相似文献   

9.
Sensitive methods for the determination of arsenate and particulate arsenic (PAs), as well as phosphate and particulate phosphorus (PP), in seawater are described. The method for arsenate and phosphate was established by applying automated liquid waveguide spectrophotometry. Because the reaction time for the formation of the arsenate-molybdate complex is longer than that for the phosphate-molybdate complex, a long Teflon tube submerged in a heating bath was installed in the conventional phosphate flow system. The arsenate was quantified as the difference between absorbances of molybdenum blue dyes with (only phosphate) and without (phosphate + arsenate) arsenate reduction treatment. Contamination was observed in the reagent for arsenate reduction and must be corrected. Linear dynamic ranges up to 1000 nM were confirmed for arsenate and phosphate. The detection limits for arsenate and phosphate were 5 and 4 nM, respectively. Freezing was a reliable sample preservation technique for both arsenate and phosphate. The method for PAs and PP was established by combining conventional persulfate oxidation of PP and the automated liquid waveguide spectrophotometry of arsenate and phosphate. The digestion efficiencies of organic As analogs were >93%. Contamination in the glass fiber filter was negligible. Field tests confirmed that the coefficients of variation (CVs) of 10–19 nM arsenate and 4–151 nM phosphate were 7–20 and 1–25%, respectively, while the CVs of 0.9 nM PAs and 10.2 nM PP were 11 and 4%, respectively.  相似文献   

10.
We conducted a multi-year sediment-trap experiment in Saanich and Jervis Inlets, British Columbia, Canada. Moorings with traps positioned at three depths were placed near the mouth and toward the head of each fjord, and deployments were monthly. We present fluxes of total mass, biogenic silica (BSi), particulate organic carbon (POC) and aluminium (Al), as well as the δ13C signal of the POC, and we compare the sediment-trap fluxes to primary-production measurements made during the experiment.Diatomaceous silica and aluminosilicates were the primary components of the settling flux, while organic matter from marine (largely diatoms) and terrestrial sources was occasionally a significant portion of the sinking material. Fluxes of BSi and POC were highest in the spring and summer, tracing maxima in local primary production. These fluxes decreased, increased or remained constant with depth due to water-column remineralisation and variability in processes that cause fluxes to increase with depth. Al fluxes followed local precipitation and river runoff at the landward stations, and with remarkable faithfulness in Saanich Inlet. Near the mouths, there was little seasonality in Al flux, and the increases of flux with depth reveal sedimentary plumes at each fjord’s sill. Tidal and deepwater-renewal components of the plumes are evident, and the plume in Saanich Inlet was particularly intense. Fluxes of Al to deep sediment traps associated with renewal flows were also observed toward the head of each fjord.Marine δ13C endmembers are estimated from relationships between δ13C and BSi concentrations, and measures of soil δ13C from each fjord were available. These endmembers are used with the δ13C record to quantify marine and terrigenous contributions to the POC flux. Marine POC composed 54-72% of the total POC caught by shallow sediment traps in spring and summer, and 36-54% in fall and winter. Primary production and sediment-trap fluxes are used to estimate annually averaged export ratios (shallow-trap flux:autotrophic assimilation) for marine POC and Si. POC export ratios (0.092-0.14) were low for these productive waters, but they compare with other results based on sediment-trap fluxes from coastal waters where terrigenous OC has been subtracted. Export ratios of Si were calculated using an estimated Si:C assimilation ratio and, therefore, are susceptible to error, but the high results (>0.8) suggest that BSi was exported more efficiently than POC. The possibility that POC was preferentially lost after interception by sediment traps is also considered. Primary production and settling fluxes were higher in Saanich Inlet than in Jervis Inlet, while export ratios of OC and Si were similar in both fjords, away from the nepheloid layer near the sill of Saanich Inlet.  相似文献   

11.
With the rising cost of oil the electric power generating companies are turning to coal as a fuel source. Large amounts of fly ash are produced as a by product of coal combustion. This fly ash must then be disposed of, with the oceans being considered an alternative to land fill disposal. This research investigated the sorptive behavior of the surface-associated arsenic and utilized the results to project arsenic's impact on the water column during the ocean disposal of fly ash.Several acid digests were investigated to determine an effective method of arsenic recovery from fly ash. Of these, the HCl digest was the most effective technique, yielding 100% arsenic recoveries from fly-ash particles. The arsenic content of the fly ashes studied varied from 69 ± 11 μg g−1 to 323 ± 24 μg g−1, reflecting differences in the arsenic content of the source coal. In both seawater and freshwater there is an increase in arsenic desorption with increasing pH. The greatest release of arsenic occurred at pH 12 with generally over 80% of the surface arsenic released.Fly ash in contact with seawater and freshwater can exhibit either acidic or alkaline tendencies depending upon the soluble elemental composition on the surface of the flyash particle. The acidic ashes were shown to leach a greater percentage of arsenic (16.9%) than the more alkaline ashes (8.2%). During these leaching studies in seawater, arsenic was found to leach in both the pentavalent and trivalent oxidation state. The pentavalent state was predominant, comprising 77% of the arsenic initially desorbed.The dissolution in seawater of arsenic was utilized to assess the possible impact of the ocean disposal of fly ash. Based upon these data it appears that the natural levels of arsenic in the water column would not be significantly increased. Further research is needed on the fate of fly-ash particles in marine sediments.  相似文献   

12.
Iodate (IO3) is the predominant dissolved species of iodine in the oxygenated waters of the Mediterranean Sea. Iodide (I) is present in significant quantities (up to 65 nM) in oxygenated waters in the photic zone and near the interface above the anoxic and saline Bannock Basin. Lesser quantities of I (< 10 nM) are found throughout the rest of the oxic water column. An additional unidentified dissolved iodine species is present immediately above the anoxic interface.Total dissolved iodine (ΣI) increases dramatically across the seawater/brine interface. Part of this increase is undoubtedly the result of the dissolution of iodine-rich evaporites during formation of the brine bodies at the Tyro and Bannock Basins. The vertical distribution of ΣI and other dissolved chemical species (particularly PO43−) in the Bannock Basin brine, however, suggests an additional, present-day, diagenetic source of dissolved iodine to the brine. Based on the increase in the concentration of the most soluble major ions across the seawater/brine interface, 5–7 μM of the 11.5-μM increase in ΣI concentration must be attributed to diagenesis.  相似文献   

13.
Saanich Inlet, British Columbia, has long been known for the presence, in most years, of anoxic bottom water. One factor contributing to this anoxia is a high level of primary production, which occurs as a major spring bloom followed by sporadic ‘mini-blooms’ throughout the summer and early fall. The process(es) by which new production is refueled after nutrient exhaustion caused by the spring bloom are not well known, since Saanich is an inverse estuary and vertical mixing driven by winds and tides is low. This study presents new observational evidence that strongly suggests that the dominant mechanism of nutrient resupply during the summer months is intermittent advective exchange, driven by pressure gradients set up by strong tidal mixing in passages outside Saanich Inlet itself. A simple box model is formulated to illustrate this mechanism. When driven by annual freshwater forcing and deepwater renewal functions characteristic of the region and measured tides for 1975, the model predicts resupply of nitrate during most of the periods observed in 1975 observations (Deep-Sea Res. 24 (1977) 775). This ‘action-at-a distance’ nutrient resupply mechanism, involving strong but localized turbulent mixing and subsequent distribution of the products of mixing over large-horizontal distances by pressure-gradient-driven flow, is likely important in other coastal regions where the estuarine circulation is weak.  相似文献   

14.
In 1984, on a transect covering the whole Baltic Sea and parts of the adjacent North Sea, 160 water samples were taken and analysed for their concentrations of particulate and dissolved metals. In addition, the suspended materials were investigated for their elemental bulk composition.The particulate fractions represented from about 5% (Cd, Cu and Ni) to 50% (Fe and Pb) of the total (particulate plus dissolved) concentrations. For some elements (Ba, Cd, Cu, Pb and Zn), the particulate matter from the surface microlayer was enriched with respect to those suspended materials taken from 0.2 m depth. This could reflect the atmospheric input of metal-rich aerosols. In anoxic deep waters, maximum contents of Zn (6400 μg g−1), Cu (1330 μg g−1) and Cd (12 μg g−1) were observed in the particulate matter, indicating sulphidic forms. On the other hand, under oxic conditions the distribution coefficients (Kd) decreased with the water depth (Cd, Fe and Pb).Relative to global background levels, the particulate matter contained metal “excesses” amounting to more than 90% of the total contents (Cd, Mn, Pb and Zn). Automated electron probe X-ray microanalysis (EPXMA) revealed that the elemental composition of sediments is mainly governed by post-depositional processes of early diagenesis and is only weakly related to the composition of suspended matter in the overlying water body. For instance, in relation to surface mud sediments of the central Baltic net-sedimentation basins, Zn, Cd, Cu and Mn had 30–100% higher levels in the suspended materials. The general pattern of metal contents of particulate matter taken from 10 m depth on a transect between the Bothnian Bay and the North Sea were—possibly as a result of anthropogenic inputs—rather similar for Pb, Zn and Cu. For Fe and Mn, the distribution patterns along the transect were probably governed by the natural loading characteristics and by the biogeochemistry of those elements.  相似文献   

15.
Dissolved iodine in waters overlying and in the Orca Basin,Gulf of Mexico   总被引:1,自引:0,他引:1  
The distribution and speciation of iodine, a biophilic redox-sensitive trace element, in waters overlying and in the Orca Basin, Gulf of Mexico, which contains hypersaline, anoxic and yet non-sulfide-bearing brine have been determined. The distribution of iodate and iodide in the oxic waters overlying the anoxic brine are similar to those reported in other oceans. However, in the oxic-anoxic mixing zone, iodate disappears while the concentration of iodide reaches a maximum of 8.1 μM, the highest concentration ever reported in open oceans. There is also a maximum in specific iodine of 30.7 nM‰?1 at this depth. Specific iodine in oxic seawater is only about 10–14 nM ‰?1. These features may be explained by the preferential dissolution of biogenic particles that have accumulated in a strong pycnocline. In the anoxic brine proper, the concentration of iodide is 3.8 μM and can be explained almost entirely by the simultaneous mobilization of chloride and iodide during the dissolution of evaporite beds as the specific iodine of 14.5 nM‰?1 is only slightly higher than those observed in the oxic waters.  相似文献   

16.
During New Euxinian time when sea level dropped below the sill connecting the Black and Marmara seas, the Black Sea became isolated and freshwater sediments were deposited. Now it is a semieuxinic basin with the oxic/anoxic boundary at 100–150 m. The seasonal changes in sedimentation are preserved in the form of laminated sequences. The counting of varves in southeastern Black Sea cores show the chronology of the O2/H2S interface. The age of the Holocene sapropel along the eastern margin ranges from 4000 to 1000 yr BP in deep water and 2500—1000 yr BP in shallower water. Sapropel formation started at 3650 yr BP at a water depth of 2200 m.  相似文献   

17.
The uppermost 5–6 cm of the sediments (between 8 and 2248 m water depths) were studied to understand the effects of varying redox conditions on the Mn distribution in the recent sediments of the Black Sea. It was found that most Mn concentrations are consistent with the average abundance in crustal and/or sedimentary rocks. There exist no important differences between Mn concentrations in oxic (shallower water; <70 m) and anoxic (deeper water; 120 m) sediments. Previously reported Mn-enrichment above the Black Sea oxic/anoxic interface, due to the peculiar redox cycling, shows no significant contribution of Mn to the bottom sediments. A marked relationship between total Mn concentrations and clay/mud contents at shelf depth along the southern Black Sea margin indicates increased accumulation of Mn in association with the fine-grained particles and eastward water circulation.  相似文献   

18.
Arsenic is not conservative in Chesapeake Bay. Inputs of man-derived arsenic, of the order of 100 kg d−1, cause substantial positive deviation from theoretical dilution. The chemical form of the arsenic varies both seasonally and along the axis of the bay. During winter, arsenic is present only as arsenate. During summer, substantial quantities of reduced and methylated forms are present in different areas, indicative of separate formation processes. Arsenite, present in low-salinity regions, may have been formed by chemical reduction in anoxic, subsurface waters and then mixed into the surface layer. Methylated arsenicals correlate highly with algal standing stocks. One particular form, methylarsonate, is highly correlated with the dominant algal genus, Chroomonas. As both arsenic reactivity and toxicity are altered by transformation of chemical form, the observed variations in arsenic speciation have considerable geochemical and ecological significance.  相似文献   

19.
The fluorescence of dissolved organic matter in seawater   总被引:3,自引:0,他引:3  
A total of 28 vertical profiles of seawater fluorescence was measured in the Sargasso Sea, the Straits of Florida, the Southern California Borderlands, and the central Pacific Ocean. In all cases, surface seawater fluorescence was low as a result of photochemical bleaching which occurs on the timescale of hours. Fluorescence of deep water was 2–2.5 times higher than that of surface waters, and was constant, implying a long residence time for fluorescent organic matter, possibly of the order of thousands of years. Fluorescence correlates well with nutrients (NO3, PO43−) in mid-depth waters (100–1000 m) in the Sargasso Sea and the central North Pacific, consistent with results in the central Pacific and the coastal seas of Japan. This suggests that regeneration or formation of fluorescent materials accompanies the oxidation and remineralization of settling organic particles.The various sources and sinks of fluorescent organic matter in the global oceans are assessed. The major sources are particles and in situ formation; rivers, rain, diffusion from sediments, and release from organisms are minor sources. The major sink is photochemical bleaching.  相似文献   

20.
Ectohydrolase activities of suspended microbiota were compared to those associated with sinking particles (sed-POM) retrieved from sediment traps deployed in the permanently anoxic Cariaco Basin. In shore-based assays, activities of aminopeptidase, β-glucosidase, chitinase and alkaline phosphatase were measured in samples obtained from oxic and anoxic depths using MUF- and MCA-labeled fluorogenic substrate analogs. Hydrolysis potentials for these enzymes in the seston varied widely over the nine cruises sampled (8 Nov 1996–3 May 2000) and among depths (15–1265 m); from <10 to over 1600 nM d?1 hydrolysate released, generally co-varying with one another and with suspended particulate organic carbon (POC) and particulate nitrogen (PN). Hydrolytic potentials, prokaryotic abundances and POC/PN concentrations in sinking debris were 400–1.3×107 times higher than in comparable volumes of seawater. However when normalized to PN, hydrolytic potentials in sediment trap samples were not demonstrably higher than in Niskin bottle samples. We estimate that PN pools in sediment trap samples were turned over 2–1400 times (medians=7–26x) slower by hydrolysis than were suspended PN pools. Median prokaryotic growth rates (divisions d?1) in sinking debris were also ~150 times slower than for bacterioplankton. Hydrolytic potentials in surface oxic waters were generally faster than in underlying anoxic waters on a volumetric basis (nM hydrolysate d?1), but were not significantly (p>0.05) different when normalized to PN or prokaryote abundances. Alkaline phosphatase was consistently the most active ectohydrolase in both sample types, suggesting that Cariaco Basin assemblages were adapted to decomposing phosphate esters in organic polymers. However, phosphorus limitation was not evident from nutrient inventories in the water column. Results support the hypothesis that efficiencies of polymer hydrolysis in anoxic waters are not inherently lower than in oxic waters.  相似文献   

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