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1.
The natural human female hormones oestrone and 17β-oestradiol have been implicated in the disruption of endocrine systems in some wildlife adjacent to sewage effluents. The sorption behaviour of these two compounds under estuarine conditions was studied by spiking either 2.55 μg of oestrone or 2.65 μg of 17β-oestradiol in kinetic experiments. In equilibrium experiments, 3 ng of oestrone or 3.2 ng of 17β-oestradiol was added in each of the centrifuge tubes. Sorption onto sediment particles was relatively slow, with sorption equilibrium being reached in about 70 and 170 h for oestrone and 17β-oestradiol, respectively. The effects of a variety of environmental parameters on sorption were studied including salinity, sediment concentration (SC), the presence of a third phase, particle size and, also, surfactant concentrations. Results show that although salinity did not induce any statistically significant effect on the sorption of 17β-oestradiol, it did statistically enhance the sorption of oestrone, and a salting constant of 0.3 l mol−1 was derived. The partition coefficient for both compounds decreased with increasing sediment concentration, a phenomenon that has been widely reported and attributed to the presence of colloids (which could enhance dissolved concentrations). In this paper, the true partition coefficients for sediment particles (Kptrue) and colloidal particles (Kctrue) have been calculated, and a Kptrue value of 141 and 102 ml g−1 was obtained for oestrone and 17β-oestradiol, respectively. In addition, Kctrue values for oestrone (222×102 ml g−1) and 17β-oestradiol (135×102 ml g−1) were two orders of magnitude higher than their respective Kptrue values, suggesting that the colloidal particles are significantly stronger sorbents for natural oestrogens than sediment particles. Particles of different sizes were found to have different partition coefficients due to the strong relationships between partition coefficients for the two compounds and particulate organic carbon (POC) contents and specific surface areas (SSAs). The presence of a surfactant was shown to reduce the partition coefficients for the two compounds, although its concentrations being used were higher than those normally found in the natural environment.  相似文献   

2.
Sediments from the lower Hudson River estuary and two other coastal environments were examined experimentally for their ability to mineralize (convert to CO2) the polycyclic aromatic hydrocarbons (PAHs) naphthalene and anthracene over a range of salinities. Routine assays employed 1:1 (vol fresh sed:vol water) sediment slurrys in order to overcome natural variability in mineralization rates among replicates. Mineralization rates were stimulated by about 2·5 fold, compared to unslurried controls, while the coefficient of variation fell from 13% to 3·5%.Rates of naphthalene mineralization in surface sediments from along the mainstem of the Hudson River (salinities from 2 to 27%) ranged from 0·011 to 1·5 nmol cm−3 day−1 (pool turnover [Tn] from 60 to 2040 days) with no discernible trends along the estuarine gradient. For two stations examined experimentally (mile point 5, salinity 23%; mile point 26, salinity 5%), microbial assemblages appeared acclimated to broad salinity variations as alter rates of mineralization compared to controls.Sediments from two upstream marshes of the Hudson (mile points 36 and 45) showed rates of naphthalene mineralization from 0·007 to 0·15 nmol cm−3 day−1 (Tn from 14 to 368 days), while sediments from a third marsh in freshwater (mile point 76) had high rates (66 nmol cm−3 day−1; Tn 40 days). For the two upstream marsh stations which rarely experienced salt intrusion, there was a substantial decrease in mineralization of naphthalene and anthracene with increasing salinity.Consistently high rates of naphthalene mineralization (780 to 1600 nmol cm−3 day−1; Tn 5 to 6 days) were observed in petroleum contaminated sediments from Port Jefferson Harbor (PJH) on the north shore of Long Island. PJH has a relatively constant salinity regime (about 27%) and imposed decreases in salinity effected decreases in rates of naphthalene and anthracene mineralization. Lowest rates of naphthalene mineralization (0·003 to 0·004 nmol cm−3 day−1; Tn from 714 days to 833 days) were found in sediments from two stations in the relatively pristine Carmans River estuary on the south shore of Long Island.The ability of increases or decreases in salinity to affect the rate of model PAH mineralization appeared to be dependent on the natural variation in the salinity regime from which a sample was obtained. Data from all the environments studied indicated a strong positive correlation between PAH concentration and the rates of mineralization of naphthalene. Rates of PAH mineralization in all environments examined appear to be primarily controlled by the extent of pollutant loading and not by natural variations in the salinity regime.  相似文献   

3.
Benzyl butyl phthalate (BBP) is an endocrine-disrupting chemical, and its sorption behaviour on marine sediments was investigated. BBP sorption on the sediments was a rapid process, which could reach equilibrium in 6 h. The sorption equilibrium results could be well described by a linear isotherm. The BBP partition coefficient, Kd, varied from 7.16 to 12.54 L/g in approximately proportion to the organic content of the sediments. After H2O2 oxidation for removing the organic material from the sediments, the Kd values were reduced by more than 70%, but the organic normalised partition coefficient averaged 2165 L/g for the H2O2-treated sediments, which was more than three times of 598 L/g for the raw sediments. The sorption of BBP on the sediments increased with a decrease in temperature and an increase in salinity. A salting constant of 1.14 L/mol was obtained for BBP in artificial seawater. These research findings are of importance to an assessment of the fate and transport of BBP and other similar endocrine-disrupting chemicals (EDCs) in seawater–sediment systems.  相似文献   

4.
本文在现场情况下,研究了自然条件下受污染海岸带沉积物中的7种多环芳烃(Polynuclear Aromatic Hydrocarbons,简称PAHs)的解吸动力学行为。结果表明,7种PAHs)的解吸动力学行为。结果表明,7种PAHs的解吸动力学行为可以用二元模型模拟。文中并将所得数据与文献报道的数据进行了比较。  相似文献   

5.
ABSTRACT

Phosphorus (P) stores in gravel-bed rivers are released for uptake by periphyton when pH levels exceed 8.5. The Tukituki River has low alkalinity water and frequently experiences periphyton blooms, and daytime pH?>?9 during summer low-flows. We measured dissolved reactive P (DRP) and EPC0, the water concentration of DRP at which no net release or sorption from the river bed occurs, in sediment samples from the Tukituki River subject to controlled pH levels before (2014) and after (2017) changes to two wastewater discharges that reduced P release to the river by 95%. DRP released from 2014 sediments at pH 8.5–10 were 30?±?10?mg/m3 above background (pH 8) whereas those released from 2017 sediments were 5?±?3?mg/m3 above background. EPC0 levels in 2014 and 2017 were 11?±?6 and 7?±?2?mg/m3, respectively. Field estimates of released DRP calculated from continuous pH and the Redfield equation suggested that most of the readily available DRP released from sediments at elevated pH is derived from material attached to recently deposited sediment. Subsequently, a reduction in wastewater inputs or agricultural runoff should reduce sediment DRP stores, and hence sediment fluxes, within a few years and mitigate periphyton blooms in addition to directly lowering water column concentrations.  相似文献   

6.
The role of organic matter in the sorption capacity of marine sediments   总被引:1,自引:0,他引:1  
Zhanfei Liu  Cindy Lee 《Marine Chemistry》2007,105(3-4):240-257
Past studies have suggested that desiccation enhances hydrophobicity of salt marsh sediment, and that drying and rewetting sediment can be used to investigate sorption mechanisms of amino acids and other organic compounds [Liu, Z., Lee, C., 2006. Drying effects on sorption capacity of coastal sediment: The importance of architecture and polarity of organic matter. Geochim. Cosmochim. Acta 70, 3313–3324]. Here we further develop this technique to study sorption of hydrophobic and hydrophilic organic compounds in a wide range of marine sediments. Our results show that hydrophilic compounds sorb strongly to wet coastal sediments; in dried sediments, sorption of hydrophilic compounds decreases, while sorption of hydrophobic compounds is greatly enhanced. Small compounds with aromatic rings sorb more in dried than wet coastal sediments, suggesting that aromatic groups have a stronger effect on sorption than polar groups like amino and carboxyl moieties. Sorption of lysine, glutamic acid and putrescine decreases greatly when sediment is pretreated with KCl, indicating the importance of cation ion exchange. However, α-amino acids sorb much more than corresponding β- or γ-amino acids, and l-alanine sorbs more than d-alanine, suggesting that amino group location and chiral selectivity play an important role in sorption. Comparison of lysine and tyrosine sorption in different sediments indicates that source and diagenetic state of organic matter are important factors determining sorption capacity. Lysine sorbs much more to organic detritus from salt marsh sediment than to fresh Spartina root materials, marine particles, lignin or humic acids, indicating the importance of structural integrity in sorption. Desorption hysteresis of glutamic acid, putrescine and lysine (in dried sediment) suggests the presence of enzyme-type sorption sites of high sorption energy or multiple binding mechanisms. Taken together, these findings suggest that organic matter plays the major role in amino acid sorption in organic-rich sediments.  相似文献   

7.
Abstract

The effect of pH on the physical and mechanical properties of a sediment was investigated through a set of experimental tests. The sediment was formed from deposition of suspended particles in a fluid. Two different types of clay soil were suspended in fluids with different pH (2, 4, 7, 9 and 11) in cylindrical tubes with volume of 1?liter and also in special cylindrical reservoirs. The height of the sediment was measured in the cylindrical tube until equilibrium was achieved. The sediment deposited in the reservoirs was dried in air and then Atterberg limit, compaction and unconfined compressive strength (UCS) tests were conducted on samples prepared from each sediment. The results showed that the final height of the settled sediment is a function of pH; the height of sediment is increased with increasing the pH. Also, the Atterberg limits increased with increasing the pH. The maximum dry unit weight and optimum water content decreased and increased with increasing the pH. The final strength of the sediment decreased with increasing pH. Based on the SEM analysis, it was found that the values of pH influence the properties of the formed sediments.  相似文献   

8.
Radionuclide activities of 210Pb and 226Ra were measured to determine bioturbation coefficients (Db) in seven sediment cores from the Korean licensed block for polymetallic nodules in the Clarion–Clipperton Fracture Zone. Variability in Db is considered in the context of the sedimentological, geochemical, and geotechnical properties of the sediments. Db values in the studied cores were estimated using a steady-state diffusion model and varied over a wide range from 1.1 to 293 cm2/yr with corresponding mixing depths (L) of 26 to 144 cm. When excepting for spurious results obtained from cores where diffusive mixing does not apply, Db values range from 1.1 to 9.0 cm2/yr with corresponding mixing depths (L) of 26 to 63 cm. Such wide variability in Db and L values is exceptional in sites with water depths of ~5000 m and is attributed in this study to an uneven distribution of sediment layers with different shear strengths and total organic carbon (TOC) contents, caused by erosion events. The studied cores can be grouped into two categories based on lithologic associations: layers with high maximum shear strength (MSS) and low TOC content, showing a narrow range of Db values (1.1–9.0 cm2/yr); and layers with low MSS and high TOC content, yielding much higher Db values of over 30 cm2/yr. The distribution of different lithologies, and the resultant spatial variability in MSS and labile organic matter content, controls the presence and maximum burrowing depth of infauna by affecting their mobility and the availability of food. This study provides a unique case showing that shear strength, which relates to the degree of sediment consolidation, might be an important factor in controlling rates of bioturbation and sediment mixing depths.  相似文献   

9.
The MnO2 adsorption method combined with voltammetry is proposed for the direct determination of metal complexation in seawater of various salinities as a more satisfactory alternative to direct voltammetric measurements and bioassay methods. A small quantity of MnO2 is equilibrated with copper ions in filtered seawater. Natural organic ligands in the seawater compete for copper with the MnO2. Total dissolved copper is measured by differential pulse anodic stripping voltammetry after filtration and acidification of the sample. Preconcentration of natural water samples is unnecessary and measurement is performed at the natural equilibrium pH of the aerated sample. The analytical limit of detection of the method depends on contamination from the filtration step, and for copper complexation a ligand concentration of 5 × 10?8 M was obtained. The sensitivity can be increased by use of radioisotopes as tracers. The method is very versatile in that complexation of various metals may be determined by any analytical method that measures total dissolved metal concentrations. Neither organic ligands nor their complexes with copper adsorb on the MnO2 at pH8, but at pH 1.8 MnO2 is an efficient scavenger for electroactive organic material.Samples of surface water from the Irish Sea and the Atlantic Ocean were found to contain ligand concentrations of 1.7 × 10?7 and 1.1 × 10?7 M, with conditional stability constants (log values) of 9.84 ± 0.13 and 9.86 ± 0.23, respectively, at pH 8.0.  相似文献   

10.
Dissolved silica can coprecipitate with zinc from seawater or distilled water that has been enriched with both elements. More than 2 ppm Si are necessary for the reaction to begin. The coprecipitation shows pH dependence. The addition of pulverized illite or natural sediment as suspended particulate material does not enhance the reaction in seawater. The organic material present in the nearshore seawater samples decreases the rate and extent of reaction, as indicated by comparisons of results of experiments using natural seawater with results obtained using UV-irradiated seawater. In unbuffered distilled water the reaction must compete with hydrolysis of zinc; however, reaction does occur, which indicates that the seawater matrix is not essential for the reaction. The coprecipitation can limit the concentration of zinc in seawater to less than the solubility concentration assumed for ZnCO3 or Zn(OH)2. The results suggest that a zinc silicate can precipitate directly from seawater or interstitial water as an authigenic mineral.  相似文献   

11.
12.
For a better understanding of the phosphorus dynamics and bioavailability in temperate climates, sequential chemical extraction techniques were used to study sediment P-pools distribution and relative importance in a eutrophicated estuary.Results indicate a shift in importance from the iron-bound P fraction to the CaCO3-bound P fraction with increasing salinity, which suggests a decrease in bioavailable P from the most inner part of the estuary seaward, as the CaCO3 associated P is believed to be less available for organisms. Salt marsh plants also influence sediment P speciation, through higher organic P fractions (mainly humic acid associated P) when compared to non-vegetated sediments. The ratio of iron-bound P to iron-oxyhydroxides may be used as an indicator of P availability, since it reflects the number of available P sorption sites in the metal oxides. This ratio was lowest in the intermediate zone of the estuary (13.7) when compared to the outer site (29.6) and the upper site (26.1), suggesting saturation of sorption sites. Co-incident with this, the intermediate site is characterized by the occurrence of macroalgal blooms during summer. In the present case, superficial sediments in the Mondego estuary do not show a clear seasonal trend, either in total amounts of exchangeable P or P speciation. Pools of exchangeable P in the surface sediment were 30 times higher than the annual net-export of P (14 ton year−1) from the estuary. The annual P release from the sediment appears diminutive in comparison with the pool-size. Management measures to reduce nutrient input into coastal water systems should therefore consider that phosphorus availability may persist as a result of sediment supply, even after reducing the external point sources.  相似文献   

13.
《Marine Chemistry》1987,22(1):71-83
Chemical variables were measured in calcium-carbonate-rich sediments inhabited by the dominant tropical seagrass, Thalassia testudinum, and in adjacent seagrass-free sediments at several locations in the Bahamas Islands. Pore-water alkalinity and pCO2 were consistently greater, while pH was consistently lower in sediment-pore waters within seagrass beds. The ammonium and molybdate-reactive phosphate concentrations in sediment-pore water were variable for vegetated, compared with unvegetated, sample locations.Thalassia testudinum can generate very large amounts of organic matter within calcium-carbonate-rich sediments. However, little of the organic matter is retained in the sediment and the effect of that organic matter on pore water chemical factors appears to be surprisingly small. These observations are markedly different from those for seagrass beds in high latitude clastic sediments and in Syringodium filiforme seagrass beds near San Salvador Island, where major influences of the seagrass beds on sediment chemistry have been observed. The generally coarser grain size of the carbonate sediments may be a primary factor contributing to these differences.  相似文献   

14.
Variations in the speciation of iron in the northern North Sea were investigated in an area covering at least two different water masses and an algal bloom, using a combination of techniques. Catalytic cathodic stripping voltammetry was used to measure the concentrations of reactive iron (FeR) and total iron (FeT) in unfiltered samples, while dissolved iron (FeD) was measured by GFAAS after extraction of filtered sea water. FeR was defined by the amount of iron that complexed with 20 μM 1-nitroso-2-napthol (NN) at pH 6.9. FeT was determined after UV-digestion at pH 2.4. Concentrations of natural organic iron complexing ligands and values for conditional stability constants, were determined in unfiltered samples by titration. Mean concentrations of 1.3 nM for FeR, 10.0 nM for FeT and 1.7 nM for FeD were obtained for the area sampled. FeR concentrations increased towards the south of the area investigated, as a result of the increased influence of continental run off. FeR concentrations were found to be enhanced below the nutricline (below 40 m) as a result of the remineralisation of organic material. Enhanced levels of FeT were observed in some surface samples and in samples collected below 30 m at stations in the south of the area studied, thought to be a result of high concentrations of biogenic particulate material and the resuspended sediments respectively. FeD concentrations varied between values similar to those of FeT in samples from the north of the area to values similar to those of FeR in the south. The bloom was thought to have influenced the distribution of both FeR and FeT, but less evidence was observed for any influence on FeR and FeD. The concentration of organic complexing ligands, which could possibly include a contribution from adsorption sites on particulate material, increased slightly in the bloom area and in North Sea waters. Iron was found to be fully (99.9%) complexed by the organic complexing ligands at a pH of 6.9 and largely complexed (82–96%) at pH 8. The ligands were almost saturated with iron suggesting that the ligand concentration could limit the concentration of iron occurring as dissolved species.  相似文献   

15.
The Pb content of natural deep-sea ferromanganese deposits decreases with depth. This is commonly explained by assuming oxidation of Pb2+ and uptake as (Mn, Pb)O2 in normally oxygenated shallow water, a process that is less likely to occur in deep water which is somewhat depleted in oxygen. This concept is discussed and rejected, both on theoretical grounds and based on experimental results of Pb2+ sorption by Mn oxides. Comparative sorption experiments on Mn oxides were carried out with Pb and Ba. It is shown that Pb is preferentially adsorbed by birnessite at pH ? 4. The uptake ratio is, however, much lower than the relative enrichment factor in natural nodule material. Suggested explanations for this discrepancy are: influence of hydrostatic pressure and extent of hydrolysis of the cations at the pH of ocean water.  相似文献   

16.
Anaerobic salt marsh sediments were amended with a variety of organic pollutants and the effects on methanogenesis, sulfate reduction and carbon dioxide evolution were examined. Addition of 1000 μg g?1 (dry weight sediment) Arochlor 1221, lindane, endrin, benzene and phenanthrene resulted in no significant effects on the activities studied. Methanogenesis was inhibited by 1000 μg g?1toxaphene, PCP, chlordane, naphthalene, DDT, Kepone and heptachlor and by 100 μg g?1 PCP and toxaphene. At 1000 μg g?1 naphthalene and toxaphene and 100 μg g?1 PCP, a period of initial inhibition of methanogenesis was followed by stimulation relative to controls. Arochlor 1254 (1000 μg g?1) and Temik (500 and 10 μg g?1) stimulated methanogenesis from the outset. Temik at 500 μg g?1 gave the greatest stimulation of methanogenesis (900% of controls) of any of the compounds studied. Sulfate reduction was inhibited by 1000 μg g?1 PCP, toxaphene, naphthalene and chlordane and by 500 μg g?1 atrazine and 100 μg g?1 heptachlor. Sustained inhibition of sulfate reduction by naphthalene, toxaphene and PCP may have contributed to the stimulation of methanogenesis. Carbon dioxide evolution was not significantly affected by most of the compounds studied except for 100 μg g?1 PCP and 1000 μg g?1 aphthalene, each of which gave significant inhibition in only one of three experiments.Concentrations of individual organic pollutants required to cause observable effects were high. It is concluded that, except for highly polluted sediments, methanogenesis, sulfate reduction and CO2 evolution would not be affected by the compounds studied here at concentrations typically found in the environment.  相似文献   

17.
Sediment samples were selected from 28 sites across the deep (212–3527 m) northern Gulf of Mexico (GOM) as part of the Deep Gulf of Mexico Benthos (DGoMB) program, and analyzed for geochemical parameters related to organic carbon (OC) distribution and characteristics. The results of this study indicate that the OC content of sediments in the deep northern GOM is controlled by several factors; including water depth, overlying water productivity, sediment carbonate content, sediment oxygen exposure time, OC sources, and regional influences. The best correlation between sediment OC content, on a CaCO3-free basis, and other parameters examined was an inverse correlation of OC with water depth. The OC/SA ratio had a wide range of values and, along with variable sources of sedimentary OC, indicated that the organism-available concentration of metabolizable organic matter may not be simply related to sedimentary OC content. This was perhaps reflected in the observation that benthic macrofaunal and meiofaunal biomass abundances were well correlated with sedimentary OC, but the abundance of bacteria in sediments was not.  相似文献   

18.
The sediment–water partitioning of radiolabelled Cd, Hg and Zn has been investigated along an estuarine salinity gradient using samples from the Mersey Estuary, UK. Partitioning was studied using untreated particles, and particles that had been extracted using either a reducing agent (NH2OH.HCl–HOAc) or an oxidising agent (H2O2) in order to qualitatively evaluate the relative roles of Fe–Mn oxides and particulate organic matter (POM), respectively, on metal uptake. The extent of Cd partitioning between sediment and water, parameterised in terms of the distribution coefficient, KD, exhibited a reduction with increasing salinity, regardless of whether or not particles had been digested. However, the magnitude of KD decreased significantly following either chemical treatment, suggesting that both oxides and organic matter are important sorbents for Cd. The KD for Hg in the presence of untreated particles increased with increasing salinity, and chemical reduction of the particles enhanced the uptake of Hg and reinforced this trend. Particle oxidation led to a significant reduction in the KD for Hg, and uptake by the particles decreased with increasing salinity. These observations suggest that POM is considerably more important than Fe–Mn oxides in the removal of aqueous Hg, and that its presence is a prerequisite for enhanced sorption (or salting out) at elevated salinities. The salinity dependence of KD for Zn displayed characteristics of both Cd (below salinities of about 5) and Hg (at greater salinities). However, the magnitude of KD for Zn uptake was relatively insensitive to either chemical treatment, suggesting that oxides, POM, and residual phases contribute to the overall sorption of Zn by estuarine particles. Regression analyses of the metal partition data suggest that sorption to oxides and POM is nonadditive, and that the salinity dependence of metal partitioning results mainly from salinity-controlled interactions between metal and organic matter. Sequential extraction of metals bound to untreated and chemically treated particles in the partitioning experiments indicated that the exchangeability or lability of all metals increased on removal of either oxides or POM. This implies that sorption sites of relatively high energy are destroyed (or become less accessible), or sorption sites of relatively low energy are created (or become more accessible) on chemical treatment. These observations support a conceptual model for the particle surface whose integrity and binding properties are only maintained by the coexistence of and interaction between oxides and organic matter.  相似文献   

19.
The Taiwan Strait region has many miles of coastline, and the Taiwan Straits Tunnel (TST) project faces many potential pollution problems as construction proceeds through sensitive areas. Conventional approaches for pollution mitigation require further examination. The recent development of nanoscale particle technology has shown distinct advantages for contaminant attenuation and ground improvement. This paper is focused on trace metals and is part of the overall effort to develop the nanoscale particle technology. Trace metals in ground and surface waters represent a continued threat to human and ecological health. One of the difficulties in removing toxic concentrations of trace metals from solution is the variable oxidation state and amphoteric nature of multiple constituents. In particular, while cationic metals (e.g., Pb2+, Cd2+, Ni2+) may be rendered less mobile under high pH conditions, anionic metals (e.g., AsO4 3?, CrO4 2?, SeO4 2?)may become more mobile. The objective of this research was to evaluate the sorption of both cationic and anionic trace elements, including arsenic (As), cadmium (Cd), chromium (Cr) and selenium (Se) under batch conditions. Mixtures of a local residual soil were tested alone and in combination with lime and zero valent iron. It was hypothesized that lime would raise the pH and precipitate positively charged metals while zero valent iron would create reducing conditions favorable to the immobilization of negatively charged metals. Results indicate that the use of lime and/or zero valent iron can increase the sorption capacity of soil. Compared to the baseline soil, sorption capacity increased with addition of lime for arsenic and cadmium while it decreased for chromium and selenium. In the case of zero valent iron addition, sorption capacity increased for cadmium, chromium and selenium, while showing no change for arsenic. When both lime and zero valent iron were used, the sorption capacity increased for all metals tested. These results suggest that the combined use of lime and zero valent iron may serve as an alternative treatment technology for removing trace metals from contaminated water systems.  相似文献   

20.
The effect of varying concentrations of soluble sewage material in river water on the sorption of Ag, Cd, Co and Zn by suspended freshwater sediments has been studied. Comparison with unpolluted natural sediment systems show that the sorption processes for trace metals are often strongly modified when the river water contains sewage materials.  相似文献   

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