首页 | 本学科首页   官方微博 | 高级检索  
相似文献
 共查询到20条相似文献,搜索用时 15 毫秒
1.
A mathematical model describing the dissolution of nuclear glass directly disposed in clay combines a first-order dissolution rate law with the diffusion of dissolved silica in clay. According to this model, the main parameters describing the long-term dissolution of the glass are etaR, the product of the diffusion accessible porosity eta and the retardation factor R, and the apparent diffusion coefficient D(app) of dissolved silica in clay. For determining the migration parameters needed for long-term predictions, four Through-Diffusion (T-D) experiments and one percolation test have been performed on undisturbed clay cores. In the Through-Diffusion experiments, the concentration decrease after injection of 32Si (radioactive labelled silica) was measured in the inlet compartment. At the end of the T-D experiments, the clay cores were cut in thin slices and the activity of labelled silica in each slice was determined. The measured activity profiles for these four clay cores are well reproducible. Since no labelled silica could be detected in the outlet compartments, the Through-Diffusion experiments are fitted by two In-Diffusion models: one model assuming linear and reversible sorption equilibrium and a second model taking into account sorption kinetics. Although the kinetic model provides better fits, due to the sufficiently long duration of the experiments, both models give approximately similar values for the fit parameters. The single percolation test leads to an apparent diffusion coefficient value about two to three times lower than those of the Through-Diffusion tests. Therefore, dissolved silica appears to be strongly retarded in Boom Clay. A retardation factor R between 100 and 300 was determined. The corresponding in situ distribution coefficient K(d) is in the range 25-75 cm(3) g(-1). The apparent diffusion coefficient of dissolved silica in Boom Clay is estimated between 2 x 10(-13) and 7 x 10(-13) m(2) s(-1). The pore diffusion coefficient is in the range from 6 x 10(-11) to 1 x 10(-10) m(2) s(-1).  相似文献   

2.
This paper presents an analytical model to describe pulse injection experiments. This model solves the advection-diffusion equation while taking into account back diffusion from the clay core to the inlet and from the outlet to the clay core. In most analytical models, back diffusion is neglected. For sufficiently high Péclet numbers, this is a good approximation. However, in experiments where the Péclet number is low, back diffusion is important and must be taken into account. An additional advantage of the present model is that both concentration and flux are conserved at the inlet and at the outlet of the clay core. This model is used to fit pulse injection experiments with iodide and tritiated water (HTO) in clay cores. The (new) model is required for fitting the experimental results since in clay layers advection is very slow leading to a low Péclet number. The experiments are performed on clay cores taken from different depths from the Boom Clay and the Ypres Clay layer under the site of the nuclear power plant of Doel (Belgium). The quality of all fits is excellent and the obtained parameter values are coherent. For HTO, the fitted value for the diffusion accessible porosity is consistent with measurements of the water content in Ypres Clay cores. In both types of clays, the apparent diffusion coefficient at zero flow is between 10(-10) and 2 x 10(-10) m(2)/s for iodide and between 2 x 10(-10) and 3 x 10(-10) m(2)/s for HTO. The dispersion length is in the order of 10(-3) m. The average value for the diffusion accessible porosity is between 0.35 and 0.4 for HTO and between 0.2 and 0.25 for iodide.  相似文献   

3.
Abstract

Metabolic fate of two dichloromethyl diaryl phosphonates (32P labelled) in/on rice plants was investigated. The test compounds were found to be less persistent on the surface of rice leaves with half lives 7.4 and 6.7 days respectively. Main degradation product from both the phosphonates were dichloromethyl phosphonic acid with trace of dichloromethyl‐O‐aryl phosphonate as a transitory intermediate product.  相似文献   

4.
A lack of information in databases for contamination risk assessment about the transport behaviour of the trivalent f-orbital elements in groundwater systems where calcite is at equilibrium motivated this study of Eu3+ uptake. The free drift technique was used to examine the effects of Eu3+ concentration, presence of Na+ or K+ and temperature, as well as calcite nucleation and precipitation kinetics, on the partitioning of calcite. Changes in surface composition and morphology resulting from exposure of single crystals of Iceland spar to Eu3+-bearing solutions were observed with X-ray photoelectron spectroscopy (XPS) and atomic force microscopy (AFM). First results confirm that calcite has high affinity for Eu3+. Rates of nucleation and precipitation strongly affect the extent of uptake but the presence of Na+ and K+ has no effect, suggesting formation of solid solution as CaCO3–EuOHCO3. Surface-sensitive techniques prove that Eu3+ is adsorbed to calcite even when the surface is dissolving and adsorption is not accompanied by precipitation of a separate Eu3+-solid phase. Adsorbed Eu modifies calcite's dissolution behaviour, roughening terraces and rounding step edges, and producing surface morphology where some surface sites appear blocked. Results imply that Eu3+ concentrations in natural calcites are limited by Eu3+ availability rather than by a lack of ability to fit into calcite's atomic structure. This behaviour can probably be expected for other trivalent rare Earth elements (REE), actinides and fission products whose behaviour is similar to that of Eu3+. These elements are likely to be incorporated within the calcite bulk in systems where it is precipitating and the demonstrated strong partitioning ensures some uptake even where calcite is at or under saturation.  相似文献   

5.
In this study, three different soils with contrasting features, spiked with 300 mg benzo[a]pyrene (BaP)/kg dry soil, were incubated at 20 °C and 60% water holding capacity for 540 days. At different time points, BaP and DNA were extracted and quantified, and DNA adducts were quantified by 32P-postlabelling. After 540 days incubation, 69.3, 81.6 and 83.2% of initial BaP added remained in Cruden Bay, Boyndie and Insch soils, respectively. Meanwhile, a significantly different amount of DNA-BaP adducts were found in the three soils exposed to BaP over time. The work demonstrates the concept that DNA adducts can be detected on DNA extracted from soil. Results suggest the technique is not able to directly reflect bioavailability of BaP transformation products. However, this new method provides a potential way to detect mutagenic compounds in contaminated soil and to assess the outcomes of soil remediation.  相似文献   

6.
7.
The effect of a biofilm on solute diffusion in fractured porous media   总被引:1,自引:0,他引:1  
At sites in fractured rock where contamination has been exposed to the rock matrix for extended periods of time, the amount of contaminant mass residing in the matrix can be considerable. Even though it may be possible to diminish concentrations by the advection of clean water through the fracture features, back diffusion from mass held in the matrix will lead to a continuing source of contamination. In such an event, the development of a biofilm (a thin film of microbial mass) on the wall of the fractures may act to limit or prevent the back diffusion process. The objective of this preliminary study is to explore the influence imparted by the presence of a biofilm on the process of matrix diffusion. The investigation was conducted using radial diffusion cells constructed from rock core in which biofilm growth was stimulated in a central reservoir. Once biofilms were developed, forward diffusion experiments were conducted in which a conservative solute migrated from the central reservoir into the intact rock sample. Diffusion experiments were performed in a total of 11 diffusion cell pairs where biofilm growth was stimulated in one member of the pair and inhibited in the other. The effect of the presence of a biofilm on tracer diffusion was determined by comparison of the diffusion curves produced by each cell pair. A semi-analytical model that accounts for the presence of a biofilm was used to investigate the effect of the biofilm on mass transfer due to changes in the effective porosity, effective diffusion coefficient, and the depth of penetration of the biofilm into the intact rock. The results show that the biofilm acted to plug the rock matrix, rather than forming a discrete layer on the reservoir surface. The reduction in effective porosity due to the biofilm ranged from 6% to 52% with the majority of the samples in the 30% to 50% range. Based on the present results, with more efficient biofilm stimulation, it is reasonable to assume that a more complete plugging of the microcrack porosity might be possible, leaving a much thicker and efficient barrier than could be achieved via a surface biofilm.  相似文献   

8.
Sorption of 137Cs, 90Sr, 154Eu and 141Ce by magnetite has been studied at varying pH (4 to 11) in the presence and absence of humic acid. The sorption studies have also been carried out at varying ionic strength (0.01 to 0.2 M NaClO4) and humic acid concentration (2 to 20 mg/L). Percentage sorption of 137Cs and 90Sr was found to be pH dependent, with the sorption increasing with increasing pH of the suspension. At any pH, the percentage sorption of 90Sr was higher than that of 137Cs. The results have been explained in terms of the electrostatic interaction between the positively charged metal ions and the surface charge of the magnetite which becomes increasingly negative with increasing pH. On the other hand, 154Eu and 141Ce were found to be strongly sorbed by the magnetite at all pH values, with the sorption being independent of pH. The strong sorption of trivalent and tetravalent metal ions suggests the role of complexation reactions during sorption, apart from the electrostatic interactions. However, in the case of 141Ce surface precipitation of Ce(III) formed by reduction of Ce(IV) in the presence of magnetite cannot be ruled out. Presence of humic acid (2 mg/L) was found to have negligible effect on sorption of all metal ions.  相似文献   

9.
The fate of 14C-labeled sulfadiazine (14C-SDZ) residues was studied in time-course experiments for 218 days of incubation using two soils (Ap horizon of loamy sand, orthic luvisol; Ap horizon of silt loam, cambisol) amended with fresh and aged (6 months) 14C-manure [40 g kg?1 of soil; 6.36 mg of sulfadiazine (SDZ) equivalents per kg of soil], which was derived from two shoats treated with 14C-SDZ. Mineralization of 14C-SDZ residues was below 2% after 218 days depending little on soil type. Portions of extractable 14C (ethanol-water, 9:1, v/v) decreased with time to 4–13% after 218 days of incubation with fresh and aged 14C-manure and both soils. Non-extractable residues were the main route of the fate of the 14C-SDZ residues (above 90% of total recovered 14C after 218 days). These residues were high immediately after amendment depending on soil type and aging of the 14C-manure, and were stable and not remobilized throughout 218 days of incubation. Bioavailable portions (extraction using CaCl2 solution) also decreased with increasing incubation period (5–7% after 218 days). Due to thin-layer chromatography (TLC), 500 μg of 14C-SDZ per kg soil were found in the ethanol-water extracts immediately after amendment with fresh 14C-manure, and about 50 μg kg?1 after 218 days. Bioavailable 14C-SDZ portions present in the CaCl2 extracts were about 350 μg kg?1 with amendment. Higher concentrations were initially detected with aged 14C-manure (ethanol-water extracts: 1,920 μg kg?1; CaCl2 extracts: 1,020 μg kg?1), probably due to release of 14C-SDZ from bound forms during storage. Consistent results were obtained by extraction of the 14C-manure-soil samples with ethyl acetate; portions of N-acetylated SDZ were additionally determined. All soluble 14C-SDZ residues contained in 14C-manure contributed to the formation of non-extractable residues; a tendency for persistence or accumulation was not observed. SDZ's non-extractable soil residues were associated with the soluble HCl, fulvic acids and humic acids fractions, and the insoluble humin fraction. The majority of the non-extractable residues appeared to be due to stable covalent binding to soil organic matter.  相似文献   

10.
Activity concentrations of 210Po and 210Pb in the species Mytilus galloprovincialis from Croatian Adriatic coast were determined. The samples were collected in thirteen sampling places which are also a part of Croatian Mediterranean mussel watch project. The results of 210Po and 210Pb activity concentrations were found to vary between (22.1 ± 2.5)-(207 ± 21) Bq kg−1 fresh weight and (2.8 ± 1.4)-(9.3 ± 0.7) Bq kg−1 fresh weight, respectively. 210Po/210Pb ratio ranged between 6.2 and 30.7. The highest measured activities were found in the enclosed basins of the Neretva channel, where the majority of Croatian mussel cultivation is taking place. The estimated consequent average total annual effective ingestion dose due to 210Po and 210Pb from mussel consumption in Croatian coastal region is 202 ± 99 μSv with 96% contribution of 210Po to the total effective dose.  相似文献   

11.
Massive blooms of the harmful benthic dinoflagellate Ostreopsis cf. ovata are of growing environmental concern in the Mediterranean, having recently caused adverse effects on benthic invertebrates and also some intoxication episodes to humans.The toxicological potential of produced palytoxin-like compounds was investigated in the present study on a typical marine sentinel species, the mussel Mytilus galloprovincialis. Organisms were sampled during various phases of a O. cf. ovata bloom, in two differently impacted sites. The presence of the algal toxins was indirectly assessed in mussels tissues (mouse test and hemolysis neutralization assay), while biological and toxicological effects were evaluated through the measurement of osmoregulatory and neurotoxic alterations (Na+/K+-ATPase and acetylcholinesterase activities), oxidative stress responses (antioxidant defences and total oxyradical scavenging capacity), lipid peroxidation processes (level of malondialdehyde), peroxisomal proliferation, organelle dysfunctions (lysosomal membrane stability, accumulation of lipofuscin and neutral lipids), immunological impairment (granulocytes percentage).Obtained results demonstrated a significant accumulation of algal toxins in mussels exposed to O. cf. ovata. These organisms exhibited a marked inhibition of the Na+/K+-ATPase activity and alterations of immunological, lysosomal and neurotoxic responses. Markers of oxidative stress showed more limited variations suggesting that toxicity of the O. cf. ovata toxins is not primarily mediated by an over production of reactive oxygen species. This study provided preliminary results on the usefulness of a multi-biomarker approach to assess biological alterations and toxicological events associated to blooms of O. cf. ovata in marine organisms.  相似文献   

12.
Results of 2 years monitoring of 210Po and 210Pb activity concentrations in soft tissue of the species Mytilus galloprovincialis from Croatian part of the Adriatic coast are presented. The samples were collected at thirteen coastal stations (some of which are also a part of the Mediterranean Mussel Watch Project) in spring and autumn of 2010 and 2011. The collected mussels were ranging between 4 cm and 6 cm in shell length. After sample pre-treatment lead and polonium were radiochemically separated on Sr resin. 210Po was determined by alpha-particle spectrometry and 210Pb was determined, via 210Bi, by a low-level gas proportional counter. The results of 210Po activity concentrations were found to vary between (104 ± 11) and (1421 ± 81) Bq kg−1 dry weight while 210Pb activity concentrations were much lower and in range (8.2 ± 5.3)–(94.1 ± 29.8) Bq kg−1 dry weight. Higher 210Po and 210Pb activity concentrations were determined in spring period. The inter-site differences seen in their activity concentrations can be due to natural background levels of sites. The 210Po/210Pb activity concentration ratios in all cases exceeded unity for all mussel samples and ranged between 4.0 and 47.9.  相似文献   

13.
针对废水中Mn2+难去除问题,利用经高温焙烧制备的膨润土-粉煤灰复合新型吸附剂对废水中的Mn2+进行吸附处理实验研究。研究了新型吸附剂在不同的吸附时间、pH、初始Mn2+浓度条件下对Mn2+的吸附去除效果影响、Fe2+、Mn2+共存时竞争吸附特性以及吸附Mn2+的吸附性能和反应动力学。实验结果表明,新型吸附剂处理Mn2+浓度为35 mg/L的废水,在温度25℃、转速100 r/min、投加量20 g/L、吸附时间120 min、pH≥7时反应条件最佳,Mn2+的去除率均可达到90%以上;Fe2+、Mn2+共存时,存在竞争吸附,Fe2+会被优先选择吸附去除,Fe2+的存在会影响Mn2+的去除效果;膨润土复合新型吸附剂对Mn2+的吸附行为符合Langmuir等温吸附模型和准二级动力学模型。新型吸附剂对废水中的Mn2+有很好的去除效果,而且能有效解决膨润土不易固液分离问题,可作为含Mn2+废水高效、廉价、环保的水处理吸附剂。  相似文献   

14.
《Chemosphere》2002,49(10)
The distribution coefficients (Kd) and desorption rates of 137Cs and 241Am radionuclides in bottom sediments at different locations in the Black Sea were studied under laboratory conditions. The Kd values were found to be 500 for 137Cs and 3800 for 241Am at the steady state and described exponential curves. Rapid uptake of the radionuclides occurred during the initial period and little accumulation happened after four days. The desorption rates for 137Cs in different bottom sediments were best described by a three-component exponential model. The desorption half-times of 137Cs ranged from 26 to 50 d at the slow components. However, the desorption rate of 241Am described one component for all sediment samples and desorption half-time was found to be 75 d. In general, the results showed that the 241Am radionuclide is more effectively transferred to bottom sediment and has longer turnover time than 137Cs under Black Sea conditions.  相似文献   

15.
评述了原位产生H2O2的电化学法污水处理技术中使用的主要电极,研究了用石墨制备高效气体扩散电极的方法。对石墨用HNO3与H3PO4的混合液改性,石墨与聚四氟乙烯的质量比为2∶1,电极经350℃煅烧1 h,对溶解O2还原产生H2O2的催化活性最高。仅在pH值很低时,电极的活性较差,在pH=3~9时,电极的活性受pH值变化影响较小。在pH=3时电解150 min,电极的电流效率始终高于72%,H2O2浓度达到了274.5 mg/L。  相似文献   

16.
Permeable reactive barriers (PRBs) are an alternative technology to treat mine drainage containing sulfate and heavy metals. Two column experiments were conducted to assess the suitability of an organic carbon (OC) based reactive mixture and an Fe0-bearing organic carbon (FeOC) based reactive mixture, under controlled groundwater flow conditions. The organic carbon mixture contains about 30% (volume) organic carbon (composted leaf mulch) and 70% (volume) sand and gravel. The Fe0-bearing organic carbon mixture contains 10% (volume) zero-valent iron, 20% (volume) organic carbon, 10% (volume) limestone, and 60% (volume) sand and gravel. Simulated groundwater containing 380 ppm sulfate, 5 ppm As, and 0.5 ppm Sb was passed through the columns at flow rates of 64 (the OC column) and 62 (the FeOC column) ml d− 1, which are equivalent to 0.79 (the OC column) and 0.78 (the FeOC column) pore volumes (PVs) per week or 0.046 m d− 1 for both columns. The OC column showed an initial sulfate reduction rate of 0.4 µmol g (OC)− 1 d− 1 and exhausted its capacity to promote sulfate reduction after 30 PVs, or 9 months of flow. The FeOC column sustained a relatively constant sulfate reduction rate of 0.9 µmol g (OC)− 1 d− 1 for at least 65 PVs (17 months). In the FeOC column, the δ34S values increase with the decreasing sulfate concentration. The δ34S fractionation follows a Rayleigh fractionation model with an enrichment factor of 21.6‰. The performance decline of the OC column was caused by the depletion of substrate or electron donor. The cathodic production of H2 by anaerobic corrosion of Fe probably sustained a higher level of SRB activity in the FeOC column. These results suggest that zero-valent iron can be used to provide an electron donor in sulfate reducing PRBs. A sharp increase in the δ13C value of the dissolved inorganic carbon and a decrease in the concentration of HCO3 indicate that hydrogenotrophic methanogenesis is occurring in the first 15 cm of the FeOC column.  相似文献   

17.
Abstract

14C‐DDT dissipated gradually from natural water under outdoor conditions and declined to 40% of the applied radioactivity after 5 months. The losses are due to adsorption to particulates and volatilization from the water surface. In natural water DDT undergoes gradual conversion to DDE as the major degradation product and to a lesser extent to DDD. It may be concluded that DDT dissipates and degrades fairly rapidly in subtropical natural waters. Adsorption to particulate matter contributes to partial “removal” of DDT.  相似文献   

18.
This report demonstrates that organic matter was an important factor in lake sediment 210Pbex dating. Sediment cores from lakes in central and western China with different-trophic levels were collected, and the 210Pbex activity and total organic carbon (TOC) were measured. The Rock-Eval pyrolysis technique was used to deconvolute TOC into free hydrocarbons (S1), thermally less-stable macromolecular organic matter (S2a), kerogen (S2b), and residual carbon (RC). The results show significant correlations between TOC and 210Pbex, particularly between S2a and 210Pbex, in all the sediment cores. This indicated that the algal-derived organic component S2a may play the most important role in controlling the distribution of 210Pbex. Scavenging by algal-derived organic matter may be the main mechanism. As chronology is the key to the understanding of pollution reconstruction and early diagenesis in sediments, more attention should be paid to the influence of organic matter on 210Pbex.  相似文献   

19.
Abstract

Degradation of trifluralin (α,α,α-trifluoro-2,6-dinitro-N,N-dipropyl-p-toluidine) was investigated in soils taken from three different locations at Harran region of Turkey under laboratory conditions. Surface (0–10 cm) soils, which were taken from a pesticide untreated field Gürgelen, Harran-1 and Ikizce regions in the Harran Plain, were incubated in biometer flasks for 350 days at 25°C. Ring-UL-14C-trifluralin was applied at the rate of 2 µg g?1 with 78.7 kBq radioactivity per 100 g soil flask. Evolved 14CO2 was monitored in KOH traps throughout the experiment. Periodically, soil sub-samples were removed and extracted by supercritical fluid extraction (SFE). Unextractable soil-bound 14C residues were determined by combustion. During the 350 days incubation period 6.6, 5.4, and 3.3% of the applied radiocarbon was evolved as 14CO2 from the Harran-1, Gürgelen, and Ikizce soil, respectively. At the end of 350 days the SFE-extractable and bound 14C-trifluralin residues were 39.0 and 29.2% of the initially applied herbicide in Gürgelen soil. The corresponding values for Harran-1 and Ikizce soils were 36.2, 28.4% and 41.6, 18.5% respectively.  相似文献   

20.
A combined mass-balance and stable isotope approach was set up to identify and quantify dissolved organic carbon (DOC) sources in a DOC-rich (9 mg L−1) eutrophic reservoir located in Western France and used for drinking water supply (so-called Rophemel reservoir). The mass-balance approach consisted in measuring the flux of allochthonous DOC on a daily basis, and in comparing it with the effective (measured) DOC concentration of the reservoir. The isotopic approach consisted, for its part, in measuring the carbon isotope ratios (δ13C values) of both allochthonous and autochthonous DOC sources, and comparing these values with the δ13C values of the reservoir DOC. Results from both approaches were consistent pointing out for a DOC of 100% allochthonous origin. In particular, the δ13C values of the DOC recovered in the reservoir (−28.5 ± 0.2‰; n = 22) during the algal bloom season (May-September) showed no trace of an autochthonous contribution (δ13C in algae = −30.1 ± 0.3‰; n = 2) being indistinguishable from the δ13C values of allochthonous DOC from inflowing rivers (−28.6 ± 0.1‰; n = 8). These results demonstrate that eutrophication is not responsible for the high DOC concentrations observed in the Rophemel reservoir and that limiting eutrophication of this reservoir will not reduce the potential formation of disinfection by-products during water treatment. The methodology developed in this study based on a complementary isotopic and mass-balance approach provides a powerful tool, suitable to identify and quantify DOC sources in eutrophic, DOC-contaminated reservoirs.  相似文献   

设为首页 | 免责声明 | 关于勤云 | 加入收藏

Copyright©北京勤云科技发展有限公司  京ICP备09084417号