全文获取类型
收费全文 | 1048篇 |
免费 | 94篇 |
国内免费 | 286篇 |
专业分类
安全科学 | 91篇 |
废物处理 | 18篇 |
环保管理 | 231篇 |
综合类 | 543篇 |
基础理论 | 147篇 |
污染及防治 | 300篇 |
评价与监测 | 53篇 |
社会与环境 | 34篇 |
灾害及防治 | 11篇 |
出版年
2024年 | 3篇 |
2023年 | 22篇 |
2022年 | 40篇 |
2021年 | 45篇 |
2020年 | 36篇 |
2019年 | 43篇 |
2018年 | 34篇 |
2017年 | 41篇 |
2016年 | 44篇 |
2015年 | 47篇 |
2014年 | 68篇 |
2013年 | 75篇 |
2012年 | 91篇 |
2011年 | 87篇 |
2010年 | 63篇 |
2009年 | 89篇 |
2008年 | 62篇 |
2007年 | 64篇 |
2006年 | 67篇 |
2005年 | 46篇 |
2004年 | 58篇 |
2003年 | 32篇 |
2002年 | 35篇 |
2001年 | 54篇 |
2000年 | 38篇 |
1999年 | 17篇 |
1998年 | 30篇 |
1997年 | 20篇 |
1996年 | 8篇 |
1995年 | 5篇 |
1994年 | 6篇 |
1993年 | 7篇 |
1992年 | 8篇 |
1991年 | 2篇 |
1990年 | 4篇 |
1989年 | 2篇 |
1988年 | 1篇 |
1987年 | 6篇 |
1986年 | 1篇 |
1985年 | 6篇 |
1984年 | 2篇 |
1982年 | 3篇 |
1981年 | 5篇 |
1980年 | 3篇 |
1979年 | 4篇 |
1978年 | 2篇 |
1972年 | 2篇 |
排序方式: 共有1428条查询结果,搜索用时 31 毫秒
71.
Biodegradation of trichloroethene (TCE) near a Dense Non Aqueous Phase Liquid (DNAPL) can enhance the dissolution rate of the DNAPL by increasing the concentration gradient at the DNAPL-water interface. Two-dimensional flow-through sand boxes containing a TCE DNAPL and inoculated with a TCE dechlorinating consortium were set up to measure this bio-enhanced dissolution under anaerobic conditions. The total mass of TCE and daughter products in the effluent of the biotic boxes was 3-6 fold larger than in the effluent of the abiotic box. However, the mass of daughter products only accounted for 19-55% of the total mass of chlorinated compounds in the effluent, suggesting that bio-enhanced dissolution factors were maximally 1.3-2.2. The enhanced dissolution most likely primarily resulted from variable DNAPL distribution rather than biodegradation. Specific dechlorination rates previously determined in a stirred liquid medium were used in a reactive transport model to identify the rate limiting factors. The model adequately simulated the overall TCE degradation when predicted resident microbial numbers approached observed values and indicated an enhancement factor for TCE dissolution of 1.01. The model shows that dechlorination of TCE in the 2D box was limited due to the short residence time and the self-inhibition of the TCE degradation. A parameter sensitivity analysis predicts that the bio-enhanced dissolution factor for this TCE source zone can only exceed a value of 2 if the TCE self-inhibition is drastically reduced (when a TCE tolerant dehalogenating community is present) or if the DNAPL is located in a low-permeable layer with a small Darcy velocity. 相似文献
72.
为了增加多壁碳纳米管(multiwall carbon nanotubers,MWNTs)对水中Cd2+的吸附量,使用混酸对多壁碳纳米管进行氧化处理,采用红外光谱进行结果表征,并探讨了吸附时间、pH值和MWNTs的使用量、Cd2+的浓度及干扰离子对镉离子吸附的影响。结果表明,吸附时间为1.5 h、pH为5.3、吸附效果最佳,随MWNTs量的增加Cd2+去除量增加,共存的阳离子会降低对Cd2+的吸附效果,对Cd2+的吸附符合Longmuir吸附定律。研究同时表明,pH小于2时Cd2+能容易从碳纳米管上解吸。初步探讨了Cd2+吸附机制。 相似文献
73.
通过静态实验研究溴代十六烷基吡啶(CPB)改性沸石和天然沸石对废水中Hg^2+的吸附特性,探讨了吸附动力学、吸附平衡和吸附热力学机制。研究表明:Langmuir方程能较好地描述2种沸石对Hg^2+的吸附,CPB改性沸石对Hg^2+的吸附率得到显著提高。实验条件下,改性沸石对Hg^2+的吸附率从67.5%提高到98.9%,吸附容量从0.521mg/g提高到3.07mg/g。利用准一级动力学方程、假二级动力学方程、颗粒内扩散模型和Elovich方程分别对动力学过程进行拟合,发现2种沸石对Hg^2+的吸附均满足假二级动力学方程,且离子的颗粒内扩散对整个吸附过程有影响。动力学拟合、D-R方程拟合和热力学研究综合表明:2种沸石对Hg^2+的吸附既存在化学吸附又存在物理吸附,吸附吉布斯自由能变(△G^0)、焓变(△H^0)、熵变(△S^0)均小于0,反应为自发的放热反应,低温有利于吸附的进行。 相似文献
74.
Inverse modeling of multicomponent reactive transport through single and dual porosity media 总被引:3,自引:0,他引:3
Compacted bentonite is foreseen as buffer material for high-level radioactive waste in deep geological repositories because it provides hydraulic isolation, chemical stability, and radionuclide sorption. A wide range of laboratory tests were performed within the framework of FEBEX (Full-scale Engineered Barrier EXperiment) project to characterize buffer properties and develop numerical models for FEBEX bentonite. Here we present inverse single and dual-continuum multicomponent reactive transport models of a long-term permeation test performed on a 2.5 cm long sample of FEBEX bentonite. Initial saline bentonite porewater was flushed with 5.5 pore volumes of fresh granitic water. Water flux and chemical composition of effluent waters were monitored during almost 4 years. The model accounts for solute advection and diffusion and geochemical reactions such as aqueous complexation, acid-base, cation exchange, protonation/deprotonation by surface complexation and dissolution/precipitation of calcite, chalcedony and gypsum. All of these processes are assumed at local equilibrium. Similar to previous studies of bentonite porewater chemistry on batch systems which attest the relevance of protonation/deprotonation on buffering pH, our results confirm that protonation/deprotonation is a key process in maintaining a stable pH under dynamic transport conditions. Breakthrough curves of reactive species are more sensitive to initial porewater concentration than to effective diffusion coefficient. Optimum estimates of initial porewater chemistry of saturated compacted FEBEX bentonite are obtained by solving the inverse problem of multicomponent reactive transport. While the single-continuum model reproduces the trends of measured data for most chemical species, it fails to match properly the long tails of most breakthrough curves. Such limitation is overcome by resorting to a dual-continuum reactive transport model. 相似文献
75.
Solute transport in fractured rocks is of major interest in many applications, from the petroleum industry to ground water management. This work focuses on the dispersion process in a transparent replica of a real single fracture. The fracture exhibits strong changes in heterogeneity, with the first half very heterogeneous and the second half fairly homogeneous. Three models have been used to interpret the tracer experiments: the classical advection-dispersion equation (ADE), the continuous time random walk (CTRW), and the stratified model. The main goals were to test these models and to study possible correlations between fitting parameters and heterogeneities. As expected, the solution derived from the ADE equation appears to be unable to model long-time tailing behavior. On the other hand, the results confirm the CTRW robustness and the coefficient beta seems well correlated to heterogeneities. Finally, the stratified model is also able to describe non-Fickian dispersion. The parameters defined by this model are correlated to the heterogeneities of the fracture. 相似文献
76.
Identification of key parameters controlling dissolved oxygen migration and attenuation in fractured crystalline rocks 总被引:1,自引:0,他引:1
In the crystalline rocks of the Canadian Shield, geochemical conditions are currently reducing at depths of 500-1000 m. However, during future glacial periods, altered hydrologic conditions could potentially result in enhanced recharge of glacial melt water containing a relatively high concentration of dissolved oxygen (O2). It is therefore of interest to investigate the physical and geochemical processes, including naturally-occurring redox reactions, that may control O2 ingress. In this study, the reactive transport code MIN3P is used in combination with 2k factorial analyses to identify the most important parameters controlling oxygen migration and attenuation in fractured crystalline rocks. Scenarios considered are based on simplified conceptual models that include a single vertical fracture, or a fracture zone, contained within a rock matrix that extends from the ground surface to a depth of 500 m. Consistent with field observations, Fe(II)-bearing minerals are present in the fractures (i.e. chlorite) and the rock matrix (biotite and small quantities of pyrite). For the parameter ranges investigated, results indicate that for the single fracture case, the most influential factors controlling dissolved O2 ingress are flow velocity in the fracture, fracture aperture, and the biotite reaction rate in the rock matrix. The most important parameters for the fracture zone simulations are flow velocity in the individual fractures, pO2 in the recharge water, biotite reaction rate, and to a lesser degree the abundance and reactivity of chlorite in the fracture zone, and the fracture zone width. These parameters should therefore receive increased consideration during site characterization, and in the formulation of site-specific models intended to predict O2 behavior in crystalline rocks. 相似文献
77.
Bauer RD Maloszewski P Zhang Y Meckenstock RU Griebler C 《Journal of contaminant hydrology》2008,96(1-4):150-168
Various abiotic and biotic processes such as sorption, dilution, and degradation are known to affect the fate of organic contaminants, such as petroleum hydrocarbons in saturated porous media. Reactive transport modeling of such plumes indicates that the biodegradation of organic pollutants is, in many cases, controlled by mixing and therefore occurs locally at the plume's fringes, where electron donors and electron-acceptors mix. Herein, we aim to test whether this hypothesis can be verified by experimental results obtained from aerobic and anaerobic degradation experiments in two-dimensional sediment microcosms. Toluene was selected as a model compound for oxidizable contaminants. The two-dimensional microcosm was filled with quartz sand and operated under controlled flow conditions simulating a contaminant plume in otherwise uncontaminated groundwater. Aerobic degradation of toluene by Pseudomonas putida mt-2 reduced a continuous 8.7 mg L(-1) toluene concentration by 35% over a transport distance of 78 cm in 15.5 h. In comparison, under similar conditions Aromatoleum aromaticum strain EbN1 degraded 98% of the toluene infiltrated using nitrate (68.5+/-6.2 mg L(-1)) as electron acceptor. A major part of the biodegradation activity was located at the plume fringes and the slope of the electron-acceptor gradient was steeper during periods of active biodegradation. The distribution of toluene and the significant overlap of nitrate at the plume's fringe indicate that biokinetic and/or microscale transport processes may constitute additional limiting factors. Experimental data is corroborated with results from a reactive transport model using double Monod kinetics. The outcome of the study shows that in order to simulate degradation in contaminant plumes, detailed data sets are required to test the applicability of models. These will have to deal with the incorporation of existing parameters coding for substrate conversion kinetics and microbial growth. 相似文献
78.
Arcos D Grandia F Domènech C Fernández AM Villar MV Muurinen A Carlsson T Sellin P Hernán P 《Journal of contaminant hydrology》2008,102(3-4):196-209
The KBS-3 underground nuclear waste repository concept designed by the Swedish Nuclear Fuel and Waste Management Co. (SKB) includes a bentonite buffer barrier surrounding the copper canisters and the iron insert where spent nuclear fuel will be placed. Bentonite is also part of the backfill material used to seal the access and deposition tunnels of the repository. The bentonite barrier has three main safety functions: to ensure the physical stability of the canister, to retard the intrusion of groundwater to the canisters, and in case of canister failure, to retard the migration of radionuclides to the geosphere. Laboratory experiments (< 10 years long) have provided evidence of the control exerted by accessory minerals and clay surfaces on the pore water chemistry. The evolution of the pore water chemistry will be a primordial factor on the long-term stability of the bentonite barrier, which is a key issue in the safety assessments of the KBS-3 concept.In this work we aim to study the long-term geochemical evolution of bentonite and its pore water in the evolving geochemical environment due to climate change. In order to do this, reactive transport simulations are used to predict the interaction between groundwater and bentonite which is simulated following two different pathways: (1) groundwater flow through the backfill in the deposition tunnels, eventually reaching the top of the deposition hole, and (2) direct connection between groundwater and bentonite rings through fractures in the granite crosscutting the deposition hole. The influence of changes in climate has been tested using three different waters interacting with the bentonite: present-day groundwater, water derived from ice melting, and deep-seated brine. Two commercial bentonites have been considered as buffer material, MX-80 and Deponit CA-N, and one natural clay (Friedland type) for the backfill. They show differences in the composition of the exchangeable cations and in the accessory mineral content. Results from the simulations indicate that pore water chemistry is controlled by the equilibrium with the accessory minerals, especially carbonates. pH is buffered by precipitation/dissolution of calcite and dolomite, when present. The equilibrium of these minerals is deeply influenced by gypsum dissolution and cation exchange reactions in the smectite interlayer. If carbonate minerals are initially absent in bentonite, pH is then controlled by surface acidity reactions in the hydroxyl groups at the edge sites of the clay fraction, although its buffering capacity is not as strong as the equilibrium with carbonate minerals. The redox capacity of the bentonite pore water system is mainly controlled by Fe(II)-bearing minerals (pyrite and siderite). Changes in the groundwater composition lead to variations in the cation exchange occupancy, and dissolution–precipitation of carbonate minerals and gypsum. The most significant changes in the evolution of the system are predicted when ice-melting water, which is highly diluted and alkaline, enters into the system. In this case, the dissolution of carbonate minerals is enhanced, increasing pH in the bentonite pore water. Moreover, a rapid change in the population of exchange sites in the smectite is expected due to the replacement of Na for Ca. 相似文献
79.
80.
The practice of contaminant transport and remediation has shown significant progress in recent years. However, despite the
significant progress made, remediation efforts are often delayed by extremely long breakthrough curve tails that render efforts
to bring the level of contaminants below the regulatory standards inefficient. One hypothesis is that these long tails are
due to the reservoir-like slow diffusive processes in soil micropore zones. This study compares the effects of micropores
at macroscopic and microscopic levels and establishes a link between these approaches for validation and calibration purposes.
The link between macroscopic and microscopic levels is established through comparisons and testing of the two models while
incorporating appropriate scale and boundary effects. Despite the differences in conceptual approaches and simulation time,
the two approaches rendered meaningful results. The link helps forecast the effects of micropore zone transport processes
in the subsurface efficiently and thus allows development of numerical tools that could contribute towards more efficient
remediation design. 相似文献