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861.
862.
Mohammednoor Altarawneh Daniel Carrizo Artur Ziolkowski Eric M. Kennedy Bogdan Z. Dlugogorski John C. Mackie 《Chemosphere》2009,74(11):1435-1443
This article reports the computational and experimental results of the thermal decomposition of permethrin, a potential source of dibenzo-p-dioxins (PCDD) and polychlorinated dibenzofurans (PCDF). We have performed a quantum chemical analysis by applying density functional theory to obtain the decomposition pathways of permethrin and the formation mechanism of dibenzofuran. We have conducted the pyrolysis experiments in a tubular reactor and identified the pyrolysis products to demonstrate the agreement between the experimental measurements and quantum chemical calculations. The initiation of the decomposition of permethrin involves principally the aromatisation of permethrin into 3-phenoxyphenylacetic acid, 2-methylphenyl ester (J) and concomitant loss of 2HCl. This rearrangement is followed by the rupture of the O–CH2 linkage in J, with a rate constant derived from the quantum chemical results of 1 × 1015 exp(−68 kcal/mol/RT) s−1 for temperatures between 700 and 1300 K. This is confirmed by finding that the rate constant for unimolecular rearrangement of permethrin into J is 1.2 × 1012 exp(−53 kcal/mol/RT) s−1 over the same range of temperatures and exceeds the direct fission rate constant at all temperatures up to 850 ± 120 °C as well as by the experimental detection of J prior to the detection of the initial products incorporating diphenyl ether, 1-methyl-3-phenoxybenzene, 3-phenoxybenzaldehyde and 1-chloromethyl-3-phenoxybenzene. As the temperature increases, we observe a rise in secondary products formed directly or indirectly (via phenol/phenoxy) including aromatics (naphthalene), biphenyls (biphenyl, 4-methyl-1,1′-biphenyl) and dibenzofuran (DF). In particular, we discover by means of quantum chemistry a direct route from 2-phenoxyphenoxy to naphthalene. We detect no polychlorinated dibenzo-p-dioxins and dibenzofurans. Unlike the case of oxidative pyrolysis [Tame, N.W., Dlugogorski, B.Z., Kennedy, E.M., 2007b. Formation of dioxins in fires of arsenic-free treated wood: Role of organic preservatives. Environ. Sci. Technol. 41, 6425–6432] where significant yields of both PCDD and PCDF were obtained, under non-oxidative conditions the thermal decomposition of permethrin does not form appreciable amounts of PCDD or PCDF and the presence of oxygen (and/or a sizable radical pool) appears necessary for the formation of dibenzo-p-dioxin itself or PCDD/F from phenol/phenoxy. 相似文献
863.
The degradation of linuron, one of phenylurea herbicides, was investigated for its reaction kinetics by different treatment processes including ultraviolet irradiation (UV), ozonation (O3), and UV/O3. The decay rate of linuron by UV/O3 process was found to be around 3.5 times and 2.5 times faster than sole-UV and ozone-alone, respectively. Experimental results also indicate overall rate constants increased exponentially with pH above 9.0 while the increase of rate constants with pH below 9 is insignificant in O3 system. All dominant parameters involved in the three processes were determined in the assistant of proposed linear models in this study. The approach was found useful in predicting the process performances through the quantification of quantum yield (rate constant for the formation of free radical HOO− from ozone decomposition at high pH), rate constant of linuron with ozone (kO3,LNR), rate constant of linuron with hydroxyl radical (kOH,LNR), and α (the ratio of the production rate of OH and the decay rate of ozone in UV/O3 system). 相似文献
864.
A global assessment of chromium pollution using sperm whales (Physeter macrocephalus) as an indicator species 总被引:1,自引:0,他引:1
John Pierce Wise Sr. Roger Payne Sandra S. Wise Carolyne LaCerte James Wise Christy Gianios Jr. W. Douglas Thompson Christopher Perkins Tongzhang Zheng Cairong Zhu Lucille Benedict Iain Kerr 《Chemosphere》2009,75(11):1461-1467
Chromium (Cr) is a well-known human carcinogen and a potential reproductive toxicant, but its contribution to ocean pollution is poorly understood. The aim of this study was to provide a global baseline for Cr as a marine pollutant using the sperm whale (Physeter macrocephalus) as an indicator species. Biopsies were collected from free-ranging whales around the globe during the voyage of the research vessel The Odyssey. Total Cr levels were measured in 361 sperm whales collected from 16 regions around the globe detectable levels ranged from 0.9 to 122.6 μg Cr g tissue−1 with a global mean of 8.8 ± 0.9 μg g−1. Two whales had undetectable levels. The highest levels were found in sperm whales sampled in the waters near the Islands of Kiribati in the Pacific (mean = 44.3 ± 14.4) and the Seychelles in the Indian Ocean (mean = 19.5 ± 5.4 μg g−1). The lowest mean levels were found in whales near the Canary Islands (mean = 3.7 ± 0.8 μg g−1) and off of the coast of Sri Lanka (mean = 3.3 ± 0.4 μg g−1). The global mean Cr level in whale skin was 28-times higher than mean Cr skin levels in humans without occupational exposure. The whale levels were more similar to levels only observed previously in human lung tissue from workers who died of Cr-induced lung cancer. We conclude that Cr pollution in the marine environment is significant and that further study is urgently needed. 相似文献
865.
The boundary between preferential flow and Richards-type flow is a priori set at a volumetric soil water content θ at which soil water diffusivity D (θ) = η (= 10− 6 m2 s− 1), where η is the kinematic viscosity. First we estimated with a hydrostatic approach from soil water retention curves the boundary, θK, between the structural pore domain, in which preferential flow occurs, and the matrix pore domain, in which Richards-type flow occurs. We then compared θK with θ that was derived from the respective soil hydrological property functions of same soil sample. Second, from in situ investigations we determined 96 values of θG as the terminal soil water contents that established themselves when the corresponding water-content waves of preferential flow have practically ceased. We compared the frequency distribution of θG with the one of θ that was calculated from the respective soil hydrological property functions of 32 soil samples that were determined with pressure plate apparatuses in the laboratory. There is support of the notion that θK ≈ θG ≈ θ, thus indicating the potential of θ to explain more generally what constitutes preferential flow. However, the support is assessed as working hypothesis on which to base further research rather than a procedure to a clear-cut identification of preferential flow and associated flow paths. 相似文献
866.
Nadeem W. Shah Steven F. Thornton Simon H. Bottrell Michael J. Spence 《Journal of contaminant hydrology》2009,103(3-4):119-133
The potential for aerobic biodegradation of MTBE in a fractured chalk aquifer is assessed in microcosm experiments over 450 days, under in situ conditions for a groundwater temperature of 10 °C, MTBE concentration between 0.1 and 1.0 mg/L and dissolved O2 concentration between 2 and 10 mg/L. Following a lag period of up to 120 days, MTBE was biodegraded in uncontaminated aquifer microcosms at concentrations up to 1.2 mg/L, demonstrating that the aquifer has an intrinsic potential to biodegrade MTBE aerobically. The MTBE biodegradation rate increased three-fold from a mean of 6.6 ± 1.6 μg/L/day in uncontaminated aquifer microcosms for subsequent additions of MTBE, suggesting an increasing biodegradation capability, due to microbial cell growth and increased biomass after repeated exposure to MTBE. In contaminated aquifer microcosms which also contained TAME, MTBE biodegradation occurred after a shorter lag of 15 or 33 days and MTBE biodegradation rates were higher (max. 27.5 μg/L/day), probably resulting from an acclimated microbial population due to previous exposure to MTBE in situ. The initial MTBE concentration did not affect the lag period but the biodegradation rate increased with the initial MTBE concentration, indicating that there was no inhibition of MTBE biodegradation related to MTBE concentration up to 1.2 mg/L. No minimum substrate concentration for MTBE biodegradation was observed, indicating that in the presence of dissolved O2 (and absence of inhibitory factors) MTBE biodegradation would occur in the aquifer at MTBE concentrations (ca. 0.1 mg/L) found at the front of the ether oxygenate plume. MTBE biodegradation occurred with concomitant O2 consumption but no other electron acceptor utilisation, indicating biodegradation by aerobic processes only. However, O2 consumption was less than the stoichiometric requirement for complete MTBE mineralization, suggesting that only partial biodegradation of MTBE to intermediate organic metabolites occurred. The availability of dissolved O2 did not affect MTBE biodegradation significantly, with similar MTBE biodegradation behaviour and rates down to ca. 0.7 mg/L dissolved O2 concentration. The results indicate that aerobic MTBE biodegradation could be significant in the plume fringe, during mixing of the contaminant plume and uncontaminated groundwater and that, relative to the plume migration, aerobic biodegradation is important for MTBE attenuation. Moreover, should the groundwater dissolved O2 concentration fall to zero such that MTBE biodegradation was inhibited, an engineered approach to enhance in situ bioremediation could supply O2 at relatively low levels (e.g. 2–3 mg/L) to effectively stimulate MTBE biodegradation, which has significant practical advantages. The study shows that aerobic MTBE biodegradation can occur at environmentally significant rates in this aquifer, and that long-term microcosm experiments (100s days) may be necessary to correctly interpret contaminant biodegradation potential in aquifers to support site management decisions. 相似文献
867.
Impact of initial and boundary conditions on preferential flow 总被引:4,自引:1,他引:3
Preferential flow in soil is approached by a water-content wave, WCW, that proceeds downward from the ground surface. WCWs were obtained from sprinkler experiments with infiltration rates varying from 5 to 40 mm h− 1. TDR-probes and tensiometers measured volumetric water contents θ(z,t) at seven depths, and capillary heads, h(z,t) at six depths in a column of an undisturbed soil. The wave is characterized by the velocity of the wetting front, cW, the amplitude, wS, and the final water content, θ. We tested with uni-variate and bi-variate linear regressions the impacts of initial volumetric water contents, θini, and input rates, qS, on cW, wS and θ.The test showed that θini influenced θ and wS and qS effected cW. The expected proportionality of wS ≈ qs1/3 was weak and cW ≈ qs2/3 was strong. 相似文献
868.
Degassing of H/He, CFCs and SF6 by denitrification: Measurements and two-phase transport simulations
Ate Visser Joris D. Schaap Hans Peter Broers Marc F.P. Bierkens 《Journal of contaminant hydrology》2009,103(3-4):206-218
The production of N2 gas by denitrification may lead to the appearance of a gas phase below the water table prohibiting the conservative transport of tracer gases required for groundwater dating. We used a two-phase flow and transport model (STOMP) to study the reliability of 3H/3He, CFCs and SF6 as groundwater age tracers under agricultural land where denitrification causes degassing. We were able to reproduce the amount of degassing (R2 = 69%), as well as the 3H (R2 = 79%) and 3He (R2 = 76%) concentrations observed in a 3H/3He data set using simple 2D models. We found that the TDG correction of the 3H/3He age overestimated the control 3He/3He age by 2.1 years, due to the accumulation of 3He in the gas phase. The total uncertainty of degassed 3H/3He ages of 6 years (± 2 σ) is due to the correction of degassed 3He using the TDG method, but also due to the travel time in the unsaturated zone and the diffusion of bomb peak 3He. CFCs appear to be subject to significant degradation in anoxic groundwater and SF6 is highly susceptible to degassing. We conclude that 3H/3He is the most reliable method to date degassed groundwater and that two-phase flow models such as STOMP are useful tools to assist in the interpretation of degassed groundwater age tracer data. 相似文献
869.
A.A.L. Oiffer J.F. Barker F.M. Gervais K.U. Mayer C.J. Ptacek D.L. Rudolph 《Journal of contaminant hydrology》2009,108(3-4):89-106
An anaerobic plume of process-affected groundwater was characterized in a shallow sand aquifer adjacent to an oil sands tailings impoundment. Based on biological oxygen demand measurements, the reductive capacity of the plume is considered minimal. Major dissolved components associated with the plume include HCO3, Na, Cl, SO4, and naphthenic acids (NAs). Quantitative and qualitative NA analyses were performed on groundwater samples to investigate NA fate and transport in the subsurface. Despite subsurface residence times exceeding 20 years, significant attenuation of NAs by biodegradation was not observed based on screening techniques developed at the time of the investigation. Relative to conservative tracers (i.e., Cl), overall NA attenuation in the subsurface is limited, which is consistent with batch sorption and microcosm studies performed by other authors. Insignificant biological oxygen demand and low concentrations of dissolved As (< 10 µg L− 1) in the plume suggest that the potential for secondary trace metal release, specifically As, via reductive dissolution reactions driven by ingress of process-affected water is minimal. It is also possible that readily leachable As is not present in significant quantities within the sediments of the study area. Thus, for similar plumes of process-affected groundwater in shallow sand aquifers which may occur as oil sands mining expands, a reasonable expectation is for NA persistence, but minimal trace metal mobilization. 相似文献
870.
Influence of titanium dioxide nanoparticles on speciation and bioavailability of arsenite 总被引:2,自引:0,他引:2
Sun H Zhang X Zhang Z Chen Y Crittenden JC 《Environmental pollution (Barking, Essex : 1987)》2009,157(4):1165-1170
In this study, the influence of the co-existence of TiO2 nanoparticles on the speciation of arsenite [As(III)] was studied by observing its adsorption and valence changing. Moreover, the influence of TiO2 nanoparticles on the bioavailability of As(III) was examined by bioaccumulation test using carp (Cyprinus carpio). The results showed that TiO2 nanoparticles have a significant adsorption capacity for As (III). Equilibrium was established within 30 min, with about 30% of the initial As (III) being adsorbed onto TiO2 nanoparticles. Most of aqueous As (III) was oxidized to As(V) in the presence of TiO2 nanoparticles under sunlight. The carp accumulated considerably more As in the presence of TiO2 nanoparticles than in the absence of TiO2 nanoparticles, and after 25-day exposure, As concentration in carp increased by 44%. Accumulation of As in viscera, gills and muscle of the carp was significantly enhanced by the presence of TiO2 nanoparticles. 相似文献