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1.
Sediments recovered from the flooded mine workings of the Penn Mine, a Cu-Zn mine abandoned since the early 1960s, were cultured for anaerobic bacteria over a range of pH (4.0 to 7.5). The molecular biology of sediments and cultures was studied to determine whether sulfate-reducing bacteria (SRB) were active in moderately acidic conditions present in the underground mine workings. Here we document multiple, independent analyses and show evidence that sulfate reduction and associated metal attenuation are occurring in the pH-4 mine environment. Water-chemistry analyses of the mine water reveal: (1) preferential complexation and precipitation by H2S of Cu and Cd, relative to Zn; (2) stable isotope ratios of 34S/32S and 18O/16O in dissolved SO4 that are 2–3 ‰ heavier in the mine water, relative to those in surface waters; (3) reduction/oxidation conditions and dissolved gas concentrations consistent with conditions to support anaerobic processes such as sulfate reduction. Scanning electron microscope (SEM) analyses of sediment show 1.5-micrometer, spherical ZnS precipitates. Phospholipid fatty acid (PLFA) and denaturing gradient gel electrophoresis (DGGE) analyses of Penn Mine sediment show a high biomass level with a moderately diverse community structure composed primarily of iron- and sulfate-reducing bacteria. Cultures of sediment from the mine produced dissolved sulfide at pH values near 7 and near 4, forming precipitates of either iron sulfide or elemental sulfur. DGGE coupled with sequence and phylogenetic analysis of 16S rDNA gene segments showed populations of Desulfosporosinus and Desulfitobacterium in Penn Mine sediment and laboratory cultures.  相似文献   

2.
3.
Humic acid extracted from a podzolic soil developed under Eucalyptus delegatensis and Pteridium aquilinum in northwestern Tasmania exhibits very strong solvent activity towards a number of minerals and metals. Aqueous solutions (0.1 per cent w/v) of this acid acting for 24 hours on mineral grains ranging in size from 297 to 590 μ, extracted varying amounts of metal. Chalcopyrite yielded 140 μg Cu whereas chalcocite released 15,000 μg Cu. Some correlation is found between relative bond strengths of sulphides and their degradation by humic acids. For example, galena is far less stable than sphalerite. Haematite and pyrolusite are quite vulnerable to humic acid attack and this may be a factor in the lack of development of extensive gossans over mineralization in western Tasmania during the current erosional cycle. Metals are particularly strongly attacked with a maximum release of 291,000 μg Pb in 24 hours. Contrary to earlier findings, Ag and Au were found to release 400 μg and 20 μg respectively of metal in a period of 6 weeks.Humic acid extracted from soils below other vegetation types in northwestern and western Tasmania are all active in mineral degradation. The variable effect of the acids is possibly the result of overall differences in complexing sites active under the conditions of experimentation and selective complexation. Several examples of minor soil organic compounds show no greater activity than humic acids and on the basis of their very low content in the soils studied, they are considered inferior to the latter as agents of weathering. Many metal humates display low solubility in water, but they are readily mobilized in the presence of humic acids. Humic acids developed under varying vegetation in a cool temperate climate are potentially very powerful solvents in the weathering cycle. Their ability to mobilize precipitated metal humates suggests that classical concepts of relative metal mobility may need modification in environments where appreciable concentrations of these substances are found.  相似文献   

4.
The acid mine drainage (AMD) discharged from the Hejiacun uranium mine in central Hunan (China) was sampled and analyzed using ICP-MS techniques. The analyzing results show that the AMD is characterized by the major ions FeTotal, Mn, Al and Si, and is concentrated with heavy metals and metalloids including Cd, Co, Ni, Zn, U, Cu, Pb, Tl, V, Cr, Se, As and Sb. During the AMD flowing downstream, the dissolved heavy metals were removed from the AMD waters through adsorption onto and co-precipitation with metal-oxhydroxides coated on the streambed. Among these metals, Cd, Co, Ni, Zn, U, Cu, Pb and Tl are negatively correlated to pH values, and positively correlated to major ions Fe, Al, Si, Mn, Mg, Ca and K. The metals/metalloids V, Cr, Se, As and Sb are conservative in the AMD solution, and negatively-correlated to major ions Na, Ca and Mg. Due to the above different behaviors of these chemical elements, the pH-negatively related metals (PM) and the conservative metals (CM) are identified; the PM metals include Cd, Co, Ni, Zn, U, Cu, Pb and Tl, and the CM metals V, Cr, Se, As and Sb. Based on understanding the geochemistry of PM and CM metals in the AMD waters, a new equation: EXT = (Acidity + PM)/pH + CM × pH, is proposed to estimate and evaluate extent of heavy-metal pollution (EXT) of AMD. The evaluation results show that the AMD and surface waters of the mine area have high EXT values, and they could be the potential source of heavy-metal contamination of the surrounding environment. Therefore, it is suggested that both the AMD and surface waters should be treated before they are drained out of the mine district, for which the traditional dilution and neutralization methods can be applied to remove the PM metals from the AMD waters, and new techniques through reducing the pH value of the downstream AMD waters should be developed for removal of the CM metals.  相似文献   

5.
The kinetic curves of aluminum release from two variable charge soils and a kaolinite within 48 h can be divided into three stages: the first stage located within the initial 30 min, at which the release rate of Al was the fastest one and the released Al dominantly originated from exchangeable Al and amorphous Al pools. The Elovich equation fit the kinetics data at this stage fairly well. The moderate and the slow stages occurred within 0.5-2 and 2-48 h, respectively. During these two stages, the released Al was mainly attributed to Al oxides, poorly crystalline kaolinite and easily weathered hydrous mica. The different linear equations also fit the kinetics data at these two stages well. The rate of Al release decreased sharply with time during the fast stage, but the rate remained constant during the moderate and slow stages. In Ultisol, Al oxides were the more important pool for Al release than poorly crystalline kaolinite and easily weathered hydrous mica during the latter two stages. In Oxisol, poorly crystalline kaolinite was the more important Al pool. Compared to the control system, the presence of organic acids increased the rate and quantity of Al release from variable charge soils. The ability of organic acids to accelerate Al release followed the order: oxalic acid > citric acid > malic acid > lactic acid. This is generally in consistent with the magnitude of the stability constants of the Al-organic complexes. The release rate of Al also increased with the rise in concentration of organic acids.  相似文献   

6.
Treatment with metallic copper for the removal of elemental sulfur from bitumen extracted from sedimentary rocks or petroleum is the most widely used method. Little attention has been paid, however, to its disadvantages. It was observed that copper can interact with some polar organic substances during conventional sulfur removal, which can strongly influence the quantitative and qualitative determination of bitumen, as has been confirmed by interaction of long-chain fatty acids with copper. The copper soap generated was analyzed by element analysis, inductively coupled plasma optical emission spectrometry (ICP-OES), thermal analysis (TG-DSC) and Fourier Transform Infrared spectroscopy (FFIR). Mechanism of the interaction was investigated and elucidated. Our experimental results would necessitate improvement of the present method for sulfur removal and/or a search for a new one.  相似文献   

7.
Mineral precipitates formed under conditions representative of acid mine drainage were prepared by oxidizing 0.1 M FeS04 · 7H20 solutions at 24°C and pH 2.3, 2.6, 3.0, 3.3 and 3.6 using a bioreactor and a strain ofThiobacillus ferrooxidans. The oxidation of dissolved Fe2+ was monitored colorimetrically and was completed within 90 to 120 h at all pHs. Schwertmannite, Fe8O8(OH)6SO4, was a major component of the precipitates and was the only phase formed at pH 3.0. Jarosite, (H,Na,K)Fe3(OH)6(SO4)2, increased in abundance with decreasing pH whereas goethite, α-FeOOH, appeared at pH 3.3 and 3.6. A similar relationship between pH and mineralogy has been reported in natural specimens of mine drainage ochres.  相似文献   

8.
9.
The risk of Pb, Zn and Cd mobility is evaluated in soils from a depleted mine at Rubiais (Lugo, Spain). This area is under special protection because of its outstanding natural value. Soils from nine different areas were selected: at the mining zone (R1, R2, R3), at minespoils (R4, R5, R6) and soils developed on the settling pond (R7, R8, R9). A control soil (RC) was sampled outside the mine. The objectives are (i) to study the characteristics of soils with high influence on metal retention, (ii) to determine the content of Pb, Zn and Cd comparing it with the generic reference levels, and (iii) to evaluate the distribution and the interactions between the metals and the soil geochemical phases by means of sequential chemical extraction, X-ray diffraction, field emission scanning electron microscopy/energy-dispersive X-ray spectroscopy (FE-SEM/EDS) and time of flight secondary ion mass spectrometry (TOF–SIMS). The concentration of Pb, Zn and Cd ranges 850–6,761, 1,754–32,287 and 1.8–43.7 mg kg?1, respectively, and the highest proportion is in the residual fraction. The Mn oxides highly influence the retention of Cd while Pb retention is mainly influenced by Fe oxides. Zn is uniformly distributed amongst the residual fraction and the Fe and Mn oxides. TOF–SIMS and SEM/EDS techniques confirm the fractionation results, showing how Pb and Zn are as sulphide and associated with Fe and Mn oxides. Nevertheless, care should be taken since oxides and sulphides could suffer sulphide oxidation processes or alteration of the oxides causing leaching and the contamination of the protected ecosystem.  相似文献   

10.
Mine tailings discharged to river systems have the potential to release significant quantities of major and trace metals to waters and soils when weathered. To provide data on the mechanisms and magnitudes of short- and long-term tailings weathering and its influence on floodplain environments, three calendar year-long column leaching experiments that incorporated tailings from Potosí, Bolivia, and soil from unaffected downstream floodplains, were carried out. These experiments were designed to model 20 cycles of wet and dry season conditions. Two duplicate columns modeled sub-aerial tailings weathering alone, a third modeled the effects of long-term floodplain tailings contamination and a fourth modeled that of a tailings dam spill on a previously contaminated floodplain. As far as was practical local climatic conditions were modeled. Chemical analysis of the leachate and column solids, optical mineralogy, XRD, SEM, EPMA, BCR and water-soluble chemical extractions and speciation modeling were carried out to determine the processes responsible for the leaching of Al, Ca, Cu, K, Na, Mg, Mn, Sn, Sr and Ti. Over the 20 cycles, the pH declined to a floor of ca. 2 in all columns. Calcium, Cu, Mg, Mn and Na showed significant cumulative losses of up to 100%, 60%, 30%, 95% and 40%, respectively, compared to those of Al, K, Sr, Sn and Ti, which were up to 3%, 1.5%, 5%, 1% and 0.05%, respectively. The high losses are attributed to the dissolution of relatively soluble minerals such as biotite, and oxidation of chalcopyrite and Cu-sulfosalts, while low losses are attributed to the presence of sparingly soluble minerals such as svanbergite, cassiterite and rutile. These results strongly suggest that the release of tailings to floodplains should be limited or prohibited, and that all tailings should be removed from floodplains following dam spills.  相似文献   

11.
This paper reports the results of a laboratory experiment conducted to investigate the effects of wollastonite dissolution on removal of potentially toxic trace elements from stream waters affected by acid mine drainage (AMD). Nearly pure wollastonite was treated with natural acid mine water (pH 2.1) for different lengths of time (15, 30, 50 and 80 days). The compositional and textural characterization of the solid reaction products suggests that wollastonite was incongruently dissolved leaving a residual amorphous silica-rich phase that preserved the prismatic morphology of the parent wollastonite. The release of Ca into solution resulted in a pH increase from 2.1 to 3.5, and subsequent precipitation of gypsum as well as poorly crystallized Fe–Al oxy-hydroxides and oxy-hydroxysulfates whose components derived from the AMD solution. A geochemical modeling approach of the wollastonite–AMD interaction using the PHREEQC code indicated supersaturation with respect to schwertmannite (saturation index = 10.7–15.7), jarosite (SI = 8.7–10.2), alunite (SI = 5.1), goethite (SI = 4.7) and jurbanite (SI = 2.2). These secondary phases developed a thin coating on the reacted wollastonite surface, readily cracked and flaked off upon drying, that acted as a sink for trace elements, especially As, Cu and Zn, as indicated by their enrichment relative to the starting wollastonite. At such low pH values, adsorption of As oxyanions on the positively charged solid particles and coprecipitation of metals (mainly Cu and Zn) with the newly formed Fe oxy-hydroxides and oxy-hydroxysulfates seem to be the dominant processes controlling the removal of trace elements.  相似文献   

12.
H+和有机酸对可变电荷土壤铝释放的动力学研究   总被引:4,自引:0,他引:4  
利用流动搅动法研究了在模拟酸雨和低分子量有机酸条件下可变电荷土壤铝释放的动力学特征,结果表明,在pH3.5的模拟酸雨作用下,红壤和黄壤中流出液铝的浓度范围约为15~40μmol/L,铝的释放快反应来源于土壤交换性铝和有机络合态铝,铝的释放慢反应对应于含铝矿物的溶解。赤红壤和砖红壤上在0~300min内流出液铝的浓度范围约为1~5μmol/L,流出液pH值大于4.5,对H 的缓冲作用表现为阳离子交换、SO24-的专性吸附释放OH-和矿物表面的质子化;当流出液pH值小于4.5时,H 开始溶解土壤中的含铝固相,铝释放的最后浓度为20~30μmol/L。用相近pH值的有机酸溶出土壤铝的浓度比pH3.5的模拟酸雨要高,特别是在砖红壤上,开始就有大量铝的释放,其浓度为20~75μmol/L,红壤上是70~150μmol/L,随时间延长,流出液中的铝浓度分别为10~20μmol/L和20~30μmol/L。有机酸作用下铝的释放机制主要是有机酸被土壤吸附后,有机酸与位于表面晶格中的铝原子形成络合体,促进了铝的溶解;其次是有机酸的吸附掩盖了土壤表面的质子化过程,增强了酸的溶解,以及有机配体对铝的络合作用,增加了铝的释放量。不同有机酸对铝的溶出能力也有不同,其释放铝能力的大小为:柠檬酸>酒石酸>苹果酸,这取决于有机配体与铝的络合能力。  相似文献   

13.
This study aimed at quantifying the total organic carbon (TOC) present in soils within the proximity of the Kgwakgwe Mn oxide ore abandoned mine, Botswana, and establish its relationship with Mn concentrations in soils and vegetation based on multivariate and Geographical Information Systems (GIS) analytical techniques. Four hundred soil samples and 200 vegetation set samples were obtained from a 4 km2 area close to the abandoned mine. The TOC in soil samples were determined using a carbon/hydrogen/moisture determinator, and Mn concentrations in soils and vegetation by atomic absorption spectrophotometry. Results were processed using the statistical package for social science (SPSS), GIS, and Remote Sensing (RS) techniques with the Integrated Land and Water Information System (ILWIS), Geosoft Oasis Montaj and ArcGIS software packages. The values for TOC in the soil samples from the study area ranged from 0 wt % to 7.91 wt %, with a mean of 1.90 wt %, and at the control area, from 4.07 wt % to 4.86 wt %. The range of concentrations of Mn in soils was from 36 mg/g to 24908 mg/g and for Mn concentrations in the vegetation samples from 26 mg/g to 3611 mg/g with a mean of 598 mg/g. Results of correlation coefficients depicted very weak negative association except Mn in soils/Mn in leaves which was weak but positive. The statistical data yielded four clusters as follows: cluster one consisted mainly of Mn in leaves, cluster two was constituted of Mn in soils, and cluster four had TOC. Cluster three was dominated by the three parameters but with negative t statistic. The spatial presentation of data presented revealed little or no vegetation in the south eastern area and those close to the mine workings, and some significant vegetation in the north western part of the study area. The low TOC in the soils is associated to low vegetation cover which is considered to have been influenced by the soil clay fraction mineralogy and high concentrations of Mn.  相似文献   

14.
The behavior of heavy metals in acid mine drainage (AMD) is mainly controlled by pH values. Therefore, a quantitative estimation of factors affecting pH values in AMD is very important in predicting the behavior of those metals. Many different factors cause pH changes in streams affected by AMD and we quantitatively estimated those factors by making simple equations from geochemical data collected from the Dalsung mine. In a stream from that mine, the pH values decrease as the stream flows downstream from the AMD source, which is different from normal streams affected by AMD. The stream shows low pH ranges (4.04–5.96), high electrical conductivity (1,407–1,664 μS/cm), and sulfate concentration (680–854 ppm). Most ion concentrations decrease or do not show noticeable changes mainly due to dilution. The change of the iron content is most significant, even though the concentration of iron is relatively low compared with other ions. The iron concentration (13.4 ppm) becomes almost 0 ppm due to precipitation. Schwertmannite is the dominant precipitated phase downstream and whitish basaluminite is observed in the upstream. From our pH estimation, precipitation is the most important process lowering pH values from 5.96 to 4.04. The dilution factor was calculated by the concentration changes in sulfate ions. Dilution increases pH values, but compared with the precipitation factor, the contribution of the dilution factor to pH is relatively small. Alkalinity is the main factor that buffers hydrogen, which is released by precipitation. The redox changes, which were calculated from the pH and Eh values, also affect pH at each sampling site. The trend of estimated pH changes is almost identical to the observed ones, but the values are slightly different. Some errors are expected mainly due to the uncertainty in the observed Eh values and the chemistry of the added water for dilution.  相似文献   

15.
This study examines the phosphorus attenuation capacity of acid mine drainage (AMD) floc (also called ocher or sludge)—generated by neutralizing AMD with ammonia, lime, and sodium hydroxide—in the face of competition from two major organic companions, citrate and oxalate, of phosphorus in manure. Lime-treated floc (LF) was the least effective of the three flocs in attenuating both inorganic phosphorus and organic phosphorus (OP: represented by inositol hexaphosphate or phytate). Out of the remaining two flocs, ammonia-treated floc (AF) attenuated more inorganic phosphorus and less organic phosphorus than did sodium hydroxide-treated floc (SF). Increasing citrate:phosphorus molar ratio in the solution from 0:1 to 1:1 decreased the inorganic P attenuation capacity (IPAC) from 53 to 29 % in AF, 33 to 16 % in LF, and from 49 % to 27 % in SF at pH 4. The corresponding figures for organic P attenuation capacity (OPAC) were from 73 to 54 % in AF, 58 to 45 % in LF, and from 76 to 58 % in SF. Increasing oxalate:phosphorus molar ratio from 0:1 to 1:1 decreased IPAC and OPAC similarly, but to a lesser extent. The competitive influence of citrate and oxalate went on weakening with increase in pH. A likely increase in pH following prolonged manure application may undermine the competitive ability of citrate and oxalate. The study shows that manure P attenuation potential of waste of AMD treatment, notwithstanding the peer anion competition to P, warrants its effectiveness in controlling buildup of P in heavily manured soils.  相似文献   

16.
The wall rocks of Sidi Driss mineralization contain continental molassic deposits: lacustrine limestones, ferruginous fragments, Ed Diss unit and Numidian unit fragments, rhyodacitic fragments, pyroclasts, and gneissic fragments. The ore is composed of pyrite, marcasite, sphalerite, galena, barite, celestite, siderite, calcite, and iron oxide-hydroxides. The abandoned wastes in Sidi Driss-Tamra district contain marcasite, galena, goethite, jarosite, anglesite, anhydrite, bassanite, and gypsum. It is very important to assess the hazards and risks that this material type poses to public health and the environment. However, evaluation of a part of toxic elements always poses problems since the associated matrix, the close relationships between some minerals, the grain sizes and their forms (oolites, compact collomorphes aggregate), the oxidation degree of metals, the chemical composition, and trace elements make it difficult to extract mobile metals from complex Sidi Driss tailings and minerals found in these acidic wastes. Nevertheless, there is no universal method that can systematically evaluate metal bioavailability. And the use of proposed sequential extraction procedures for sediments with simple mineralogical composition did not yield any reproducible results for this type of acid mine drainage sediments. Consequently, the methods of controlling and mitigating the risks of hazardous materials should be considered. Many extraction procedures have been applied to better evaluate the mobility of hazardous materials (metals), the characterization of their degree of toxicity, and their chemical behavior in these complex mine tailings. Reproducible results were obtained with lab-scale washing of sediments using distilled water, CaCl2 and Na2-EDTA solutions, and BCR sequential extraction. The results showed that the BCR extraction approach was the most efficient procedure for these types of wastes. The extraction with distilled water is recommended for identification of the total quantity of mobile Cr and Fe.  相似文献   

17.
Dispersed alkaline substrates (DAS) have been successfully used in passive treatment of highly contaminated acid mine drainage (AMD) to limit coating and clogging issues. However, further optimization of DAS systems is still needed, especially for their long-term efficiency during the treatment of ferriferous AMD. In the present study, three types of DAS comprised of natural alkaline materials (wood ash, calcite, dolomite), in different proportions (20%v/v, 50%v/v, 80%v/v), and a substrate with high surface area (wood chips) were tested in 9 batch reactors. The testing was carried out, in duplicate, for a period of 91 days, to evaluate the comparative performance of the mixtures for iron pre-treatment in ferriferous AMD (2500 mg/L Fe, at pH 4). Results showed increasing of pH (between 4.15 and 7.12), regardless of the proportion of alkaline materials in the DAS mixtures. Among the tested mixtures, wood ash type DAS were more effective for Fe removal (99.9%) than calcite or dolomite type DAS (up to 66%). All tested DAS had limited efficiency for sulfate removal and an additional treatment unit, such as a sulfate-reducing biochemical reactor, is needed. Moreover, due to the similar performances of the calcite and dolomite DAS, they could be potentially substituted and rather be used in a polishing treatment unit. Based on these findings, the most promising mixture was the 50% wood ash type DAS (WA50-DAS).  相似文献   

18.
广西八一锰矿区土壤和主要农作物重金属含量的研究   总被引:7,自引:0,他引:7  
对广西八一锰矿废弃地土壤基本理化性质及重金属全量(浓HC l 浓HNO3 HF HC lO4消解)、有效态含量(0.1MHC l浸提)和主要农作物重金属含量(浓HNO3 HC lO4消解)进行了测定(AA S)。结果表明:土壤营养缺乏和重金属污染是本矿区生态恢复面临的主要问题。土壤中全磷和全氮含量低于正常指标,且部分C/N比值偏高,同时土壤存在严重的Cd污染,并可能受到M n污染。在锰矿恢复区种植的主要农作物中,部分样品中Pb、M n含量与全部样品的C r、Cd含量超出了植物正常含量范围。农作物的食用部分中Cd、C r、Pb含量普遍超过国家食品限量卫生标准,不宜食用。  相似文献   

19.
The technique of competitive ligand-exchange/anodic stripping voltammetry (CLE-SV) was used to investigate effects of pH and Ca concentration on cadmium complexation by fulvic acid (FA), as well as Cd speciation in two different freshwaters, a hardwater Lake Greifen and a softwater River Wyre. Binding of Cd to Suwannee river FA (10 mg/l) was determined at different pH (7–8.5) and in the presence of various concentration of Ca2+ (0–2 mmol/l). The results from one-ligand discrete models were compared to simulations by the WHAM VI model. In Lake Greifen, the determined dissolved [Cd2+] ranged from 10−13 to 10−12 mol/l, and the conditional stability constant with natural ligands was log K CdL about 9.5–10.5 (pH 8.6–8.8) with ligand concentrations of 1.2–7.8 × 10−6 mol/g C. In the softwater River Wyre, dissolved [Cd2+] ranged from 4 × 10−12 to 1 × 10−11 mol/l, and the ligands were weaker (log K CdL 8.9–9.8, pH 8.0) with lower ligand concentrations (0.9–2.3 × 10−6 mol/g C). The titration curves of FA samples were close to the simulated curves by the WHAM VI model at pH 8.0–8.5, but deviated more from the model at lower pH, indicating that the results determined with CLE-SV for Cd-FA complexation are relevant to the data base in the model. Calculation of the Ca competition for Cd binding by FA showed a competition effect of similar strength as the measured one, but indicated a systematic difference between measured and modeled data at pH 7.5. Using the WHAM model for comparison with FA, the complexation of Cd by the River Wyre ligands was close to that of FA, whereas stronger complexation was observed in the Lake Greifen water. These differences may originate from different ligand composition in the lake and the river.  相似文献   

20.
Heavy metal distribution in karst soils from Croatia and Slovakia   总被引:1,自引:1,他引:0  
With the use of the optimised three-step BCR sequential-extraction procedure it was possible to assess the mobility of selected elements in soil profiles from Croatian and Slovakian karst terrains. The soils in the Croatian karst were enriched in Cr, Ni, V, Mn, Cu, Cd and Mo, while soils from the Slovak Karst had high Pb and Zn concentrations. It was determined that the elements were most readily mobilised from the topsoil and the degree of mobility decreased with depth. Cr and Ni were mainly bound to the residual fraction, and Pb in the oxidisable fraction. Cu mobility was high in samples treated with agrochemicals throughout the soil profile.  相似文献   

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