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1.
Ferrihydrite, prepared in the presence of 0 to 20 mole % Cd in the solution, was used to study the transformation of ferrihydrite into crystalline products. The result showed that the presence of Cd strongly retards the transformation of ferrihydrite into crystalline products, suppressing the formation of goethite and leading to a product which eventually consists entirely of hematite at pH 8 and at 70 °C. The fraction of hematite in the transformation products increased with increasing level of Cd in the system. When 9 mole % Cd was present, the transformation product consisted entirely of hematite. The chemical analysis and XRD data showed that Cd was incorporated into the lattice of iron oxides, Cd-hematite and Cd-goethite being formed. The mole % Cd which replaced iron in the iron oxides increased with increasing level of Cd in the system below 9 mole % Cd. Above this value, but below 20 mole % the mole % of Cd incorporated in the lattice of iron oxides was constant at about 2.9 mole %. The volume of the unit cell of Cd-goethite increased with increasing level of Cd in the system until the goethite production was entirely suppressed. The volume of the unit cell of Cd-hematite also increased with increasing level of Cd, below 9 mole % of Cd in the system. Above this value, it was constant. Scanning electron microscopic examination showed that the presence of Cd affected the morphology of hematite more than that of goethite. The goethite grew from ferrihydrite as acicular crystals independent of the amount of Cd in the system. The shape of hematite particles varied from irregular platelets with lower Cd level, to ellipsoids, with higher Cd level in the system, and it also suggested that Cd prevented the formation of goethite by hindering the dissolution of ferrihydrite rather than by interfering with nucleation and growth of goethite from solution. The rate of transformation was studied at pH 8, 50 °C and 70 °C. The transformations were first order reactions at both temperatures.  相似文献   

2.
The presence of phosphate retards the transformation of ferrihydrite into crystalline products. Increasing phosphate from 0 to 1 mole % results in an order of magnitude decrease in the rate of transformation of ferrihydrite at pH 12. Levels of phosphate of ~1 mol % suppress the formation of goethite (α-FeO(OH)) and result in the formation of a product consisting ofη-Fe2O3. Higher levels of phosphate result in the ferrihydrite remaining amorphous, even after several hundred hours. Phosphate prevents formation of goethite by hindering the dissolution of ferrihydrite rather than by interfering with nucleation and growth of goethite in solution. The transformation rate of pure ferrihydrite is also strongly inhibited in the presence of dissolved phosphate. This is due to surface complexation. The transformation rate was measured at temperatures of 60 °C and 70 °C. The rate of transformation was found to be described by either (i) a solid-state reaction equation for powdered compacts or (ii) a zero-order reaction controlled by desorption. The transformation of the ferrihydrite matrix was accompanied by the loss of the phosphate trace component. X-ray diffraction indicates that no solid solution involving phosphate substitution intoη-Fe2O3 is formed. Transmission electron microphotographs of the original precipitates containing phosphate confirm the presence of the phosphate and demonstrate its involvement in linking together extremely small particles of ferrihydrite.  相似文献   

3.
Synthetic ferrihydrite preparations are metastable and on oven-drying are shown to undergo significant transformation to more stable crystalline products the composition of which depends on the properties of the initial ferrihydrite. For a poorly ordered sample produced by rapid neutralization of a ferric nitrate solution, the dominant product was well-crystalline hematite (α-Fe2O3), the amount depending on the temperature at which drying was accomplished. Freeze-drying prevented alteration of the ferrihydrite to more crystalline forms and, compared with any of the oven dried samples, minimized the change in rate of dissolution in acid ammonium oxalate solution. For a more ordered ferrihydrite produced by slow neutralization, oven-drying caused the formation of some goethite (α-FeOOH) with little or no hematite. The different transformation pathway for the more ordered ferrihydrite is attributed to 1) formation of larger polymers by slow growth during neutralization, resulting in a limited supply of the very small polymers which transform readily to hematite on heating, and 2) the probability of concomitant growth of goethite nuclei within the ferrihydrite allowing preferred transformation to goethite during oven-drying.  相似文献   

4.
Partial reduction of iron(III) oxides with hydrogen in the presence of a platinum catalyst leads to an equilibrium state after 4–20 h. From the measured Eh, pH, and Fe2+ concentration conditional standard potentials can be calculated using the formula Eo (volt) = Eh + 0.059 lg(Fe2+) + 0.18 pH which indicate the stability of Fe oxides against reduction. The reduceability decreases following the order ferrihydrite > lepidocrocite > hematite > goethite. The difference between hematite and goethite was more pronounced than that predicted from thermodynamic data.  相似文献   

5.
阴离子对可变电荷土壤吸附铜离子的影响机理   总被引:1,自引:0,他引:1  
根据NO-3、Cl-和SO24-对可变电荷土壤和恒电荷土壤吸附Cu2+的影响的比较,探讨了阴离子对可变电荷土壤吸附Cu2+的影响机理。结果表明,当3种阴离子的浓度相同时,在SO24-体系中铁质砖红壤对Cu2+的吸附率较在NO3-和Cl-体系中大得多,而在浓度相同的3种阴离子体系中,黄棕壤对Cu2+的吸附率相差不大。在离子强度相近的NaCl体系中,砖红壤对Cu2+的吸附率相近。在3种阴离子体系中,随着pH升高,砖红壤对Cu2+的吸附率均增大;但在NO-3体系和Cl-体系中Cu2+的吸附率相近;而在SO24-体系中Cu2+的吸附率最大。随着Na2SO4浓度的增大,铁质砖红壤和砖红壤对Cu2+的吸附率减小。但在0.005 mol L-1和0.05 mol L-1Na2SO4体系中,Cu2+的吸附率大于在不含Na2SO4的体系中者。而在0.5 mol L-1Na2SO4体系中,Cu2+吸附率小于在不含Na2SO4体系中者。在3种浓度的Na2SO4体系中,黄棕壤对Cu2+的吸附率均小于在不含Na2SO4体系中者。总之,阴离子可通过离子强度、专性吸附和形成离子对影响土壤对Cu2+的吸附。在可变电荷土壤中,阴离子对Cu2+吸附的影响机理较在恒电荷土壤中复杂得多。  相似文献   

6.
用吸附平衡法研究了不同草酸浓度、体系pH对针铁矿 (G)吸附Cd2+的影响与机制以及电解质 (KNO3)浓度对针铁矿、草酸化针铁矿 (G+40 )吸附Cd2+的影响差别及原因。结果表明 ,低浓度草酸 (1mmolL-1 )促进Cd2+的吸附 ;高浓度草酸 (1mmolL-1/sup )抑制Cd2+的吸附。已吸附在针铁矿表面的草酸对Cd2+ 吸附的影响与液相中草酸的影响不同 ,这主要与草酸引起的针铁矿表面电荷性质的变化、草酸在固液两相间的分配、草酸与Cd2+的配合作用和竞争作用有关。电解质 (KNO3)浓度对针铁矿和草酸化针铁矿吸附Cd2+的影响明显不同 ,随KNO3 浓度的提高 ,针铁矿的Cd吸附率由 44.5%增至 95%以上 ,而草酸化针铁矿吸附率由 29%降至6.2% ,这主要决定于二者的电荷零点 (PZC)和体系pH变化的不同。  相似文献   

7.
Abstract

The “Four-plane model” is one of the surface complexation models developed for analyzing the electrostatic charge of synthetic oxides. This model which was applied to the B horizon of Andisols, was equilibrated with an electrolyte solution containing KCl, KNO3, K2SO4 in the concentration range of 0.0033, 0.01, 0.033, 0.1 M, and pH range of 2 to 11. The amounts of NO3 -, Cl-, SO4 2-, and K+ adsorbed were determined from the products remaining in the liquid phase. The increase in the pH value results in the increase of K+ adsorption, and decrease of anion adsorption. The increase in the equilibrium concentration increased both K+ and anion adsorption. The parameters of the model were determined by measurements and the iterative method. The model have a good agreement between calculated and measured values of cation and anion adsorption. Among the anion species, the amount of adsorbed anions was in the order of SO4 2-?Cl->NO3 -. The differences in the degree of adsorption were mainly associated with the differences in the equilibrium constants of surface complexation. The surface complexation of the anions produced a negative charge and increased cation adsorption. The degree of surface complexation was most significant in the K2SO4 solution, and the phenomenon was considered to be important not only for anion adsorption but also for cation adsorption on Andisols.  相似文献   

8.
本工作研究了阴离子吸附和PH对恒电荷土壤(黄棕壤和黑土)和可变电荷土壤(砖红壤)动电性质的影响。结果表明,砖红壤吸附不同阴离子后的ζ电位随PH升高由正电位移至负电位,在ζ电位-PH曲线上均有一个等电点(IEP)在PH3.5~8之间,相同PH升高由正电红壤的ζ电位随吸附阴离子的负移顺序是HPO4^2-〉F^-〉SO4^2-〉Cl^-〉NO3^-。作为恒电荷土壤的黄棕壤和黑土,在不同电解发质溶液中的ε  相似文献   

9.
采前营养液处理对水培小白菜硝酸盐积累的影响   总被引:10,自引:0,他引:10  
开展了在采收前减少小白菜营养液中的氮量或在去除硝态氮的基础上加入渗调离子以试图降低小白菜的硝酸盐积累的试验。结果表明,在去除营养液中的硝态氮后,在营养液中加入Cl-、SO42-、苹果酸根离子、山梨酸根离子、乙酸根离子是降低溶液培养小白菜硝酸盐积累的有效措施,但处理后采收的时间不可推迟太久。而只减少营养液中氮肥用量会使产量迅速下降,硝酸盐含量降低却缓慢,加入渗调离子可缓解因去除氮肥引起的小白菜产量的下降。  相似文献   

10.
对 3种可变电荷土壤和 4种恒电荷土壤在不同 pH、不同浓度、不同相伴阴阳离子下混合体系中Cl-和NO3-的吸附进行了测定。结果表明 ,在Cl-和NO3- 共存体系中 ,Cl-比例增大使可变电荷土壤Na+吸附量及OH-释放量增加 ,而对恒电荷土壤影响不大。Cl-和NO3-吸附量随平衡Cl-和NO3-浓度增加而增大 ,随pH升高而减少。但恒电荷土壤在上述各种条件下对Cl-和NO3-吸附均相同 ,而可变电荷土壤对Cl-吸附量大于NO3-的吸附量 ;NO3-、Cl-的选择系数为 0.51~0.78,Cl-和NO3-的相对吸附量分别为56.9%和 43.1%。在不同相伴阳离子下 ,可变电荷土壤平衡溶液Cl-/NO3-比值均小于 1,且为Na+K+Ca2+Mg2+Fe3+;而恒电荷土壤Cl-/NO3-比值为 1左右 ,且不受阳离子类型的影响。由此认为 ,Cl-和NO3-在两类土壤中均以电性吸附为主 ,恒电荷土壤对Cl-和NO3-的亲合力及吸附机理相同 ;而可变电荷土壤对Cl-的亲合力 NO3- ,Cl-存在着专性吸附  相似文献   

11.
Temporal changes in major solute concentrations in six Czech Republic lakes were monitored during the period 1984–1995. Four chronically-acidic lakes had decreasing concentrations of strong-acid anions (CSA = SO4 2- + NO3 - + Cl-), at rates of 3.0 to 9.0 μeq L-1 yr-1. Decreases in SO4 2-, NO3 -, and Cl- (at rates up to 5.1 μeq L-1 yr-1, 3.2 μeq L-1 yr-1, and 0.6 μeq L-1 yr-1, respectively) occurred. The response to the decrease in deposition of S was rapid and annual decline of SO4 2- in lake water was directly proportional to SO4 2- concentrations in the acidified lakes. Changes in NO3 - concentrations were modified by biological consumption within the lakes. The decline in CSA was accompanied in the four most acidic lakes by decreases in AlT, increases in pH at rates of 0.011 to 0.016 pH yr- 1, and decreases of Ca2+ and Mg2+ (but not Na+) in three lakes. The acid neutralizing capacity (ANC) increased significantly in all six lakes. Increases in base cation concentrations (CB = Ca2+ + Na+ + Mg2+ + K+) were the principal contributing factor to ANC increases in the two lakes with positive ANC, whereas decrease in CSA was the major factor in ANC increases in the four chronically-acidic lakes. The continued chemical recovery of these lakes depends on the uncertain trends in N deposition, the cycling of N in the lakes and their catchments, and the magnitude of the future decrease in S deposition.  相似文献   

12.
Precipitation samples were collected at two coastal sites on the Korean Peninsula, Kangwha on the western coast and Yangyang on the eastern coast, from September 1991 to February 1997. The samples were analyzed for concentrations of major ions, in addition to pH and electrical conductivity. The annual volume-weighted mean pH values were 4.89 and 5.05 at Kangwha and Yangyang, respectively. The pH was generally lower at Kangwha than that at Yangyang, especially during the winter, because of reduced neutralizing inputs and greater acid inputs in winter. Dominant ions were different with NH4 + and SO4 2- most important at Kangwha and Na+ and Cl- at Yangyang. Neglecting sea salt components, nss-SO4 2- and NO3 - were important anions and nss-Ca2+ and NH4 + were important cations at both sites. Concentrations of these ions were 1.2–1.6 times higher at Kangwha than at Yangyang. Annual mean concentrations of these ions varied little during the study, while larger seasonal variations were observed. Annual mean nss-SO4 2-/NO3 - ratios at Kangwha and Yangyang were 2.8 and 2.6. The 5 yr annual mean values of nss-SO4 2-/NO3 - showed no trend at Kangwha but a decreasing tendency at Yangyang. The decreasing trend is similar to the decreasing trend in emissions of SO2/NOx in South Korea. Regional differences in chemical composition between Kangwha and Yangyang appear to be associated with long-range transport of acidic gases and alkaline dust originated from other regions.  相似文献   

13.
Snow samples from 18 sites in Estonia were collected in February and March 1996 after 72–110 days of permanent snow cover. Three snow layers corresponding to different snow accumulation periods were separated in each sampling site. Snow water samples were analysed for sulphate (SO4 2-), nitrate (NO3 -), and chloride (Cl-) ions and elemental composition. Deposition fluxes of 27 chemical species were used for factor, cluster and correlation analysis. The effects of cement dust, oil shale fly ash, sulphur dioxide and chlorine from emissions of thermal power plants were distinguished. A large number of trace metals are strongly correlated with each other (R > 0.8) and with macro-components (except NO3 -), which refers to a common origin, identified as the mineral part of oil shale. Deposition fluxes of Ca, Mg, SO4 2- and a number of mineral components exceed near the power plants 1–2 decimal orders the background value. The deposition fluxes in forested sites are up to 2 times higher than in open land sites. This difference may be caused by more efficient turbulent transfer over rougher surface. It is suggested, that NO3 - and Zn originate mainly and Pb, Cd and Cu partially from non-local or diffuse sources (traffic, domestic heating, far transport). The results of this research could be used to evaluate the air pollution deposition models and for ecological impact estimations.  相似文献   

14.
利用长期定位试验 ,比较了长期施用含SO42-和Cl- 化肥 22年后稻田土壤的 pH值、养分状况及其吸附解吸特性。结果表明 ,长期施用含SO42-化肥 ,土壤有机质、速效氮和速效钾的含量较高 ,但全量氮磷钾的含量较低 ;长期施用含Cl- 化肥 ,土壤全量氮磷钾和速效磷的含量较高 ,但pH值相对较低。长期施用含上述二种阴离子的化肥后 ,土壤对H2PO4-的最大吸附量均较大 ,且在Cl- 处理下土壤对H2PO4-吸附的结合能较大 ,而SO42-处理下土壤在同等吸附量时对H2PO4-的解吸量相应较多。长期施用含SO42-的化肥亦使土壤对钾素的供应强度较大 (ΔK0的绝对值较大 )、缓冲能力增强 (AR0值较高 ) ,而长期施用含Cl- 的化肥时则与SO42-相反  相似文献   

15.
Mine waste rock can produce acid rock drainage (ARD) when constituent sulphide minerals (for example, pyrite) oxidize upon exposure to the atmosphere. Outdoor experiments were performed to test techniques for preventing and controlling ARD in a pyritic mine waste rock. The experiments involved lysimeter (plastic drum) experiments in which the crushed (25–50 mm particle sizes), amended and unamended waste rock was exposed to natural weather conditions (rain, drying, freezing and thawing) for 125 weeks. The amendments consisted of separately covering the waste rock with compacted soil, wood bark and water and mixing with limestone and phosphate rock at 1 and 3%. Waters draining the various rocks were collected and analyzed for acidity, pH, sulphate and metals. In general, concentrations of SO4 2-, Fe, As, Cu, Al and Mg in the drainage from the control rock increased gradually in the first year, peaked in the second year and increased further in the third year, reflecting increasing acid generation with time. SO4 2- displayed strong positive correlation (0.91 to 0.98) with Al, As, Cu, Fe and Mg.Concentrations of Zn, Mn and Cd reached their maximumin the second year. Geochemical analysis of thecomplete water quality data using the equilibriumspeciation model WATEQ4F suggested waste rockoxidation was most likely controlled by Fe3+. Al, SO4 2- and Fe concentrations in thecontrol rock appeared to be controlled by alunite(KAl3(SO4)2(OH)6), jarosite(KFe3(SO4)2(OH)6) and amorphousferric hydroxide [(am)Fe(OH)3] during the firstyear. Ion activity product data (log IAP) forFe3+ and OH- generally ranged between –37and –34 in the first two years but decreased to –39and –40 in the third year, suggesting that amorphousferric hydroxides were beginning to crystallize intomore stable forms such as ferrihydrite (Fe[OH]3)and goethite (FeOOH) in the third year. The addedlimestone lost its effectiveness after a while,probably because of precipitation of secondaryminerals on the limestone particles. The phosphaterock could not sustain the drainage pH above 6 andlost its effectiveness before the limestone did. Underthe conditions of the experiments, the soil cover didnot work as expected, probably because of sidewallpassage of oxygen and water. The water cover was themost effective control method, reducing the acidproduction rate data from 41 to only 0.08 mgCaCO3 week-1 kg-1 waste rock. The wood bark was theworst performer and accelerated acid production by 170%.  相似文献   

16.
A simple ion chromatographic method is proposed for the simultaneous quantification of five inorganic anions in samples derived from tea system with a suppressed conductivity detector. For this purpose extracts of leaves, roots and soils of tea obtained at room temperature yielded chromatographic profiles with substantial differences in the relative contents of fluoride (F?), chloride (Cl?), nitrate (NO3?) and sulfate (SO4 2-). Although Cl? and SO42- were common to each extracted sample in different categories and accounted for the majority of the anions present, one additional anion peak was detected in root and leaf tissues. Irrespective of the clone and sample investigated the average F? content varied from 253 to 1664 mg kg?1, Cl? varied between 60 and 1789 mg kg?1, NO3? varied from 119 to 188 mg kg?1 and SO42- varied between 55 and 6779 mg kg?1. The anionic load was at its crest in clone UPASI – 3 in all the three categories of samples with few exceptions. Among the samples investigated, tea roots contained a considerable amount of major anions, while tea soils had the lowest amount of the detected anions. The recovery of all the quantified anions was above 95%. The correlation coefficient for all anions where above 99.50%. The concentration of nitrite (NO2?) was below the limits of detection based on the analytical technique adopted. Anion nitrate was not detected in tea root and tea leaf extracts.  相似文献   

17.
Elution of Cl?, SO4 2?, NO3 ?, and H+ often occurred in that order at a site in the central Sierra Nevada, California, that receives an annual average of 1000 cm of snowfall which is low in acidic components. During eight winter periods of above-base level snowpack outflow, and one spring melt period, on the average 25% of the ions were discharged at the following percentages of outflow volumes: Cl? at 11%, NO3 ? at 13%, SO4 2? at 18%, and H+ at 20%. Seven of eight winter outflows were associated with low ionic strength rainfall onto the snowpack. Mean solute concentrations during the first 25% and first 50% of the total outflow were significantly greater than during the last 75% and last 50% of the total outflow for Cl?, NO3 ?, and SO4 2?, but not for H+. Maximum solute concentrations were up to 2.9 times the overall event volume-weighted mean concentrations for Cl?, 3.7 times for NO3 ?, 3.0 times for SO4 2?, and 2.9 times for H+.  相似文献   

18.
Chemical Composition of Precipitation in Beijing Area, Northern China   总被引:1,自引:0,他引:1  
Variations of anions (SO4 2-, NO3 -,NO2 -, Cl- and F-),cations (K+,Na+, Ca2+, Mg2+ and +) and pH values in precipitation, througfall and stemflow samples collected overa four-year period (1995–1998) in Beijing (two sitesZhongguancun and Mangshan) are presented. The annualvolume-weighted range of pH values were 6.57–7.11 inprecipitation, 5.46–6.86 in thoughfall and 5.32–6.41 instemflow. The fominant anion was , while Ca+and NH4 + were the main cations in precipitation,throughfall and stemflow. Most of ion concentrations with precipitation, throughfall and stemflow volume showed negative correlation, except for some ones. Significant correlationvalues were also found between ions (SO4 2-,NO3 -, Cl-, F-, Ca2+,Mg2+ andNa+) in precipitation, throughfall and stemflow indicatedthe common sources of these ions such as coal combustion,automobile emission and fertilizers application. Compared toprecipitation, there was an increased ion concentration inthroughfall or in stemflow. Changes of ion concentrations werein Quercus liatungensis Koiz. and Pinus tabulaefornisCarr. throughfall (or stemflow) because of different crown andbark qualities of tree species.  相似文献   

19.
The quality of 109 water samples, comprised of 70 drinking waterand 39 irrigation water samples, in Al-Gassim Region of SaudiArabia was investigated with respect to total dissolved salts(TDS), electric conductivity (EC), pH, total hardness and themajor cations (Ca2+, Mg2+, Na+ and K+) andanions (Cl-, SO4 2-, NO3 -,F- andHCO3 -) beside coliform bacteria as an indicator offaecal contamination.The concentrations of TDS varied widely, from 109 to 6995 mgL-1, with a mean of 1427 mg L-1. Of the 109 watersamples examined, 81 (74.3%) comply with the maximumpermissible drinking water limits set by the local and international standards and guidelines and 28 (25.7%) were abovethe limits of these standards. The concentrations of the cationsand anions (with the exception of NO3 - and F-)follow, more or less, a trend similar to TDS. NO3 - concentrations (range 0–30 mg L-1) comply with the limitof 50 mg L-1 NO3 - as the highest tolerableNO3 - content. The concentrations of F- indrinking water (range 0.2–1.5 mg L-1) are alarming since88% of samples were below the lower permissible limit of 0.6 mgL-1 set by SASO (1984), the guideline of the WHO is 1.5 mgL-1 while the EEC maximum concentration lies within the range 0.7–1.5 mg L-1. Microbiological analyses showednegative coliform tests, which confirms that they are devoid ofany faecal contamination.  相似文献   

20.
Iron hydroxides are subdivided into thermodynamically unstable (ferrihydrite, feroxyhyte, and lepidocrocite) and stable (goethite) minerals. Hydroxides are formed either from Fe3+ (as ferrihydrite) or Fe2+ (as feroxyhyte and lepidocrocite). The high amount of feroxyhyte in ferromanganic concretions is proved, which points to the leading role of variable redox conditions in the synthesis of hydroxides. The structure of iron hydroxides is stabilized by inorganic elements, i.e., ferrihydrite, by silicon; feroxyhyte, by manganese; lepidocrocite, by phosphorus; and goethite, by aluminum. Ferrihydrite and feroxyhyte are formed with the participation of biota, whereas the abiotic formation of lepidocrocite and goethite is possible. The iron hydroxidogenesis is more pronounced in podzolic soils than in chernozems, and it is more pronounced in iron-manganic nodules than in the fine earth. Upon the dissolution of iron hydroxides, iron isotopes are fractioned with light-weight 54Fe atoms being dissolved more readily. Unstable hydroxides are transformed into stable (hydr)oxides, i.e., feroxyhyte is spontaneously converted to goethite, and ferrihydrite, to hematite or goethite.  相似文献   

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