Pedotransfer functions to assess adsorbed phosphate using iron oxide content and magnetic susceptibility in an Oxisol

Adsorbed phosphate in soils can be chemically extracted; however, this process is both time‐consuming and not cost‐effective if large numbers of samples have to be analysed. Indirect assessment of adsorbed phosphate by pedotransfer functions (PTFs) can help optimize fertilizer strategies. This study aimed to evaluate the spatial variability of adsorbed phosphate (P_ads), iron oxides and magnetic susceptibility (MS) in oxisols and to calibrate PTFs to predict P_ads. A total of 308 soil samples were collected from Hapludox and Eutrudox soils formed from sandstone in Brazil. The contents of clay (196–607 g/kg), iron oxides (40–165 g/kg), MS (1.2–29 × 10^?6 m³/kg) and P_ads (327–842 mg/kg) were in the range of typical values for these highly weathered soils. This study showed that the attributes studied were spatially dependent. Geomorphic surfaces enabled understanding of spatial variability and helped to develop a more efficient sampling scheme to calibrate PTFs. Moreover, the adsorbed phosphate in these oxisols could be predicted by a PTF using iron oxides and MS as predictors. The MS attribute enabled the most accurate prediction (concordance coefficient = 0.95, root‐mean‐square error = 46 mg/kg and relative improvement in root‐mean‐square error = ?4.12) of spatial variability through PTF compared to other predictors.     

Adsorption of Cr(VI) ion on synthetic hydrated oxides of iron

Abstract

The adsorption of Cr(VI) ion on synthetic hydrated oxides of iron (goethite (α-FeOOH) and lepidocrocite (γ-FeOOH)) with different crystallinities was studied in order to remove the Cr(VI) ion from polluted water. At pH 4.5, the amounts of the adsorbed Cr(V1) ion on goethite and lepidocrocite were 51.9 and 62.2 mmol g^?, respectively. Probably, this is due to the fact that the structure of lepidocrocite is more open than that of goethite. Lepidocrocite, therefore, is more effective for the removal of Cr( V1) ion from Cr(Vl)-contaminated and acidic groundwater and sewage.     

镉在针铁矿、针铁矿-腐植酸复合胶体中吸附解吸行为比较研究

采用批平衡试验法,比较研究了重金属镉在针铁矿和针铁矿-腐植酸复合胶体中的吸附热力学和动力学行为。结果表明,在试验浓度范围内,两种吸附剂对Cd2＋的等温吸附特征均可用Langmuir、Freundlich和Linear方程加以描述。其中以Langmuir方程的拟合效果最佳,线性相关系数为：0.991、0.999,由此推导出的最大吸附量分别为41.667和45.455mg·g^-1,表明腐植酸与针铁矿复合胶体较单一针铁矿的吸附力有所提高,且所吸附的镉均难以解吸,平均解吸率分别为5.871%和1.068%。胶体对Cd^2＋的吸附是一个快速反应过程,4h达到吸附平衡。Elovich方程是拟合吸附动力学过程的最优方程（相关系数分别为0.987和0.997）。通过计算镉在针铁矿和针铁矿-腐植酸复合胶体中的吸附自由能变化量（ΔG的绝对值均〈40kJ·mol^-1）,推测镉在两种胶体中的吸附为物理吸附过程,其吸附机理可能有氢键、偶极作用力和范德华力等作用,而不存在化学键合作用。     

铁铝氧化物吸附磷的研究

用得到x-射线衍射及电子显微镜和红外光谱确证的人工合成针铁矿与三水铝石进行磷吸附的研究。结果表明,针铁矿和三水铝石具有强烈吸附磷的能力,所得吸附数据可用吸附等温方程——Langmuir方程,Freu-ndlich方程和Temkin方程描述,Langmuir方程的适用性较好。从方程得到的吸附参数Xm值和a值,三水铝石要比针铁矿高一倍,其ΔG值也高于针铁矿。这两种人工合成矿物的吸附参数同天然的高岭石、蒙脱石明显不同。此外,在高pH时,这两种合成矿物吸附的磷量均少于低pH时的吸附量,而当有竞争离子腐殖质或氟离子存在时,它们仍然能够强烈地吸附磷。     

有机酸对针铁矿和三羟铝石吸附镉离子的影响

应用平衡吸附法研究了不同浓度的草酸、柠檬酸对针铁矿、三羟铝石竞争吸附与次级吸附Cd^2 的影响。结果表明：草酸、柠檬酸对供试矿物Cd^2 竞争吸附量的影响均表现为峰形曲线，草酸、柠檬酸浓度分别低于1mmol/L和0.1-0.4mmol/L峰值浓度时对Cd^2 的吸附有促进作用，高于其峰值浓度时对Cd^2 的吸附有抑制作用，这种现象的产生与有机酸在固、两相间的分配有关。草酸、柠檬酸对针铁矿、三羟铝石次级吸附Cd^2 的影响效果与竞争吸附明显不一样；低于峰值浓度（0.3-1mmol/L）的有机酸能显著提高Cd^2 的次级吸附量，有机酸浓度大于峰值浓度时，Cd^2 次级吸附量则趋于恒定或略有降低，这主要与矿物吸附有机酸后，其表面净吸附点位的数量有关。     

与有机物质的分解相关的还原作用对红壤磁性质的影响

Five soils derived from different parent materials were sampled from red soil region of southern China and studied by magnetic methodology to understand to what extent iron reduction would affect soil magnetic properties and how iron reduction would affect the magnetic minerals in soils.Reduction associated with organic matter decomposition strongly affected soil magnetic parameters at low pH.The losses of original soil magnetic signals in terms of magnetic susceptibility(χ),‘Soft’ isothermal remanent magnetization (‘Soft’ IRM),anhysteretic remanent magnetization(ARM) and saturation isothermal remanent magnetization(SIRM) at pH 4-6 during the two-month saturation treatment,were 66%-94%,54%-90%,64%-95% and 33%-83%,respectively.These changes were interpreted as a consequence of substantial dissolution of maghaemite and haematite in the soils.At pH 10,however,there was no significant magnetic change observed.Moreover,stable single domain soil maghaemite grains were also sensitive to reduction,which suggested that both pedogenic and detrital maghaemite were not stable in acid and reducing environments.Goethite,instead,was the most stable iron form under reducing conditions.     

The Remobilization of Metals from Iron Oxides and Sediments by Metal-EDTA Complexes

Synthetic chelating agents such as EDTA form strong complexes with heavy metals and therefore have the potential to remobilize metals from sediments and aquifers. In natural waters EDTA is present almost exclusively in the form of metal-complexes. Therefore, remobilization of metals is always a metal-metal-EDTA exchange reaction. We have investigated, to our knowledge for the first time, the remobilization of metals from the surface of synthetic iron oxides and from a river sediment by different metal-EDTA complexes. The metals are exchanged as follows:MeEDTA_dissolved + Me^ast _adsorbed Me^astEDTA_dissolved + Me_adsorbed The order of the remobilization rate of Zn²⁺ from goethite is CaEDTA > Fe(III)EDTA, reflecting the slow exchange reaction of Fe(III)EDTA. For the remobilization of Pb²⁺ from goethite, the rate was found to be Fe(III)EDTA > CaEDTA > ZnEDTA. Here, Fe(III)EDTA has surprisingly the fastest exchange rate. Only very limited remobilization of Pb²⁺ is possible from hydrous ferric oxide at pH 8 due to the very strong adsorption of Pb²⁺. The order of remobilization of Zn²⁺ from a natural river sediment was found to be CaEDTA > CuEDTA > Fe(III)EDTA. The remobilization rate of Zn²⁺ with Fe(III)EDTA is only 12% of the rate with CaEDTA, illustrating the importance of EDTA speciation for assessing remobilization.     

pH对针铁矿表面磷酸盐吸附的化学形态的影响

Chemical forms of the phosphate adsorbed on goethite surfaces and characteristics of the coordinate groups which exchange with P on goethite surfaces in solutions with different pll values were investigated.Results showed that the chemical forms of P on goethite surfaces changed from the dominance of monodentate corrdination to that of bidentate one with increasing pH of the solution.By influencing types of phosphate ions in solutions,pH affected the chemical forms of P on goethite surfaces,The amount of OH^- displaced by phosphae on goethite surfaces was the most at pH 7.0,the second at pH 9.0,and the least at pH 4.5.     

Iron oxide‐humic acid coprecipitates as iron source for cucumber plants

In soil, iron (Fe) solubility depends on complex interactions between Fe minerals and organic matter, but very little is known about plant availability of Fe present in Fe oxides associated with humic substances. For this purpose, this study investigates the effect of Fe mineral crystallinity in the presence of humic acids (HA) on Fe availability to plants. Four Fe–HA mineral coprecipitates were prepared, either in the presence or absence of oxygen, i.e., two goethite (G)‐HA samples containing large amounts of Fe as nanocrystalline goethite and ferrihydrite mixed phases, and two magnetite (M)‐HA samples containing crystalline magnetite. Bioavailability studies were conducted in hydroponic systems on cucumber plants (Cucumis sativus L.) grown under Fe deficient conditions and supplied with the Fe–HA coprecipitates containing goethite or magnetite. Results showed that plants grown in the presence of Fe–HA coprecipitates exhibited a complete recovery from Fe deficiency, albeit less efficiently than plants resupplied with Fe‐chelate fertilizer used as control (Fe‐diethylene triamine penta acetic acid, Fe‐DTPA). However, the supply with either G‐ or M–HA coprecipitates produced different effects on plants: G–HA‐treated plants showed a higher Fe content in leaves, while M–HA‐treated plants displayed a higher leaf biomass and SPAD (Soil–Plant Analysis Development) index recovery, as compared to Fe‐DTPA. The distribution of macronutrients in the leaves, as imaged by micro X‐ray fluorescence (µXRF) spectroscopy, was different in G–HA and M–HA‐treated plants. In particular, plants supplied with the poorly crystalline G–HA coprecipitate with a lower Fe/HA ratio showed features more similar to those of fully recovered plants (supplied with Fe‐DTPA). These results highlight the importance of mineral crystallinity of Fe–HA coprecipitates on Fe bioavailability and Fe uptake in hydroponic experiments. In addition, the present data demonstrate that cucumber plants can efficiently mobilize Fe, even from goethite and ferrihydrite mixed phases and magnetite, which are usually considered unavailable for plant nutrition.     

土壤及铁氧化物对马尿酸的吸附解吸特性研究

为了探明土壤及针铁矿、水铁矿对马尿酸(HA)的吸附解吸特性,并为其在环境中的风险性评价提供理论依据。通过批平衡吸附试验,对马尿酸(HA)在土壤、针铁矿、水铁矿中的吸附解吸行为进行了研究。结果表明,Langmuir模型可以对马尿酸在物质上的吸附和解吸数据进行良好的非线性拟合,平均拟合系数为0.992,试验中马尿酸在3种物质上的吸附和解吸不同程度地偏离线性模型;通过拟合得出的水铁矿和针铁矿对HA的最大吸附量分别为434.5 mg/kg和103.5 mg/kg,为土壤最大吸附量的20.89倍和5.22倍,而水铁矿是针铁矿的4.20倍;吸附容量lgKf顺序为水铁矿 > 针铁矿 > 土壤;HA在土壤、针铁矿、水铁矿中的解吸存在滞后现象。由此可见,水铁矿对马尿酸(HA)吸附能力及吸附强度均最强。