Characterization of iron oxides in Fe-rich concretions from an imperfectly-drained Greek soil: a study by selective-dissolution techniques and X-ray diffraction

Fe-rich concretions commonly occur in Greek soils with alternating drying and waterlogging periods. This study was conducted to characterize the iron oxides in Fe-rich concretions from the upper solum of an Alfisol with seasonal perched water table by the combination of selective dissolution and X-ray diffraction (XRD) techniques. The results showed that more than 75% of the total iron (Fet) was associated with the crystalline and the amorphous Fe oxides, indicating a strong accumulation of free iron oxides (Fed) in concretions. Amorphous iron compounds (Feo) was present at high concentrations and fluctuated with profile depth. The active Fe ratio (Feo/Fed) values that ranged from 0.35 to 0.41 reflected an association of poorly crystalline goethite with some ferrihydrite. The XRD data showed that the Fe-rich concretions consisted of quartz, feldspars, illite and gypsum. The mineralogy of iron oxides in concretions was determined by comparison of XRD patterns for dithionite-citrate-bicarbonate (DCB) treated (deferrated) and untreated (non-deferrated) samples. Poorly crystalline goethite as demonstrated by broad lines in the diffraction patterns and ferrihydrite were the iron oxides detected in the concretions. This mineral assemblage appears to be related to the pedoenvironmental conditions in which the concretions were formed and indicates that the mechanisms governing the formation of crystalline Fe oxides from ferrihydrite are retarded by the presence of crystallization inhibitors.     

Extractability of manganese and iron oxides in typical Japanese soils by 0.5 mol L−1 hydroxylamine hydrochloride (pH 1.5)

We investigated the extractability of manganese (Mn) and iron (Fe) oxides from typical Japanese soils (Entisols, Inceptisols, and Andisols) by 0.5?mol?L^?1 hydroxylamine hydrochloride (NH₂OH-HCl) extraction (pH 1.5; 16?h shaking at 25°C; soil:solution ratio 1:40), referred as to HH_mBCR, which is Step 2 (used for the reducible fraction) of the modified BCR (Community Bureau of Reference) sequential extraction procedure. The HH_mBCR procedure extracted almost all Mn oxides from the non-Andisol samples, but failed to extract a part of the Mn oxides from some Andisol samples. The procedure extracted most short-range ordered Fe oxides from non-Andisol samples, but it extracted only 7.5% and 13% of the short-range ordered Fe oxides from allophanic and non-allophanic Andisol samples, respectively. This remarkably low extractability of Fe oxides suggests that the HH_mBCR method is not suitable for extracting oxide-occluded heavy metals from Andisols. Since the extraction rate of short-range ordered Fe oxides from various soils with the extractant was negatively correlated with the amounts of oxalate- and pyrophosphate-extractable Al even when the variability of the extraction pH was reduced by increasing the soil:solution ratio from 1:40 to 1:500, the extractability of Fe oxides would be negatively affected by the presence of active Al, including allophane/imogolite, amorphous Al, and Al-humus complexes. Because these Al constituents are abundant in Andisols, they would be at least partially responsible for the lower extractability of Fe oxides by HH_mBCR from Andisols.     

纳米铁氧化物催化类Fenton反应降解抗生素磺胺

采用纳米铁矿物(赤铁矿α-Fe₂O₃、磁赤铁矿γ-Fe₂O₃、磁铁矿Fe₃O₄、水铁矿Fe₅HO₈·4H₂O)为催化剂与H₂O₂构成类Fenton反应,进行抗生素磺胺的氧化降解研究,并考察磺胺初始浓度、铁氧化物投加量、H₂O₂浓度、溶液pH等对磺胺氧化降解过程的影响。结果表明,磺胺初始浓度2 mg·L^-1、赤铁矿投加量1 g·L^-1、H₂O₂浓度30 mL·L^-1、溶液pH 3.6和温度25 ℃条件下,反应72 h后磺胺的降解率为99.27%。利用LC-MS进行产物分析,表明铁氧化物催化类Fenton反应降解磺胺主要是催化氧化反应,磺胺分子结构中的对位氨基被氧化成硝基。     

运用简单线性水库模型计算Pothwar黄土平原（巴基斯坦）磷灰石损失情况

Apatite is the dominant phosphorus （P） mineral in early stages of soil development, and its redistribution as labile forms under pedogenesis controls terrestrial bioavailability. Quantitative distribution of labile forms of P and apatite-P was examined in Pothwar Loess Plain, Pakistan where the degree of pedogenesis varied with relief. Four soil types, Typic Ustorthents （Rajar）, Typic Calciustepts （Missa）, Udic Calciustepts （Basal）, and Udic Haplustalfs （Guliana）, were sampled from three replicated locations at genetic horizon level. With the exception of total P value at surface, the mean total and apatite-P decreased towards the surface in Udic Haplustalfs and Udic Calciustepts where dicalcium and octacalcium phosphate increased toward surface. Iron （oxides and oxyhydroxides） adsorbed and occluded P forms were also in greater quantities in Udic Haplustalfs and increased toward the surface, whereas they were lowest and uniform in the Typic Ustorthents. Aluminum- and organic P correlated with soil organic matter. Apatite-P decreased exponentially with an increase in the sum of iron adsorbed and occluded P fractions, and fitted the equation M（x） =M0[1 - exp（-wx）] with r^2=0.996, where M（x） is the mean apatite-P concentration in solum, M0 is the apatite-P content in the loess sediments, x is the cumulative iron adsorbed and occluded P, and w is an empirical factor indicating the change rate of apatite-P in the loess. From the calculated apatite-P of 740 mg kg^-1 at the time of deposition, mean apatite-P loss was 60% in Udic Haplustalfs, 33% in Udic Calciustepts, 23% in Typic Calciustepts, and 8% in Typic Ustorthents. The transformation of soil P to labile forms was faster and deeper in level or slight depressions followed by gently sloping areas in wide plains, and was the least in the gullied land.     

波兰喀尔巴阡山麓漂白淋溶土中铁锰结核的分布、形态和化学组成研究

Iron and manganese oxides are common components of soils. They frequently occur in nodules constituting important soil sorbents and play a crucial role in a number of chemical reactions in the soil environment. In addition, the oxides are very sensitive to environmental changes (moisture, pH, Eh) constituting important indicators of soil-forming processes and water movement in the landscape. The objectives of the study were: i) to examine the distribution and size of Fe-Mn nodules in Albeluvisols containing a fragipan horizon; ii) to determine the morphology and chemical composition of the nodules, and iii) to estimate the effect of the fragipan horizon on water movement within the soil profile. An investigation was carried out on five soil profiles containing a fragipan horizon and classified as Fragic Albeluvisols within the Carpathian Foothills in Poland. In the Albeluvisols studied, the maximum concentration of Fe-Mn nodules occurred in the horizon lying directly on the fragipan horizon. This suggests that the pan acts as a natural barrier restricting water infiltration and leads to the seasonal development of a perched water table promoting redox processes. The most common are coarse (1--0.5 mm) and medium (0.5--0.25 mm) irregular Fe-Mn nodules showing a gradual boundary and undifferentiated internal fabric. Eluvial horizons contained also larger amounts of round and dense nodules with a sharp boundary, suggesting frequent oxidation and reduction. The fragipan horizon contained mainly irregular and soft nodules, suggesting longer saturation with water during the year. Concentrations of trace elements (Cu, Zn) and P were higher within Fe-Mn nodules than in the surrounding soil materials, showing that iron and manganese oxides adsorbed and immobilised these elements.     

过渡金属氧化物对木粉/PVC复合材料燃烧性能的影响

用锥形量热仪(CONE)和热重分析法(TGA)研究金属氧化物CuO、La2O<,3>和TiO2对木粉/PVC复合材料(WF-PVC)燃烧性能的影响.结果表明,这3种过渡金属氧化物的加入对WF-PVC均有阻燃作用.其中,CuO使热释放速率(HRR)和总热释放量(THR)降低较多,阻燃效果明显;加入金属氧化物使WF-PVC的烟释放速率(SPR)和总烟释放量(TSP)都有所降低,其中,CuO在有焰燃烧阶段烟释放量最低,抑烟效果最好.这3种氧化物都能增加成炭量.结合热重分析的结果,3种金属氧化物对WF-PVC的热降解影响是不同的.PVC和木粉之间存在相互作用,PVC显著促进了木粉的热降解,木粉的加入推迟了PVC的降解,明显提高了PVC体系的成炭量;WF-PVC的热降解行为,具有更多的PVC降解的特征.     

柠檬酸对三种人工合成氧化铁磷吸附特性的影响

试验采用了3种人工合成的氧化铁为材料,研究了氧化铁对磷的吸附以及柠檬酸对氧化铁磷吸附特性的影响。结果表明:3种人工合成的氧化铁对磷的吸附特性及柠檬酸对氧化铁吸附磷的影响都可用Langumir方程来描述,都达到了极显著水平。从磷的最大吸附量(Sm)、吸附反应常数(K)和最大缓冲容量(MBC)来看,未加入柠檬酸时,水铁矿对磷的吸附在容量和强度方面均为最高;而在加入柠檬酸时,3种人工合成的氧化铁对磷的吸附能力的顺序并无差别,水铁矿和针铁矿的磷Sm和MBC要比赤铁矿大很多。     

红壤主要土壤组分对低分子量有机酸吸附的研究

通过一次平衡法研究了双氧水去除有机质、添加1%腐殖酸和DCB法(连二亚硫酸钠-柠檬酸钠-碳酸氢钠)去除游离氧化铁、铝对红黏土发育的红壤吸附草酸、柠檬酸、酒石酸和苹果酸的影响。结果表明,去除有机质后,由于受溶液pH、表面吸附点位变化、土壤结构变化、表面基团活性变化、草酸根生成等多种因素的影响,红壤对低分子量有机酸的吸附量虽略有增加,但增加并不明显。添加腐殖酸培养一个月后,由于受土壤表面电荷变化、吸附点位覆盖、氧化铁活性改变、基团质子化等因素的影响,红壤对低分子量有机酸的吸附量虽有轻微的减少,但减少也不明显。去除占土壤总量3.79%的游离氧化铁、铝后,土壤表面正电荷将会显著减少,而导致红壤对低分子量有机酸的吸附量显著减少,其减少程度因有机酸种类而异,与原土对有机酸的最大吸附量(Sm)大小顺序相反。     

潮汕地区地面臭氧浓度的变化特征

对潮汕地区汕头、揭阳和潮州市3个代表性的监测点7月份的地面臭氧（O3）浓度进行了监测与评价,并对该地区3市O3的污染状况和O3与NOx、气温和相对湿度的相关性,以及O3浓度变化的特征进行了分析.结果表明,该地区受O3污染程度较轻,3个城市中又以汕头市的受污染程度最轻,其次是潮州市.O3与NOx浓度及其与空气湿度的变化呈负相关,与气温变化呈正相关.高温、低湿的气象条件更利于O3的产生和累积.     

砖红壤中铬的溶出和外源三价铬的氧化转化*

砖红壤铬（Cr）的背景值和锰氧化物的含量均较高,当土壤中Cr溶出或者受到Cr(III)污染,可能被氧化生成毒性较高的Cr(VI),从而对周围的环境造成威胁。为考察砖红壤中Cr的环境风险,以云南、海南和广东采集的部分砖红壤为对象,研究土壤中Cr的溶出和外源Cr(III)的氧化。连二亚硫酸钠-柠檬酸钠-重碳酸钠法提取和电子探针扫描分析的结果表明,砖红壤中的Cr主要与铁氧化物和硅酸盐矿物结合,呈非活性状态。盐酸和柠檬酸的酸化和络合作用促进了Cr的溶出,但即使1 mol?L-1的盐酸也仅使海南3和广东9砖红壤中3.68%和3.54%的Cr溶出。向砖红壤中添加Cr(III)并培养42 d,发现少量添加的Cr(III)氧化为Cr(VI),但不同土壤中Cr(VI)的生成量与亚锰的净产生量不一致,说明土壤中Cr(III)氧化生成的Cr(VI)可能会被土壤有机质重新还原为Cr(III)。去除土壤有机质后,一次平衡实验中观察到外源添加的Cr(III)氧化为Cr(VI),氧化量与土壤易还原锰的含量一致。随着溶液pH的增加,Cr(III)的氧化量呈先上升后降低的趋势,在pH4.5时Cr(III)氧化量达最大值,但Cr(III)的氧化转化量在Cr(III)添加量中的占比很小,外源Cr(III)在土壤中氧化转化的风险也很低。虽然砖红壤的背景Cr和易还原锰的含量较高,但自然条件下Cr的溶解和Cr(III)的氧化反应很难发生,Cr(III)不易转化为Cr(VI),因此不需要过度担忧砖红壤中Cr的风险。