XANES analysis of the mechanisms of arsenic removal in biological iron and manganese treatment unit

Biological iron and manganese removal utilizing indigenous iron and manganese oxidizing bacteria （IRB hereafter） in groundwater can also be applied to arsenic removal according to our pilot-scale test. The arsenic removal probably occurred through sorption and complexation of arsenic to iron and manganese oxides formed by enzymic action of IRB. We investigated the chemical properties of iron and manganese oxides in IRB floc and the valence state of arsenic sorbed to the floc to clarify the mechanisms of the arsenic [especially As （Ⅲ）] removal. The floc samples were collected from two drinking water plants using IRB （Jyoyo and Yamatokoriyama, Japan）, and our pilot - scale test site where arsenic and iron removal using IRB is under way （Mukoh, Japan）. The Jyoyo and Yamatokoriyama IRB floc samples were subjected to As （Ⅲ） and As（Ⅴ） sorption experiments. The elemental composition of the floc samples was measured. XANES spectra were collected on As, Fe and Mn K-edges at synchrotron radiation facility Spring 8 （Hyogo, Japan）. FT-IR and the X-ray diffraction spectra of the samples were also obtained. The IRB floc contained ca. 35 % Fe, 0.3%-3.5% Mn and 2%-6% P. The samples were highly amorphous and contained ferrihidrites and hydrated iron phosphate. According to XANES analyses of IRB, As associated with IRB was in ＋5 valence state when As （Ⅲ） （or As （Ⅴ）） was added in laboratory sorption test, Fe in ＋3 valence state, and Mn a mixture of＋3 and ＋4 valence states. Small shift was observed in the XANES spectra of IRB on As K-edge as the equilibration time of the sorption experiment was increased. Gradual oxidation of a small amount of As （Ⅲ） associated with IRB or change in arsenic binding with sorption site were the probable mechanism.     

蛇纹石化过程中铁活动性的高温高压实验研究

蛇纹石化过程中铁的活动性影响铁氧化物的形成和体系的氧逸度。然而,关于橄榄岩蛇纹石化过程中各矿物(橄榄石、斜方辉石和单斜辉石)蚀变过程中铁的活动性仍没有详细的研究。本文报道了80~200℃、饱和蒸气压下,不同的初始流体、水岩比条件下,橄榄岩蛇纹石化过程中铁的活动性。结果表明,蛇纹石化流体的铁含量较低(0.0~0.7mmol/kg),没有形成铁氧化物或铁氢氧化物,铁主要富集在蛇纹石和未反应的初始矿物中(例如,橄榄石和辉石)。由橄榄石蚀变形成的蛇纹石和由斜方辉石蚀变生成的蛇纹石化学组成相差较大,前者富铁而贫铝,后者贫铁而富铝。但当初始流体为碱性的0.5mol/L Na Cl(aq)时,两种不同来源的蛇纹石组成相差不大。尤为重要的是,单斜辉石蚀变生成的蛇纹石铁含量较高,8.1%~10.2%Fe O,远高于单斜辉石的铁含量(2.6%Fe O)。以上表明,低温蛇纹石化过程中,铁不能够大规模、长距离的运移,但在微米尺度上是活动的。     

The degree of oxidation of iron in synthetic iron-magnesian biotites

Summary Chemical analytical and pyrolytical methods have been used to study the Fe⁺²/Fe⁺³ ratios and dehydroxylation reactions in synthetic biotites. It has been found for the biotites with Fe/(Fe + Mg) of 20 to 70 mole % that the oxidation degree decreases from 26 to 16% with increasing iron. Based on the measured amounts of water and hydrogen released during pyrolysis it is inferred that the deprotonization is a dominant reaction at low temperatures (T 600°C), accompanied by dehydration as the temperature increases. Depending on the composition, a complete dehydroxylation takes place at T 900 °C, and the measured amount of water corresponds to the iron oxidation degree in the starting samples. The results of this study have important implications with respect to determination of the formation conditions of biotite-bearing rocks, and also for improvement of the techniques for determination of different valence of iron and water.

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Le degré d'oxidation du fer en biotites synthétiques contenants le fer et le magnésium

Résumé Des méthodes chimiques et pyrolitiques ont été utilisées pour l'étude des rapports Fe⁺²/Fe⁺³ et de la réaction de la déhydroxilation en biotites synthétiques. On a trouvé pour les biotites avec Fe/(Fe + Mg) de 20-70 mole % que le degré d'oxidation décroît à partir de 26 jusqu'à 16% pendent que le contenu du fer s'accroît. Sur la base de la quantité d'eau et hydrogène liberée pendant la pyrolyse, on infère que la déprotonisation est une réaction dominante à températures basses (T = 600°C), mais quand la température s'accroît, la déprotonisation est accopagnée de la déhydratation. Dépendant de la composition il y a une déhydroxilation complète à T = 900°C, et la quantité de l'eau mesurée correspond au degré d'oxidation du fer dans les specimens initials. Les résultats de cette étude infuencent la détermination des conditions de formation des roches contenantes biotite et aussi l'amélioration des techniques de la détermination du fer de valences différentes et de l'eau.

     

主要铁氧化物催化H2O2 氧化地下水中硝基苯实验

实验研究了含水层介质中主要铁氧化物催化H2O2 氧化地下水中硝基苯的机理和主要影响因素,为硝基苯污染地下水的原位化学修复技术提供了一定的理论依据。实验模拟在地下环境温度8 ℃ ～ 10 ℃条件下,利用动力学方程对硝基苯的衰减进行拟合,结果表明,其衰减系数K = 0. 044 3 min － 1 ; 硝基苯与H2O2 的最佳摩尔比为1∶200; 主要铁氧化物催化H2O2 氧化硝基苯能力依次为: 磁铁矿＞ 针铁矿＞ 氢氧化铁＞ 赤铁矿。     

氢气还原针铁矿紫外光协同催化双氧水氧化气体中甲醛

甲醛作为一种致畸、致癌的高毒性有机污染物,对人体健康构成威胁,如何有效去除气体中的甲醛是关注的热点问题之一。采用粒径0.84～3.35 mm的天然针铁矿矿石于300℃氢还原转化为磁铁矿纳米材料,将纳米磁铁矿固定床非均相Fenton氧化反应器与紫外光催化双氧水氧化反应器串接,对比研究了双氧水、双氧水-紫外光、磁铁矿-双氧水、磁铁矿-双氧水-紫外光4种不同反应体系中双氧水投加量、甲醛初始浓度、载气流量对甲醛净化效率的影响。通过小型质谱仪对甲醛Fenton光催化氧化产物进行在线监测及TOC碳平衡分析,探讨甲醛净化的机理。结果显示制备的磁铁矿作为催化剂去除甲醛气体效果明显,在紫外光-10%双氧水-磁铁矿协同作用下,最高去除率可达98%,且在不同气速下对气体中不同浓度的甲醛都有很好的净化效果。研究结果表明,制备的磁铁矿纳米材料催化剂在去除甲醛气体过程中起着重要作用,经紫外光均相催化的双氧水协同作用可以在常温下很好地把气体中的甲醛氧化为CO₂,是一种低成本的有机废气净化技术方法。     

Cu and Fe associated with humic acids in sediments of a tropical coastal lagoon

The amount of Cu and Fe associated with humic acids was estimated in five sediment cores from a tropical coastal lagoon (Piratininga Lagoon, Rio de Janeiro, Brazil). Core samples were analysed for humic acid contents, total Fe and Cu content. Fe and Cu associated with humic acids were also measured. Results show amounts of humic acids ranging from 0.7 to 21.7% of the dry weight of sediment (average 4.6%, standard deviation 4.4%). Concentrations of Fe and Cu ranged from 0.3 to 6.0% (average 2.2%, S.D. 1.2%) and from <1.0 to 65.0 μg g⁻¹ (average 28.6 μg g⁻¹, S.D. 16.4 μg g⁻¹), respectively. The results of strongly bound metals show that while humic acids are the main carrier for Cu, Fe does not seems to be significantly associated with this organic matter.     

碱熔除铁氟化物置换容量法测定铁矿石中的三氧化二铝

试样经氢氧化钠碱熔,过滤分离铁等元素,将滤液酸化、DETA络合、氟化钠置换,再用硫酸铜标准溶液回滴释放出来的EDTA,从而实现对铝的测定,通过本方法对铁矿石标准物质及样品的测定,结果的相对标准偏差在0.93%~2.95%之间,且铁矿石标准物质测定值与认定值相符。     

柱子淋洗模拟研究磷酸铁膜抑制黄铁矿氧化效果

自然室温条件下用柱子淋洗模拟研究了接氧化亚铁硫杆菌（Ｔｈｉｏｂａｃｉｌｌｕｓ ｆｅｒｒｏｏｘｉｄａｎｓ,简称Ｔ．Ｆ菌）时磷酸铁膜抑制黄铁矿氧化的效果。试验结果首次指出：用ＫＨ２ＰＯ４与Ｈ２Ｏ２淋洗黄铁矿,在其表面形成的磷酸铁膜不能抑制黄铁矿的生物氧化,反而在一定程度上加速其氧化进程。经包膜后的黄铁矿矿石柱子间歇循环淋洗一年后的收集液中ＳＯ４＾２－累积量高达３３７５６．１ｍｇ;为对照组的１．６倍,是     

电化学循环井驱动模拟含水层化学氧化降解三氯乙烯

传统原位化学氧化地下水修复技术存在氧化剂迁移距离短和利用率低等问题。本研究在双井循环模式促进传质的基础上,通过注水井中的地下水电解原位提供O₂和H₂,配合乙二胺四乙酸(ethylenediamine tetraacetic acid,EDTA)络合溶解出含水层Fe(Ⅱ),活化O₂产生羟基自由基(•OH),实现地下水三氯乙烯(TCE)的氧化降解。在填充了砂土和黏土互层的二维砂槽中,设置电流为0.2 A、流速为72 cm/d、初始TCE浓度为3 mg/L,经过9 d的连续通电处理后,TCE浓度降低到1 mg/L,降解率达到67%。通电前投加0.5 mmol/L EDTA,经过1 d水流循环后含水层中溶解态Fe(Ⅱ)浓度从02 mg/L增加到414 mg/L,黏土区域较高。通电过程中,循环井促进O₂、Fe(Ⅱ)-EDTA和TCE的有效接触与反应,使TCE氧化降解。通电初期,黏土区域Fe(Ⅱ)氧化速率、TCE降解速率较周围慢,后期差异逐渐减小。未通电时加入醋酸钠可促进Fe(Ⅲ)还原,使含水层中铁循环利用。该修复过程通过循环井提升了氧化剂迁移距离,使用源于含水层的Fe(Ⅱ)-EDTA和稳定性较好的O₂提高了氧化剂利用率,有望应用于有机污染地下水修复。     

The Paleoclimatic Variation Records of Carbonate and Iron Oxides in the Weinan Loess Section

The contents and distributions of CaCO3,Fe2O3.FeO and free Fe2O3 in the Weinan loess section of Shaanxi Province of China were investigated through dense sampling.The results show that the contents of CaCO3 and the ration of Fe2O3/FeO may be chosen as proxy in dices for the precipitation and temperature changes in the formation time of the strata,respectively.According to these geochemical indices,six stages of plaeoclimate evolution are proposed in this region since 142 ka B.P.,and secondary climate changes are discussed as well based on the curves of geochemical indices.     

高温微生物铁还原条件下绿脱石对有机质的保存作用研究

粘土矿物在地表环境中广泛存在,并且与环境中的有机质紧密结合在一起。前人的研究发现,粘土矿物的可膨胀层间域可以有效地保存有机质,防止其在微生物诱导的氧化还原环境的波动的环境中被矿化。然而这一过程在高温条件下是否同样成立尚属未知。本文选取一种代表性有机质12-氨基十二酸(ALA)与典型含铁粘土矿物绿脱石(NAu-2)合成有机质-粘土矿物复合体,在两株高温-超高温铁还原细菌的作用后,通过多种水化学和矿物学的表征手段,研究其矿物结构的变化、有机质的结合稳定性和脱附情况。结果发现细菌对绿脱石结构铁的还原过程中造成的矿物结构的破坏(还原性溶解)是控制ALA从NAu-2中脱附的主要原因。高温条件也会略微促进ALA从NAu-2的层间域中脱附出来。总体来说,受限于微生物对结构铁的还原程度(30%),最终在结构铁还原反应结束后还是有相当大量的ALA在层间保存了下来。这一结果证明了粘土矿物的层间域在高温条件下同样也能够作为有机质保存的有效场所。     

霍邱矿田李老庄铁矿地质与地球化学特征及对沉积环境的指示

李老庄铁矿位于华北克拉通南缘安徽霍邱铁矿田中部.铁矿体赋存于角闪斜长片岩(片麻岩)和大理岩中,其原岩为细碎屑岩和富镁碳酸盐岩.铁矿石主要以条带状、浸染状和块状构造为主.本文主要对李老庄铁矿进行了岩石学、矿物学研究,对矿区铁建造和围岩的主量和微量元素进行了分析.结果显示李老庄铁矿石主要由Fe2O3、SiO2和MgO组成,具有较低的Al2O3和TiO2含量,微量元素含量和稀土总量均较低,矿石(La/Yb) PAAS=0.2～0.5,显示重稀土富集,具有明显的La(La/La* =2.07 ～4.03)、Eu(Eu/Eu*=1.72 ～3.60)、Y(Y/Y*=1.50 ～ 1.87)的正异常,较高Y/Ho比值(Y/Ho=38.4 ～47.31,平均42.12)和Sr/Ba比值(Sr/Ba =4.92 ～28.90,平均13.68).这些特征表明李老庄条带状铁矿成矿物质主要来源于海底热液与海水混合的贡献.条带状铁矿无明显的Ce负异常(Ce/Ce*=0.67 ～0.81),且矿石Fe2O3T/FeO值偏低(Fe2O3T/FeO =2.60 ～3.19,平均2.95),表明矿石类型为原生矿.此外地球化学分析表明,作为李老庄铁矿层夹层的片岩、片麻岩的原岩可能为形成于大陆边缘环境的粘土或砂质沉积岩,其FeO/Fe2O3T比值为0.72 ～0.77,暗示了铁矿沉淀时的海水为低氧逸度的还原环境,球粒陨石标准化稀土配分型式呈现明显的轻稀土亏损,重稀土富集的特征,(La/Yb)N=8.46 ～25.78,平均19.48,暗示其沉积物质可能来源于陆源供给.综合分析认为,李老庄BIF铁矿为形成于活动大陆边缘局限盆地且受海底热液喷流作用影响的BIF铁矿.     

Fractal properties of multi-order folding as a tool for exploration of low-grade banded iron ores in the Krivoy Rog basin (Ukraine)

The low-grade Palaeoproterozoic stratabound banded iron ores of the Krivoy Rog basin (Ukraine) underwent strong tectonometamorphic deformation into superimposed folds of several orders, with amplitudes from centimetres to hundreds of metres. The across-strike sections of bed surfaces defining the low-grade ore bodies resemble self-similar fractal curves; hence, a fractal geometrical model was developed in order to quantify the complexity and sinuosity of bed contours. Two different methods of measurement (polygonal approximation and two-dimensional grid cell counting) were used for 5–8 different scales. Factual similarity dimension D and other model parameters have been estimated by means of linear regression and compared for both measurement methods. From the fractal model a sinuosity coefficient of contours of the folded bed surfaces K _s and a coefficient of degree of exploration of iron ore bodies K _e were constructed. It is pointed out that parameters of the model can be used for determination of the optimal exploration length scales.     

Variable190Os/184Os ratio in acid residues of iron meteorites

In residual materials obtained on dissolution of iron meteorites in 2M H₂SO₄, the ratio of¹⁹⁰Os/¹⁸⁴Os has been measured by radiochemical neutron activation analysis. Most residues have a normal isotopic ratio (to within ±2%). However, in some residues both positive and negative deviations in the isotopic ratio are seen. The most spectacular deviations are in the insoluble fragments (nuggets) from Sikhote Alin iron meteorite where the¹⁹⁰Os/¹⁸⁴Os ratio is about 50% of the normal value. The new results confirm our earlier observations that iron meteorites contain pre-solar grains.     

辽宁眼前山铁矿元素地球化学特征与沉积古环境研究

辽宁眼前山铁矿位于鞍山地区南北向和东西向铁矿构造变形带的复合部位,为鞍山地区鞍山式铁矿床的典型代表。本文对眼前山铁矿的岩石学、矿物学进行了研究,对该区铁建造和围岩的主量和微量元素地球化学进行了分析。该区铁建造以条带状为主,少量为块状,其顶底板围岩及矿体夹层主要为太古宇鞍山群千枚岩。主量分析结果表明,铁矿石主要由Si O2和铁的氧化物组成,Al2O3含量较低,LOI较大。矿石微量元素分配曲线属于右倾型,强不相容元素和大离子亲石元素富集,具有显著的Eu正异常,是海底高温热液(300℃)与海水混合的结果,表明了该区BIF形成与海底热液活动关系密切。该区BIF中富集重稀土元素,Y/Ho大于26,La和Eu具有正异常。由于缺少陆源碎屑物质,要形成稳定的条带状构造,推断该区的BIF形成于海水深度大于200 m的浅海环境,形成机制应该是富含铁的海底热液运移到相对浅水区发生氧化沉积所致。通过A-C-FM原岩恢复,结合Zr/Ti O2-Ni图解可知千枚岩为变质沉积岩;Sm/Nd比值也显示了沉积岩的特点。该区千枚岩中Th的变化范围为7.9×10-6~22.5×10-6,平均为15.8×10-6;La的变化范围为17.9×10-6~71.7×10-6,平均为38.4×10-6;La/Sc的平均值为2.3;Th/Sc的平均值为1.0;La/Th的平均值为2.4。这些值都接近大陆岛弧沉积岩特征。综合分析认为,眼前山铁矿成矿环境相当于弧后盆地。     

Chemical Forms of Heavy Metals in Carbonate—Derived Laterite and Enrichment of Its Iron Oxide Minerals

In this paper the seven-step continuous extracting method was employed in the study of chemical forms of the six heavy metals Co,Zn,Pb,Cu,Cr and Mn,The result shows that the etals in the laterite are present in the chemical form of crystalline iron oxides and residues,and they are transformed towared organic and exchangeable forms in the surface soil.Linear regression analysis indicates that the above heavy metals have a positive correlation with the crystalline iron oxide minerals.The crystalline iron oxide minerals have a very important role to play in the enrichment of heavy metals,especially the solid components in the laterite.     

Influence of extractable soil manganese on oxidation capacity of different soils in Korea

We examined the relationship between soil oxidation capacity and extractable soil manganese, iron oxides, and other soil properties. The Korean soils examined in this study exhibited low to medium Cr oxidation capacities, oxidizing 0.00–0.47 mmol/kg, except for TG-4 soils, which had the highest capacity for oxidizing added Cr(III) [>1.01 mmol/kg of oxidized Cr(VI)]. TG and US soils, with high Mn contents, had relatively high oxidation capacities. The Mn amounts extracted by dithionite-citrate-bicarbonate (DCB) (Mn^d), NH₂OH·HCl (Mn^h), and hydroquinone (Mn^r) were generally very similar, except for the YS1 soils, and were well correlated. Only small proportions of either total Mn or DCB-extractable Mn were extracted by NH₂OH·HCl and hydroquinone in the YS1 soils, suggesting inclusion of NH₂OH·HCl and hydroquinone-resistant Mn oxides, because these extractants are weaker reductants than DCB. No Cr oxidation test results were closely related to total Mn concentrations, but Mn^d, Mn^h, and Mn^r showed a relatively high correlation with the Cr tests (r = 0.655–0.851; P < 0.01). The concentrations of Mn^d and Mn^h were better correlated with the Cr oxidation tests than was the Mn^r concentration, suggesting that the oxidation capacity of our soil samples can be better explained by Mn^d and Mn^h than by Mn^r. The first component in principal components analysis indicated that extractable soil Mn was a main factor controlling net Cr oxidation in the soils. Total soil Mn, Fe oxides, and the clay fraction are crucial for predicting the mobility of pollutants and heavy metals in soils. The second principal component indicated that the presence of Fe oxides in soils had a significant relationship with the clay fraction and total Mn oxide, and was also related to heavy-metal concentrations (Zn, Cd, and Cu, but not Pb).     

河北阳原盆地井儿洼钻孔岩心氧化铁变化的古环境记录

系统分析了阳原盆地西部井儿洼钻孔剖面的Fe2O3、FeO、TFe(全铁)、Fe3 /Fe2 的变化特点,探讨了阳原古湖氧化铁地球化学特征及其所记录的气候变迁规律。结果表明,阳原盆地的沉积环境相对富集铁,气候总体较温和,垂向上的变化记录了气候的变化过程分为7个明显的阶段。0.2Ma以前以还原环境为主,以后以氧化环境为主。井儿洼岩心沉积物中全铁谱分析表明,0.78Ma之后,具有显著的21.7ka岁差周期,证明了天文因素对气候的影响,而100ka的周期不明显,这与黄土、深海沉积物的记录存在差别。另外还存在390ka、156ka、52ka、33.9ka及14.4ka等周期,表现了湖泊记录的古气候周期的复杂性。     

海水中钢铁锈层的微生物成因及其环境效应

研究了海水环境中钢铁腐蚀产物即锈层中的厌氧微生物群落和锈层矿物特征及其相关性。微生物富集培养和初步的分子生物学分析结果表明,海水钢铁锈层中至少生存有硫酸盐还原细菌和铁还原细菌两种厌氧细菌。使用扫描电子显微镜和电子能谱、X-射线衍射仪等对锈层样品进行了矿物学观察和分析。在外锈层和中间锈层,主要是α,β,γ-FeOOH等铁(水合)氧化物。铁水合硫酸盐即绿锈则主要出现在内锈层。初步讨论了厌氧细菌作用下的铁腐蚀矿物生成和转化过程,并提出钢铁锈层微生物和矿物在海洋环境的微生物修复中可能具有重要作用。     

Redox cycling of iron and manganese in sediments of the Kalix River estuary, Northern Sweden

Iron and manganese redox cycling in the sediment — water interface region in the Kalix River estuary was investigated by using sediment trap data, pore-water and solid-phase sediment data. Nondetrital phases (presumably reactive Fe and Mn oxides) form substantial fractions of the total settling flux of Fe and Mn (51% of Fe_total and 84% of Mn_total). A steady-state box model reveals that nondetrital Fe and Mn differ considerably in reactivity during post-depositional redox cycling in the sediment. The production rate of dissolved Mn (1.6 mmol m^–2 d^–1) exceeded the depositional flux of nondetrital Mn (0.27 mmol m^–2 d^–1) by a factor of about 6. In contrast, the production rate of upwardly diffusing pore-water Fe (0.77 mmol m^–2 d^–1) amounted to only 22% of the depositional flux of nondetrital Fe (3.5 mmol m^–2 d^–1). Upwardly diffusing pore-water Fe and Mn are effectively oxidized and trapped in the oxic surface layer of the sediment, resulting in negligible benthic effluxes of Fe and Mn. Consequently, the concentrations of nondetrital Fe and Mn in permanently deposited, anoxic sediment are similar to those in the settling material. Reactive Fe oxides appear to form a substantial fraction of this buried, non-detrital Fe. The in-situ oxidation rates of Fe and Mn are tentatively estimated to be 0.51 and 0.16–1.7 mol cm^–3 d^–1, respectively.