川东地区华蓥山海相三叠系不同类型岩石对海水信息的保存性评估

通过对川东地区华蓥山海相三叠系不同岩石类型样品的微观组构、阴极发光和微量元素等分析表明:川东地区华蓥山海相三叠系不同的岩石类型样品具有不同的抵抗成岩蚀变能力,其对海水信息的保存程度也不一致;钙质泥岩所记录的有关信息已基本不能代表海水,多数微晶灰岩所记录的有关信息可以较好地代表海水,而粉晶白云岩只有部分样品可以代表海水的...     

Ferromanganese nodules from the Kara Sea: Interrelation between organic matter and ore elements

This study presents data on Fe–Mn nodules first recovered from the northeastern part of the Kara Sea. Analysis of the geochemical indicators of organic matter and major and trace element compositions of nodules showed that samples with strong Mn enrichment (Mn/Fe = 2.38, on average) are dominated by terrestrial organic matter (OM), whereas Fe-rich samples (Mn/Fe = 0.20, on average) are dominated by marine biogenic OM. The variation in the n-alkane abundances in the studied nodules is independent of the sampling sites and nodule morphology. This study was conducted for the first time in the Artic region.

     

The distribution of elements between co-existing phases in some marine ferromanganese-oxide deposits

Analyses of ferromanganese oxides from the Indian and Atlantic Oceans for the elements Mn, Fe, Co, Ni, Cu, Zn, Pb, Ca, AI, Ti, Cr and Cd have helped to elucidate some of the controls on their geochemistry. In most samples virtually all of the Mn and much of the Fe are present as acid-reducible phyllomanganates and Fe oxyhydroxides respectively. By contrast, in samples in which goethite was identified, much of the Fe and significant amounts of the Mn. are not acid-reducible. The partition patterns of the minor elements reflect to varying extents the mineralogy of the hydrous Mn and Fe oxide phases. In δ-Mn-O₂-rich samples the ratio of adsorbed to crystallographically-bound Ni. Cu and Zn, is higher than in todorokite-rich samples, but in each case these metals are virtually entirely phyllomanganate-associated. In goethite-rich samples, however, significant amounts of Ni. Cu and Zn may be associated with the goethite itself rather than with phyllomanganate minerals. Cobalt shows very close association with the phyllomanganates irrespective of the specific mineralogy, but Pb behaves in a way which cannot yet be fully characterised. The non-reducible fractions of the samples contain most of the Ca, Al. Ti and Cr. Some Ca however is also present in the phyllomanganates.     

Application of multivariate statistical approach to identify heavy metal sources in sediment and waters: a case study in Yangzhong,China

Multivariate statistical approach is used to identify the sources of heavy metals (Bi, Cd, Co, Cr, Mn, Pb, U, V, and Zn) in surface water and freshly deposited riverine sediment samples in Yangzhong city, China. The metal concentration data for the water and sediment samples are reported in terms of basic statistical parameters and metal-to-metal correlations. In both surface water and sediment samples, significant correlations are observed between some metals. Principal component analysis and cluster analysis distinguishes factors of lithogenic and anthropogenic origin. Bismuth, Cd, Co, and Pb (Co only for water samples) contents are controlled by the regional lithogenic high background factor; Co, Mn, U, and V (Co only for sediment samples) are interpreted to be mainly inherited from soil parent materials, while Cr, Zn, and Mn in the two kinds of samples are recognized as the tracer of industrial pollution. Obvious similarity between factor loadings of the two kinds of samples is observed, evidencing that metal variability in the two kinds of samples is controlled by the same sources. Statistical analysis agrees with discussion based on background value and field survey of point-source pollutant affected sediment, making this statistical discussion more convincing.     

贵州水城二叠系茅口组含锰岩系地质地球化学特征与锰矿成因分析

贵州水城二叠系茅口组内发现新锰矿。通过对含锰岩系的地质地球化学研究,其富集Zn,Ni,As,Sb,Sr,Ba,Ga,Ag,V,U元素;锰含量较高层位,Th/U比值小于1,锰含量较低层位,Th/U比值往往高达4～5。Co/Ni比值小于1。含锰岩石的(Fe+Mn)/Ti均大于47,高于20,特别是含锰高的岩石,其(Fe+Mn)/Ti值在300以上。含锰岩石的Al/(Al+Fe+Mn)均远远低于0.35,一般为小于0.02。稀土配分模式与峨眉山玄武岩相似,∑REE较高,LREE/HREE值偏低等特征。根据锰岩系地球化学和区域构造特征分析,水城二叠系茅口组含锰岩系属于热水喷流沉积的产物。     

十三陵盖柿营养成分和产地土壤地球化学特征研究

对十三陵盖柿果的营养成分研究表明,柿果中糖度和维生素C含量高,并且富含钾、钠、钙、镁、铜、锌、铁、锰、磷、硫和硼等矿质元素,主产区泰陵、康陵地区的盖柿品质最优。盖柿产地土壤氧化铁、锰、硼、钼、铜、氧化钙、氧化镁、氧化钾和氧化钠含量高,土壤速效钾、有效铜、有效锌、有效铁和有效锰等养分大部分属于富足状态。     

用软锰矿直接制备高纯高比表面四氧化三锰

软锰矿经中性浸出,通过除杂净化,制备出高纯硫酸锰溶液;碱化沉淀,采用微波加热进行控制氧化合成四氧化三锰,确定了该方法的最佳工艺参数.分别用扫描电镜、透射电镜、X射线衍射仪和全自动氮吸附比表面仪对样品进行了检测,结果表明:该方法成功制备了高纯四氧化三锰,比表面积高达28.27 m2/g.     

彩色电气石致色离子的化学状态研究

为探究不同颜色电气石中致色元素的化学状态及其化学环境,利用X射线光电子能谱方法对绿色调（墨绿色、蓝绿色、淡绿色）和粉红色调电气石样品进行分析。结果表明,绿色调和粉红色调电气石样品中均含有少量的过渡金属离子,如Fe,Mn,Ti,Cr,且不含Li和Be。不同颜色的电气石晶体中过渡金属阳离子的化学状态相同,且分别为Fe3＋,Mn4＋,Ti4＋,Cr3＋,但其与阴离子配位的环境有所差别。绿色调电气石样品中虽然Fe的质量分数有较大的差别,但均有部分Fe元素与F结合,即占据晶体结构中的Y位;粉红色电气石样品中,Fe离子没有与F形成配位,仅占据结构中的Z位。相反,在粉红色电气石样品中,Mn主要与F结合配位的方式存在,占据结构中的Y位,而绿色调电气石样品中大部分的Mn与O配位成键,只有少部分的Mn与F结合配位。由于Fe3＋,Mn4＋离子对之间电荷转移的可能性不大,故电气石的颜色可能主要由于d—d电子跃迁和氧与金属离子（O2--M）间电荷转移吸收引起,尤其是由于化学环境的差异（包括配位阴离子种类、杂质缺陷、结构畸变等）所引起。     

Ship-borne geochemical investigations of deep-sea manganese-nodule deposits in the Pacific using a radioisotope energy-dispersive X-ray system

A radioisotope energy-dispersive X-ray (EDX) system has been used on board the German research vessel “Valdivia” during an exploration expedition in the northern equatorial Pacific in 1973. The instrumentation used consisted of an X-ray detection system incorporating a 30 mm² effective-area Si (Li) detector with a measured energy resolution of 195 eV for Mn Kα X-rays, standard nuclear electronics, a 1024-channel analyser and a data read-out unit. The X-ray spectra in the manganese-nodule samples were excited by a 30-mCi ²³⁸Pu source.The six elements Mn, Fe, Co, Ni, Cu and Zn were analysed on board. Precision values for the analyses were less than 3% for Mn, Fe, Ni, Cu and Zn and about 5% for Co. A total amount of 350 analyses was carried out during a one-month cruise.Average contents of 190 analysed whole manganese-nodule samples from all the sampling sites of the covered area were 23.3% Mn, 6.7% Fe, 0.23% Co, 1.16% Ni, 0.94% Cu and 0.10% Zn. The average content of the base metals expressed as the sum of the Co, Ni, Cu and Zn contents was 2.48%. A linear relationship between Mn and Ni in all analysed samples, including whole manganese-nodule samples, zones of manganese nodules and manganese crusts, was observed. The Mn/Ni ratio calculated by regression analysis was 23.0. Zonal variations of the chemical contents of the six elements in the manganese nodules were found. A size classification of the manganese nodules has been suggested. Geochemical correlations of Cu and Ni versus Mn/Fe in the investigated samples are given.     

Heavy metals contamination in road dust in Delhi city,India

Road dust samples were collected from four different areas having different landuse patterns: industrial, heavy traffic, residential and mixed use in Delhi city of India. The samples were analyzed for Ba, Co, Cr, Cu Fe, Mn, Ni, Pb and Zn by ICP-AES. Results indicate high levels of Co, Cr, Cu, Mn and Ni in samples collected from industrial area. Ba, Pb and Zn showed higher concentration levels in heavy traffic area while Fe did not show any discernible variation between the localities. The concentrations of Fe, Mn, Ba, Zn, Cr, Cu, Pb, Ni and Co showed a decreasing trend. The content of heavy metals was comparable to those in other cities in the world. A multivariate statistical approach which includes Pearson’s correlations and principal component analysis was used to identify the possible sources of metals in the road dust. Enrichment factors were estimated for further confirming the sources of contamination. Significant positively correlations between road dust metals Cu–Mn–Co–Cr–Ni suggest that major common source of origin is industrial activities. A meaningful correlation between Ba and Zn, and a moderate positive correlation between Pb and Ba indicate the influence of traffic activities. Enrichment factors calculation indicated that Pb, Cu, Cr and Zn are moderately enriched whereas Co, Ni and Mn are less enriched while Ba exhibited very low enrichment in the dust samples. The results indicate that industrial and vehicular traffic are the two major sources. Traffic appears to be responsible for the high levels of Zn, Cu and Ba. High concentration of Co, Cr, Cu and Mn may be due to industrial sources.     

黔东松桃南华系大塘坡组锰矿层物源:来自Sr同位素的证据

锰矿床的物质来源是锰矿床研究的难点问题之一.辨别黔东松桃地区南华系大塘坡组锰矿沉积的物质来源有助于加深对锰矿成矿过程的理解.对黔东松桃地区南华系大塘坡组锰矿沉积的Sr同位素研究显示,15个锰矿石、锰质页岩及炭质页岩样品87Sr/86Sr同位素比值变化范围为0.705 727~0.732 536,其中炭质页岩样品具有最高的Sr同位素比值0.732 536,含锰岩系样品87Sr/86Sr同位素比值平均值为0.711 128.样品中87Sr/86Sr比值随着Al含量的上升,分别出现87Sr/86Sr比值上升与下降的两个分异趋势.87Sr/86Sr比值随Mn含量的上升总体呈现下降的趋势,但该趋势无显著相关性,残差分析显示这主要是由于样品中87Sr/86Sr比值随着Mn含量上升出现收敛性波动造成.上述现象是由于陆源碎屑成分和海底热液成分混合输入造成.通过与大塘坡组同时代(约660 Ma)古海水Sr同位素组成,世界范围内不同时代锰矿沉积以及现代红海沉积物的Sr同位素结果对比,发现黔东松桃地区南华系锰矿层中Sr同位素比值分布范围较宽,部分锰矿样品87Sr/86Sr比值低于古海水87Sr/86Sr比值,与典型大洋成因的锰矿层或铁锰结核具有不同的Sr同位素特征.联系黔东南华系大塘坡组锰矿层形成时期的特殊地质背景,认为锰质积累过程与沉淀过程为不同阶段产物——锰质的积累过程在Sturtian冰期盆地缺氧水体中完成,可能主要以海底热液喷溢系统完成;而锰矿的沉淀过程则是在间冰期伊始古海洋化学条件动荡的水体中完成.      

滇东南锰矿物源区分析及锰质来源

应用薄片物源分析技术和石英阴极发光技术,对采自越北古陆北缘斗南和汤得地区含锰岩系法郎组砂砾岩样品进行分析,追踪陆源碎屑源区,判别锰质来源的岩性和层位：越北古陆北缘法郎组地层中的锰质主要来源于越北古陆泥盆系含锰硅质层。阴极发光特征反映最初物源区的母岩特征。     

The luminescence decay-time of Mn2+ activated calcite

Luminescence decay time data are presented for 17 samples of synthetic calcite and a natural calcite between room temperature and approximately 15 K. The majority of the samples have Mn concentration in the range 0.0001–0.01 atoms per formula unit (apfu). Their spectra are consistent with a single exponential decay. It was necessary to use a “stretched” exponential to obtain adequate fits to the spectra of two samples having Mn concentrations of 0.036 and 0.091 apfu. The decay time at room temperature ranges from approximately 40–57 ms. At low temperature the corresponding range is 51–120 ms, indicating that thermal quenching of the decay time takes place. The decay time is dependent on the concentration of Mn, reaching a maximum (at both room- and low-temperature) in the range 0.001–0.003 apfu. The composition dependence is greater at low temperature. The results are discussed in terms of the Mott-Seitz and multiphonon mechanisms of thermal quenching. It is concluded that the latter provides a better fit to the data and is more consistent with models of the luminescence process in calcite:Mn.     

石家庄地区浅层地下水铁锰分布特征及影响因素分析

铁锰离子作为石家庄地区浅层超Ⅲ类地下水的主要贡献指标,严重威胁着当地供水水质安全及居民身体健康。本文在资料收集和水文地质调查的基础上,通过对138组地下水水样的采集和分析,研究了地下水中铁锰的空间分布特征,考虑水文地质条件差异和地下水开采、地表污染输入等人为因素,分析铁锰分布成因,并进行多元回归建立了影响因子和铁锰问题之间的数理关系,确定了区内铁锰分布的主控因素。结果表明:研究区Fe、Mn质量浓度平均值分别为0.2和0.04 mg/L,超Ⅲ类水样点分别占总水样点的15.2%、5.8%。其低值点主要分布在冲洪积扇顶部单元、地下水降落漏斗区域,主要受地下水开采影响,超采区易形成氧化环境使低价铁锰被氧化成高价难溶铁锰化合物,导致了铁锰浓度降低。铁锰中值点主要分布于冲洪积扇中部单元,中部单元岩性变细、水力梯度变小、易形成还原环境是导致铁锰集中在中部单元的天然优势。高值点呈点状或带状分布于石家庄市区北部、正定县、灵寿县南部等局部地区,主要由地表污染输入所贡献,污染物输入导致了氧化还原和酸碱环境的改变,促进了铁锰的还原溶解,造成铁锰浓度的升高。     

Timing and duration of supergene mineralization at the Xinrong manganese deposit,western Guangdong Province,South China: cryptomelane <Superscript>40</Superscript>Ar/<Superscript>39</Superscript>Ar dating

Supergene Mn-oxide deposits are widely distributed in Guangxi, Guangdong, Yunnan, and Hunan Provinces, South China, accounting for 18% of the total Mn reserves in the country. Direct dating of supergene Mn enrichment, however, is lacking. In this paper, we present high-resolution ⁴⁰Ar/³⁹Ar ages of Mn oxides from the Xinrong Mn deposit, western Guangdong, to place numerical constraints on the timing and duration of supergene Mn enrichment. A total of ten cryptomelane samples, spanning a vertical extent of 67 m, were dated using the ⁴⁰Ar/³⁹Ar laser incremental heating technique, with seven samples yielding well-defined plateau or pseudo-plateau ages ranging from 23.48 ± 0.91 to 2.06 ± 0.05 Ma (2σ). One sample yields a staircase spectrum that does not reach a plateau; the spectrum, however, indicates the presence of two or more generations of Mn oxides in the sample, whose ages are best estimated at 22.34 ± 0.31 and 10.2 ± 0.86 Ma, respectively. The remaining two samples gave meaningless or uninterpretable results due to significant ³⁹Ar recoil and contamination by old phases. The ⁴⁰Ar/³⁹Ar data thus reveal a protracted history of weathering and supergene Mn enrichment that started at least in the end of the Oligocene or beginning of Miocene and extending into the latest Pliocene. Staircase-apparent age spectra, resulting from banded or botryoidal samples, yield an average growth rate of Mn oxides at 0.6–0.7 × 10⁻³ mm kyr⁻¹. The values indicate that a 1-mm grain of Mn oxides may host minerals precipitated during a time span of ca. 1.5 m.y., and accumulation of Mn oxides to form economic deposits under weathering environments may take millions of years. The distribution of weathering ages shows that the oldest Mn oxides occur on the top of the profile, whereas the youngest minerals are found at the bottom, suggesting downward propagation of weathering fronts. However, two samples located at the intermediate depths of the profile yield ages comparable with those occurring at the highest elevations. Such a complexity of age distribution is interpreted in terms of preferential penetration of Mn-rich weathering solutions along more permeable fault zones, or as a result of multi stages of dissolution and re-precipitation of Mn oxides. A synthesis of geochronological and geological data suggests that formation of the Xinrong deposit was a consequence of a combination of favorable lithological, climatic, and structural conditions. Because the climatic and structural conditions are similar among the provinces of South China during the Cenozoic, the geochronological results obtained at Xinrong may also have implications for the timing of supergene Mn enrichment throughout South China.     

Carbonates — a guide to hydrocarbons

Unfrozen samples of pure water and 10% v/v nitric acid, stored in acid-cleaned linear (high-density) polyethylene containers, are used as contamination blank controls for hydrogeochemical samples preserved by deep-freezing in similar vessels. After four years the maximum levels of metal contaminants in these blanks are (in μg/1) Fc 0.4; Cr 0.6; Ni 1.0; TI 0.6; Co 1.5; Mn 0.14; Ag 0.17; Cu 1.5; Cd 0.17; Pb 2.4; Zn 2.4. Values slightly lower than these are found for Co, Mn, Ag, Cu, Zn and Pb in the pure water samples. Approximately 0.5–1.0 μg/l of both Zn and Pb are derived from the nitric acid.     

吉林蛇纹石玉特征初步研究

对产自吉林省白山市抚松县沿江乡的蛇纹石玉样品分别从地质背景、激光诱导离解光谱、X射线粉末衍射和红外吸收光谱等方面进行了研究,并与辽宁岫玉样品进行了对比。结果表明,吉林蛇纹石玉样品的主要颜色为深浅不一的绿色,主要含Si,Al,Cr,Fe,Mn,Mg,Ca,Sr和Na等元素,其中Ca与Mg的谱线较强,Al,Mn与Sr的质量分数少;X射线粉末衍射结果显示,样品的主要矿物组成为纤蛇纹石,红外光谱结果也显示了其具有纤蛇纹石峰值的特征。     

Total organic carbon in soils and its relation with manganese concentrations in soils and vegetation close to an abandoned manganese mine

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.     

南海西北陆缘多金属结核地球化学特征及成因

对取自南海西北陆缘海域的大型多金属结核进行了电子探针、X射线粉晶衍射(XRD)、等离子质谱仪(ICP-MS) 和等离子光谱仪(ICP-AES) 等方面的分析.结核核心部位的主要矿物组成为石英、伊利石、钠长石和绿泥石, 壳层的主要矿物为δMnO₂等.铁、锰组分呈现Fe含量高、Mn含量低和Mn/Fe低的特征.Si含量高, Cu、Co、Ni含量低; 稀土元素(REE) 含量高, 平均为1472.30×10-6, 轻稀土与重稀土的比值(LREE/HREE) 达19.54, 并且存在较强的Ce正异常.元素含量的变化显示: 从结核内壳层到外壳层, Fe、Mn、Cu、Co等元素含量呈不规律变化, 具有典型的边缘海特征, 该特征反映结核在形成过程中受到边缘海沉积环境波动变化的影响, 陆源物质供应量的增加对Fe、REE、Si等元素的富集起到了促进作用, 而对Mn、Ca等元素的富集则产生明显的稀释作用.多金属结核Mn/Fe比及Mn-Fe- (Cu+Ni) ×10三组分图解显示, 南海北部陆缘多金属结核为水成成因, 该成因与结核所赋存的边缘海环境密切相关, 反映了结核成长发育的过程中, 南海典型的边缘海沉积条件和多变的古海洋环境因素对其产生了重要影响.      

双台河口土壤中Mn、Zn和Rb的变化规律及其原因分析

选取辽宁盘锦双台河口滩涂翅碱蓬生长消亡区的20个土壤样本点,比较其与翅碱蓬生长繁茂区的11种微量元素含量,并对其变化量进行主成分分析,得出双台河口滩涂土壤中含量变化显著的微量元素为Mn、Zn和Rb。通过这3种微量元素含量变化曲线图,可以看出其含量变化趋势大体上是减少的,且距离拦海大坝越近,含量越高,距离拦海大坝越远,含量越低。研究区河口底泥中Mn、Zn和Rb的含量分别占研究区滩涂土壤中的47.6%、64.3%和78.5%,表明了研究区滩涂土壤中3种元素主要是由河口地区的沉积物带来的。河口地区水中的沉积物主要由两部分组成:一部分是由河水携带的泥沙颗粒直接在河口地区沉积形成;另一部分是由河水携带的大量胶体,在入海口处产生胶凝作用形成。