Zinc speciation in the Northeastern Atlantic Ocean

Measurements of zinc and zinc complexation by natural organic ligands in the northeastern part of the Atlantic Ocean were made using cathodic stripping voltammetry with ligand competition. Total zinc concentrations ranged from 0.3 nM in surface waters to 2 nM at 2000 m for open-ocean waters, whilst nearer the English coast, zinc concentrations reached 1.5 nM in the upper water column. In open-ocean waters zinc speciation was dominated by complexation to a natural organic ligand with conditional stability constant (log K_ZnL′) ranging between 10.0 and 10.5 and with ligand concentrations ranging between 0.4 and 2.5 nM. The ligand was found to be uniformly distributed throughout the water column even though zinc concentrations increased with depth. Organic ligand concentrations measured in this study are similar to those published for the North Pacific. However the log K_ZnL′ values for the North Atlantic are almost and order of magnitude lower than those reported by Bruland [Bruland, K.W., 1989. Complexation of zinc by natural organic-ligands in the central North Pacific. Limnol. Oceanogr., 34, 269–285.] using anodic stripping voltammetry for the North Pacific. Free zinc ion concentrations were low in open-ocean waters (6–20 pM) but are not low enough to limit growth of a typical oceanic species of phytoplankton.     

Evaporites,brines and base metals: Low‐temperature ore emplacement controlled by evaporite diagenesis

Salt beds and salt allochthons are transient features in most sedimentary basins, which through their dissolution can carry, focus and fix base metals. The mineralisation can be subsalt, intrasalt or suprasalt, and the salt body or its breccia can be bedded or halokinetic. In all these evaporite‐associated low‐temperature diagenetic ore deposits there are four common factors that can be used to recognise suitably prepared ground for mineralisation: (i) a dissolving evaporite bed acts either as a supplier of chloride‐rich basinal brines capable of leaching metals, or as a supplier of sulfur and organics that can fix metals; (ii) where the dissolving bed is acting as a supplier of chloride‐rich brines, there is a suitable nearby source of metals that can be leached by these basinal brines (redbeds, thick shales, volcaniclastics, basalts); (iii) there is a stable redox interface where these metalliferous chloride‐rich waters mix with anoxic waters within a pore‐fluid environment that is rich in organics and sulfate/sulfide/H₂S; and (iv) there is a salt‐induced focusing mechanism that allows for a stable, long‐term maintenance of the redox front, e.g. the underbelly of the salt bed or allochthon (subsalt deposits), dissolution or halokinetically maintained fault activity in the overburden (suprasalt deposits), or a stratabound intrabed evaporite dissolution front (intrasalt deposits). The diagenetic evaporite ‐ base‐metal association includes world‐class Cu deposits, such as the Kupferschiefer‐style Lubin deposits of Poland and the large accumulations in the Dzhezkazgan region of Kazakhstan. The Lubin deposits are subsalt and occur where long‐term dissolution of salt, in conjunction with upwelling metalliferous basin brines, created a stable redox front, now indicated by the facies of the Rote Faule. The Dzhezkazgan deposits (as well as smaller scale Lisbon Valley style deposits) are suprasalt halokinetic features and formed where a dissolving halite‐dominated salt dome maintained a structural focus to a regional redox interface. Halokinesis and dissolution of the salt bed also drove the subsalt circulation system whereby metalliferous saline brines convectively leached underlying sediments. In both scenarios, the resulting redox‐precipitated sulfides are zoned and arranged in the order Cu, Pb, Zn as one moves away from the zone of salt‐solution supplied brines. This redox zonation can be used as a regional pointer to both mineralisation and, more academically, to the position of a former salt bed. In the fault‐fed suprasalt accumulations the feeder faults were typically created and maintained by the jiggling of brittle overburden blocks atop a moving and dissolving salt unit. A similar mechanism localises many of the caprock replacement haloes seen in the diapiric provinces of the Gulf of Mexico and Northern Africa. Evaporite‐associated Pb–Zn deposits, like Cu deposits, are focused by brine flows associated with both bedded and halokinetic salt units or their residues. Stratabound deposits, such as Gays River and Cadjebut, have formed immediately adjacent to or within the bedded salt body, with the bedded sulfate acting as a sulfur source. In allochthon/diapir deposits the Pb–Zn mineralisation can occur both within a caprock or adjacent to the salt structure as replacements of peridiapiric organic‐rich pyritic sediments. In the latter case the conditions of bottom anoxia that allowed the preservation of pyrite were created by the presence of brine springs and seeps fed from the dissolution of nearby salt sheets and diapirs. The deposits in the peridiapiric group tend to be widespread, but individual deposits tend to be relatively small and many are subeconomic. However, their occurrence indicates an active metal‐cycling mechanism in the basin. Given the right association of salt allochthon, tectonics, source substrate and brine ponding, the system can form much less common but world‐class deposits where base‐metal sulfides replaced pyritic laminites at burial depths ranging from centimetres to kilometres. This set of diagenetic brine‐focusing mechanisms are active today beneath the floor of the Atlantis II Deep and are thought to have their ancient counterparts in some Proterozoic sedex deposits. The position of the allochthon, its lateral continuity, and the type of sediment it overlies controls the size of the accumulation and whether it is Cu or Pb–Zn dominated.     

西藏扎西康锌多金属矿床地质特征及银的赋存状态研究

扎西康锌多金属矿床位于西藏特提斯喜马拉雅板片的"金锑多金属"成矿带东段。研究显示,矿体主要呈脉状、透镜状产于近南北向的张性断裂中。热液成矿作用主要可划分为早、晚2个成矿阶段,7个成矿亚阶段,早期以铅锌矿化为主,晚期以锑(铅)矿化为主。岩矿石镜下鉴定和电子探针分析表明,扎西康矿床矿石种类繁多,矿物组合和成矿元素均呈现明显的分带现象,由深至浅(W→E)为含锡(铁)闪锌矿+铁锰碳酸盐+少量方铅矿+少量黄铜矿(深部)→(铁)闪锌矿+铁锰碳酸盐+少量方铅矿+黄铁矿+毒砂+少量银黝铜矿+少量石英(中深部)→方铅矿+闪锌矿+脆硫锑铅矿+铁锰碳酸盐+硫锑铅矿+少量银黝铜矿+石英(中部)→辉锑矿+方铅矿+少量闪锌矿+石英+少量铁锰碳酸盐(浅部),对应的元素分带为Zn(Pb+Ag+Cu+Sn)→Zn(Pb+Ag)→Zn+Pb(Sb+Ag)→Pb+Sb+Ag+Zn。矿区银矿化主要集中在Ⅴ号矿体ZK2703-ZK2302、ZK1502-ZK1105和ZK806三个区域,与铅锑矿化关系密切。矿石中银主要以类质同象的形式存在,独立银矿物相对较少。其中,类质同象银主要赋存在方铅矿中,少量赋存在硫锑铅矿、脆硫锑铅矿、毒砂、黄铁矿等金属硫化物中;独立银矿物有少量的银黝铜矿、硫锑铅银矿、银(含银)硫铜锑矿。成矿流体中铅、锌、锑、银的运移和富集沉淀是受体系中温度、压力、浓度、pH值等多种因素综合控制的结果。     

Crystal structure refinement of hendricksite,A Zn- and Mn-rich trioctahedral potassium mica: A contribution to the crystal chemistry of zinc-bearing minerals

Summary The crystal structure of hendricksite, a trioctahedral mica of biotite type, characterized by high Zn²⁺ and Mn²⁺ contents has been refined by least square methods. The structural formula is: (K_0.89Na_0.10Ba_0.04)(Mg_1.57Zn_0.54Mn _0.40 ²⁺ Fe _0.25 ²⁺ Al_0.07Ti_0.07Cr_0.01)(Si_2.92Al_1.08)O₁₀ (OH)₂. The space group isC2/m and the cell parameters are:a=5.340(2) Å,b=9.524(2) Å,c=10.235(3) Å, =100.07(2)^o, the cell volume isV=497.98 ų. The final unweightedR=0.072. Average cation-anion distances in polyhedra are: T–O=1.659 Å, M(1)–O=2.093 Å, M(2)–O=2.088 Å, A–O_long=3.316 Å and A–O_short=3.004 Å; A is the alkaline cation. The rotation angle of tetrahedra is =6.7°. The analysis of electron densities, of the dimensions and distorsions of polyhedra shows that Zn²⁺ is exclusively in octahedral sites; there is no order between six-fold coordinated cations. A comparison between the structural features of hendricksite and those of the two main end-members of biotites, phlogopite and annite, is presented.The effect of the strong covalence of Zn–O bonds is particularly visible on the dimensions and orientations of the thermal ellipsoids of octahedral sites M(1) and M(2) which contain zinc. In all the published structures of trioctahedral micas, the ellipsoids of cationic sites are uniaxial positive, elongated parallel toc ^*. In hendricksite, this is observed only for the two zinc-free sites (T and A; in the octahedra M(1) and M(2), which contain zinc, the ellipsoids are approximately uniaxial negative, flattened parallel toa, which is a unique situation.Zinc which habitually favours the tetrahedral coordinations with oxygen, enters the octahedra only, i.e. the chemically anisotropic sites, in hendricksite. The strong polarizability of Zn²⁺ is proposed to explain this behaviour.An examination of the behaviour of Zn²⁺ in other compounds shows that this situation is general, zinc favours chemically anisotropic sites and specially those adjacent to OH or H₂O.

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Affinement de la structure cristalline de la hendricksite, mica trioctaédrique potassique riche en Zn et Mn; une contribution à la connaissance cristallochimique des minéraux zincifères

Résumé On a affiné par moindres carrés la structure de la hendricksite, mica trioctaédrique de type biotite, caractérisé par une teneur élevée en Zn²⁺ et Mn²⁺. La formule structurale de ce mica est: (K_0m89Na_0,10Ba_0,04)(Mg_1,57Zn_0,54Mn _0,40 ²⁺ Fe _0,25 ²⁺ Al_0,07Ti_0,07Cr_0,01)(Si_2,92Al_1,08)O₁₀(OH)₂. Le groupe spatial estC2/m et les paramètres de la maille:a=5,340(2) Å,b=9,254(2) Å,c=10,235(3) Å, =100,07(2)°; le volume de la maille estV=497,98 ų. Le résidu final non-pondéré estR=0,072. Les distances cation-anion moyennes dans les polyèdres sont les suivantes: T–O=1,659 Å, M(1)–O=2,093 Å, M(2)–O=2,088 Å, A–O_long=3,316 Å et A–O_court=3,004 Å où A désigne le cation alcalin. L'angle de rotation tétraédrique, =6,7°, est très semblable à celui de la phlogopite. L'analyse des densités électroniques, des dimensions et distorsions des polyèdres montre que Zn²⁺ est exclusivement en coordinance octaédrique et qu'il n'y a pas d'ordre entre les cations hexacoordonnés. On présente une comparaison des caractères structuraux de la hendricksite avec ceux des deux principaux pôles des biotites, la phlogopite et l'annite.L'effet de la forte covalence de la liaison Zn–O est particulièrement visible sur les dimensions et orientations des ellipsoides d'agitation thermique des deux sites octaédriques, sites zincifères. Dans toutes les structures de micas trioctaédriques publiées, les ellipsoides des sites cationiques sont uniaxes positifs, allongés parallèlement àc ^*, ce qui s' observe effectivement dans les deux sites non-zincifères (T et A) de la hendricksite, par contre, dans les octaèdres M(1) et M(2), qui contiennent le zinc, les ellipsoides sont approximativement uniaxes négatifs, applatis parallèlement àa, ce qui est une situation unique.Le zinc, qui se fixe généralement en sites tétraédriques dans les structures de type oxyde, occupe les sites octaédriques, c'est-à-dire les sites chimiquement anisotropes dans la hendricksite. La forte polarisabilité de Zn²⁺ est proposée pour expliquer ce comportement.Un examen du comportement de Zn²⁺ dans d'autres phases montre que cette situation est tout à fait générale, le zinc privilégiant les sites chimiquement anisotropes et en particulier ceux adjacents à OH où H₂O.

     

云南保山核桃坪铅-锌矿床地质特征

保山核桃坪铅-锌矿为一中型铅-锌矿床。矿体赋存于上寒武统核桃坪组,主要受近SN向的层间断裂(F1)及次级断裂构造控制,岩石(性)控矿也十分明显,成矿作用与矽卡岩化密切相关。通过对该矿床地质特征的系统分析以及对矿床围岩蚀变、控矿因素的深入研究,认为该矿床主要矿化作用是深部高温成矿流体贯入并与围岩发生矽卡岩化蚀变,随后发生矿化作用。矿床应属矽卡岩型铅-锌矿床。     

水泥固化锌污染土电阻率与强度特性研究

以标准砂及普通硅酸盐水泥为试验材料,制作水泥固化锌污染土样,进行了一系列电阻率和无侧限抗压强度试验。研究了交流电频率对水泥固化锌污染土电阻率的影响、不同含量锌离子对水泥缓凝作用的影响、锌离子含量和龄期分别对水泥土电阻率和强度的影响、电阻率与无侧限抗压强度的关系。结果表明：电阻率随电流频率的增加而明显降低,尤其当频率低于50 kHz时为甚;不同含量的锌离子对水泥土的缓凝作用影响明显,随着锌离子含量的增大,水泥土强度的充分发挥所需时间逐渐增长,但在锌离子含量为500 mg/kg时,缓凝作用表现异常;电阻率和强度均随龄期的增加而增长,随锌离子的含量的增加上下波动,电阻率在锌离子含量为50 mg/kg和500 mg/kg时出现极值,强度在锌离子含量为100 mg/kg和500 mg/kg时出现极值;在各个龄期下,电阻率与强度均呈现出很好的线性关系。     

根际环境锌镉镍的形态变化与植物有效性

以抚顺西露天采场60平盘5种修复植物根际与非根际土为研究对象，运用顺序提取实验和数理统计分析方法研究了根际与非根际土中Zn、Cd、Ni的形态分布与植物有效性。结果表明，Zn、Ni在根际与非根际土中主要以硫化物态存在；而Cd在非根际土中以硫化物态为主，在根际土中以可交换态和松、紧有机态为主。与Ni相比，非根际土中Zn的紧有机态、氧化物态和Cd的紧有机态、氧化物态、可交换态比例明显偏大；与非根际土相比，根际土中Zn的铁锰氧化物态和硫化物态含量增加，碳酸盐态含量降低，松有机态、紧有机态和可交换态Zn在不同植物根际变化不同。Cd的硫化物态降低，可交换态、松有机态、碳酸盐态、氧化物态和紧有机态含量在不同植物根际变化不同。Ni的紧有机态显著增加，可交换态、碳酸盐态和硫化物态明显降低，松有机态在不同植物根际变化不同；根际Cd的碳酸盐态增加和氧化物态降低有利于植物Cd的吸收；碳酸盐态Zn的减少可促进植物Zn的增高。     

西藏玛圭铅锌多金属矿成矿地质特征及找矿远景

西藏玛圭铅锌多金属矿在冈底斯铅锌银成矿带已发现的矽卡岩型多金属矿床中处于最西段。通过目前的预查工作,在矿区内共发现有14条矿体,初步预测可达到中-大型矿床规模。冈底斯中东段目前研究程度已较高,而西段与之具有相同的良好的矽卡岩型多金属矿成矿地质条件,但发现的矿床却很少。玛圭矿床的发现为该成矿带向西延伸和扩大规模提供了依据,并增加了进一步向西寻找同类型矿床的信心。     

甘肃省肃南县雪泉铜(锌)矿床找矿勘查思路探讨

雪泉塞浦路斯型富铜(锌)块状硫化物矿床地处北祁连山西段奥陶纪弧后盆地火山岩带内,矿床的形成受火山热液喷流中心控制,每个喷流中心的成矿遵循"蘑菇"状的成矿模式,目前已发现矿区存在多个热液喷流中心,与此相对应的矿体表现出呈群出现,分段集中的特点。结合矿区地形特点,笔者提出矿床下一步的找矿勘查应按照"面上展开——利用地质测量、物探扫面进行探寻热液喷流中心;分段深入——在每个热液喷流中心主要利用硐探工程进行探矿验证"的思路开展工作。     

Mineralogy of metal contaminated estuarine sediments,Derwent estuary,Hobart, Australia: implications for metal mobility

The mobility, bioaccessibility and transfer pathways of metals and metalloids in estuarine sediments have been the focus of much detailed research. However, to date, few studies have examined the mineralogical siting of metals and metalloids in such sediments. This is despite the fact the mineralogy of sediments is an important factor that controls which and how much of a particular metal is released to pore waters and overlying water columns. This study reports on the mineralogical siting of metals in contaminated estuarine sediments, Hobart, Australia, and aims to evaluate the mobility of metals in the contaminated substrates. Mineralogical, mineral chemical and bulk chemical analyses demonstrate that the sediments contain very high levels of several metals and metalloids. The contaminated sediments have concentrations of zinc (Zn), lead (Pb), copper (Cu) and cadmium (Cd) ranging from 0.55 to 4.23 wt%, 0.16 to 0.70 wt%, 415 to 951 mg/kg and 23 to 300 mg/kg, respectively. Franklinite and lesser sphalerite are the main repositories of Zn, whereas much of the Pb and Cu is hosted by sulfides, organic matter and undetermined iron (Fe) oxides. While the release of contaminant loads from franklinite through dissolution is likely to be insignificant, even small releases of metals from the highly contaminated sediments can still cause the deterioration of local water quality. The contaminated sediments represent long-term sources of metal pollutants, particularly Zn, to local waters. This study demonstrates that mineralogical analyses are a vital tool to recognise the potential mobility of trace metals in estuarine environments.