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.     

云南会泽麒麟厂铅锌矿床构造地球化学及定位预测

在论述构造地球化学基本理论与方法的基础上，深入讨论了会泽麒麟厂铅锌矿床构造地球化学特点，认为构造地球化学异常集中区是进行隐伏矿定位预测的重要依据，提出了1571中段44－62剖面线间的深部等重点定位找矿靶区，已被验证工程证实，新发现八号隐伏矿体。该方法对隐伏矿定位预测和评价具有重要指导意义。     

An Acetic Acid‐Based Extraction Protocol for the Recovery of U,Th and Pb from Calcium Carbonates for U‐(Th)‐Pb Geochronology

A new method for the simultaneous recovery of U, Th and Pb from ca. 0.5 g calcium carbonate samples for the purpose of U‐(Th)‐Pb geochronometry is presented. The protocol employs ion‐exchange chromatography. Standard anion exchange resin (AG 1‐X8 100–200 mesh) was used as the static phase, and 90% acetic acid was used as the mobile phase to elute the unwanted matrix components; dilute nitric acid was used to elute the U, Th and Pb. Blanks of 1.8 pg Th, 6.4 pg Pb and 8.4 pg U were obtained. The protocol was evaluated by determining the isotopic composition of U‐Th‐Pb separates obtained from an in‐house reference material (prepared from a natural speleothem) by MC‐ICP‐MS. An independently dated speleothem was also reanalysed. Based on these tests, the extraction protocol had an acceptable blank and produced a Pb separate sufficiently free of matrix‐induced instrumental biases to be appropriate for U‐Th‐Pb chronology.     

Accurate and Precise Elemental Abundance of Zinc in Reference Materials by an Isotope Dilution Mass Spectrometry TIMS Technique

A thermal ionisation mass spectrometric technique enabled the abundance of Zn in geological and biological reference materials and water samples to be measured by double spiking isotope dilution mass spectrometry enriched in the ⁶⁷Zn and ⁷⁰Zn isotopes. In the past, thermal ionisation mass spectrometry proved to be difficult for low-level zinc isotopic measurements. The size of Zn samples used for isotopic determination, in particular the biological RMs, represents an important breakthrough. These results represent the most accurate and precise concentrations measured for Zn in these samples. The maximum fractional uncertainty was that for TILL-3 (2%), while the minimum fractional uncertainty was 0.7% for both BCR-1 and W-2. The inhomogeneity of Zn in HISS-1 was revealed while other reference materials appeared homogeneous at the 95% confidence uncertainty. The certified concentration of Zn in HISS-1 and IMEP-19 by their producers are 28% and 3.8% higher than the values measured in this work. These are the first Zn concentration measurements in these materials by the isotope dilution-TIMS technique, except for BCR-1, NIES N^o 9 and IMEP-19. Reducing the blank enabled accurate measurement in water at the ng g^-1 level demonstrating the applicability of the technique for low-level Zn samples.     

Influence of core property on multi-electron process in slow collisions of isocharged sequence ions with neon

Influence of core property on multi-electron process in the collisions of q=6-9 and 11 isocharged sequence ions with Ne is investigated in the keV/u region. The cross-section ratios of double-, triple-, quadruple- and total multi-electron processes to the single electron capture process as well as the partial ratios of different reaction channels to the relevant multi-electron process are measured by using position-sensitive and time-of-flight techniques. The experimental data are compared with the theoretical predictions including the extended classical over-barrier model, the molecular Columbic barrier model and the semi-empirical scaling law. Results show a core effect on multi-electron process of isocharge ions colliding with Neon, which is consistent with the results of Helium we obtained previously.     

Determination of cadmium(II), copper(II), manganese(II) and nickel(II) species in Antarctic seawater with complexing resins

The strong species of cadmium(II), copper(II), manganese(II) and nickel(II) in an Antarctic seawater sample are investigated by a method based on the sorption of metal ions on complexing resins. The resins compete with the ligands present in the sample to combine with the metal ions. Two resins with different adsorbing strengths were used. Very stable metal complexes were investigated with the strong sorbent Chelex 100 and weaker species with the less strong resin, Amberlite CG-50. Strong species were detected for three of the considered metal ions, but not for Mn(II). Cu(II) is completely linked to species with a side reaction coefficient as high as log α_M(I) = 11.6 at pH = 7.3. The ligand concentration was found to be similar to that of the metal ion, and the conditional stability constant was around 10²⁰ M^− 1. In the considered sample, only a fraction of the metal ions Cd(II) and Ni(II) is bound to the strong ligands, with side reaction coefficients equal to log α_M(I) = 5.5 and 6.5 at pH = 7.3 for Cd(II) and Ni(II), respectively. These findings were confirmed by the test with the weaker sorbent Amberlite CG-50. It can be calculated from the sorption equilibria that neither Mn(II) nor Ni(II) is adsorbed on Amberlite CG-50 under the considered conditions and, in fact, only a negligible fraction of Mn(II) and Ni(II) was adsorbed. A noticeable fraction of Cd(II) was adsorbed on Amberlite CG-50, meaning that cadmium(II) is partially linked to weak ligands, possibly chloride, while no copper(II) was adsorbed on this resin, confirming that copper(II) is only combined in strong species. These results are similar, but not identical, to those obtained for other seawater samples examined in previous investigations.     

Spectrum characteristics of major ion concentrations at Wuhan sectoin of the Changjiang Rriver

Spectrum analyses of water quality time series have been carried out for five hydrometric stations including Wuhan hydrometric station of the Changjiang(Yangtze) River, etc. The fluctuations of Ca²⁺, Mg²⁺ and HCO ₃ ⁻ concentrations in river water under different physical geography conditions have about two-year cycle which is corresponding to hydrometeorological quasi-biannual-oscillation (QBO). Na⁺, Cl⁻ SO ₄ ²⁻ have about two-year cycle in the area lightly affected by human activities while two-year cycle doesn’t exist in the area heavily affected by human activities. All the fluctuations of major ions have about three-month cycle. The river diseharge fluctuation accounts for 43.9%, 45.1%, 54.3%, 33.9%, 30.3% and 42.7% of the variance of Ca²⁺, Mg²⁺, HCO ₃ ⁻ , Na⁺, Cl⁻, SO ₄ ²⁻ , respectively, at Wuhan from 1962 to 1985. According to the spectrum characteristic of major ions, the duration of the time series has to be at least 13 years for trend analysis of monthly water quality data. Foundation item: Under the auspices of the National Natural Science Foundation of China (No. 49671017). Biography: XIA Xing-hui(1971-), female, a native of Hunan Province, Ph. D. Her research interest includes environmental chemistry.     

珠江三角洲滨海小流域离子化学特征及来源分析

在分析中山大学滨海小流域水循环综合试验基地内雨水、河水和地下水离子组分的基础上,讨论了该小流域内水体离子化学组分的特征及来源。结果显示:①河水中TDS变化范围为28.97～44.64 mg/l,平均值为33.90 mg/l;在离子化学组成中,阳离子以Na++K+为主,阴离子以Cl-和HCO3-为主;雨水中TDS的变化范围为0.88～26.07 mg/l,平均值为8.42 mg/l,离子含量变化幅度较大;地下水TDS变化范围为39.49～113.16 mg/l,均值为58.11 mg/l,约为流域河水的2倍,雨水的7倍;②海盐沉降中Ca2+、Mg2+、Na+、K+、SO42-的贡献率:雨季分别为6%、60%、47%、2%和15%,旱季分别为3%、41%、54%、2%、9%;③硅酸盐风化中,雨季:(Ca/Na)sil=0.31,(Mg/K)sil=0.21;旱季:(Ca/Na)sil=0.36,(Mg/K)sil=0.27;CO2消耗率为12.4 t/(km2.a);④河水中的NO3-和(SO42-)res主要来源于大气酸沉降,且具有旱季含量低、雨季含量高的特点;⑤R1潜水井受到一定程度的NO3-污染,NO3-的...     

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.     

Temporal variations in aerosol composition at Lanzhou City,Northwestern China

Although Lanzhou is one of the most heavily polluted cities in China, the composition of its air pollutants have not yet been studied in detail. The data of four months on the concentrations and compositions of ions from daily air-filter samples in the winter and spring during 2007–2008 were analyzed to investigate temporal trends and their possible causes. The results indicate that mean concentrations of almost all the aerosol components are greater in winter than in spring due to stronger emissions in winter and weaker localized dispersion. Spring dust storms are the major cause of the highest peak PM10 concentrations recorded during the study period; however, these elevated levels were transient. Ion concentrations related to coal combustion show the greatest reduction from winter to spring, while the concentrations of strong crustal components show a less-pronounced reduction. Strong cycles in the levels of particulate matter (PM) and all ions are also observed during the winter months due to meteorological conditions. Depending on the season, nine different ions accounted for 20%–50% of the PM concentration. The particle size of polluting ions was constant at times of increasing PM concentrations (particularly during winter), whereas the particle size of crustal ions increased dramatically during spring dust storms. Local meteorological conditions (especially wind speed) have a strong influence on the levels of pollutants. Four dust storms were noted, including one during winter. In summary, the regional transport of desert dust from the Gobi can significantly affect air quality and the chemical composition of aerosols in Lanzhou. The dust storms can strongly increase concentration of crustal ions, which are characteristics of deserts in northwestern China. This observation is in agreement with back-trajectories, which show reduced levels of pollutant ions during dust storms. Data on nitrate:sulfate ratios indicate that stationary point sources are the main source of ions rather than mobile sources.