Trace and minor elements in sphalerite: A LA-ICPMS study

Sphalerite is an important host mineral for a wide range of minor and trace elements. We have used laser-ablation inductively coupled mass spectroscopy (LA-ICPMS) techniques to investigate the distribution of Ag, As, Bi, Cd, Co, Cu, Fe, Ga, Ge, In, Mn, Mo, Ni, Pb, Sb, Se, Sn and Tl in samples from 26 ore deposits, including specimens with wt.% levels of Mn, Cd, In, Sn and Hg. This technique provides accurate trace element data, confirming that Cd, Co, Ga, Ge, In, Mn, Sn, As and Tl are present in solid solution. The concentrations of most elements vary over several orders of magnitude between deposits and in some cases between single samples from a given deposit. Sphalerite is characterized by a specific range of Cd (typically 0.2-1.0 wt.%) in each deposit. Higher Cd concentrations are rare; spot analyses on samples from skarn at Baisoara (Romania) show up to 13.2 wt.% (Cd²⁺ ↔ Zn²⁺ substitution). The LA-ICPMS technique also allows for identification of other elements, notably Pb, Sb and Bi, mostly as micro-inclusions of minerals carrying those elements, and not as solid solution. Silver may occur both as solid solution and as micro-inclusions. Sphalerite can also incorporate minor amounts of As and Se, and possibly Au (e.g., Magura epithermal Au, Romania). Manganese enrichment (up to ∼4 wt.%) does not appear to enhance incorporation of other elements. Sphalerite from Toyoha (Japan) features superimposed zoning. Indium-sphalerite (up to 6.7 wt.% In) coexists with Sn-sphalerite (up to 2.3 wt.%). Indium concentration correlates with Cu, corroborating coupled (Cu⁺In³⁺) ↔ 2Zn²⁺ substitution. Tin, however, correlates with Ag, suggesting (2Ag⁺Sn⁴⁺) ↔ 3Zn²⁺ coupled substitution. Germanium-bearing sphalerite from Tres Marias (Mexico) contains several hundred ppm Ge, correlating with Fe. We see no evidence of coupled substitution for incorporation of Ge. Accordingly, we postulate that Ge may be present as Ge²⁺ rather than Ge⁴⁺. Trace element concentrations in different deposit types vary because fractionation of a given element into sphalerite is influenced by crystallization temperature, metal source and the amount of sphalerite in the ore. Epithermal and some skarn deposits have higher concentrations of most elements in solid solution. The presence of discrete minerals containing In, Ga, Ge, etc. also contribute to the observed variance in measured concentrations within sphalerite.     

Impacts of Invasive <Emphasis Type="Italic">Phragmites australis</Emphasis> on Diamondback Terrapin Nesting in Chesapeake Bay

The range expansion of exotic plant species, including the invasive reed Phragmites australis, causes widespread structural and functional changes to coastal ecosystems along the Atlantic and Gulf Coasts of North America. Native estuarine species, such as the diamondback terrapin (Malaclemys terrapin), are at risk of adverse effects from rapid habitat changes due to exotic invasions. Diamondback terrapins currently face population threats including by-catch mortality in crab pots, predation, and habitat loss, and populations may continue to suffer if deleterious plant invasions into preferred nesting habitats are left unchecked. We examined the extent to which Phragmites affects nesting of a breeding population of diamondback terrapins at Fisherman Island National Wildlife Refuge on the eastern shore of Virginia, where Phragmites has recently expanded into known areas of terrapin nesting. With data collected from the 2015 nesting season, we quantified the extent to which Phragmites shading could impact nest incubation temperature and determined how Phragmites density impacts the risk of rhizome invasion into nests. We conclude that Phragmites cover greater than 50% would decrease incubation temperatures of terrapin nests sufficiently to produce predominantly male hatchlings. Phragmites cover had no observed effect on root growth into simulated nests, but cover by other dune plant species explained observed trends in root growth. These results suggest that terrapins may be negatively impacted by Phragmites expansion into open nesting sites. Breeding site fidelity exhibited by terrapins and other estuarine species could limit the ability of their populations to adjust to rapid coastal expansion of invasive plant species.     

Mineralogy and textural relationships among sulphosalts and related minerals in the Bleikvassli Zn-Pb-(Cu) deposit, Nordland, Norway

Several distinct assemblages of Pb-Sb, Pb-As, Cu-Pb-Sb and Cu-Fe-Zn-Sn sulphosalts are identified in sulphide samples from Bleikvassli mine, Norway. Detailed optical microscopy and electron probe microanalysis have permitted investigation of textural relationships between minerals and compositional variations between different ore types. Tetrahedrite, typically containing 10–16?wt.% Ag (rare freibergite containing 25–30?wt.% Ag has also been identified in two samples), stannite (Cu₂(Fe>Zn)SnS₄), and meneghinite, CuPb₁₃Sb₇S₂₄, are widely distributed as trace constituents throughout massive pyritic and galena-rich ores. Native antimony and pyrargyrite occur in trace amounts in all ore types, as the breakdown products of earlier sulphosalts. Several distinct types of wall-rock mineralisation are present at Bleikvassli. Of considerable mineralogical interest are the coarse-grained sulphide mobilisates within the wall rock which contain a distinct?and characteristic suite of Pb-As sulphosalts:?tennantite?+?jordanite (Pb₁₄As₆S₂₃)?+?seligmannite (CuPbAsS₃) ± dufrenoysite (Pb₂As₂S₅). Bournonite (CuPbSbS₃) is the only Sb-bearing sulphosalt recognised in significant amounts within the mobilisates, meneghinite and tetrahedrite being conspicuously absent. These mobilisates display considerable Au enrichment; electrum can be confirmed, intimately associated with jordanite and tennantite. Appreciable Sb (up to 3?wt.%) is contained within galena in the mobilisates, in contrast to galena from massive ores which contains only negligible Sb. Contents of Ag and Bi in galena vary considerably in all ore types, but confirm earlier suggestions that galena is a major Ag-carrier at Bleikvassli. Boulangerite (Pb₅Sb₄S₁₁), jamesonite (FePb₄Sb₆S₁₄) and gudmundite (FeSbS) occur in trace amounts. Sn-sulphosalts are represented by kësterite, (Cu₂(Zn> Fe)SnS₄), but commonly zoned with respect to Zn/Fe ratio, in the mobilisates, rather than by stannite. A rare type of mobilisate, also in the wall rock, in which chalcocite and bornite are the main minerals, contains native Ag, stromeyerite (AgCuS), mckinstryite ((Ag,Cu)₂?S), Ag-free tetrahedrite, an unnamed Cu-Ag-Fe sulphide (Cu₃Ag₂FeS₄) and native Bi, myrmekitically intergrown with chalcocite. Although a comprehensive genetic model for the wall-rock mineralisation at Bleikvassli is largely impossible given the limitations in the present state of knowledge regarding mechanisms involved in remobilisation processes, a multi-stage model of remobilisation during regional metamorphism is considered to best explain the observations. An interplay of different solid- and liquid-state remobilisation mechanisms, in various combinations, is required to account for the macro- and microscopic observations. Remobilisation probably began during the earlier stages of metamorphism, with crystallisation and further remobilisation taking place during the entire metamorphic cycle, giving rise to the extensive chemical and mineralogical diversity observed today. Preserved mineral assemblages and their textural relationships reflect a complex sequence of replacement and decomposition reactions taking place during the latest phase of late-metamorphic crystallisation and subsequent cooling.     

A contribution to the migration of gold in the biosphere of the humid mild zone

The content of gold in plants has been used as an indicator in the prospecting for gold. For this purpose non-destructive analytical methods have been developed. In the humid mild zone — where the process of weathering is of a kaolinitic character — there is practically no migration of gold, and consequently its increased content indicates the presence of a gold deposit.     

Effect of mining and related activities on the sediment trace element geochemistry of lake coeur D'Alene,idaho, USA. Part I: Surface sediments

During the summer of 1989 surface sediment samples were collected in Lake Coeur d'Alene, the Coeur d'Alene River and the St Joe River, Idaho, at a density of approximately one sample per square kilometre. Additional samples were collected from the banks of the South Fork of the Coeur d'Alene and the Coeur d'Alene Rivers in 1991. All the samples were collected to determine trace element concentrations, partitioning and distribution patterns, and to relate them to mining, mining related and discharge operations that have occurred in the Coeur d'Alene district since the 1880s, some of which are ongoing. Most of the surface sediments in Lake Coeur d'Alene north of Conkling Point and Carey Bay are substantially enriched in Ag, As, Cu, Cd, Hg, Pb, Sb and Zn relative to unaffected sediments in the southern portion of the lake near the St Joe River. All the trace element enriched sediments are extremely fine grained (mean grain sizes « 63 μm). Most of the enriched trace elements, based on both the chemical analyses of separated heavy and light mineral fractions and a two step sequential extraction procedure, are associated with an operationally defined Fe oxide phase; much smaller percentages are associated either with operationally defined organics/sulphides or refractory phases. The presence, concentration and distribution of the Fe oxides and heavy minerals indicates that a substantial portion of the enriched trace elements are probably coming from the Coeur d'Alene River, which is serving as a point source. Within the lake, this relatively simple point source pattern is complicated by a combination of (1) the formation of trace element rich authigenic Fe oxides that appear to have reprecipitated from material solubilized from anoxic bed sediments and (2) physical remobilization by currents and wind driven waves. The processes that have caused the trace element enrichment in the surface sediments of Lake Coeur d'Alene are likely to continue for the foreseeable future.     

Burial-exhumation history of the central Apennines (Italy), from the foreland to the chain building: thermochronological and geological data

A clear correlation between regional unconformities and related exhumation events was documented by thermochronological and geological data in the central Apennines. This approach allowed: (i) two major exhumation episodes to be identified, corresponding to turning points in the long-term burial history, from rifting to convergent margin development, and (ii) a quantification of the amount of section removed during the two exhumation events. The first exhumation event was connected with the foreland buckling process associated with the coupling between the Alpine–Apennines system, the Dinarides chain and their common foreland. During the Neogene a thrust-system development, the superposition of an allochthonous unit is envisaged to explain the second palaeoheating event. The dismantling of this additional load in central Apennines has been related to the formation of the Middle Pliocene Unconformity, during the development of the Pliocene–Quaternary frontal thrust of the Apennine Chain.