Archean high-Mg monzodiorite–syenite,epidote skarn,and biotite–sericite gold lodes in the Granny Smith–Wallaby district,Australia: U–Pb and Re–Os chronometry of two intrusion-related hydrothermal systems

The Granny Smith (37 t Au production) and Wallaby deposits (38 t out of a 180 t Au resource) are located northeast of Kalgoorlie, in 2.7 Ga greenstones of the Eastern Goldfields Province, the youngest orogenic belt of the Yilgarn craton, Western Australia. At Granny Smith, a zoned monzodiorite–granodiorite stock, dated by a concordant titanite–zircon U–Pb age of 2,665 ± 3 Ma, cuts across east-dipping thrust faults. The stock is fractured but not displaced and sets a minimum age for large-scale (1 km) thrust faulting (D2), regional folding (D1), and dynamothermal metamorphism in the mining district. The local gold–pyrite mineralization, controlled by fractured fault zones, is younger than 2,665 ± 3 Ma. In augite–hornblende monzodiorite, alteration progressed from a hematite-stained alkali feldspar–quartz–calcite assemblage and quartz–molybdenite–pyrite veins to a late reduced sericite–dolomite–albite assemblage. Gold-related monazite and xenotime define a U–Pb age of 2,660 ± 5 Ma, and molybdenite from veins a Re–Os isochron age of 2,661 ± 6 Ma, indicating that mineralization took place shortly after the emplacement of the main stock, perhaps coincident with the intrusion of late alkali granite dikes. At Wallaby, a NE-trending swarm of porphyry dikes comprising augite monzonite, monzodiorite, and minor kersantite intrudes folded and thrust-faulted molasse. The conglomerate and the dikes are overprinted by barren (<0.01 g/t Au) anhydrite-bearing epidote–actinolite–calcite skarn, forming a 600-m-wide and >1,600-m-long replacement pipe, which is intruded by a younger ring dike of syenite porphyry pervasively altered to muscovite + calcite + pyrite. Skarn and syenite are cut by pink biotite–calcite veins, containing magnetite + pyrite and subeconomic gold–silver mineralization (Au/Ag = 0.2). The veins are associated with red biotite–sericite–calcite–albite alteration in adjacent monzonite dikes. Structural relations and the concordant titanite U–Pb age of the skarn constrain intrusion-related mineralization to 2,662 ± 3 Ma. The main-stage gold–pyrite ore (Au/Ag >10) forms hematite-stained sericite–dolomite–albite lodes in stacked D2 reverse faults, which offset skarn, syenite, and the biotite–calcite veins by up to 25 m. The molybdenite Re–Os age (2,661 ± 10 Ma) of the ore suggests a genetic link to intrusive activity but is in apparent conflict with a monazite–xenotime U–Pb age (2,651 ± 6 Ma), which differs from that of the skarn at the 95% confidence level. The time relationships at both gold deposits are inconsistent with orogenic models invoking a principal role for metamorphic fluids released during the main phase of compression in the fold belt. Instead, mineralization is related in space and time to late-orogenic, magnetite-series, high-Mg monzodiorite–syenite intrusions of mantle origin, characterized by Mg/(Mg + Fe_TOTAL) = 0.31–0.57, high Cr (34–96 ppm), Ni (22–63 ppm), Ba (1,056–2,321 ppm), Sr (1,268–2,457 ppm), Th (15–36 ppm), and rare earth elements (total REE: 343–523 ppm). At Wallaby, shared Ca–K–CO₂ metasomatism and Th-REE enrichment (in allanite) link Au–Ag mineralization in biotite–calcite veins to the formation of the giant epidote skarn, implicating a Th + REE-rich syenite pluton at depth as the source of the oxidized hydrothermal fluid. At Granny Smith, lead isotope data and the Rb–Th–U signature of early hematite-bearing wall-rock alteration point to fluid released by the source pluton of the differentiated alkali granite dikes.     

Palaeoenvironmental significance of Late Permian palaeosols in the South‐Eastern Iberian Ranges,Spain

The Late Permian (Wuchiapingian) Alcotas Formation in the SE Iberian Ranges consists of one red alluvial succession where abundant soil profiles developed. Detailed petrographical and sedimentological studies in seven sections of the Alcotas Formation allow six different types of palaeosols, with distinctive characteristics and different palaeogeographical distribution, to be distinguished throughout the South‐eastern Iberian Basin. These characteristics are, in turn, related to topographic, climatic and tectonic controls. The vertical distribution of the palaeosols is used to differentiate the formation in three parts from bottom to top showing both drastic and gradual vertical upwards palaeoenvironmental changes in the sections. Reconstruction of palaeoenvironmental conditions based on palaeosols provides evidence for understanding the events that occurred during the Late Permian, some few millions of years before the well‐known Permian‐Triassic global crisis.     

Methane‐related microbial gypsum calcitization in stromatolites of a marine evaporative setting (Münder Formation,Upper Jurassic,Hils Syncline,north Germany)

Fossil stromatolites may reveal information about their hydrochemical palaeoenvironment, provided that assignment to a specific microbial community and a corresponding biogeochemical mechanism of formation can be made. Tithonian stromatolites of the Münder Formation at Thüste, north Germany, have traditionally been considered as formed by intertidal cyanobacterial communities. However, thin sections of the stromatolites show elongated angular traces of former gypsum crystals in a dense arrangement, but no algal or cyanobacterial filament traces. Moreover, high Fe²⁺ and Mn²⁺ contents, oxygen‐isotope and sulphur‐isotope ratios of carbonate‐bound sulphates, and sulphurized hydrocarbon biomarkers of the stromatolitic carbonate indicate that CaCO₃ precipitation occurred near the oxic–anoxic interface as a result of intensive bacterial sulphur cycling rather than photosynthetic activity. Furthermore, anaerobic oxidation of methane by Archaea may have driven CaCO₃ precipitation in deeper parts of the biofilm community, as reflected by high concentrations of squalane with a strongly negative δ¹³C in conjunction with evaporite pseudomorphs showing extremely low δ¹³C_Carb ratios. Consequently, the Thüste stromatolites are now interpreted as having initially formed by gypsum impregnation of biofilms. Subsequently, early Mg‐calcitic calcitization within the biofilms occurred because of combined bacterial iron, manganese and sulphate reduction, with an increasing contribution of anaerobic oxidation of methane with depth. This model plausibly explains the prominent preservation of signals derived from oxygen‐independent metabolic pathways, whereas virtually no geochemical record exists for an aerobic community that may, nevertheless, have prevailed at the stromatolite surface. Photic‐zone stromatolites with a prominent signal of anaerobic oxidation of methane may be common in, and indicative of, oxygen‐depleted sulphate‐bearing environments with high rates of methane production, conditions that possibly were fulfilled at the Archaean to Proterozoic transition.     

SHRIMP zircon dating and Sm/Nd isotopic investigations of Neoproterozoic granitoids, Eastern Desert, Egypt

There is an increasing evidence for the involvement of pre-Neoproterozoic zircons in the Arabian–Nubian Shield, a Neoproterozoic crustal tract that is generally regarded to be juvenile. The source and significance of these xenocrystic zircons are not clear. In an effort to better understand this problem, older and younger granitoids from the Egyptian basement complex were analyzed for chemical composition, SHRIMP U–Pb zircon ages, and Sm–Nd isotopic compositions. Geochemically, the older granitoids are metaluminous and exhibit characteristics of I-type granites and most likely formed in a convergent margin (arc) tectonic environment. On the other hand, the younger granites are peraluminous and exhibit the characteristics of A-type granites; these are post-collisional granites. The U–Pb SHRIMP dating of zircons revealed the ages of magmatic crystallization as well as the presence of slightly older, presumably inherited zircon grains. The age determined for the older granodiorite is 652.5 ± 2.6 Ma, whereas the younger granitoids are 595–605 Ma. Xenocrystic zircons are found in most of the younger granitoid samples; the xenocrystic grains are all Neoproterozoic, but fall into three age ranges that correspond to the ages of other Eastern Desert igneous rocks, viz. 710–690, 675–650 and 635–610 Ma. The analyzed granitoids have (+3.8 to +6.5) and crystallization ages, which confirm previous indications that the Arabian–Nubian Shield is juvenile Neoproterozoic crust. These results nevertheless indicate that older Neoproterozoic crust contributed to the formation of especially the younger granite magmas.     

Anoxic nitrification: Evidence from Humber Estuary sediments (UK)

Conventional understanding of the nitrogen cycle in marine sediments has changed in recent years with the discovery of an alternative pathway for ammonia oxidation via the reduction of manganese oxides (during anoxic nitrification). In anoxic sediments, the potential for manganese oxides to serve as oxidant for nitrification may be considerable yet previous work on manganese-rich sediments has suggested anoxic nitrification may not be significant. In this study, the potential for anoxic nitrification in a range of sediment types was investigated. Laboratory incubation of sediment from three sites on the Humber Estuary, a microbially diverse environment, showed anoxic accumulation of nitrate, nitrite and dinitrogen gas, with and without the addition of synthetic manganese oxides. Incubation experiments confirmed anoxic nitrification as microbially mediated, with heat-killed controls yielding negative results. The anoxic nitrification reaction significantly depleted ammonia concentrations, and occurred simultaneously with manganese-, iron- and sulphate reduction, and methanogenesis. Taken in conjunction with other studies, results suggest anoxic nitrification may not only be dependent on total manganese concentrations but on manganese dynamics. Anoxic nitrification may be explained as a non-steady state reaction, dependent on the recent stability of a sediment system. Physical perturbation of sediments may cause the redistribution and/or introduction of manganese oxides and promote anoxic nitrification. The significance and persistence of anoxic nitrification is likely to depend on the frequency and magnitude of sediment perturbation, which explains why the reaction varies so widely across studied sites, and why it may not occur in some manganese-rich sediment.     

Using ALSM to map sinkholes in the urbanized covered karst of Pinellas County,Florida—1, methodological considerations

Comparison of a database of interpreted sinkholes made using airborne laser swath mapping (ALSM) with databases of sinkholes made from interpretation of aerial photographs reveals substantial disagreement. The discrepancies involve the location, number, areas, and circularity of interpreted sinkholes. Methodological factors that contribute to the discrepancies include blockage of ALSM laser returns in thick vegetation, multi-path reflections, and misrepresentation of the true extent of sinkholes. Comparison of two ALSM-derived databases made (1) independently from versus (2) in combination with earlier air photo analysis in undeveloped regions had the following result: one-fourth of the sinkholes interpreted by using the composite method were missed by the independent analysis, and one-third of the sinkholes that were interpreted from the independent analysis were not interpreted as sinkholes using the composite method. Subjective interpretation leads to a high level of uncertainty such that the results of the remote sensing studies are suspect, if not invalid.     

Multiple discriminant analysis of the Drava River alluvial plain sediments

Three discriminant function models are raised and cross-compared in order to distinguish geochemical patterns characteristic for the Drava River floodplain sediments. Based on data representing total element concentrations in samples collected from alluvium (A), terrace (T), and unconsolidated bedrock (B) at the border of a floodplain, four element clusters emerged accounting for discrimination between the referred groups of sediments. The most prominent is contaminant/carbonate cluster characteristic for alluvium. The other two are: silicate cluster typical for unconsolidated geological substrate (Neogene sedimentary rocks); and naturally dispersed heavy metal cluster separating terrace from the former two groups. Models introducing depth intervals and single profiles as grouping criteria reveal identical sediment-heavy metal matrices. The second important issue of this paper is possibility of reclassification of samples originally assigned to one of the a priori defined groups of sediments, based on established geochemical pattern. The mapped geological units can be reconsidered by the post hoc assignments to a different group if geological border between alluvium and terrace or between terrace and bedrock can not be established geologically with absolute certainty.     

Magnesium isotope systematics of the lithologically varied Moselle river basin, France

Magnesium and strontium isotope signatures were determined during different seasons for the main rivers of the Moselle basin, northeastern France. This small basin is remarkable for its well-constrained and varied lithology on a small distance scale, and this is reflected in river water Sr isotope compositions. Upstream, where the Moselle River drains silicate rocks of the Vosges mountains, waters are characterized by relatively high ⁸⁷Sr/⁸⁶Sr ratios (0.7128-0.7174). In contrast, downstream of the city of Epinal where the Moselle River flows through carbonates and evaporites of the Lorraine plateau, ⁸⁷Sr/⁸⁶Sr ratios are lower, down to 0.70824.Magnesium in river waters draining silicates is systematically depleted in heavy isotopes (δ²⁶Mg values range from −1.2 to −0.7‰) relative to the value presently estimated for the continental crust and a local diorite (−0.5‰). In comparison, δ²⁶Mg values measured in soil samples are higher (∼0.0‰). This suggests that Mg isotope fractionation occurs during mineral leaching and/or formation of secondary clay minerals. On the Lorraine plateau, tributaries draining marls, carbonates and evaporites are characterized by low Ca/Mg (1.5-3.2) and low Ca/Sr (80-400) when compared to local carbonate rocks (Ca/Mg = 29-59; Ca/Sr = 370-2200), similar to other rivers draining carbonates. The most likely cause of the Mg and Sr excesses in these rivers is early thermodynamic saturation of groundwater with calcite relative to magnesite and strontianite as groundwater chemistry progressively evolves in the aquifer. δ²⁶Mg of the dissolved phases of tributaries draining mainly carbonates and evaporites are relatively low and constant throughout the year (from −1.4‰ to −1.6‰ and from −1.2‰ to −1.4‰, respectively), within the range defined for the underlying rocks. Downstream of Epinal, the compositions of the Moselle River samples in a δ²⁶Mg vs. ⁸⁷Sr/⁸⁶Sr diagram can be explained by mixing curves between silicate, carbonate and evaporite waters, with a significant contribution from the Vosgian silicate lithologies (>70%). Temporal co-variation between δ²⁶Mg and ⁸⁷Sr/⁸⁶Sr for the Moselle River throughout year is also observed, and is consistent with a higher contribution from the Vosges mountains in winter, in terms of runoff and dissolved element flux. Overall, this study shows that Mg isotopes measured in waters, rocks and soils, coupled with other tracers such as Sr isotopes, could be used to better constrain riverine Mg sources, particularly if analytical uncertainties in Mg isotope measurements can be improved in order to perform more precise quantifications.     

Growing up green on serpentine soils: Biogeochemistry of serpentine vegetation in the Central Coast Range of California

Serpentine soils derived from the weathering of ultramafic rocks and their metamorphic derivatives (serpentinites) are chemically prohibitive for vegetative growth. Evaluating how serpentine vegetation is able to persist under these chemical conditions is difficult to ascertain due to the numerous factors (climate, relief, time, water availability, etc.) controlling and affecting plant growth. Here, the uptake, incorporation, and distribution of a wide variety of elements into the biomass of serpentine vegetation has been investigated relative to vegetation growing on an adjacent chert-derived soil. Soil pH, electrical conductivity, organic C, total N, soil extractable elements, total soil elemental compositions and plant digestions in conjunction with spider diagrams are utilized to determine the chemical relationships of these soil and plant systems. Plant available Mg and Ca in serpentine soils exceed values assessed in chert soils. Magnesium is nearly 3 times more abundant than Ca in the serpentine soils; however, the serpentine soils are not Ca deficient with Ca concentrations as high as 2235 mg kg⁻¹. Calcium to Mg ratios (Ca:Mg) in both serpentine and chert vegetation are greater than one in both below and above ground tissues. Soil and plant chemistry analyses support that Ca is not a limiting factor for plant growth and that serpentine vegetation is actively moderating Mg uptake as well as tolerating elevated concentrations of bioavailable Mg. Additionally, results demonstrate that serpentine vegetation suppresses the uptake of Fe, Cr, Ni, Mn and Co into its biomass. The suppressed uptake of these metals mainly occurs in the plants’ roots as evident by the comparatively lower metal concentrations present in above ground tissues (twigs, leaves and shoots). This research supports earlier studies that have suggested that ion uptake discrimination and ion suppression in the roots are major mechanisms for serpentine vegetation to tolerate the chemistry of serpentine soils.     

The presence of anomalous trace element levels in present day Jamaican soils and the geochemistry of Late-Miocene or Pliocene phosphorites

High levels of Cd and Zn in Jamaican soils observed in geochemical surveys are related to the presence of phosphorites of possible Late-Miocene or Pliocene age. The trace element and REE geochemistry of the phosphorites, together with SEM studies, indicate a guano origin for the phosphorites. No specific host minerals for Cd could be identified in the fossiliferous phosphorite which is characterized by uniquely high levels of Cd, Zn, Ag, Be, U and Y. However, in the soil Cd is present in lithiophorite and a complex history of pedological development is preserved in the aluminous–goethite present in the soil. The unique guano signature is preserved in the soil despite the fact that guanos themselves have either not been observed or have been destroyed by continuing karst and soil development. The phosphorite geochemical signature can be traced in the data of a 1988 island-wide soil geochemical survey, identifying areas where the Palaeo-environment that supported bird ‘rookeries’ existed in the Late-Miocene or Pliocene.