Fluid sources for the La Guitarra epithermal deposit (Temascaltepec district, Mexico): Volatile and helium isotope analyses in fluid inclusions

The La Guitarra deposit (Temascaltepec district, South-Central Mexico), belongs to the low/intermediate sulfidation epithermal type, has a polymetallic character although it is currently being mined for Ag and Au. The mineralization shows a polyphasic character and formed through several stages and sub-stages (named I, IIA, IIB, IIC, IID, and III). The previous structural, mineralogical, fluid inclusion and stable isotope studies were used to constrain the selection of samples for volatile and helium isotope analyses portrayed in this study. The N₂/Ar overall range obtained from analytical runs on fluid inclusion volatiles, by means of Quadrupole Mass Spectrometry (QMS), is 0 to 2526, and it ranges 0 to 2526 for stage I, 0 to 1264 for stage IIA, 0 to 1369 for stage IIB, 11 to 2401 for stage IIC, 19 to 324 for stage IID, and 0 to 2526 for stage III. These values, combined with the CO₂/CH₄ ratios, and N₂-He-Ar and N₂-CH₄-Ar relationships, suggest the occurrence of fluids from magmatic, crustal, and shallow meteoric sources in the forming epithermal vein deposit. The helium isotope analyses, obtained by means of Noble Gas Mass Spectrometry, display R/Ra average values between 0.5 and 2, pointing to the occurrence of mantle-derived helium that was relatively diluted or “contaminated” by crustal helium. These volatile analyses, when correlated with the stable isotope data from previous works and He isotope data, show the same distribution of data concerning sources for mineralizing fluids, especially those corresponding to magmatic and crustal sources. Thus, the overall geochemical data from mineralizing fluids are revealed as intrinsically consistent when compared to each other.The three main sources for mineralizing fluids (magmatic, and both deep and shallow meteoric fluids) are accountable at any scale, from stages of mineralization down to specific mineral associations. The volatile and helium isotope data obtained in this paper suggest that the precious metal-bearing mineral associations formed after hydrothermal pulses of predominantly oxidized magmatic fluids, and thus it is likely that precious metals were carried by fluids with such origin. Minerals from base-metal sulfide associations record both crustal and magmatic sources for mineralizing fluids, thus suggesting that base metals could be derived from deep leaching of crustal rocks. At the La Guitarra epithermal deposit there is no evidence for an evolution of mineralizing fluids towards any dominant source. Rather than that, volatile analyses in fluid inclusions suggest that this deposit formed as a pulsing hydrothermal system where each pulse or set of pulses accounts for different compositions of mineralizing fluids.The positive correlation between the relative content of magmatic fluids (high N₂/Ar ratios) and H₂S suggests that the necessary sulfur to carry mostly gold as bisulfide complexes came essentially from magmatic sources. Chlorine necessary to carry silver and base metals was found to be abundant in inclusion fluids and although there is no evidence about its source, it is plausible that it may come from magmatic sources as well.     

Can stable isotopes be used to monitor landfill leachate impact on surface waters?

Bacterially mediated methanogenesis in municipal solid waste landfills has been shown to cause an enrichment of carbon stable isotope ratios of dissolved inorganic carbon and hydrogen stable isotope ratios of water in landfill leachate. In the present study, we investigate the universality of this enrichment in leachate obtained from four diverse landfill sites in New Zealand. At each site, surface water samples upstream and downstream of landfills were analysed to examine the applicability of stable isotope ratios as a tool for monitoring leachate contamination in landfill-associated streams. The design of leachate collection systems, operational history, and landfill location appeared to strongly influence leachate isotopic values and the effectiveness of isotope ratios as an environmental monitoring tool for surface water.     

Hydrochemical and isotopical tracers in the lacustrine aquifer of the Cerro Prieto area, Baja California, México

A series of patterns in the chemical and isotopic composition of the groundwater of the Cerro Prieto area have been recognized. These patterns were used to define four hydrochemical and isotopical zones in the area. One of these areas located at the east side was found to be the source of recharge, while another in the central part is where an older aquifer exist in lacustrine deposits. The low permeability of the area causes the aquifer to act as an aquitard, which at least is partly surrounded by an interface zone where mixing of waters occurs. Tritium and radiocarbon method revealed that the aquitard is an isolate system whose residence time is of 32 ka.     

Constraints of stable isotopes on the origin of alunite from advanced argillic alteration systems in Bulgaria

Voluminous areas of advanced argillic alteration (AAA) constitute major exploration targets for surficial Cu–Au epithermal and potentially underlying porphyry-type deposits. In Bulgaria, more than 30 alunite occurrences are recognised, few of them being associated with a mineralised system. A mineralogical study combined with a stable isotopic (O, H, S) study has been carried out on nine alunite occurrences of advanced argillic zones hosted by volcanic rocks of Late Cretaceous age in the Srednogorie belt and of Oligocene age in the Rhodopes belt. This work was realised in order to constrain the origin of alunite and to define criteria to discriminate alunite from ore deposits and alunite from large barren alteration systems.Mineralogy of the nine occurrences consists of alunite + quartz + minor alumino-phospho-sulphates, associated with more or less kaolinite, dickite, pyrophyllite, diaspore and zunyite, depending on formation temperature. Alunite generally occurs as tabular crystals but is also present as fine-crystalline pseudocubic phases at Boukovo and Sarnitsa, in Eastern Rhodopes. In the advanced argillic alterations associated with economic ore, the presence of zunyite in the deeper parts indicates acid–fluorine–sulphate hydrothermal systems, whereas it is absent in uneconomic and barren advanced argillic alteration. All occurrences are formed at temperatures between 200 and 300 °C.(H, O, S) isotopic signatures of alunite combined with mineralogical features from all the studied occurrences, whatever their type, show characteristics of magmatic-hydrothermal systems. Sulphur data indicate essentially a magmatic origin for sulphur. Oxygen and hydrogen data suggest that hydrothermal fluids result from a mixing between magmatic fluids and an external component, which is identified as seawater-derived fluids or meteoric water in the vicinity of a sea. In most of the alunite occurrences, magmatic fluids are dominant and H₂S/SO₄ ratios are estimated to be higher than 2. Two exceptions exist in the Rhodopes. At Boukovo and Sarnitsa, where the estimated formation temperatures of alunite are the lowest, the external fluids are dominant and H₂S/SO₄ratios are estimated to be lower than or close to 1.At this stage of the work, the mineralogical and isotopic criteria do not enable a clear distinction between economic and uneconomic systems. However, some features are common in the economic ore deposits: the presence of zunyite in the deeper part of the system, the relatively high temperatures suggested by the zunyite + pyrophyllite + alunite + diaspore assemblages, the (O, H, S) signature of alunite, which is characteristic of dominant magmatic–hydrothermal acid–sulphate–fluorine systems.     

Are the South and North Liaohe Groups of North China Craton different exotic terranes? Nd isotope constraints

The Liaohe Group is an important Paleoproterozoic stratigraphic unit in the northeastern part of the North China Craton and is traditionally subdivided into the North and South Liaohe Groups. Associated with both the North and South Liaohe Groups are voluminous Paleoproterozoic granitoid rocks, named the Liaoji granitoids. Different tectonic models, including terrane amalgamation, continent–arc collision and rift closure, have been proposed to interpret the tectonic setting and evolution of the North and South Liaohe Groups and associated Liaoji granitoids. At the centre of the controversy between these models is whether or not the North and South Liaohe Groups developed on the same Archean basement. Nd isotopic geochemistry of the Liaoji granitoids provides important constraints on this controversial issue. The Liaoji granitoids associated with the North and South Liaohe Groups display similar ε_Nd values, restricted to a narrow range from 0 to 2, implying that these granitoid rocks were derived from the same or a similar magma source. Moreover, the Liaoji granitoids associated with the North and South Liaohe Groups have similar Nd model ages (T_DM), ranging from 2.4 to 2.6 Ga, suggesting that the protoliths of the Liaoji granitoids associated with both groups may have formed simultaneously, and that the basement rocks underneath the Liaoji granitoids and associated North and South Liaohe Groups belong to the same continental block rather than two different blocks. Combining lithological, structural and geochronological considerations, we interpret the North and South Liaohe Groups as having developed on a single late Archean basement that underwent Paleoproterozoic rifting associated with the intrusion of the Liaoji granitoids and the formation of the Liaohe Group, and closed upon itself in the Paleoproterozoic.     

Charnockite genesis across the Archaean–Proterozoic terrane boundary in the South Indian Granulite Terrain: Constraints from major–trace element geochemistry and Sr–Nd isotopic systematics

Major, trace element compositions and Sr–Nd isotopic characteristics of charnockitic gneisses from the Southern Granulite Terrain (SGT), South India are presented. The study region encompasses the central segment of the Cauvery Shear Zone system (CSZ) and regions within the Madurai Block (MB) immediately south of it (designated here as the CSZ/MB and MB domains). Differences in the compositions and source characteristics between charnockitic rocks of the CSZ vis-à-vis those of the CSZ/MB and MB regions are highlighted. Foremost, the charnockites and enderbites of the CSZ show highly fractionated REE patterns with positive Eu-anomalies, depleted HREE, Y and near chondritic εNd₀ and initial-⁸⁷Sr/⁸⁶Sr at ca. 2.5 Ga, consistent with hydrous partial melting of amphibolitic crust with residual garnet and hornblende for the parental melts. By contrast, modeled at ca. 1.8 Ga and 0.8 Ga, the CSZ/MB and MB charnockitic rocks, which show a wider range of Ti and P, relatively lower degree of HREE depletion, commonly negative Eu-anomalies and undepleted Y, present clear evidence for involvement of Archaean crustal components in sources of their magmatic protoliths. There is also evidence for significant intracrustal melting processes within a thickened crust at elevated temperatures between 800 and 1000 °C. Implications to the controversial Archaean–Neoproterozoic terrane boundary problem of the SGT are discussed.     

Lower Eocene carbonate-cemented “chimney” structures (Varna, Bulgaria) — Control of seepage rates on their formation and stable isotopic signature

The genesis of Lower Eocene calcite-cemented columns, “pisoid”-covered structures and horizontal interbeds, clustered in dispersed outcrops in the Pobiti Kamani area (Varna, Bulgaria) is related to fossil processes of hydrocarbon migration. Field observations, petrography and stable isotope geochemistry of the cemented structures and associated early-diagenetic veins, revealed that varying seepage rates of a single, warm hydrocarbon-bearing fluid, probably ascending along active faults, controlled the type of structure formed and its geochemical signature. Slow seepage allowed methane to oxidize within the sediment under ambient seafloor conditions (δ¹⁸O = − 1 ± 0.5‰ V-PDB), explaining columns' depleted δ¹³C ratios of − 43‰. Increasing seepage rates caused methane to emanate into the water column (δ¹³C = − 8‰) and raised precipitation temperatures (δ¹⁸O = − 8‰). Calcite-cemented conduits formed and upward migrating fluids also affected interbed cementation. Even higher-energy fluid flow and temperatures likely controlled the formation of “pisoids”, whereby sediment was whirled up and cemented.     

A pronounced dry event recorded around 4.2 ka in brine sediments from the northern Red Sea

Partly laminated sediments were sampled from the brine-filled, anoxic Shaban Deep basin in the northern Red Sea. At about 4200 cal yr BP more than two millennia of anoxic sedimentation is replaced by a sub-oxic facies strongly suggesting the episodic absence of the brine. At the same time stable oxygen isotopes from surface dwelling foraminifera show a sharp increase (within less than 100 yr) pointing to a strong positive salinity anomaly at the sea surface. This major evaporation event significantly enhanced the renewal of deep water and the subsequent ventilation of the small Shaban Deep basin. The timing and strength of the reconstructed environmental changes around 4200 cal yr BP suggest that this event is the regional expression of a major drought event, which is widely observed in the neighboring regions, and which strongly affected Middle East agricultural civilizations.     

Up-temperature flow of surface-derived fluids in the mid-crust: the role of pre-orogenic burial of hydrated fault rocks

The Walter‐Outalpa shear zone in the southern Curnamona Province of NE South Australia is an example of a shear zone that has undergone intensely focused fluid flow and alteration at mid‐crustal depths. Results from this study have demonstrated that the intense deformation and ductile shear zone reactivation, at amphibolite facies conditions of 534 ± 20 °C and 500 ± 82 MPa, that overprint the Proterozoic Willyama Supergroup occurred during the Delamerian Orogeny (c. 500 Ma) (EPMA monazite ages of 501 ± 16 and 491 ± 19 Ma). This is in contrast to the general belief that the majority of basement deformation and alteration in the southern Curnamona Province occurred during the waning stages of the Olarian Orogeny (c. 1610–1580 Ma). These shear zones contain hydrous mineral assemblages that cut wall rocks that have experienced amphibolite facies metamorphism during the Olarian Orogeny. The shear zone rock volumes have much lower δ¹⁸O values (as low as 1‰) than their unsheared counterparts (7–9‰), and calculated fluid δ¹⁸O values (5–8‰) consistent with a surface‐derived fluid source. Hydrous minerals show a decrease in δD_(H2O) from ?14 to ?22‰, for minerals outside the shear zones, to ?28 to ?40‰, for minerals within the shear zones consistent with a contribution from a meteoric source. It is unclear how near‐surface fluids initially under hydrostatic pressure penetrate into the middle crust where fluid pressures approach lithostatic, and where fluid flow is expected to be dominantly upward because of pressure gradients. We propose a mechanism whereby faulting during basin formation associated with the Adelaidean Rift Complex (c. 700 Ma) created broad hydrous zones containing mineral assemblages in equilibrium with surface waters. These panels of fault rock were subsequently buried to depths where the onset of metamorphism begins to dehydrate the fault rock volumes evolving a low δ¹⁸O fluid that is channelled through shear zones related to Delamerian Orogenic activity.     

GGR Critical Review of Analytical Developments in 2004–2005

In 2005 Geostandards and Geoanalytical Research embarked upon a new initiative for its readers. Key researchers in various fields of geoanalytical technique development and their application were identified and invited to provide reviews pertinent to their expertise. As noted in the first of these publications "…instead of revisiting the historical context or decades of development in each analytical technique, the goal here has been to capture a snapshot of "hot topics" across a range of fields as represented in the… literature" (Hergt et al . 2005). Rather than prepare an annual review, a decision was taken earlier this year to provide a biennial summary of progress and accomplishments, in this case for the years 2004–2005. The principal techniques employed in Earth and environmental sciences are covered here, and include laser ablation and multicollector ICP-MS, ICP-AES, thermal ionisation and secondary ion mass spectrometry, as well as neutron activation analysis, X-ray fluorescence and atomic absorption spectrometry. A comprehensive review of the development of reference materials, often essential to these techniques, is also provided. The contributions assembled serve both to keep readers informed of advances they may be unfamiliar with, but also as a means of showcasing examples of the breadth and depth of work being conducted in these fields.