Colloidal arsenic composition from abandoned gold mine tailing leachates in Nova Scotia,Canada

Asymmetric-Flow Field-Flow Fractionation (AsFlFFF) coupled to an inductively coupled plasma-mass spectrometer (ICP-MS) was used to determine whether colloidal As exists in mine tailings from abandoned Au mine sites in Nova Scotia. Using this technique, the chemical composition and the size of the colloidal material was determined. Tailings samples were collected from the sites and leachates were analyzed. The resulting fractograms showed the presence of colloidal As. Arsenic co-elutes with Fe and Al suggesting that the As is associated with colloids containing these elements. The colloidal material present in the samples has a calculated median size of 7 nm. The leachates were also analyzed for totalAs, Fe and Al using ICP-MS. The colloidal fraction was determined to account for approximately 20% of the total dissolved As present in these samples. Dissolved As concentrations at the selected mine sites are very high and the arbitrary cutoff for dissolved still incorporates colloidal material. Therefore. it is important to distinguish between truly dissolved and colloidal As as the speciation will affect the toxicity and mobility of As at these locations.     

Elemental and mineralogical changes in soils due to bioturbation along an earthworm invasion chronosequence in Northern Minnesota

Minnesota forested soils have evolved without the presence of earthworms since the last glacial retreat. When exotic earthworms arrive, enhanced soil bioturbation often results in dramatic morphological and chemical changes in soils with negative implications for the forests’ sustainability. However, the impacts of earthworm invasion on geochemical processes in soils are not well understood. This study attempts to quantify the role of earthworm invasion in mineral chemical weathering and nutrient dynamics along an earthworm invasion chronosequence in a sugar maple forest in Northern Minnesota. Depth and rates of soil mixing can be tracked with atmospherically derived short lived radioisotopes ²¹⁰Pb and ¹³⁷Cs. Their radioactivities increase in the lower A horizon at the expense of the peak activities near the soil surface, which indicate that soil mixing rate and its depth reach have been enhanced by earthworms. Enhanced soil mixing by earthworms is consistent with the ways that the vertical profiles of elemental and mineralogical compositions were affected by earthworm invasion. Biologically cycled Ca and P have peak concentrations near the soil surface prior to earthworm invasion. However, these peak abundances significantly declined in the earthworm invaded soils presumably due to enhanced soil mixing. It is clear that enhanced soil mixing due to earthworms also profoundly altered the vertical distribution of most mineral species within A horizons. Though the mechanisms are not clear yet, earthworm invasion appears to have contributed to net losses of clay mineral species and opal from the A horizons. As much as earthworms vertically relocated minerals and elements, they also intensify the contacts between organic matter and cations as shown in the increased amount of Ca and Fe in organically complexed and in exchangeable pools. With future studies on soil mixing rates and elemental leaching, this study will quantitatively and mechanically address the role of earthworms in geochemical evolution of soils and forests’ nutrient dynamics.     

Lattice distortion in a zircon population and its effects on trace element mobility and U–Th–Pb isotope systematics: examples from the Lewisian Gneiss Complex, northwest Scotland

Zircon is a key mineral in geochemical and geochronological studies in a range of geological settings as it is mechanically and chemically robust. However, distortion of its crystal lattice can facilitate enhanced diffusion of key elements such as U and Pb. Electron backscatter diffraction (EBSD) analysis of ninety-nine zircons from the Lewisian Gneiss Complex (LGC) of northwest Scotland has revealed five zircons with lattice distortion. The distortion can take the form of gradual bending of the lattice or division of the crystal into subgrains. Zircon lattices are distorted because of either post-crystallisation plastic distortion or growth defects. Three of the five distorted zircons, along with many of the undistorted zircons in the population, were analysed by ion microprobe to measure U and Pb isotopes, Ti and REEs. Comparison of Th/U ratio, ²⁰⁷Pb/²⁰⁶Pb age, REE profile and Ti concentration between zircons with and without lattice distortion suggests that the distortion is variably affecting the concentration of these trace elements and isotopes within single crystals, within samples and between localities. REE patterns vary heterogeneously, sometimes relatively depleted in heavy REEs or lacking a Eu anomaly. Ti-in-zircon thermometry records temperatures that were either low (~700 °C) or high (>900 °C) relative to undistorted zircons. One distorted zircon records apparent ²⁰⁷Pb/²⁰⁶Pb isotopic ages (?3.0 to +0.3 % discordance) in the range of ~2,420–2,450 Ma but this does not correlate with any previously dated tectonothermal event in the LGC. Two other distorted zircons give discordant ages of 2,331 ± 22 and 2,266 ± 40 Ma, defining a discordia lower intercept within error of a late amphibolite-facies tectonothermal event. This illustrates that Pb may be mobilised in distorted zircons at lower metamorphic grade than in undistorted zircons. These differences in trace element abundances and isotope systematics in distorted zircons relative to undistorted zircons are generally interpreted to have been facilitated by subgrain walls. Trace elements and isotopes would have moved from undistorted lattice into these subgrain walls as their chemical potential is modified due to the presence of the dislocations which make up the subgrain wall. Subgrain walls provided pathways for chemical exchange between crystal and surroundings. Only five per cent of zircons in this population have lattice distortion suggesting it will not have a major impact on zircon geochronology studies, particularly as three of the five distorted zircons are from strongly deformed rocks not normally sampled in such studies. However, this does suggest there may be a case for EBSD analysis of zircons prior to geochemical analysis when zircons from highly deformed rocks are to be investigated.     

Geochemistry and geochronology of meta-igneous rocks from the Tokat Massif, north-central Turkey: implications for Tethyan reconstructions

Located in the eastern Pontides of the Sakarya Zone in north-central Turkey, the Tokat Massif records the closure of both the Paleo-Tethyan (Karakaya Complex) and Neo-Tethyan ocean basins. Meta-igneous samples collected from the region were studied to determine their sources and ages. We find significant geochemical differences between metagabbros of the Karakaya and Neo-Tethyan units in terms of their trace elements: Neo-Tethyan rocks are consistent with generation in an island arc setting, whereas Karakaya assemblages were likely generated in an oceanic spreading-center environment. Karakaya metagabbros also contain glaucophane, consistent with subduction subsequent to formation. Small (2–50 μm) zircon and baddeleyite grains from four Karakaya metagabbros were dated in thin section using an ion microprobe. The results demonstrate the reliability of the method to directly constrain the tectonomagmatic history of these types of assemblages. The rocks yield Late Permian/Early Triassic ²³⁸U/²⁰⁶Pb crystallization ages of 258 ± 14 Ma (±1σ, zircon) and 254 ± 8 Ma (±1σ, baddeleyite) and an Early Cretaceous minimum metamorphic age of 137 ± 8 Ma (±1σ, zircon). Some zircon grains and baddeleyite grains with zircon overgrowths yield Early to Middle Jurassic ages. Here we present a model in which metamorphism and deformation in this region occurred during northward subduction and closure of a Paleo-Tethyan ocean basin and accretion of the Karakaya units to the Laurasian continental margin. This was followed by the onset of closure of the Neo-Tethys during the Campanian-Paleocene and accretion of island arc units to the Tokat region.     

Uranium and Thorium Concentration and Isotopic Composition in Five Glass (BHVO‐2G,BCR‐2G,NKT‐1G,T1‐G,ATHO‐G) and Two Powder (BHVO‐2, BCR‐2) Reference Materials

Here we report uranium and thorium isotopic ratios and elemental concentrations measured in solid reference materials from the USGS (BHVO‐2G, BCR‐2G, NKT‐1G), as well as those from the MPI‐DING series (T1‐G, ATHO‐G). Specifically created for microanalysis, these naturally‐sourced glasses were fused from rock powders. They cover a range of compositions, elemental concentrations and expected isotopic ratios. The U‐Th isotopic ratios of two powdered source materials (BCR‐2, BHVO‐2) were also characterised. These new measurements via multi‐collector thermal ionisation mass spectrometry and multi‐collector inductively coupled plasma‐mass spectrometry can now be used to assess the relative performance of techniques and facilitate comparison of U‐Th data amongst laboratories in the geoscience community for in situ and bulk analyses.     

GGR Biennial Critical Review: Analytical Developments Since 2014

This GGR biennial critical review covers developments and innovations in key analytical methods published since January 2014, relevant to the chemical, isotopic and crystallographic characterisation of geological and environmental materials. In nine selected analytical fields, publications considered to be of wide significance are summarised, background information is provided and their importance evaluated. In addition to instrumental technologies, this review also presents a summary of new developments in the preparation and characterisation of rock, microanalytical and isotopic reference materials, including a précis of recent changes and revisions to ISO guidelines for reference material characterisation and reporting. Selected reports are provided of isotope ratio determinations by both solution nebulisation MC‐ICP‐MS and laser ablation‐ICP‐MS, as well as of radioactive isotope geochronology by LA‐ICP‐MS. Most of the analytical techniques elaborated continue to provide new applications for geochemical analysis; however, it is noted that instrumental neutron activation analysis has become less popular in recent years, mostly due to the reduced availability of nuclear reactors to act as a neutron source. Many of the newer applications reported here provide analysis at increasingly finer resolution. Examples include atom probe tomography, a very sensitive method providing atomic scale information, nanoscale SIMS, for isotopic imaging of geological and biological samples, and micro‐XRF, which has a spatial resolution many orders of magnitude smaller than conventional XRF.     

GGR Critical Review of Analytical Developments in 2003

The articles that comprise this critical review serve to draw attention to research papers published in specific fields of interest during 2003, provide critical comment on the relevance and importance of individual publications in these fields, and offer an overview of the comparative importance of advances in particular areas. In this way, these articles aim to assist experts in the field by keeping them informed of relevant recent publications, as well as providing an important resource for students or early career researchers who are embarking on studies in an area new to them. This year, five papers provide summaries of developments in bulk sample determinations employing (1) ICP-AES and ICP-MS (trace elements), (2) XRF and atomic absorption spectrometry and INAA, (3) isotope ratio measurements (TIMS, MC-ICP-MS, ICP-MS, ToF), as well as in situ measurements conducted using (4) secondary ion mass spectrometry and (5) laser ablation ICP-MS (trace element and isotope ratio determinations).     

Reaction pathways for quartz dissolution determined by statistical and graphical analysis of macroscopic experimental data

In light of recent work on the reactivity of specific sites on large (hydr)oxo-molecules and the evolution of surface topography during dissolution, we examined the ability to extract molecular-scale reaction pathways from macroscopic dissolution and surface charge measurements of powdered minerals using an approach that involved regression of multiple datasets and statistical graphical analysis of model fits. The test case (far-from-equilibrium quartz dissolution from 25 to 300 °C, pH 1-12, in solutions with [Na⁺] ? 0.5 M) avoids the objections to this goal raised in these recent studies. The strategy was used to assess several mechanistic rate laws, and was more powerful in distinguishing between models than the statistical approaches employed previously. The best-fit model included three mechanisms—two involving hydrolysis of Si centers by H₂O next to neutral (>Si-OH⁰) and deprotonated (>Si-O⁻) silanol groups, and one involving hydrolysis of Si centers by OH⁻. The model rate law is

     

Subglacial comminution in the deforming bed: Inferences from SEM analysis

This study investigates the variations in erosional processes beneath Briksdalsbreen; a Norwegian valley glacier, with a thin coarse grained deforming bed. The subglacial zone was investigated in situ, close to the central glacial flow line (Site A) and close to the valley wall (Site B), via boreholes. The till was collected using two different sediment samplers and the bed was examined using a borehole video camera. In order to evaluate how representative borehole sampling was of the subglacial environment, the results from in situ subglacial samples were compared with random samples taken from an exposed subglacial surface in the glacier foreland, as well as a sample taken from the site after glacier retreat. The results indicated that the texture of the exposed subglacial surface was similar to in situ samples from subglacial Site B (close to the valley wall), and that the samples collected with the ‘small’ sediment sampler had the closest fit. SEM analysis revealed eroded quartz grains at both sites as a result of rotation (abrasion) and fracture. The samples from close to the valley wall were very poorly sorted, with evidence for rounding and preservation of pre-weathered surfaces, which suggest that a relatively simple pattern of erosion from crushing to rotation dominated. However, the till from the centre of the glacier was better sorted, more angular, and with few pre-weathered surfaces. We suggest that this results from a more complex glacial erosional history associated with greater strain and longer residence time within the deforming layer. When compared with other deformation tills, it was confirmed that there is a relationship between grain size and erosional style. Clay-rich tills show little comminution, fine sand-rich tills generate a significant silt component, whilst the coarse sand-rich tills at Briksdalsbreen showed complex deformational styles but no significant silt component.