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.     

Determination of Halogens (F, Cl, Br, I), Sulfur and Water in Seventeen Geological Reference Materials

Fluorine, chlorine, bromine, iodine and sulfur were determined in seventeen geological reference materials after extraction by pyrohydrolysis. Fluorine, Cl and S (as sulfate ions) were determined in the extraction solution by ion chromatography with detection limits of around 0.2 mg l⁻¹. Bromine and I were measured by ICP-MS with detection limits of 1 μg l⁻¹ for Br and 0.1 μg l⁻¹ for I. For rock samples, using normal extraction conditions (500 mg of sample and 100 ml of final solution) detection limits were 40 mg kg⁻¹ for F and Cl, 15 mg kg⁻¹ for S, 0.2 mg kg⁻¹ for Br and 0.02 mg kg⁻¹ for I. These detection limits may be improved by increasing the amount of sample and hence the concentration of the final solution. Water was also determined using an extraction technique based on H₂O degassing, reduction on zinc at 1000 °C and H₂ manometry. Our results for fluorine, chlorine, sulfur and water are in good agreement with literature data. Very few reference materials have recommended values for bromine and especially for iodine. Among the analysed samples, three are new reference materials: BHVO-2, BCR-2 and AGV-2.     

The role of temperature on treeline migration for an eastern African mountain during the Last Glacial Maximum

Paleo-data suggest that East African mountain treelines underwent an altitudinal shift during the Last Glacial Maximum (LGM). Understanding the ecological and physiological processes underlying treeline response to such past climate change will help to improve forecasts of treeline change under future global warming. In spite of significant improvements in paleoclimatic reconstruction, the climatic conditions explaining this migration are still debated and important factors such as atmospheric CO₂ concentration, the impact of lapse rate decreasing temperature along altitudinal gradients and rainfall modifications due to elevation have often been neglected or simplified. Here, we assess the effects of these different factors and estimate the influence of the most dominant factors controlling changes in past treeline position using a multi-proxy approach based on simulations from BIOME4, a coupled biogeography and biogeochemistry model, modified to account for the effect of elevation on vegetation, compared with pollen, and isotopic data. The results indicate a shift in mountain vegetation at the LGM was controlled by low pCO₂ and low temperatures promoting species morphologically and physiologically better adapted to LGM conditions than many trees composing the forest belt limit. Our estimate that the LGM climate was cooler than today’s by ?4.5 °C (range: ?4.3 to ?4.6 °C) at the upper limit of the treeline, whereas at 831 m it was cooler by ?1.4 °C (range: ?2.6 to ?0.6 °C), suggests that a possible lapse rate modification strongly constrained the upper limit of treeline, which may limit its potential extension under future global warming.     

Trends in the frequency of synoptic types in central-southern Chile in the period 1961–2012 using the Jenkinson and Collison synoptic classification

Atmospheric circulation patterns in southern Chile (42° 30′ S) were studied in order to determine and analyse the most characteristic synoptic types and their recent trends, as well as to gain an understanding of how they are associated with low-frequency variability patterns. According to the Jenkinson and Collison (J&C) classification method, a 16-point grid of sea-level pressure data was employed. The findings reveal that some synoptic types show statistically significant trends with a 95% confidence level, positively for anticyclonic westerly hybrids (AW) and advective types for third and fourth quadrant wind flows (W, NW, and N) and negatively for SW and cyclonic hybrids (CS and CSW). A model has been constructed of the linear regression of some weather types with teleconnections that most affect Chile: the undetermined types (U), AW were associated with El Niño or the warm phase of the Pacific Decadal Oscillation (PDO), whereas the cyclonic northerly and cyclonic northeasterly types (CN and CNE) were associated with La Niña or cool phase of the PDO. The weather types associated with Antarctic Oscillation (AAO) in its positive phase are anticyclonic northerly and northeasterly and northerly advection types, while in its negative phase are cyclonic southwesterly and advection types.     

The Removal of Dissolved Metals by Hydroxysulphate Precipitates during Oxidation and Neutralization of Acid Mine Waters, Iberian Pyrite Belt

This study examines the removal of dissolved metals during the oxidation and neutralization of five acid mine drainage (AMD) waters from La Zarza, Lomero, Esperanza, Corta Atalaya and Poderosa mines (Iberian Pyrite Belt, Huelva, Spain). These waters were selected to cover the spectrum of pH (2.2–3.5) and chemical composition (e.g., 319–2,103 mg/L Fe; 2.85–33.3 g/L SO₄⁼) of the IPB mine waters. The experiments were conducted in the laboratory to simulate the geochemical evolution previously recognized in the field. This evolution includes two stages: (1) oxidation of dissolved Fe(II) followed by hydrolysis and precipitation of Fe(III), and (2) progressive pH increase during mixing with fresh waters. Fe(III) precipitates at pH < 3.5 (stages 1 and 2) in the form of schwertmannite, whereas Al precipitates during stage 2 at pH 5.0 in the form of several hydroxysulphates of variable composition (hydrobasaluminite, basaluminite, aluminite). During these stages, trace elements are totally or partially sorbed and/or coprecipitated at different rates depending basically on pH, as well as on the activity of the SO₄⁼ anion (which determines the speciation of metals). The general trend for the metals which are chiefly present as aqueous free cations (Pb²⁺, Zn²⁺, Cu²⁺, Cd²⁺, Mn²⁺, Co²⁺, Ni²⁺) is a progressive sorption at increasing pH. On the other hand, As and V (mainly present as anionic species) are completely scavenged during the oxidation stage at pH < 3.5. In waters with high activities (> 10⁻¹) of the SO ₄⁼ ion, some elements like Al, Zn, Cd, Pb and U can also form anionic bisulphate complexes and be significantly sorbed at pH < 5. The removal rates at pH 7.0 range from around 100% for As, V, Cu and U, and 60–80% for Pb, to less than 20% for Zn, Co, Ni and Mn. These processes of metal removal represent a significant mechanism of natural attenuation in the IPB.     

Regional retrograde alteration of sub-greenschist facies chlorite to smectite

Dioctahedral smectite is present as a retrograde alteration product of chlorite in Permian-Triassic red slates of the Malaguide Complex in Sierra de Espuña (Betic Cordillera). Mineral assemblages and textures, illite crystallinity indices, and fluid inclusion data indicate sub-greenschist facies conditions that reached at least 180°C in the higher-grade tectonic unit of the Malaguide Complex, preceding formation of smectite. Smectite, having K as the dominant interlayer cation, occurs ubiquitously intercalated with trioctahedral chlorite as thin packets of layers and as individual layers that commonly change to chlorite along layers. Although some chlorite is typically homogeneous and trioctahedral, much chlorite shows signs of alteration and has compositions corresponding to different degrees of smectite contaimination. The incompatibility of metamorphic grade with the occurrence of smectite, the general association of chlorite and smectite, and the textural relations collectively show that dioctahedral smectite is derived through replacement of trioctahedral chlorite. Such replacement occurs on a regional basis and demonstrates that caution must be used in interpreting the occurrence of smectite in pelites as being due to prograde processes. Alteration of trioctahedral chlorite under oxidizing conditions due to introduction of phreatic water after uplift of the Betic Cordillera is proposed as the cause of formation of smectite.     

The Catoca kimberlite pipe, Republic of Angola: A paleovolcanological model

The Catoca kimberlite pipe is among the world’s largest primary diamond deposits. The Catoca volcanic edifice is only slightly eroded. Kimberlitic rocks of various facies compose a crater of about 1 km in diameter and a diatreme. The structure of the pipe and mining conditions of the deposit are complicated by intense intrapipe tectonic processes related to large-amplitude subsidence. Based on geological data, we propose a structural model of the deposit and a paleovolcanological model of the Catoca pipe formed during a full cycle beginning with a stage of active volcanism and completed by stages of gradually waning volcanic activity and sedimentation. It is suggested that the banded tuffisitic kimberlite of the crater zone was deposited at the stage of active volcanic eruption from specific pyroclastic suspension as a low-viscosity mixture of crystals and aqueous sol rich in serpentine.     

Hydrogeology and sustainable future groundwater abstraction from the Agua Verde aquifer in the Atacama Desert,northern Chile

The hyper-arid conditions prevailing in Agua Verde aquifer in northern Chile make this system the most important water source for nearby towns and mining industries. Due to the growing demand for water in this region, recharge is investigated along with the impact of intense pumping activity in this aquifer. A conceptual model of the hydrogeological system is developed and implemented into a two-dimensional groundwater-flow numerical model. To assess the impact of climate change and groundwater extraction, several scenarios are simulated considering variations in both aquifer recharge and withdrawals. The estimated average groundwater lateral recharge from Precordillera (pre-mountain range) is about 4,482 m³/day. The scenarios that consider an increase of water withdrawal show a non-sustainable groundwater consumption leading to an over-exploitation of the resource, because the outflows surpasses inflows, causing storage depletion. The greater the depletion, the larger the impact of recharge reduction caused by the considered future climate change. This result indicates that the combined effects of such factors may have a severe impact on groundwater availability as found in other groundwater-dependent regions located in arid environments. Furthermore, the scenarios that consider a reduction of the extraction flow rate show that it may be possible to partially alleviate the damage already caused to the aquifer by the continuous extractions since 1974, and it can partially counteract climate change impacts on future groundwater availability caused by a decrease in precipitation (and so in recharge), if the desalination plant in Taltal increases its capacity.     

Flow dynamics at the origin of thin clayey sand lacustrine turbidites: Examples from Lake Hazar,Turkey

Turbidity currents and their deposits can be investigated using several methods, i.e. direct monitoring, physical and numerical modelling, sediment cores and outcrops. The present study focused on thin clayey sand turbidites found in Lake Hazar (Turkey) occurring in eleven clusters of closely spaced thin beds. Depositional processes and sources for three of those eleven clusters are studied at three coring sites. Bathymetrical data and seismic reflection profiles are used to understand the specific geomorphology of each site. X‐ray, thin sections and CT scan imagery combined with grain‐size, geochemical and mineralogical measurements on the cores allow characterization of the turbidites. Turbidites included in each cluster were produced by remobilization of surficial slope sediment, a process identified in very few studies worldwide. Three types of turbidites are distinguished and compared with deposits obtained in flume studies published in the literature. Type 1 is made of an ungraded clayey silt layer issued from a cohesive flow. Type 2 is composed of a partially graded clayey sand layer overlain by a mud cap, attributed to a transitional flow. Type 3 corresponds to a graded clayey sand layer overlain by a mud cap issued from a turbulence‐dominated flow. While the published experimental studies show that turbulence is damped by cohesion for low clay content, type 3 deposits of this study show evidence for a turbulence‐dominated mechanism despite their high clay content. This divergence may in part relate to input variables, such as water chemistry and clay mineralogy, that are not routinely considered in experimental studies. Furthermore, the large sedimentological variety observed in the turbidites from one coring site to another is related to the evolution of a sediment flow within a field‐scale basin made of a complex physiography that cannot be tackled by flume experiments.     

Mean flow-transient perturbation interaction in the Southern Hemisphere: a simulation using a variable-resolution GCM

The ability of an atmospheric general circulation model to reproduce fundamental features of the wintertime extratropical Southern Hemisphere (SH) circulation is evaluated with emphasis on the daily variability of the SH mean flow and the mean flow-transient perturbations interaction. Two 10-year simulations using a new version of the LMDZ GCM with a stretched grid scheme centered at 45 °S and forced by climatological SST are performed: a high (144Ꮡ) and low (64Ꭹ) horizontal resolution runs. The performance of both simulations was determined by comparing several simulated fields (zonal wind, temperature, kinetic energy, transient eddy momentum and heat fluxes, Eliassen-Palm fluxes, Eady growth rate and baroclinic conversion term) against the European Centre for Medium Range Weather Forecast reanalyses (ERA). High and low-resolution simulations are similar in many respects; in particular, both experiments reproduce the main patterns of the southern extratropical large-scale circulation satisfactorily. Increasing resolution does not improve universally some spurious aspects of the low resolution simulation (e.g. the cold bias in the high polar troposphere, the debilitated subtropical jet, the low baroclinic conversion rate). Those aspects present little sensitivity to the model resolution. The interaction between transient eddies and zonal mean flow are examined. The low-resolution experiment is able to qualitatively represent the acceleration/deceleration of the mean flow by transient perturbations, south/north of 30 °S with an accuracy similar to that of the high-resolution experiment. Although both experiments represent the baroclinic structure of the mean flow satisfactorily, the model underestimates some transient properties due to the underestimation of the baroclinic conversion term in middle latitudes. Such misrepresentation does not improve with increasing resolution and is related to the relatively weak meridional temperature gradient and the inadequate geographical distribution of the eddy heat fluxes. In particular, the eddy kinetic energy is always underestimated. Eddy kinetic energy does not improve convincingly with increasing resolution, suggesting that the adequate representation of the storm tracks is highly influenced by the physical parametrizations.