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.     

Picophytoplankton and bacterioplankton in the Mississippi River plume and its adjacent waters

Picoplankton abundance and distribution in the Mississippi River plume and its adjacent waters were studied during two cruises in April (high discharge) and October (low discharge) 2000 using flow cytometry. Concentrations of photosynthetic picoplankton,Synechococcus and picoeukaryotes were low in the turbid plume water but high in the coastal waters—i.e., the green waters resulting from mixing of river and oceanic waters. In this region, three types ofSynechococcus, characterized by their phycoerythrin chromophore composition, were found:Synechococcus cells with a low phycourobilin to phycoerythrobilin ratio (PUB:PEB) occurred throughout the region and dominated the totalSymechococcus abundance during both seasons; high PUB:PEB cells, which are the dominant strains in the open or blue ocean, occurred only at the outer shelf stations; and PEB-onlySynechococcus were abundant in most of the surveyed area during april, but were not observed during October.Prochlorococcus cyanobacteria only occurred at the oceanic stations, but extended farther inshore in October compared to April. This was a consequence of the reduced discharge and plume size during October. Picophytoplankton were a less important component of total phytoplankton biomass in the turbid river water and more important in the oligotrophic Gulf water. Seasonally, the contribution of picophytoplankton to total phytoplankton biomass in the surveyed area was higher during low discharge in October than during high discharge in April, even though the spring 2000 river discharge was unusually low and might not present a typical high discharge scenario. The abundance of heterotrophic bacteria was weakly correlated to chlorophylla (chla) concentration, but better correlated to picophytoplankton biomass. A higher proportion of High DNA bacteria occurred in the river-impacted regions during both seasons, with the ratio of High DNA bacteria to Low DNA bacteria significantly higher in April.     

准噶尔盆地玛湖凹陷西斜坡三叠系百口泉组扇三角洲优质储集层预测

针对准噶尔盆地玛湖凹陷西斜坡风南地区三叠系百口泉组扇三角洲砂岩物性空间变化大、优质储集层(孔隙度大于7.4%,渗透率大于0.05×10^-3μm²)预测难的问题,在沉积岩石学、地震沉积学以及地震反演和解释理论指导下,综合利用测井、岩心和三维地震等资料开展了高精度层序地层划分、沉积微相描述和优质储集层地震反演研究。建立了风南井区四级层序地层格架,明确了扇三角洲多期水进水退的充填过程,指出SSQ3和SSQ5是优质储集层的发育层系;识别出扇三角洲平原分流河道、河道间和扇三角洲前缘水下分流水道、河口坝、席状砂等沉积微相,指出扇三角洲平原是优质储集层发育相带;通过应用高分辨层序地层纵向边界和沉积相横向边界约束,进行分层相控叠后地震波阻抗反演,提升储集层预测精度,在SSQ3和SSQ5预测5个优质储集层发育区,提出3口井的井位建议,钻探均获工业油流。     

藏南沉错湖泊沉积多指标揭示的2万年以来环境变化

通过对藏南沉错湖芯TC1孔的研究,分析了TC1孔的粒度、TOC、TN、C/N、Fe/Mn、Sr/Ba以及环境磁学参数等环境代用指标,基本上获得了这一地区2万年以来的环境变化记录。结果显示约19 800~18 000 Cal aBP的温度下降在各指标中具有明显的反映;约16 000 Cal aBP左右,温度在一次跃动上升之后,随即出现急剧下降;约15 200~12 000 Cal aBP,是降温之后的缓慢回升过程;约12 000~9 500 Cal aBP,各种指标均显示湖区环境处于不适宜阶段,特别是11 600~10 400 Cal aBP,湖区环境显著恶化。进入全新世后,湖区环境经历了3次明显的暖期(约9 500~7 600 Cal aBP、约6 800~5 800 Cal aBP、约4 800~3 800 Cal aBP) 和2次冷期(约7 600~6 800 Cal aBP、约5 800~4 800 Cal aBP),呈现出暖干/冷湿的交替规律,具有南亚季风(西南季风) 区气候变化的特征。沉错湖区2万年来的气候环境变化序列中的某些特征时段与格陵兰冰芯记录和青藏高原其他记录相比具有较好的一致性,反映了湖区及藏南地区的气候环境演变特征具有全球性特征。     

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.     

Climate Change Impacts for the Conterminous USA: An Integrated Assessment

Here we simulate dryland agriculture in the United States in order to assess potential future agricultural production under a set of general circulation model (GCM)-based climate change scenarios. The total national production of three major grain crops—corn, soybeans, and winter wheat—and two forage crops—alfalfa and clover hay—is calculated for the actual present day core production area (CPA) of each of these crops. In general, higher global mean temperature (GMT) reduces production and higher atmospheric carbon dioxide concentration ([CO₂]) increases production. Depending on the climatic change scenarios employed overall national production of the crops studied changes by up to plus or minus 25% from present-day levels. Impacts are more significant regionally, with crop production varying by greater than ±50% from baseline levels. Analysis of currently possible production areas (CPPAs) for each crop indicates that the regions most likely to be affected by climate change are those on the margins of the areas in which they are currently grown. Crop yield variability was found to be primarily influenced by local weather and geographic features rather than by large-scale changes in climate patterns and atmospheric composition. Future US agronomic potential will be significantly affected by the changes in climate projected here. The nature of the crop response will depend primarily on to what extent precipitation patterns change and also on the degree of warming experienced.     

The effect of chemical composition and oxygen fugacity on the electrical conductivity of dry and hydrous garnet at high temperatures and pressures

The in situ electrical conductivity of hydrous garnet samples (Py₂₀Alm₇₆Grs₄–Py₇₃Alm₁₄Grs₁₃) was determined at pressures of 1.0–4.0 GPa and temperatures of 873–1273 K in the YJ-3000t apparatus using a Solartron-1260 impedance/gain-phase analyzer for various chemical compositions and oxygen fugacities. The oxygen fugacity was controlled by five solid-state oxygen buffers (Fe₂O₃ + Fe₃O₄, Ni + NiO, Fe + Fe₃O₄, Fe + FeO, and Mo + MoO₂). Experimental results indicate that within a frequency range from 10⁻² to 10⁶ Hz, electrical conductivity is strongly dependent on signal frequency. Electrical conductivity shows an Arrhenius increase with temperature. At 2.0 GPa, the electrical conductivity of anhydrous garnet single crystals with various chemical compositions (Py₂₀Alm₇₆Grs₄, Py₃₀Alm₆₇Grs₃, Py₅₆Alm₄₃Grs₁, and Py₇₃Alm₁₄Grs₁₃) decreases with increasing pyrope component (Py). With increasing oxygen fugacity, the electrical conductivity of dry Py₇₃Alm₁₄Grs₁₃ garnet single crystal shows an increase, whereas that of a hydrous sample with 465 ppm water shows a decrease, both following a power law (exponents of 0.061 and −0.071, respectively). With increasing pressure, the electrical conductivity of this hydrous garnet increases, along with the pre-exponential factors, and the activation energy and activation volume of hydrous samples are 0.7731 ± 0.0041 eV and −1.4 ± 0.15 cm³/mol, respectively. The results show that small hopping polarons ( \textFe_\textMg ^· ) \left( {{\text{Fe}}_{\text{Mg}}^{ \cdot } } \right) and protons ( \textH ^· {\text{H}}^{ \cdot } ) are the dominant conduction mechanisms for dry and wet garnet single crystals, respectively. Based on these results and the effective medium theory, we established the electrical conductivity of an eclogite model with different mineral contents at high temperatures and high pressures, thereby providing constraints on the inversion of field magnetotelluric sounding results in future studies.     

Release of heavy metals during weathering of the Lower Cambrian Black Shales in western Hunan,China

Weathering of heavy metal enriched black shales may be one of the most important sources of environmental contamination in areas where black shales are distributed. Heavy metal release during weathering of the Lower Cambrian Black Shales (LCBS) in western Hunan, China, was investigated using traditional geochemical methods and the ICP-MS analytical technique. Concentrations of 16 heavy metals, 8 trace elements and P were measured for samples from selected weathering profiles at the Taiping vanadium ore mine (TP), the Matian phosphorous ore mine (MT), and Taojiang stone-coal mine (TJ). The results show that the bedrock at these three profiles is enriched with Sc, V, Cr, Co, Ni, Cu, Zn, Pb, Th, U, Mo, Cd, Sb, Tl, and P. Based on mass-balance calculation, the percentages of heavy metals released (in % loss) relative to immobile element Nb were estimated. The results show significant rates of release during weathering of: V, Cr, Co, Ni, Cu, Zn, U, Mo, Cd, Sn, Sb, and Tl for the TP profile; Sc, Cr, Mn, Co, Ni, Cu, Zn, Pb, Th, Cd, and Sn for the MT profile; and Sc, Mn, Co, Ni, Zn, Th, Cd, Sn, and Tl for the TJ profile. Among these heavy metals, Co, Ni, Zn, Cd, and Sn show very similar features of release from each of the three weathering profiles. The heavy metals released during weathering may affect the environment (especially topsoil and surface waters) and are possibly related to an observed high incidence of endemic diseases in the area.     

Micro- and nano-textural evidence of Ti(–Ca–Fe) mobility during fluid–rock interactions in carbonaceous lawsonite-bearing rocks from New Zealand

Understanding the mobility of chemical elements during fluid–rock interactions is critical to assess the geochemical evolution of a rock undergoing burial and metamorphism and, more generally, to constrain the geochemical budget of the subduction factory. In particular, determining the behavior and mobility of Ti in aqueous fluids constitutes a great challenge that is still under scrutiny. Here, we study plant fossils preserved in blueschist metasedimentary rocks from the Marybank Formation (New Zealand). Using scanning and transmission electron microscopies (SEM and TEM), we show that the carbonaceous material (CM) composing the fossils contains abundant nano-inclusions of Ti- and Fe-oxides. These nanocrystals are mainly anatase, rutile, and Fe–Ti oxides. The mineral composition observed within the fossils is significantly different from that detected in the surrounding rock matrix. We propose that Ti and Fe might have been mobilized by the alteration of a detrital Ti–Fe-rich protolith during an early diagenetic event under acidic and reducing conditions. Aqueous fluids rich in organic ligands released by the degradation of organic matter may have been involved. Moreover, using mass balance and petrological observations, we show that the contrasted mineralogy between the rock matrix and the fossil CM might be the consequence of the chemical isolation of fossil CM during the prograde path of the rock. Such an isolation results from the early formation of quartz and Fe-rich phyllosilicate layers enclosing the fossil as characterized by SEM and TEM investigations. Overall, this study shows that investigating minerals associated with CM down to the nanometer scale in metamorphic rocks can provide a precious record of early prograde geochemical conditions.     

<Superscript>10</Superscript>Be, <Superscript>18</Superscript>O and radiogenic isotopic constraints on the origin of adakitic signatures: a case study from Solander and Little Solander Islands,New Zealand

Subduction-related Quaternary volcanic rocks from Solander and Little Solander Islands, south of mainland New Zealand, are porphyritic trachyandesites and andesites (58.20–62.19 wt% SiO₂) with phenocrysts of amphibole, plagioclase and biotite. The Solander and Little Solander rocks are incompatible element enriched (e.g. Sr ~931–2,270 ppm, Ba ~619–798 ppm, Th ~8.7–21.4 ppm and La ~24.3–97.2 ppm) with MORB-like Sr and Nd isotopic signatures. Isotopically similar quench-textured enclaves reflect mixing with intermediate (basaltic-andesite) magmas. The Solander rocks have geochemical affinities with adakites (e.g. high Sr/Y and low Y), whose origin is often attributed to partial melting of subducted oceanic crust. Solander sits on isotopically distinct continental crust, thus excluding partial melting of the lower crust in the genesis of the magmas. Furthermore, the incompatible element enrichments of the Solander rocks are inconsistent with partial melting of newly underplated mafic lower crust; reproduction of their major element compositions would require unrealistically high degrees of partial melting. A similar argument precludes partial melting of the subducting oceanic crust and the inability to match the observed trace element patterns in the presence of residual garnet or plagioclase. Alternatively, an enriched end member of depleted MORB mantle source is inferred from Sr, Nd and Pb isotopic compositions, trace element enrichments and εHf ? 0 CHUR in detrital zircons, sourced from the volcanics. ¹⁰Be and Sr, Nd and Pb isotopic systematics are inconsistent with significant sediment involvement in the source region. The trace element enrichments and MORB-like Sr and Nd isotopic characteristics of the Solander rocks require a strong fractionation mechanism to impart the high incompatible element concentrations and subduction-related (e.g. high LILE/HFSE) geochemical signatures of the Solander magmas. Trace element modelling shows that this can be achieved by very low degrees of melting of a peridotitic source enriched by the addition of a slab-derived melt. Subsequent open-system fractionation, involving a key role for mafic magma recharge, resulted in the evolved andesitic adakites.