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.     

Performance of Full‐Scale Enhanced Reductive Dechlorination in Clay Till

At a low permeability clay till site contaminated with chlorinated ethenes (Gl. Kongevej, Denmark), enhanced reductive dechlorination (ERD) was applied by direct push injection of molasses and dechlorinating bacteria. The performance was investigated by long‐term groundwater monitoring, and after 4 years of remediation, the development of degradation in the clay till matrix was investigated by high‐resolution subsampling of intact cores. The formation of degradation products, the presence of specific degraders Dehalococcoides spp. with the vinyl chloride (VC) reductase gene vcrA, and the isotope fractionation of trichloroethene, cis‐dichloroethene (cis‐DCE), and VC showed that degradation of chlorinated ethenes occurred in the clay till matrix as well as in sand lenses, sand stringers, and fractures. Bioactive sections of up to 1.8 m had developed in the clay till matrix, but sections, where degradation was restricted to narrow zones around sand lenses and stringers, were also observed. After 4 years of remediation, an average mass reduction of 24% was estimated. Comparison of the results with model simulation scenarios indicate that a mass reduction of 85% can be obtained within approximately 50 years without further increase in the narrow reaction zones if no donor limitations occur at the site. Long‐term monitoring of the concentration of chlorinated ethenes in the underlying chalk aquifer revealed that the aquifer was affected by the more mobile degradation products cis‐DCE and VC generated during the remediation by ERD.     

Intra-oceanic settings of the western Mexico Late Jurassic-Early Cretaceous arc sequences. Implications for the Pacific-Tethys geodynamic relationships during the Cretaceous

Abstract

The Guerrero suspect terrane composed of Late Jurassic-Early Cretaceous sequences, extends from Baja California up to Acapulco and is considered to be coeval with the Late Mesozoic igneous and sedimentary arc sequences of the Greater Antilles, Venezuela and Western Cordillera of Colombia. New geological, petrological and geochemical data from central and southern Mexico, led us to propose a new model for the building of the Alisitos-Teloloapan arc. This arc, partly built on the Pacific oceanic lithosphere and partly on continental fragments, could be related to the subduction of an oceanic basin - the Arperos basin - under the Paleo-Pacific plate. This subduction was dipping southwest.

At the beginning of the magmatic activity of the oceanic segment of this arc, depleted tholeiitic basalts were emitted in a submarine environnement below the CCD. While subduction was going on, the arc magmas evolved from LREE depleted tholeiites to slightly LREE enriched tholeiites and then, to calc-alkaline basalts and andesites enriched in LREE and HFSE. Concurrently, the arc sedimentary environment changed from deep oceanic to neritic with the deposition of Aptian-Albian reefal limestones, at the end of the arc building. In the continent-based segment, the arc magmas are exclusively differentiated calc-alkaline suites depleted in HREE and Y, formed of predominantly siliceous lavas and pyroclastic rocks, emitted in a sub-aerial or shallow marine environment.

Thus, taking into account this above mentioned model, the Cretaceous volcanic series, accreted to the margins of cratonal America, in Colombia, Venezuela, Greater Antilles and Mexico, could be related to the same west-south-west dipping subduction of oceanic basins, fringing the North and South American continental cratons and connected directly with the inter-American Tethys. While the subduction was proceeding, this magmatic arc drifted towards the North and South American cratons and finally, collided with the continental margins at different periods during the Cretaceous.     

Broadband frequency-dependent amplification of seismic waves across Bucharest, Romania

The determination of seismic amplitude amplification is a fundamental contribution to seismic hazard assessment. While often only high-frequency amplitude variations (>1 Hz) are taken into account, we analyse broadband waveforms from 0.14 to 8.6 Hz using a temporary network of 32 stations in and around the earthquake-prone city of Bucharest. Spectral amplitudes are calculated with an adaptive multiple-taper approach. Across our network (aperture 25 km × 25 km), we find a systematic northwest/southeast-oriented structural influence on teleseismic P-wave amplitudes from 0.14 to 0.86 Hz that can be explained by constructive interference in the dipping Cenozoic sedimentary layers. For higher frequencies (1.4–8.75 Hz), more local site effects prevail and can be correlated partly among neighbouring stations. The transition between systematic and localised amplitude variations occurs at about 1 Hz.     

Effects of sediment organic matter quality on bioaccumulation, degradation, and distribution of pyrene in two macrofaunal species and their surrounding sediment

Sediment dwelling macrofauna (infauna) are important vectors for the transfer of sediment-associated contaminants to higher trophic levels. Sedimenting organic matter constitutes an important food source for all benthic organisms and changes seasonally in terms of quantity and quality. Sediment organic matter (SOM) quality affects organism activity and feeding behaviour, and is therefore also likely to affect contaminant fate in benthic systems. We investigated the impact of SOM quality (enrichment with either labile Tetraselmis sp. or refractory lignin) on the accumulation and metabolism of sediment-associated pyrene in Nereis diversicolor (Annelida) and Amphiura filiformis (Echinodermata), as well as the combined effect of SOM quality and infaunal bioturbation on pyrene distribution and metabolism in the sediment. After 45 d of exposure, SOM quality almost doubled pyrene bioaccumulation in both species, while pyrene metabolism remained unaffected. Metabolites comprised approximately 80% of the total tissue pyrene in N. diversicolor and approximately 40% in A. filiformis. A. filiformis arms contained one fifth of the disk pyrene concentration. Approximately 20% of the pyrene found in A. filiformis arms was found to be covalently bound to, e.g. DNA, RNA or proteins, thus reducing pyrene bioavailability to arm-cropping predators. The sedimentary pyrene distribution and metabolism was species-dependent, but correlated poorly with prevailing knowledge on species-specific bioturbation patterns. This was attributed to the comparably high biodegradability of the contaminant thus altering its sorptive characteristics and function as inert tracer. Subduction of pyrene and metabolites occurred, and the fraction of pyrene covalently bound to SOM increased with depth, thereby removing pyrene from the bioavailable pool. Our results imply that bioaccumulation and trophic transfer of sediment-associated PAH should increase following fresh organic matter input, e.g. after sedimentation of phytoplankton blooms. We stress the importance of considering behavioural characteristics of infauna and the trophic situation of the system when assessing fate and effects of sediment-associated contaminants.     

Trace Element Determination by ICP-AES and ICP-MS: Developments and Applications Reported During 2004 and 2005

This review describes significant developments in trace element determination using inductively coupled plasma-atomic emission spectrometry (ICP-AES) and inductively coupled plasma-mass spectrometry (ICP-MS) that were reported in 2004 and 2005. It focuses on the application of ICP techniques to geological and environmental samples; fundamental studies in ICP-MS and ICP-AES instrumentation are not included. The literature reviewed indicated that the majority of new publications concerned advances in ICP-MS analysis rather than ICP-AES. However, ICP-AES developments are still being published, particularly in the areas of sample preconcentration and sample introduction. The trend in increasing publication of developments in hyphenated speciation techniques looks set to persist as knowledge of elemental speciation becomes critical for many environmental studies. Collision or reactions cells were the most reported technique for spectral interference removal in ICP-MS, probably reflecting the growing adoption of cell instruments in laboratories during the last few years.     

The deep layers of a Paleozoic arc: geochemistry of the Copley-Balaklala series, northern California

REE, Zr, Nb concentrations and Sr, Nd isotope compositions have been measured in Copley basalts and andesites, Balaklala rhyolites, and Mule Mountain trondhjemites (northern California) which represent the deep layers of a well preserved intra-oceanic island arc of Siluro-Devonian age.⁸⁷Sr/⁸⁶Sr is shifted towards high values (up to 0.707) whereas Ce is preferentially removed from rhyolites. A large proportion of the analyzed samples including some acidic rocks shows a pronounced depletion in light REE. The ε_Nd(T) values of most Copley, Balaklala, and Mule Mountain rocks fall in the range +6 to +8 which suggests that they originated from a normal MORB-type source (ε_Nd(T) ≈ +9) contaminated with either sediments or an OIB-type component.In modern island arcs, only the shallow levels are accessible: comparison with the Copley-Balaklala-Mule Mountain Series suggests that, at depth, an immature island arc is likely to comprise thick layers of LILE-depleted tholeiites and rhyolites intensely altered by pervasive circulation of seawater. Least-square solutions of trace element models suggest that rhyolites and trondhjemites represent remelting of mafic volcanics from the arc basement rather than residual melts of basalt-andesite differentiation.     

Geodynamic significance of the Raspas Metamorphic Complex (SW Ecuador): geochemical and isotopic constraints

The Raspas Metamorphic Complex of southwestern Ecuador is regarded as the southernmost remnant of oceanic and continental terranes accreted in the latest Jurassic–Early Cretaceous. It consists of variably metamorphosed rock types. (1) Mafic and ultramafic rocks metamorphosed under high-pressure (HP) conditions (eclogite facies) show oceanic plateau affinities with flat REE chondrite-normalized patterns, Nd_{150 Ma} ranging from +4.6 to 9.8 and initial Pb isotopic ratios intermediate between MORB and OIB. (2) Sedimentary rocks metamorphosed under eclogitic conditions exhibit LREE enriched patterns, strong negative Eu anomalies, Rb, Nb, U, Th, Pb enrichments, low Nd_{150 Ma} values (from −6.4 to −9.5), and high initial ⁸⁷Sr/⁸⁶Sr and ^206,207,208Pb/²⁰⁴Pb isotopic ratios suggesting they were originally sediments derived from the erosion of an old continental crust. (3) Epidote-bearing amphibolites show N-MORB affinities with LREE depleted patterns, LILE, Zr, Hf and Th depletion, high Nd_{150 Ma} (>+10) and low initial Pb isotopic ratios.The present-day well defined internal structure of the Raspas Metamorphic Complex seems to be inconsistent with the formerly proposed interpretation of a “tectonic mélange”. The association of oceanic plateau rocks and continent-derived sediments both metamorphosed in HP conditions suggests that the thin edge of the oceanic plateau first entered the subduction zone and dragged sediments downward of the accretionary wedge along the Wadatti–Benioff zone. Subsequently, when its thickest part arrived into the subduction zone, the oceanic plateau jammed the subduction processes, due to its high buoyancy.In Ecuador and Colombia, the latest Jurassic–Early Cretaceous suture involves HP oceanic plateau rocks and N-MORB rocks metamorphosed under lower grades, suggesting a composite or polyphase nature for the latest Jurassic–Early Cretaceous accretionary event.