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).     

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.     

GGR Biennial Review: Atomic Absorption,Inductively Coupled Plasma-Atomic Emission Spectrometry,Neutron Activation Analysis and X-Ray Fluorescence Spectrometry Review for 2008–2009

This review describes developments major and in trace element determination using atomic absorption spectroscopy (AAS), inductively coupled plasma-atomic emission spectrometry (ICP-AES), instrumental neutron activation analysis (INAA), and X-ray fluorescence (XRF) spectrometry that were reported in 2008 and 2009. Publication levels were comparable to those of previous years, except for XRF which showed an increase in the number of articles published in the past 2 years. In terms of number of publications and impact, the most active field was AAS, while INAA was the least active. As expected for well-established and mature methods, novel developments for all four analytical techniques were relatively sparse. For AAS, the most notable publications concerned developments in sample introduction, particularly focussing on solid samples, increasing analyte sensitivity, and higher sample throughput. For ICP-AES, publication of developments in sample introduction, remediation of matrix effects and calibration continues. Compared with past years, there was a clear focus on sample preconcentration methods, but very few publications reporting new hyphenated speciation methods. For INAA, there were several publications exploring the accuracy and robustness of the method, as well as the requirements for INAA to meet criteria for a primary method of measurement. Two other related techniques, delayed neutron activation analysis, and prompt gamma activation analysis, were also described. Hyphenated XRF techniques showed interesting developments in enabling XRF and XRD analysis on the same spot, and further work characterising and calibrating three-dimensional micro-XRF shows promising results for investigating sample heterogeneity.     

Trends in the solubility of iron,aluminium, manganese and phosphorus in aerosol collected over the Atlantic Ocean

The solubility of iron, aluminium, manganese and phosphorus has been determined in aerosol samples collected between 49°N and 52°S during three cruises conducted in the Atlantic Ocean as part of the European Union funded IRONAGES programme. Solubilities (defined at pH 4.7) determined for Fe and Al in samples of Saharan dust were significantly lower (medians 1.7% and 3.0%, respectively) than the solubilities of these metals in aerosols from other source regions (whole dataset medians 5.2% and 9.0%, respectively). Mn solubility also varied with aerosol source, but the median solubility of Mn in Saharan dust was very similar to the median for the dataset as a whole (55% and 56%, respectively). The observed solubility of aerosol P was ∼ 32%, with P solubility in Saharan aerosol perhaps as low as 10%. Laboratory studies have indicated that aerosol Fe solubility is enhanced by acid processing. No relationship could be found between Fe solubility and the concentrations of acid species (non-seasalt SO₄²⁻, NO₃⁻) nor the net acidity of the aerosol, so we are unable to confirm that this process is significant in the atmosphere. In terms of the supply of soluble Fe to oceanic ecosystems on a global scale, the observed higher solubility for Fe in non-Saharan aerosols is probably not significant because the Sahara is easily the dominant source of Fe to the Atlantic. On a smaller scale however, higher solubility for aerosol Fe may alter our understanding of Fe cycling in regions such as the remote Southern Ocean.     

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.     

Quadrupole ICP‐MS: Introduction to Instrumentation,Measurement Techniques and Analytical Capabilities

The low detection limits and multi‐element capability of inductively coupled plasma‐mass spectrometry (ICP‐MS) makes it an attractive option in a wide range of environmental, medical, biological, industrial and archaeological applications. Quadrupole ICP‐MS is used to determine element concentrations in a diverse range of sample types, often very different from the geological applications for which ICP‐MS was originally developed. Whilst modern instruments are robust and capable of a high degree of automation, it is essential that users of both instrumentation and data are aware of the strengths and limitations of the technique. Many people who are now involved with the operation and application of ICP‐MS instruments are not specialists in the field, as was usually the case amongst early operators. This back‐to‐basics review is aimed at the novice user and includes a guide to ICP‐MS instrumentation and performance. Whilst solids, liquids and gases can all be measured by ICP‐MS, discussion of sample introduction is limited to liquids. Requirements for producing good quality data, including aspects of sample preparation, calibration, and methods of interference limitation are also discussed.     

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 2006 and 2007

This review describes 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 2006 and 2007. It focuses on the application of ICP techniques to geological and environmental samples; fundamental studies in ICP‐MS and ICP‐AES instrumentation have largely been ignored. New advances in ICP‐MS and ICP‐AES were incremental over this period, partly because both techniques are now well‐established. A continuing shift towards the hyphenation of low‐flow separation techniques has sparked activity in the development of appropriate low‐flow interfaces, and papers discussing interference removal also contribute significantly to the volume of research for both ICP‐AES and ICP‐MS. Whereas the majority of new ICP publications concerned advances in ICP‐MS analysis rather than ICP‐AES, development for ICP‐AES still occurs in almost all areas, particularly in sample introduction and hyphenated techniques.