Applied Geochemistry (v.24, #6)

by Brian Hitchon (1043).

This is the author’s speech at the meeting in Cologne (2007) to celebrate the 40th anniversary of the International Association of Geochemistry and Cosmochemistry, which the author served as the President in 2000 to 2004. The paper narrates the author’s personal involvement in important scientific programs during the last 4 decades, including implementation of isotope techniques, oil-and-gas research, diamond research, deep-sea drilling, space research, molecular biology and the origin of life.

Subduction fluxes through geologic time by John Ludden (1052-1057).
Much of the author’s research career has been spent working both on modern oceanic volcanic systems and at the same time looking at their Archaean counterparts. Many authors have attempted to make inferences on early Earth models based on modern processes which can be increasingly well constrained. In this short review it will be shown how we are beginning to understand and quantify inputs to modern subduction systems and some questions are posed as to how these processes may have affected Earth’s evolution in its distant past.Geochemical models have convincingly demonstrated that sediment and altered oceanic crust must be recycled into the mantle through subduction zones. These ‘subduction factories’ use these components, along with molten mantle, to create arc magmas. The ‘residue’ from this process is recycled into the mantle and has a modified chemical and mineralogical composition. The altered oceanic crust input function in the current plate tectonic cycle seems to be relatively constant in composition, but the chemical compositions of the sediment fluxes into subduction zones vary widely and control many of the end-member compositions of arc magmas. They must also control the compositions of fluids and gases derived from these magmas and ultimately ore-deposition and atmospheric fluxes associated with arc volcanoes.There is relatively strong evidence for subduction processes for at least the past 3.5 Ma and some would argue that exogenic components have been recycled into the mantle since at least ∼4.3 Ma. How might the subduction fluxes have changed through time, and how might they have influenced crust, ocean and atmospheric compositions? Can different ore regimes in temporal and spatial distribution on Earth be related to the change in inputs and residues from the subduction factory through time?

As part of the events celebrating 40 a of IAGC, it is fitting to trace the modern evolution and development of hydrogeochemistry. However, fascination with water quality can be traced back more than 2 ka. In the post-war years, hydrogeochemistry was influenced heavily by the advances in other disciplines including physical chemistry, metallurgy and oceanography. Hydrological applications of isotope science also developed rapidly at this time, and important advances in analytical chemistry allowed multi-element and trace element applications to be made. Experimental studies on equilibrium processes and reaction kinetics allowed bench-scale insight into water–rock interaction. Consolidation of knowledge on processes in groundwaters and the current awareness of hydrogeochemistry by water professionals owe much to the work of Robert Garrels, John Hem, and co-workers in the early 1960s. Studies of down-gradient evolution enabled a field-scale understanding of groundwater quality and geochemical processes as a function of residence time (dissolution and precipitation processes in carbonate and non-carbonate aquifers; redox processes; cation exchange and salinity origins).Emerging water resource and water quality issues in the 1960s and 70s permitted the application of hydrogeochemistry to contaminant and related problems and this trend continues. The impacts of diffuse pollution from intensive agriculture, waste disposal and point source pollution from urban and industrial sources relied on geochemistry to solve questions of origin and attenuation. In semi-arid regions facing water scarcity, geochemical approaches have been vital in the assessment of renewability and characterising palaeowaters. The protection and new incoming regulation of water resources will rely increasingly on a sound geochemical basis for management.

Geochemical fingerprinting is a rapidly expanding discipline in the earth and environmental sciences. It is anchored in the recognition that geological processes leave behind chemical and isotopic patterns in the rock record. Many of these patterns, informally referred to as geochemical fingerprints, differ only in fine detail from each other. For this reason, the approach of fingerprinting requires analytical data of very high precision and accuracy.It is not surprising that the advancement of geochemical fingerprinting occurred alongside progress in geochemical analysis techniques. In this brief treatment, a subjective selection of drivers behind the analytical progress and its implications for geochemical fingerprinting are discussed. These include the impact of the Apollo lunar sample return program on quality of geochemical data and its push towards minimizing required sample volumes. The advancement of in situ analytical techniques is also identified as a major factor that has enabled geochemical fingerprinting to expand into a larger variety of fields.For real world applications of geochemical fingerprinting, in which large sample throughput, reasonable cost, and fast turnaround are key requirements, the improvements to inductively-coupled-plasma quadrupole mass spectrometry were paramount. The past 40 years have witnessed how geochemical fingerprinting has found its way into everyday applications. This development is cause for celebrating the 40 years of existence of the IAGC.

Geochronology – Aims and reminiscences by Stephen Moorbath (1087-1092).

Potential environmental issues of CO2 storage in deep saline aquifers: Geochemical results from the Frio-I Brine Pilot test, Texas, USA by Yousif K. Kharaka; James J. Thordsen; Susan D. Hovorka; H. Seay Nance; David R. Cole; Tommy J. Phelps; Kevin G. Knauss (1106-1112).
Sedimentary basins in general, and deep saline aquifers in particular, are being investigated as possible repositories for large volumes of anthropogenic CO2 that must be sequestered to mitigate global warming and related climate changes. To investigate the potential for the long-term storage of CO2 in such aquifers, 1600 t of CO2 were injected at 1500 m depth into a 24-m-thick “C” sandstone unit of the Frio Formation, a regional aquifer in the US Gulf Coast. Fluid samples obtained before CO2 injection from the injection well and an observation well 30 m updip showed a Na–Ca–Cl type brine with ∼93,000 mg/L TDS at saturation with CH4 at reservoir conditions; gas analyses showed that CH4 comprised ∼95% of dissolved gas, but CO2 was low at 0.3%. Following CO2 breakthrough, 51 h after injection, samples showed sharp drops in pH (6.5–5.7), pronounced increases in alkalinity (100–3000 mg/L as HCO3) and in Fe (30–1100 mg/L), a slug of very high DOC values, and significant shifts in the isotopic compositions of H2O, DIC, and CH4. These data, coupled with geochemical modeling, indicate corrosion of pipe and well casing as well as rapid dissolution of minerals, especially calcite and iron oxyhydroxides, both caused by lowered pH (initially ∼3.0 at subsurface conditions) of the brine in contact with supercritical CO2.These geochemical parameters, together with perfluorocarbon tracer gases (PFTs), were used to monitor migration of the injected CO2 into the overlying Frio “B”, composed of a 4-m-thick sandstone and separated from the “C” by ∼15 m of shale and siltstone beds. Results obtained from the Frio “B” 6 months after injection gave chemical and isotopic markers that show significant CO2 (2.9% compared with 0.3% CO2 in dissolved gas) migration into the “B” sandstone. Results of samples collected 15 months after injection, however, are ambiguous, and can be interpreted to show no additional injected CO2 in the “B” sandstone. The presence of injected CO2 may indicate migration from “C” to “B” through the intervening beds or, more likely, a short-term leakage through the remedial cement around the casing of a 50-year old well. Results obtained to date from four shallow monitoring groundwater wells show no brine or CO2 leakage through the Anahuac Formation, the regional cap rock.

Genesis of yellow manganese-rich elbaite from the Canary mining area, Lundazi, Zambia by Brendan M. Laurs; William B. Simmons; Alexander U. Falster; Björn Anckar (1113-1124).
The most important source of yellow gem elbaite is the Canary mining area in the Lundazi District of eastern Zambia. The tourmaline has been mined since 1983 from both pegmatite and eluvial/alluvial deposits, in colors typically ranging from yellow-green to yellow to orange and brown; much of the orange-to-brown material is heated to attain a ‘golden’ or ‘canary’ yellow color. The elbaite is Mn-rich (up to 9.18 wt% MnO documented in the literature) and contains small amounts of Ti and little or no Fe. The distinctive composition of this tourmaline is probably the result of the early crystallization of abundant schorl from an unusual B-rich, Li-poor pegmatite melt, which depleted Fe while conserving Mn until the late-stage crystallization of gem pockets. The simple mineralogy of the pegmatite consists of feldspars, quartz, and tourmaline; the lack of micas, phosphates, or Li minerals, and the presence of very little garnet, allowed Mn to fractionate to high levels during pegmatite crystallization. The presence of abundant gem tourmaline in a Li-poor pegmatite is highly unusual.

LIBS analysis of geomaterials: Geochemical fingerprinting for the rapid analysis and discrimination of minerals by Russell S. Harmon; Jeremiah Remus; Nancy J. McMillan; Catherine McManus; Leslie Collins; Jennifer L. Gottfried; Frank C. DeLucia; Andrzej W. Miziolek (1125-1141).
Laser-induced breakdown spectroscopy (LIBS) is a simple atomic emission spectroscopy technique capable of real-time, essentially non-destructive determination of the elemental composition of any substance (solid, liquid, or gas). LIBS, which is presently undergoing rapid research and development as a technology for geochemical analysis, has attractive potential as a field tool for rapid man-portable and/or stand-off chemical analysis. In LIBS, a pulsed laser beam is focused such that energy absorption produces a high-temperature microplasma at the sample surface resulting in the dissociation and ionization of small amounts of material, with both continuum and atomic/ionic emission generated by the plasma during cooling. A broadband spectrometer-detector is used to spectrally and temporally resolve the light from the plasma and record the intensity of elemental emission lines. Because the technique is simultaneously sensitive to all elements, a single laser shot can be used to track the spectral intensity of specific elements or record the broadband LIBS emission spectra, which are unique chemical ‘fingerprints’ of a material. In this study, a broad spectrum of geological materials was analyzed using a commercial bench-top LIBS system with broadband detection from ∼200 to 965 nm, with multiple single-shot spectra acquired. The subsequent use of statistical signal processing approaches to rapidly identify and classify samples highlights the potential of LIBS for ‘geochemical fingerprinting’ in a variety of geochemical, mineralogical, and environmental applications that would benefit from either real-time or in-field chemical analysis.

The Bayesian approach is an effective method of identifying the probability of mineralogical and geochemical type (MGT) mineralization of trace elements in galena, pyrite and other distributions in ore mineralization. Monomineralic samples have been identified using a computer-based Bayesian method and exploration geochemical techniques of Au deposits for MGT. In order to employ the method, a data bank was used consisting of the results of analysis of more than 12,000 monomineralic samples collected from the main hydrothermal Au deposits in Tajikistan (a territory of CIS). The Bayesian approach applied to geochemical data, such as posterior probabilities and discriminant analysis, provide numerical and graphical means through which the relationships between the trace elements and samples can be studied. The method used here, along with GIS, to find MGT can be used as geochemical indicators of regions with Au mineralization. The results of analyzing 100 monomineralic samples of pyrite from the Au–Ag Shkolnoe deposit (Tajikistan) show a multi-MGT anomaly superposition which is a combination of three MGT: (1) Au–Ag type (85% and more), (2) Au–sulfide-polymetallic type (46%), and (3) Au–sulfide type (40%). Mineralogical and geochemical maps (MGM) can be drawn based on results of MGT anomalies in a GIS environment. These maps can replace traditional metallogenic maps. The advantage of MGM substitutions is that a qualitative tool is replaced by a quantitative one. This helps one to make optimal managerial and more economical decisions.