Analysis of Rock Varnish from the Mojave Desert by Handheld Laser-Induced Breakdown Spectroscopy.

Laser-induced breakdown spectroscopy (LIBS) is a form of optical emission spectroscopy that can be used for the rapid analysis of geological materials in the field under ambient environmental conditions. We describe here the innovative use of handheld LIBS for the in situ analysis of rock varnish. This thinly laminated and compositionally complex veneer forms slowly over time on rock surfaces in dryland regions and is particularly abundant across the Mojave Desert climatic region of east-central California (USA). Following the depth profiling examination of a varnished clast from colluvial gravel in Death Valley in the laboratory, our in situ analysis of rock varnish and visually similar coatings on rock surfaces was undertaken in the Owens and Deep Spring valleys in two contexts, element detection/identification and microchemical mapping. Emission peaks were recognized in the LIBS spectra for the nine elements most abundant in rock varnish-Mn, Fe, Si, Al, Na, Mg, K, Ca and Ba, as well as for H, Li, C, O, Ti, V, Sr and Rb. Focused follow-up laboratory and field studies will help understand rock varnish formation and its utility for weathering and chronological studies.

Isotopic history of seawater: the stable isotope character of the global ocean at present and in the geological past.

After the atmosphere, the ocean is the most well-mixed and homogeneous global geochemical reservoir. Both physical and biological processes generate elemental and isotope variations in seawater. Contrasting geochemical behaviors cause elements to be susceptible to different fractionation mechanisms, with their isotopes providing unique insights into the composition and evolution of the ocean over the course of geological history. Supplementing the traditional stable isotopes (H, C, O, N, S) that provide information about ocean processes and past environmental conditions, radiogenic isotope (Sr, Nd, Os, Pb, U) systems can be used as time markers, indicators of terrestrial weathering, and ocean water mass mixing. Recent instrumentation advances have made possible the measurement of natural stable isotope variations produced by both mass-dependent and mass-independent fractionation for an ever-increasing number of metal elements (e.g. Li, B, Mg, Si, Ca, V, Cr, Fe, Ni, Cu, Zn, Se, Mo, Cd, Tl, U). The major emphasis in this review is on the isotopic composition of the light elements based on a comparatively large literature. Unlike O, H and S, the stable isotopes of C, N and Si do not have a constant isotopic composition in the modern ocean. The major cations Ca, Mg, and Sr fixed in carbonate shells provide the best proxies for reconstruction of the composition of the ocean in the past. Exhibiting large isotope enrichments in ocean water, B and Li are suitable for the investigation of water/rock interactions and can act as monitors of former oceanic pH. The bioessential elements Zn, Cd, and Ni are indicators of paleoproductivity in the ocean. Characteristic isotope enrichments or depletions of the multivalent elements V, Cr, Fe, Se, Mo, and U record the past redox state of the ocean/atmosphere system. Case studies describe how isotopes have been used to define the seawater composition in the geological past.

Advanced signal processing analysis of laser-induced breakdown spectroscopy data for the discrimination of obsidian sources.

Obsidian is a natural glass of volcanic origin and a primary resource used by indigenous peoples across North America for making tools. Geochemical studies of obsidian enhance understanding of artifact production and procurement and remain a priority activity within the archaeological community. Laser-induced breakdown spectroscopy (LIBS) is an analytical technique being examined as a means for identifying obsidian from different sources on the basis of its 'geochemical fingerprint'. This study tested whether two major California obsidian centers could be distinguished from other obsidian localities and the extent to which subsources could be recognized within each of these centers. LIBS data sets were collected in two different spectral bands (350±130 nm and 690±115 nm) using a Nd:YAG 1064 nm laser operated at ~23 mJ, a Czerny-Turner spectrograph with 0.2-0.3 nm spectral resolution and a high performance imaging charge couple device (ICCD) detector. Classification of the samples was performed using partial least-squares discriminant analysis (PLSDA), a common chemometric technique for performing statistical regression on high-dimensional data. Discrimination of samples from the Coso Volcanic Field, Bodie Hills, and other major obsidian areas in north-central California was possible with an accuracy of greater than 90% using either spectral band.

Can the provenance of the conflict minerals columbite and tantalite be ascertained by laser-induced breakdown spectroscopy?

Conflict minerals is a term applied to ores mined in conditions of armed conflict and human rights abuse. Niobium and tantalum are two rare metals whose primary natural occurrence is in the complex oxide minerals columbite and tantalite, the ore of which is commonly referred to as coltan. The illicit export of coltan ore from the Democratic Republic of the Congo is thought to be responsible for financing the ongoing civil conflicts in this region. Determining the chemical composition of an ore is one of the means of ascertaining its provenance. Laser-induced breakdown spectroscopy (LIBS) offers a means of rapidly distinguishing different geographic sources for a mineral because the LIBS plasma emission spectrum provides the complete chemical composition (i.e., "chemical fingerprint") of any material in real time. To test this idea for columbite-tantalite, three sample sets were analyzed. Partial least squares discriminant analysis (PLSDA) allows correct sample-level geographic discrimination at a success rate exceeding 90%.

Physical controls and ENSO event influence on weathering in the Panama Canal Watershed.

Recent empirical studies have documented the importance of tropical mountainous rivers on global silicate weathering and suspended sediment transport. Such field studies are typically based on limited temporal data, leaving uncertainty in the strength of observed relationships with controlling parameters over the long term. A deficiency of long-term data also prevents determination of the impact that multi-year or decadal climate patterns, such as the El Niño Southern Oscillation (ENSO), might have on weathering fluxes. Here we analyze an 18-year hydrochemical dataset for eight sub-basins of the Panama Canal Watershed of high-temporal frequency collected between 1998 and 2015 to address these knowledge gaps. We identified a strongly positive covariance of both cation (Ca2+, Mg2+, K+, Na+) and suspended sediment yields with precipitation and extent of forest cover, whereas we observed negative relationships with temperature and mosaic landcover. We also confirmed a statistical relationship between seasonality, ENSO, and river discharge, with significantly higher values occurring during La Niña events. These findings emphasize the importance that long-term datasets have on identifying short-term influences on chemical and physical weathering rates, especially, in ENSO-influenced regions.

Use of laser induced breakdown spectroscopy in the determination of gem provenance: beryls.

The provenance of gem stones has been of interest to geologists, gemologists, archeologists, and historians for centuries. Laser induced breakdown spectroscopy (LIBS) provides a minimally destructive tool for recording the rich chemical signatures of gem beryls (aquamarine, goshenite, heliodor, and morganite). Broadband LIBS spectra of 39 beryl (Be(3)Al(2)Si(6)O(18)) specimens from 11 pegmatite mines in New Hampshire, Connecticut, and Maine (USA) are used to assess the potential of using principal component analysis of LIBS spectra to determine specimen provenance. Using this technique, beryls from the three beryl-bearing zones in the Palermo #1 pegmatite (New Hampshire) can be recognized. However, the compositional variation within this single mine is comparable to that in beryls from all three states. Thus, a very large database with detailed location metadata will be required to routinely determine gem beryl provenance.

Stable isotope signatures of seasonal precipitation on the Pacific coast of central Panama.

As calculated from data archived in the IAEA-WMO Global Network of Isotopes in Precipitation programme, the amount-weighted local meteoric water line for the Pacific coast of central Panama is: δ(2)H = 7.63(±0.08) × Î´(18)O + 6.51(±0.49). Amount-weighted mean isotopic values were regressed against the sea surface temperature (SST) fields of the adjacent tropical oceans. A negative correlation of precipitation isotope composition with Caribbean SSTs is observed only for the early wet season (May-June), whilst the mid-summer dry period is characterized by positive correlation with eastern Pacific SSTs, similar to the late wet season (October-November). The negative response of May-June rainfall isotopic composition to Caribbean SSTs is explained by a SST-mediated change in stratiform rain fraction from organized convective systems proximal to the Inter Tropical Convergence Zone (ITCZ). The positive correlation for the rest of the wet season, when the organized convective zone of ITCZ and its attached stratiform belt are distant from the Pacific coast of Panama, is interpreted as simple evaporative temperature effect on isotopic fractionation.

Laser-induced breakdown spectroscopy analysis of complex silicate minerals--beryl.

Beryl (Be3Al2Si6O18) is a chemically complex and highly compositionally variable gem-forming mineral found in a variety of geologic settings worldwide. A methodology and analytical protocol were developed for the analysis of beryl by laser-induced breakdown spectroscopy (LIBS) that minimizes the coefficient of variance for multiple analyses of the same specimen. The parameters considered were laser energy/pulse, time delay and crystallographic orientation. Optimal analytical conditions are a laser energy/pulse of 102 mJ and a time delay of 2 micros. Beryl compositions measured parallel and perpendicular to the c axis were identical within analytical error. LIBS analysis of 96 beryls from 16 countries (Afghanistan, Brazil, Canada, China, Colombia, India, Ireland, Italy, Madagascar, Mexico, Mozambique, Namibia, Norway, Russia, Tanzania and United States), Antarctica, and ten US states (AZ, CA, CO, CT, ID, ME, NC, NH, NM and UT) were undertaken to determine whether or not LIBS analysis can be used to determine the provenance of gem beryl.

LIBS for landmine detection and discrimination.

The concept of utilizing laser-induced breakdown spectroscopy (LIBS) technology for landmine detection and discrimination has been evaluated using both laboratory LIBS and a prototype man-portable LIBS systems. LIBS spectra were collected for a suite of landmine casings, non-mine plastic materials, and "clutter-type" objects likely to be present in the soil of a conflict area or a former conflict area. Landmine casings examined included a broad selection of anti-personnel and anti-tank mines from different countries of manufacture. Other materials analyzed included rocks and soil, metal objects, cellulose materials, and different types of plastics. Two "blind" laboratory tests were conducted in which 100 broadband LIBS spectra were obtained for a mixed suite of landmine casings and clutter objects and compared with a previously-assembled spectral reference library. Using a linear correlation approach, "mine/no mine" determinations were correctly made for more than 90% of the samples in both tests. A similar test using a prototype man-portable LIBS system yielded an analogous result, validating the concept of using LIBS for landmine detection and discrimination.

Laser-induced breakdown spectroscopy analysis of energetic materials.

A number of energetic materials and explosives have been studied by laser-induced breakdown spectroscopy (LIBS). They include black powder, neat explosives such as TNT, PETN, HMX, and RDX (in various forms), propellants such as M43 and JA2, and military explosives such as C4 and LX-14. Each of these materials gives a unique spectrum, and generally the spectra are reproducible shot to shot. We observed that the laser-produced microplasma did not initiate any of the energetic materials studied. Extensive studies of black powder and its ingredients by use of a reference spectral library have demonstrated excellent accuracy for unknown identification. Finally, we observed that these nitrogen- and oxygen-rich materials yield LIBS spectra in air that have correspondingly different O:N peak ratios compared with air. This difference can help in the detection and identification of such energetic materials.