Laser Ablation ICP-MS Developments and Trends for 2003

This annual review of laser-ablation inductively coupled plasma-mass spectrometry (LA-ICP-MS) covers the year 2003. Significant advances were made in understanding laser-sample interactions. In particular, research defined the distribution of particle sizes produced by the interplay of laser wavelength, laser pulse width and the gas environment of ablation. A link between particle sizes and elemental and isotopic fractionation at both the ablation site and in the ICP was established. Experimental 15 7 nm and femtosecond laser systems were tested with promising results. The number of applications of LA-ICP-MS in geology and environmental Earth science continued to grow with particular interest in element concentration and isotope ratio profiling of materials, linking composition to time scales. In situ isotopic ratio measurements were increasingly made using multicollector magnetic sector ICP-MS instruments. Other applications of wide interest included bulk sampling of rocks and ores prepared as lithium borate glasses; low level analysis of platinum-group elements, rhenium and gold in sulfides, metal and silicates; in situ uranium-lead zircon geochronology; and melt and fluid inclusion analysis.     

U/Pb and Pb/Pb zircon ages for arc-related intrusions of the Bolu Massif (W Pontides, NW Turkey): evidence for Late Precambrian (Cadomian) age

We present new U/Pb and Pb/Pb radiometric age data from two tectono-stratigraphic units of the regionally extensive Bolu Massif, in the W Pontides (İstanbul Fragment), N Turkey. A structurally lower unit (Sünnice Group) is cut by small meta-granitic intrusions, whereas the structurally higher unit comprises meta-volcanic rocks (Çaşurtepe Fm) cut by meta-granitic plutons (Tüllükiriş and Kapıkaya plutons). U/Pb single-crystal dating of zircons from the Kapıkaya Pluton yielded a concordant cluster, with a mean ²³⁸U/²⁰⁶Pb age of 565.3 ± 1.9 Ma. Zircons from the Tüllükiriş Pluton (affected by Pb loss) gave a ²⁰⁷Pb/²⁰⁶Pb age of 576 ± 6 Ma age (Late Precambrian). Small meta-granitic intrusions cutting the Sünnice Group yielded a less precise ²⁰⁷Pb/²⁰⁶Pb age of 262 ± 19 Ma (Early Permian). The older ages from the Bolu Massif confirm the existence of latest Precambrian arc magmatism related to subduction of a Cadomian ocean. We infer that the Bolu Massif represents a fragment of a Cadomian active margin. Cadomian orogenic units were dispersed as exotic terranes throughout the Variscan and Tethyan orogens, and the Bolu Massif probably reached its present position prior to latest Palaeozoic time. Our dating results also confirm that NW Turkey was affected by Hercynian magmatism related to subduction of Palaeotethys, as inferred for other areas of the Pontides.     

Seismic velocities of granulite-facies xenoliths from Central Ireland: Implications for lower crustal composition and anisotropy

V_p and V_s values have been measured experimentally and calculated for granulite-facies lower crustal xenoliths from central Ireland close to the Caledonian Iapetus suture zone. The xenoliths are predominantly foliated and lineated metapelitic (garnet–sillimanite–K-feldspar) granulites. Their metapelitic composition is unusual compared with the mostly mafic composition of lower crustal xenoliths world-wide. Based on thermobarometry, the metapelitic xenoliths were entrained from depths of c. 20–25 ± 3.5 km and rare mafic granulites from depths of 31–33 ± 3.4 km. The xenoliths were emplaced during Lower Carboniferous volcanism and are considered to represent samples of the present day lower crust.V_p values for the metapelitic granulites range between 6.26 and 7.99 km s^{− 1} with a mean value of 7.09 ± 0.4 km s^{− 1}. Psammite and granitic orthogneiss samples have calculated V_p values of 6.51 and 6.23 km s^{− 1}, respectively. V_s values for the metapelites are between 3.86 and 4.34 km s^{− 1}, with a mean value of 4.1 ± 0.15 km s^{− 1}. The psammite and orthogneiss have calculated V_s values of 3.95 and 3.97 km s^{− 1}, respectively.The measured seismic velocities correlate with density and with modal mineralogy, especially the high content of sillimanite and garnet. V_p anisotropy is between 0.15% and 13.97%, and a clear compositional control is evident, mainly in relation to sillimanite abundance. Overall V_s anisotropy ranges from 1% to 11%. Poisson's ratio (σ) lies between 0.25 and 0.35 for the metapelitic granulites, mainly reflecting a high V_p value due to abundant sillimanite in the sample with the highest σ. Anisotropy is probably a function of deformation associated with the closure of the Iapetus ocean in the Silurian as well as later extension in the Devonian. The orientation of the bulk strain ellipsoid in the lower crust is difficult to constrain, but lineation is likely to be NE–SW, given the strike-slip nature of the late Caledonian and subsequent Acadian deformation.When corrected for present-day lower crustal temperature, the experimentally determined V_p values correspond well with velocities from the ICSSP, COOLE I and VARNET seismic refraction lines. Near the xenolith localities, the COOLE I line displays two lower crustal layers with in situ V_p values of 6.85–6.9 and 6.9–8.0 km s^{− 1}, respectively. The upper (lower velocity) layer corresponds well with the metapelitic granulite xenoliths while the lower (higher velocity) layer matches that of the basic granulite xenoliths, though their metamorphic pressures suggest derivation from depths corresponding to the present-day upper mantle.     

Arsenic mobility in the ambient sulfidic environment: Sorption of arsenic(V) and arsenic(III) onto disordered mackinawite

Arsenate, As(V), sorption onto synthetic iron(II) monosulfide, disordered mackinawite (FeS), is fast. As(V) sorption decreases above the point of zero surface charge of FeS and follows the pH-dependent concentration of positively charged surface species. No redox reaction is observed between the As(V) ions and the mineral surface over the time span of the experiments. This observation shows that As(V) dominantly forms an outer-sphere complex at the surface of mackinawite. Arsenite, As(III), sorption is not strongly pH-dependent and can be expressed by a Freundlich isotherm. Sorption is fast, although slower than that of As(V). As(III) also forms an outer-sphere complex at the surface of mackinawite. In agreement with previous spectroscopic studies, complexation at low As(V) and As(III) concentration occurs preferentially at the mono-coordinated sulfide edge sites. The K_d (L g⁻¹) values obtained from linear fits to the isotherm data are ∼9 for As(V) and ∼2 for As(III). Stronger sorption of As(V) than As(III), and thus a higher As(III) mobility, may be reflected in natural anoxic sulfidic waters when disordered mackinawite controls arsenic mobility.     

Chemical weathering in the Upper Huang He (Yellow River) draining the eastern Qinghai-Tibet Plateau

We examined the fluvial geochemistry of the Huang He (Yellow River) in its headwaters to determine natural chemical weathering rates on the northeastern Qinghai-Tibet Plateau, where anthropogenic impact is considered small. Qualitative treatment of the major element composition demonstrates the dominance of carbonate and evaporite dissolution. Most samples are supersaturated with respect to calcite, dolomite, and atmospheric CO₂ with moderate (0.710-0.715) ⁸⁷Sr/⁸⁶Sr ratios, while six out of 21 total samples have especially high concentrations of Na, Ca, Mg, Cl, and SO₄ from weathering of evaporites. We used inversion model calculations to apportion the total dissolved cations to rain-, evaporite-, carbonate-, and silicate-origin. The samples are either carbonate- or evaporite-dominated, but the relative contributions of the four sources vary widely among samples. Net CO₂ consumption rates by silicate weathering (6-120 × 10³ mol/km²/yr) are low and have a relative uncertainty of ∼40%. We extended the inversion model calculation to literature data for rivers draining orogenic zones worldwide. The Ganges-Brahmaputra draining the Himalayan front has higher CO₂ consumption rates (110-570 × 10³ mol/km²/yr) and more radiogenic ⁸⁷Sr/⁸⁶Sr (0.715-1.24) than the Upper Huang He, but the rivers at higher latitudes are similar to or lower than the Upper Huang He in CO₂ uptake by silicate weathering. In these orogenic zones, silicate weathering rates are only weakly coupled with temperature and become independent of runoff above ∼800 mm/yr.