International Association of Geoanalysts' Protocol for the Certification of Geological and Environmental Reference Materials: A Supplement

The International Association of Geoanalysts (IAG) published a protocol for the certification of reference materials in close accord with the International Organisation for Standardisation (ISO) guidelines (Kane et al. 2003). This article supplements that protocol, providing additional discussion of best approaches for pre-selecting laboratories for participation in certification projects. This discussion also makes a distinction between inter-laboratory certifications, where n = 15 is the general standard, and expert laboratory certifications, where a much smaller number of laboratories will be deemed qualified to provide data of the quality needed for certification.     

The origin of high δ<Superscript>18</Superscript>O zircons: marbles,megacrysts, and metamorphism

The oxygen isotope ratios (δ¹⁸O) of most igneous zircons range from 5 to 8‰, with 99% of published values from 1345 rocks below 10‰. Metamorphic zircons from quartzite, metapelite, metabasite, and eclogite record δ¹⁸O values from 5 to 17‰, with 99% below 15‰. However, zircons with anomalously high δ¹⁸O, up to 23‰, have been reported in detrital suites; source rocks for these unusual zircons have not been identified. We report data for zircons from Sri Lanka and Myanmar that constrain a metamorphic petrogenesis for anomalously high δ¹⁸O in zircon. A suite of 28 large detrital zircon megacrysts from Mogok (Myanmar) analyzed by laser fluorination yields δ¹⁸O from 9.4 to 25.5‰. The U–Pb standard, CZ3, a large detrital zircon megacryst from Sri Lanka, yields δ¹⁸O = 15.4 ± 0.1‰ (2 SE) by ion microprobe. A euhedral unzoned zircon in a thin section of Sri Lanka granulite facies calcite marble yields δ¹⁸O = 19.4‰ by ion microprobe and confirms a metamorphic petrogenesis of zircon in marble. Small oxygen isotope fractionations between zircon and most minerals require a high δ¹⁸O source for the high δ¹⁸O zircons. Predicted equilibrium values of Δ¹⁸O(calcite-zircon) = 2–3‰ from 800 to 600°C show that metamorphic zircon crystallizing in a high δ¹⁸O marble will have high δ¹⁸O. The high δ¹⁸O zircons (>15‰) from both Sri Lanka and Mogok overlap the values of primary marine carbonates, and marbles are known detrital gemstone sources in both localities. The high δ¹⁸O zircons are thus metamorphic; the 15–25‰ zircon values are consistent with a marble origin in a rock-dominated system (i.e., low fluid_(external)/rock); the lower δ¹⁸O zircon values (9–15‰) are consistent with an origin in an external fluid-dominated system, such as skarn derived from marble, although many non-metasomatized marbles also fall in this range of δ¹⁸O. High δ¹⁸O (>15‰) and the absence of zoning can thus be used as a tracer to identify a marble source for high δ¹⁸O detrital zircons; this recognition can aid provenance studies in complex metamorphic terranes where age determinations alone may not allow discrimination of coeval source rocks. Metamorphic zircon megacrysts have not been reported previously and appear to be associated with high-grade marble. Identification of high δ¹⁸O zircons can also aid geochronology studies that seek to date high-grade metamorphic events due to the ability to distinguish metamorphic from detrital zircons in marble.     

A laboratory study of the bidirectional reflectance from particulate samples

The Hapke (Hapke, B. [1981]. J. Geophys. Res. 86, 3039-3054) photometric model and its modifications are widely used to characterize telescopic, spacecraft, and laboratory observations of the bidirectional reflectance of particulate surfaces. Following work and methods laid out in a companion paper (Helfenstein, P., Shepard, M.K. [2011]. Icarus, in press), we deconstruct the Hapke model and, separating all empirical and ad hoc parameters (opposition surge, particle phase function, surface roughness), combine them into a single parameter called the surface phase function, F(α). We illustrate how to extract this function from scattering data sets acquired with the Bloomsburg University Goniometer (BUG). We show how this method can be used to rapidly and accurately characterize bidirectional reflectance data sets from laboratory and spacecraft measurements, often giving better fits to the data. We examine samples with strong color contrasts in different wavelengths. This allows us to examine the exact same surface, changing only the albedo to investigate how the amplitude and the detailed shape of the surface phase function might systematically depend on wavelength and albedo. We also examine the changes in scattering behavior that result when samples are compacted and find the surface phase function and single scattering albedo to be significantly changed. We suggest that these observations support the hypothesis that much of the scattering behavior attributed to the single particle phase function is instead cause by the surface micro-structure.     

Grain size along two gravel-bed rivers: statistical variation,spatial pattern and sedimentary links

A new set of field data facilitates a detailed analysis of variations in bed material grain size within two confluent gravel-bed rivers in northeastern British Columbia, Canada. A preliminary assessment of grain-size variability establishes a basis for examination of the spatial pattern of grain-size change. Standard ANOVA techniques are inappropriate because individual samples have unequal variances and are not normally distributed. Alternative tests for homoscedasticity and comparison of means are therefore utilized. Within-site, between-sample variability is not significant. The grain-size distributions that were obtained at individual sites are therefore representative of the depositional environments that were sampled. In both rivers mean grain size does vary significantly between sites and there is therefore a basis for examining the data for spatial patterns such as downstream fining. Textural variations along the two rivers studied here are complex and show negligible overall fining (in over 100 km). This is the consequence of a large number of tributary inputs and non-alluvial sediment sources which are the legacy of Late Pleistocene glaciation. The identification of lateral sources like these is fundamental for understanding textural changes within rivers. The sedimentary link (a channel reach between significant lateral sediment inputs) provides a means of isolating fluvial maturation processes (abrasion and sorting) from contingent lateral inputs. Strong fining trends are apparent in most links and classification of grain-size measurements according to their location within particular links greatly improves the statistical explanation of textural variation. Identification of sedimentary links provides a means of applying models of fluvial fining processes, so isolation of link networks will aid the development of basin-scale models of textural variation. © 1998 John Wiley & Sons, Ltd.     

Distribution and Abundance of Arsenic in the Soils and Sediments of O‘ahu,Hawai‘i

Lack of high-spatial-resolution soil and sediment arsenic data for Hawai‘i has generated substantial disagreement between researchers and regulators regarding the magnitude of natural levels of arsenic in Hawai‘i and rendered difficult the defining of areas of anthropogenically elevated arsenic. Our earlier research into the occurrence of arsenic in terrestrial and marine environments revealed widely disparate concentrations of arsenic with no apparent spatial pattern. To better understand the distribution and abundance of arsenic in soils and sediments of O‘ahu, we collected an additional 64 samples at locations chosen to represent different environments with varying degrees of human impact. We found surface arsenic values that ranged from 0.28 to 740 ppm with a median concentration of 8.1 ppm, which is above the global median of 5 ppm and US soil median of 5.2 ppm. Higher concentrations of arsenic (up to 913 ppm) were encountered at depth in soil cores. The median arsenic in streambed sediments from one of our earlier studies of 6.1 ppm was comparable to the conterminous US median of 6.3 ppm; however, we encountered arsenic concentrations as high as 43.9 ppm (median = 8.60 ppm, n = 75) in marine sediments in recent work off the leeward coast of O‘ahu. Overall, arsenic in the soils and sediments of O‘ahu is elevated relative to world and national values, but there still is no readily discernible pattern in the distribution of arsenic to explain these elevated values.     

Nutrient Fluxes from Sediments in the San Francisco Bay Delta

In September 2011 and March 2012, benthic nutrient fluxes were measured in the San Francisco Bay Delta, across a gradient from above the confluence of the Sacramento and San Joaquin Rivers to Suisun Bay. Dark and illuminated core incubation techniques were used to measure rates of denitrification, nutrient fluxes (phosphate, ammonium, nitrate), and oxygen fluxes. While benthic nutrient fluxes have been assessed at several sites in northern San Francisco Bay, such data across a Delta–Bay transect have not previously been determined. Average September rates of DIN (nitrate, nitrite, ammonium) flux were net positive across all sites, while March DIN flux indicated net uptake of DIN at some sites. Denitrification rates based on the N₂/Ar ratio approach were between 0.6 and 1.0 mmol m^?2 day^?1, similar to other mesotrophic estuarine sediments. Coupled nitrification–denitrification was the dominant denitrification pathway in September, with higher overlying water nitrate concentrations in March resulting in denitrification driven by nitrate flux into the sediments. Estimated benthic microalgal productivity was variable and surprisingly high in Delta sediments and may represent a major source of labile carbon to this ecosystem. Variable N/P stoichiometry was observed in these sediments, with deviations from Redfield driven by processes such as denitrification, variable light/dark uptake of nutrients by microalgae, and adsorption of soluble reactive phosphorus.     

Characterization of high molecular weight biomarkers in crude oils

High-temperature gas chromatography (HTGC) has enhanced our ability to characterize hydrocarbons extending to C₁₂₀ in crude oils. As a result, hydrocarbons in waxes (> C₂₀) have been observed to vary significantly between crude oils, even those presumed to originate from the same source. Prior to this development, microcrystalline waxes containing hydrocarbons above C₄₀ were not characterized on a molecular level due to the analytical limitations of conventional gas chromatography. Routine screenings of high pour-point crude oils by high-temperature gas chromatography has revealed that high molecular weight hydrocarbons (> C₄₀) are very common in most oils and may represent 2% of the crude oil. Precise structures, origins, and significance of these high molecular weight compounds remain elusive. As a preliminary step to expand our knowledge of these compounds their general molecular structures and formulas have been investigated in this study. Initial results suggest that the major high molecular weight compounds include a homologous series of n-alkanes, methylbranched alkanes, alkylcyclopentanes, alkylcyclohexanes, alkylbenzenes and alkylcycloalkanes.     

Another Year of Record Heat for the Oceans

Changes in ocean heat content(OHC), salinity, and stratification provide critical indicators for changes in Earth’s energy and water cycles. These cycles have been profoundly altered due to the emission of greenhouse gasses and other anthropogenic substances by human activities, driving pervasive changes in Earth’s climate system. In 2022, the world’s oceans, as given by OHC, were again the hottest in the historical record and exceeded the previous 2021 record maximum.According to IAP/CAS data, ...     

Conventional and combined pump-and-treat systems under nonuniform background flow

We investigate the performance of vertical hydraulic barriers in combination with extraction wells for the partial hydraulic isolation of contaminated aquifer areas. The potential advantage of such combinations compared to a conventional pump-and-treat system has already been demonstrated in a previous study. Here we extend the scope of the performance analysis to the impact of uncertainty in the regional flow direction as well as to highly heterogeneous aquifer transmissivity distributions. In addition, two new well-barrier scenarios are proposed and analyzed. The hydraulic efficiency of the scenarios is rated based on the expected (mean) reduction of the pumping rate that is required to achieve downgradient contaminant capture. The uncertain spatial distribution of aquifer transmissivity is considered by means of unconditioned Monte Carlo simulations. The significance of uncertain background flow conditions is incorporated by computing minimized pumping rates for deviations of the regional flow direction up to 30 degrees from a normative base case. The results give an answer on how pumping rates have to be changed for each barrier-well combination in order to achieve robust systems. It is exposed that in comparison to installing exclusively wells, the barrier-supported approach generally yields savings in the (average) pumping rate. The particular efficiency is shown to be highly dependent on the interaction of variance and integral scale of transmissivity distribution, well and barrier position, as well as direction of background flow.