The Development of Laser Ablation ICP-MS and Calibration Strategies: Examples from the Analysis of Trace Elements in Volcanic Glass Shards and Sulfide Minerals

This contribution presents a review of the recent developments in laser ablation inductively coupled plasma-mass spectrometry. We describe the important developments which have occurred in the laser systems used, leading to a spatial resolution of around 20 (im, and give an overview of the major instrument developments which have affected the geological applications of laser ablation ICP-MS. We describe the calibration of laser ablation for the analysis of trace elements in two different matrices: volcanic glass shards and sulfide minerals. We show how single glass shards can be analysed using the National Institute of Standards and Technology (NIST) glass certified reference materials for calibration and demonstrate the effect of using single spot analyses compared to rastering of the calibration sample. We show the importance of inter-shard variation and demonstrate that averaged single shard analyses produce data which compare well with bulk analyses. The calibration of the laser system for sulfide mineral analysis is discussed and two different strategies are proposed, one using spiked pressed powder pellets of sulfides and the other metal reference materials. We present conclusions and recommendations for the calibration of laser ablation ICP-MS instruments.     

Sublethal Effects of Crude Oil on the Community Structure of Estuarine Phytoplankton

While the ecological impacts of crude oil exposure have been widely studied, its sublethal effects on phytoplankton community structure in salt marsh estuaries have not been well documented. The purpose of this study was to simulate oil spill conditions using a microcosm design to examine short-term (2 day) changes in phytoplankton community composition and total biomass following exposure to crude oil obtained from the Deepwater Horizon oil spill and a mixture of Texas crude oils. Microcosm experiments were performed in situ in North Inlet Estuary near Georgetown, SC. A control and six replicated experimental treatments of crude oil additions at final concentrations of 10, 50, or 100 μl l⁻¹ of either Deepwater Horizon spill oil or the Texas crude mixture were incubated under in situ conditions. Photopigments were analyzed using high-performance liquid chromatography and community composition was determined using ChemTax. Total phytoplankton biomass (as chl a) declined with increasing crude oil concentrations. Prasinophytes, the most abundant microalga in both experiments, showed no response to oil exposure in one experiment and a significant negative response in the other. Diatoms euglenophytes and chlorophytes appeared relatively resistant to oil contamination at the exposure levels used in this study, maintaining or increasing their relative abundance with increasing oil concentrations. Chlorophytes and cyanobacteria increased in relative abundance while cryptophyte abundance decreased with increasing oil concentrations. The results of these experiments suggest that low levels of crude oil exposure may reduce total biomass and alter phytoplankton community composition with possible cascade effects at higher trophic levels in salt marsh estuaries.     

Groundwater-level response to land-use change and the implications for salinity management in the West Moorabool River catchment, Victoria, Australia

The connection between the removal of native vegetation, rising water tables and increasing stream salinity has been established for many catchments across Australia. However, the West Moorabool River in south west Victoria is an example of a catchment where there has been little discernable effect on groundwater levels following land clearing. Over the past 150 years, a significant portion of the catchment has been cleared of dense forest for agricultural development. Historic standing water-level records from 1870–1871 and 1881 are compared with contemporary measurements (1970s to 2007) recorded in the government bore databases. The data show that the earliest recorded groundwater levels are well within the seasonal range of values observed today. By integrating geology and hydrogeology with historical observations of groundwater levels, climate data and land use, the contemporary field observations of stream salinity are linked to the changed water use and shift in rainfall. In contrast to the normally accepted axiom, reafforestation as a management strategy to mitigate the rising salinity in the West Moorabool River catchment would seem inappropriate.     

Polycyclic aromatic hydrocarbon concentrations in urban soils representing different land use categories in Shanghai

An extensive soil survey was carried out in Shanghai to investigate the spatial distribution and possible sources of polycyclic aromatic hydrocarbons (PAHs) in urban soils. Soil samples were collected from highways, iron-smelting plants, steel-smelting plants, shipbuilding yards, coking plants, power plants, chemical plants, urban parks, university campuses and residential areas and were analyzed for 16 PAHs by gas chromatography with mass detection. High PAH concentrations were found in all locations investigated, with mean values of soil total PAH concentrations in the range 3,279–38,868 μg/kg DM, and the PAH concentrations were significantly influenced by soil organic matter content. Soil PAH profiles in all districts were dominated by PAHs with 4–6 rings. Principal components analysis and diagnostic ratios of PAHs indicate that they were mainly derived from coal combustion and petroleum but in soils from highways the PAHs were derived largely from vehicle exhaust emissions. The high concentrations of PAHs found indicate that many urban soils in Shanghai represent a potential hazard to public health.     

Refractory metal nuggets within presolar graphite: First condensates from a circumstellar environment

Transmission electron microscope (TEM) investigations have revealed Os, Ru, Mo‐rich refractory metal nuggets within four different presolar graphites, from both the high‐density (HD) Murchison (MUR) and low‐density (LD) Orgueil (ORG) fractions. Microstructural and chemical data suggest that these are direct condensates from the gas, rather than forming later by exsolution. The presolar refractory metal nugget (pRMN) compositions are variable (e.g., from 8 < Os atom% < 77), but follow the same chemical fractionation trends as isolated refractory metal nuggets (mRMNs) previously found in meteorites (Berg et al. 2009). From these compositions one can infer a temperature of last equilibration with the gas of 1405–1810 K (e.g., Berg et al. 2009 at approximately 100 dyne cm^?2 pressure), which implies that the host graphites form over roughly the same range (in agreement with predictions) and that the pRMNs are chemically isolated from the gas when captured by graphite. Further, the pRMN compositions give evidence that HD graphites form at a higher T than LD ones. Chemical and phase similarities with the isolated mRMNs suggest that the mRMNs also condense directly from a gas, although from the early solar nebula rather than a presolar environment. Although the pRMNs themselves are too small for detection of isotopic anomalies, NanoSIMS isotopic measurements of their host graphites confirm a presolar origin for the assemblages. The two pRMN‐containing LD graphites show evidence of a supernova (SN) origin, whereas the stellar origins of the pRMNs in HD graphite are unclear, because only less‐diagnostic ¹²C enrichments are detectable (as is commonly true for HD graphites).     

The characteristics of the seismic signals induced by landslides using a coupling of discrete element and finite difference methods

Landslide seismic signals support researchers to estimate magnitudes and locations of landslides. They can serve as a crucial data for landslide warning systems. However, the randomness of landslide locations makes the acquisition of landslide-induced seismic signals difficult and limits the number of available field data. The objectives of this study are to establish a numerical modeling approach to examine the characteristics of seismic signals induced by landslides and perform parametrical study. The two-dimensional particle flow code (PFC) and Fast Lagrangian Analysis of Continua (FLAC) are coupled to simulate the landslide process. The force and velocity data at the coupled interfaces of FLAC and PFC are transferred back and forth via a Socket I/O connection. Four locations were monitored for the induced vertical seismic signals, including velocity, acceleration, and stress histories. The signals were analyzed by Hilbert-Huang transform to obtain the time-frequency spectrograms for examining the characteristics of the signals. The particle size, wall friction, particle friction, and parallel bond of PFC input parameters were parametrically investigated. The Xiaolin landslide in 2009 was successfully simulated, and the characteristics of the seismic signals were studied and compared with the data from a broadband seismic station. These results demonstrate that terrain and transition in the movement type of a complex landslide do influence the seismic signals. A landslide with larger rock particles generates lower-frequency content seismic signals. Also, there can be approximately 40 s to escape before a large-scale landslide hits if seismic instrumentation is installed. The method proposed can be further applied for studies on many other large-scale rock avalanches to verify recorded signals and further correlate the signals with the landslide characteristics.     

A double-differenced cycle slip detection and repair method for GNSS CORS network

The difficulty to detect and repair cycle slip of carrier phase measurements is a key limit for continuously high accuracy of GNSS positioning and navigation services. We propose an automated cycle slip detection and repair method for data preprocessing of a CORS network. The method jointly uses double-differenced (DD) geometry-free (GF) combination and ionospheric-free observation corrected for the computed geometrical distance (IF-OMC) to estimate the cycle slips in dual-frequency observations. The DD GF combination, which is only affected by the ionospheric residual, can be used to detect cycle slips with high reliability except for special pairs such as (77, 60) on GPS L1/L2 frequencies. The detection principle of the IF-OMC observable is such that there is a large discontinuity related to the previous epoch when cycle slips occur at the present epoch. The disadvantages of these two combinations can be overcome employing the proposed detection method. The cycle slip pair (77, 60) has no effect on the GF combination, while a change of 14.65 m is derived from GPS L1/L2 observations using the IF-OMC algorithm. Using pre-determined station coordinates as precise values, we found that the accuracy of the DD IF-OMC combination was 18 mm for a 200-km CORS baseline. Therefore, cycle slips in dual-frequency observations can be correctly and uniquely determined using DD GF and IF-OMC equations. The proposed method was verified by adding simulated cycle slips in observations collected from the CORS network under a quiet ionosphere and shown to be effective. Moreover, the method was assessed with observations made during intense ionospheric activity, which generated extensive cycle slips. The results show that the algorithm can detect and repair all cycle slips apart from two exceptions relating to long data gaps.     

Geochemistry of sedimentary rocks from Permian–Triassic boundary sections of Tethys Himalaya: implications for paleo-weathering,provenance, and tectonic setting

The geochemical characteristics of two sections—the Permian–Triassic boundary (PTB) Guryul Ravine section, Kashmir Valley, Jammu and Kashmir, India; and the Attargoo section, Spiti Valley, Himachal Pradesh, India—have been studied in the context of provenance, paleo-weathering, and plate tectonic setting. These sections represent the siliciclastic sedimentary sequence from the Tethys Himalaya. The PTB siliciclastic sedimentary sequence in these regions primarily consists of sandstones and shales with variable thickness. Present studied sandstones and shales of both sections had chemical index of alteration values between 65 and 74; such values reveal low-to-moderate degree of chemical weathering. The chemical index of weathering in studied samples ranged from 71 to 94, suggesting a minor K-metasomatism effect on these samples. Plagioclase index of alteration in studied sections ranged from 68 to 92, indicating a moderate degree of weathering of plagioclase feldspars. The provenance discriminant function diagram suggests that the detritus involved in the formation of present studied siliciclastic sedimentary rocks fall in quartzose sedimentary and felsic igneous provenances. These sediments were deposited in a passive continental margin plate tectonic setting according to their location on a Si₂O versus K₂O/Na₂O tectonic setting diagram.     

Hydrogeological Zoning of the Central Minusinsk Basin by the Conditions of Formation of Fresh Groundwater Resources

A detailed hydrogeological zoning of the central part of the Minusinsk artesian basin is performed. Local basins confined to smaller plicated structures, as well as hydrogeological massifs of local scale, are recognized within large block structures. Direction of subsurface streams and their role in the formation of groundwater resources and composition are discussed. Forecast resources of fresh groundwater are estimated for every recognized structure.