Trace Element Determination by ICP-AES and ICP-MS: Developments and Applications Reported During 2004 and 2005

This review describes significant developments in trace element determination using inductively coupled plasma-atomic emission spectrometry (ICP-AES) and inductively coupled plasma-mass spectrometry (ICP-MS) that were reported in 2004 and 2005. It focuses on the application of ICP techniques to geological and environmental samples; fundamental studies in ICP-MS and ICP-AES instrumentation are not included. The literature reviewed indicated that the majority of new publications concerned advances in ICP-MS analysis rather than ICP-AES. However, ICP-AES developments are still being published, particularly in the areas of sample preconcentration and sample introduction. The trend in increasing publication of developments in hyphenated speciation techniques looks set to persist as knowledge of elemental speciation becomes critical for many environmental studies. Collision or reactions cells were the most reported technique for spectral interference removal in ICP-MS, probably reflecting the growing adoption of cell instruments in laboratories during the last few years.     

Impact of Carbonate Precipitation on Riverine Inorganic Carbon Mass Transport from a Mid-continent, Forested Watershed

Physiochemical controls on the carbonate geochemistry of large river systems are important regulators of carbon exchange between terrestrial and marine reservoirs on human time scales. Although many studies have focused on large-scale river carbon fluxes, there are few investigations of mechanistic aspects of carbonate mass balance and transport at the catchment scale. We determined elemental and carbonate geochemistry and mass balances for net carbonate dissolution fluxes from the forested, mid-latitude Huron River watershed, established on carbonate-rich unconfined glacial drift aquifers. Shallow groundwaters are near equilibrium with respect to calcite at pCO₂ values up to 25 times atmospheric values. Surface waters are largely groundwater fed and exhibit chemical evolution due to CO₂ degassing, carbonate precipitation in lakes and wetlands, and anthropogenic introduction of road salts (NaCl and CaCl₂). Because the source groundwater Mg²⁺/HCO₃ ^? ratio is fairly constant, this parameter permits mass balances to be made between carbonate dissolution and back precipitation after groundwater discharge. Typically, precipitation does not occur until IAP/K calcite values exceed 10 times supersaturation. Stream chemistry changes little thereafter even though streams remain highly supersaturated for calcite. Our data taken together with historical United States Geological Survey (USGS) data show that alkalinity losses to carbonate precipitation are most significant during periods of lowest discharge. Thus, on an annual basis, the large carbon flux from carbonate dissolution in soil zones is only decreased by a relatively small amount by the back precipitation of calcium carbonate.     

Steppin' in it: postcoloniality in northern Pakistan

This paper examines the transcultural relations between researchers and research subjects in a postcolonial research setting. I draw from my experience doing dissertation research in northern Pakistan to discuss how my research subjects' effectively constructed me as a sahib, or what I saw as a colonial subject position. I examine the ways that my research subjects and I co-constructed, although unequally, my position and location as a researcher. The asymmetries of power relations in research are exacerbated by postcolonial relations in this contact zone. The contribution of those I researched is significant towards understanding our locations as postcolonial subjects in this research setting, and the location from which I produced the research. While it was difficult to do research as anyone other than a sahib during my research, the stories I tell and metaphors I employ in this paper attempt to destabilize my location as a colonial sahib, an authority. The scatological references that run throughout this paper are an attempt to write against the inherently colonial epistemologies that underpin geographic research more generally.     

Trace Element Determination by ICP‐AES and ICP‐MS: Developments and Applications Reported During 2006 and 2007

This review describes developments in trace element determination using inductively coupled plasma‐atomic emission spectrometry (ICP‐AES) and inductively coupled plasma‐mass spectrometry (ICP‐MS) that were reported in 2006 and 2007. It focuses on the application of ICP techniques to geological and environmental samples; fundamental studies in ICP‐MS and ICP‐AES instrumentation have largely been ignored. New advances in ICP‐MS and ICP‐AES were incremental over this period, partly because both techniques are now well‐established. A continuing shift towards the hyphenation of low‐flow separation techniques has sparked activity in the development of appropriate low‐flow interfaces, and papers discussing interference removal also contribute significantly to the volume of research for both ICP‐AES and ICP‐MS. Whereas the majority of new ICP publications concerned advances in ICP‐MS analysis rather than ICP‐AES, development for ICP‐AES still occurs in almost all areas, particularly in sample introduction and hyphenated techniques.     

Herbicide contamination and the potential impact to seagrass meadows in Hervey Bay, Queensland, Australia

Low concentrations of herbicides (up to 70 ng l(-1)), chiefly diuron (up to 50 ng l(-1)) were detected in surface waters associated with inter-tidal seagrass meadows of Zostera muelleri in Hervey Bay, south-east Queensland, Australia. Diuron and atrazine (up to 1.1 ng g(-1) dry weight of sediment) were detected in the sediments of these seagrass meadows. Concentration of the herbicides diuron, simazine and atrazine increased in surface waters associated with seagrass meadows during moderate river flow events indicating herbicides were washed from the catchment to the marine environment. Maximum herbicide concentration (sum of eight herbicides) in the Mary River during a moderate river flow event was 4260 ng l(-1). No photosynthetic stress was detected in seagrass in this study during low river flow. However, with moderate river flow events, nearshore seagrasses are at risk of being exposed to concentrations of herbicides that are known to inhibit photosynthesis.     

GCM Hindcasts of SST Forced Climate Variability over Agriculturally Intensive Regions

The NASA/Goddard Institute for Space Studies (GISS) climatemodel is forced with globally observed sea-surfacetemperatures (SST) in five simulations, 1969–1991,with individual runs beginning from altered initialatmospheric conditions. The interannual variability ofmodeled anomalies of the Southern Oscillation Index,mid-tropospheric temperatures, 850 mb zonal winds andOutgoing Longwave Radiation over the tropical PacificOcean, which has the largest SST anomaly forcing, arestrongly correlated with observed trends which reflectENSO cycles. The model's rainfall variability overthree agriculturally intensive regions, two tropicaland one mid-latitude, is investigated in order toevaluate the potential usefulness of GCM predictionsfor agricultural planning. The correct sign ofZimbabwe seasonal precipitation anomalies was hindcastwithin a useful range of consensus only for selectseasons corresponding to extreme ENSO events for whichanomalous circulation patterns were ratherrealistically simulated. The correlation betweenhindcasts of Nordeste monthly precipitation andobservations increases with time smoothing, reaching0.64 for 5-month running means. Consensus betweenindividual runs is directly proportional to theabsolute value of Niño3 SST so that during ElNiño and La Niña years most simulations agreeon the sign of predicted Nordeste rainfall anomalies.We show that during selected seasons the uppertropospheric divergent circulation and near surfacemeridional displacements of the ITCZ are realisticallyrepresented by the ensemble mean of the simulations.This realistic simulation of both the synopticmechanisms and the resulting precipitation changesincreases confidence in the GCM's potential forseasonal climate prediction.     

Solubility and solution mechanisms of C-O-H volatiles in silicate melt with variable redox conditions and melt composition at upper mantle temperatures and pressures

Solubility and solution mechanisms in silicate melts of oxidized and reduced C-bearing species in the C-O-H system have been determined experimentally at 1.5 GPa and 1400 °C with mass spectrometric, NMR, and Raman spectroscopic methods. The hydrogen fugacity, f_H2, was controlled in the range between that of the iron-wüstite-H₂O (IW) and the magnetite-hematite-H₂O (MH) buffers. The melt polymerization varied between those typical of tholeiitic and andesitic melts.The solubility of oxidized (on the order of 1-2 wt% as C) and reduced carbon (on the order of 0.15-0.35 wt% as C) is positively correlated with the NBO/Si (nonbridging oxygen per silicon) of the melt. At given NBO/Si-value, the solubility of oxidized carbon is 2-4 times greater than under reducing conditions. Oxidized carbon dioxide is dissolved as complexes, whereas the dominant reduced species in melts are CH₃-groups forming bonds with Si⁴⁺ together with molecular CH₄. Formation of complexes results in silicate melt polymerization (decreasing NBO/Si), whereas solution of reduced carbon results in depolymerization of melts (increasing NBO/Si).Redox melting in the Earth’s interior has been explained with the aid of the different solution mechanisms of oxidized and reduced carbon in silicate melts. Further, effects of oxidized and reduced carbon on melt viscosity and on element partitioning between melts and minerals have been evaluated from relationships between melt polymerization and dissolved carbon combined with existing experimental data that link melt properties and melt polymerization. With total carbon contents in the melts on the order of several mol%, mineral/melt element partition coefficients and melt viscosity can change by several tens to several hundred percent with variable redox conditions in the range of the Earth’s deep crust and upper mantle.     

Ferruginous thermal spring complexes, northwest Tasmania: evidence that far-field stresses acting on a fracture mesh can open and maintain vertical flow in carbonate terrains

Far-field stress changes in the southern Australian plate since 5 Ma have produced significant areas of uplift and seismicity. In northwest Tasmania, there is evidence that this stress reorientation to maximum horizontal NW?CSE stress has influenced meteoric-derived thermal (15?C20°C) discharge patterns of confined karstic aquifers, by placing pre-existing NW-trending faults/fractures into a dilated state or a critically stressed state. Previous studies have shown that spring discharge has operated continuously for at least 65,000 years, and has transported large volumes of solutes to the surface to be deposited as mounds of calcite-goethite-silica up to 7 m high. The thermal spring chemistry at one site, Mella, is consistent with descent to at least 1.2?C1.5 km, although the hinterland within 50 km is less than 500 m elevation. Thermal spring chemistry is consistent with most of the deep water?Crock interaction occurring in low-strontium Smithton Dolomite. While some of this water is discharged at springs, some instead intersects shallow zones of NE-fracture-controlled rock (2?×?4 km in area) with karstic permeability where, although confined and subject to a NE-directed hydraulic gradient, it circulates and cools to ambient temperature, with only minor mixing with other groundwaters.     

Sources of Terrestrial Organic Carbon in the Mississippi Plume Region: Evidence for the Importance of Coastal Marsh Inputs

High sedimentation rates along river-dominated margins make these systems important repositories for organic carbon derived from both allochthonous and autochthonous sources. Using elemental carbon/nitrogen ratios, molecular biomarker (lignin phenol), and stable carbon isotopic (bulk and compound-specific) analyses, this study examined the sources of organic carbon to the Louisiana shelf within one of the primary dispersive pathways of the Mississippi River. Surface sediment samples were collected from stations across the inner, mid, and outer Louisiana shelf, within the Mississippi River plume region, during two cruises in the spring and fall of 2000. Lignin biomarker data showed spatial patterns in terrestrial source plant materials within the river plume, such that sediments near the mouth of the Mississippi River were comparatively less degraded and richer in C₄ plant carbon than those found at mid-depth regions of the shelf. A molecular and stable isotope-based mixing model defining riverine, marsh, and marine organic carbon suggested that the highest organic carbon inputs to the shelf in spring were from marine sources (55?C61% marine organic carbon), while riverine organic carbon was the highest (63%) in fall, likely due to lower inputs of marine organic carbon at this time compared with the spring season. This model also indicated that marsh inputs, ranging from 19 to 34% and 3?C15% of the organic carbon in spring and fall, respectively, were significantly more important sources of organic carbon on the inner Louisiana shelf than previously suggested. Finally, we propose that the decomposition of terrestrial-derived organic carbon (from the river and local wetlands sources) in mobile muds may serve as a largely unexplored additional source of oxygen-consuming organic carbon in hypoxic bottom waters of the Louisiana shelf.