Assessing the Comparability of Ammonium,Nitrate and Sulfate Concentrations Measured by Three Air Quality Monitoring Networks

Airborne fine particulate matter across the United States is monitored by different networks, the three prevalent ones presently being the Clean Air Status and Trend Network (CASTNet), the Interagency Monitoring of PROtected Visual Environment Network (IMPROVE) and the Speciation and Trend Network (STN). If combined, these three networks provide speciated fine particulate data at several hundred locations throughout the United States. Yet, differences in sampling protocols and samples handling may not allow their joint use. With these concerns in mind, the objective of this study is to assess the spatial and temporal comparability of the sulfate, nitrate and ammonium concentrations reported by each of these networks. One of the major differences between networks is the sampling frequency they adopted. While CASTNet measures pollution levels on seven-day integrated samples, STN and IMPROVE data pertain to 24-hour samples collected every three days. STN and IMPROVE data therefore exhibit considerably more short-term variability than their CASTNet counterpart. We show that, despite their apparent incongruity, averaging the data with a window size of four to six weeks is sufficient to remove the effects of differences in sampling frequency and duration and allow meaningful comparison of the signals reported by the three networks of concern. After averaging, all the sulfate and, to a lesser degree, ammonium concentrations reported are fairly similar. Nitrate concentrations, on the other hand, are still divergent. We speculate that this divergence originates from the different types of filters used to collect particulate nitrate. Finally, using a rotated principal component technique (RPCA), we determined the number and the geographical organization of the significant temporal modes of variation (clusters) detected by each network for the three pollutants of interest. For sulfate and ammonium, the clusters’ geographical boundaries established for each network and the modes of variations within each cluster seem to correspond. RPCA erformed on nitrate concentrations revealed that, for the CASTNet and IMPROVE networks, the modes of variation do not correspond to unified geographical regions but are found more sporadically. For STN, the clustered areas are unified and easily delineable. We conclude that the possibility of jointly using the data collected by CASTNet, IMPROVE and STN has to be weighed pollutant by pollutant. While sulfate and ammonium data show some potential for joint use, at this point, combining the nitrate data from these monitoring networks may not be a judicious choice.     

Citizens as sensors: the world of volunteered geography

In recent months there has been an explosion of interest in using the Web to create, assemble, and disseminate geographic information provided voluntarily by individuals. Sites such as Wikimapia and OpenStreetMap are empowering citizens to create a global patchwork of geographic information, while Google Earth and other virtual globes are encouraging volunteers to develop interesting applications using their own data. I review this phenomenon, and examine associated issues: what drives people to do this, how accurate are the results, will they threaten individual privacy, and how can they augment more conventional sources? I compare this new phenomenon to more traditional citizen science and the role of the amateur in geographic observation.     

Mineralogy and chemical composition of the clay fraction of Neogene shales from the Surma Group in the Bengal basin,Bangladesh

Mineralogical and chemical investigations (<2μm clay separates) of shale samples from the Neogene-age Surma Group obtained from four wells (Habiganj-11, Shahbazpur-1, Titas-11, Titas-15) in the Bengal basin, Bangladesh, were carried out in order to reveal the clay mineral composition as reservoir exploration and exploitation requires a good understanding of the clay minerals. The samples were analyzed by X-ray diffraction (XRD), scanning electron microscope (SEM) and X-Ray fluorescence spectrometry (XRF). Mineralogically, the sub-surface Surma Group shales comprise predominantly quartz, plagioclase, illite, chlorite, kaolinite, with lesser amounts of K-feldspar, dolomite and smectite, and minor to trace amounts of calcite, siderite and pyrite. The chemical composition of the <2 μm clay separates also suggests an illite and chlorite-rich composition. With increasing burial depth, the Surma Group shales are enriched in illite. The gradual decreasing of the smectite clays with depth and ultimate disappearance at greater depths (≥ 3000 m) may have been responsible for the presence of the diagenetic illite. Based on the mineralogical composition it is most likely that the illite-chlorite associations together with quartz and feldspar were predominantly detrital in origin and thus reflect the presence of a rapidly-rising source terrain not subjected to intense weathering.     

The effects of soil sand contents on characteristics of humic acids along soil profiles

It is generally accepted that the compositions and properties of soil organic matter (SOM) are influenced by many factors. In order to reveal the effects of soil texture on characteristics and dynamics of SOM and its sub-fraction, humic acid (HA), along two soil profiles, a yellow soil profile and a purplish soil profile, under the same climate and vegetation conditions were determined. Results indicate that the decomposition and humification degrees of SOM and HA of the purplish soils are higher than those of the corresponding yellow soils indicated by A/O–A ratios of HAs, TOCs and HA yields of bulk soil samples, nevertheless, the development degree of the purplish soil is lower than that of the yellow soil. The variations of E₄/E₆ ratios of HAs along the soil profiles indicate the overall molecular sizes of HAs decreased downward along the soil profiles. A/O–A ratios of HAs decreased downward along both the soil profiles indicate that humification processes decrease downward along both the soil profiles. Leaching of SOM shows significant effects on the distribution and characteristics of HAs in the yellow soil profile but the purplish soil profile, which is consistent with the higher hydrophobicity of HAs in purplish soils, shows that the distribution characteristics of SOM along the soil profiles are a complex result of the combination of soil texture and characteristics of SOM itself. The remarkably different sand contents are concluded tentatively as one of reasons to the different distributions and dynamics of HAs along the soil profiles, however, to profoundly understand the evolution and transport of SOM along soil profiles needs more researches.     

Emplacement age and thermal footprint of the diamondiferous Ellendale E9 lamproite pipe, Western Australia

The diamondiferous Ellendale 9 (E9) pipe is a funnel-shaped maar-diatreme volcano consisting of inward-dipping tuff sequences intruded by lamproite plugs and dykes. The host rocks for the E9 pipe are Permian sandstones. The multiple lithological contacts exposed within the mined maar volcano provide a natural laboratory in which to study the effect of volcanic processes on U–Th–Pb–He systematics. Zircon from the regional sandstone and E9 lamproite display a bimodal distribution of ages on (U–Th)/He–U/Pb plots. The zircon U/Pb ages for the E9 pipe (n?=?52) range from 440 to 2,725 Ma, while the cluster of (U–Th)/He ages for the lamproite dyke zircon indicate that dyke emplacement occurred at 20.6?±?2.8 Ma, concordant with a maximum emplacement age of about ≤22 Ma from phlogopite ⁴⁰Ar/³⁹Ar. These ages indicate a xenocrystic origin for the zircon entrained in the E9 dyke. The U/Pb ages of detrital zircon from the regional sandstone host (373–3,248 Ma; n?=?41) are indistinguishable from those of the lamproite zircon xenocrysts, whereas the detrital zircon in the host sandstone yield (U–Th)/He ages from 260 to 1,500 Ma. A thermochronology traverse across the E9 lamproite dyke reveals that the zircon (U–Th)/He ages in the host sandstone have not been significantly thermally reset during dyke emplacement, even at the contact. The capability of the zircon (U–Th)/He method to distinguish deep, mantle source lithologies from upper crustal source lithologies could be used in geochemical exploration for diamonds. Pre-screening of detrital samples using etching and helium assay methods will improve the efficiency and decrease the cost of greenfields exploration.     

The effect of annealing on the luminescence decay-time of synthetic calcite:Mn

Calcite was synthesized by four methods, and the luminescence decay-time was measured for nine samples before and after heating hydrothermally in the temperature range 200–400°C. Decay-time data were collected between room temperature and approximately 15 K. The decay time at room temperature is approximately 50 ms, with little difference between a given calcite before and after hydrothermal treatment. The decay time at 15 K is always greater than at room temperature as the effect of thermal quenching diminishes. Differences in decay time before and after heating are more apparent at low temperature owing to this reduction in thermal quenching. The decay time decreased significantly in two samples, and an increase in decay time was observed in the remaining seven samples following heating. Among the latter group, the change in decay time was insignificant in three samples. The results are compared with previous data in which it was shown that the effect of heating is to increase the intensity of luminescence.     

Iron isotopic analyses of geological reference materials on MC-ICP-MS with instrumental mass bias corrected by three independent methods

Here we report iron (Fe) isotopic data of three pure Fe solution standards (IRMM-014, GSB Fe, and NIST 3126a) and five widely used geological reference materials (RMs) from the United States Geological Survey and Geological Survey of Japan obtained on a Neptune Plus multi-collector–inductively coupled plasma–mass spectrometer (MC-ICP-MS) in our laboratory over the past 3 years. The instrumental mass bias was corrected by three independent methods: sample-standard bracketing (SSB), Ni doping?+?SSB, and ⁵⁷Fe–⁵⁸Fe double spike?+?SSB. Measurements reveal that both the Ni doping and double spike methods helped calibrate short-term fluctuations in mass bias. Collectively, almost all measurements of RMs yielded δ⁵⁶Fe within?±?0.05 of recommended values, provided that each sample was measured four times on MC-ICP-MS. For the first time, new recommended values for NIST SRM3126a are reported (δ⁵⁶Fe?=?0.363?±?0.006, 2SE, 95% CI; and δ⁵⁷Fe?=?0.534?±?0.010, 2SE).     

Selection of hazardous waste dumpsites based on parameters effecting soil adsorption capacity – a case study

A careful selection of waste dumpsites, particularly hazardous ones, is very important for sustainable water resources management. Several laboratory experiments were carried out on the field samples to study adsorption capacity using p-dichlorobenzene (a solvent used in various industrial processes) as the test contaminant. The effect of parameters such as organic matter, clay, and iron and aluminium oxides, which are known to influence the soil adsorption capacity, are studied in the present work. Several soil samples from the Patancheru Industrial Area (Hyderabad, India) were collected and characterized. Only three soils, which had a comparatively high percentage of organic matter, clay, iron and aluminium oxide contents were used for the adsorption studies. The results clearly indicated a decrease in the adsorption capacity of the soils by as much as 75% when organic matter was removed. The other parameters such as clay and iron and aluminium oxides also play an important role in adsorption (57 and 39.8% reduction respectively). It was observed that out of the selected factors organic matter in the soils has the maximum effect regarding the adsorption of p-dichlorobenzene. Since the selected soils contain comparatively more organic matter, clay and iron and aluminium oxides in the selected industrial area, these can be used as sites for dumping hazardous waste, which can be further treated by methods like bioremediation.     

Effects of natural attenuation processes on groundwater contamination caused by abandoned waste sites in Berlin

The aim of this research project is to identify, characterize and quantify natural attenuation (NA) processes in groundwater affected by emissions of abandoned waste disposal sites in Berlin-Kladow/Gatow, Germany. It is part of the funding priority called KORA established by the Federal Ministry for Education and Research (BMBF) to explore the extent to which NA can be used for remedial purposes for varied forms of soil and groundwater contamination. Information on the emission behaviour of individual parameters is generated on the basis of hydrogeochemical comparison of 20 years old and new data. Using groundwater-modelling and CFC-analysis, information on the transport and retention of pollutants in groundwater is compiled. The microbial colonization of contaminated aquifers is characterized by molecular biological methods [polymerase chain reaction (PCR) and denaturing gradient gel electrophoresis (DGGE)] to differentiate between contaminated and not contaminated zones.     

Chromium speciation in oxide-type compounds: application to minerals,gems, aqueous solutions and silicate glasses

Cr K-edge XANES spectra were obtained for a variety of Cr-bearing model compounds containing Cr(II), Cr(III), Cr(IV), Cr(V) and Cr(VI), in which the Cr-site symmetry is D4h, Oh and Td. The centroid position of the pre-edge feature is a better indicator of the Cr valence than the edge position. In Cr-rich oxides, higher-energy transitions must be excluded in order to refine a robust valence for Cr. The pre-edge for chromates is not unique and varies as a function of the CrO₄ ^2? moiety distortion, which is often related to Cr-polymerization (monochromate vs. dichromate). Both the analogy with the Mn K-pre-edge information and ab initio FEFF calculations of the pre-edge feature for Cr(III) and Cr(VI) confirm the experimental trends. This methodology is applied to the Cr K-edge pre-edge feature collected in gems (emerald, spinel and ruby), the layered minerals fuchsite and kämmererite, two Cr-bearing aqueous solutions and a set of sodo-calcic silicate glasses used for bottling sparkling white wine. In emerald and fuchsite, the Cr-site is differently distorted than its ruby or spinel counterpart. In a Cr(III)-bearing aqueous solution and sodo-calcic glass, no evidence for Cr(III) with Td and C3v symmetry is detected. However, minor amounts of chromate moieties (most likely monomeric) are detected in a glass synthesized in air. Preliminary spectra for the wine bottle glass suggest that only trace amounts of chromates might possibly be present in these glasses.