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A. Kolker

Publications and source records attributed to A. Kolker.

13 recordsLinked to original sources
USGS2010

Patterns of mercury dispersion from local and regional emission sources, rural Central Wisconsin, USA

Simultaneous real-time changes in mercury (Hg) speciation-reactive gaseous Hg (RGM), elemental Hg (Hg??), and fine particulate Hg (Hg-PM 2.5 ), were determined from June to November 2007, in ambient air at three locations in rural Central Wisconsin. Known Hg emission sources within the airshed of the monitoring sites include: 1) a 1114 megawatt (MW) coal-fired electric utility generating station; 2) a Hg-bed chlor-alkali plant; and 3) a smaller (465 MW) coal-burning electric utility. Monitoring sites, showing sporadic elevation of RGM, Hg o and Hg-PM 2.5 , were positioned at distances of 25, 50 and 100 km northward of the larger electric utility. A series of RGM events were recorded at each site. The largest, on 23 September, occurred under prevailing southerly winds, with a maximum RGM value (56.8 pg m -3 ) measured at the 100 km site, and corresponding elevated SO 2 (10.41 ppbv; measured at 50 km site). The finding that RGM, Hg o , and Hg-PM 2.5 are not always highest at the 25 km site, closest to the large generating station, contradicts the idea that RGM decreases with distance from a large point source. This may be explained if: 1) the 100 km site was influenced by emissions from the chlor-alkali facility or by RGM from regional urban sources; 2) the emission stack height of the larger power plant promoted plume transport at an elevation where the Hg is carried over the closest site; or 3) RGM was being generated in the plume through oxidation of Hg o . Operational changes at each emitter since 2007 should reduce their Hg output, potentially allowing quantification of the environmental benefit in future studies.

Atmospheric Chemistry and Physics Discussions↗
USGS2009

Mercury and trace element contents of Donbas coals and associated mine water in the vicinity of Donetsk, Ukraine

Mercury-rich coals in the Donets Basin (Donbas region) of Ukraine were sampled in active underground mines to assess the levels of potentially harmful elements and the potential for dispersion of metals through use of this coal. For 29 samples representing c 11 to m 3 Carboniferous coals, mercury contents range from 0.02 to 3.5 ppm (whole-coal dry basis). Mercury is well correlated with pyritic sulfur (0.01 to 3.2 wt.%), with an r 2 of 0.614 (one outlier excluded). Sulfides in these samples show enrichment of minor constituents in late-stage pyrite formed as a result of interaction of coal with hydrothermal fluids. Mine water sampled at depth and at surface collection points does not show enrichment of trace metals at harmful levels, indicating pyrite stability at subsurface conditions. Four samples of coal exposed in the defunct open-cast Nikitovka mercury mines in Gorlovka have extreme mercury contents of 12.8 to 25.5 ppm. This coal was formerly produced as a byproduct of extracting sandstone-hosted cinnabar ore. Access to these workings is unrestricted and small amounts of extreme mercury-rich coal are collected for domestic use, posing a limited human health hazard. More widespread hazards are posed by the abandoned Nikitovka mercury processing plant, the extensive mercury mine tailings, and mercury enrichment of soils extending into residential areas of Gorlovka.

Donbas mines↗
USGS2008

Mercury, trace elements and organic constituents in atmospheric fine particulate matter, Shenandoah National Park, Virginia, USA: A combined approach to sampling and analysis

Compliance with U.S. air quality regulatory standards for atmospheric fine particulate matter (PM 2.5 ) is based on meeting average 24 hour (35 μ m −3 ) and yearly (15 μg m −3 ) mass‐per‐unit‐volume limits, regardless of PM 2.5 composition. Whereas this presents a workable regulatory framework, information on particle composition is needed to assess the fate and transport of PM 2.5 and determine potential environmental/human health impacts. To address these important non‐regulatory issues an integrated approach is generally used that includes (1) field sampling of atmospheric particulate matter on filter media, using a size‐limiting cyclone, or with no particle‐size limitation; and (2) chemical extraction of exposed filters and analysis of separate particulate‐bound fractions for total mercury, trace elements and organic constituents, utilising different USGS laboratories optimised for quantitative analysis of these substances. This combination of sampling and analysis allowed for a more detailed interpretation of PM 2.5 sources and potential effects, compared to measurements of PM 2.5 abundance alone. Results obtained using this combined approach are presented for a 2006 air sampling campaign in Shenandoah National Park (Virginia, USA) to assess sources of atmospheric contaminants and their potential impact on air quality in the Park. PM 2.5 was collected at two sampling sites (Big Meadows and Pinnacles) separated by 13.6 km. At both sites, element concentrations in PM 25 were low, consistent with remote or rural locations. However, element/Zr crustal abundance enrichment factors greater than 10, indicating anthropogenic input, were found for Hg, Se, S, Sb, Cd, Pb, Mo, Zn and Cu, listed in decreasing order of enrichment. Principal component analysis showed that four element associations accounted for 84% of the PM 2.5 trace element variation; these associations are interpreted to represent: (1) crustal sources (Al, REE); (2) coal combustion (Se, Sb), (3) metal production and/or mobile sources (Mo, Cd, Pb, Cu, Zn) and (4) a transient marine source (Sr, Mg). Concentrations of Hg in PM 2.5 at background levels in the single pg m −3 were shown by collection and analysis of PM 2.5 on filters and by an automated speciation analyser set up at the Big Meadows air quality site. The speciation unit revealed periodic elevation of reactive gaseous mercury (RGM) that co‐occurred with peaks in SO 2 , indicating an anthropogenic source. GC/MS total ion current chromatograms for the two sites were quite similar indicating that organic signatures were regional in extent and/or that the same compounds were present locally at each site. Calculated carbon preference index values for n ‐alkanes indicated that plant waxes rather than anthropogenic sources, were the dominant alkane source. Polycyclic aromatic hydrocarbons (PAHs) were detected, with a predominance of non‐alkylated, and higher molecular weight PAHs in this fraction, suggestive of a combustion source (fossil fuel or forest fires).

Virginia↗
USGS2008

Characterization and cycling of atmospheric mercury along the central US Gulf Coast

Concentrations of atmospheric Hg species, elemental Hg (Hg ∘ ), reactive gaseous Hg (RGM), and fine particulate Hg (Hg-PM 2.5 ) were measured at a coastal site near Weeks Bay, Alabama from April to August, 2005 and January to May, 2006. Mean concentrations of the species were 1.6 ± 0.3 ng m −3 , 4.0 ± 7.5 pg m −3 and 2.7 ± 3.4 pg m −3 , respectively. A strong diel pattern was observed for RGM (midday maximum concentrations were up to 92.7 pg m −3 ), but not for Hg ∘ or Hg-PM 2.5 . Elevated RGM concentrations (>25 pg m −3 ) in April and May of 2005 correlated with elevated average daytime O 3 concentrations (>55 ppbv) and high light intensity (>500 W m −2 ). These conditions generally corresponded with mixed continental-Gulf and exclusively continental air mass trajectories. Generally lower, but still elevated, RGM peaks observed in August, 2005 and January–March, 2006 correlated significantly ( p < 0.05) with peaks in SO 2 concentration and corresponded to periods of high light intensity and lower average daytime O 3 concentrations. During these times air masses were dominated by trajectories that originated over the continent. Elevated RGM concentrations likely resulted from photochemical oxidation of Hg ∘ by atmospheric oxidants. This process may have been enhanced in and by the near-shore environment relative to inland sites. The marine boundary layer itself was not found to be a significant source of RGM. Size segregation determination, using a limited dataset from two different methods, suggested that a significant fraction of particulate Hg was bound to coarse particles (>2.5 μm). A potential source of the large fraction of coarse particulate Hg in the study area is sequestration of RGM within sea salt aerosols. The presence of rapidly depositing RGM and coarse particulate Hg may be important sources of Hg input along the Gulf Coast. However, the impact of these species on deposition rates is yet to be determined.

Applied Geochemistry↗
USGS2008

Biomarkers of mercury exposure at a mercury recycling facility in Ukraine

This study evaluates biomarkers of occupational mercury exposure among workers at a mercury recycling operation in Gorlovka, Ukraine. The 29 study participants were divided into three occupational categories for analysis: (1) those who worked in the mercury recycling operation (Group A, n = 8), (2) those who worked at the facility but not in the yard where the recycling was done (Group B, n = 14), and (3) those who did not work at the facility (Group C, n = 7). Urine, blood, hair, and nail samples were collected from the participants, and a questionnaire was administered to obtain data on age, gender, occupational history, smoking, alcohol consumption, fish consumption, tattoos, dental amalgams, home heating system, education, source of drinking water, and family employment in the former mercury mine/smelter located on the site of the recycling facility. Each factor was tested in a univariate regression with total mercury in urine, blood, hair, and nails. Median biomarker concentrations were 4.04 μg/g-Cr (urine), 2.58 μg/L (blood), 3.95 μg/g (hair), and 1.16 μg/g (nails). Occupational category was significantly correlated (p < 0.001) with both blood and urinary mercury concentrations but not with hair or nail mercury. Four individuals had urinary mercury concentrations in a range previously found to be associated with subtle neurological and subjective symptoms (e.g., fatigue, loss of appetite, irritability), and one worker had a urinary mercury concentration in a range associated with a high probability of neurological effects and proteinuria. Comparison of results by occupational category found that workers directly involved with the recycling operation had the highest blood and urinary mercury levels. Those who worked at the facility but were not directly involved with the recycling operation had higher levels than those who did not work at the facility.

Journal of Occupational and Environmental Hygiene↗
USGS2001

Determination of element affinities by density fractionation of bulk coal samples

A review has been made of the various methods of determining major and trace element affinities for different phases, both mineral and organic in coals, citing their various strengths and weaknesses. These include mathematical deconvolution of chemical analyses, direct microanalysis, sequential extraction procedures and density fractionation. A new methodology combining density fractionation with mathematical deconvolution of chemical analyses of whole coals and their density fractions has been evaluated. These coals formed part of the IEA-Coal Research project on the Modes of Occurrence of Trace Elements in Coal. Results were compared to a previously reported sequential extraction methodology and showed good agreement for most elements. For particular elements (Be, Mo, Cu, Se and REEs) in specific coals where disagreement was found, it was concluded that the occurrence of rare trace element bearing phases may account for the discrepancy, and modifications to the general procedure must be made to account for these.

Fuel↗
USGS2000

Mode of occurrence of chromium in four US coals

The mode of occurrence of chromium in three US bituminous coals and one US subbituminous has been examined using both X-ray absorption fine structure (XAFS) spectroscopy and a selective leaching protocol supplemented by scanning electron microscopy (SEM) and electron microprobe measurements. A synthesis of results from both methods indicates that chromium occurs principally in two forms in the bituminous coals: the major occurrence of chromium is associated with the macerals and is not readily leached by any reagent, whereas a second, lesser occurrence, which is leachable in hydrofluoric acid (HF), is associated with the clay mineral, illite. The former occurrence is believed to be a small particle oxyhydroxide phase (CrO(OH)). One coal also contained a small fraction (<5%) of the chromium in the form of a chromian magnetite, and the leaching protocol indicated the possibility of a similar small fraction of chromium in sulfide form in all three coals. There was little agreement between the two techniques on the mode of occurrence of chromium in the subbituminous coal; however, only a limited number of subbituminous coals have been analyzed by either technique. The chromium in all four coals was trivalent as no evidence was found for the Cr6+ oxidation state in any coal.

Fuel Processing Technology↗
USGS2000

Mode of occurrence of arsenic in four US coals

An integrated analytical approach has been used to determine the mode of occurrence of arsenic in samples of four widely used US coals: the Pittsburgh, Illinois #6, Elkhorn/Hazard, and Wyodak. Results from selective leaching, X-ray absorption fine structure (XAFS) spectroscopy, and electron microprobe analysis show that pyrite is the principal source of arsenic in the three bituminous coals, but the concentration of As in pyrite varies widely. The Wyodak sample contains very little pyrite; its arsenic appears to be primarily associated with organics, as As3+, or as arsenate. Significant (10-40%) fractions of arsenate, derived from pyrite oxidation, are also present in the three bituminous coal samples. This information is essential in developing predictive models for arsenic behavior during coal combustion and in other environmental settings.

Fuel Processing Technology↗
USGS2000

Distribution of trace elements in selected pulverized coals as a function of particle size and density

Trace elements in coal have diverse modes of occurrence that will greatly influence their behavior in many coal utilization processes. Mode of occurrence is important in determining the partitioning during coal cleaning by conventional processes, the susceptibility to oxidation upon exposure to air, as well as the changes in physical properties upon heating. In this study, three complementary methods were used to determine the concentrations and chemical states of trace elements in pulverized samples of four US coals: Pittsburgh, Illinois No. 6, Elkhorn and Hazard, and Wyodak coals. Neutron Activation Analysis (NAA) was used to measure the absolute concentration of elements in the parent coals and in the size- and density-fractionated samples. Chemical leaching and X-ray absorption fine structure (XAFS) spectroscopy were used to provide information on the form of occurrence of an element in the parent coals. The composition differences between size-segregated coal samples of different density mainly reflect the large density difference between minerals, especially pyrite, and the organic portion of the coal. The heavy density fractions are therefore enriched in pyrite and the elements associated with pyrite, as also shown by the leaching and XAFS methods. Nearly all the As is associated with pyrite in the three bituminous coals studied. The sub-bituminous coal has a very low content of pyrite and arsenic; in this coal arsenic appears to be primarily organically associated. Selenium is mainly associated with pyrite in the bituminous coal samples. In two bituminous coal samples, zinc is mostly in the form of ZnS or associated with pyrite, whereas it appears to be associated with other minerals in the other two coals. Zinc is also the only trace element studied that is significantly more concentrated in the smaller (45 to 63 ??m) coal particles.

Fuel Processing Technology↗
USGS2000

Stanford-USGS shrimp-RG ion microprobe: A new approach to determining the distribution of trace elements in coal

The distribution of Cr and other trace metals of environmental interest in a range of widely used U.S. coals was investigated using the Stanford-USGS SHRIMP-RG ion microprobe . Using the oxygen ion source, concentrations of Cr (11 to 176 ppm), V (23 to 248 ppm), Mn (2 to 149 ppm), Ni (2 to 30 ppm), and 13 other elements were determined in illite/smectite, a group of clay minerals commonly present in coal. The results confirm previous indirect or semi-quantitative determinations indicating illite/smectite to be an important host of these metals. Calibration was achieved using doped aluminosilicate-glass synthetic standards and glasses prepared from USGS rock standards. Grains for analysis were identified optically, and confirmed by 1) precursory electron microprobe analysis and wavelength-dispersive compositional mapping, and 2) SHRIMP-RG major element data obtained concurrently with trace element results. Follow-up investigations will focus on the distribution of As and other elements that are more effectively ionized with the cesium primary beam currently being tested.

ACS Division of Fuel Chemistry, Preprints↗
USGS2000

Direct comparison of XAFS spectroscopy and sequential extraction for arsenic speciation in coal

The speciation of arsenic in an Ohio bituminous coal and a North Dakota lignite has been examined by the complementary methods of arsenic XAFS spectroscopy and sequential extraction by aqueous solutions of ammonium acetate, HCl, HF, and HNO3. In order to facilitate a more direct comparison of the two methods, the arsenic XAFS spectra were obtained from aliquots of the coal prepared after each stage of the leaching procedure. For the aliquots, approximately linear correlations (r2 > 0.98 for the Ohio coal, > 0.90 for the ND lignite) were observed between the height of the edge-step in the XAFS analysis and the concentration of arsenic measured by instrumental neutron activation analysis. Results from the leaching sequence indicate that there are two major arsenic forms present in both coals; one is removed by leaching with HCl and the other by HNO3. Whereas the XAFS spectral signatures of the arsenic leached by HCl are compatible with arsenate for both coals, the arsenic leached by HNO3 is identified as arsenic associated with pyrite for the Ohio coal and as an As3+ species for the North Dakota lignite. Minor arsenate forms persist in both coals after the final leaching with nitric acid. The arsenate forms extracted in HCl are believed to be oxidation products derived from the other major arsenic forms upon exposure of the pulverized coals to air.

ACS Division of Fuel Chemistry, Preprints↗
USGS1982

Mineralogy and geochemistry of Fe-Ti oxide and apatite (nelsonite) deposits and evaluation of the liquid immiscibility hypothesis.

Modal mineralogy determined for 32 Fe-Ti oxide and apatite rocks from localities in Virginia, New York, Quebec, Norway, and Sweden largely supports the 2:1 oxide:apatite ratio suggested as a eutectic mixture by Philpotts (1967). A fairly consistent suite of accessory minerals, including biotite, clinoamphibole, spinel, zircon, and sulfides, is present. Some silicate accessory minerals tend to form glomeroporphyritic intergrowths in an equigranular matrix of nelsonite, suggesting that the accessories are xenocrysts that have been trapped in an oxide-apatite liquid. This liquid may represent an extreme case of partitioning of high charge-density cations into a low silica, phosphorus-enriched immiscible melt. Temperature and oxygen fugacity estimates for oxide pairs in nelsonites range from 600 degrees to 1,000 degrees C and 10 (super -20) to 10 (super -11) atm f (sub o 2 ) and bracket an equilibration path that is close to the FMQ buffer curve. Several stages of exsolution are evident in Fe-Ti oxides of some deposits. Nelsonites contain fluorapatite that is enriched in light lanthanides. The occurrence of nelsonite "dikes" in Roseland anorthosite and associated rocks of the Roseland-Piney River district of Virginia is explained by the infilling of fractures with nelsonite liquid that has settled out of an overlying ferrodiorite pluton.

Economic Geology↗