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Biomedical subjects

Gerald J Keeler

Publications and source records attributed to Gerald J Keeler.

At least 19 recordsLinked to original sources
PubMed2006

Sources of mercury wet deposition in Eastern Ohio, USA.

In the fall of 2002, an enhanced air monitoring site was established in Steubenville, Ohio as part of a multi-year comprehensive mercury monitoring and source apportionment study to investigate the impact of local and regional coal combustion sources on atmospheric mercury deposition in the Ohio River Valley. This study deployed advanced monitoring instrumentation, utilized innovative analytical techniques, and applied state-of-the-art statistical receptor models. This paper presents wet deposition data and source apportionment modeling results from daily event precipitation samples collected during the calendar years 2003-2004. The volume-weighted mean mercury concentrations for 2003 and 2004 were 14.0 and 13.5 ng L(-1), respectively, and total annual mercury wet deposition was 13.5 and 19.7 microg m(-2), respectively. Two new EPA-implemented multivariate statistical models, positive matrix factorization (PMF) and Unmix, were applied to the data set and six sources were identified. The dominant contributor to the mercury wet deposition was found by both models to be coal combustion (approximately 70%). Meteorological analysis also indicated that a majority of the mercury deposition found at the Steubenville site was due to local and regional sources.

Air Pollutants↗
PubMed2006

Mass balance assessment for mercury in Lake Champlain.

A mass balance model for mercury in Lake Champlain was developed in an effort to understand the sources, inventories, concentrations, and effects of mercury (Hg) contamination in the lake ecosystem. To construct the mass balance model, air, water, and sediment were sampled as a part of this project and other research/monitoring projects in the Lake Champlain Basin. This project produced a STELLA-based computer model and quantitative apportionments of the principal input and output pathways of Hg for each of 13 segments in the lake. The model Hg concentrations in the lake were consistent with measured concentrations. Specifically, the modeling identified surface water inflows as the largest direct contributor of Hg into the lake. Direct wet deposition to the lake was the second largest source of Hg followed by direct dry deposition. Volatilization and sedimentation losses were identified as the two major removal mechanisms. This study significantly improves previous estimates of the relative importance of Hg input pathways and of wet and dry deposition fluxes of Hg into Lake Champlain. It also provides new estimates of volatilization fluxes across different lake segments and sedimentation loss in the lake.

Ecosystem↗
PubMed2005

Automated speciated mercury measurements in Michigan.

Automated speciated mercury measurements were made at a rural (Dexter, MI) and an urban (Detroit, MI) site in Michigan during selected times from 1999 to 2002 to assess the concentrations of elemental (Hg0), reactive gaseous (RGM), and particulate mercury (Hgp) in these environments. Here we present the first-ever reported values for RGM in Michigan. Median RGM concentrations were 2.21-2.93 pg m(-3) at Dexter and were 3-11 times higher in Detroit at 6.41-22.0 pg m(-3). Maximum RGM concentrations of 38.7 pg m(-3) and 270 pg m(-3) were observed in Dexter and Detroit, respectively. Measured RGM/Hg0 ratios were in the range of 0.04-11.60% indicating that at times RGM comprises greater than the currently held view of 5% of total gaseous mercury in the air. Well-pronounced diurnal patterns of RGM were observed at the rural site, whereas the urban site exhibited patterns that were influenced by nighttime emissions and regional transport. An analysis of RGM/Hgp ratios at the urban site when combined with trajectory analysis suggests that the site receives mercury inputs from both local and regional sources. Episodes of elevated ozone concentrations which were accompanied by increases in RGM concentrations were observed to occur in the late afternoon and overnight. These may be evidence of advection of ozone and RGM over long distances to the site.

Air Pollutants↗
PubMed2005

Estimation and mapping of wet and dry mercury deposition across northeastern North America.

Whereas many ecosystem characteristics and processes influence mercury accumulation in higher trophic-level organisms, the mercury flux from the atmosphere to a lake and its watershed is a likely factor in potential risk to biota. Atmospheric deposition clearly affects mercury accumulation in soils and lake sediments. Thus, knowledge of spatial patterns in atmospheric deposition may provide information for assessing the relative risk for ecosystems to exhibit excessive biotic mercury contamination. Atmospheric mercury concentrations in aerosol, vapor, and liquid phases from four observation networks were used to estimate regional surface concentration fields. Statistical models were developed to relate sparsely measured mercury vapor and aerosol concentrations to the more commonly measured mercury concentration in precipitation. High spatial resolution deposition velocities for different phases (precipitation, cloud droplets, aerosols, and reactive gaseous mercury (RGM)) were computed using inferential models. An empirical model was developed to estimate gaseous elemental mercury (GEM) deposition. Spatial patterns of estimated total mercury deposition were complex. Generally, deposition was higher in the southwest and lower in the northeast. Elevation, land cover, and proximity to urban areas modified the general pattern. The estimated net GEM and RGM fluxes were each greater than or equal to wet deposition in many areas. Mercury assimilation by plant foliage may provide a substantial input of methyl-mercury (MeHg) to ecosystems.

Air Pollutants↗
PubMed2005

Long-term atmospheric mercury wet deposition at Underhill, Vermont.

Section 112(m) of the 1990 Clean Air Act Amendments, referred to as the Great Waters Program, mandated an assessment of atmospheric deposition of hazardous air pollutants (HAPs) to Lake Champlain. Mercury (Hg) was listed as a priority HAP and has continued to be a high priority for a number of national and international programs. An assessment of the magnitude and seasonal variation of atmospheric Hg levels and deposition in the Lake Champlain basin was initiated in December 1992 which included event precipitation collection, as well as collection of vapor and particle phase Hg in ambient air. Sampling was performed at the Proctor Maple Research Center in Underhill Center, VT. The range in the annual volume-weighted mean concentration for Hg in precipitation was 7.8-10.5 ng/l for the 11-year sampling period and the average amount of Hg deposited with each precipitation event was 0.10 microg/m2. The average amount of Hg deposited through precipitation each year from 1993 to 2003 was 9.7 microg/m2/yr. A seasonal pattern for Hg in precipitation is clearly evident, with increased Hg concentrations and deposition observed during spring and summer months. While a clear trend in the 11-year event deposition record at Underhill was not observed, a significant decrease in the event max-to-monthly ratio was observed suggesting that a major source influence was controlled over time. Discrete precipitation events were responsible for significant fractions of the monthly and annual loading of Hg to the forested ecosystem in Vermont. Monthly-averaged temperatures were found to be moderately correlated with monthly volume-weighted mean Hg concentrations (r2 = 0.61) and Hg deposition (r2 = 0.67) recorded at the Vermont site. Meteorological analysis indicated the highest levels of Hg in precipitation were associated with regional transport from the west, southwest, and south during the warmer months.

Air Pollutants↗
PubMed2005

Characterization of complex mixtures in urban atmospheres for inhalation exposure studies.

A real-world assessment of the source-to-receptor pathways for ambient particulate matter (PM), as opposed to in a laboratory environment, was crucial for gaining a better understanding of the types of particles to which people are actually exposed in their daily lives, and of the human-health risks for source-specific PM. However, obtaining scientific evidence linking specific source emissions to health responses was not an easy task; ambient PM possesses diverse chemical, physical and thermodynamic properties, and is subjected to numerous complex atmospheric processes in which source type, source strength, sinks, and meteorology interact continuously. Our collaborative PM health research studies utilized an integrated approach that employs detailed characterization of ambient PM concurrent with inhalation toxicology studies using animal models and concentrated fine air particulates (CAPs). Ambient PM2.5 (PM less than 2.5 microm in mean aerodynamic diameter) was concentrated with a Harvard fine particle concentrator housed in AirCARE1, a unique mobile air research laboratory which enables inhalation exposure studies in real-world settings. This paper discusses the importance of comprehensive characterization of ambient PM2.5, CAPs and their sources, and the associated challenges. In a southwest Detroit community where the pediatric asthma rate is about three times the national average, a detailed assessment was performed including: characterization of ambient PM2.5 and CAPs; identification of major emission sources of PM2.5; and quantification of trace elements in lung tissues of laboratory rats that were exposed to CAPs, all in an effort to define source-receptor pathways for ambient PM2.5. Our findings to date constitute evidence of the retention of ambient urban particulates from local combustion sources within animal tissues from short-term exposures, and possible associations between the observed health effects and source-specific PM2.5. However, a complete understanding of the effects of complex mixtures of air pollutants and their toxicological impacts still faces many challenges.

Air Pollutants↗
PubMed2005

Air pollution-associated changes in lung function among asthmatic children in Detroit.

In a longitudinal cohort study of primary-school-age children with asthma in Detroit, Michigan, we examined relationships between lung function and ambient levels of particulate matter < or = 10 microm and < or = 2.5 microm in diameter (PM10 and PM2.5) and ozone at varying lag intervals using generalized estimating equations. Models considered effect modification by maintenance corticosteroid (CS) use and by the presence of an upper respiratory infection (URI) as recorded in a daily diary among 86 children who participated in six 2-week seasonal assessments from winter 2001 through spring 2002. Participants were predominantly African American from families with low income, and > 75% were categorized as having persistent asthma. In both single-pollutant and two-pollutant models, many regressions demonstrated associations between higher exposure to ambient pollutants and poorer lung function (increased diurnal variability and decreased lowest daily values for forced expiratory volume in 1 sec) among children using CSs but not among those not using CSs, and among children reporting URI symptoms but not among those who did not report URIs. Our findings suggest that levels of air pollutants in Detroit, which are above the current National Ambient Air Quality Standards, adversely affect lung function of susceptible asthmatic children.

Adrenal Cortex Hormones↗
PubMed2004

Direct identification of trace metals in fine and ultrafine particles in the Detroit urban atmosphere.

Exposure to airborne particulates containing low concentrations of heavy metals, such as Pb, As, and Se, may have serious health effects. However, little is known about the speciation and particle size of these airborne metals. Fine- and ultrafine particles with heavy metals in aerosol samples from the Detroit urban area, Michigan, were examined in detail to investigate metal concentrations and speciation. The characterization of individual particles was completed using high-angle annular dark-field scanning transmission electron microscopy (HAADF-STEM) combined with conventional high-resolution TEM techniques. The trace elements, Pb, As, La, Ce, Sr, Zn, Cr, Se, Sn, Y, Zr, Au, and Ag, were detected, and the elemental distributions were mapped in situ atthe nanoscale. The crystal structures of the particles containing Pb, Sr, Zn, and Au were determined from their electron diffraction patterns. Based on the characterization of the representative trace element particles, the potential health effects are discussed. Most of the trace element particles detected in this study were within a range of 0.01-1.0 microm in size, which has the longest atmospheric residence time (approximately 100 days). Increased chemical reactivity owing to the size of nanoparticles may be expected for most of the trace metal particles observed.

Aerosols↗
PubMed2004

Effects of concentrated fine ambient particles on rat plasma levels of asymmetric dimethylarginine.

The health effects of ambient fine particulate matter (PM(2.5)) and its potential impact on vascular endothelial function have not been thoroughly investigated. As endothelial dysfunction plays an important role in the pathogenesis of atherosclerosis and its complications, we examined the effects of concentrated fine ambient particles (CAPs) on the plasma level of asymmetric dimethylarginine (ADMA) in a pilot study. ADMA is a circulating endogenous inhibitor of nitric oxide synthase (NOS) that is associated with impaired vascular function and increased risk for cardiovascular events. A mobile air research laboratory (AirCARE 1) was used to provide "real-world" CAPs exposures for this study conducted in Detroit, MI. Fourteen Brown Norway rats were exposed to filtered air (FA) (n = 7) or CAPs (0.1-2.5 microm) (n = 7) for 3 consecutive days (8 h/day) in July 2002. Rats were exposed during these periods to average particle mass concentrations of 354 microg/m(3). Rat plasma samples were collected 24 h postexposure. Plasma concentrations of ADMA were significantly elevated in rats exposed to CAPs versus those exposed to FA (mean +/- standard deviation = 1.49 +/- 0.18 vs. 1.29 +/- 0.26 microM, p =.05 by one-tailed t-test). Analyses of meteorological data and CAPs trace element composition suggest that local particle emission sources contributed largely to overall mass of CAPs. Results of this pilot study suggest that exposure to PM(2.5) at high concentrations may trigger an acute increase in circulating ADMA level. This finding has implications for the regulation of vasomotor tone by particulate pollutants and the propensity for adverse cardiovascular events.

Air Pollutants↗
PubMed2004

Characterization of ultrafine particle number concentration and size distribution during a summer campaign in southwest Detroit.

This paper presents results from a study conducted in southwest Detroit from July 20 to July 30, 2002, to characterize ambient ultrafine particles (dP < 0.1 microm), and to examine the effect of local sources and meteorological parameters on the ultrafine number concentration and size distribution. The number concentrations of ambient particles in the size range of 0.01-0.43 microm were obtained from a scanning mobility particle sizer (SMPS). Meteorological parameters including ambient temperature, relative humidity, wind speed, wind direction, rainfall, and solar radiation flux were also monitored concurrently atop a 10-m tower. On average, ultrafine particles ranged from 1.4 x 10(4) to 2.5 x 10(4) cm(-3), with significant diurnal and daily variations, and accounted for approximately 89% of the total number concentration (0.01 < dP < 0.43 microm). Time-series plots of the 5-min number concentrations revealed that peak concentrations often occurred during morning rush hour and/or around solar noon when photochemical activity was at a maximum. The morning traffic-related peak coincided with the NOx peak, whereas the photochemical-related peak correlated with solar radiation flux. On some days, the noon peak concentration was many times higher than the morning peak concentration. Although the number size distribution varied considerably over the course of the study, it typically exhibited one to three modes, with diameters around 0.01, 0.05, and 0.09 microm. Analysis of the influence of wind direction indicated that stationary sources could be one of the contributors to elevated ultrafine particle concentration. Overall, the data indicated that fossil fuel combustion and atmospheric gas-to-particle conversion of precursor gases are the major sources of ultrafine particles in the southwest Detroit area during the summer.

Air Pollutants↗
PubMed2003

Mercury and trace elements in cloud water and precipitation collected on Mt. Mansfield, Vermont.

The lack of high quality measurements of Hg and trace elements in cloud and fog water led to the design of a new collector for clean sequential sampling of cloud and fog water. Cloud water was collected during nine non-precipitating cloud events on Mt. Mansfield, VT in the northeastern USA between August 1 and October 31, 1998. Sequential samples were collected during six of these events. Mercury cloud water concentrations ranged from 7.5 to 71.8 ng l(-1), with a mean of 24.8 ng l(-1). Liquid water content explained about 60% of the variability in Hg cloud concentrations. Highest Hg cloud water concentrations were found to be associated with transport from the Mid-Atlantic and Ohio River Valley, and lowest concentrations with transport from the north of Mt. Mansfield out of Canada. Twenty-nine event precipitation samples were collected during the ten-week cloud sampling period near the base of Mt. Mansfield as part of a long-term deposition study. The Hg concentrations of cloud water were similar to, but higher on average (median of 12.5 ng l(-1)) than Hg precipitation concentrations (median of 10.5 ng l(-1)). Cloud and precipitation samples were analyzed for fifteen trace elements including Mg, Cu, Zn, As, Cd and Pb by ICP-MS. Mean concentrations were higher in cloud water than precipitation for elements with predominately anthropogenic, but not crustal origin in samples from the same source region. One possible explanation is greater in-cloud scavenging of crustal elements in precipitating than non-precipitating clouds, and greater below-cloud scavenging of crustal than anthropogenic aerosols.

Air Pollutants↗
PubMed2003

Cloud water and throughfall deposition of mercury and trace elements in a high elevation spruce-fir forest at Mt. Mansfield, Vermont.

As part of the Lake Champlain Basin watershed study of mercury (Hg) and pollutant deposition, cloud water and cloud throughfall collections were conducted at the south summit (1204 m) of Mt. Mansfield, Vermont between August 1 and October 31, 1998, for multi-element chemical analysis. A passive Teflon string collector was deployed during non-precipitating events to sample cloud/fog water at timberline, while three sets of paired funnels collected cloud throughfall under the red spruce-balsam fir canopy. Samples were analyzed for concentrations of Hg, major ions, and 10 trace elements. Ultra-clean sampling and analysis techniques were utilized throughout the study. Six events were sampled for cloud water alone and four events were sampled for both cloud water and cloud throughfall. Cloud throughfall chemistry showed substantial modification from incident cloud water. Much higher concentrations of Hg (2.3 x), base cations (Ca2+, K-, Mg2+; 3-18 x) and certain trace elements (Ni, Cu, Mn, Rb, Sr; 2-34 x) were observed in throughfall than in cloud water. These results confirm that cloud water can leach a wide variety of elements from tree foliage and wash off dry deposited elements. Cloud water deposited an average of 0.42 +/- 0.12 mm of water per hour. Estimated cloud water deposition of Hg was 7.4 microg m(-2) for the period August 1-October 31, approximately twice that deposited by rain during this period at a nearby low elevation Hg monitoring site. Our results indicate that cloud water and Hg deposition at Mt. Mansfield are likely to have considerable ecological effects.

Air Pollutants↗
PubMed2002

Uraninite and fullerene in atmospheric particulates.

Particulates emitted from coal-burning power plants typically contain very small amounts of uranium (<10 ppm). Because of the extremely low concentrations, the form of the uranium has been unknown. Using a variety of advanced electron microscopy techniques, we have identified for the first time nanocrystals of uraninite, UO2+x, encapsulated in carbonaceous matter (< or = 50 nm) similar to fullerene. We have also identified, for the first time, closely associated fullerenes, C60. The "carbon-caged" nanocrystals of uraninite are protected from the immediate oxidation that would lead to increased mobility of uranium in the environment. Still, the presence of uranium in the very fine fraction of atmospheric particulates provides another pathway for radiation exposure.

Air Pollutants↗
PubMed2002

Atmospheric mercury in the Lake Michigan basin: influence of the Chicago/Gary urban area.

The relative importance of the Chicago/Gay urban area was investigated to determine its impact on atmospheric mercury (Hg) concentrations and wet deposition in the Lake Michigan basin. Event wet-only precipitation, total particulate, and vapor phase samples were collected for Hg, and trace element determinations from five sites around Lake Michigan from July 1994 through October 1995 as part of the Lake Michigan Mass Balance Study (LMMBS). In addition, intensive over-water measurements were conducted aboard the EPA research vessel Lake Guardian during the summer of 1994 and the winter of 1995 as part of the Atmospheric Exchange Over Lakes and Oceans Study. Atmospheric Hg concentrations were found to be significantly higher in the Chicago/Gary urban area than surrounding sites: Hg in precipitation was a factor of 2 and particulate Hg was a factor of 6 times higher. Overwater measurements found elevated Hg concentrations 19 km off shore of Chicago/Gary suggesting an enhanced near field atmospheric deposition to Lake Michigan. Meteorological transport analyses also determined that local sources in the Chicago/Gary urban area significantly impacted all of the LMMBS sites indicating a broad impact to the entire Lake Michigan basin.

Air Pollutants↗
PubMed2002

Atmospheric mercury deposition to Lake Michigan during the Lake Michigan Mass Balance Study.

Wet and dry mercury (Hg) deposition were calculated to Lake Michigan using a hybrid receptor modeling framework. The model utilized mercury monitoring data collected during the Lake Michigan Mass Balance Study and the Atmospheric Exchange Over Lakes and Oceans Studytogether with high-resolution over-water meteorological date provided by the National Oceanic and Atmospheric Administration (July, 1994-October, 1995). Atmospheric deposition was determined to be the primary pathway for mercury inputto Lake Michigan, contributing approximately 84% of the estimated 1403 kg total annual input (atmospheric deposition + tributary input). Wet (10.6 microg m(-2)) and dry deposition (9.7 microg m(-2)) contributed almost equally to the annual atmospheric Hg deposition of 20.3 microg m(-2) (1173 kg). Re-emission of dissolved gaseous Hg from the lake was also significant (7.8 microg m(-2)), reducing the net atmospheric deposition to 12.5 microg m(-2) (720 kg). A strong urban influence was observed in the over-water mercury deposition estimates in the southern portion of the lake. The Chicago/Gary urban area was estimated to contribute approximately 20% (127 kg) of the annual atmospheric mercury deposition to Lake Michigan. The magnitude of local anthropogenic mercury sources in the Chicago/Gary urban area suggests that emission reductions could significantly reduce atmospheric mercury deposition into Lake Michigan.

Air Movements↗
PubMed2002

Deposition and emission of gaseous mercury to and from Lake Michigan during the Lake Michigan Mass Balance Study (July, 1994-October, 1995).

This paper presents measurements of dissolved gaseous mercury (DGM) concentrations in Lake Michigan and the application of a mechanistic approach to estimate deposition and emission fluxes of gaseous mercury (Hg2+ and Hg0) to and from Lake Michigan. Measurements of DGM concentrations made during May and July, 1994 and January, 1995 indicate that Lake Michigan was supersaturated with DGM suggesting that transfer of Hg0 occurs from the water to the atmosphere. Over-water concentrations of gaseous Hg2+ were estimated from total gaseous Hg (TGM) concentrations measured at five sites in the basin and used to model dry deposition fluxes of Hg2+. The modeling approach combines estimates of dry deposited Hg2+ with known photochemical and biotic reduction rates to form Hg0, which is available for re-emission. The model accounts for temporal and spatial variations in the deposition velocity of gaseous Hg2+ and the transfer velocity of Hg0 using high temporal and spatial resolution meteorological data. The modeled DGM concentrations agree well with the observed DGM concentrations in Lake Michigan. The modeled dry deposition fluxes of Hg2+ (286-797 kg yr(-1)) are very similar to the emission fluxes of Hg0 (320-959 kg yr(-1)), depending on the gaseous Hg2+ concentration used in the model.

Environmental Monitoring↗
PubMed2002

Comparison of methods for particulate phase mercury analysis: sampling and analysis.

Accurate and reliable sampling and analysis of mercury forms is an overriding aim of any atmospheric monitoring effort which seeks to understand the fate and transport of the metal in the environment. Although a fraction of the total mercury forms found in the atmosphere, particulate phase mercury, Hg(p), is believed to play a prominent role in both wet and dry deposition to the terrestrial and aquatic environments. Currently, microwave acid extraction and thermoreductive methodologies for analysis of Hg(p) samples are widely used. We report on the potential for the use of a thermoreductive method for Hg(p) analysis to evaluate and optimize it for use in routine monitoring networks. Pre-baked quartz filters can be placed in particulate samplers with well-characterized size cuts, such as dichotomous samplers and microoriface impactors. The thermoreductive methodology facilitates rapid analysis after sample collection. It requires no chemical extraction thereby eliminating the potential for contamination and generation of hazardous waste. Our results indicate that, on average, the thermoreductive method yields 30% lower values for fine fraction Hg(p) when compared with microwave acid digestion. This may be due to matrix interferents that reduce the collection efficiency of mercury onto gold preconcentration traps. Results for total particulate mercury samples indicate that on average the thermoreductive method yields 56% lower values for the coarse fraction when compared with microwave acid digestion. Experiments were also conducted in Detroit, MI, USA to investigate whether elevated reactive gaseous mercury (Hg(2+)(g)) in an urban environment can lead to an artifact during the collection of filters for Hg(p) analysis. Our results indicate a significantly higher amount of Hg(p) collected onto a filter using the conventional methodology as compared to a filter collected downstream of KCl-coated annular denuders in the absence of Hg(2+)(g). These results point to the presence of Hg(2+)(g) as an artifact during Hg(p) measurement. These results indicate that a denuder must be utilized upstream of a filter for Hg(p) collection to prevent significant Hg(2+)(g) artifact formation.

Journal Article↗