Pat E. Rasmussen

A multi-element profile of housedust in relation to exterior dust and soils in the city of Ottawa, Canada.

This paper presents multi-element profiles of indoor dust versus exterior soils and dusts from 50 residences located in 10 neighborhoods across Ottawa, the capital city of Canada. Mercury concentrations were determined using nitric-sulphuric acid digestion and cold vapor AAS. Concentrations of 31 other elements were determined using nitric-hydrofluoric acid digestion and ICP-MS. Comparisons of household dust, garden soil and street dust at the individual residence scale and at the community scale were based on a consistent 100-250-microm particle size fraction. Results showed housedust samples to contain significantly higher concentrations of many key elements, including lead, cadmium, antimony and mercury, than either street dust or garden soil samples. Also, housedust profiles revealed a distinct multi-element signature in relation to exterior dust and soil samples. Interestingly, garden soil contained higher concentrations of aluminum, barium and thallium than either house or street dust. Geometric mean concentrations (mg/kg) of these elements in household dust/garden soil were: lead 233/42; cadmium 4.42/0.27; antimony 5.54/0.25; mercury 1.728/0.055; aluminum 24281/55677; barium 454/763; and thallium 0.14/0.29. Street dust contained lower geometric mean concentrations than garden soil for 23 out of a total of 32 elements. In general, indoor/outdoor concentration ratios varied widely from one element to another, and from one residence to another within the community. In the case of Ottawa, which is a city with a low concentration of heavy industries, it would be difficult-to-impossible to accurately predict indoor dust concentrations based on exterior soil data. It is concluded that dust generated from sources within the house itself can contribute significantly to exposures to certain elements, such as lead, cadmium, antimony and mercury.

Nevada STORMS project: Measurement of mercury emissions from naturally enriched surfaces

Diffuse anthropogenic and naturally mercury-enriched areas represent long- lived sources of elemental mercury to the atmosphere. The Nevada Study and Tests of the Release of Mercury From Soils (STORMS) project focused on the measurement of mercury emissions from anaturally enriched area. During the project, concurrent measurements of mercury fluxes from naturally mercury-enriched substrate were made September 1-4, 1997, using four micrometeorological methods and seven field flux chambers. Ambient air mercury concentrations ranged from 2 to nearly 200 ng m- 3 indicating that the field site is a source of atmospheric mercury. The mean day time mercury fluxes, durin p conditions of no precipitation, measured with field chambers were 50 to 360 ng m -2 h - , and with the micrometeorological methods we re 230 to 600 ng m- 2 h -1. This wide range in mercury emission rates reflects differences in method experimental designs and local source strengths. Mercury fluxes measured by many field chambers were significantly different (p < 0.05) but linearly correlated. This indicates that field chambers responded similarly to environmental conditions, but differences in experimental design and site heterogeneity had a significant influence on the magnitude of mercury fluxes. Data developed during the field study demonstrated that field flux chambers are ideal for assessment of the physicochemical processes driving mercury flux and development of an understanding of the magnitude of the influence of individual factors on flux. In general, mean mercury fluxes measured with micrometeorological methods during day time periods were nearly 3 times higher than me an fluxes measured with field flux chambers. Micrometeorological methods allow for derivation of a representative mercury flux occurring from an unconstrained system and provide an assessment of the actual magnitude and variability of fluxes occurring from an area.

Current methods of estimating atmospheric mercury fluxes in remote areas.

Evaluation of the impact of anthropogenic mercury (Hg) emissions to the atmosphere requires an understanding of natural background levels and cycling processes. Baseline geochemical surveys indicate that Hg is a significant and highly variable natural constituent of bedrock, surficial sediments, and vegetation. To evaluate the geological contribution of Hg to aquatic systems and to the atmosphere, methods are needed to translate existing spatial geochemical data into annual flux estimates. At the global scale, estimates of the geological component of the atmospheric Hg cycle vary widely, depending on which sources are considered, the magnitude of the Hg emission factors used, and the geographic area to which these emission factors are applied

Role of sediment composition in trace metal distribution in lake sediments

Sediment cores were collected from 20 lakes from the Muskoka region of Ontario, Canada, to study vertical changes in trace metal concentrations with depth and the distribution of metals amongst humic material, amorphous and crystalline Fe and Mn oxides, insoluble organics/sulphides, and silicates. Based on their total concentrations, trace elements displayed different degrees of affinity for the organic fraction (represented by organic C) and the mineral fraction (represented by Al). Certain elements (Hg, As, Sb, Pb, Cd, and Zn) displayed a positive correlation with organic C, a negative correlation with Al, and enrichment in surface sediments (with enrichment factors ranging from 2 to 24). Detailed speciation studies revealed that these elements were associated mainly with humic material and to a lesser extent with oxides in surface sediments. Other elements (Al, Cr, Co, Fe, and Mn) displayed a negative correlation with organic C, a positive correlation with Al, and no consistent enrichment in their total concentration at the surface. The speciation study revealed that metals of the latter group were mainly associated with the silicate fraction in both surface and deep sediments. This study shows that relative affinities for organic and mineral fractions play an important role in the distribution of trace metals during burial and diagenesis, and hence in the shape of their vertical profiles.

The analysis of vegetation for total mercury

Over four hundred vegetation samples were collected for total Hg determination as part of a biogeochemical survey in the Precambrian Shield region near Huntsville, Ontario. An objective of the survey was to obtain accurate data describing the spatial and temporal variation of Hg concentrations in vegetation. Five tree species, clubmosses, mosses, lichen and fungi were collected along three transects each 8 to 10 km long. The samples were digested using a hot H2SO4/HNO3 mixture followed by cold-vapor AAS detection. Very low detection limits (less than 1.0 ng g−1) were achieved by performing the analyses in a clean, Hg-free laboratory. The Hg concentration of coniferous needles did not vary significantly over eight weeks of the summer, but did vary significantly between first and second year growth. In all tree species examined, Hg concentrations in needles/leaves were two to three times as high (by dry weight) as that in twig tissue from the same branch. Differences in Hg content between tissues of different types and ages constituted a major source of within-site variation between plants of the same species.

Validation of continuous particle monitors for personal, indoor, and outdoor exposures

Continuous monitors can be used to supplement traditional filter-based methods of determining personal exposure to air pollutants. They have the advantages of being able to identify nearby sources and detect temporal changes on a time scale of a few minutes. The Windsor Ontario Exposure Assessment Study (WOEAS) adopted an approach of using multiple continuous monitors to measure indoor, outdoor (near-residential) and personal exposures to PM2.5, ultrafine particles and black carbon. About 48 adults and households were sampled for five consecutive 24-h periods in summer and winter 2005, and another 48 asthmatic children for five consecutive 24-h periods in summer and winter 2006. This article addresses the laboratory and field validation of these continuous monitors. A companion article (Wheeler et al., 2010) provides similar analyses for the 24-h integrated methods, as well as providing an overview of the objectives and study design. The four continuous monitors were the DustTrak (Model 8520, TSI, St. Paul, MN, USA) and personal DataRAM (pDR) (ThermoScientific, Waltham, MA, USA) for PM2.5; the P-Trak (Model 8525, TSI) for ultrafine particles; and the Aethalometer (AE-42, Magee Scientific, Berkeley, CA, USA) for black carbon (BC). All monitors were tested in multiple co-location studies involving as many as 16 monitors of a given type to determine their limits of detection as well as bias and precision. The effect of concentration and electronic drift on bias and precision were determined from both the collocated studies and the full field study. The effect of rapid changes in environmental conditions on switching an instrument from indoor to outdoor sampling was also studied. The use of multiple instruments for outdoor sampling was valuable in identifying occasional poor performance by one instrument and in better determining local contributions to the spatial variation of particulate pollution. Both the DustTrak and pDR were shown to be in reasonable agreement (R2 of 90 and 70%, respectively) with the gravimetric PM2.5 method. Both instruments had limits of detection of about 5 μg/m3. The DustTrak and pDR had multiplicative biases of about 2.5 and 1.6, respectively, compared with the gravimetric samplers. However, their average bias-corrected precisions were <10%, indicating that a proper correction for bias would bring them into very good agreement with standard methods. Although no standard methods exist to establish the bias of the Aethalometer and P-Trak, the precision was within 20% for the Aethalometer and within 10% for the P-Trak. These findings suggest that all four instruments can supply useful information in environmental studies.

Influence of Matrix Composition on the Bioaccessibility of Copper, Zinc, and Nickel in Urban Residential Dust and Soil

ABSTRACT This study examines factors affecting oral bioaccessibility of metals in household dust, in particular metal speciation, organic carbon content, and particle size, with the goal of addressing risk assessment information requirements. Investigation of copper (Cu) and zinc (Zn) speciation in two size fractions of dust (< 36 μ m and 80–150 μ m) using synchrotron X-ray absorption spectroscopy (XAS) indicates that the two metals are bound to different components of the dust: Cu is predominately associated with the organic phase of the dust, while Zn is predominately associated with the mineral fraction. Total and bioaccessible Cu, nickel (Ni), and Zn were determined (on dry weight basis) in the < 150 μ m size fraction of a set of archived indoor dust samples (n = 63) and corresponding garden soil samples (n = 66) from the City of Ottawa, Canada. The median bioaccessible Cu content is 66 μ g g−1 in dust compared to 5 μ g g−1 in soil; the median bioaccessible Ni content is 16 μ g g−1 in dust compared to 2 μ g g−1 in soil; and the median bioaccessible Zn content is 410 μ g g−1 in dust compared to 18 μ g g−1 in soil. For the same data set, the median total Cu content is 152 μ g g−1 in dust compared to 17 μ g g−1 in soil; the median total Ni content is 41 μ g g−1 in dust compared to 13 μ g g−1 in soil; and the median total Zn content is 626 μ g g−1 in dust compared to 84 μ g g−1 in soil. Organic carbon is elevated in indoor dust (median 28%) compared to soil (median 5%), and is a key factor controlling metal partitioning and therefore bioaccessibility. The results show that house dust and soil have distinct geochemical signatures and should not be treated as identical media in exposure and risk assessments. Separate measurements of the indoor and outdoor environment are essential to improve the accuracy of residential risk assessments.

Application of a laboratory gas exchange chamber for assessment of in situ mercury emissions

The potential for the use of a laboratory gas exchange system to estimate of mercury emissions from naturally and anthropogenically mercury-enriched areas was assessed by comparison of mercury fluxes measured from the same substrate in situ and in the laboratory. In general, mercury emissions measured with the laboratory chamber for daytime conditions were of the same magnitude as mean mercury emissions measured in situ with field chambers. Mercury emissions measured with both the field chamber and laboratory chamber were lower than those measured with micrometeorological methods. Within the controlled experimental regime of the laboratory chamber, data were developed that demonstrated that substrate mercury concentrations and light are important parameters in controlling mercury emissions. However, with light and other parameters interacting with the soil, the correlation between mercury fluxes and substrate mercury concentrations declined. Mercury emissions from a variety of substrates in the dark were ∼25% of those emissions measured in the light at the same soil surface temperature.

The impact of drinking water, indoor dust and paint on blood lead levels of children aged 1–5 years in Montréal (Québec, Canada)

Lead is neurotoxic at very low dose and there is a need to better characterize the impact of domestic sources of lead on the biological exposure of young children. A cross-sectional survey evaluated the contribution of drinking water, house dust and paint to blood lead levels (BLLs) of young children living in old boroughs of Montréal (Canada). Three hundred and six children aged 1 to 5 years and currently drinking tap water participated in the study. For each participant, residential lead was measured in kitchen tap water, floor dust, windowsill dust and house paint and a venous blood sample was analyzed. Multivariate logistic regression was used to evaluate the association between elevated BLL in the children (≥ 75th percentile) and indoor lead contamination by means of odds ratios (OR) using 95% confidence intervals (CI). There was an association between BLL ≥75th percentile (1.78 μg/dL) and water lead when the mean water concentration was >3.3 μg/L: adjusted OR=4.7 (95% CI: 2.1–10.2). Windowsill dust loading >14.1 μg/ft2 was also associated with BLL ≥1.78 μg/dL: adjusted OR=3.2 (95% CI: 1.3–7.8). Despite relatively low BLLs, tap water and house dust lead contribute to an increase of BLLs in exposed young children.

Variability of bioaccessibility results using seventeen different methods on a standard reference material, NIST 2710

Bioaccessibility is a measurement of a substances solubility in the human gastro-intestinal system, and is often used in the risk assessment of soils. The present study was designed to determine the variability among laboratories using different methods to measure the bioaccessibility of 24 inorganic contaminants in one standardized soil sample, the standard reference material NIST 2710. Fourteen laboratories used a total of 17 bioaccessibility extraction methods. The variability between methods was assessed by calculating the reproducibility relative standard deviations (RSDs), where reproducibility is the sum of within-laboratory and between-laboratory variability. Whereas within-laboratory repeatability was usually better than (<) 15% for most elements, reproducibility RSDs were much higher, indicating more variability, although for many elements they were comparable to typical uncertainties (e.g., 30% in commercial laboratories). For five trace elements of interest, reproducibility RSDs were: arsenic (As), 22–44%; cadmium (Cd), 11–41%; Cu, 15–30%; lead (Pb), 45–83%; and Zn, 18–56%. Only one method variable, pH, was found to correlate significantly with bioaccessibility for aluminum (Al), Cd, copper (Cu), manganese (Mn), Pb and zinc (Zn) but other method variables could not be examined systematically because of the study design. When bioaccessibility results were directly compared with bioavailability results for As (swine and mouse) and Pb (swine), four methods returned results within uncertainty ranges for both elements: two that were defined as simpler (gastric phase only, limited chemicals) and two were more complex (gastric + intestinal phases, with a mixture of chemicals).