Carcinogenic metal(loid)s in house dust compared to soil: Concentrations and gastric bioaccessibility.

As a sink and a source of chemicals, house dust represents a relevant medium to assess indoor exposure to metal(loid)s via incidental ingestion or inhalation. However, nationally representative indoor data are scarce. Results from the Canadian House Dust Study (CHDS, 2007-2010; n = 1025) provide nationally representative mean, median and 95th percentile concentrations for 38 elements in typical urban house dust, along with their gastric bioaccessibility. Total concentrations (median/95th percentile) of carcinogenic metal(loid)s in Canadian house dust (µg g-1) are as follows: As (9.0/40), Be (0.4/0.9), Cd (3.5/17), Co (5.6/19), Cr (99/214), Ni (62/322) and Pb (100/760). Total As and Pb concentrations in house dust exceed residential soil guidelines for the protection of human health in about one-third of Canadian homes. Percent bioaccessibilities (median) are: Cd (65%) > Pb (63%) > Be âˆ¼ Ni (36%) > Co (35%) > As (20%) > Cr (15%). Lead, Cd and Co concentrations are significantly greater in older houses (< 1976). Data from two pilot studies (n = 66 + 51) further demonstrate the distinct geochemistry of house dust compared to soils, notably enrichment of carcinogenic metal(loid)s and their increased bioaccessibility. These results provide essential baseline values to refine risk assessment and inform on health risk at contaminated sites.

Viable Clostridium botulinum spores not detected in the household dust of major Canadian cities.

Clostridium botulinum causes infant botulism by colonising the intestines and producing botulinum neurotoxin in situ. Previous reports have linked infant botulism cases to C. botulinum spores in household dust, yet the baseline incidence of C. botulinum spores in residential households is currently unknown. Vacuum cleaner dust from 963 households in 13 major Canadian cities was tested for C. botulinum using a novel real-time PCR assay directed against all known subtypes of the botulinum neurotoxin gene. None of the samples tested positive for C. botulinum. Analysis of a random subset of samples by MALDI Biotyper revealed that the most common anaerobic bacterial isolates were of the genus Clostridium and the most common species recovered overall was Clostridium perfringens. Dust that was spiked with C. botulinum spores of each toxin type successfully produced positive real-time PCR reactions. These control experiments indicate that this is a viable method for the detection of C. botulinum spores in household dust. We make several recommendations for future work that may help discover a common environmental source of C. botulinum spores that could lead to effective preventative measures for this rare but deadly childhood disease.

Selection of metric for indoor-outdoor source apportionment of metals in PM2.5 : mg/kg versus ng/m3.

Trends in the elemental composition of fine particulate matter (PM2.5 ) collected from indoor, outdoor, and personal microenvironments were investigated using two metrics: ng/m3 and mg/kg. Pearson correlations that were positive using one metric commonly disappeared or flipped to become negative when the other metric was applied to the same dataset. For example, the correlation between Mo and S in the outdoor microenvironment was positive using ng/m3 (p < 0.05) but negative using mg/kg (p < 0.05). In general, elemental concentrations (mg/kg) within PM2.5 decreased significantly (p < 0.05) as PM2.5 concentrations (µg/m3 ) increased-a dilution effect that was observed in all microenvironments and seasons. An exception was S: in the outdoor microenvironment, the correlation between wt% S and PM2.5  flipped from negative in the winter (p < 0.01) to positive (p < 0.01) in the summer, whereas in the indoor microenvironment, this correlation was negative year-round (p < 0.05). Correlation analyses using mg/kg indicated that elemental associations may arise from Fe-Mn oxyhydroxide sorption processes that occur as particles age, with or without the presence of a common anthropogenic source. Application of mass-normalized concentration metrics (mg/kg or wt%), enabled by careful gravimetric analysis, revealed new evidence of the importance of indoor sources of elements in PM2.5 .

Toward setting public health guidelines for chemicals in indoor settled dust?

Indoor settled dust may result in substantial human exposure to chemicals, especially by ingestion following hand-to-mouth or hand-to-object-to-mouth contact. As with other environmental media related to exposure, dust may thus be subject to regulation. An international scientific workshop was convened in Paris in September 2019 firstly to assess the relevance for public health of setting guidelines for indoor settled dust, and secondly to discuss scientific and technical challenges related to such guidelines. The main discussions and conclusions, with consensus achieved, are reported herein. Discussions concerned general considerations, objectives and definitions, relevance for a health-based guideline, units of measure, and finally derivation of the guideline. These points should be addressed when considering an indoor settled dust guideline as part of a policy to reduce exposure indoors to a given chemical or group of chemicals.

Physical and chemical characterization of McIntyre Powder: An aluminum dust inhaled by miners to combat silicosis.

McIntyre Powder (MP) is a finely ground aluminum powder that was used between 1943 and 1979 as a prophylaxis for silicosis. Silicosis is a chronic lung disease caused by the inhalation of crystalline silica dust and was prevalent in the Canadian mining industry during this time period. The McIntyre Research Foundation developed, patented, and produced the MP and distributed it to licensees in Canada, the United States, Mexico, Chile, Belgian Congo, and Western Australia. In the province of Ontario, Canada it is estimated that at least 27,500 miners between 1943 and 1979 were exposed to MP. The present study was undertaken to examine the chemical and physical characteristics of two variations of MP (light grey and black). Chemical analyses (using X-ray Fluorescence and Inductively Coupled Plasma approaches) indicate that the black MP contains significantly higher concentrations of aluminum and metal impurities than the light grey MP (p < 0.001). X-ray diffractometry shows that while aluminum hydroxide dominates the aluminum speciation in both variations, the higher total aluminum content in the black MP is attributable to a greater proportion of elemental aluminum. Physical characterization (using electron microscopy, light microscopy, and dynamic light scattering) indicates that the light grey MP consists of particles ranging from 5 nm to 5 µm in diameter. Atomic Force Microscopy shows that the light grey MP particles in the nanoparticle range (<100 nm) have a mode between 5 and 10 nm. Consequently, it is possible that inhaled smaller MP nanoparticles may be transported via blood and lymph fluid circulation to many different organs including the brain. It is also possible for inhaled larger MP particles to deposit onto lung tissue and for potential health effects to arise from inflammatory responses through immune activation. This MP characterization will provide crucial data to help inform future toxicological, epidemiological, and biological studies of any long-term effects related to the inhalation of aluminum dust and nanomaterials.

Detection of Carbon Nanotubes in Indoor Workplaces Using Elemental Impurities.

This study investigated three area sampling approaches for using metal impurities in carbon nanotubes (CNTs) to identify CNT releases in workplace environments: air concentrations (µg/m3), surface loadings (µg/cm2), and passive deposition rates (µg/m2/h). Correlations between metal impurities and CNTs were evaluated by collecting simultaneous colocated area samples for thermal-optical analysis (for CNTs) and ICP-MS analysis (for metals) in a CNT manufacturing facility. CNTs correlated strongly with Co (residual catalyst) and Ni (impurity) in floor surface loadings, and with Co in passive deposition samples. Interpretation of elemental ratios (Co/Fe) assisted in distinguishing among CNT and non-CNT sources of contamination. Stable isotopes of Pb impurities were useful for identifying aerosolized CNTs in the workplace environment of a downstream user, as CNTs from different manufacturers each had distinctive Pb isotope signatures. Pb isotopes were not useful for identifying CNT releases within a CNT manufacturing environment, however, because the CNT signature reflected the indoor background signature. CNT manufacturing companies and downstream users of CNTs will benefit from the availability of alternative and complementary strategies for identifying the presence/absence of CNTs in the workplace and for monitoring the effectiveness of control measures.

Zinc in house dust: speciation, bioaccessibility, and impact of humidity.

Indoor exposures to metals arise from a wide variety of indoor and outdoor sources. This study investigates the impact of humid indoor conditions on the bioaccessibility of Zn in dust, and the transformation of Zn species during weathering. House dust samples were subjected to an oxygenated, highly humid atmosphere in a closed chamber for 4 to 5 months. Zinc bioaccessibility before and after the experiment was determined using a simulated gastric acid extraction. Bulk and micro X-ray absorption structure (XAS) spectroscopy was used to speciate Zn in dust. Exposure to humid conditions led to a significant increase in Zn bioaccessibility in all samples, which was due to a redistribution of Zn from inorganic forms toward the organic pools such as Zn adsorbed on humates. ZnO readily dissolved under humid conditions, whereas ZnS persisted in the dust. Elevated humidity in indoor microenvironments may sustain higher Zn bioaccessibility in settled dust compared to drier conditions, and part of this change may be related to fungal growth in humid dust. These results help to explain the greater bioaccessibility of certain metals in house dust compared to soils.

Evaluating the capabilities of aerosol-to-liquid particle extraction system (ALPXS)/ICP-MS for monitoring trace metals in indoor air.

This study investigates the application of the Aerosol-to-Liquid Particle Extraction System (ALPXS), which uses wet electrostatic precipitation to collect airborne particles, for multi-element indoor stationary monitoring. Optimum conditions are determined for capturing airborne particles for metal determination by inductively coupled plasma-mass spectrometry (ICP-MS), for measuring field blanks, and for calculating limits of detection (LOD) and quantification (LOQ). Due to the relatively high flow rate (300 L min(-1)), a sampling duration of 1 hr to 2 hr was adequate to capture airborne particle-bound metals under the investigated experimental conditions. The performance of the ALPXS during a building renovation demonstrated signal-to-noise ratios appropriate for sampling airborne particles in environments with elevated metal concentrations, such as workplace settings. The ALPXS shows promise as a research tool for providing useful information on short-term variations (transient signals) and for trapping particles into aqueous solutions where needed for subsequent characterization. As the ALPXS does not provide size-specific samples, and its efficiency at different flow rates has yet to be quantified, the ALPXS would not replace standard filter-based protocols accepted for regulatory applications (e.g., exposure measurements), but rather would provide additional information if used in conjunction with filter based methods. Implications: This study investigates the capability of the Aerosol-to-Liquid Particle Extraction System (ALPXS) for stationary sampling of airborne metals in indoor workplace environments, with subsequent analysis by ICP-MS. The high flow rate (300 L/min) permits a short sampling duration (< 2 hr). Results indicated that the ALPXS was capable of monitoring short-term changes in metal emissions during a renovation activity. This portable instrument may prove to be advantageous in occupational settings as a qualitative indicator of elevated concentrations of airborne metals at short time scales.

Chemical transformations of lead compounds under humid conditions: implications for bioaccessibility.

This short communication documents chemical transformations caused by weathering of two Pb compounds that commonly occur in house dust. Chamber experiments were designed to simulate humid indoor environment conditions to determine whether Pb compounds undergo chemical transformations influencing bioaccessibility. Reference compounds of Pb metal (12 % bioaccessibility) and Pb sulfate (14 % bioaccessibility) were subjected to an oxygenated, humidified atmosphere in closed chambers for 4 months. X-ray diffraction (XRD) and X-ray absorption near-edge structure (XANES) spectroscopy were used to characterize the main Pb species, and the change in Pb bioaccessibility was determined using a simulated gastric acid digestion. At the end of the weathering period a small amount of Pb carbonate (9 % of total Pb) appeared in the Pb sulfate sample. Weathering of the Pb metal sample resulted in the formation of two compounds, hydrocerussite (Pb hydroxyl carbonate) and Pb oxide, in significant amounts (each accounted for 26 % of total Pb). The formation of highly bioaccessible Pb carbonate (73 % bioaccessibility), hydrocerussite (76 % bioaccessibility), and Pb oxide (67 % bioaccessibility) during weathering resulted in a measurable increase in the overall Pb bioaccessibility of both samples, which was significant (p = .002) in the case of the Pb metal sample. This study demonstrates that Pb compounds commonly found in indoor dust can 'age' into more bioaccessible forms under humid indoor conditions.

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

Bioaccessibility is a measurement of a substance's 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).

Determination of synthetic musk compounds in indoor house dust by gas chromatography-ion trap mass spectrometry.

A new method for the simultaneous determination of 11 synthetic musks and one fragrance compound in house dust was developed. The nitro musks included musk ketone (MK, 4-tert-butyl-3,5-dinitro-2,6-dimethylacetophenone), musk xylene (MX, 1-tert-butyl-3,5-dimethyl-2,4,6-trinitrobenzene), musk ambrette (1-tert-butyl-2-methoxy-4-methyl-3,5-dinitrobenzene) and musk moskene (1,1,3,3,5-pentamethyl-4,6-dinitroindane). The polycyclic musk compounds were 1,3,4,6,7,8-hexahydro-4,6,6,7,8,8-hexamethylcyclopenta-(γ)-2-benzopyran (HHCB), 7-acetyl-1,1,3,4,4,6-hexamethyl-1,2,3,4-tetrahydronaphthalene (AHTN), 4-acetyl-1,1-dimethyl-6-tert-butylindane, 6-acetyl-1,1,2,3,3,5-hexamethylindane, 5-acetyl-1,1,2,6-tetramethyl-3-isopropylindane, 6,7-dihydro-1,1,2,3,3-pentamethyl-4(5H)-indanon. The one macrocyclic musk was 1,4-dioxacycloheptadecane-5,17-dione. The bicyclic hydrocarbon fragrance compound (1,2,3,4,5,6,7,8-octahydro-2,3,8,8-tetramethylnaphthalen-2yl)ethan-1-one (OTNE) and HHCB-lactone (4,6,6,7,8,8-hexamethyl-1H,3H,4H,6H,7H, 8H-indeno[5,6-c]pyran-1-one), a degradation product of HHCB, were also analysed. NIST SRM 2781 (domestic sludge) and SRM 2585 (organic contaminants in house dust) were analysed for these target compounds. The method was applied for the analysis of 49 paired samples collected using two vacuum sampling methods: a sample of fresh or "active" dust (FD) collected using a Pullman-Holt vacuum sampler, and a household dust (HD) sample taken from the participants' vacuum cleaners. Method detection limits and recoveries ranged from 12 to 48 ng/g and 54 to 117 %, respectively. AHTN, HHCB, OTNE and HHCB-lactone were detected in all samples, with median concentrations of 552, 676, 252 and 453 ng/g for FD samples, respectively; and 405, 992, 212 and 492 ng/g for HD samples, respectively. MX and MK were detected with high frequencies but with much lower concentrations. The two sampling methods produced comparable results for the target analytes. Widely scattered concentration levels were observed for target analytes from this set of 49 house dust samples, suggesting a wide variability in Canadian household exposure to synthetic musks.

Relationships between House Characteristics and Exposures to Metal(loid)s and Synthetic Organic Contaminants Evaluated Using Settled Indoor Dust.

This study investigates associations between house characteristics and chemical contaminants in house dust, collected under the nationally representative Canadian House Dust Study (2007−2010). Vacuum samples (<80 µm fraction) were analysed for over 200 synthetic organic compounds and metal(loid)s. Spearman rank correlations between contaminant concentrations in dust and presence of children and pets, types of flooring, heating styles and other characteristics suggested a number of indoor sources, pointing to future research directions. Numerous synthetic organics were significantly associated with reported use of room deodorizers and with the presence of cats in the home. Hardwood flooring, which is a manufactured wood product, emerged as a source of metal(loid)s, phthalates, organophosphate flame retardants/plasticizers, and obsolete organochlorine pesticides such as ∑DDT (but not halogenated flame retardants). Many metal(loid)s were significantly correlated with flame-retardant compounds used in building materials and heating systems. Components of heating appliances and heat distribution systems appeared to contribute heat-resistant chemicals and alloys to settled dust. Carpets displayed a dual role as both a source and repository of dust-borne contaminants. Contaminant loadings (<80 µm fraction) were significantly elevated in heavily carpeted homes, particularly those located near industry. Depending on the chemical (and its source), the results show that increased dust mass loading may enrich or dilute chemical concentrations in dust. Research is needed to improve the characterisation of hidden indoor sources such as flame retardants used in building materials and heating systems, or undisclosed ingredients used in common household products, such as air fresheners and products used for companion animals.

Lead speciation in house dust from Canadian urban homes using EXAFS, micro-XRF, and micro-XRD.

X-ray absorption fine-structure (XAFS) spectroscopy, micro-X-ray fluorescence (µXRF), and micro-X-ray diffraction (µXRD) were used to determine the speciation of Pb in house dust samples from four Canadian urban homes having elevated Pb concentrations (>1000 mg Pb kg(-1)). Linear combination fitting of the XAFS data, supported by µXRF and µXRD, shows that Pb is complexed in a variety of molecular environments, associated with both the inorganic and organic fractions of the dust samples. The inorganic species of lead identified were as follows: Pb metal, Pb carbonate, Pb hydroxyl carbonate, Pb oxide, and Pb adsorbed to iron oxyhydroxides. Pb carbonate and/or Pb hydroxyl carbonate occurred in all four dust samples and accounted for 28 to 75% of total Pb. Pb citrate and Pb bound to humate were the organic species identified. The results of this study demonstrate the ability of XAFS to identify Pb speciation in house dust and show the potential to identify Pb sources from new homes versus older homes. Understanding Pb speciation and how it influences bioaccessibility is important for human health risk assessment and risk management decisions which aim to improve indoor environmental health.

Canadian house dust study: lead bioaccessibility and speciation.

Vacuum samples were collected from 1025 randomly selected urban Canadian homes to investigate bioaccessible Pb (Pb(S)) concentrations in settled house dust. Results indicate a polymodal frequency distribution, consisting of three lognormally distributed subpopulations defined as "urban background" (geomean 58 µg g(-1)), "elevated" (geomean 447 µg g(-1)), and "anomalous" (geomean 1730 µg g(-1)). Dust Pb(S) concentrations in 924 homes (90%) fall into the "urban background" category. The elevated and anomalous subpopulations predominantly consist of older homes located in central core areas of cities. The influence of house age is evidenced by a moderate correlation between house age and dust Pb(S) content (R(2) = 0.34; n = 1025; p < 0.01), but it is notable that more than 10% of homes in the elevated/anomalous category were built after 1980. Conversely, the benefit of home remediation is evidenced by the large number of homes (33%) in the background category that were built before 1960. The dominant dust Pb species determined using X-ray Absorption Spectroscopy were as follows: Pb carbonate, Pb hydroxyl carbonate, Pb sulfate, Pb chromate, Pb oxide, Pb citrate, Pb metal, Pb adsorbed to Fe- and Al-oxyhydroxides, and Pb adsorbed to humate. Pb bioaccessibility estimated from solid phase speciation predicts Pb bioaccessibility measured using a simulated gastric extraction (R(2) = 0.85; n = 12; p < 0.0001). The trend toward increased Pb bioaccessibility in the elevated and anomalous subpopulations (75% ± 18% and 81% ± 8%, respectively) compared to background (63% ± 18%) is explained by the higher proportion of bioaccessible compounds used as pigments in older paints (Pb carbonate and Pb hydroxyl carbonate). This population-based study provides a nationally representative urban baseline for applications in human health risk assessment and risk management.

Windsor, Ontario exposure assessment study: design and methods validation of personal, indoor, and outdoor air pollution monitoring.

The Windsor, Ontario Exposure Assessment Study evaluated the contribution of ambient air pollutants to personal and indoor exposures of adults and asthmatic children living in Windsor, Ontario, Canada. In addition, the role of personal, indoor, and outdoor air pollution exposures upon asthmatic children's respiratory health was assessed. Several active and passive sampling methods were applied, or adapted, for personal, indoor, and outdoor residential monitoring of nitrogen dioxide, volatile organic compounds, particulate matter (PM; PM-2.5 pm [PM2.5] and < or =10 microm [PM10] in aerodynamic diameter), elemental carbon, ultrafine particles, ozone, air exchange rates, allergens in settled dust, and particulate-associated metals. Participants completed five consecutive days of monitoring during the winter and summer of 2005 and 2006. During 2006, in addition to undertaking the air pollution measurements, asthmatic children completed respiratory health measurements (including peak flow meter tests and exhaled breath condensate) and tracked respiratory symptoms in a diary. Extensive quality assurance and quality control steps were implemented, including the collocation of instruments at the National Air Pollution Surveillance site operated by Environment Canada and at the Michigan Department of Environmental Quality site in Allen Park, Detroit, MI. During field sampling, duplicate and blank samples were also completed and these data are reported. In total, 50 adults and 51 asthmatic children were recruited to participate, resulting in 922 participant days of data. When comparing the methods used in the study with standard reference methods, field blanks were low and bias was acceptable, with most methods being within 20% of reference methods. Duplicates were typically within less than 10% of each other, indicating that study results can be used with confidence. This paper covers study design, recruitment, methodology, time activity diary, surveys, and quality assurance and control results for the different methods used.

Extending wipe sampling methodologies to elements other than lead.

Wipe sampling is the USA regulatory protocol for determination of "dust lead loadings" in residential environments. Few studies have applied the wipe sampling method to metals other than lead (Pb) for the purpose of residential exposure assessments. This study was undertaken to develop and expand the wipe method for quantifying additional metal(loid)s including arsenic (As), cadmium (Cd), chromium (Cr), copper (Cu), nickel (Ni), and antimony (Sb); and to provide information on typical background loadings for these metals in urban Canadian homes. A total of 932 wipe samples, 220 field blanks, and 220 duplicate wipes were collected from 222 homes located in three cities in Ontario, Canada using the ASTM 1728 standard. The wipes were digested using a modified version of the ASTM 1644 standard for Pb, which prescribes a hot nitric acid/hydrogen peroxide digestion. The key modification was the addition of hydrofluoric acid to improve recoveries of the target elements, and determination using Inductively Coupled Plasma-Mass Spectrometry (ICP-MS). Generally, a large proportion of the results fell below the limits of detection (LOD) and quantification (LOQ). To distinguish "elevated" metal loadings from loadings characterized as "urban background", an upper background threshold for each element was derived using a normality (Q-Q) plot. LOQ was determined to be the appropriate minimum threshold based on quality assurance criteria. It is concluded that wipes are a useful sampling option to investigate multi-element loadings in residential environments.

Lead speciation in indoor dust: a case study to assess old paint contribution in a Canadian urban house.

Residents in older homes may experience increased lead (Pb) exposures due to release of lead from interior paints manufactured in past decades, especially pre-1960s. The objective of the study was to determine the speciation of Pb in settled dust from an urban home built during WWII. X-ray absorption near-edge structure (XANES) and micro-X-ray diffraction (XRD) analyses were performed on samples of paint (380-2,920 mg Pb kg(-1)) and dust (200-1,000 mg Pb kg(-1)) collected prior to renovation. All dust samples exhibited a Pb XANES signature similar to that of Pb found in paint. Bulk XANES and micro-XRD identified Pb species commonly found as white paint pigments (Pb oxide, Pb sulfate, and Pb carbonate) as well as rutile, a titanium-based pigment, in the <150 µm house dust samples. In the dust fraction <36 µm, half of the Pb was associated with the Fe-oxyhydroxides, suggesting additional contribution of outdoor sources to Pb in the finer dust. These results confirm that old paints still contribute to Pb in the settled dust for this 65-year-old home. The Pb speciation also provided a clearer understanding of the Pb bioaccessibility: Pb carbonate > Pb oxide > Pb sulfate. This study underscores the importance of taking precautions to minimize exposures to Pb in house dust, especially in homes where old paint is exposed due to renovations or deterioration of painted surfaces.

Characterizing the sources, concentrations and resuspension potential of metals and metalloids in the thoracic fraction of urban road dust.

Road dust is a sink and source of metals and metalloids of human health concern. To date, many studies have examined the composition of road dust but there remain critical knowledge gaps on the chemistry of thoracic fractions (< 10 µm) and their patterns of deposition and resuspension. The goal of this study is to characterize the elemental concentrations and sources of thoracic fractions of road dust and their resuspension potential for Toronto, Ontario, Canada. Bulk and thoracic road sweepings were acid digested (HF, HClO4, HNO3 and HCl) and the elemental concentrations measured using ICP-MS. Principal component analysis (PCA) was applied to infer source emissions. Annual elemental loadings to roads were estimated using data on total sweepings collected by the City of Toronto. The mass amounts of metals and metalloids (< 10 µm) available for resuspension were calculated assuming a contribution of 10% to total loadings for this fraction. The median trace element concentrations in city sweepings (n = 64) ranged from highest to lowest as follows: Mn > Zn > Ba > Cr > Cu > Pb > V > Ni > Sn > Mo > Co > As > Sb > Cd. Iron, Cr, Ni, Co, Mo and Cu levels were significantly associated with road class, with the highest concentrations measured for the expressway. Most elements, especially Sb and Zn, were enriched in thoracic sweepings. The PCA results demonstrate the importance of non-fossil fuel, traffic-related elemental emissions. Difficulties in identifying sources, given uncertainties regarding overlapping chemical profiles, are also highlighted. Significant elemental loadings to roads were estimated to occur, with the largest amounts identified for Fe, Al, Mn, Zn, Cr and Cu. Road dust resuspension is predicted to be the most important source of emissions for Fe, Al, Mn, Cr, V, Sn, Mo, Co and Sb.

Buoyancy-corrected gravimetric analysis of lightly loaded filters.

Numerous sources of uncertainty are associated with the gravimetric analysis of lightly loaded air filter samples (< 100 microg). The purpose of the study presented here is to investigate the effectiveness and limitations of air buoyancy corrections over experimentally adjusted conditions of temperature (21-25 degrees C) and relative humidity (RH) (16-60% RH). Conditioning (24 hr) and weighing were performed inside the Archimedes M3 environmentally controlled chamber. The measurements were performed using 20 size-fractionated samples of resuspended house dust loaded onto Teflo (PTFE) filters using a Micro-Orifice Uniform Deposit Impactor representing a wide range of mass loading (7.2-3130 microg) and cut sizes (0.056-9.9 microm). By maintaining tight controls on humidity (within 0.5% RH of control setting) throughout pre- and postweighing at each stepwise increase in RH, it was possible to quantify error due to water absorption: 45% of the total mass change due to water absorption occurred between 16 and 50% RH, and 55% occurred between 50 and 60% RH. The buoyancy corrections ranged from -3.5 to +5.8 microg in magnitude and improved relative standard deviation (RSD) from 21.3% (uncorrected) to 5.6% (corrected) for a 7.2 microg sample. It is recommended that protocols for weighing low-mass particle samples (e.g., nanoparticle samples) should include buoyancy corrections and tight temperature/humidity controls. In some cases, conditioning times longer than 24 hr may be warranted.

Influence of household smoking habits on inhalation bioaccessibility of trace elements and light rare earth elements in Canadian house dust.

In this study, total concentration and inhalation bioaccessibility (dissolution in simulated biological solution) of trace elements (TE) and rare earth elements (REE) were assessed in PM10 from Canadian house dust samples with smoking (n = 25) and non-smoking (n = 25) status. Compared to the natural background concentrations in Canadian soils, median Zn, Pb, Cd and Cu concentrations in PM10 were 10-23 fold higher, while median La, Ce and Pr concentrations were 1.6-2.4 fold higher. Mann-Whitney tests (α = 0.05) indicated no difference between the median TE concentrations based on the smoking status of the household; however, median REE concentrations were significantly higher in the PM10 of smoking households. Additionally, Cd and Ni were positively correlated (Spearman r, p < 0.05) to La, Ce and Nd in smoking households, suggesting that tobacco combustion may have contributed REE in the PM10 of these households. Median inhalation-ingestion bioaccessibility assay outcomes of arsenic (As) and lead (Pb) was higher in the non-smoking households when compared to smoking households (Mann Whitney test, α = 0.05), suggesting that tobacco combustion products may be associated with less soluble species of As and Pb. Although REE bioaccessibility was negligible in simulated lung epithelial fluid regardless of the smoking status of the household, bioaccessibility in the lung-gastric phase was 23.6-27.6% in the smoking household and 34.7-36.7% in the non-smoking households, indicating a significantly lower REE dissolution in PM10 of smoking households. In contrast, between 17 and 21.9% bioaccessibility of REE was observed when artificial lysosomal fluid was used, where the outcome was not significantly affected by the smoking status. This study indicates that despite a higher median REE concentration in the PM10 of smoking households, inhalation bioaccessibility may be significantly influenced by the mineralogy.