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.

Toxicity of Metal Oxide Nanoparticles: Looking through the Lens of Toxicogenomics.

The impact of solubility on the toxicity of metal oxide nanoparticles (MONPs) requires further exploration to ascertain the impact of the dissolved and particulate species on response. In this study, FE1 mouse lung epithelial cells were exposed for 2-48 h to 4 MONPs of varying solubility: zinc oxide, nickel oxide, aluminum oxide, and titanium dioxide, in addition to microparticle analogues and metal chloride equivalents. Previously published data from FE1 cells exposed for 2-48 h to copper oxide and copper chloride were examined in the context of exposures in the present study. Viability was assessed using Trypan Blue staining and transcriptomic responses via microarray analysis. Results indicate material solubility is not the sole property governing MONP toxicity. Transcriptional signaling through the 'HIF-1α Signaling' pathway describes the response to hypoxia, which also includes genes associated with processes such as oxidative stress and unfolded protein responses and represents a conserved response across all MONPs tested. The number of differentially expressed genes (DEGs) in this pathway correlated with apical toxicity, and a panel of the top ten ranked DEGs was constructed (Hmox1, Hspa1a, Hspa1b, Mmp10, Adm, Serpine1, Slc2a1, Egln1, Rasd1, Hk2), highlighting mechanistic differences among tested MONPs. The HIF-1α pathway is proposed as a biomarker of MONP exposure and toxicity that can help prioritize MONPs for further evaluation and guide specific testing strategies.

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.

The High-Throughput In Vitro CometChip Assay for the Analysis of Metal Oxide Nanomaterial Induced DNA Damage.

Metal oxide nanomaterials (MONMs) are among the most highly utilized classes of nanomaterials worldwide, though their potential to induce DNA damage in living organisms is known. High-throughput in vitro assays have the potential to greatly expedite analysis and understanding of MONM induced toxicity while minimizing the overall use of animals. In this study, the high-throughput CometChip assay was used to assess the in vitro genotoxic potential of pristine copper oxide (CuO), zinc oxide (ZnO), and titanium dioxide (TiO2) MONMs and microparticles (MPs), as well as five coated/surface-modified TiO2 NPs and zinc (II) chloride (ZnCl2) and copper (II) chloride (CuCl2) after 2-4 h of exposure. The CuO NPs, ZnO NPs and MPs, and ZnCl2 exposures induced dose- and time-dependent increases in DNA damage at both timepoints. TiO2 NPs surface coated with silica or silica-alumina and one pristine TiO2 NP of rutile crystal structure also induced subtle dose-dependent DNA damage. Concentration modelling at both post-exposure timepoints highlighted the contribution of the dissolved species to the response of ZnO, and the role of the nanoparticle fraction for CuO mediated genotoxicity, showing the differential impact that particle and dissolved fractions can have on genotoxicity induced by MONMs. The results imply that solubility alone may be insufficient to explain the biological behaviour of MONMs.

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 .

Dissolution Behaviour of Metal-Oxide Nanomaterials in Various Biological Media.

Toxicological effects of metal-oxide-engineered nanomaterials (ENMs) are closely related to their distinct physical-chemical properties, especially solubility and surface reactivity. The present study used five metal-oxide ENMs (ZnO, MnO2, CeO2, Al2O3, and Fe2O3) to investigate how various biologically relevant media influenced dissolution behaviour. In both water and cell culture medium (DMEM), the metal-oxide ENMs were more soluble than their bulk analogues, with the exception that bulk-MnO2 was slightly more soluble in water than nano-MnO2 and Fe2O3 displayed negligible solubility across all tested media (regardless of particle size). Lowering the initial concentration (10 mg/L vs. 100 mg/L) significantly increased the relative solubility (% of total concentration) of nano-ZnO and nano-MnO2 in both water and DMEM. Nano-Al2O3 and nano-CeO2 were impacted differently by the two media (significantly higher % solubility at 10 mg/L in DMEM vs. water). Further evaluation of simulated interstitial lung fluid (Gamble's solution) and phagolysosomal simulant fluid (PSF) showed that the selection of aqueous media significantly affected agglomeration and dissolution behaviour. The solubility of all investigated ENMs was significantly higher in DMEM (pH = 7.4) compared to Gamble's (pH 7.4), attributable to the presence of amino acids and proteins in DMEM. All ENMs showed low solubility in Gamble's (pH = 7.4) compared with PSF (pH = 4.5), attributable to the difference in pH. These observations are relevant to nanotoxicology as increased nanomaterial solubility also affects toxicity. The results demonstrated that, for the purpose of grouping and read-across efforts, the dissolution behaviour of metal-oxide ENMs should be evaluated using aqueous media representative of the exposure pathway being considered.

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.

Impact of copper oxide particle dissolution on lung epithelial cell toxicity: response characterization using global transcriptional analysis.

The in vitro and in vivo toxicity of copper oxide nanoparticles (CuO NPs) is attributed to both particle and dissolved copper ion species. However, a clear understanding of (1) the specific cellular responses that are modulated by the two species and (2) the temporal dynamics in toxicity, as the proportional amount of particulate and ionic forms change over time, is lacking. In the current study, in vitro responses to microparticulate CuO (CuO MPs), CuO NPs, and dissolved Cu2+ were characterized in order to elucidate particle and ion-induced kinetic effects. Particle dissolution experiments were carried out in a relevant cell culture medium, using CuO NPs and MPs. Mouse lung epithelial cells were exposed for 2-48 h with 1-25 µg/mL CuO MPs, CuO NPs, or 7 and 54 µg/mL CuCl2. Cellular viability and genome-wide transcriptional responses were assessed. Dose and time-dependent cytotoxicity were observed in CuO NP exposed cells, which was delayed and subtle in CuCl2 and not observed in CuO MPs treated cells. Analyses of differentially expressed genes and associated pathway perturbations showed that dissolved ions released by CuO NPs in the extracellular medium are insufficient to account for the observed potency and cytotoxicity. Further organization of gene expression results in an Adverse Outcome Pathway (AOP) framework revealed a series of key events potentially involved in CuO NPs toxicity. The AOP is applicable to toxicity induced by metal oxide nanoparticles of varying solubility, and thus, can facilitate the development of in vitro alternative strategies to screen their toxicity.

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.

Characterization of Commercial Metal Oxide Nanomaterials: Crystalline Phase, Particle Size and Specific Surface Area.

Physical chemical characterization of nanomaterials is critical to assessing quality control during production, evaluating the impact of material properties on human health and the environment, and developing regulatory frameworks for their use. We have investigated a set of 29 nanomaterials from four metal oxide families (aluminum, copper, titanium and zinc) with a focus on the measurands that are important for the basic characterization of dry nanomaterials and the determination of the dose metrics for nanotoxicology. These include crystalline phase and crystallite size, measured by powder X-ray diffraction, particle shape and size distributions from transmission electron microscopy, and specific surface area, measured by gas adsorption. The results are compared to the nominal data provided by the manufacturer, where available. While the crystalline phase data are generally reliable, data on minor components that may impact toxicity is often lacking. The crystal and particle size data highlight the issues in obtaining size measurements of materials with broad size distributions and significant levels of aggregation, and indicate that reliance on nominal values provided by the manufacturer is frequently inadequate for toxicological studies aimed at identifying differences between nanoforms. The data will be used for the development of models and strategies for grouping and read-across to support regulatory human health and environmental assessments of metal oxide nanomaterials.

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.

Characterization of Airborne Particles Emitted During Application of Cosmetic Talc Products.

A pilot study was undertaken to characterize the concentration, duration and particle size distribution of the talc cloud that forms in the personal breathing zone (PBZ) during application of certain talc-containing cosmetics. Multiple direct-reading instruments were employed to simultaneously monitor PM4 concentrations (particulate matter with aerodynamic diameter < 4 µm; mg/m3) at different distances from each of three subjects while they applied talc products. Results indicated that the purpose and method of applying the talc product, combined with behavioral and physical differences amongst subjects, all strongly influenced airborne talc concentrations and the duration of the cloud. Air concentrations of talc in the PBZ averaged around 1.0 mg/m3, and the duration of exposure varied from less than one minute to more than ten minutes. The real-time monitors captured the occasional formation of secondary clouds, likely caused by resuspension of talc particles from skin or other surfaces. Measurements of aerosolized baby powder, face powder, and two adult body powders indicated that the median aerodynamic diameter of the talc cloud ranged from 1.7 to 2.0 µm. These direct-reading approaches were valuable for providing detailed characterization of short duration exposures to airborne talc particles, and will be useful to support future exposure assessments of talc and other powders in consumer products.

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.

Short-chain and medium-chain chlorinated paraffins in Canadian house dust and NIST SRM 2585.

A method for the analysis of short-chain and medium-chain chlorinated paraffins (SCCPs and MCCPs) in house dust was developed. The method is based on sonication extraction, sample cleanup by solid phase extraction (SPE), and separation and detection by gas chromatography coupled with mass spectrometry (GC/MS) operated in electron capture negative ion (ECNI) chemical ionization mode. The method is sensitive, with method detection limits (MDLs) down to 0.22 µg/g for SCCPs and 0.55 µg/g for MCCPs. The overall recoveries of the method were 104 (± 11)% and 108 (± 16)% for SCCPs and MCCPs, respectively. The method was successfully applied to the analysis of SCCPs and MCCPs in NIST standard reference material (SRM 2585, organic contaminants in house dust) and a subset of house dust samples collected under the Canadian House Dust Study (CHDS). Average concentrations of SCCPs and MCCPs in SRM 2585 (n = 12 replicates) were 7.58 (± 0.43) µg/g for SCCPs and 16.4 (± 2.1) µg/g for MCCPs, respectively. A comparison was made between CP concentrations in paired dust samples collected using two different methods from the same homes: fresh or "active" dust (FD) collected by technicians and a sample taken from the household vacuum cleaner (HD). Spearman rank analysis showed a significant positive correlation (p < 0.01) between FD and HD samples for both MCCPs and SCCPs. CPs were detected in every house dust sample (n = 48 HD samples), with median (range) concentrations of 6.2 (4.0 - 57) µg/g and 19 (5.9-901) µg/g for SCCPs and MCCPs, respectively. Widely scattered CP levels and 100% detection frequency in this preliminary set of 48 HD samples suggest a wide variability in Canadian household exposures to CPs.

An assessment of the inhalation bioaccessibility of platinum group elements in road dust using a simulated lung fluid.

Metal enrichment of road dust is well characterized but available data on the bioaccessibility of metals in particle size fractions relevant to human respiratory health remain limited. The study goal was to investigate the bioaccessibility of platinum group elements (PGE), which are used as catalysts in automotive exhaust converters, in the inhalable fraction of road dust. Street sweepings were provided by the City of Toronto, Canada, collected as part of its Clean Roads to Clean Air program.The particle size relevance of road dust for inhalation exposures was confirmed using a laser diffraction particle size analyzer (mean Dx(50): 9.42 µm). Total PGE were determined in both bulk and inhalable fractions using nickel sulfide (NiS) fire-assay and instrumental neutron-activation analysis (INAA). PGE lung solubility was examined for the inhalable fraction using Gamble's extraction. Sample digests were co-precipitated with Te-Sn, to pre-concentrate and isolate PGE, prior to their measurement using inductively coupled plasma mass spectrometry (ICP-MS).Total PGE concentrations were enriched in the inhalable fraction of road sweepings. Geomean concentrations in the inhalable fraction were: palladium (Pd) (152 µg/kg), platinum (Pt) (55 µg/kg), rhodium (Rh) (21 µg/kg) and iridium (Ir) (0.23 µg/kg). Osmium (Os) concentrations were below the limit of detection (LOD). Bioaccessible PGEs (n = 16) using Gamble's solution were below LOD for Ir and ruthenium (Ru). For the remainder, the geomean % bioaccessibility was highest for platinum (16%), followed by rhodium (14%) and palladium (3.4%). This study provides evidence that PGE in road dust are bioaccessible in the human lung.

Analysis of Bisphenol A, Alkylphenols, and Alkylphenol Ethoxylates in NIST SRM 2585 and Indoor House Dust by Gas Chromatography-Tandem Mass Spectrometry (GC/MS/MS).

Background: Ingestion of house dust has been demonstrated to be an important exposure pathway to several contaminants in young children. These compounds include bisphenol A (BPA), alkylphenols (APs), and alkylphenol ethoxylates (APEOs). Analysis of these compounds in house dust is challenging because of the complex composition of the sample matrix. Objective: The objective was to develop a simple and sensitive method to measure BPA, APs, and APEOs in indoor house dust. Methods: An integrated method that involved solvent extraction using sonication, sample cleanup by solid-phase extraction, derivatization by 2,2,2-trifluoro-N-methyl-N-(trimethylsilyl)acetamide, and analysis by GC coupled with tandem MS was developed for the simultaneous determination of BPA, APs, and APEOs in NIST Standard Reference Material (SRM) 2585 (Organic contaminants in house dust) and in settled house dust samples. Results: Target analytes included BPA, 4-tert-octylphenol (OP), OP monoethoxylate, OP diethoxylate, 4-n-nonylphenol (4nNP), 4nNP monoethoxylate (4nNP1EO), branched nonylphenol (NP), NP monoethoxylate, NP diethoxylate, NP triethoxylate, and NP tetraethoxylate. The method was sensitive, with method detection limits ranging from 0.05 to 5.1 µg/g, and average recoveries between 82 and 115%. All target analytes were detected in SRM 2585 and house dust except 4nNP and 4nNP1EO. Conclusions: The method is simple and fast, with high sensitivity and good reproducibility. It is applicable to the analysis of target analytes in similar matrixes, such as sediments, soil, and biosolids. Highlights: Values measured in SRM 2585 will be useful for future research in method development and method comparison.

Comparison of Gastric versus Gastrointestinal PBET Extractions for Estimating Oral Bioaccessibility of Metals in House Dust.

Oral bioaccessibility estimates for six metals which are prevalent as contaminants in Canada (zinc, lead, cadmium, copper, nickel, and chromium) are investigated for house dust using the simple gastric phase versus the two-phase physiologically-based extraction technique (PBET). The purpose is to determine whether a complete gastrointestinal (GI) assay yields a more conservative (i.e., higher) estimate of metal bioaccessibility in house dust than the gastric phase alone (G-alone). The study samples include household vacuum dust collected from 33 homes in Montreal, Canada, plus four certified reference materials (NIST 2583, NIST 2584, NIST 2710 and NIST 2710a). Results indicate that percent bioaccessibilities obtained using G-alone are generally greater than or equivalent to those obtained using the complete GI simulation for the six studied metals in house dust. Median bioaccessibilities for G-alone/GI in household vacuum dust samples (n = 33) are 76.9%/19.5% for zinc, 50.4%/6.2% for lead, 70.0%/22.4% for cadmium, 33.9%/30.5% for copper and 28.5%/20.7% for nickel. Bioaccessible chromium is above the detection limit in only four out of 33 samples, for which G-alone results are not significantly different from GI results (p = 0.39). It is concluded that, for the six studied metals, a simple G-alone extraction provides a conservative and cost-effective approach for estimating oral bioaccessibility of metals in house dust.

Determination of Metal Impurities in Carbon Nanotubes Sampled Using Surface Wipes.

Residual metal impurities in carbon nanotubes (CNTs) provide a means to distinguish CNT from non-CNT sources of elemental carbon in environmental samples. A practical and cost-effective analytical approach is needed to support routine surface monitoring of CNT metal tracers using wipe sampling. Wipe sampling for CNT metal tracers is considered a qualitative indicator of the presence of CNTs, not a quantitative exposure metric. In this study, two digestion approaches (microwave-assisted nitric acid/H2O2 digestion and ultrasonic nitric/HF acid digestion) in conjunction with Inductively Coupled Plasma Mass Spectrometry (ICP-MS) determination were evaluated for their ability to extract metal impurities from CNT particles captured on wipe substrates. Aliquots of different carbon nanotubes (including NIST 2483 single-wall CNT) with and without GhostWipes™ (ASTM E-1792 compliant) were used to compare the performance of the digestion methods. The microwave digestion method accommodated the bulky wipe sample and also eliminated potential ICP-MS signal interferences related to incomplete digestion. Although quantitative recoveries requiring lengthy multistep digestion protocols may be necessary in other applications, the near-total recoveries achieved in the present study for CNT catalyst elements were adequate for identifying surface contamination of CNTs in the workplace using wipe sampling.

Non-PBDE halogenated flame retardants in Canadian indoor house dust: sampling, analysis, and occurrence.

An analytical method was developed for the measurement of 18 novel halogenated flame retardants in house dust. Sample preparation was based on ultrasound-assisted solvent extraction and clean up with solid phase extraction (SPE). Sample extracts were analyzed by gas chromatography-mass spectrometry (GC/MS) operated in electron capture negative ion (ECNI) chemical ionization mode. Baseline data from 351 fresh (active) dust samples collected under the Canadian House Dust Study (CHDS) revealed that five out of 18 target chemicals were present with detection frequencies higher than 90 %. Median (range) concentrations for these five compounds were as follows: 104 (<1.5-13,000) ng/g for 2-ethylhexyl-2,3,4,5-tetrabromobenzoate (EHTBB), 8.5 (<1.7-2390) ng/g for 1,2-bis(2,4,6-tribromophenoxy)ethane (BTBPE), 10.2 (<1.7-430) ng/g for hexabromobenzene (HBB), 2.9 (<1.2-1410) ng/g for syn-dechlorane plus (syn-DP) and 5.6 (<1.9-1570) ng/g for anti-dechlorane plus (anti-DP). A comparison of two sampling methods in a subset of 40 homes showed significant positive correlations between samples of "active" dust and samples taken directly from the household vacuum cleaner for all target compounds having median values above their corresponding method detection limits (MDLs). In addition, the method was also applied to the analysis of the targeted compounds in National Institute of Standards and Technology (NIST) standard reference material (SRM 2585, organic contaminants in house dust). Results from the current study could contribute to the potential certification of target chemicals in SRM 2585.