Identification, semi-quantification and risk assessment of contaminants of emerging concern in Flemish indoor dust through high-resolution mass spectrometry.

Indoor dust can contribute substantially to human exposure to known and contaminants of emerging concern (CECs). Novel compounds with high structural variability and different homologues are frequently discovered through screening of the indoor environment, implying that constant monitoring is required. The present study aimed at the identification and semi-quantification of CECs in 46 indoor dust samples collected in Belgium by liquid chromatography high-resolution mass spectrometry. Samples were analyzed applying a targeted and suspect screening approach; the latter based on a suspect list containing >4000 CECs. This allowed the detection of a total of 55 CECs, 34 and 21 of which were identified with confidence level (CL) 1/2 or CL 3, respectively. Besides numerous known contaminants such as di(2-ethylhexyl) phthalate (DEHP), di(2-ethylhexyl) adipate (DEHA) or tris(2-butoxyethyl) phosphate (TBOEP) which were reported with detection frequencies (DFs) > 90%, several novel CECs were annotated. These included phthalates with differing side chains, such as decyl nonyl and decyl undecyl phthalate detected with DFs >80% and identified through the observation of characteristic neutral losses. Additionally, two novel organophosphate flame retardants not previously described in indoor dust, i.e. didecyl butoxyethoxyethyl phosphate (DDeBEEP) and bis(butoxyethyl) butyl phosphate (BBEBP), were identified. The implementation of a dedicated workflow provided semi-quantitative concentrations for a set of suspects. Such data obtained for novel phthalates were in the same order of magnitude as the concentrations observed for legacy phthalates indicating their high relevance for human exposure. From the semi-quantitative data, estimated daily intakes and resulting hazard quotients (HQs) were calculated to estimate the exposure and potential health effects. Neither of the obtained HQ values exceeded the risk threshold, indicating no expected adverse health effects.

Identification and characterization of quaternary ammonium compounds in Flemish indoor dust by ion-mobility high-resolution mass spectrometry.

Quaternary ammonium compounds (QACs) are a class of surfactants commonly used in disinfecting and cleaning products. Their use has substantially increased during the COVID-19 pandemic leading to increasing human exposure. QACs have been associated with hypersensitivity reactions and an increased risk of asthma. This study introduces the first identification, characterization and semi-quantification of QACs in European indoor dust using ion-mobility high-resolution mass spectrometry (IM-HRMS), including the acquisition of collision cross section values (DTCCSN2) for targeted and suspect QACs. A total of 46 indoor dust samples collected in Belgium were analyzed using target and suspect screening. Targeted QACs (n = 21) were detected with detection frequencies ranging between 4.2 and 100 %, while 15 QACs showed detection frequencies > 90 %. Semi-quantified concentrations of individual QACs showed a maximum of 32.23 µg/g with a median ∑QAC concentration of 13.05 µg/g and allowed the calculation of Estimated Daily Intakes for adults and toddlers. Most abundant QACs matched the patterns reported in indoor dust collected in the United States. Suspect screening allowed the identification of 17 additional QACs. A dialkyl dimethyl ammonium compound with mixed chain lengths (C16:C18) was characterized as a major QAC homologue with a maximum semi-quantified concentration of 24.90 µg/g. The high detection frequencies and structural variabilities observed call for more European studies on potential human exposure to these compounds. For all targeted QACs, drift tube IM-HRMS derived collision cross section values (DTCCSN2) are reported. Reference DTCCSN2 values allowed the characterization of CCS-m/z trendlines for each of the targeted QAC classes. Experimental CCS-m/z ratios of suspect QACs were compared with the CCS-m/z trendlines. The alignment between the two datasets served as an additional confirmation of the assigned suspect QACs. The use of the 4bit multiplexing acquisition mode with consecutive high-resolution demultiplexing confirmed the presence of isomers for two of the suspect QACs.

Do ICP-MS based methods fulfill the EU monitoring requirements for the determination of elements in our environment?

Undoubtedly, the most important advance in the environmental regulatory monitoring of elements of the last decade is the widespread introduction of ICP-mass spectrometry (ICP-MS) due to standards developed by the European Committee for Standardization. The versatility of ICP-MS units as a tool for the determination of major, minor and trace elements (Al, As, Ba, Ca, Cd, Co, Cr, Cu, Fe, Hg, K, Mg, Mn, Mo, Na, Ni, P, Pb, Sb, Se, Sn, Ti, V and Zn) in surface water, groundwater, river sediment, topsoil, subsoil, fine particulates and atmospheric deposition is illustrated in this paper. Ranges of background concentrations for major, minor and trace elements obtained from a regional case study (Flanders, Belgium) are summarized for all of these environmental compartments and discussed in the context of a harmonized implementation of European regulatory monitoring requirements. The results were derived from monitoring programs in support of EU environmental quality directives and were based on a selection of (non-polluted) background locations. Because of the availability of ICP-MS instruments nowadays, it can be argued that the main hindrance for meeting the European environmental monitoring requirements is no longer the technical feasibility of analysis at these concentration levels, but rather (i) potential contamination during sampling and analysis, (ii) too limited implementation of quality control programs, validating the routinely applied methods (including sampling and low level verification) and (iii) lack of harmonization in reporting of the chemical environmental status between the individual member states.

Land use regression models as a tool for short, medium and long term exposure to traffic related air pollution.

BACKGROUND AND AIMS: In the HEAPS (Health Effects of Air Pollution in Antwerp Schools) study the importance of traffic-related air pollution on the school and home location on children's health was assessed. 130 children (aged 6 to 12) from two schools participated in a biomonitoring study measuring oxidative stress, inflammation and cardiovascular markers. METHODS: Personal exposure of schoolchildren to black carbon (BC) and nitrogen dioxide (NO2) was assessed using both measured and modeled concentrations. Air quality measurements were done in two seasons at approximately 50 locations, including the schools. The land use regression technique was applied to model concentrations at the children's home address and at the schools. RESULTS: In this paper the results of the exposure analysis are given. Concentrations measured at school 2h before the medical examination were used for assessing health effects of short term exposure. Over two seasons, this short term BC exposure ranged from 514 ng/m(3) to 6285 ng/m(3), and for NO2 from 11 µg/m(3) to 36 µg/m(3). An integrated exposure was determined until 10 days before the child's examination, taking into account exposures at home and at school and the time spent in each of these microenvironments. Land use regression estimates were therefore recalculated into daily concentrations by using the temporal trend observed at a fixed monitor of the official air quality network. Concentrations at the children's homes were modeled to estimate long term exposure (from 1457 ng/m(3) to 3874 ng/m(3) for BC; and from 19 µg/m(3) to 51 µg/m(3) for NO2). CONCLUSIONS: The land use regression technique proved to be a fast and accurate means for estimating long term and daily BC and NO2 exposure for children living in the Antwerp area. The spatial and temporal resolution was tailored to the needs of the epidemiologists involved in this study.

Wintertime spatio-temporal variation of ultrafine particles in a Belgian city.

Simultaneous measurements of ultrafine particles (UFPs) were carried out at four sampling locations situated within a 1 km(2) grid area in a Belgian city, Borgerhout (Antwerp). All sampling sites had different orientation and height of buildings and dissimilar levels of anthropogenic activities (mainly traffic volume). The aims were to investigate: (i) the spatio-temporal variation of UFP within the area, (ii) the effect of wind direction with respect to the volume of traffic on UFP levels, and (iii) the spatial representativeness of the official monitoring station situated in the study area. All sampling sites followed similar diurnal patterns of UFP variation, but effects of local traffic emissions were evident. Wind direction also had a profound influence on UFP concentrations at certain sites. The results indicated a clear influence of local weather conditions and the more dominant effect of traffic volumes. Our analysis indicated that the regional air quality monitoring station represented the other sampling sites in the study area reasonably well; temporal patterns were found to be comparable though the absolute average concentrations showed differences of up to 35%.

Dispersion modelling of traffic induced ultrafine particles in a street canyon in Antwerp, Belgium and comparison with observations.

The aim of this study is to investigate the dispersion of ultrafine particles and its spatial distribution in a street canyon and its neighbourhood with the 3D CFD model ENVI-met®. The performance of the model at street scale is evaluated and the importance of the boundary conditions like wind field and traffic emissions on the UFP concentration is demonstrated. To support and validate the modelled results, a short-term measurement campaign was conducted in a street canyon in Antwerp, Belgium. The UFP concentration was measured simultaneously with P-TRACK (TSI Model 8525) at four different locations in the canyon. The modelled UFP concentrations compare well with the measured data (correlation coefficient R from 0.44 to 0.93) within the standard deviation of the measurements. Despite the moderate traffic flow in the street canyon, UFP concentrations in the canyon are in general double of the background concentrations, indicating the high local contribution for this particle number concentration. Some of the observed concentration profiles are not resembled by the model simulations. For these specific anomalies, further analysis is performed and plausible explanations are put forward. The role of wind direction and traffic emissions is investigated. The performance evaluation of ENVI-met® shows that in general the model qualitatively and quantitatively describes the dispersion of UFP in the street canyon study.

Size resolved ultrafine particles emission model--a continues size distribution approach.

A new parameterization for size resolved ultrafine particles (UFP) traffic emissions is proposed based on the results of PARTICULATES project (Samaras et al., 2005). It includes the emission factors from the Emission Inventory Guidebook (2006) (total number of particles, #/km/veh), the shape of the corresponding particle size distribution given in PARTICULATES and data for the traffic activity. The output of the model UFPEM (UltraFine Particle Emission Model) is a sum of continuous distributions of ultrafine particles emissions per vehicle type (passenger cars and heavy duty vehicles), fuel (petrol and diesel) and average speed representative for urban, rural and highway driving. The results from the parameterization are compared with measured total number of ultrafine particles and size distributions in a tunnel in Antwerp (Belgium). The measured UFP concentration over the entire campaign shows a close relation to the traffic activity. The modelled concentration is found to be lower than the measured in the campaign. The average emission factor from the measurement is 4.29E+14 #/km/veh whereas the calculated is around 30% lower. A comparison of emission factors with literature is done as well and in overall a good agreement is found. For the size distributions it is found that the measured distributions consist of three modes--Nucleation, Aitken and accumulation and most of the ultrafine particles belong to the Nucleation and the Aitken modes. The modelled Aitken mode (peak around 0.04-0.05 µm) is found in a good agreement both as amplitude of the peak and the number of particles whereas the modelled Nucleation mode is shifted to smaller diameters and the peak is much lower that the observed. Time scale analysis shows that at 300 m in the tunnel coagulation and deposition are slow and therefore neglected. The UFPEM emission model can be used as a source term in dispersion models.

Appraisal of measurement methods, chemical composition and sources of fine atmospheric particles over six different areas of Northern Belgium.

Daily and seasonal variation in the total elemental, organic carbon (OC) and elemental carbon (EC) content and mass of PM(2.5) were studied at industrial, urban, suburban and agricultural/rural areas. Continuous (optical Dustscan, standard tapered element oscillating micro-balance (TEOM), TEOM with filter dynamics measurement system), semi-continuous (Partisol filter-sampling) and non-continuous (Dekati-impactor sampling and gravimetry) methods of PM(2.5) mass monitoring were critically evaluated. The average elemental fraction accounted for 2-6% of the PM(2.5) mass measured by gravimetry. Metals, like K, Mn, Fe, Cu, Zn and Pb were strongly inter-correlated, also frequently with non-metallic elements (P, S, Cl and/or Br) and EC/OC. A high OC/EC ratio (2-9) was generally observed. The total carbon content of PM(2.5) ranged between 3 and 77% (averages: 12-32%), peaking near industrial/heavy trafficked sites. Principal component analysis identified heavy oil burning, ferrous/non-ferrous industry and vehicular emissions as the main sources of metal pollution.

Mass and ionic composition of atmospheric fine particles over Belgium and their relation with gaseous air pollutants.

Mass, major ionic components (MICs) of PM2.5, and related gaseous pollutants (SO2, NO(x), NH3, HNO2, and HNO3) were monitored over six locations of different anthropogenic influence (industrial, urban, suburban, and rural) in Belgium. SO4(2-), NO3-, NH4+, and Na+ were the primary ions of PM2.5 with averages diurnal concentrations ranging from 0.4-4.5, 0.3-7.6, 0.9-4.9, and 0.4-1.2 microg m(-3), respectively. MICs formed 39% of PM2.5 on an average, but it could reach up to 80-98%. The SO2, NO, NO2, HNO2, and HNO3 levels showed high seasonal and site-specific fluctuations. The NH3 levels were similar over all the sites (2-6 microg m(-3)), indicating its relation to the evenly distributed animal husbandry activities. The sulfur and nitrogen oxidation ratios for PM2.5 point towards a low-to-moderate formation of secondary sulfate and nitrate aerosols over five cities/towns, but their fairly intensive formation over the rural Wingene. Cluster analysis revealed the association of three groups of compounds in PM2.5: (i) NH4NO3, KNO3; (ii) Na2SO4; and (iii) MgCl2, CaCl2, MgF2, CaF2, corresponding to anthropogenic, sea-salt, and mixed (sea-salt + anthropogenic) aerosols, respectively. The neutralization and cation-to-anion ratios indicate that MICs of PM2.5 appeared mostly as (NH4)2SO4 and NH4NO3 salts. Sea-salt input was maximal during winter reaching up to 12% of PM2.5. The overall average Cl-loss for sea-salt particles of PM2.5 at the six sites varied between 69 and 96% with an average of 87%. Principal component analysis revealed vehicular emission, coal/wood burning and animal farming as the dominating sources for the ionic components of PM2.5.