Publications by authors named "Jaroslav Schwarz"

23 Publications

  • Page 1 of 1

Three-Year Study of Markers of Oxidative Stress in Exhaled Breath Condensate in Workers Producing Nanocomposites, Extended by Plasma and Urine Analysis in Last Two Years.

Nanomaterials (Basel) 2020 Dec 6;10(12). Epub 2020 Dec 6.

J. Heyrovský Institute of Physical Chemistry CAS, Dolejškova 3, 182 23 Prague 8, Czech Republic.

Human data concerning exposure to nanoparticles are very limited, and biomarkers for monitoring exposure are urgently needed. In a follow-up of a 2016 study in a nanocomposites plant, in which only exhaled breath condensate (EBC) was examined, eight markers of oxidative stress were analyzed in three bodily fluids, i.e., EBC, plasma and urine, in both pre-shift and post-shift samples in 2017 and 2018. Aerosol exposures were monitored. Mass concentration in 2017 was 0.351 mg/m during machining, and 0.179 and 0.217 mg/m during machining and welding, respectively, in 2018. In number concentrations, nanoparticles formed 96%, 90% and 59%, respectively. In both years, pre-shift elevations of 50.0% in EBC, 37.5% in plasma and 6.25% in urine biomarkers were observed. Post-shift elevation reached 62.5% in EBC, 68.8% in plasma and 18.8% in urine samples. The same trend was observed in all biological fluids. Individual factors were responsible for the elevation of control subjects' afternoon vs. morning markers in 2018; all were significantly lower compared to those of workers. Malondialdehyde levels were always acutely shifted, and 8-hydroxy-2-deoxyguanosine levels best showed chronic exposure effect. EBC and plasma analysis appear to be the ideal fluids for bio-monitoring of oxidative stress arising from engineered nanomaterials. Potential late effects need to be targeted and prevented, as there is a similarity of EBC findings in patients with silicosis and asbestosis.
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http://dx.doi.org/10.3390/nano10122440DOI Listing
http://www.ncbi.nlm.nih.gov/pmc/articles/PMC7762143PMC
December 2020

Nuclear Magnetic Resonance Aerosolomics: A Tool for Analysis of Polar Compounds in Atmospheric Aerosols.

ACS Omega 2020 Sep 3;5(36):22750-22758. Epub 2020 Sep 3.

Institute of Chemical Process Fundamentals, v.v.i., The Czech Academy of Sciences, Rozvojová 1/135, Prague 6 165 02, Czech Republic.

Nuclear magnetic resonance aerosolomics was proposed as a new approach to the analysis of the water-soluble organic compound fraction in aerosol particulate matter. The identification of individual compounds is based on a comparison of precise chemical shifts in the H NMR spectrum with the signals in the standards library. For this purpose, Chenomx metabolomics software and a comprehensive spectra library of 150 compounds known from chemistry of aerosols were used. This approach enabled the identification of 60 compounds in real aerosol samples collected at a suburban site in Prague. Using the metabolomic spectra library, three new compounds were identified in aerosols for the first time, and an association of four other compounds to the atmospheric particulate matter was confirmed. The obtained concentration profiles of all identified chemical individuals were subsequently subjected to advanced statistical analysis. NMR aerosolomics clearly differentiates between summer and winter aerosol samples via multivariate statistical analysis and revealed some interesting trends in composition, according to aerosol particle size. Furthermore, the univariate statistical analysis was applied to highlight compounds responsible for the group separation, and possible sources of these compounds were suggested.
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http://dx.doi.org/10.1021/acsomega.0c01634DOI Listing
http://www.ncbi.nlm.nih.gov/pmc/articles/PMC7495480PMC
September 2020

Spatial-temporal variability of aerosol sources based on chemical composition and particle number size distributions in an urban settlement influenced by metallurgical industry.

Environ Sci Pollut Res Int 2020 Nov 5;27(31):38631-38643. Epub 2020 Jul 5.

Department of Public Health Sciences, University of Rochester Medical Center, 265 Crittenden Boulevard, Rochester, NY, 14642-0708, USA.

The Moravian-Silesian region of the Czech Republic with its capital city Ostrava is a European air pollution hot spot for airborne particulate matter (PM). Therefore, the spatiotemporal variability assessment of source contributions to aerosol particles is essential for the successful abatement strategies implementation. Positive Matrix Factorization (PMF) was applied to highly-time resolved PM chemical composition (1 h resolution) and particle number size distribution (PNSD, 14 nm - 10 μm) data measured at the suburban (Ostrava-Plesná) and urban (Ostrava-Radvanice) residential receptor sites in parallel during an intensive winter campaign. Diel patterns, meteorological variables, inorganic and organic markers, and associations between the chemical composition factors and PNSD factors were used to identify the pollution sources and their origins (local, urban agglomeration and regional). The source apportionment analysis resolved six and four PM sources in Plesná and Radvanice, respectively. In Plesná, local residential combustion sources (coal and biomass combustion) followed by regional combustion sources (residential heating, metallurgical industry) were the main contributors to PM. In Radvanice, local residential combustion and the metallurgical industry were the most important PM sources. Aitken and accumulation mode particles emitted by local residential combustion sources along with common urban sources (residential heating, industry and traffic) were the main contributors to the particle number concentration (PNC) in Plesná. Additionally, accumulation mode particles from local residential combustion sources and regional pollution dominated the particle volume concentration (PVC). In Radvanice, local industrial sources were the major contributors to PNC and local coal combustion was the main contributor to PVC. The source apportionment results from the complementary datasets elucidated the relevance of highly time-resolved parallel measurements at both receptor sites given the specific meteorological conditions produced by the regional orography. These results are in agreement with our previous studies conducted at this site. Graphical abstract.
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http://dx.doi.org/10.1007/s11356-020-09694-0DOI Listing
November 2020

DNA Methylation Profiles in a Group of Workers Occupationally Exposed to Nanoparticles.

Int J Mol Sci 2020 Mar 31;21(7). Epub 2020 Mar 31.

Department of Machining and Assembly, Department of Engineering Technology, Department of Material Science, Faculty of Mechanical Engineering, Technical University in Liberec, Studentska 1402/2 Liberec, Czech Republic.

The risk of exposure to nanoparticles (NPs) has rapidly increased during the last decade due to the vast use of nanomaterials (NMs) in many areas of human life. Despite this fact, human biomonitoring studies focused on the effect of NP exposure on DNA alterations are still rare. Furthermore, there are virtually no epigenetic data available. In this study, we investigated global and gene-specific DNA methylation profiles in a group of 20 long-term (mean 14.5 years) exposed, nanocomposite, research workers and in 20 controls. Both groups were sampled twice/day (pre-shift and post-shift) in September 2018. We applied Infinium Methylation Assay, using the Infinium MethylationEPIC BeadChips with more than 850,000 CpG loci, for identification of the DNA methylation pattern in the studied groups. Aerosol exposure monitoring, including two nanosized fractions, was also performed as proof of acute NP exposure. The obtained array data showed significant differences in methylation between the exposed and control groups related to long-term exposure, specifically 341 CpG loci were hypomethylated and 364 hypermethylated. The most significant CpG differences were mainly detected in genes involved in lipid metabolism, the immune system, lung functions, signaling pathways, cancer development and xenobiotic detoxification. In contrast, short-term acute NP exposure was not accompanied by DNA methylation changes. In summary, long-term (years) exposure to NP is associated with DNA epigenetic alterations.
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http://dx.doi.org/10.3390/ijms21072420DOI Listing
http://www.ncbi.nlm.nih.gov/pmc/articles/PMC7177382PMC
March 2020

Characterization of Equivalent Black Carbon at a regional background site in Central Europe: Variability and source apportionment.

Environ Pollut 2020 May 20;260:113771. Epub 2020 Jan 20.

CzechGlobe - Global Change Research Institute CAS, Brno, 60300, Czech Republic; Research Centre for Toxic Compounds in the Environment, Masaryk University, Brno, 62500, Czech Republic.

Characterizing Black Carbon (BC) at regional background areas is important for better understanding its impact on climate forcing and health effects. The variability and sources of Equivalent Black Carbon (EBC) in PM (atmospheric particles with aerodynamic diameter smaller than 10 μm) have been investigated during a 5-year measurement period at the National Atmospheric Observatory Košetice (NAOK), Czech Republic. Ground based measurements were performed from September 2012 to December 2017 with a 7-wavelength aethalometer (AE31, Magee Scientific). The contributions of fossil fuel (EBC) and biomass burning (EBC) were estimated using the aethalometer model. Seasonal, diurnal and weekly variations of EBC were observed that can be related to the sources fluctuations and transport characteristic of pollutants predominantly associated with regional air masses recirculating over the Czech Republic and neighboring countries. The absorption Ångström exponent (α-value) estimated in summer (1.1 ± 0.2) was consistent with reported value for traffic, while the mean highest value (1.5 ± 0.2) was observed in winter due to increased EBC accounting for about 50% of the total EBC. This result is in agreement with the strong correlation between EBC and biomass burning tracers (levoglucosan and mannosan) in winter. During this season, the concentrations of EBC and Delta-C (proxy for biomass burning) reached a maximum in the evening when increasing emissions of wood burning in domestic heating devices (woodstoves/heating system) is expected, especially during the weekend. The diurnal profile of EBC displays a typical morning peak during the morning traffic rush hour and shows a decreasing concentration during weekends due to lower the traffic emission.
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http://dx.doi.org/10.1016/j.envpol.2019.113771DOI Listing
May 2020

The repeated cytogenetic analysis of subjects occupationally exposed to nanoparticles: a pilot study.

Mutagenesis 2019 09;34(3):253-263

Department of Machining and Assembly, Technical University in Liberec, Liberec, Czech Republic.

The application of nanomaterials has been rapidly increasing during recent years. Inhalation exposure to nanoparticles (NP) may result in negative toxic effects but there is a critical lack of human studies, especially those related to possible DNA alterations. We analyzed pre-shift and post-shift a group of nanocomposite researchers with a long-term working background (17.8 ± 10.0 years) and matched controls. The study group consisted of 73.2% males and 26.8% females. Aerosol exposure monitoring during a working shift (involving welding, smelting, machining) to assess the differences in exposure to particulate matter (PM) including nanosized fractions <25-100 nm, and their chemical analysis, was carried out. A micronucleus assay using Human Pan Centromeric probes, was applied to distinguish between the frequency of centromere positive (CEN+) and centromere negative (CEN-) micronuclei (MN) in the binucleated cells. This approach allowed recognition of the types of chromosomal damage: losses and breaks. The monitoring data revealed differences in the exposure to NP related to individual working processes, and in the chemical composition of nanofraction. The cytogenetic results of this pilot study demonstrated a lack of effect of long-term (years) exposure to NP (total frequency of MN, P = 0.743), although this exposure may be responsible for DNA damage pattern changes (12% increase of chromosomal breaks-clastogenic effect). Moreover, short-term (daily shift) exposure could be a reason for the increase of chromosomal breaks in a subgroup of researchers involved in welding and smelting processes (clastogenic effect, P = 0.037). The gender and/or gender ratio of the study participants was also an important factor for the interpretation of the results. As this type of human study is unique, further research is needed to understand the effects of long-term and short-term exposure to NP.
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http://dx.doi.org/10.1093/mutage/gez016DOI Listing
September 2019

Leukocyte telomere length is not affected by long-term occupational exposure to nano metal oxides.

Ind Health 2019 Nov 28;57(6):741-744. Epub 2019 Mar 28.

Institute of Chemical Process Fundamentals CAS, Czech Republic.

The aim of this study was to ascertain whether long-term occupational exposure to nanoparticles would affect relative leukocyte telomere length (LrTL). We analysed occupational exposure to size-resolved aerosol particles, with special emphasis on nanoparticles at two workshops: i/ the production of nanocomposites containing metal oxides; ii/ laboratory to test experimental exposure of nano-CuO to rodents. Thirty five exposed researchers (age 39.5 ± 12.6 yr; exposure duration 6.0 ± 3.7 yr) and 43 controls (40.4 ± 10.5 yr) were examined. LrTL did not significantly (p=0.14) differ between the exposed researchers (0.92 ± 0.13) and controls (0.86 ± 0.15). In addition, no significant correlation (r=-0.22, p=0.22) was detected between the duration of occupational exposure and LrTL. The results remained non-significant after multiple adjustments for age, sex and smoking status. Our pilot results suggest that relative leukocyte telomere length is not affected by occupational exposure to nanoparticles.
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http://dx.doi.org/10.2486/indhealth.2018-0146DOI Listing
http://www.ncbi.nlm.nih.gov/pmc/articles/PMC6885603PMC
November 2019

Assessment of air pollution origin based on year-long parallel measurement of PM and PM at two suburban sites in Prague, Czech Republic.

Sci Total Environ 2019 May 1;664:1107-1116. Epub 2019 Feb 1.

Czech Hydrometeorological Institute, Na Šabatce 17, 143 06 Prague 4, Czech Republic.

From 2nd April 2008 to 28th March 2009, a total 248 daily samples of the PM and PM were collected every sixth day parallel at two suburban sites (Libuš and Suchdol) located at the two opposite sides (south and north, respectively) of Prague, Czech Republic. The PM samples were analyzed for ions by ion chromatography (IC), organic and elemental carbon (OC and EC) by OC/EC analyzer and PM samples also for 56 elements by inductively coupled plasma-mass spectrometry (ICP-MS). The average annual PM and PM was 24.4 ± 13.0 μg m and 26.7 ± 15.1 μg m, respectively, in Prague-Libuš, and 25.1 ± 22.1 μg m and 27.1 ± 23.2 μg m, respectively, in Prague-Suchdol. Since the species forming large part of the aerosol mass were strongly correlated (Spearman's rank correlation coefficient r > 0.80), the variability of PM and PM concentration was mainly driven by the local meteorology or regional and/or long range transport. PM mass closure was calculated based on analytical results with the average percentage of recalculated mass of 77 ± 19% in Prague-Libuš and 86 ± 16% in Prague-Suchdol. The most abundant groups in PM at both sites during the four seasons were OM (Prague-Libuš 34% and Prague-Suchdol 37%) and SIA (Prague-Libuš 30% and Prague-Suchdol 34%). The Positive Matrix Factorization (PMF) was applied to the chemical composition of PM from both sites (124 samples) together to determine its sources. The nine factors were assigned as: mixed factor secondary sulphate and biomass burning, secondary sulphate, traffic, secondary nitrate, road dust, residential heating, aged sea salt, industry and mixed factor road salt along with aged sea salt. According to the polar plots and ventilation index (VI) east/west classification analysis the sources were separated based on origin to four categories local, urban agglomeration, regional and long range transport (LRT). The mixed source secondary sulphate and biomass burning, residential heating and industry were common sources of local origin at both sites. Prague-Suchdol was influenced by traffic related pollution from the urban agglomeration more than Prague-Libuš where the traffic and road dust/salt were of local origin. The regional pollution by secondary sulphates and nitrate was also relevant at both sites along with long range transport of sea salt from North Atlantic Ocean, Norwegian Sea and North Sea. The contribution of the local sources to PM was significant mainly at Prague-Libuš site. However, the sources of regional origin were also important and influence of urban agglomeration pollution to PM is not negligible as well.
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http://dx.doi.org/10.1016/j.scitotenv.2019.01.426DOI Listing
May 2019

The influence of local emissions and regional air pollution transport on a European air pollution hot spot.

Environ Sci Pollut Res Int 2019 Jan 17;26(2):1675-1692. Epub 2018 Nov 17.

Department of Aerosols Chemistry and Physics, Institute of Chemical Process Fundamentals of the Czech Academy of Sciences, v.v.i, Rozvojová 1/135, 165 02, Prague 6 - Suchdol, Czech Republic.

The EU air quality standards have been frequently exceeded in one of the European air pollution hot spots: Ostrava. The aim of this study was to perform an air quality comparison between an urban site (Radvanice), which has a nearby metallurgical complex, and a suburban site (Plesná) to estimate air pollution sources and determine their local and/or regional origins. Twenty-four hour PM and PM (particular matter) concentrations, detailed mass size distributions (MSDs) to distinguish the sources of the fine and coarse PM, and their chemical compositions were investigated in parallel at both sites during the winter of 2014. Positive matrix factorization (PMF) was applied to the PM and PM chemical compositions to investigate their sources. During the measurement campaign, prevailing northeastern-southwestern (NE-SW) wind directions (WDs) were recorded. Higher average PM concentration was measured in Radvanice than in Plesná, whereas PM concentrations were similar at both sites. A source apportionment analysis revealed six and five sources for PM and PM, respectively. In Radvanice, the amount of PM and the most chemical species were similar under SW and NE WD conditions. The dominant sources were industrial (43% for PM and 27% for PM), which were caused by a large metallurgical complex located to the SW, and biomass burning (25% for PM and 36% for PM). In Plesná, the concentrations of PM and all species significantly increased under NE WD conditions. Secondary inorganic aerosols were dominant, with the highest contributions deriving from the NE WD. Therefore, regional pollution transport from the industrial sector in Silesian Province (Poland) was evident. Biomass burning contributed 22% and 24% to PM and PM, respectively. The air quality in Ostrava was influenced by local sources and regional pollution transport. The issue of poor air quality in this region is complex. Therefore, international cooperation from both states (the Czech Republic and Poland) is needed to achieve a reduction in air pollution levels.
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http://dx.doi.org/10.1007/s11356-018-3670-yDOI Listing
January 2019

Deep Airway Inflammation and Respiratory Disorders in Nanocomposite Workers.

Nanomaterials (Basel) 2018 Sep 16;8(9). Epub 2018 Sep 16.

UMass, Lowell, Department of Biomedical and Nutritional Sciences, Zuckerberg College of Health Sciences, Lowell, MA 01854, USA.

Thousands of researchers and workers worldwide are employed in nanocomposites manufacturing, yet little is known about their respiratory health. Aerosol exposures were characterized using real time and integrated instruments. Aerosol mass concentration ranged from 0.120 mg/m³ to 1.840 mg/m³ during nanocomposite machining processes; median particle number concentration ranged from 4.8 × 10⁴ to 5.4 × 10⁵ particles/cm³. The proportion of nanoparticles varied by process from 40 to 95%. Twenty employees, working in nanocomposite materials research were examined pre-shift and post-shift using spirometry and fractional exhaled nitric oxide (FeNO) in parallel with 21 controls. Pro-inflammatory leukotrienes (LT) type B4, C4, D4, and E4; tumor necrosis factor (TNF); interleukins; and anti-inflammatory lipoxins (LXA4 and LXB4) were analyzed in their exhaled breath condensate (EBC). Chronic bronchitis was present in 20% of researchers, but not in controls. A significant decrease in forced expiratory volume in 1 s (FEV1) and FEV1/forced vital capacity (FVC) was found in researchers post-shift ( ˂ 0.05). Post-shift EBC samples were higher for TNF ( ˂ 0.001), LTB4 ( ˂ 0.001), and LTE4 ( ˂ 0.01) compared with controls. Nanocomposites production was associated with LTB4 ( ˂ 0.001), LTE4 ( ˂ 0.05), and TNF ( ˂ 0.001), in addition to pre-shift LTD4 and LXB4 (both ˂ 0.05). Spirometry documented minor, but significant, post-shift lung impairment. TNF and LTB4 were the most robust markers of biological effects. Proper ventilation and respiratory protection are required during nanocomposites processing.
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http://dx.doi.org/10.3390/nano8090731DOI Listing
http://www.ncbi.nlm.nih.gov/pmc/articles/PMC6164906PMC
September 2018

Markers of Oxidative Stress in the Exhaled Breath Condensate of Workers Handling Nanocomposites.

Nanomaterials (Basel) 2018 Aug 10;8(8). Epub 2018 Aug 10.

Department of Biomedical and Nutritional Sciences, Zuckerberg College of Health Sciences, Lowell, MA 01854, USA.

Researchers in nanocomposite processing may inhale a variety of chemical agents, including nanoparticles. This study investigated airway oxidative stress status in the exhaled breath condensate (EBC). Nineteen employees (42.4 ± 11.4 y/o), working in nanocomposites research for 18.0 ± 10.3 years were examined pre-shift and post-shift on a random workday, together with nineteen controls (45.5 ± 11.7 y/o). Panels of oxidative stress biomarkers derived from lipids, nucleic acids, and proteins were analyzed in the EBC. Aerosol exposures were monitored during three major nanoparticle generation operations: smelting and welding (workshop 1) and nanocomposite machining (workshop 2) using a suite of real-time and integrated instruments. Mass concentrations during these operations were 0.120, 1.840, and 0.804 mg/m³, respectively. Median particle number concentrations were 4.8 × 10⁴, 1.3 × 10⁵, and 5.4 × 10⁵ particles/cm³, respectively. Nanoparticles accounted for 95, 40, and 61%, respectively, with prevailing Fe and Mn. All markers of nucleic acid and protein oxidation, malondialdehyde, and aldehydes C₆⁻C were elevated, already in the pre-shift samples relative to controls in both workshops. Significant post-shift elevations were documented in lipid oxidation markers. Significant associations were found between working in nanocomposite synthesis and EBC biomarkers. More research is needed to understand the contribution of nanoparticles from nanocomposite processing in inducing oxidative stress, relative to other co-exposures generated during welding, smelting, and secondary oxidation processes, in these workshops.
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http://dx.doi.org/10.3390/nano8080611DOI Listing
http://www.ncbi.nlm.nih.gov/pmc/articles/PMC6116291PMC
August 2018

Comparison of PM chemical composition and sources at a rural background site in Central Europe between 1993/1994/1995 and 2009/2010: Effect of legislative regulations and economic transformation on the air quality.

Environ Pollut 2018 Oct 14;241:841-851. Epub 2018 Jun 14.

Department of Aerosol Chemistry and Physics, Institute of Chemical Process Fundamentals of the Czech Academy of Sciences, Rozvojová 1/135, 165 02 Prague 6, Czech Republic.

From December 1993 to January 1995 and from October 2009 to October 2010, a total of 320 and 365 daily samples of the PM were collected at a rural background site (National Atmospheric Observatory Košetice) in Central Europe. The PM samples were analyzed for 29 and 26 elements respectively by Particle-Induced X-ray Emission (PIXE) and water-soluble inorganic ions by Ion Chromatography (IC) in 2009/2010. The Positive Matrix Factorization (PMF) was applied to the chemical composition of PM to determine its sources. The decreasing trends of almost all elements concentrations, especially the metals regulated by the EU Directive (2004/107/EC) are evident. The annual median ratios indicate a decrease in concentrations of the PM elements. The slight increase of K concentrations and Spearman's rank correlation coefficient r 0.09 K/Se points to a rise in residential wood combustion. The S concentrations are nearly comparable (higher mean in 2009/2010, while the annual median ratio is under 1). The five major source types in the mid-1990s were ascribed to brown coal combustion, oil combustion, sea salt and dust - long-range transport, re-suspended dust and black coal combustion. The industrial combustion of brown and/or black coal (r 0.75 Se/As, r 0.57 Ga/Ge and r 0.20 As/Zn) and oil (r 0.72 V/Ni) of the regional origin dominated. In the 1990s, the potential source regions were the border area of Czech Republic, German and Poland (brown coal), the Moravia-Silesia region at the Czech-Polish border (black coal), and Slovakia, Austria, Hungary, and the Balkans (oil). In 2009/2010, the apportioned sources were sulfate, residential heating, nitrate, industry, re-suspended dust, and sea salt and dust - long-range transport. The secondary sulfate from coal combustion and residential biomass burning (r 0.96, K/K) of local origin dominated. The declining trend of the elemental concentrations and change in the source pattern of the regional background PM2.5 in Central Europe between the mid-1990s and 2009/10 reflects the economic transformation and impact of stricter legislation in Central Europe.
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http://dx.doi.org/10.1016/j.envpol.2018.06.015DOI Listing
October 2018

Single Usage of a Kitchen Degreaser Can Alter Indoor Aerosol Composition for Days.

Environ Sci Technol 2017 Jun 10;51(11):5907-5912. Epub 2017 May 10.

Institute of Chemical Process Fundamentals of the CAS , Prague CZ-165 02, Czech Republic.

To the best of our knowledge, this study represents the first observation of multiday persistence of an indoor aerosol transformation linked to a kitchen degreaser containing monoethanol amine (MEA). MEA remaining on the cleaned surfaces and on a wiping paper towel in a trash can was able to transform ammonium sulfate and ammonium nitrate into (MEA)SO and (MEA)NO. This influence persisted for at least 60 h despite a high average ventilation rate. The influence was observed using both offline (filters, impactors, and ion chromatography analysis) and online (compact time-of-flight aerosol mass spectrometer) techniques. Substitution of ammonia in ammonium salts was observed not only in aerosol but also in particles deposited on a filter before the release of MEA. The similar influence of other amines is expected based on literature data. This influence represents a new pathway for MEA exposure of people in an indoor environment. The stabilizing effect on indoor nitrate also causes higher indoor exposure to fine nitrates.
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http://dx.doi.org/10.1021/acs.est.6b06050DOI Listing
June 2017

Markers of nucleic acids and proteins oxidation among office workers exposed to air pollutants including (nano)TiO2 particles.

Neuro Endocrinol Lett 2016 Dec;37(Suppl1):13-16

Charles University and General University Hospital in Prague, 1st Faculty of Medicine, Department of Occupational Medicine, Prague, Czech Republic.

Objectives: Experimental studies using nanoscale TiO2 have documented lung injury, inflammation, oxidative stress, and genotoxicity. Human health data are extremely scarce.

Methods: In exhaled breath condensate (EBC) and urine of 22 office employees occupationally exposed to TiO2 during their visit in the production workshops for average 14±9 min/day a panel of biomarkers of nucleic acids and proteins oxidation was studied, specifically 8-hydroxy-2-deoxyguanosine (8-OHdG), 8-hydroxyguanosine (8-OHG), 5-hydroxymethyl uracil (5-OHMeU), o-tyrosine (o-Tyr), 3-chlorotyrosine (3-ClTyr), and 3-nitrotyrosine (3-NOTyr). Examination was performed also in 14 comparable controls.

Results: The median respirable TiO2 mass concentration in the workshops was 0.40 mg/m3, median number concentration was 2.32×104 particles/cm3 with 80% of the particles being <100 nm in diameter. All 6 markers of oxidation were elevated in EBC in factory office employees relative to controls (p<0.01). Significant association was found between their job in TiO2 production plant and 5 markers of oxidation (except 3-NOTyr) in the EBC in multivariate analysis. No elevation of markers was detected in the urine.

Conclusion: This pilot study suggests that even short nanoTiO2 exposure may lead to pulmonary oxidative stress; however this effect may be short-term and reversible. The clinical significance of these findings is unclear and more studies are needed.
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December 2016

Physical properties and lung deposition of particles emitted from five major indoor sources.

Air Qual Atmos Health 2017 25;10(1):1-14. Epub 2016 Aug 25.

Division of Environmental Health & Risk Management, School of Geography, Earth & Environmental Sciences, University of Birmingham, Edgbaston, Birmingham B15 2TT UK ; Department of Environmental Sciences/Center of Excellence in Environmental Studies, King Abdulaziz University, PO Box 80203, Jeddah, 21589 Saudi Arabia.

The physical properties of indoor particles were measured with an Scanning Mobility Particle Sizer (SMPS) system (14.6-850 nm), an Aerodynamic Particle Sizer (APS, 0.54-18 μm) and an Hygroscopic Tandem Differential Mobility Analyzer (H-TDMA) in an apartment located in an urban background site in Prague (Czech Republic) from 15 August to 8 September, 2014. The total particle maximum number concentration was 9.38 × 10, 1.46 × 10, 2.89 × 10, 2.25 × 10 and 1.57 × 10 particles cm for particles released from vacuum cleaning, soap/W5 cleaning spray, smoking, incense burning and cooking (frying) activities, respectively. Particles emitted from cleaning activities showed unimodal number size distributions, with the majority of particles (>98.2 %) in the ultrafine size range (Dp <100 nm) and modes at a diameter of 19.8 nm for vacuum cleaning and 30.6 nm for soap/W5 cleaning. Smoking and incense burning predominantly generated particles in the accumulation mode with a count median diameter around 90-150 nm while cooking emissions showed a bimodal structure with a main mode at 47.8 nm. Particles from vacuum cleaning, incense burning, smoking and cooking emissions were found to be "nearly hydrophobic" with an average growth factor (G) around 1.01-1.10, while particles emitted from desk cleaning using organic compounds were found to be "less-hygroscopic" (G ∼1.12-1.16). Based on an adjusted MPPD model with a consideration of the hygroscopic properties of particles, the total lung deposition fractions of these particles by number when they penetrate into the human lung were 0.73 ± 0.02, 0.62 ± 0.03, 0.37 ± 0.03, 0.32 ± 0.03 and 0.49 ± 0.02 for vacuum cleaning, desk cleaning, smoking, incense burning and cooking, respectively.
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http://dx.doi.org/10.1007/s11869-016-0424-1DOI Listing
http://www.ncbi.nlm.nih.gov/pmc/articles/PMC5216066PMC
August 2016

Markers of lipid oxidative damage in the exhaled breath condensate of nano TiO production workers.

Nanotoxicology 2017 02 9;11(1):52-63. Epub 2016 Dec 9.

h UMass Lowell, Department of Public Health , College of Health Sciences , Lowell, MA , USA.

Nanoscale titanium dioxide (nanoTiO) is a commercially important nanomaterial. Animal studies have documented lung injury and inflammation, oxidative stress, cytotoxicity and genotoxicity. Yet, human health data are scarce and quantitative risk assessments and biomonitoring of exposure are lacking. NanoTiO is classified by IARC as a group 2B, possible human carcinogen. In our earlier studies we documented an increase in markers of inflammation, as well as DNA and protein oxidative damage, in exhaled breath condensate (EBC) of workers exposed nanoTiO. This study focuses on biomarkers of lipid oxidation. Several established lipid oxidative markers (malondialdehyde, 4-hydroxy-trans-hexenal, 4-hydroxy-trans-nonenal, 8-isoProstaglandin F2α and aldehydes C-C) were studied in EBC and urine of 34 workers and 45 comparable controls. The median particle number concentration in the production line ranged from 1.98 × 10 to 2.32 × 10 particles/cm with ∼80% of the particles <100 nm in diameter. Mass concentration varied between 0.40 and 0.65 mg/m. All 11 markers of lipid oxidation were elevated in production workers relative to the controls (p < 0.001). A significant dose-dependent association was found between exposure to TiO and markers of lipid oxidation in the EBC. These markers were not elevated in the urine samples. Lipid oxidation in the EBC of workers exposed to (nano)TiO complements our earlier findings on DNA and protein damage. These results are consistent with the oxidative stress hypothesis and suggest lung injury at the molecular level. Further studies should focus on clinical markers of potential disease progression. EBC has reemerged as a sensitive technique for noninvasive monitoring of workers exposed to engineered nanoparticles.
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http://dx.doi.org/10.1080/17435390.2016.1262921DOI Listing
February 2017

Markers of lipid oxidative damage among office workers exposed intermittently to air pollutants including nanoTiO2 particles.

Rev Environ Health 2017 Mar;32(1-2):193-200

Nanoscale titanium dioxide (nanoTiO2) is a commercially important nanomaterial used in numerous applications. Experimental studies with nanotitania have documented lung injury and inflammation, oxidative stress, and genotoxicity. Production workers in TiO2 manufacturing with a high proportion of nanoparticles and a mixture of other air pollutants, such as gases and organic aerosols, had increased markers of oxidative stress, including DNA and protein damage, as well as lipid peroxidation in their exhaled breath condensate (EBC) compared to unexposed controls. Office workers were observed to get intermittent exposures to nanoTiO2 during their process monitoring. The aim of this study was to investigate the impact of such short-term exposures on the markers of health effects in office workers relative to production workers from the same factory. Twenty-two office employees were examined. They were occupationally exposed to (nano)TiO2 aerosol during their daily visits of the production area for an average of 14±9 min/day. Median particle number concentration in office workers while in the production area was 2.32×104/cm3. About 80% of the particles were <100 nm in diameter. A panel of biomarkers of lipid oxidation, specifically malondialdehyde (MDA), 4-hydroxy-trans-hexenal (HHE), 4-hydroxy-trans-nonenal (HNE), 8-isoprostaglandin F2α (8-isoprostane), and aldehydes C6-C12, were studied in the EBC and urine of office workers and 14 unexposed controls. Nine markers of lipid oxidation were elevated in the EBC of office employees relative to controls (p<0.05); only 8-isoprostane and C11 were not increased. Significant association was found in the multivariate analysis between their employment in the TiO2 production plant and EBC markers of lipid oxidation. No association was seen with age, lifestyle factors, or environmental air contamination. The EBC markers in office employees reached about 50% of the levels measured in production workers, and the difference between production workers and office employees was highly significant (p<0.001). None of these biomarkers were elevated in urine. The approach presented here seems to be very sensitive and useful for non-invasive monitoring of employees exposed to air pollutants, including gases, organic aerosols, and nanoTiO2, and may prove useful for routine biomonitoring purposes. Among them, aldehydes C6, C8, C9, and C10 appear to be the most sensitive markers of lipid oxidation in similar occupational cohorts. One major challenge with sensitive biomonitoring techniques, however, is their non-specificity and difficulty in interpreting the meaning of their physiological values in the context of chronic disease development and damage-repair kinetics.
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http://dx.doi.org/10.1515/reveh-2016-0030DOI Listing
March 2017

Leukotrienes in exhaled breath condensate and fractional exhaled nitric oxide in workers exposed to TiO2 nanoparticles.

J Breath Res 2016 06 30;10(3):036004. Epub 2016 Jun 30.

Department of Occupational Medicine, First Faculty of Medicine, Charles University in Prague and General University Hospital in Prague, Na Bojišti 1, 128 00 Prague 2, Czech Republic.

Human health data regarding exposure to nanoparticles are extremely scarce and biomonitoring of exposure is lacking in spite of rodent pathological experimental data. Potential markers of the health-effects of engineered nanoparticles were examined in 30 workers exposed to TiO2 aerosol, 22 office employees of the same plant, and 45 unexposed controls. Leukotrienes (LT) B4, C4, E4, and D4 were analysed in the exhaled breath condensate (EBC) and urine via liquid chromatography-electrospray ionization-tandem mass spectrometry (LC-ESI-MS/MS). Fractional exhaled nitric oxide (FeNO) and spirometry was also measured. The median particle number concentration of the aerosol in the production ranged from 1.98  ×  10(4) to 2.32  ×  10(4) particles cm(-3); about 80% of the particles were  <100 nm in diameter. Median total mass concentration varied between 0.4 and 0.65 mg m(-3). All LT levels in workers' EBC were elevated relative to the controls (p  <  0.01). LTs in the EBC sample were correlated with titanium levels. Urinary LTs were not elevated in the workers and office employees. Office workers had higher LTB4 in EBC (p  <  0.05), and higher levels of FeNO (p  <  0.01). FeNO was higher in office employees with allergic diseases and was negatively correlated with smoking (p  <  0.01). In spirometry significant impairment in the workers was seen only for %VCIN and %PEF (both p  <  0.01). Multiple regression analysis confirmed a significant association between production of TiO2 and all cysteinyl LTs in EBC (p  <  0.01) and impaired %VCIN and %PEF (both p  <  0.01). LTB4 was also associated with smoking (p  <  0.01). LT levels complemented our earlier findings of DNA, protein, and lipid damage in the EBC of workers with nanoTiO2 exposures. Cysteinyl LTs in EBC analysis suggest inflammation and potential fibrotic changes in the lungs; they may be helpful for monitoring the biological effect of (nano)TiO2 on workers. Spirometry was not sensitive enough.
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http://dx.doi.org/10.1088/1752-7155/10/3/036004DOI Listing
June 2016

Oxidative stress markers are elevated in exhaled breath condensate of workers exposed to nanoparticles during iron oxide pigment production.

J Breath Res 2016 Feb 1;10(1):016004. Epub 2016 Feb 1.

Charles University in Prague and General University Hospital in Prague, First Faculty of Medicine, Department of Occupational Medicine, Na Bojišti 1, 128 00 Prague 2, Czech Republic.

Markers of oxidative stress and inflammation were analysed in the exhaled breath condensate (EBC) and urine samples of 14 workers (mean age 43  ±  7 years) exposed to iron oxide aerosol for an average of 10  ±  4 years and 14 controls (mean age 39  ±  4 years) by liquid chromatography-electrospray ionization-mass spectrometry/mass spectrometry (LC-ESI-MS/MS) after solid-phase extraction. Aerosol exposure in the workplace was measured by particle size spectrometers, a scanning mobility particle sizer (SMPS) and an aerodynamic particle sizer (APS), and by aerosol concentration monitors, P-TRAK and DustTRAK DRX. Total aerosol concentrations in workplace locations varied greatly in both time and space. The median mass concentration was 0.083 mg m(-3) (IQR 0.063-0.133 mg m(-3)) and the median particle concentration was 66 800 particles cm(-3) (IQR 16,900-86,900 particles cm(-3)). In addition, more than 80% of particles were smaller than 100 nm in diameter. Markers of oxidative stress, malondialdehyde (MDA), 4-hydroxy-trans-hexenale (HHE), 4-hydroxy-trans-nonenale (HNE), 8-isoProstaglandin F2α (8-isoprostane) and aldehydes C6-C12, in addition to markers of nucleic acid oxidation, including 8-hydroxy-2-deoxyguanosine (8-OHdG), 8-hydroxyguanosine (8-OHG), 5-hydroxymethyl uracil (5-OHMeU), and of proteins, such as o-tyrosine (o-Tyr), 3-chlorotyrosine (3-ClTyr), and 3-nitrotyrosine (3-NOTyr) were analysed in EBC and urine by LC-ESI-MS/MS. Almost all markers of lipid, nucleic acid and protein oxidation were elevated in the EBC of workers comparing with control subjects. Elevated markers were MDA, HNE, HHE, C6-C10, 8-isoprostane, 8-OHdG, 8-OHG, 5-OHMeU, 3-ClTyr, 3-NOTyr, o-Tyr (all p  <  0.001), and C11 (p  <  0.05). Only aldehyde C12 and the pH of samples did not differ between groups. Markers in urine were not elevated. These findings suggest the adverse effects of nano iron oxide aerosol exposure and support the utility of oxidative stress biomarkers in EBC. The analysis of urine oxidative stress biomarkers does not support the presence of systemic oxidative stress in iron oxide pigment production workers.
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http://dx.doi.org/10.1088/1752-7155/10/1/016004DOI Listing
February 2016

Raman microspectroscopy of exhaled breath condensate and urine in workers exposed to fine and nano TiO2 particles: a cross-sectional study.

J Breath Res 2015 Jul 14;9(3):036008. Epub 2015 Jul 14.

Charles University in Prague and General University Hospital in Prague, First Faculty of Medicine, Department of Occupational Medicine, Na Bojisti 1, 128 00 Prague 2, Czech Republic.

The health effects of engineered nanoparticles in humans are not well-understood; however experimental data support the theory of oxidative stress promoting fibrogenesis and carcinogenicity. The aim of this study was to detect TiO2 particles in exhaled breath condensate (EBC) and urine samples to ascertain their presence and potential persistence and excretion in urine.EBC and urine samples were collected from 20 workers exposed to TiO2 aerosol; among them, 16 had a higher risk level of exposure (production workers) and four had medium risk level (research workers); in addition to 20 controls. Titanium levels in EBC and urine were analysed using the inductively coupled plasma mass spectrometry (ICP-MS) method. A Raman microspectroscopic analysis was performed in EBC and urine to identify the phase composition of TiO2 particles observed. Aerosol exposure in the workplaces was measured using SMPS and APS spectrometers and P-TRAK and DustTRAK DRX monitors.The median concentration of TiO2 aerosol was 1.98 × 10(4) particles cm(-3), the interquartile range (IQR) was 1.50 × 10(4) - 3.01 × 10(4) particles cm(-3) and the median mass concentration was 0.65 mg m(-3) (IQR 0.46-.0.83 mg m(-3)); 70-82% of the particles were smaller than 100 nm in diameter. In any part of the plant, the median TiO2 air concentration did not exceed the national airborne exposure limit of 10 mg m(-3) for inert dust. Particles of rutile and/or anatase were found in the EBC of exposed workers in 8/20 (40%) of the pre-shift and 14/20 (70%) of the post-shift samples. In the urine of workers, TiO2 particles were detected in 2/20 post-shift urine samples only. The mean concentration of titanium in the EBC in production workers was 24.1 ± 1.8 µg/l. In the research workers the values were below the limit of quantitation; LOQ = 4.0 ± 0.2 µg/l), as well as in the controls. In the urine samples of all of the subjects, titanium was under the limit of detection (LOD = 1.2 µg/l). Raman microanalysis of EBC in the workers confirmed the presence of TiO2 anatase and/or rutile crystal phases in the pre-shift samples and their persistence from previous shifts in the workers.
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http://dx.doi.org/10.1088/1752-7155/9/3/036008DOI Listing
July 2015

Detailed comparison of OC/EC aerosol at an urban and a rural Czech background site during summer and winter.

Sci Total Environ 2015 Jun 13;518-519:424-33. Epub 2015 Mar 13.

Institute of Chemical Process Fundamentals of the CAS, v.v.i., Rozvojová 2/135, 165 02, Prague 6 - Suchdol, Czech Republic.

Winter and summer measurements of organic carbon and elemental carbon (OC and EC) in PM2.5 were performed in parallel at two sites, the rural background station Košetice and the Prague-Suchdol urban background site, with a 2-h time resolution using semi-online field OC/EC analysers. Seasonal and site differences were found in the OC and EC contents of PM2.5. Overall, the highest concentrations of both OC and EC were during winter at the urban site. The average urban impact was 50% for OC and 70% for EC. The summer season gives similar concentrations of OC at both sites. However, higher concentrations of EC, caused by higher traffic, were found at the urban site with an average urban increase of 50%. Moreover, an analysis of four OC fractions depending on the volatility (OC1 - most volatile, OC4 - least volatile) and pyrolytic carbon (PC) is provided. A similar level of each OC fraction at both sites was found in summer, except for higher OC1 at urban and higher PC at the rural site. In winter, the differences between the urban and rural sites were dominated by a large increase of the OC1 fraction in comparison with the rural site. A diurnal pattern of concentration and share of OC1 and PC suggests a prevailing influence of local sources on their concentrations at the urban site in winter. The OC3 and OC4 diurnal cycles suggest their more regional or long range transport origin in both seasons. The prevalent influence of OC1 at any urban site has not been previously reported. The minimisation of semi-volatile carbon losses during semi-continuous sampling and analysis, in comparison with off-line sampling methods, is a probable reason for the observed differences.
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http://dx.doi.org/10.1016/j.scitotenv.2015.03.029DOI Listing
June 2015

FTIR analysis of surface functionalities on particulate matter produced by off-road diesel engines operating on diesel and biofuel.

Environ Sci Pollut Res Int 2015 Mar 16;22(6):4534-44. Epub 2014 Oct 16.

Skobeltzyn Institute of Nuclear Physics, Lomonosov Moscow State University, 119991, Moscow, Russia,

Fourier transform infrared spectroscopy is applied as a powerful analytic technique for the evaluation of the chemical composition of combustion aerosols emitted by off-road engines fuelled by diesel and biofuels. Particles produced by burning diesel, heated rapeseed oil (RO), RO with ethylhexylnitrate, and heated palm oil were sampled from exhausts of representative in-use diesel engines. Multicomponent composition of diesel and biofuel particles reveal the chemistry related to a variety of functional groups containing carbon, hydrogen, oxygen, sulfur, and nitrogen. The most intensive functionalities of diesel particles are saturated C-C-H and unsaturated C=C-H aliphatic groups in alkanes and alkenes, aromatic C=C and C=C-H groups in polyaromatics, as well as sulfates and nitrated ions. The distinguished features of biofuel particles were carbonyl C=O groups in carboxylic acids, ketones, aldehydes, esters, and lactones. NO2, C-N and -NH groups in nitrocompounds and amines are found to dominate biofuel particles. Group identification is confirmed by complementary measurements of organic carbon (OC), elemental carbon, and water-soluble ion species. The relationship between infrared bands of polar oxygenated and non-polar aliphatic functionalities indicates the higher extent of the surface oxidation of biofuel particles. Findings provide functional markers of organic surface structure of off-road diesel emission, allowing for a better evaluation of relation between engine, fuel, operation condition, and particle composition, thus improving the quantification of environmental impacts of alternative energy source emissions.
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http://dx.doi.org/10.1007/s11356-014-3688-8DOI Listing
March 2015

On airborne nano/micro-sized wear particles released from low-metallic automotive brakes.

Environ Pollut 2011 Apr 17;159(4):998-1006. Epub 2011 Jan 17.

Technical University Ostrava, Nanotechnology Center, Ostrava-Poruba, Czech Republic.

The paper addresses the wear particles released from commercially available "low-metallic" automotive brake pads subjected to brake dynamometer tests. Particle size distribution was measured in situ and the generated particles were collected. The collected fractions and the original bulk material were analyzed using several chemical and microscopic techniques. The experiments demonstrated that airborne wear particles with sizes between 10 nm and 20 μm were released into the air. The numbers of nanoparticles (< 100 nm) were by three orders of magnitude larger when compared to the microparticles. A significant release of nanoparticles was measured when the average temperature of the rotor reached 300°C, the combustion initiation temperature of organics present in brakes. In contrast to particle size distribution data, the microscopic analysis revealed the presence of nanoparticles, mostly in the form of agglomerates, in all captured fractions. The majority of elements present in the bulk material were also detected in the ultra-fine fraction of the wear particles.
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http://dx.doi.org/10.1016/j.envpol.2010.11.036DOI Listing
April 2011