Investigation of RH effect on uncommon limonene ozonolysis products and SOA formation in indoor air with real time measurement techniques.

Scientific interest in SOA influence on indoor air quality increases since last 20 years. It is well known, that particles of nano-sized diameter pose a threat for human health causing, among others: eye, upper airway irritation, inflammatory response in cells, worsening asthma, hypertension, diabetes, and central nervous dysfunction. Terpenes are reactive VOCs, commonly emitted in indoor air and considered to be SOA precursors by oxidation reactions. The aim of this study was to investigate the relative humidity influence on i) formation of limonene ozonolysis products and ii) SOA formation process - especially the first steps of it. We managed to determine 4 uncommon limonene ozonolysis products (m/z: 43, 83, 99 and 110) appearing in the PTR-TOF-MS mass spectra with the same frequency as well-known formaldehyde, acetone, acetic acid and formic acid. We also detected m/z 75 and m/z 115 formed under dry conditions and m/z 111 and m/z 125 formed under humid conditions. Detected masses formula is proposed with probability >70 % and the probability is derived from the deviation of the exact mass to the measured one and the isotope distribution. SMPS data analysis allowed us to conclude that RH around 40% increases particle mass concentration, regardless initial limonene concentration. Unfortunately, conclusions about RH influence on particle number concentration are inconsistent. Under low initial terpene concentration, RH around 40% decreases particle number concentration. However, for high initial limonene concentration, RH around 40% caused increase in particle number concentration. Obtained results allowed to conclude, that i) RH influences both particle number and particle mass concentration, ii) initial substrate concentration influences SOA formation altering the RH effect, iii) comparison of results and drawing conclusions is difficult due to different experimental protocols in the literature and due to the number of factors influencing SOA formation initiated by terpene oxidation.

Recent advances on SOA formation in indoor air, fate and strategies for SOA characterization in indoor air - A review.

Recent studies proves that indoor air chemistry differs in many aspects from atmospheric one. People send up to 90 % of their life indoors being exposed to pollutants present in gas, particle and solid phase. Particle phase indoor is composed of particles emitted from various sources, among which there is an indoor source - secondary chemical reactions leading to formation of secondary organic aerosol (SOA). Lately, researchers' attentions turned towards the ultrafine particles, for there are still a lot of gaps in knowledge concerning this field of study, while there is evidence of negative influence of ultrafine particles on human health. Presented review sums up current knowledge about secondary particle formation in indoor environment and development of analytical techniques applied to study those processes. The biggest concern today is studying ROS, for their lifetime in indoor air is very short due to reactions at the very beginning of terpene oxidation process. Another interesting aspect that is recently discovered is monoterpene autooxidation process that leads to HOMs formation that in turn can influence SOA formation yield. A complex studies covering gas phase and particle phase characterization, but also toxicological studies are crucial to fully understand indoor air chemistry leading to ultrafine particle formation.

Investigation on air quality of specific indoor environments-spa salons located in Gdynia, Poland.

Due to excessive application of essential oils and scented products in spa salons during aromatherapy and massage sessions, the elevated concentration of total volatile organic compounds (TVOCs), particularly terpenes, which are known as secondary organic aerosol (SOA) precursors, is expected there. This study was aimed at determination of VOCs with a particular regard to terpenes in air samples collected in selected spa salons located in Northern Poland. Active air sampling was conducted before and after treatments. Samples were analyzed with the use of thermal desorption gas chromatography coupled with flame-ionization detector (TD-GC-FID) and mass spectrometer (TD-GC-MS). Obtained results allowed to characterize chemical composition of indoor air of spa salons and also to relate the dependence between applied essential oil and indoor air chemical composition. It has been proved that (i) spa salons are characterized by TVOC concentrations exceeding recommended values of 300-400 µg m-3 in most of examined cases, reaching up to several thousand of micrograms per cubic meter, (ii) TVOC concentration is strictly related to salon characteristics and carried out treatments, (iii) terpenes constitute a significant part of TVOCs present in spa indoor air, from 22 up to 86%, (iv) most commonly investigated terpenes in the literature (D-limonene, α-pinene, camphene, and linalool) were also determined at the highest concentration levels in this study and (v) VOC chemical composition is strictly dependent on the type of applied essential oils. On the basis of obtained results, it may be stated that extensive application of essential oils rich in terpenes can significantly alter indoor air chemistry of spa salons, thereby influencing health and well-being of employees working there. Graphical abstract.

Investigation of the Dynamism of Nanosized SOA Particle Formation in Indoor Air by a Scanning Mobility Particle Sizer and Proton-Transfer-Reaction Mass Spectrometry.

Terpenes are VOCs of particular importance, since they are emitted from a wide range of indoor sources and are considered to be precursors of Secondary Organic Aerosol (SOA) formation. It has been proven that SOA particles, especially nanosized ones, pose a threat to human health. In this research, experiments with the application of an environmental chamber and real-time measurement techniques were carried out to investigate in a complimentary way the formation of monoterpene oxidation products and nanosized SOA particles initiated by monoterpene ozonolysis. Proton-Transfer-Reaction Mass Spectrometry with a Time-Of-Flight analyzer (PTR-TOF-MS) and a Scanning Mobility Particle Sizer (SMPS) were applied to determine in real time the dynamism of the formation of the corresponding terpene ozonolysis products and submicron SOA particles. Results proved that firstly, oxidation products were formed, and then, they underwent nucleation and condensation, forming particles whose diameters grew with time. The oxidation products formed were different depending on the type of terpenes applied. The comparison of the results obtained during the experiments with gaseous standard mixtures and real samples commonly present and used in indoor air revealed that the diversified chemical composition of the emission source had implications for both the particle formation initiated by the oxidation of essential oil components and the chemical reactions occurring via the oxidation process. With the instrumentation utilized, the concentration changes at the level of a few ppbv could be monitored.