Gas chromatographic/mass spectrometric determination of benzene and its alkyl derivatives in indoor and outdoor air in Fuji, Japan

An analytical method was established for the determination of benzene and 13 of its alkyl derivatives. The method was applied to a survey of indoor pollution that investigated the usefulness of the method, concentration levels, seasonal variations, profiles, correlations between compounds, and factors that affected indoor pollution by these compounds. The survey was performed in 21 houses in the summer of 1999 and 20 houses in the winter of 1999-2000 in Fuji, Japan. All the target compounds were detected in the indoor and outdoor air of all houses. Outdoor concentrations of benzene ranged from 0.779 to 3.17 microg/m3 in summer and from 1.35 to 6.04 microg/m3 in winter, whereas indoor concentrations of benzene ranged from 0.694 to 3.11 microg/m3 in summer and from 1.65 to 6.89 microg/m3 in winter. Indoor concentrations of the target compounds, except for benzene, were elevated, compared with outdoor concentrations. Because indoor and outdoor concentrations of benzene and its derivatives in summer were lower than in winter, the emission of these compounds may be increased by use of a heater and other variables present in winter. Profiles of the compounds, correlations between the compounds, and factors that affected indoor pollution (determined by multiple regression analysis) were investigated. These results suggested that indoor benzene predominantly penetrated from outdoors and that other benzene derivatives were emitted from indoor sources, such as paint solvents and kerosene heaters.     

Highly sensitive automatic analysis of polycyclic aromatic hydrocarbons in indoor and outdoor air

A method for the quantitation of polycyclic aromatic hydrocarbons (PAHs) in indoor and outdoor air by high-performance liquid chromatography (HPLC) with a spectrofluorometric detection and programmed excitation and emission wavelength pairs is proposed. The mobile phase is a linear gradient of methanol-water. The relative standard deviations (n = 5) are in the range 0.38-1.7% at concentration levels of 0.69-11.40 ng ml(-1). The determination limits (S N = 10 ) are 0.5-15.9 pg. The proposed method was successfully applied to quantitate 12 PAHs in gas phase and particulates in indoor and outdoor air. The recoveries of PAHs from gas phase and particulates were 95.7-117.5 and 94.8-112.4%, respectively. This highly sensitive automatic HPLC analysis for PAHs both in gas phase and particulates can be applied to indoor and outdoor survey.     

Study of the winter and summer changes of the air composition in the church of Szalowa, Poland, related to conservation

The St. Michael Archangel’s Church in Szalowa, Poland, was selected for closer investigation with respect to the indoor/outdoor air exchange and its influence on the air quality and work arts preservation. Chemical composition, size and abundance of particulate matter and concentration of gases NO₂, SO₂, O₃ inside and outside the church were determined. To study seasonal variation of the weather condition (temperature, inversion level, wind direction) and the influence of seasonal sources of the air pollution (like heating of the nearby houses), samples were collected in winter and summer time. It was stated that suspended particulate matter inside the wooden church has in general an outdoor source. Several groups of particles were distinguished such as the organic ones, soil dust, nitrates and sulphates. In case of organic and soil dust particles, the concentration inside was higher than outside. From the results, in comparison to literature data, one can conclude that accumulation of particulate suspended matter in the church is more intense than in other types of buildings. Gaseous pollutants were detected but their concentration was negligible.     

Temporal variation of atmospheric polycyclic aromatic hydrocarbon concentrations in PM10 from the Kathmandu Valley and their gas-particle concentrations in winter

The concentrations of polycyclic aromatic hydrocarbons (PAHs) in particulate matter (PM) with a diameter <10 µm (PM₁₀, 50% cut off) were investigated in the Kathmandu Valley, Nepal, during 2003. In order to understand the dynamics of atmospheric PAHs in winter, the PAH concentrations in total PM and in the gaseous phase were investigated in the valley in December 2005. Total of 45 PAH compounds (∑45PAHs) were analysed by high-resolution gas chromatography/high-resolution mass spectrometry (HRGC/HRMS). In 2003, the ∑45PAH concentrations in PM₁₀ ranged between 4.3 and 89 ng m^?3 (annual average; 27 ± 24 ng m^?3). The average concentrations of ∑45PAHs in December 2005 were 210 ± 33 ng m^?3 in total PM and 430 ± 90 ng m^?3 in the gaseous phase. The ∑45PAH concentration in PM accounted for more than 30% of the sum of their particulate and gaseous forms. Phenanthrene (Ph) was the most predominant compound in the gaseous phase, whereas four- to seven-ring PAHs were predominant in total PM. The highest values of ∑45PAHs occurred in the winter and spring. Estimates of emission sources based on diagnostic molecular ratios showed that atmospheric PAHs in the Kathmandu Valley mainly originated from the exhaust gas of diesel engine. In the winter and spring, PAH pollution would be accelerated by the operations of brick kilns and the frequent formation of an atmospherically stable layer in the valley.     

A review of monitoring of airborne polycyclic aromatic hydrocarbons: An African perspective

In this review, we focus on the status of the monitoring of polycyclic aromatic hydrocarbons (PAHs) in ambient air as well as in living (indoor) and working environments in Africa from 2000 to 2018. This is important as PAHs are ubiquitous in the environment and are known to be potentially carcinogenic. Aspects of sampling such as collection media for particle bound and gaseous PAHs are discussed. The efficiency and basic quality assurance data of commonly employed extraction techniques for separating target PAHs from sampling media using conventional solvent-based and emerging solvent-free approaches were also evaluated. Polyurethane foam and quartz fiber filters are generally the most commonly used collection media for gaseous and particle bound PAHs, respectively. A wide range of total PAH concentrations in ambient air has been reported across the continent of Africa, with the highest levels found at sampling sites close to high density traffic and industrial areas. A rapidly increasing population, commercial and industrial development, poor urban transportation infrastructure and the use of low quality oil products were the main causes of high total gas and particulate PAH concentrations (1.6–103 μg/m³) in West African port cities such as Cotonou, Benin. With regards to indoor environments, gas phase PAHs were detected at the highest total concentrations in rural areas ranging from 1 to 43 μg/m³ in Burundi with naphthalene being the most prevalent. Firewood burning was the major emission source in most developing countries and resulted in benzo[a]pyrene concentrations above the European permissible risk level of 1 ng/m³.     

A passive sampler-GC/ECD method for analyzing 18 volatile organohalogen compounds in indoor and outdoor air and its application to a survey on indoor pollution in Shizuoka, Japan

A simple and reliable method was developed for analysis of 18 volatile organohalogen compounds (VOHCs) both indoors and outdoors, consisting of VOHC collection by a passive sampler, extraction with toluene by mechanical shaking, and automatic separation analysis by capillary gas-chromatography with electron capture detector (GC/ECD). The passive sampler is a porous polytetrafluoroethylene (PTFE) tube (30.30+/-0.37 mm net collection length, 5.0 mm inside diameter, 0.990 g weight) uniformly packed with activated charcoal (194.4+/-3.8 mg). The procedure was applied to a field survey on indoor and outdoor VOHC pollution in Shizuoka, Japan. Ten VOHCs, including trichloroethylene, tetrachloroethylene, chloroform, carbon tetrachloride, and p-dichlorobenzene, were detected from indoor and outdoor air samples. The ratios of maximum to minimum VOHC concentrations, both outdoors and indoors, were large. The indoor and outdoor concentrations of 1,1-dichloroethylene, dichloromethane, 1,1,1-trichloroethylene, carbon tetrachloride and trichloroethylene were found to be similar. Indoor concentrations of trihalomethanes, p-dichlorobenzene and tetrachloroethylene were higher than those of outdoors.     

广州市夏、冬季室内外PM2.5中元素组分的特征与来源

通过采集广州市9个居民住宅室内、外的PM2.5样品,测定分析PM2.5中18个元素组分的质量浓度,分析讨论其污染、分布特征并解析其污染来源。经过比较得知,广州市PM2.5中元素污染较严重;不同类型住宅PM2.5中元素浓度存在空间分布特征;大部分元素浓度具有夏季比冬季低的变化特征;室内与室外元素浓度比值介于0.4974～2.0497之间;元素浓度的室内、室外相关拟合结果说明冬季室内空气受室外空气影响比夏季时情况更明显;基于富集因子分析,Se、As、S、Pb、Br、Zn和Cl元素高度富集;Ni、V、Cu元素中等富集,主要来自人为源,而Cr、Sr、K、Mn、Ca和Ti元素不富集,主要来自自然源。     

Urban air pollutants and their micro effects on medieval stained glass windows

Levels of urban gaseous and particulate pollutants were investigated in the Cathedral of Cologne, Germany in the framework of the EU-project “VIDRIO”. The purpose of this study was to evaluate the influence of a protective double glazing system on the preservation of ancient stained glass windows by sampling at protected and unprotected windows (indoors, in the interspace and outdoor of the Cathedral). The interspace between the ancient stained glass window and the protective glazing is flushed in the Cathedral by indoor air, hence isolating the historic glass from the outdoor air and exposing it to indoor air on both sides of the glass panels. Concentrations of aggressive gaseous pollutants such as NO₂, SO₂, O₃ and CO₂ as well as elemental concentrations of bulk particles and relative abundances of single particles were surveyed at all sampling locations. Elemental concentrations in bulk particulate matter were found to be significantly lower inside the Cathedral in comparison to the outdoor air. This result is advantageous for the stained glass windows. Single particle analysis of the samples from Cologne showed also soil dust and organic particles as well as sulphates and nitrates, from which the latter two compounds are dangerous for the stained glass windows. On the base of the obtained results, it can be concluded that the protective glazing system in the Cathedral of Cologne can be considered as predominantly advantageous from both the gases' point of view (except for NO₂-candles burning) and from the particles' point of view.     

Long term and equilibrium factor indoor radon measurements

This paper presents the annual radon gas concentrations obtained during the 1994–1995 monitoring campaign using passive electret system (type E-PERM). Radon levels were measured in 154 single family dwellings, in normal occupancy conditions (open house condition) in the metropolitan zone of Mexico City. At the same time radon monitoring was performed outdoors. The results show the general log-normal distribution of integrated indoor radon concentration with an annual indoor mean of 3.8 pCi·l⁻¹. The seasonal variations show the minimum mean values in the summer season which are 39% lower than that in autumn. Equilibrium factors (F) were measured in 12 typical houses both in autumn and winter using a continuous working level monitor for short-lived radon decay products and H-chamber loaded with a short term electret (HST, E-PERM) for radon gas. The obtained total mean equilibrium factors are:F=0.41±0.17 andF=0.29±0.04 for indoor and outdoor, respectively. A quality program was also improved.     

Volatile organic compounds in indoor air and in expired air as markers of activities

Summary Volatile organic compounds (VOC) are present in indoor air at concentrations generally higher than in outdoor air. In this study VOC concentrations in the air of two classrooms differing in insulation, and in the expired air of children in them, were investigated. Qualitative and quantitative determinations were done by gas chromatography-mass spectrometry techniques. Differences in the concentrations of VOC in indoor air and in the expired air of the children were linked to the endogeneous or exogeneous origin of the compounds, to the activities of the children and to the quality of indoor-outdoor air exchanges.     

Long-term sampling: Suitable monitoring strategy for determination of semi-volatile PAHs at outdoor and indoor sites

Summary A new, molecular diffusion-based, sampling device (Analyst 2) has been used for the determination of semi-volatile PAHs in air. It has been developed from a previous model (Analyst), which is suitable for volatile hydrocarbons. The new model is capable of collecting enough gaseous PAHs for GC-MS analysis of enriched samples after 2 months exposure to both urban and suburban air. The adsorbent material adopted for enriching PAHs from air (Carbopack C) gives good recoveries of analytes from naphthalene to chrysene when a single solvent extraction is run at ambient temperature. The results of an experiment for assessing the internal consistency of this device are presented here. Data collected indicate that the “uptake rate” is constant for a 6-month sampling period. Results are also presented and discussed for indoor and outdoor determination of volatile PAHs, collected at both urban and suburban sites over a 12-month period in 2-monthly steps.     

Determination of polycyclic aromatic hydrocarbons in atmospheric particulate matter of Valencia city

Summary Polycyclic aromatic hydrocarbons (PAHs) were determined in atmospheric particulate matter in 11 sites of the Valencia area and at several times during the year. Sample analysis was carried out by ultrasonic acetonitrile extraction followed by reverse phase HPLC separation and fluorescence detection. The maximum concentration of total PAH developed in winter and spring. Mean values per sampling site varied from 0.193 to 1.668 g/m³ of filtered air. Environmental noise and temperature were determined at those same 11 sites and correlated with PAH levels.     

Radon and thoron concentrations in offices and dwellings of the Gunma prefecture, Japan

Summary Aone year survey of indoor radon and thoron concentrations was carried out in offices and dwellings of the Gunma prefecture, Japan. A passive integrating radon and thoron discriminative monitor was used in the survey. The annual mean radon concentration was 22±14 Bq ^. m^-3, and ranged from 12 to 93 Bq ^. m^-3 among the 56 surveyed rooms. Radon concentration in offices was generally higher than that in the dwellings, with the arithmetic averages of 29 and 17 Bq ^. m^-3, respectively. Radon concentrations were generally lower in the traditional Japanese wooden houses than those houses built with other building materials. Seasonal variation of indoor radon was also observed in this survey. Compared to summer and autumn, radon concentrations were generally higher in spring and winter. The mean value of thoron to radon ratio was estimated to be 1.3, higher values were observed in the dwellings than in the offices. The annual effective dose from the exposure to indoor radon was estimated to be 0.47 mSv after taking the occupancy factors of offices and dwellings into account.     

Radon and thoron progeny levels in air samples at Udagamandalam region of Nilgiris in India

Measurement of concentration of radon and thoron daughter products in various indoor environment covering four seasons of a year in Udagamandalam Taluk of Nilgiris biosphere has been carried out using a high volume air sampler to asses the inhalation dose to the population which delivers higher dose than the radon and thoron gas alone. The potential alpha-energy concentrations of the radon and thoron progeny ranged from 0.97 to 12.72 mWL and from 1.63 to 15.83 mWL with a geometric mean of 6.02 and 7.89 mWL, respectively, taking all seasons into account. These measurements have yielded a wealth of data on the variation among the indoor radon and thoron progeny in various places during different seasons. The radon and thoron progeny levels are higher in winter seasons and are less in summer season with autumn and spring data lie in between winter and summer. Using the dose conversion factor for indoor exposures given in UNSCEAR 93 report the internal equivalent dose to the inhalation of radon progeny is evaluated to be 1357 mSv^.y^–1 and the corresponding annual effective dose equivalent value has been found to be 2.13 mSv^.y^–1. It can be observed that the mean value of radon is higher than the Indian average. Also it is found the radon and thoron progeny levels are higher in the case of houses built with rock and granite and in tiled type houses of nearly 100 years old. The levels are less in the case of houses built with brick and cement. The observed results for different types of houses and seasons are discussed in this paper.     

Analysis of industrial contaminants in indoor air: Part 1. Volatile organic compounds,carbonyl compounds,polycyclic aromatic hydrocarbons and polychlorinated biphenyls

This article reviews recent literature on the analysis of industrial contaminants in indoor air in the framework of the REACH project, which is mainly intended to improve protection of human health and the environment from the risks of more than 34 millions of chemical substances. Industrial pollutants that can be found in indoor air may be of very different types and origin, belonging to the volatile organic compounds (VOCs) and semivolatile organic compounds (SVOCs) categories. Several compounds have been classified into the priority organic pollutants (POPs) class such as polychlorinated biphenyls (PCBs), polychlorinated dibenzo-p-dioxins and furans (PCDD/PCDFs) and related polychlorinated compounds, and polycyclic aromatic hydrocarbons (PAHs). Many of these compounds are partially associated to the air gas phase, but also to the suspended particulate matter. Furthermore, settled dust can act as a concentrator for the less volatile pollutants and has become a matrix of great concern for indoors contamination. Main literature considered in this review are papers from the last 10 years reporting analytical developments and applications regarding VOCs, aldehydes and other carbonyls, PCBs, PCDDs, PCDFs, and PAHs in the indoor environment. Sample collection and pretreatment, analyte extraction, clean-up procedures, determination techniques, performance results, as well as compound concentrations in indoor samples, are summarized and discussed. Emergent contaminants and pesticides related to the industrial development that can be found in indoor air are reviewed in a second part in this volume.     

Determination of selected oxygenated polycyclic aromatic hydrocarbons (oxy-PAHs) in diesel and air particulate matter standard reference materials (SRMs)

Oxygenated polycyclic aromatic hydrocarbons (oxy-PAHs) have recently received much attention in discussions regarding the negative impacts of particulate matter (PM) on human health and the environment. The National Institute of Standards and Technology provides several environmental matrix standard reference materials (SRMs) with certified and reference values for polycyclic aromatic hydrocarbons (PAHs) and nitrated PAHs. In this study, the concentrations of oxygenated PAHs are determined in three air PM SRMs (1649b, 1648a, and 2786) and three diesel PM SRMs (1650b, 2975, and 1975) using two independent gas chromatography–mass spectrometry methods. Concentrations of oxy-PAHs were at the milligrams per kilogram level with higher overall concentrations in diesel PM (up to 50 mg/kg for 9,10-anthraquinone). One of the highest oxy-PAH concentrations (up to 5 mg/kg) measured in the air particulate SRMs was for 7,12-benz[a]anthracenquinone. These results suggest that oxygenated PAHs should not be neglected in the analysis of PM as their concentrations can be as high as those of some PAHs and are one to two orders of magnitude higher than those for nitro-PAHs.     

Polycyclic aromatic hydrocarbons (PAHs) in surface sediments of Monastir Bay (Tunisia,Central Mediterranean): distribution,origin and seasonal variations

To assess PAH contamination state of Monastir Bay, surface sediments were collected and analysed for 17 selected parent PAHs by GC/MS. Sediments were sampled from five sites in wet and dry seasons. Total PAH concentrations were in the range of 25.6 to 576.8?ng/g d.wt in winter and 44.9–395.8?ng/g d.wt in summer. Comparison of results with Sediment Quality Guidelines suggested no eco-toxicological risk for benthic organisms. The use of molecular indices has shown that PAHs in surface sediments originate mainly from pyrolytic sources. Total PAH concentrations in surface sediments showed no significant correlations with organic matter content and pelite fraction. The analysis of spatial and seasonal variations of PAHs in surface sediments has demonstrated that final distribution of PAHs in surface sediments is mainly governed by hydrological conditions.     

Outdoor absorbed dose rate in air in relation to airborne natural radioactivity and meteorological conditions at Bucharest (Romania)

Summary The results of environmental absorbed dose rate measurements performed over a 3-year period (1996-1999) at the Bucharest Environmental Radioactivity Surveillance Station are presented. The outdoor absorbed dose rate levels were analyzed in connection to airborne natural radioactivity and meteorological parameters, such as precipitation, air temperature and pressure.The minimum values were recorded in winter and the maximum values at the end of summer or beginning of autumn, mainly as a consequence of changes in weather and soil conditions (rain, ground moisture, snow cover).Significant statistical correlations were obtained between the outdoor absorbed dose rate and the air temperature and atmospheric pressure, respectively.     

Polycyclic aromatic hydrocarbons in the atmosphere: monitoring, sources, sinks and fate. II: Sinks and fate

This paper reviews the transformation processes that polycyclic aromatic hydrocarbons (PAHs) undergo in the atmosphere. These processes can take place both in the gas phase and in the particulate/aerosol one. Among the gas-phase processes, the most important ones are the daytime reaction with *OH and the nighttime reaction with *NO3. The relative importance of the two processes depends on the particular PAH molecule. For instance, gaseous naphthalene is mainly removed from the atmosphere upon reaction with *OH, while gaseous phenanthrene is mainly removed by reaction with *NO3. Oxy-, hydroxy-, and nitro-PAHs are the main transformation intermediates. Reaction with ozone and photolysis play a secondary role in the transformation of gaseous PAHs. The particle-associated processes are usually slower than the gas-phase ones, thus the gas-phase PAHs usually have shorter atmospheric lifetimes than those found on particulate. Due to the higher residence time on particulate when compared with the gas phase, direct or assisted photolysis plays a relevant role in the transformation of particle-associated PAHs. Among the other processes taking place in the condensed phase, nitration plays a very important role due to the health impact of nitro-PAHs, some of them being the most powerful mutagens found so far in atmospheric particulate extracts.     

A seasonal study of atmospheric conditions influenced by the intensive tourist flow in the Royal Museum of Wawel Castle in Cracow, Poland

Increasing mass tourism can generate important microclimatic perturbations and also elevate indoor pollution by the transport of fine particulate matter. The purpose of this research was to study the indoor air conditions in the Royal Museum of Wawel Castle in Cracow, Poland, displaying amongst other valuable works of art also a unique collection of Flemish tapestries. The investigation involved in the determination of transport and deposition of particulate matter brought in by visitors. The microclimate inside the exhibition rooms was also monitored. Samples of suspended particulates were collected inside and outside the museum in winter and summer 2006. On days with intensive tourist visits the concentration of total suspended particulates was significantly higher (i.e., 130 µg/m³ in winter and 49 µg/m³ in summer) than on those days without tourists (i.e., 73 µg/m³ and 22 µg/m³ in winter and summer, respectively). The concentrations of all investigated elements were also considerably higher during the tourist flow. This was especially valid for soil dust associated elements (Si, K, Ca, Al, and Ti), with considerably higher levels in summer than winter. This could be linked with much more frequent tourist activity in the summer period. Also, the concentration of Cl was much higher in winter than summer, due to the use of de-icing salts on the roads and pavements.