Monitoring individual exposure. Measurements of volatile organic compounds in breathing-zone air, drinking water, and exhaled breath

Methods for determining individual exposure to volatile organic compounds (VOC) during normal daily activities were field tested on university student volunteers in Texas and North Carolina. The equipment tested included a personal monitor employing Tenax GC® to collect organic vapors for later analysis by GC-MS, and a specially designed spirometer for collecting samples of expired human breath on duplicate Tenax cartridges. The personal monitor and spirometer proved feasible for collecting abundant quantitative data on most of the 15 target organics. Air exposures to many VOC varied widely, sometimes over three orders of magnitude, among students on the same campus who had been monitored over the same time period and day. A log-linear relationship between breathing-zone air exposures and concentrations in exhaled breath was suggested for three chemicals: tetrachloroethylene, 1,1,1-trichloroethane, and vinylidene chloride. Air was the main route of exposure for all target compounds except the two trihalomethanes (chloroform and bromodichloromethane), which were transmitted mainly through water. Estimated total daily intake through air and water of the target organics ranged from 0.3 to 12.6 mg, with 1,1,1-trichloroethane at the highest concentrations in both geographic areas.     

Volatile organic compounds in indoor environment and photocatalytic oxidation: state of the art

Volatile organic compounds (VOCs) are the major pollutants in indoor air, which significantly impact indoor air quality and thus influencing human health. A long-term exposure to VOCs will be detrimental to human health causing sick building syndrome (SBS). Photocatalytic oxidation of VOCs is a cost-effective technology for VOCs removal compared with adsorption, biofiltration, or thermal catalysis. In this paper, we review the current exposure level of VOCs in various indoor environment and state of the art technology for photocatalytic oxidation of VOCs from indoor air. The concentrations and emission rates of commonly occurring VOCs in indoor air are presented. The effective catalyst systems, under UV and visible light, are discussed and the kinetics of photocatalytic oxidation is also presented.     

Screening of household products for the emission of volatile organic compounds

10 household products, eight waxes or polishes, and two detergents have been screened by a headspace technique for the emission of volatile organic compounds (VOC). Using Tenax sampling and analysis by combined gas chromatography-mass spectrometry (GC-MS) more than 80 single compounds or groups of isomers have been identified, and semiquantitative data on the initial emission rates (emission rate immediately after application) have been obtained. Products fall into two groups: those containing water as a main (80 to 90%) constituent and those without water. The initial emission rate of the first group ranged from 0.2 to 2 μg cm⁻²min⁻¹, whereas the second group had higher emission rates of up to 430 μg cm⁻²min⁻¹. Products of the second group emit essentially hydrocarbons (alkanes, alkenes, and terpenes), whereas most products of the first group emit oxygenated compounds including terpene alcohols and their acetates, aliphatic alcohols and esters, and alkoxy-alcohols.     

Sorption of volatile organic compounds on typical carpet fibers

Measurements of adsorption isotherms for three volatile organic compounds (VOCs) (toluene, 1,2-dichlorobenzene and 1,1,1-trichloroethane) on polyacrylonitrile carpet fibers over the temperature range 25-45 degrees C were carried out in a thermogravimetric analyzer (TGA). Linear isotherms were observed in all cases with values of the Henry coefficient ranging from 0.063 to 0.941 mm. The results of additional experiments carried out in a simple test chamber containing a single source of VOC showed that the carpet fibers acted as a significant sink causing a prolonged elevation of VOC concentration in the air within the chamber. An unsteady-state model is presented, which adequately described the adsorption and desorption phenomena occurring in the test chamber and yielded realistic values of the adsorption and desorption rate constants. There was good agreement between the equilibrium and kinetic constants obtained in the TGA and test chamber experiments.     

Identification of nonvolatile neutral organic compounds in tap water

Nonvolatile neutral organic compounds in tap water were examined by high-pressure liquid chromatography, infrared spectrometry, ¹H- and ¹³C-FT-NMR, gel permeation chromatography, elementary analysis, and field desorption mass spectrometry. Neutral organic compounds in 10 m³ of tap water were continuously extracted by the Amberlite XAD-2 resin column, and separated into four fractions by silica-gel column chromatography. Removal of volatile compounds in fraction 3 including polar oxygenated compounds was carried out with microdistillation column under high vacuum by using a diffusion pump. Nonvolatile organic compounds isolated from tap water were identified as poly(vinyl acetate) derivatives with molecular weights ranging from 300 to 1300.     

Environmental significance of nitrogenous organic compounds in aquatic sources

The presence of nitrogenous organic compounds in raw water sources for municipal supplies is of environmental concern because many of them exert significant chlorine demand, while some produce complex stable mutagenic products upon chlorination or are precursors to haloform formation. Seven N-organic compounds have been identified in municipal water concentrates (adenine, 5-chlorouracil, cytosine, guanine, purine, thymine, and uracil) at concentrations ranging from 20 to 860 μg/L. Eight compounds (adenine, cytosine, purine, pyrrole, thymine, tryptophan, tyrosine, and uracil) have been found in filtrates from cultures of either Anabaena flos aquae or Oscillatoria tenuis. Calculated CHCl₃ levels which might have formed at pH 7 in the water supplies were well below the maximum contaminant level (MCL) of 0.1 mg/L proposed by the U.S. Environmental Protection Agency (USEPA) for total trihalogenated methanes. Calculated levels of CHCl₃ which might have been formed under more alkaline conditions, however, were more than 10% of the MCL and were therefore significant. Calculated levels of combined forms of chlorine yielding falsely positive tests for free chlorine in some samples were slightly less or exceeded the 0.5 mg/L free chlorine residual generally taken as an acceptable level of disinfection. The demonstration of a parallel increase in organic nitrogen content with population density in two laboratory grown blue-green algal cultures, and the finding of elevated organic nitrogen values in a water supply sample collected during the occurrence of a blue-green algal bloom, suggested that summer algal bloom occurrence can add considerably to the organic nitrogen content and the trihalomethane potential of water supplies.     

The analysis of free chlorine in the presence of nitrogenous organic compounds

Comparative analyses for aqueous chlorine using Standard Methods indicated that in chlorinated solutions containing nitrogenous organic compounds, none of these methods gave a reliable measurement of free available chlorine. Examination of the cyanuric acid-aqueous chlorine system showed that combined chlorine reacted as if it were free chlorine in all the Standard Methods. The implication of these studies for water and wastewater chlorination is that in waters containing nitrogenous organic compounds, N-Chloro compounds form which may result in an overestimation of the disinfecting potential of the added chlorine, when free chlorine is measured by Standard Methods.     

Kinetics of photocatalytic oxidation of trace organic compounds over titanium dioxide

The 350 nm UV-illuminated slurries of titanium dioxide were used to study the photocatalyzed degradation kinetics of dissolved organic carbon (DOC) as water contaminants. The initial rate data were well described by the Langmuir-Hinshelwood rate equation and the simplified Langmuir-Hinshelwood rate equation (i.e., ln(C₀/C)=K′t). The latter will be more easily used for predicting the degradation of DOC concentration at various elapsed times. In different DOC initial concentrations the apparent first-order rate constant (K′) decreased and half-life increased when the initial DOC concentration decreased. The Langmuir-Hinshelwood rate form will be the most convenient to describe the oxidation rate of DOC in the drinking water resources, if it is as brief as v=kKC.     

Twelve-year trends in ambient concentrations of volatile organic compounds in a community of the Alberta Oil Sands Region,Canada

Environmental exposure to volatile organic compounds (VOCs) in ambient air is one of a number of concerns that the First Nation Community of Fort McKay, Alberta has related to development of Canada's oil sands. An in-depth investigation of trends in ambient air VOC levels in Fort McKay was undertaken to better understand the role and possible significance of emissions from Alberta's oil sands development. A non-parametric trend detection method was used to investigate trends in emissions and ambient VOC concentrations over a 12-year (2001 − 2012) period. Relationships between ambient VOC concentrations and production indicators of oil sands operations around Fort McKay were also examined. A weak upward trend (significant at 90% confidence level) was found for ambient concentrations of total VOCs based on sixteen detected species with an annual increase of 0.64 μg/m³ (7.2%) per year (7.7 μg/m³ increase per decade). Indicators of production (i.e., annual bitumen production and mined oil sands quantities) were correlated with ambient total VOC concentrations. Only one of 29 VOC species evaluated (1-butene) showed a statistically significant upward trend (p = 0.05). Observed geometric (arithmetic) mean and maximum ambient concentrations of selected VOCs of public health concern for most recent three years of the study period (2010 − 2012) were below chronic and acute health risk screening criteria of the U.S. Agency for Toxic Substances and Disease Registry and U.S. Environmental Protection Agency. Thirty-two VOCs are recommended for tracking in future air quality investigations in the community to better understand whether changes are occurring over time in relation to oil sands development activities and to inform policy makers about whether or not these changes warrant additional attention.     

Investigation of volatile organic compounds and phthalates present in the cabin air of used private cars

The presence of selected volatile organic compounds (VOCs) including aromatic, aliphatic compounds and low molecular weight carbonyls, and a target set of phthalates were investigated in the interior of 23 used private cars during the summer and winter. VOC concentrations often exceeded levels typically found in residential indoor air, e.g. benzene concentrations reached values of up to 149.1 µg m^− 3. Overall concentrations were 40% higher in summer, with temperatures inside the cars reaching up to 70 °C. The most frequently detected phthalates were di-n-butyl-phthalate and bis-(2-ethylhexyl) phthalate in concentrations ranging from 196 to 3656 ng m^− 3.     

Quantitative determination of volatile organic compounds in indoor dust using gas chromatography-UV spectrometry

A novel technique, gas chromatography-UV spectrometry (GC-UV), was used to quantify volatile organic compounds (VOCs) in settled dust from 389 residences in Sweden. The dust samples were thermally desorbed in an inert atmosphere and evaporated compounds were concentrated by solid phase micro extraction and separated by capillary GC. Eluting compounds were then detected, identified, and quantified using a diode array UV spectrophotometer. Altogether, 28 compounds were quantified in each sample; 24 of these were found in more than 50% of the samples. The compounds found in highest concentrations were saturated aldehydes (C5-C10), furfuryl alcohol, 2,6-di-tert-butyl-4-methylphenol (BHT), 2-furaldehyde, and benzaldehyde. Alkenals were also found, notably 2-butenal (crotonaldehyde), 2-methyl-propenal (methacrolein), hexenal, heptenal, octenal, and nonenal. The concentrations of each of the 28 compounds ranged between two to three orders of magnitude, or even more. These results demonstrate the presence of a number of VOCs in indoor dust, and provide, for the first time, a quantitative determination of these compounds in a larger number of dust samples from residents. The findings also illustrate the potential use of GC-UV for analysing volatile compounds in indoor dust, some of which are potential irritants (to the skin, eyes or respiratory system) if present at higher concentrations. The potential use of GC-UV for improving survey and control of the human exposure to particle-bound irritants and other chemicals is inferred.     

Chronic risk assessment of exposure to volatile organic compounds in the atmosphere near the largest Mediterranean industrial site

This study focuses on characterising the risk of exposure to volatile organic compounds (VOCs) by means of inhalation in people living in the vicinity of the largest chemical production site in the Mediterranean area. Eighty-six VOCs were initially selected for this study based on their adverse environmental and health effects. The monitoring campaign was conducted for 276 days in three different locations around the chemical site. The analytical method used for the characterisation was based on European standard method EN-14662-2, which consists of the active sampling of air for 24 h in charcoal tubes, followed by extraction with carbon disulphide and GC-MS analysis. Forty-four VOCs with toxicological data available concerning their carcinogenic and non-carcinogenic health effects were quantified during the monitoring campaign. None of the quantified VOCs showed average concentrations exceeding their chronic reference concentrations and, therefore, no non-carcinogenic health effects are expected as a result of this exposure. However, the global average cancer risk due to VOC exposure in the area (3.3 × 10^− 4) was found to be above the values recommended by the WHO and USEPA.The influence of the analytical method was also evaluated by comparing cancer risk estimates using a thermal desorption (TD) method based on method EN-14662-1. The results of the 24-h samples for the solvent extraction method were compared with the average of 12 daily samples of 2-h for the TD method for 24 sampling days. Although the global estimated lifetime cancer risk was statistically comparable for both methods, some differences were found in individual VOC risks.To our knowledge, this is the first study that estimates the carcinogenic and non-carcinogenic risks posed by the inhalation of VOCs in people living near a chemical site of this size, and compares the estimated cancer risk obtained using two different standard analytical methods.     

The effect of suspended particles coated by humic acid on the toxicity of pharmaceuticals, estrogens, and phenolic compounds

The sorption characteristics of 10 organic chemicals, categorized as pharmaceuticals, estrogens and phenols, onto synthetic suspended particle (i.e., alumina) coated with humic acid were investigated according to their octanol-water partition coefficient (K(ow)). Chemical analyses were performed with gas chromatography and mass spectrometry (GC/MS) and high performance liquid chromatography (HPLC). The effects of particles on the toxicity reduction were evaluated using bioassay tests, using Daphnia magna and Vibrio fisheri for phenols and pharmaceuticals, and the human breast cancer cell MCF-7 for estrogens. Sorption studies revealed that 22 and 38% of octylphenol and pentachlorophenol, respectively, were removed by suspended particle, whereas 2,4-dichlorophenol was not removed, which was directly proportional to the logK(ow) value. Similar to the sorption tests, suspended particles significantly reduced the acute toxicities of octylphenol and pentachlorophenol to D. magna and V. fisheri (p<0.01), but there was no significant difference in the toxicity of 2,4-dichlorophenol to D. magna (p=0.8374). Pharmaceuticals, such as ibuprofen, gemfibrozil and tolfenamic acid, showed no discernible sorption to the suspended particle, with the exception of diclofenac, which revealed 11% sorption. For estrogens, such as estrone, 17beta-estradiol and 17alpha-ethynylestradiol, the results indicated no reduction in the sorption test. This may be attributed to the polar interaction by functional groups in sorption between pharmaceuticals and estrogens and suspended particles. In the bioassays, presence of suspended particles did not significantly modify the toxicity of pharmaceuticals (regardless of their K(ow) values) to D. magna, V. fisheri or E-screen.