Olivier Ramalho

Detection of fungal development in closed spaces through the determination of specific chemical targets

In addition to the biodegradation problems encountered in buildings, exposure of their occupants to moulds is responsible for numerous diseases: infections (invasive nosocomial aspergillosis), immediate or delayed allergies, food-borne infections and different types of irritation. In this context, the aim of our work has been to determine specific chemical tracers for fungal development on construction materials. More generally, by detecting a specific chemical fingerprint of fungal development, our objective was to propose a microbiological alert system which could control systems and/or procedures for the microbiological treatment of indoor areas. We therefore characterized the chemical emissions from six types of construction material contaminated artificially by moulds. Chemical fingerprints were established for 19 compounds arising specifically from fungal metabolism: 2-ethylhexanoic acid methyl ester, 1-octen-3-ol, 3-heptanol, 3-methyl-1-butanol, 2-methyl-1-butanol, 1,3-octadiene, 2-(5H)-furanone, 2-heptene, alpha-pinene, 2-methylisoborneol, 4-heptanone, 2-methylfuran, 3-methylfuran, dimethyldisulfide, methoxybenzene, a terpenoid and three sesquiterpenes. Determining the origin of these compounds and their specific links with a growth substrate or fungal species made it possible to judge the pertinence of choosing these compounds as tracers. Thus the detecting specific volatile organic compounds emitted as from the second day of fungal growth demonstrated that this approach had the advantage of detecting fungal development both reliably and rapidly before any visible signs of contamination could be detected.

Detection of fungal development in a closed environment through the identification of specific VOC : Demonstration of a specific VOC fingerprint for fungal development

The occurrence of disease amongst the occupants of mouldy environments has been widely described in the literature. However, the detection of such moulds in closed environments remains difficult, particularly in the event of recent (before the first deterioration) or masked contamination (behind a material). In this context, the present study aimed to determine a specific chemical fingerprint for fungal development detectable in closed environments (dwellings, office, museum...). To achieve this, chemical emissions from sterile and artificially contaminated by moulds materials were analyzed and compared using a descriptive statistical method. Principal Component Analysis is thus chosen to analyze the results. PCA generated optimum and similar graphical representations of the scatterplot representing the data matrix. This statistical approach made it possible to identify an emission fingerprint without applying any preconception as to the type of emitted compound. Statistical analysis of the data then enabled confirmation of the impact of moulds on total VOC emissions. This emission of specific compounds resulted in obtaining a signature for the presence of fungal development in an environment, defined by specific ions. This analysis, and use of these ions applied to dwellings, made it possible to distinguish those with proven fungal development from those with no sign of mould or with a context favorable to fungal development, thus demonstrating that a chemical fingerprint specific to fungal development could be detected in indoor environments.

Distributions of the particle/gas and dust/gas partition coefficients for seventy-two semi-volatile organic compounds in indoor environment.

Particle/gas and dust/gas partition coefficients (Kp and Kd) are two key parameters that address the partitioning of semi-volatile organic compounds (SVOCs) between gas-phase, airborne particles, and settled dust in indoor environment. A number of empirical equations to calculate the values of Kp and Kd have been reported in the literature. Therefore, the difficulty lies in the selection of a specific empirical equation in a given situation. In this study, we retrieved from the literature 38 empirical equations for calculating Kp and Kd values from the SVOC saturation vapor pressure and octanol/air partition coefficient. These values were calculated for 72 SVOCs: 9 phthalates, 9 polybrominated diphenyl ethers (PBDEs), 11 polychlorinated biphenyls (PCBs), 22 biocides, 14 polycyclic aromatic hydrocarbons (PAHs), 3 alkylphenols, 2 synthetic musks, tributylphosphate, and bisphenol A. The mean and median values of log10Kp or log10Kd for most SVOCs were of the same order of magnitude. The distribution of log10Kp values was fitted to either a normal distribution (for 27 SVOCs) or a log-normal distribution (for 45 SVOCs). This work provides a reference distribution of the log10Kp for 72 SVOCs, and its use may reduce the bias associated with the selection of a specific value or equation.

Temperature dependence of the particle/gas partition coefficient: An application to predict indoor gas-phase concentrations of semi-volatile organic compounds

The indoor gas-phase concentrations of semi-volatile organic compounds (SVOCs) can be predicted from their respective concentrations in airborne particles by applying the particle/gas partitioning equilibrium. The temperature used for partitioning is often set to 25°C. However, indoor temperatures frequently differ from this reference value. This assumption may result in errors in the predicted equilibrium gas-phase SVOC concentrations. To improve the prediction model, the temperature dependence of the particle/gas partition coefficient must be addressed. In this paper, a theoretical relationship between the particle/gas partition coefficient and temperature was developed based on the SVOC absorptive mechanism. The SVOC particle/gas partition coefficients predicted by employing the derived theoretical relationship agree well with the experimental data retrieved from the literature (R>0.93). The influence of temperature on the equilibrium gas-phase SVOC concentration was quantified by a dimensionless analysis of the derived relationship between the SVOC particle/gas partition coefficient and temperature. The predicted equilibrium gas-phase SVOC concentration decreased by between 31% and 53% when the temperature was lowered by 6°C, while it increased by up to 750% when the indoor temperature increased from 15°C to 30°C.

Measurements of semi-volatile organic compounds in settled dust: influence of storage temperature and duration

Indoor dust samples cannot always be analyzed immediately after collection. However, little information is currently available on how storage conditions may affect measurements. This study was designed to determine how sample storage conditions may affect the concentration of semi-volatile organic compounds (SVOCs) in the dust. A composite dust was prepared using a Standard Reference Material (SRM 2585) with real indoor dust samples. The composite dust was stored in various types of packaging, at different temperatures (-18°C, 5°C, 20°C, and 35°C), and in different light conditions. The concentration of SVOCs was measured after various storage durations. No effect on SVOC concentrations was observed for the composite dust stored in an amber glass vial at -18°C for 36xa0months. At 5°C, 20°C, and 35°C, losses occurred for the more volatile compounds. The experimental storage conditions clearly showed that temperature and duration affected the concentrations of SVOCs in the composite dust. The type of packaging material (polyethylene zip bag or polyethylene garbage bag) did not seem to have a systematic effect on the preservation of SVOCs in the composite dust. Maximum storage duration times are proposed for each compound at various temperatures. For most compounds, samples can be stored for 2xa0months at 20°C. For samples that cannot be analyzed immediately, we recommend to store them in the dark at -18°C to ensure a good recovery of all tested compounds.

Cleaning practices and cleaning products in nurseries and schools: to what extent can they impact indoor air quality?

In the framework of a nationwide survey on indoor air quality conducted from September 2009 to June 2011 in 310 nurseries, kindergartens, and elementary schools in all regions of France, cleaning practices and products were described through an extensive questionnaire completed on-site by expert building inspectors. The questionnaire included the cleaning frequencies and periods, cleaning techniques, whether windows were open during cleaning, and the commercial names of the products used. Analysis of the questionnaire responses showed that cleaning was generally performed daily for furniture and floors. It was performed mostly in the evening with wet mopping and with one or more windows open. Five hundred eighty-four different cleaning products were listed, among which 218 safety data sheets (SDSs) were available and analyzed. One hundred fifty-two chemical substances were identified in the SDSs. The typical substances in cleaning products included alcohols, chlorides, terpenes, aldehydes, and ethers; more than half of them are irritants. Two endocrine disruptors, 2-phenylphenol and Galaxolide, were identified in two cleaning products used every day to clean the floors, in seven kindergartens and in a nursery respectively. Eleven reactive substances containing C=C double bonds, mostly terpenes, were identified in a wide variety of cleaning products.

Dermal absorption of semivolatile organic compounds from the gas phase: Sensitivity of exposure assessment by steady state modeling to key parameters

Recent research has demonstrated the importance of dermal exposure for some semivolatile organic compounds (SVOCs) present in the gas phase of indoor air. Though models for estimating dermal intake from gaseous SVOCs exist, their predictions can be subject to variations in input parameters, which can lead to large variation in exposure estimations. In this sensitivity analysis for a steady state model, we aimed to assess these variations and their determinants using probabilistic Monte Carlo sampling for 8 SVOCs from different chemical families: phthalates, bisphenols, polycyclic aromatic hydrocarbons (PAHs), organophosphorus (OPs), organochlorines (OCs), synthetic musks, polychlorinated biphenyls (PCBs) and polybromodiphenylethers (PBDEs). Indoor SVOC concentrations were found to be the most influential parameters. Both Henrys law constant (H) and octanol/water partition coefficient (Kow) uncertainty also had significant influence. While exposure media properties such as volume fraction of organic matter in the particle phase (fom-part), particle density (ρpart), concentration ([TSP]) and transport coefficient (ɣd) had a slight influence for some compounds, human parameters such as body weight (W), body surface area (A) and daily exposure (t) make a marginal or null contribution to the variance of dermal intake for a given age group. Inclusion of a parameter sensitivity analysis appears essential to reporting uncertainties in dermal exposure assessment.

Indoor residential exposure to semivolatile organic compounds in France

Multiple chemicals are emitted in residential accommodation. Aggregate Daily Doses (ADD) (ng/kg-bw/d) were estimated for 32 semivolatile organic compounds (SVOCs) of different chemical families that are frequently detected in French dwellings in both air and settled dust. Daily doses were determined using steady-state models for the population, categorized into 11 age groups covering birth to age 30. Three routes of exposure were taken into account: dust ingestion, inhalation (gaseous and particulate phases) and dermal contact with the gaseous phase of air. Contamination levels were preferentially retrieved from large, nationwide representative datasets. A two-dimensional probabilistic approach was used to assess parametric uncertainty and identify the most influential factors. For children aged 2 to 3years, ADD estimates spanned orders of magnitude, with median values ranging from 8.7pg/kg-bw/d for 2,2,3,4,4-pentabromodiphenylether (BDE 85) to 1.3μg/kg-bw/d for di-isobutyl phthalate (DiBP). Inhalation, ingestion and dermal pathway contributed at varying levels, and depending on compound, air was the dominant medium for 28 of the 32 compounds (either by inhalation or dermal contact). Indoor exposure estimate variance was mainly driven by indoor contamination variability, and secondarily by uncertainty in physical and chemical parameters. These findings lend support to the call for cumulative risk assessment of indoor SVOCs.

Bioaccessibility and bioavailability of environmental semi-volatile organic compounds via inhalation: A review of methods and models

Semi-volatile organic compounds (SVOCs) present in indoor environments are known to cause adverse health effects through multiple routes of exposure. To assess the aggregate exposure, the bioaccessibility and bioavailability of SVOCs need to be determined. In this review, we discussed measurements of the bioaccessibility and bioavailability of SVOCs after inhalation. Published literature related to this issue is available for 2,3,7,8-tetrachlorodibenzo-p-dioxin and a few polycyclic aromatic hydrocarbons, such as benzo[a]pyrene and phenanthrene. Then, we reviewed common modeling approaches for the characterization of the gas- and particle-phase partitioning of SVOCs during inhalation. The models are based on mass transfer mechanisms as well as the structure of the respiratory system, using common computational techniques, such as computational fluid dynamics. However, the existing models are restricted to special conditions and cannot predict SVOC bioaccessibility and bioavailability in the whole respiratory system. The present review notes two main challenges for the estimation of SVOC bioaccessibility and bioavailability via inhalation in humans. First, in vitro and in vivo methods need to be developed and validated for a wide range of SVOCs. The in vitro methods should be validated with in vivo tests to evaluate human exposures to SVOCs in airborne particles. Second, modeling approaches for SVOCs need to consider the whole respiratory system. Alterations of the respiratory cycle period and human biological variability may be considered in future studies.

Influence of indoor environmental factors on mass transfer parameters and concentrations of semi-volatile organic compounds

Semi-volatile organic compounds (SVOCs) in indoor environments can partition among the gas phase, airborne particles, settled dust, and available surfaces. The mass transfer parameters of SVOCs, such as the mass transfer coefficient and the partition coefficient, are influenced by indoor environmental factors. Subsequently, indoor SVOC concentrations and thus occupant exposure can vary depending on environmental factors. In this review, the influence of six environmental factors, i.e., indoor temperature, humidity, ventilation, airborne particle concentration, source loading factor, and reactive chemistry, on the mass transfer parameters and indoor concentrations of SVOCs was analyzed and tentatively quantified. The results show that all mass transfer parameters vary depending on environmental factors. These variations are mostly characterized by empirical equations, particularly for humidity. Theoretical calculations of these parameters based on mass transfer mechanisms are available only for the emission of SVOCs from source surfaces when airborne particles are not present. All mass transfer parameters depend on the temperature. Humidity influences the partition of SVOCs among different phases and is associated with phthalate hydrolysis. Ventilation has a combined effect with the airborne particle concentration on SVOC emission and their mass transfer among different phases. Indoor chemical reactions can produce or eliminate SVOCs slowly. To better model the dynamic SVOC concentration indoors, the present review suggests studying the combined effect of environmental factors in real indoor environments. Moreover, interactions between indoor environmental factors and human activities and their influence on SVOC mass transfer processes should be considered.