Sulphur Compounds: Comparison of Different Sorbent Tubes for their Detection

Different techniques have been developed for the analysis of gaseous sulphur pollutants, to maximize the analytical signals. In a complex matrix, such as odorous emissions, the detection of sulphur compounds can be critical in GC analysis, due to the lower concentration of these pollutants and the disturbing effect of co-eluting hydrocarbons. However, their detection is fundamental because they have a non-negligible odour impact. In the field of gaseous emissions analytics, it is common to use sorbent tubes for the sampling step. This technology uses different adsorbent materials, with different selectivity depending on the nature of the gas to be analysed. This work aims to evaluate the ability of three different sorbent tubes to collect different sulphur compounds, belonging to the classes of mercaptans, thioethers and aromatic heterocyclic compounds. A standard solution of 10 sulphur compounds was prepared by diluting in methanol 50 µL of each liquid standard into a 10 mL flask. Subsequently, this solution was diluted in methanol to obtain sulphur standards at five different concentrations (approximately 5-500 ng/µL). The tubes were loaded with the standard solutions with an aliquot of each solution, using a gas chromatograph packed column injector and subsequently analysed by TD-GC-MS. By the results obtained - average Response Factor (RF) and its Relative Standard Deviation (% RSD), it is possible to conduct a comparison among these tubes and evaluate their performance. From the comparison of the tubes, discussing % RSD, it is possible to highlight a slightly better performance, in terms of the number of compounds with % RSD ≤ 30%, for tubes specific for sulphur compounds. Focusing on RF values, multi-sorbent bed tubes show slightly higher RFs for very volatile sulphur compounds, but Sulphur tubes present higher RF values for 6 compounds out of 10 compounds considered. The performance of Tenax TA tubes, instead, appears strictly correlated with the compound’s volatility and therefore they don’t appear useful for sorption of very volatile compounds

An indoor air quality study at the Ambrosiana Art Gallery (Milan)

Indoor air quality in historical buildings and museums is receiving increasing concern nowadays among the scientific community. Many sources of pollutants, both gases and particles, are responsible for the accelerated decay of the works of art. Knowing the levels of indoor pollutants is of critical importance to apply conservation and preservation strategies of cultural heritage [1, 2]. Air quality at the Ambrosiana Art Gallery in Milan has been monitored (in the two periods October-November 2017 and March 2018) inside the room where the preparatory cardboard of the School of Athens (1509-1511), one of most important masterpieces by Raffaello Sanzio, is stored. The cardboard is currently undergoing restoration and will be exposed in a new showcase that will be realized according to the specific environmental and microclimatic conditions of the room. The objective of this study was to monitor the concentration and chemical composition of the aerosol particulate matter (PM) up to the nano fraction, which represents the most dangerous fraction for the works of art surfaces. The monitoring campaigns have been carried out in parallel in the Raffaello room (at present not accessible to visitors) and in a nearby room open to visitors. The set of instuments employed included: a TSP sampler (total suspended particles) (Tecora, Pollution Check, Bravo M2); a DustMonit (Contec) analyzer that measures the concentration of dust up to PM1 and provides 13 granulometric classes (up to 300 nm); a NanoScan Nanoparticle sizer 3910 (TSI) instrument that measures particles concentration up to 10 nm; two instruments for the determination of black carbon (BC) in continuous and in particular a SILIIS instrument (Sphere-Integrated Laser Induced Incandescence Spectroscopy) and a micro aethalometer (AE51 Magee Scientific). Quartz fiber filters have been employed to collect TSP samples to be submitted to chemical analysis. The filters have been fully chemically characterized: main ionic constituents and the carbonaceous fraction (i.e organic carbon, OC and elemental carbon, EC) have been analyzed by IC (ion chromatography) and TOT (thermal optical transmittance) respectively. A particles morphological characterization has been carried out on PM collected on polycarbonate filters by means of SEM-EDX (scanning electron microscopy coupled with energy dispersive X-ray spectroscopy). Outdoor PM concentrations, obtained for the two seasons (autumn 2017 and spring 2018) from ARPA monitoring stations placed in the city center, have been correlated with indoor data

Occupational safety for panellists involved in dynamic olfactometry: A comparison of available risk assessment models

Dynamic olfactometry is now a days the most diffused technique to quantify odour emitted from industrial plants. The methodology, standardized by EN 13725:2003, involves human assessors, who are potentially exposed to hazardous pollutant present in odorous samples. A standardized method to evaluate the exposure risk for panellist during olfactometric analysis is not yet available. However, two different models to evaluate the occupation risk for panellists have been proposed within the scientific literature. Therefore, this paper reviews the available models and discusses their application to a real sample to estimate the occupation exposure risk for workers involved in olfactometric analyses. After a brief models' description, these are both applied to a real odour sample, highlighting the differences between them and the most critical aspects of applying the suggested procedures for the toxicological assessment of the exposure risk for panellists. This discussion highlights that the absence of a unique standardised assessment method and uniform reference concentrations can lead to significant differences in toxicological evaluations. In addition, the presence of compounds for which no toxicity threshold is available can cause an underestimation of the minimum dilution value to be adopted to protect the health of panellists

Evaluation of occupational exposure risk for employees working in dynamic olfactometry: Focus on non-carcinogenic effects correlated with exposure to landfill emissions

This work aims to evaluate the non-carcinogenic health effects related to landfill odor emissions, therefore focusing on workers involved in dynamic olfactometry. Currently, the most common technique to quantify odor emissions is dynamic olfactometry, a sensorial analysis involving human assessors. During the analysis, assessors are directly exposed, at increasing concentrations, to odor samples, and thus to the hazardous pollutants contained therein. This entails the need to estimate the associated exposure risk to guarantee examiners’ safety. Therefore, this paper evaluates the exposure risk for olfactometric examiners to establish the minimum dilution level to be adopted during the analysis of landfills’ odorous samples to guarantee panelists’ safety. For this purpose, an extensive literature review regarding the pollutants emitted by landfill odor sources was conducted, comparing compounds’ chemical concentrations and threshold limit values (TLVs) to calculate the Hazard Index (HI) and thus establish a minimum dilution value. The data collected indicate that a non-negligible non-carcinogenic risk exists for all landfill emissions considered. However, from the data considered, the minimum dilution factor to be adopted is lower than the typical odor concentration observed for these sources. Therefore, the olfactometric analysis of landfill samples can be generally conducted in safe conditions

Lights and shadows of the VOC emission quantification

Now a days, Volatile Organic Compounds (VOC) are a class of air pollutants increasingly studied in the scientific literature, due to the well-known impact on human health and the environment. They can be emitted from different sources, including various types of industrial plants, such as oil refinery and petrochemical plants. For these reasons, the attention of control agencies on VOC emissions has increased and with it the request to quantify the total amount of VOC emitted by a plant, to monitor and to reduce this emission. However, several critical aspects still exist related to the classification of VOCs and their quantification. Indeed, different definitions of VOC are reported in scientific and technical literature. These diversities result in multiple strategies for quantifying the VOCs emitted by an industrial plant. Therefore, this paper reviews the available regulation about the quantification of VOC emitted from industrial plants, focusing on refineries and petrochemical plants, to underline some formal inconsistencies in VOC estimation procedures. From this comparison, it appears clear that VOC quantification can be addressed in different manners, obtaining a substantial non-uniformity of the VOC emission data. The data difference can conduct to a misleading estimation of emission rate

Estimation of emission factors for hazardous air pollutants from petroleum refineries

The hazardous air pollutants (HAPs) group is composed of 187 chemicals that are known to be potentially carcinogenic and dangerous for human health. Due to their toxicological impact, HAPs are an increasingly studied class of compounds. Of the different HAPs sources, refineries are one of the major sources. In order to obtain a preliminary assessment of the impact of a refinery in terms of emissions, a useful instrument is the determination of the emission factor (EF). For this reason, this work, focusing on the USA refining scenario, aims to provide evidence for a generic trend in refinery emissions to evaluate a correlation between the plant size and the amount of its emissions, in particular the HAPs emissions. Based on the analysis of the data collected from the U.S. Environmental Protection Agency (US EPA), a general trend in the emissions from refinery plants was established, showing a positive correlation between the HAPs emissions and the refinery size, represented by a value of the Pearson correlation coefficient r close to 1. Once this correlation was highlighted, a purpose of this work became the estimation of an organic HAPs emission factor (EF): from a whole refining plant, the EF of the total organic HAPs is equal to 10 g emitted for each ton of crude oil processed. Moreover, it was also possible to undertake the same evaluation for two specific HAP molecules: benzene and formaldehyde. The benzene and formaldehyde EFs are equal to, respectively, 0.8 g and 0.2 g for each ton of processed crude oil. This work provides a simple rule of thumb for the estimation of hazardous substances emitted from petroleum refineries in their mean operating conditions

Definition of an emission factor for VOC emitted from Italian and European refineries

Refineries are a major source of atmospheric emissions, which typically include CO, SO2, NOX, particulates, and volatile organic compounds (VOCs). There has been an increasing level of attention toward the emissions of VOCs related to their environmental impact as well as their potential to cause adverse effects on human health and the discomfort associated with their unpleasant odor. In general, an emission factor (EF) represents a model for a first order estimate of emissions, which correlates the quantity of pollutant released into the atmosphere with a so-called "activity index" related to the release of that pollutant. Based on the study of the scientific and technical literature regarding the Italian and European refining scenarios, an attempt was made to verify the existence of a correlation between the size of a refinery and the related total VOC emissions. Once this correlation was evaluated, it was possible to develop an emission factor for VOC emissions considering the plant capacity as the related activity index. After collecting and analyzing data concerning operative capacity and total VOCs emitted from 15 refineries in 2018, the resulting emission factor turned out to be equal to 188 ± 166 g per ton of crude oil processed. This value is in agreement with the range of 50-1000 g/ton reported in the European Best Available Techniques Reference Document for the Refining of Mineral Oil and Gas

Non-carcinogenic occupational exposure risk related to foundry emissions: focus on the workers involved in olfactometric assessments

The scope of this work is the evaluation of the non-carcinogenic occupational risk related to foundry emissions, focusing on the category of workers involved in olfactometric assessments. Odor pollution from industrial activities such as foundries is a serious environmental concern. Sensorial techniques (e.g. dynamic olfactometry, EN13725:2003) currently represent the preferred method for odor emission characterization. During olfactometric analyses, human assessors are directly exposed to the odor at increasing concentrations, thus requiring the assessment of the associated exposure risk to guarantee workers’ safety. This paper presents an investigation aiming to produce an inventory of compounds emitted from foundries together with their odor thresholds and toxicological limits (TLVs), with the final objective to propose a procedure for ensuring workers’ safety during olfactometric analyses. Looking at the database resulting from this study, among the >100 compounds emitted by foundries, 8 have a maximum concentration above their TLV. Among those, ammonia, H2S, phenol, toluene and trimethylamine, produce an odor stimulus before they reach a toxic concentration, thus not representing a risk for olfactometric workers. Benzene, formaldehyde and SO2 are identified as the most critical compounds because they may reach toxic concentrations in foundry emissions, and they start being perceived by humans above their TLV. The proposed procedure entails a minimum dilution factor of 27’000 to be applied to odor samples analyzed by olfactometry, which however might result inapplicable in practical cases, thus pointing out the necessity to adopt chemical measurements to investigate specifically the concentration of the most critical compounds identified in this study

Determination of Air Pollutants: Application of a Low-Cost Method for Preparation of VOC Mixtures at Known Concentration

Gas chromatography (GC) is an excellent tool to obtain qualitative and quantitative information on volatile organic compounds (VOCs) present in gaseous samples. However, to carry out an appropriate quantitative analysis of unknown samples, the use of known concentration gas mixtures, to exploit as standards, is required. Commonly, these mixtures are obtained from cylinders of compressed gas at known concentrations: this involves a considerable economic outlay and problems relating to their handling. This paper aims to apply a method, proposed as a versatile, simple, and economical alternative to the use of such cylinders, for preparing gaseous calibration standards useful to obtain calibration curves for quantification of air pollutants. In addition, the operative limits of this method were investigated. The method involves the continuous injection of volatile compounds in liquid form into a stream of neutral gas, such as air or nitrogen. Exploiting the high volatility of the compounds used, it is possible to generate a continuous gas stream containing the chosen VOC at the desired concentration based on the mass balance of the system. This method proved to be suitable for compounds with volatility ranging from 36 kPa to 0.1 kPa at 293 K and it showed relative bias and relative standard deviation (RSD) values of less than 16% and 8%, respectively. The described dynamic method results are repeatable and accurate. It can be used effectively for compounds with vapour pressure values within the stated limits and provides a more versatile and cost-effective alternative to compressed gas cylinders

Rischio occupazionale e olfattometria dinamica: proposta di un metodo per la valutazione del rischio per gli esaminatori coinvolti nelle analisi olfattometriche

L'olfattometria dinamica coinvolge degli esaminatori, i quali sono esposti durante le analisi a molecole potenzialmente pericolose presenti nei campioni odorigeni, per cui risulta fondamentale valutare il rischio di esposizione per questi lavoratori. Nonostante la sua rilevanza, ancora non esiste un metodo normato per valutare il rischio occupazionale per gli esaminatori olfattometrici. Inoltre, i modelli proposti all’interno della letteratura scientifica presentano alcune criticità. Pertanto, questo lavoro mira a suggerire un nuovo modello per la valutazione del rischio, basato sul calcolo dell’Hazard Index (HI) e del inhalation risk (IR), approfondendo le problematiche evidenziate durante lo studio di campioni reali. Questo approccio, infatti, propone una gerarchia tra le diverse tipologie di valori limite disponibili, per calcolare, in modo robusto, il valore minimo di diluizione da adottare durante le analisi.Dynamic olfactometry involves directly examiners, who are exposed to hazardous pollutants potentially present in odorous samples and it is fundamental to evaluate the occupational exposure risk for these workers. Despite the importance of this topic, a standardized method to evaluate this risk is not yet provided. In addition, the models described in the scientific literature present some critical aspects. Therefore, this work aims to suggest a new model for the risk assessment of olfactometric workers, based on the determination of Hazard Index (HI) and inhalation risk (IR). The novelty of this approach is the overcoming of critical aspects observed in the literature models if applied to real odorous samples, proposing a hierarchical selection from the different databases available. These implementations allow calculating, in a robust manner, the minimum dilution value to be adopted during olfactometric analysis