Chemical and olfactometric inventory of gaseous spot vents in Mt. Amiata volcanic-geothermal area (Italy).

Geothermal areas are typically characterised by the presence of gases and odours in the background atmosphere, stemming from natural emissions and possible mining exploitation of the area. This study presents the first olfactometric investigation of endogenous gas emissions from natural and archaeo-industrial vents in a geothermal area. Mt. Amiata is known for its complex geology and historical cinnabar mining. This study offers an inventory of spot gas emissions, not only in terms of odour and chemical concentration but also including flux data, a ground-breaking achievement in this field. The primary challenge of this investigation was estimating the emitted flow from ground holes or mine entrances, posing the risk of hazardous anoxic conditions. To address this challenge, an innovative and adaptive approach was adopted. The main breakthrough method involved the adaptation of a balometer, typically employed for indoor ventilation systems, to measure the flow of endogenous gases. Field surveys revealed odour concentrations that can exceed 106 of ouE/m3, surpassing industrial emission level considerably. Chemical concentrations, primarily consisted of CO2 (80/90 %v/v) and CH4 (∼10%v/v), providing critical insights into the global warming potential (GWP) associated with natural emissions. Moreover, these spots, often located at ground level and lacking a substantial atmospheric dilution, pose potential risks to nearby individuals, with concentrations of gases such as H2S surpassing safety thresholds. Total emissive flux of the investigated spot vents in the Mt. Amiata area, showed that the emission rate of H2S is notably substantial (55 kg/h), roughly equivalent to emissions from approximately four 20 MW geothermal plants, as along with odour emission rates in the order of 107 ouE/s. Considering the GWP derived from emitted gases, the total inventory assessment of the spot vents resulted in 36 t/h or 23 t/h CO2eq, depending on the time horizon considered (GWP20 or GWP100 respectively).

Validation study of WindTrax reverse dispersion model coupled with a sensitivity analysis of model-specific settings.

In last years, atmospheric dispersion models have reached considerable popularity in environmental research field. In this regard, given the difficulties associated to the estimation of emission rate for some kind of sources, and due to the importance of this parameter for the reliability of the results, Backward dispersion models may represent promising tools. In particular, by knowing a measured downwind concentration in ambient air, they provide a numerical value for the emission rate. This paper discusses a critical validation of the WindTrax Backward model: the investigation does not only deal with the strict reliability of the model but also assesses under which conditions (i.e. stability class, number, and location of the sensors) the model shows the greatest accuracy. For this purpose, WindTrax results have been compared to observed values obtained from available experimental datasets. In addition, a sensitivity study regarding model-specific parameters required by WindTrax to replicate the physics and the random nature of atmospheric dispersion processes is discussed. This is a crucial point, since, for these settings, indications on the numerical values to be adopted are not available. From this study, it turns out that the investigated model specific settings do not lead to a significant output variation. Concerning the validation study, a general tendency of the model to predict the observed values with a good level of accuracy has been observed, especially under neutral atmospheric conditions. In addition, it seems that WindTrax underestimates the emission rate during unstable stratification and overestimates during stable conditions. Finally, by the definition of alternative scenarios, in which only a portion of the concentration sensors was considered, WindTrax performance appears better than acceptable even with a small number of concentration sensors, as long as the positioning is in the middle of the plume and not in the strict vicinity of the source.

Experimental evaluation on liquid area sources: Influence of wind velocity and temperature on the wind tunnel sampling of VOCs emissions from wastewater treatment plants.

The investigation of Volatile Organic Compounds (VOCs) emission from wastewater basins is a challenging issue. In particular, the quantification of an accurate emission rate appears quite tricky, since the release of VOC compounds from this type of source, and the subsequent dispersion into the atmosphere, is ruled by different complex phenomena, potentially affected by a variety of external chemical and physical parameters. In this regard, the wind velocity and the liquid temperature represent variables that are worth investigating. Given this, the present paper discusses an experimental study aimed at evaluating the influence of these variables on the emission rate of VOCs (i.e. acetone, toluene and butanol) in solution with water at low concentrations (0.5 mL/L and 5 mL/L). The experimental trials are conducted using a wind tunnel system, changing the sweep air flow from 0.02 m/s to about 0.06 m/s and the liquid temperature from 20 °C to 35 °C. This study reveals that while the wind velocity seems to slightly influence the emission rate of VOCs estimated by wind tunnel sampling, the effect of the temperature appears much more significant. This behaviour is also confirmed by experimental trials conducted on real-case industrial wastewater, coming from an equalization tank. In view of this, the approach commonly applied to evaluate the influence of wind velocity (i.e. a dependence of the odour emission rate on the square root of the wind velocity) appears not fully consistent with the experimental results obtained at low concentrations by wind tunnel sampling. Also, the influence of temperature seems more pronounced in the case of butanol, in accordance with the theoretical trend of Henry constant as a function of temperature.

Micrometeorological Methods for the Indirect Estimation of Odorous Emissions.

Odors are typically released into the atmosphere as diffuse emissions from area and volume sources, whose detailed quantification in terms of odor emission rate is often hardly achievable by direct source sampling. Indirect methods, involving the use of micrometeorological methods in order to correlate downwind concentrations to the emission rates, are already mentioned in literature, but rarely found in real applications for the quantification of odor emissions. The instrumentation needed for the development of micrometeorological methods has nowadays become accessible in terms of prices and reliability, thus making the implementation of such methods to industrial applications more and more interesting. For this reason, this work aims to provide an overview of micrometeorological methods and investigate their effective applicability to odors, thereby providing a short description of the physics related to such methods and analyzing the relevant scientific literature. The theoretical basis of these methods is presented, and their advantages and disadvantages are discussed. Moreover, their applicability to the estimation of odor emissions is discussed by providing some suggestions about the suitable ways to evaluate the most critical parameters needed for the calculation of the odor emission rate.

Application of different packing media for the biofiltration of gaseous effluents from waste composting.

A pilot-scale experiment was implemented in a waste bioreactor with an inner capacity of 1 m3 in order to simulate a real-scale composting process. The waste underwent composting conditions that are typical of the initial bio-oxidation phase, characterised by a high production of volatile organic compounds (VOCs), hydrogen sulphide (H2S) and odorants. The waste bioreactor was fed with an intermittent airflow rate of 6 Nm3/h. The target of this study was to investigate the air treatment performance of three biofilters with the same size, but filled with different filtering media: (1) wood chips, (2) a two-layer combination of lava rock (50%) and peat (50%), and (3) peat only. The analyses on air samples taken upstream and downstream of the biofilters showed that the combination of lava rock and peat presents the best performance in terms of mean removal efficiency of odour (96%), total VOCs (95%) and H2S (77%) concentrations. Wood chips showed the worst abatement performance, with respective mean removal efficiencies of 90%, 88% and 62%. From the results obtained, it is possible to conclude that the combination of lava rock and peat can be considered as a promising choice for air pollution control in waste composting facilities.

Dynamic Olfactometry and Oil Refinery Odour Samples: Application of a New Method for Occupational Risk Assessment.

Refineries are characterized by relevant odour impacts, and the control and monitoring of this pollutant have become increasingly important. Dynamic olfactometry, a sensorial analysis that involves human examiners, is currently the most common technique to obtain odour quantification. However, due to the potential presence of hazardous pollutants, the conduction of occupational risk assessment is necessary to guarantee examiners' safety. Nevertheless, the occupational risk for olfactometric examiners, specifically correlated with oil refineries emissions, has not been investigated yet. Therefore, this paper applies a new methodology of risk assessment for workers involved in dynamic olfactometry, focusing on odorous refineries emissions. The chemical characterization of refinery emissions was obtained by TD-GC-MS, analysing odorous samples collected at different refinery odour sources. A database of chemical pollutants emitted from a refinery plant was built up, and the minimum dilution values to be adopted during the analysis of refinery odorous samples was calculated. In particular, this evaluation highlighted that, in this scenario, a non-negligible carcinogenic risk may exist for panellists exposed to refineries' samples, and the carcinogenic risk is sometimes higher than what is acceptable. Therefore, a minimum dilution value between 1.01 and 5, according to the specific sample, must be set to guarantee the examiners' safety.

Simulating Pollutant Dispersion from Accidental Fires with a Focus on Source Characterization.

BACKGROUND: Storage tanks in oil and gas processing facilities contain large volumes of flammable compounds. Once the fuel-air mixture is ignited, it may break out into a large fire or explosion. The growing interest in monitoring air quality and assessing health risks makes the evaluation of the consequences of a fire an important issue. Atmospheric dispersion models, which allow for simulation of the spatial distribution of pollutants, represent an increasingly widespread tool for this type of evaluations. OBJECTIVES: The present study discusses the set up and results of a modeling study relevant to a hypothesized fire in an oil refinery. METHODS: After choosing the most suitable dispersion models, i.e. the Lagrangian model SPRAY and the puff model CALPUFF, estimation of the required input data is discussed, focusing on the source variables, which represent the most uncertain input data. The results of the simulations were compared to regulatory limits to effectively evaluate the environmental consequences. Finally, a sensitivity analysis was employed to identify the most influential variables. RESULTS: The simulation results revealed that ground concentration values were far below the cited long-term limits. However, the most interesting outcome is that depending on the dispersion model and the source type modeled, different results may be obtained. In addition, the sensitivity study indicates that the source area is the most critical variable, since it determines a significantly different behavior depending on the modeled source types, producing, in some cases, variability in the pollutant ground concentrations on selected receptors up to +/- 60%. CONCLUSIONS: Depending on the selected model and the algorithms available to describe the physics of emission, the results showed a different sensitivity to the input variables. Although this can be explained from a mathematical point of view, the problem remains of choosing case by case the option that best approximates the real behavior of the incidental source under investigation. COMPETING INTERESTS: The authors declare no competing financial interests.

Toxicological assessment method for evaluating the occupational risk of dynamic olfactometry assessors.

The paper aims to propose a new method to evaluate the occupational exposure risk for examiners involved in dynamic olfactometry. Indeed, examiners are possibly exposed to hazardous pollutants potentially present in odorous samples. A standardized method to evaluate the examiners' occupational safety is not yet available and the existing models present some critical aspect if applied to real odorous samples (no uniform reference concentrations applied and presence of compounds for which no toxicity threshold is available). A deepening of assessment procedure to evaluate the occupation exposure risk for olfactometric assessors is necessary. This paper proposes a standardized approach for risk assessment in dynamic olfactometry. The proposed approach allows the quantification synthetic and conservative risk indices. In this model, the use of the hazard index for the odorous mixture was proposed to assess the non-carcinogenic risk; the calculation of the inhalation risk was applied to estimate the carcinogenic risk. Different databases can be used to retrieve proper occupational exposure limits, according to the proposed hierarchical basis. These implementations allow obtaining the complete characterization of real samples which can be used to calculate the minimum dilution factor for protecting the panellists' health.

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.

Odour impact assessment by considering short-term ambient concentrations: A multi-model and two-site comparison.

Short-term events are one of the specific aspects that differentiate odour nuisance problems from conventional air quality pollutants. Atmospheric dispersion modelling has been considered the gold standard to realise odour impact assessments and to calculate separation distances. Most of these models provide predictions of concentrations of a pollutant in ambient air on an hourly basis. Even when the hourly mean odour concentration is lower than the perception threshold, concentration peaks above the threshold may occur during this period. The constant peak-to-mean factor is nowadays the most widespread method for evaluating short-term concentrations from the long-term ones. Different approaches have been proposed in the scientific literature to consider non-constant peak-to-mean factors. Two prominent approaches to do so are the i) variable peak-to-mean factor which considers the distance from the source and atmospheric stability and the ii) concentration-variance transport. In this sense, the aim of this work is to compare the results of three different freely available dispersion models (namely, CALPUFF, LAPMOD and GRAL), which implement three distinct ways to evaluate the short-term concentration values. Two sites, one in Austria and the other in Italy, were selected for the investigation. Dispersion model results were compared and discussed both in terms of long-term (hourly) concentrations and short-term. An important outcome of this work is that the dispersion models provided more equivalent results for hourly mean concentrations, in particular in the far-field. On the contrary, the method to evaluate short-term concentrations can deliver disparate results, thereby revealing a potential risk of poor assessment conclusions. The utilistion of a multiangle methodological approach (dispersion models, study site locations, algorithms to incorporate short-term concentrations) allowed providing useful information for future studies and policymaking in this field. Accordingly, our findings call for awareness on how the use of a particular dispersion model and its sub-hourly peak calculation method can affect odour impact assessment conclusions and compliance demonstrations.

A model for the evaluation of organic compounds emission from aerated liquid surfaces.

The purpose of this study is to deepen the knowledge of the various emission phenomena present in aerated tanks, widely used systems for municipal and industrial wastewater treatment. In order to investigate the emission mechanism, a specific model was developed. The theoretical model proposes to consider three different contributions to the emission of organic compounds from aerated wastewater tanks: the convection due to the sweep air flow rate, the rising bubbles stripping and the aerosol formation and successive evaporation. To compare the modeled results, an experimental campaign was conducted with two different solutes, acetone and butanol. The sampling was carried out with a Wind Tunnel system and the outflow gas samples were analysed with gas chromatographic technique. Moreover, this study investigates the dependence of the concentration in the gaseous phase from the speed of the air on the surface (1-5 cm/s) and from the flow of air diffused inside the liquid body (50-200 L/h). The empirical data were compared with theoretical curves. The results confirm two facts: the gas solute concentration decreases as the air velocity increases and, instead, increases with the air flow diffused through the tank.

Review and Comparison of Cancer Biomarker Trends in Urine as a Basis for New Diagnostic Pathways.

Cancer is one of the major causes of mortality worldwide and its already large burden is projected to increase significantly in the near future with a predicted 22 million new cancer cases and 13 million cancer-related deaths occurring annually by 2030. Unfortunately, current procedures for diagnosis are characterized by low diagnostic accuracies. Given the proved correlation between cancer presence and alterations of biological fluid composition, many researchers suggested their characterization to improve cancer detection at early stages. This paper reviews the information that can be found in the scientific literature, regarding the correlation of different cancer forms with the presence of specific metabolites in human urine, in a schematic and easily interpretable form, because of the huge amount of relevant literature. The originality of this paper relies on the attempt to point out the odor properties of such metabolites, and thus to highlight the correlation between urine odor alterations and cancer presence, which is proven by recent literature suggesting the analysis of urine odor for diagnostic purposes. This investigation aims to evaluate the possibility to compare the results of studies based on different approaches to be able in the future to identify those compounds responsible for urine odor alteration.

Assessment of the chemical-physical variables affecting the evaporation of organic compounds from aqueous solutions in a sampling wind tunnel.

The aim of this work is the evaluation and the analysis of the different chemical-physical variables that affect the emission of volatile organic compounds (VOC) and odours from passive liquid area sources inside a wind tunnel, which is typically used for emission sampling. Three different compounds (acetone, butanol and ethanol), having different volatilization properties (e.g., boiling point, solubility), were studied in solution with water at different concentrations. The following physical parameters affecting the VOC volatilization in the Wind Tunnel system were evaluated: the velocity of the air flowing through the device, in a range from 0.01 to about 0.05 m/s, and the temperature of both the liquid source and the sweep air flow, in a range from 12 °C to 42 °C. The experimental results were compared with the existing volatilization models available in literature. In most cases the proposed theoretical model predicts well the experimentally measured concentration. Some discrepancies were observed for lower velocities and also by moving from the room temperature (20 °C); and those were discussed by making some considerations about the volatilization phenomenon. Moreover, the study clearly shows that it is not the gas phase temperature that controls the emission, but the temperature of the liquid phase, due to the effect of the latter on the vapour pressure of the compound, which is the main driving force of the phenomenon.

Innovative Diagnostic Methods for Early Prostate Cancer Detection through Urine Analysis: A Review.

Prostate cancer is the second most common cause of cancer death among men. It is an asymptomatic and slow growing tumour, which starts occurring in young men, but can be detected only around the age of 40–50. Although its long latency period and potential curability make prostate cancer a perfect candidate for screening programs, the current procedure lacks in specificity. Researchers are rising to the challenge of developing innovative tools able of detecting the disease during its early stage that is the most curable. In recent years, the interest in characterisation of biological fluids aimed at the identification of tumour-specific compounds has increased significantly, since cell neoplastic transformation causes metabolic alterations leading to volatile organic compounds release. In the scientific literature, different approaches have been proposed. Many studies focus on the identification of a cancer-characteristic “odour fingerprint” emanated from biological samples through the application of sensorial or senso-instrumental analyses, others suggest a chemical characterisation of biological fluids with the aim of identifying prostate cancer (PCa)-specific biomarkers. This paper focuses on the review of literary studies in the field of prostate cancer diagnosis, in order to provide an overview of innovative methods based on the analysis of urine, thereby comparing them with the traditional diagnostic procedures.

Sampling method for the determination of methane emissions from landfill surfaces.

The first aim of this work is the definition and the study of a suitable sampling method for the measurement of landfill gas (LFG) emissions from landfill surfaces, since, up to now, there are no codified nor universally accepted sampling methods for this specific task. The studied sampling method is based on the use of a static hood. The research work involves a preliminary theoretical study for the hood design, experimental tests for the definition of the optimal sampling procedures, and simulations of the hood fluid-dynamics for the system validation. The second aim of this study is the investigation of the correlations between LFG emissions and meteorological conditions, whose identification would be very useful in terms of effective landfill management and pollution control. This involved a wide literature study for the selection of those parameters that seem to have an influence on LFG emission, and the collection of a great number of experimental data on a target site, which led to the conclusion that atmospheric pressure and soil humidity are the parameters that mostly affect LFG emissions.

Dust emission and dispersion from mineral storage piles.

Dust pollution is a complex problem of growing interest because of its environmental, health, economic and political impact. Environmental impact assessment methods for dust pollution management are often based on the simulation of dust dispersion, which requires a precise characterization of the source term and of the source parameters. The source term model should be as simple and as accurate as possible and requires low time consumption in order to be easily connected to a more complex algorithm for the dispersion calculations. This work focuses on dust emissions from mineral storage piles, which are usually modelled as source terms by means of the algorithm proposed in the AP-42 US EPA standard. Unfortunately, this algorithm tends to overestimate emissions, and when coupled with a Gaussian dispersion model, it leads to inaccurate results in terms of estimation of both concentration and spatial distribution. This paper proposes a new methodology drawn from the original standard US EPA AP-42 https://www3.epa.gov/ttnchie1/ap42/ch13/ scheme with the purpose to account for the actual dynamics of erosion and to enhance the accuracy of the concentration and the pollutant spatial distribution assessment, thereby considering the effects of the wind interactions. The standard EPA methodology and the new one were compared by means of the AERMOD and CALPUFF dispersion models. Results are superimposable in terms of concentration values, leading to a quantification of the same order of magnitude, although with a different and more variable spatial distribution.

H2S Loss through Nalophan™ Bags: Contributions of Adsorption and Diffusion.

Hydrogen-sulfide (H2S) is a molecule of small dimensions typically present in the odor emissions from different plants. The European Standard EN 13725:2003 set a maximum storage time allowed of 30 hours, during which the sampling bag has to maintain the mixture of odorants with minimal changes. This study investigates the H2S losses through Nalophan bags and it shows that nonnegligible losses of H2S can be observed. The percent H2S loss after 30 hrs with respect to the initial concentration is equal to 33% ± 3% at a relative humidity of 20% and equal to 22% ± 1% at a relative humidity of 60%. The average quantity of adsorbed H2S at 30 h is equal to 2.17 105 gH2S/gNalophan at a storage humidity of 20% and equal to 1.79 105 gH2S/gNalophan at a storage humidity of 60%. The diffusion coefficients of H2S through Nalophan, for these two humidity conditions tested, are comparable (i.e., 7.5 10-12 m2/sec at 20% humidity and 6.6 10-12 m2/sec at 60% humidity).

Assessment of the Indoor Odour Impact in a Naturally Ventilated Room.

Indoor air quality influences people's lives, potentially affecting their health and comfort. Nowadays, ventilation is the only technique commonly used for regulating indoor air quality. CO2 is the reference species considered in order to calculate the air exchange rates of indoor environments. Indeed, regarding air quality, the presence of pleasant or unpleasant odours can strongly influence the environmental comfort. In this paper, a case study of indoor air quality monitoring is reported. The indoor field tests were conducted measuring both CO2 concentration, using a photoacoustic multi-gas analyzer, and odour trends, using an electronic nose, in order to analyze and compare the information acquired. The indoor air monitoring campaign was run for a period of 20 working days into a university room. The work was focused on the determination of both CO2 and odour emission factors (OEF) emitted by the human activity and on the evaluation of the odour impact in a naturally ventilated room. The results highlighted that an air monitoring and recycling system based only on CO2 concentration and temperature measurements might be insufficient to ensure a good indoor air quality, whereas its performances could be improved by integrating the existing systems with an electronic nose for odour detection.

Proposal of Odor Nuisance Index as Urban Planning Tool.

This article analyzes the state of the art of the methods and models used for the characterization of odor annoyance and it preliminary advances some proposals for the evaluation of the olfactory nuisance. The use of a sensorial technique, such as dynamic olfactometry, is proposed for the analysis of odor concentrations, odor emission rates, and odor dispersions. A simple model for the quantification of environmental odor nuisance, based on the use of FIDOL factors, that are, frequency, intensity, duration, hedonic tone, and location, is proposed.

Application and Uses of Electronic Noses for Clinical Diagnosis on Urine Samples: A Review.

The electronic nose is able to provide useful information through the analysis of the volatile organic compounds in body fluids, such as exhaled breath, urine and blood. This paper focuses on the review of electronic nose studies and applications in the specific field of medical diagnostics based on the analysis of the gaseous headspace of human urine, in order to provide a broad overview of the state of the art and thus enhance future developments in this field. The research in this field is rather recent and still in progress, and there are several aspects that need to be investigated more into depth, not only to develop and improve specific electronic noses for different diseases, but also with the aim to discover and analyse the connections between specific diseases and the body fluids odour. Further research is needed to improve the results obtained up to now; the development of new sensors and data processing methods should lead to greater diagnostic accuracy thus making the electronic nose an effective tool for early detection of different kinds of diseases, ranging from infections to tumours or exposure to toxic agents.