Nieves Durana

Automatic on-line monitoring of atmospheric volatile organic compounds: gas chromatography-mass spectrometry and gas chromatography-flame ionization detection as complementary systems.

Traditionally air quality networks have been carrying out the continuous, on-line measurement of volatile organic compounds (VOC) in ambient air with GC-FID. In this paper some identification and coelution problems observed while using this technique in long-term measurement campaigns are described. In order to solve these problems a GC-MS was set up and operated simultaneously with a GC-FID for C2-C11 VOCs measurement. There are few on-line, unattended, long term measurements of atmospheric VOCs performed with GC-MS. In this work such a system has been optimized for that purpose, achieving good repeatability, linearity, and detection limits of the order of the GC-FID ones, even smaller in some cases. VOC quantification has been made by using response factors, which is not frequent in on-line GC-MS. That way, the identification and coelution problems detected in the GC-FID, which may led to reporting erroneous data, could be corrected. The combination of GC-FID and GC-MS as complementary techniques for the measurement of speciated VOCs in ambient air at sub-ppbv levels is proposed. Some results of the measurements are presented, including concentration values for some compounds not found until now on public ambient air VOC databases, which were identified and quantified combining both techniques. Results may also help to correct previously published VOC data with wrongly identified compounds by reprocessing raw chromatographic data.

Rise of moist plumes from tall stacks in turbulent and stratified atmospheres

Abstract This paper, developed as a part of the European project RECAPMA (REgional Cycles of Air Pollution in the Mediterranean Area), presents a plume rise model capable of dealing with complex atmospheric profiles-wind shear and thermal stratification-since it performs a numerical integration, along the plume trajectory, of a set of differential equations derived from the balance of mass, momentum and energy in the plume. The classical parametrization for entrainment of air into plume due to self-generated turbulence has been completed with entrainment-detrainment processes in turbulent winds. The model deals with a mixture of four components-dry combustion gas, dry air, water vapor and liquid water-to allow for condensation and/or re-evaporation within the plume. Profile shapes of temperature and velocity of the plume cross sections are assumed to have axisymmetrical distributions and they can vary with the longitudinal distance to stack. Twenty field observations of plume trajectories and final rise in two power plants were compared to the numerical model predictions and a set of classical formulations used for regulatory models: effects like plume merger in a multiple source, condensation and re-evaporation, rise in turbulent winds, rise in light winds and in stratified atmosphere with wind shear, are discussed and tested separately. The results show that much of the scatter between classical model prediction and experimental results is due to the presence of complexities not allowed for in that formulation: some of the discrepancies are favorable because models underestimate plume rise, but caution has to be exercised, especially under negative wind shear-wind decreasing with height-combined with the presence of high inversions since plume rise is systematically overestimated. Our numerical model performs better under all those circumstances and can be used to calculate impacts downwind, by using the three-dimensional trajectories coupled with a dispersion model for the pollutant to be traced. A case study is presented in which impacts at long distances in turbulent winds and in a quasi-adiabatic atmosphere can be explained by using a model of uniform vertical distribution of pollutants under a subsidence inversion.

Online Hourly Determination of 62 VOCs in Ambient Air: System Evaluation and Comparison with Another Two Analytical Techniques

Abstract This paper presents results of the processing and validation of data collected by an automatic gas chromato-graph (AGC). This system was used to monitor 62 volatile organic compounds (VOCs) in urban air in the Basque Country, Spain. The nonpolar compounds (C2–C10) identified—paraffins, olefins, aromatics, and chlorinated compounds—accounted for 88% of the mass of total non-methane hydrocarbons (TNMHCs) in ambient air. The evaluation of linearity, precision, detection limits (DLs), and stability of retention times (RTs) indicates that the equipment is suitable for measuring ambient air automatically for prolonged periods (6 months). The calibration of the equipment using response factors calculated on the basis of the effective carbon number (ECN) showed variations of over 10% for acetylene, isoprene, and n-hexane. The results provided by the automatic chromatograph correlated significantly with simultaneous results from other widely used techniques for determining VOCs in ambient air: (1) portable GC, equipped with photoionization detector (PID), and (2) active adsorption on Tenax-TA followed by thermal des-orption and chromatographic analysis.

Determination of volatile organic compounds in the atmosphere using two complementary analysis techniques

During a preliminary field campaign of volatile organic compound (VOC) measurements carried out in an urban area, two complementary analysis techniques were applied to establish the technical and scientific bases for a strategy to monitor and control VOCs and photochemical oxidants in the Autonomous Community of the Basque Country. Integrated sampling was conducted using Tenax sorbent tubes and laboratory analysis by gas chromatography, and grab sampling and in situ analysis also were conducted using a portable gas chromatograph. With the first technique, monocyclic aromatic hydrocarbons appeared as the compounds with the higher mean concentrations. The second technique allowed the systematic analysis of eight chlorinated and aromatic hydrocarbons. Results of comparing both techniques, as well as the additional information obtained with the second technique, are included.

Chemometric determination of PAHs in aerosol samples by fluorescence spectroscopy and second‐order data analysis algorithms

The development of a method based on the combination of excitation–emission fluorescence matrices (EEMs) and second‐order algorithms is proposed to identify and quantify 10 polycyclic aromatic hydrocarbons (PAHs) in extracts of aerosol samples, a particularly complex sample matrix because of the low amount of PAHs and the numerous fluorescent interferences. Parallel factor analysis, unfolded partial least squares coupled to residual bilinearization (RBL) and multivariate curve resolution – alternating least squares offered satisfactory results for their identification and quantification and were also helpful for the optimization of the extraction procedure for these substances by means of analysis of a standard reference material.

Trichloroethylene, tetrachloroethylene and carbon tetrachloride in an urban atmosphere: mixing ratios and temporal patterns

The measurement of halogenated hydrocarbons in the atmosphere is a matter of great interest owing to their adverse effects on the human health and the environment. This work is focused on the measurement of three toxic chlorinated hydrocarbons: trichloroethylene (TCE), tetrachloroethylene (PCE), and carbon tetrachloride (CTC). Moreover, CTC is a greenhouse gas and an ozone depleting gas, restricted under the Montreal Protocol. Owing to their low reactivity, the target chlorinated hydrocarbons are considered to be persistent and, thus, many measurements only address their mean mixing ratios (a concentration measure expressed as mol/mol). Consequently, most of the reported data have low temporal resolution as daily, seasonal or yearly mean mixing ratios, obtained with few measurements. In the study reported in this paper hourly measurements were performed for a long period of time: almost two years for TCE and PCE, and one year for CTC. The main objective was to study the temporal variability of the chlorinated hydrocarbons with high temporal resolution in order to identify their main sources and to enhance the understanding of their atmospheric processes. During the measurement period, March 2007–February 2008 with N = 3290 valid data, CTC showed a mean mixing ratio of 0.16 ppbv (SD = 0.13) with lower temporal variability than the majority of non-methane hydrocarbons (NMHCs), being very well mixed in the urban atmosphere owing to its long lifetime. TCE and PCE mean mixing ratios for the May 2006–February 2008 period, were 0.13 ppbv (SD = 0.42, N = 4601) and 0.25 ppbv (SD = 0.54, N = 4709) respectively, with a larger temporal variability. The study of the sources of TCE and PCE reveals that both compounds have industrial and/or commercial origin, but with different main sources.

Atmospheric carbon tetrachloride in rural background and industry surrounded urban areas in Northern Iberian Peninsula: Mixing ratios, trends, and potential sources

Latest investigations on atmospheric carbon tetrachloride (CTC) are focused on its ozone depleting potential, adverse effects on the human health, and radiative efficiency and Global Warming Potential as a greenhouse gas. CTC mixing ratios have been thoroughly studied since its restriction under the Montreal Protocol, mostly in remote areas with the aim of reporting long-term trends after its banning. The observed decrease of the CTC background mixing ratio, however, was not as strong as expected. In order to explain this behavior CTC lifetime should be adjusted by estimating the relative significance of its sinks and by identifying ongoing potential sources. Looking for possible sources, CTC was measured with high-time resolution in two sites in Northern Spain, using auto-GC systems and specifically developed acquisition and processing methodologies. The first site, Bilbao, is an urban area influenced by the surrounding industry, where measurements were performed with GC-MSD for a one-year period (2007-2008). The second site, at Valderejo Natural Park (VNP), is a rural background area where measurements were carried out with GC-FID and covering CTC data a nonsuccessive five-year period (2003-2005, 2010-2011, and 2014-2015years). Median yearly CTC mixing ratios were slightly higher in the urban area (120pptv) than in VNP (80-100pptv). CTC was reported to be well mixed in the atmosphere and no sources were noticed to impact the rural site. The observed long-term trend in VNP was in agreement with the estimated global CTC emissions. In the urban site, apart from industrial and commercial CTC sources, chlorine-bleach products used as cleaning agents were reported as promotors of indoor sources.

Summertime high resolution variability of atmospheric formaldehyde and non-methane volatile organic compounds in a rural background area

On rural background areas atmospheric formaldehyde (HCHO) is important for its abundance and chemical reactivity, directly linked to the tropospheric ozone formation processes. HCHO is also toxic and carcinogenic to humans. Atmospheric HCHO was continuously measured in summer 2016 during 81 days (N = 6722, average: 1.42 ppbv) in a rural background area in Northern Spain, Valderejo Natural Park (VNP) using a Hantzsch fluorimetric system. To better characterize the photochemical processes the database was completed with hourly measurements of 63 Non-Methane Hydrocarbons (NMHC) performed by gas chromatography and other common atmospheric pollutants and meteorological parameters. HCHO mixing ratios were highly correlated with ozone and isoprene. Cloudy and rainy days, with low temperature and radiation, led to low HCHO mixing ratios, with maxima (<2 ppbv) registered around 14 UTC. On days with increased radiation and temperature HCHO maxima occurred slightly later (<6 ppbv, ≈16:00 UTC). During clear summer days with high temperature and radiation, two HCHO peaks were registered daily, one synchronized with the radiation maximum (≈3-4 ppbv, ≈13:00 UTC) and an absolute maximum (<10 ppbv, ≈18:00 UTC), associated with the addition of HCHO coming into VNP due to inbound transport of old polluted air masses. In the ozone episode studied, the processes of accumulation and recharge of ozone and of HCHO ran in parallel, leading to similar daily patterns of variation. Finally, HCHO mixing ratios measured in VNP were compared with other measurements at rural, forested, and remote sites all over the world, obtaining similar values.

Optimization and Validation of Thermal Desorption Gas Chromatography-Mass Spectrometry for the Determination of Polycyclic Aromatic Hydrocarbons in Ambient Air

Thermal desorption (TD) coupled with gas chromatography/mass spectrometry (TD-GC/MS) is a simple alternative that overcomes the main drawbacks of the solvent extraction-based method: long extraction times, high sample manipulation, and large amounts of solvent waste. This work describes the optimization of TD-GC/MS for the measurement of airborne polycyclic aromatic hydrocarbons (PAHs) in particulate phase. The performance of the method was tested by Standard Reference Material (SRM) 1649b urban dust and compared with the conventional method (Soxhlet extraction-GC/MS), showing a better recovery (mean of 97%), precision (mean of 12%), and accuracy (±25%) for the determination of 14 EPA PAHs. Furthermore, other 15 nonpriority PAHs were identified and quantified using their relative response factors (RRFs). Finally, the proposed method was successfully applied for the quantification of PAHs in real 8 h-samples (PM10), demonstrating its capability for determination of these compounds in short-term monitoring.

High Temporal Resolution Measurements and Numerical Simulation of Ozone Precursors in a Rural Background

High-resolution numerical modelling results - using RAMS and HYPACT - of an ozone precursors episode, detected on a rural background area in Northern Iberia, are shown. The episode was identified by data analysis of a continuous VOC measurement system. Simulation results show that, when low temporal and spatial resolutions are used, the origin of polluted air masses affecting targets at low heights may be wrongly interpreted.