J. Iza

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.

Daily precipitation in Northern Iberia: Understanding the recent changes after the circulation variability in the North Atlantic sector

Trends in the characteristics of daily precipitation over Northern Iberia (NIB) are analyzed after 14 daily records covering the last 40 years plus seven century-length time series. Results reveal an evolution to drier conditions with subregional variations: in western and central subregions, the decrease in both the occurrence and the intensity of wet days results in a statistically significant decline of total precipitation. Contrary to other regions in the Iberian Peninsula, the lack of correlation between the North Atlantic Oscillation (NAO) index and the observed rainfall anomalies within NIB suggests that the dominance of a positive NAO mode from the late 1970s to 2002 cannot explain the trends. The land-sea and mountain distribution creates sharp rainfall transitions depending on the pathways of the moisture-laden winds. Consequently, NIB and other mountainous regions in the margins of the European continental water divide are sensitive to small changes in the NAO pressure centers and can exhibit both positive and negative rainfall anomalies for each NAO mode. A novel methodology for identifying changes in the NAO modes, consistent with the observed pressure/precipitation anomalies at both continental and regional scales, is presented. After the disaggregation of each dominant NAO wet season into two categories, the main rainfall changes in the NIB region can be explained in the context of the NAO variability during the last decades. The reported (sub)regional rainfall differences stress the need of caution when using NAO reconstructions, based in site specific rainfall anomalies, for the interpretation of the past climate precipitation variability in areas of complex terrain.

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.

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.