Application of comprehensive gas chromatography (GCxGC) to measurements of volatile organic species in ambient air

The focus of this thesis was the in-situ application of the new analytical technique "GCxGC" in both the marine and continental boundary layer, as well as in the free troposphere. Biogenic and anthropogenic VOCs were analysed and used to characterise local chemistry at the individual measurement sites. The first part of the thesis work was the characterisation of a new set of columns that was to be used later in the field. To simplify the identification, a time-of-flight mass spectrometer (TOF-MS) detector was coupled to the GCxGC. In the field the TOF-MS was substituted by a more robust and tractable flame ionisation detector (FID), which is more suitable for quantitative measurements. During the process, a variety of volatile organic compounds could be assigned to different environmental sources, e.g. plankton sources, eucalyptus forest or urban centers. In-situ measurements of biogenic and anthropogenic VOCs were conducted at the Meteorological Observatory Hohenpeissenberg (MOHP), Germany, applying a thermodesorption-GCxGC-FID system. The measured VOCs were compared to GC-MS measurements routinely conducted at the MOHP as well as to PTR-MS measurements. Furthermore, a compressed ambient air standard was measured from three different gas chromatographic instruments and the results were compared. With few exceptions, the in-situ, as well as the standard measurements, revealed good agreement between the individual instruments. Diurnal cycles were observed, with differing patterns for the biogenic and the anthropogenic compounds. The variability-lifetime relationship of compounds with atmospheric lifetimes from a few hours to a few days in presence of O3 and OH was examined. It revealed a weak but significant influence of chemistry on these short-lived VOCs at the site. The relationship was also used to estimate the average OH radical concentration during the campaign, which was compared to in-situ OH measurements (1.7 x 10^6 molecules/cm^3, 0.071 ppt) for the first time. The OH concentration ranging from 3.5 to 6.5 x 10^5 molecules/cm^3 (0.015 to 0.027 ppt) obtained with this method represents an approximation of the average OH concentration influencing the discussed VOCs from emission to measurement. Based on these findings, the average concentration of the nighttime NO3 radicals was estimated using the same approach and found to range from 2.2 to 5.0 x 10^8 molecules/cm^3 (9.2 to 21.0 ppt). During the MINATROC field campaign, in-situ ambient air measurements with the GCxGC-FID were conducted at Tenerife, Spain. Although the station is mainly situated in the free troposphere, local influences of anthropogenic and biogenic VOCs were observed. Due to a strong dust event originating from Western Africa it was possible to compare the mixing ratios during normal and elevated dust loading in the atmosphere. The mixing ratios during the dust event were found to be lower. However, this could not be attributed to heterogeneous reactions as there was a change in the wind direction from northwesterly to southeasterly during the dust event.

The formation of OH radicals from Criegee intermediates: a LIF-FAGE study from laboratory to ambient

Das Hydroxyl Radikal ist, auf globalem Maßstab, das bedeutendste Oxidant in der Atmosphäre. Es initiiert den Abbauprozess vieler, teilweise schädlicher, Spurengase und insbesondere den von flüchtigen Kohlenwasserstoffen (VOC). Die OH Konzentration ist somit ein gutes Maß für die augenblickliche Selbstreinigungskapazität der Atmosphäre. Messungen zu nächtlicher Zeit mit LIF-FAGE-Instrumenten (engl.: laser-induced fluorescence - fluorescence assay by gas expansion) haben Konzentrationen des Hydroxylradikals (OH) ergeben, die signifikant höher waren, als sich mit der bekannten Chemie erklären ließ. Um herauszufinden, ob ein solches Signal wirklich atmosphärisches OH ist oder von einer störenden Spezies stammt, die im Messinstrument OH produziert, wurde das LIF-FAGE-Instrument des Max-Planck-Instituts für Chemie (MPIC) im Rahmen dieser Doktorarbeit modifiziert und getestet. Dazu wurde ein so genannter Inlet Pre-Injector (IPI) entwickelt, mit dem in regelmäßigen Abständen ein OH-Fänger in die Umgebungsluft abgegeben werden kann, bevor das OH vom Instrument erfasst wird. Mit dieser Technik ist es möglich, ein Hintergrund-OH (OHbg), d. h. ein im Instrument erzeugtes OH-Signal, vom gemessenen OH-Gesamtsignal (OHtot) zu trennen. Die Differenz zwischen OHtot und OHbg ist die atmosphärische OH-Konzentration (OHatm). Vergleichsmessungen mit der hier entwickelten Technik, dem IPI, in zwei verschiedenen Umgebungen mit Instrumenten basierend auf Massenspektrometrie mit chemischer Ionisation (CIMS, engl.: chemical ionization mass spectrometry) als alternativer Methode des OH-Nachweises, zeigten eine weitgehende Übereinstimmung. Eine umfassende Beschreibung des Systems zur Ermittlung der Ursache des OHbg hat ergeben, dass es weder von einem Artefakt des Instruments noch von hinlänglich bekannten und beschriebenen LIF-FAGE-Interferenzen stammt. Zur Bestimmung der Spezies, die das OHbg-Signal verursacht, wurden verschiedene Laborstudien durchgeführt. Die Arbeit im Rahmen dieser Doktorarbeit hat ergeben, dass das LIF-FAGE-Instrument leicht auf OH reagiert, das beim monomolekularen Zerfall stabilisierter Criegee-Intermediate (SCI) im Niederdruckbereich des Instruments gebildet wird. Criegee-Intermediate oder Carbonyloxide entstehen bei der Ozonolyse ungesättigter flüchtiger Kohlenwasserstoffverbindungen (VOC, engl.: volatile organic compounds) und können daher in der Umgebungsluft vorkommen. Anhand von Tests mit verschiedenen Verweilzeiten der SCI im Niederdruckbereich des Instruments in Verbindung mit einem detaillierten Modell mit der neuesten SCI-Chemie wurde die monomolekulare Zerfallsgeschwindigkeit von 20  10 s-1 für den syn-Acetaldehyd-Oxykonformer bestimmt. Der in Feldkampagnen gemessene OHbg-Wert wurde dahingehend untersucht, ob SCI die Quelle des beobachteten Hintergrund-OH im Feld sein könnten. Das Budget für die SCI-Konzentration, das für die Kampagnen HUMPPA-COPEC 2010 und HOPE 2012 berechnet wurde, ergab eine SCI-Konzentration zwischen ca. 103 und 106 Molekülen pro cm3. In der Kampagne HUMPPA-COPEC 2010 ergab die Schwefelsäurekonzentration, dass die OH-Oxidation von SO2 allein die gemessene H2SO4-Konzentration nicht erklären konnte. In dieser Arbeit konnte gezeigt werden, dass das Hintergrund-OH mit dieser ungeklärten Produktionsrate von H2SO4 korreliert und somit die Oxidation von SO2 durch SCI als mögliche Erklärung in Frage kommt. Ferner korreliert das Hintergrund-OH in der Kampagne HOPE 2012 mit dem Produkt aus Ozon und VOC und konnte mit SO2 als SCI Fänger entfernt werden. Qualitativ zeigen wir somit, dass das in der Umgebungsluft gemessene Hintergrund-OH wahrscheinlich durch den monomolekularen Zerfall von SCI verursacht wird, doch sind weitere Studien notwendig, um die quantitativen Beziehung für diese Spezies und dem Hintergrund-OH in unserem Instrument zu bestimmen.

Estimation of the postmortem interval by means of ¹H MRS of decomposing brain tissue: influence of ambient temperature

Standard methods for the estimation of the postmortem interval (PMI, time since death), based on the cooling of the corpse, are limited to about 48 h after death. As an alternative, noninvasive postmortem observation of alterations of brain metabolites by means of (1)H MRS has been suggested for an estimation of the PMI at room temperature, so far without including the effect of other ambient temperatures. In order to study the temperature effect, localized (1)H MRS was used to follow brain decomposition in a sheep brain model at four different temperatures between 4 and 26°C with repeated measurements up to 2100 h postmortem. The simultaneous determination of 25 different biochemical compounds at each measurement allowed the time courses of concentration changes to be followed. A sudden and almost simultaneous change of the concentrations of seven compounds was observed after a time span that decreased exponentially from 700 h at 4°C to 30 h at 26°C ambient temperature. As this represents, most probably, the onset of highly variable bacterial decomposition, and thus defines the upper limit for a reliable PMI estimation, data were analyzed only up to this start of bacterial decomposition. As 13 compounds showed unequivocal, reproducible concentration changes during this period while eight showed a linear increase with a slope that was unambiguously related to ambient temperature. Therefore, a single analytical function with PMI and temperature as variables can describe the time courses of metabolite concentrations. Using the inverse of this function, metabolite concentrations determined from a single MR spectrum can be used, together with known ambient temperatures, to calculate the PMI of a corpse. It is concluded that the effect of ambient temperature can be reliably included in the PMI determination by (1)H MRS.

Impact of environmental regulations on lead concentrations in Texas ambient air and water: 1970--1990

In the last two decades, the significance of lead has been addressed in a number of environmental regulations at the national and state levels. This project investigated the environmental regulations (Clean Air Act and Amendments, 1970-1990 and Clean Water Act of 1977) and their cumulative effects on lead in ambient air and water in the state of Texas. For this purpose, historical records from the Texas Water Development Board, Texas Natural Resources Conservation Commission, and the United States Geological Survey have been assembled and analyzed for temporal and spatial trends. These trends might correspond to the phase out of lead in gasoline and other regulations.^ This study concluded that there is a significant correlation (p $\leq$.001) between environmental regulations of lead in gasoline and the concentration of lead in ambient air. Lead concentrations in ambient air have been reduced by over 90 percent in the past twenty years. An overall significant difference (p $\leq$.001) was found in mean (94, 15 respectively) lead concentrations in surface water between two time periods, one at the beginning of the twenty year period and one at the end of the study period. There has been an overall reduction of lead concentrations in surface water in Texas of approximately 84 percent. However, this reduction cannot be statistically associated with any one regulation. Groundwater data could not be analyzed for lead concentrations because of limitations of reporting data as "less than". Approximately two percent of the groundwater data was analyzed by Oneway ANOVA and no significant difference was found between the means (18, 19 respectively) of two time periods, 1977-1979 and 1988-1990. This data is consistent with the regulations having a contributory affect on declining concentrations, but other factors cannot be ruled out as having added to these declines. This study can also serve as a starting point for a more in-depth study of environmental regulations and their impact on the environment. ^

BENZENE TOXICITY AND THE OCCURRENCE OF BENZENE IN THE AMBIENT AIR OF THE HOUSTON AREA

This study was conducted by either literature review or actual field survey. Results are summarized as follows: (1) Long-term occupational exposure of workers to benzene vapor at levels of 3-7 ppm, 2-3 ppm and 1.6 ppm may result in a decreased level of leucocyte alkaline phosphates, an increased incidence of chromosome aberrations and an increased level of ALA in erythrocytes, respectively; (2) Benzene is capable of causing fetotoxic effects in animals at levels as low as 10 ppm by volume; (3) Exposure of animals to or less than 1 ppm benzene vapor may result in leucopenia, an inverse ratio of muscle antagonist chronaxy and a decreased level of ascorbic acid in fetus's and mother's liver as well as whole embryo; (4) Benzene is causally associated with the increased incidence of pancytopenia, including unicytopenia, bicytopenia and aplastic anemia, and chromosome aberrations in occupational exposure population, and at best benzene must also be considered as a leukemogen; (5) Since it can be emitted into the atmosphere from both man-made and natural sources, benzene in some concentrations is present everywhere in the various compartments of the environment; (6) The findings of the emission of benzene from certain natural sources indicate that reducing benzene to a zero-level of exposure is theoretically impossible; (7) The annual average of benzene concentration detected in the Houston ambient air is 2.50 ppb, which is about 2.4 times higher than the nation-wide annual average exposure level and may have been some health implications to the general public; (8) In the Houston area, stationary sources are more important than mobile sources in contributing to benzene in the ambient air. ^

Nd and Mn concentration in planktonic foraminifera

Neodymium isotopes are becoming widely used as a palaeoceanographic tool for reconstructing the source and flow direction of water masses. A new method using planktonic foraminifera which have not been chemically cleaned has proven to be a promising means of avoiding contamination of the deep ocean palaeoceanographic signal by detrital material. However, the exact mechanism by which the Nd isotope signal from bottom waters becomes associated with planktonic foraminifera, the spatial distribution of rare earth element (REE) concentrations within the shell, and the possible mobility of REE ions during changing redox conditions, have not been fully investigated. Here we present REE concentration and Nd isotope data from mixed species of planktonic foraminifera taken from plankton tows, sediment traps and a sediment core from the NW Atlantic. We used multiple geochemical techniques to evaluate how, where and when REEs become associated with planktonic foraminifera as they settle through the water column, reside at the surface and are buried in the sediment. Analyses of foraminifera shells from plankton tows and sediment traps between 200 and 2938 m water depth indicate that only ~20% of their associated Nd is biogenically incorporated into the calcite structure. The remaining 80% is associated with authigenic metal oxides and organic matter, which form in the water column, and remain extraneous to the carbonate structure. Remineralisation of these organic and authigenic phases releases ions back into solution and creates new binding sites, allowing the Nd isotope ratio to undergo partial equilibration with the ambient seawater, as the foraminifera fall through the water column. Analyses of fossil foraminifera shells from sediment cores show that their REE concentrations increase by up to 10-fold at the sediment-water interface, and acquire an isotopic signature of bottom water. Adsorption and complexation of REE3+ ions between the inner layers of calcite contributes significantly to elevated REE concentrations in foraminifera. The most likely source of REE ions at this stage of enrichment is from bottom waters and from the remineralisation of oxide phases which are in chemical equilibrium with the bottom waters. As planktonic foraminifera are buried below the sediment-water interface redox-sensitive ion concentrations are adjusted within the shells depending on the pore-water oxygen concentration. The concentration of ions which are passively redox sensitive, such as REE3+ ions, is also controlled to some extent by this process. We infer that (a) the Nd isotope signature of bottom water is preserved in planktonic foraminifera and (b) that it relies on the limited mobility of particle reactive REE3+ ions, aided in some environments by micron-scale precipitation of MnCO3. This study indicates that there may be sedimentary environments under which the bottom water Nd isotope signature is not preserved by planktonic foraminifera. Tests to validate other core sites must be carried out before downcore records can be used to interpret palaeoceanographic changes.

Aerosol total mass concentration and optical depth during IPY 2007-2008 at Maitri and Larsemann Hills Station

The properties of background aerosols and their dependence on meteorological, geographical and human influence are examined using measured spectral aerosol optical depth (AOD), total mass concentration (Mt) and derived number size distribution (NSD) over two distinct coastal locations of Antarctica; Maitri (70°S, 12°E, 123 m m.s.l.) and Larsemann Hills (LH; 69°S, 77°E, 48 m m.s.l.) during southern hemispheric summer of 2007-2008 as a part of the 27th Indian Scientific Expedition to Antarctica (ISEA) during International Polar Year (IPY). Our investigations showed comparable values for the mean columnar AOD at 500 nm over Maitri (0.034±0.005) and LH (0.032±0.006) indicating good spatial homogeneity in the columnar aerosol properties over the coastal Antarctica. Estimation of Angstrom exponent a showed accumulation mode dominance at Maitri (alpha ~1.2±0.3) and coarse mode dominance at LH (0.7±0.2). On the other hand, mass concentration (M(T)) of ambient aerosols showed relatively high values (~8.25±2.87 µg/m**3) at Maitri in comparison to LH (6.03±1.33 µg/m**3).

Air concentration of polybrominated diphenyl ethers around the Great Lakes and the Arctic

Atmospheric PBDEs were measured on a monthly basis in 2002-2004 at Point Petre, a rural site in the Great Lakes. Average air concentrations were 7.0 ± 13 pg/m**3 for the sum of 14BDE (excluding BDE-209), and 1.8 ± 1.5 pg/m**3 for BDE-209. Concentrations of 3 dominant congeners (i.e., BDE-47, 99, and 209) were comparable to previous measurements at remote/rural sites around the Great Lakes, but much lower than those at urban areas. Weak temperature dependence and strong linear correlations between relatively volatile congeners suggest importance of advective inputs of gaseous species. The significant correlation between BDE-209 and 183 implies their transport inputs associated with particles. Particle-bound percentages were found greater for highly brominated congeners than less brominated ones. These percentages increase with decreasing ambient temperatures. The observed gas/particle partitioning is consistent with laboratory measurements and fits well to the Junge-Pankow model. Using air mass back-trajectories, atmospheric transport to Point Petre was estimated as 76% for BDE-47, 67% for BDE-99, and 70% for BDE-209 from west-northwest and southwest directions. During the same time period, similar congener profiles and concentration levels were found at Alert in the Canadian High Arctic. Different inter-annual variations between Point Petre and Alert indicate that emissions from other regions than North America could also contribute PBDEs in the Arctic. In contrast to weak temperature effect at Point Petre, significant temperature dependence in the summertime implies volatilization emissions of PBDEs at Alert. Meanwhile, episodic observations in the wintertime were likely associated with enhanced inputs through long-range transport during the Arctic Haze period.

Seawater carbonate chemistry and concentration boundary layers around complex assemblages of macroalgae in a laboratory experiment

Metabolic processes have the potential to modulate the effects of ocean acidification (OA) in nearshore macroalgal beds. We investigated whether natural mixed assemblages of the articulate coralline macroalgae Arthrocardia corymbosa and understory crustose coralline algae (CCA) altered pH and O2 concentrations within and immediately above their canopies. In a unidirectional flume, we tested the effect of water velocity (0-0.1 m/s), bulk seawater pH (ambient pH 8.05, and pH 7.65), and irradiance (photosynthetically saturating light and darkness) on pH and O2 concentration gradients, and the derived concentration boundary layer (CBL) thickness. At bulk seawater pH 7.65 and slow velocities (0 and 0.015 m/s), pH at the CCA surface increased to 7.90-8.00 in the light. Although these manipulations were short term, this indicates a potential daytime buffering capacity that could alleviate the effects of OA. Photosynthetic activity also increased O2 concentrations at the surface of the CCA. However, this moderating capacity was flow dependent; the CBL thickness decreased from an average of 26.8 mm from the CCA surface at 0.015 m/s to 4.1 mm at 0.04 m/s. The reverse trends occurred in the dark, with respiration causing pH and O2 concentrations to decrease at the CCA surface. At all flow velocities the CBL thicknesses (up to 68 mm) were much greater than those previously published, indicating that the presence of canopies can alter the CBL substantially. In situ, the height of macroalgal canopies can be an order of magnitude larger than those used here, indicating that the degree of buffering to OA will be context dependent.

Seawater carbonate chemistry, nutrients, growth rate and phytoplnkton community response to increasing CO2 concentration during experiments, 2011

This paper reports for the first time upon the effects of increasing CO2 concentrations on a natural phytoplankton assemblage in a tropical estuary (the Godavari River Estuary in India). Two short-term (5-day) bottle experiments were conducted (with and without nutrient addition) during the pre-monsoon season when the partial pressure of CO2 in the surface water is quite low. The results reveal that the concentrations of total chlorophyll, the phytoplankton growth rate, the concentrations of particulate organic matter, the photosynthetic oxygen evolution rates, and the total bacterial count were higher under elevated CO2 treatments, as compared to ambient conditions (control). delta13C of particulate organic matter (POM) varied inversely with respect to CO2, indicating a clear signature of higher CO2 influx under the elevated CO2 levels. Whereas, delta13CPOM in the controls indicated the existence of an active bicarbonate transport system under limited CO2 supply. A considerable change in phytoplankton community structure was noticed, with marker pigment analysis by HPLC revealing that cyanobacteria were dominant over diatoms as CO2 concentrations increased. A mass balance calculation indicated that insufficient nutrients (N, P and Si) might have inhibited diatomgrowth compared to cyanobacteria, regardless of increased CO2 supply. The present study suggests that CO2 concentration and nutrient supply could have significant effects on phytoplankton physiology and community composition for natural phytoplankton communities in this region. However, this work was conducted during a non-discharge period (nutrient-limited conditions) and the responses of phytoplankton to increasing CO2 might not necessarily be the same during other seasons with high physicochemical variability. Further investigation is therefore needed.

Analysis of Contributions to NO2 Ambient Air Quality Levels in Madrid City (Spain) through Modeling. Implications for the Development of Policies and Air Quality Monitoring

As environmental standards become more stringent (e.g. European Directive 2008/50/EC), more reliable and sophisticated modeling tools are needed to simulate measures and plans that may effectively tackle air quality exceedances, common in large cities across Europe, particularly for NO2. Modeling air quality in urban areas is rather complex since observed concentration values are a consequence of the interaction of multiple sources and processes that involve a wide range of spatial and temporal scales. Besides a consistent and robust multi-scale modeling system, comprehensive and flexible emission inventories are needed. This paper discusses the application of the WRF-SMOKE-CMAQ system to the Madrid city (Spain) to assess the contribution of the main emitting sectors in the region. A detailed emission inventory was compiled for this purpose. This inventory relies on bottom-up methods for the most important sources. It is coupled with the regional traffic model and it makes use of an extensive database of industrial, commercial and residential combustion plants. Less relevant sources are downscaled from national or regional inventories. This paper reports the methodology and main results of the source apportionment study performed to understand the origin of pollution (main sectors and geographical areas) and define clear targets for the abatement strategy. Finally the structure of the air quality monitoring is analyzed and discussed to identify options to improve the monitoring strategy not only in the Madrid city but the whole metropolitan area.

Effects of elevated atmospheric CO2 concentration on leaf dark respiration of Xanthium strumarium in light and in darkness

Leaf dark respiration (R) is an important component of plant carbon balance, but the effects of rising atmospheric CO2 on leaf R during illumination are largely unknown. We studied the effects of elevated CO2 on leaf R in light (RL) and in darkness (RD) in Xanthium strumarium at different developmental stages. Leaf RL was estimated by using the Kok method, whereas leaf RD was measured as the rate of CO2 efflux at zero light. Leaf RL and RD were significantly higher at elevated than at ambient CO2 throughout the growing period. Elevated CO2 increased the ratio of leaf RL to net photosynthesis at saturated light (Amax) when plants were young and also after flowering, but the ratio of leaf RD to Amax was unaffected by CO2 levels. Leaf RN was significantly higher at the beginning but significantly lower at the end of the growing period in elevated CO2-grown plants. The ratio of leaf RL to RD was used to estimate the effect of light on leaf R during the day. We found that light inhibited leaf R at both CO2 concentrations but to a lesser degree for elevated (17–24%) than for ambient (29–35%) CO2-grown plants, presumably because elevated CO2-grown plants had a higher demand for energy and carbon skeletons than ambient CO2-grown plants in light. Our results suggest that using the CO2 efflux rate, determined by shading leaves during the day, as a measure for leaf R is likely to underestimate carbon loss from elevated CO2-grown plants.

Ambient ozone pollution and daily mortality in three megacities in China

Thesis (Master's)--University of Washington, 2016-06

Age determination in individual wild-caught Drosophila serrata using pteridine concentration

Fluorescence spectrophotometry can reliably detect levels of the pteridine 6-biopterin in the heads of individual Drosophila serrata Malloch 1927. Pteridine content in both laboratory and field captured flies is typically a level of magnitude higher than the minimally detectable level (mean(lab)=0.54 units, mean(field)=0.44 units, minimum detectable level=0.01 units) and can be used to predict individual age in laboratory populations with high certainty (r(2)=57%). Laboratory studies of individuals of known age ( from 1 to 48 days old) indicate that while pteridine level increases linearly with age, they also increase in a linear manner with rearing temperature and ambient light levels, but are independent of sex. As expected, the longevity of laboratory-reared males ( at least 48 days) is higher than the range of predicted ages of wild-caught males based on individual pteridine levels (40 days). However, the predictive equation based on pteridine level alone suggested that a number of wild-caught males were less than 0 days old, and the 95% confidence for these predictions based on the inverse regression broad. The age of the oldest wild-caught male is to fall within the range of 2 to 50 days. The effects of temperature and light intensity determined in laboratory study (effect sizes omega(2)=14.3 and respectively) suggests that the calibration of the prediction equation for field populations would significantly improved when combined with fine scaled studies of habitat temperature and light conditions. ability to determine relative age in individual wild-caught D. serrata presents great opportunities for a variety evolutionary studies on the dynamics of populations.