Urban air pollutants and their micro effects on medieval stained glass windows

Levels of urban gaseous and particulate pollutants were investigated in the Cathedral of Cologne, Germany in the framework of the EU-project “VIDRIO”. The purpose of this study was to evaluate the influence of a protective double glazing system on the preservation of ancient stained glass windows by sampling at protected and unprotected windows (indoors, in the interspace and outdoor of the Cathedral). The interspace between the ancient stained glass window and the protective glazing is flushed in the Cathedral by indoor air, hence isolating the historic glass from the outdoor air and exposing it to indoor air on both sides of the glass panels. Concentrations of aggressive gaseous pollutants such as NO₂, SO₂, O₃ and CO₂ as well as elemental concentrations of bulk particles and relative abundances of single particles were surveyed at all sampling locations. Elemental concentrations in bulk particulate matter were found to be significantly lower inside the Cathedral in comparison to the outdoor air. This result is advantageous for the stained glass windows. Single particle analysis of the samples from Cologne showed also soil dust and organic particles as well as sulphates and nitrates, from which the latter two compounds are dangerous for the stained glass windows. On the base of the obtained results, it can be concluded that the protective glazing system in the Cathedral of Cologne can be considered as predominantly advantageous from both the gases' point of view (except for NO₂-candles burning) and from the particles' point of view.     

Enamels in stained glass windows: Preparation, chemical composition, microstructure and causes of deterioration

Stained glass windows incorporating dark blue and purple enamel paint layers are in some cases subject to severe degradation while others from the same period survived the ravages of time. A series of dark blue, green–blue and purple enamel glass paints from the same region (Northwestern Europe) and from the same period (16–early 20th centuries) has been studied by means of a combination of microscopic X-ray fluorescence analysis, electron probe micro analysis and transmission electron microscopy with the aim of better understanding the causes of the degradation. The chemical composition of the enamels diverges from the average chemical composition of window glass. Some of the compositions appear to be unstable, for example those with a high concentration of K₂O and a low content of CaO and PbO. In other cases, the deterioration of the paint layers was caused by the less than optimal vitrification of the enamel during the firing process. Recipes and chemical compositions indicate that glassmakers of the 16–17th century had full control over the color of the enamel glass paints they made. They mainly used three types of coloring agents, based on Co (dark blue), Mn (purple) and Cu (light-blue or green–blue) as coloring elements. Blue–purple enamel paints were obtained by mixing two different coloring agents. The coloring agent for red–purple enamel, introduced during the 19th century, was colloidal gold embedded in grains of lead glass.     

Determination of gaseous and particulate129I in atmospheric air by neutron activation analysis

A method for determining¹²⁹I in atmospheric air is presented. It consists of the following stages: sampling (of aerosol and gas fractions separately), preparation of a sample for irradiation in a reactor by a destructive distillation method, irradiation of samples in a reactor, radiochemical separation and¹³⁰I activity measurements by slow coincidences. Iodine isotopes (including¹²⁹I) in the atmospheric air have mostly been found in gas fractions (except¹³²I). Gas compounds and percentages of radioactive and stable iodine isotopes coincide.Presented at the MTAA-8 Conference, September 16–20, 1991, Vienna, Austria.     

Determination of gaseous and particulate carbonyls in air by gradient-elution micellar electrokinetic capillary chromatography

A new continuous-flow gradient-elution micellar electrokinetic capillary chromatography method is developed for the determination of airborne carbonyls after derivatization with 2,4-dinitrophenylhydrazine. A total of 16 carbonyls can be determined with detection limits ranging from 0.94 to 8.50 mg/L, working range from 4.72 to 346 mg/L, and repeatabilities (relative standard deviation, n=5) from 1.23 to 4.6% or 3.93 to 7.6% for migration time and peak area, respectively. Coupling with denuder-filter sampling, a preliminary survey has been conducted to determine gaseous and particulate carbonyls from air sampled at a roadside station. The method is shown to have sufficient sensitivity for 1-h sampling of ambient carbonyls with detection limits ranging from 0.045 to 1.2 microg/m3 and working range from 0.11 to 43.3 microg/m3 at a flow rate of 10 Lpm. The method requires minimal modification of commercially available capillary electrophoresis equipment and can differentiate gaseous and particulate carbonyls to provide essential information and objective data for adopting effective measures to combat the discharge of carbonyl compounds to the atmosphere.     

The stained glass window of the southern transept of St. Anthony's Basilica (Padova, Italy): study of glasses and grisaille paint layers

This work reports results from a chemico-physical study of the stained glass window of the southern transept of St. Anthony's Basilica (Padova, Italy), dated to the late 19th century AD. Selected samples of glass with or without grisailles were characterised by means of various X-ray spectrometric techniques, such as wavelength dispersive X-ray fluorescence, electron microprobe, and scanning electron microscopy with energy dispersive X-ray microanalysis, coupled, in some cases, with X-ray powder diffraction. Integration of analytical results revealed many types of glass related to different phases of the “life” of stained glass, and the production technology of grisailles. In addition, the degree of damage undergone throughout the last century due to materials used in the production of windows was studied, to design and optimise a combined conservation and restoration strategy. Lastly, another important aim of the present study was to amplify the database on 19th-century stained glass windows, little documented in the literature.     

华中地区偏远站点金沙站气态污染物的变化特征

对于2006年6月到2007年7月在华中地区的金沙区域大气本底站站址科学论证实验期间获得的近地面O₃、SO₂、NO_x和CO等观测资料进行分析, 讨论其浓度水平、变化特征和影响因素. 结果表明, 观测期间O₃、SO₂、NO_x和CO的平均浓度分别为24.6±17.0 ppb、2.8±5.5 ppb、5.6±5.5 ppb和502±222 ppb, 低于同纬度位于长三角地区的临安大气本底站的同期观测水平. 金沙站局地O₃光化学生成不显著, 一次污染物的平均日变化比较平稳, 有别于临安和位于华北地区的上甸子大气本底站的变化特征. 由于观测点相对孤立且海拔相对较高, 可受到自由大气的影响, 使O₃浓度持续多日保持较高水平, 而一次污染物浓度很低, 相对湿度显著降低且与O₃浓度变化明显反相关. 因此, 该站数据可以在更大的尺度上反映出区域本底信号的变化情况.     

Versatile microanalytical system with porous polypropylene capillary membrane for calibration gas generation and trace gaseous pollutants sampling applied to the analysis of formaldehyde, formic acid, acetic acid and ammonia in outdoor air

The analytical determination of atmospheric pollutants still presents challenges due to the low-level concentrations (frequently in the μg m⁻³ range) and their variations with sampling site and time. In this work, a capillary membrane diffusion scrubber (CMDS) was scaled down to match with capillary electrophoresis (CE), a quick separation technique that requires nothing more than some nanoliters of sample and, when combined with capacitively coupled contactless conductometric detection (C⁴D), is particularly favorable for ionic species that do not absorb in the UV-vis region, like the target analytes formaldehyde, formic acid, acetic acid and ammonium. The CMDS was coaxially assembled inside a PTFE tube and fed with acceptor phase (deionized water for species with a high Henry's constant such as formaldehyde and carboxylic acids, or acidic solution for ammonia sampling with equilibrium displacement to the non-volatile ammonium ion) at a low flow rate (8.3 nL s⁻¹), while the sample was aspirated through the annular gap of the concentric tubes at 2.5 mL s⁻¹. A second unit, in all similar to the CMDS, was operated as a capillary membrane diffusion emitter (CMDE), generating a gas flow with know concentrations of ammonia for the evaluation of the CMDS. The fluids of the system were driven with inexpensive aquarium air pumps, and the collected samples were stored in vials cooled by a Peltier element. Complete protocols were developed for the analysis, in air, of NH₃, CH₃COOH, HCOOH and, with a derivatization setup, CH₂O, by associating the CMDS collection with the determination by CE-C⁴D. The ammonia concentrations obtained by electrophoresis were checked against the reference spectrophotometric method based on Berthelot's reaction. Sensitivity enhancements of this reference method were achieved by using a modified Berthelot reaction, solenoid micro-pumps for liquid propulsion and a long optical path cell based on a liquid core waveguide (LCW). All techniques and methods of this work are in line with the green analytical chemistry trends.     

Simultaneous analysis of gaseous and particulate sulfur in the atmosphere by X-ray fluorescence spectrometry

An analytical technique for the simultaneous measurement of the atmospheric concentrations of SO₂ gas and sulfur absorbed by aerosol particles has been developed. Aerosol particles are collected on membrane filter and at the same time SO₂ gas is captured on alkali impregnated filter. The sulfur content in each filter is measured by an energy dispersive X-ray fluorescence spectrometer consisting of a Si(Li) semiconductor detector connected to a multichannel pulse height analyzer and an excitation source of⁵⁵Fe. Two methods are acceptable for the determination of the sulfur content in impregnated filter by X-ray fluorescence analysis. In the first method X-ray fluorescence analysis is made after the collected sulfur has diffused and distributed uniformly enough throughout the filter, and in the second method X-ray fluorescence analysis has to be finished before the diffusion of the collected sulfur becomes appreciable. Some results of simultaneous analysis of SO₂ gas and particulate sulfur in the atmosphere are presented.     

PCDD, PCDF, and PCB contamination of air and inhalable particulate in Rome

Summary The isomer specific determination of PCDD, PCDF and PCB was carried out on samples of air and inhalable particulate from Rome. Samples were taken daily for six months and pooled to yield two samples per month. Normal PCDD+PCDF concentrations expressed in TEQ ranged from 48 to 87 fg/m³, while total PCB ranged from 0.1 to 1.4 ng/m³. The 2, 3, 7, 8-substituted PCDD and PCDF congener pattern is shown together with the PCB congener pattern.     

Photolysis-assisted, long-path FT-IR detection of air pollutants in the presence of water and carbon dioxide

Seven important air pollutants have been investigated by photolysis-assisted FT-IR spectroscopy. This technique renders invisible the spectra of water and carbon dioxide, which are two of the main concerns in long-path infrared spectroscopy. A cell, equipped with a UV lamp, was used to oxidise the analyte in the air sample and the spectrum recorded was used as a new background for the original sample spectrum. The optimum UV irradiation time and correctness of the concentrations were determined for this technique and compared with those from traditional methods. The signal-to-noise (S/N) ratios of the so-called “shadow spectra” were better than, or at least comparable to, the S/N ratios in the absorbance spectra obtained by using as background an air or an evacuated cell reference and subtraction of the spectra of water and carbon dioxide from a spectral library. The detection limits for the volatile organic compounds investigated have been improved by using this new method in which an appropriate background spectrum can be obtained quickly. The limitations of the method are that it cannot be applied to non-UV reactive compounds, such as methane, and the detection limits can be appreciably degraded when bands due to ozone in the shadow spectra overlap with those of the compounds under investigation.     

Trace element analysis of airborne particulate matters in relation to air pollution in Benin City, Nigeria

The methods of neutron activation analysis (NAA) and atomic absorption spectrometry (AAS) have been employed to determine the concentration levels of 18 trace elements in filter-collected airborne aerosols over an urban area in Nigeria. The highest concentrations measured in the samples were for Cl, Na, Al, Pb, Ca and Zn. The aerosol particles were found to contain higher concentrations of soil-derived trace elements, such as Al, Ti, K and Na than those derived from combustion and industrial activities such as As, Cd, Mn, Zn, Pb, Ni and Sb. The average precision of measurements varied between +/- 5.2% and 13% for most elements. Possible sources of the elements are also discussed.     

Aerosol and gaseous radioidine concentration in the air of Prague after the Chernobyl accident

Data on¹³¹I concentration in the atmosphere of Prague observed during the first days after the Chernobyl accident are presented. The sampling device enabling the differentiation between aerosol-fixed and gaseous form of¹³¹I is briefly described. The highest total¹³¹I concentration, 63 Bq.m^–3, was observed between 30 April and 1 May. Until 9 May the level of¹³¹I activity ranged between 14 and 1 Bq.m^–3 and then dropped below 1 Bq.m^–3. The content of gaseous¹³¹I was found to be a significant and represented on average 60–80% of its total activity.     

Unraveling the evolving nature of gaseous and dissolved carbon dioxide in champagne wines: A state-of-the-art review,from the bottle to the tasting glass

In champagne and sparkling wine tasting, the concentration of dissolved CO₂ is indeed an analytical parameter of high importance since it directly impacts the four following sensory properties: (i) the frequency of bubble formation in the glass, (ii) the growth rate of rising bubbles, (iii) the mouth feel, and (iv) the nose of champagne, i.e., its so-called bouquet. In this state-of-the-art review, the evolving nature of the dissolved and gaseous CO₂ found in champagne wines is evidenced, from the bottle to the glass, through various analytical techniques. Results obtained concerning various steps where the CO₂ molecule plays a role (from its ingestion in the liquid phase during the fermentation process to its progressive release in the headspace above the tasting glass) are gathered and synthesized to propose a self-consistent and global overview of how gaseous and dissolved CO₂ impact champagne and sparkling wine science.     

Application of NAA to air particulate matter collected at thirteen sampling sites in eight Asian countries: A collaborative study

Air particulate matter (APM) samples (PM_2.5 and PM_10–2.5) were collected at 13 sampling points in 8 Asian countries and their chemical compositions were determined by using neutron activation analysis (NAA) with the k ₀-standardization method in addition to conventional comparative method of NAA. Analytical data showed that mass concentration and elemental composition of the APM collected are variable in terms of time and space, and are related to the characteristics of the sampling sites concerned. NAA was proved to be highly effective for the regional characterization of APM in chemical composition.     

Study of the winter and summer changes of the air composition in the church of Szalowa, Poland, related to conservation

The St. Michael Archangel’s Church in Szalowa, Poland, was selected for closer investigation with respect to the indoor/outdoor air exchange and its influence on the air quality and work arts preservation. Chemical composition, size and abundance of particulate matter and concentration of gases NO₂, SO₂, O₃ inside and outside the church were determined. To study seasonal variation of the weather condition (temperature, inversion level, wind direction) and the influence of seasonal sources of the air pollution (like heating of the nearby houses), samples were collected in winter and summer time. It was stated that suspended particulate matter inside the wooden church has in general an outdoor source. Several groups of particles were distinguished such as the organic ones, soil dust, nitrates and sulphates. In case of organic and soil dust particles, the concentration inside was higher than outside. From the results, in comparison to literature data, one can conclude that accumulation of particulate suspended matter in the church is more intense than in other types of buildings. Gaseous pollutants were detected but their concentration was negligible.     

Development of a gas chromatography-mass spectrometry method for the determination of pesticides in gaseous and particulate phases in the atmosphere

A reliable multi-residue method for determining gaseous and particulate phase pesticides in atmospheric samples has been developed. This method, based on full scan gas chromatography–mass spectrometry (GC–MS), allowed the proper determination of sixteen relevant pesticides, in a wide range of concentrations and without the influence of interferences. The pesticides were benfluralin, bitertanol, buprofezin, chlorfenvinphos, chlorpyrifos, chlorpyrifos-methyl, ethalfluralin, fenthion, lindane, malathion, methidathion, propachlor, propanil, pyriproxifen, tebuconazol and trifluralin. Comparisons of two types of sampling filters (quartz and glass fibre) and four types of solid-phase cartridges (XAD-2, XAD-4, Florisil and Orbo-49P) showed that the most suitable supports were glass fibre filter for particulate pesticides and XAD-2 and XAD-4 cartridges for gaseous pesticides (>95% recovery). Evaluations of elution solvents for ultrasonic-assisted extraction demonstrated that isooctane is better than ethylacetate, dichloromethane, methanol or a mixture of acetone:hexane (1:1).Recovery assays and the standard addition method were performed to validate the proposed methodology. Moreover, large simulator chamber experiments allowed the best study of the gas-particle partitioning of pesticides for testing the sampling efficiency for the validation of an analytical multiresidue method for pesticides in air. Satisfactory analytical parameters were obtained, with a repeatability of 5 ± 1%, a reproducibility of 13 ± 3% and detection limits of 0.05–0.18 pg m⁻³ for the particulate phase and 26–88 pg m⁻³ for the gaseous phase. Finally, the methodology was successfully applied to rural and agricultural samples in the Mediterranean area.     

Sampling of water, soil and sediment to trace organic pollutants at a river-basin scale

Sampling is considered a crucial step in the analysis of organic compounds in the environment. This review describes field sampling techniques and provides detailed step-by-step procedures for collection and preservation of all major environmental matrices (water, sediment and soil) integrated as part of the river-basin water cycle. Attention is given to the prerequisites for obtaining reliable samples, and the practical issues of sample collection (planning, field sampling, sampling strategies and equipment and data quality assessment) are considered. Considering the heterogeneity of environmental matrices, special considerations for each matrix are given to solve typical problems and to find the most appropriate solutions to ensure the quality of the sample. The procedures described in the next sections are commonly used protocols that reflect true field conditions and current state-of-the-art techniques used in the sampling of organic compounds. The aim is to signify the importance of sampling to the overall analytical procedure. Finally, quality control issues to be considered in environmental sampling are given.