Optical Absorption Spectroscopy Technique Research Articles

Spectrum sensing of trace C(2)H(2) detection in differential optical absorption spectroscopy technique.

An improved algorithm for trace C(2)H(2) detection is presented in this paper. The trace concentration is accurately calculated by focusing on the absorption spectrum from the frequency domain perspective. The advantage of the absorption spectroscopy frequency domain algorithm is its anti-interference capability. First, the influence of the background noise on the minimum detectable concentration is greatly reduced. Second, the time-consuming preprocess of spectra calibration in the differential optical absorption spectroscopy technique is skipped. Experimental results showed the detection limit of 50 ppm is achieved at a lightpath length of 0.2 m. This algorithm can be used in real-time spectrum analysis with high accuracy.

Green synthesis of Au nanoparticles using potato extract: stability and growth mechanism

We report on the synthesis of spherical, well-dispersed colloidal gold nanoparticles of 17.5–23.5 nm average sizes in water using potato extract (PE) both as reducing and stabilizing agent. The effects of PE content and the pH value of the reaction mixture have been studied. Formation and growth dynamics of the Au nanoparticles in the colloids were studied using transmission electron microscopy and UV-Vis optical absorption spectroscopy techniques. While the reductor content and, hence, the nucleation and growth rates of the nanoparticles could be controlled by controlling the PE content in the reaction solution, the stability of the nanoparticles depended strongly on the pH of the reaction mixture. The mechanisms of Au ion reduction and stabilization of Au nanoparticles by potato starch have been discussed. The use of common natural solvent like water and biological reductor like PE in our synthesis process opens up the possibility of synthesizing Au nanoparticles in fully green (environmental friendly) way, and the Au nanoparticles produced in such way should have good biocompatibility.

Tropospheric column amount of ozone retrieved from SCIAMACHY limb–nadir-matching observations

Abstract. Tropospheric ozone (O3), has two main sources: transport from the stratosphere and photochemical production in the troposphere. It plays important roles in atmospheric chemistry and climate change. Its amount and destruction are being modified by anthropogenic activity. Global measurements are needed to test our understanding of its sources and sinks. In this paper, we describe the retrieval of tropospheric O3 columns (TOCs) from the combined limb and nadir observations (hereinafter referred to as limb–nadir-matching (LNM)) of the SCanning Imaging Absorption spectroMeter for Atmospheric CHartographY (SCIAMACHY) instrument, which flew as part of the payload onboard the European Space Agency (ESA) satellite Envisat (2002–2012). The LNM technique used in this study is a residual approach that subtracts stratospheric O3 columns (SOCs), retrieved from the limb observations, from the total O3 columns (TOZs), derived from the nadir observations. The technique requires accurate knowledge of the SOCs, TOZs, tropopause height, and their associated errors. The SOCs were determined from the stratospheric O3 profiles retrieved in the Hartley and Chappuis bands from SCIAMACHY limb scattering measurements. The TOZs were also derived from SCIAMACHY measurements, but in this case from the nadir viewing mode using the Weighting Function Differential Optical Absorption Spectroscopy (WFDOAS) technique in the Huggins band. Comparisons of the TOCs from SCIAMACHY and collocated measurements from ozonesondes in both hemispheres between January 2003 and December 2011 show agreement to within 2–5 DU (1 DU = 2.69 × 1016 molecules cm−2). TOC values from SCIAMACHY have also been compared to the results from the Tropospheric Emission Spectrometer (TES) and from the LNM technique exploiting Ozone Monitoring Instrument (OMI) and Microwave Limb Sounder (MLS) data (hereinafter referred to as OMI/MLS). All compared data sets agree within the given data product error range and exhibit similar seasonal variations, which, however, differ in amplitude. The spatial distributions of tropospheric O3 in the SCIAMACHY LNM TOC product show characteristic variations related to stratosphere–troposphere exchange (STE) processes, anthropogenic activities and biospheric emissions.

Advancing measurements of tropospheric NO2 from space: New algorithm and first global results from OMPS

AbstractWe present a new algorithm based on the iterative spectral fitting technique for direct retrieval of nitrogen dioxide (NO2) vertical columns from hyperspectral satellite measurements, and a new spatial technique for separating the stratospheric and tropospheric contributions to the total NO2 vertical columns. This direct vertical column fitting (DVCF) algorithm allows more complete treatment of underlying algorithm physics compared to the differential optical absorption spectroscopy technique and enables more accurate accounting for the effects of spectral and altitude variations in NO2 measurement sensitivities. This DVCF algorithm and the stratosphere‐troposphere separation scheme are applied to ultraviolet measurements from the Nadir Mapper of the Ozone Mapping and Profiler Suite (OMPS) on the Suomi National Polar‐orbiting Partnership spacecraft. The first results demonstrate the potential of OMPS for sensitive global monitoring of tropospheric NO2. Comparisons show good agreement with Aura Ozone Monitoring Instrument (OMI) tropospheric NO2 data and that OMPS data have sufficient quality to continue and extend OMI NO2 data records.

Chemometric methods for studying the relationships between trace elements in laryngeal cancer and healthy tissues.

A quick and reliable method for the evaluation and classification of two types of tissues is presented. Several chemometric methods were applied to evaluate multivariate data of the tissue samples with respect to the content of trace elements. The content of Pb, Al, Zn, Cd, Cu, Ni and Co was determined in samples of healthy and cancerous tissue obtained from 26 patients. Determination was done at milligram/kilogram level with inductively coupled plasma optical emission spectrometry (ICP-OES) and atomic absorption spectroscopy (AAS) techniques. Contents of trace metals in studied tissues are not normally distributed; however, normal distribution was confirmed for log values. There is a statistically significant difference in the content of Zn, Cd, Cu and Al (p < 0.01) and Ni and Co (p < 0.05) when healthy tissue is compared to cancerous one. Correlation between contents of trace elements for studied tissues was positive; the highest was found between Zn and Cu. A chemometric methodology seems to be a promising tool for classifications of the tissue samples.

Vector Interpretation of Orthogonal Optical Absorption Spectroscopy

The basic ideas of the technique of orthogonal optical absorption spectroscopy are illustrated with a simple example employing a vector representation of the functions of wavelength.

Trans-Boundary Volcanic SO2 Detected over Pakistan from Satellite Observations during the Time Period 2004-2012

This study emphasizes on the amount of trans-boundary Sulfur dioxide (SO_2) present in the atmosphere of Pakistan as a consequence of various global volcanic eruptions, by using satellite data. The data products of SCanning Imaging Absorption spectroMeter for Atmospheric CHartographY (SCIAMACHY), Ozone Monitoring Instrument (OMI) and Global Ozone Monitoring Experiment-2 (GOME-2) were used for the time period of 2004-2012. SO_2 columns retrieved with Differential Optical Absorption Spectroscopy (DOAS) technique were used to perform both spatial and temporal analyses. The Nabro volcano eruption during 2011 had caused high SO_2 columns over East Africa, Middle East and South Asian regions. Daily satellite observations were used to study SO_2 plume pathway during this event. Other significant volcanic eruptions and their effects on atmospheric composition of Pakistan are also discussed. Back trajectory analysis is also performed to track the origin of air masses enriched with SO_2 column densities detected over Pakistan. Maximum SO_2 column densities of 9.4 Dobson Units (DU) were measured over Pakistan caused by Dalafilla volcanic eruption during November 2008.

Spatio-Temporal Analyses of Atmospheric Sulfur Dioxide Column Densities over Pakistan by Using SCIAMACHY Data

This paper presents the results of atmospheric Sulfur dioxide (SO_2) column densities obtained from satellite observation over Pakistan during the time period of 2004-2012. The level-2 data product of the Scanning Imaging Absorption Spectrometer for Atmospheric Chartography (SCIAMACHY) instrument on-board ENVISAT-l is used. S02 column densities are retrieved by applying differential optical absorption spectroscopy (DOAS) technique. The spatio-temporal distribution of SO_2 column densities along with the seasonal variation over main cities and regions of Pakistan are discussed. The Nabro volcano eruption in the year 2011 caused high SO_2 levels over East Africa, the Middle East and South and Southeast Asia. Satellite images exhibited several episodes of volcanic SO_2 column densities transported to Pakistan. The temporal trend in SO_2 column densities was calculated, and the significance of the data set was tested with statistical analysis. An overall increase of about 70% (8.7% per year) in SO_2 column densitiies over Pakistan during the time period of 2004-2012 has been calculated. This study presents the first spatial and temporal analyses of SO_2 column densities over Pakistan by using satellite observation.

Spectroscopic data and Stark broadening of Cu I and Ag I spectral lines: Selection and analysis

Optical emission and linear laser absorption spectroscopy techniques were used in investigation of plasma with copper and silver admixture. The method of selection of spectral lines and spectroscopic data with the aim of diagnostics of multicomponent air plasma with two metal vapors admixture was developed. Energy level populations behavior on the Boltzmann plot were used for Cu I and Ag I spectroscopic data selection. In this way the selection of spectroscopic data for some of Cu I and Ag I lines was realized. Stark broadening parameters of Cu I and Ag I were examined. Experimentally obtained temperature and electron density radial distributions were used in the calculation of plasma composition in the assumption of local thermodynamic equilibrium. Linear laser absorption spectroscopy was used to examine the state of plasma.

Argon metastable and resonant densities in a low-pressure Ar–N2 inductively coupled plasma

Argon metastable (3P2 and 3P0) and resonant (3P1 and 1P1) atom densities have been measured in a low-pressure (1–20 mTorr) inductively coupled plasma generated in argon–nitrogen gas mixtures with nitrogen contents ranging from 0 to 90% using optical absorption spectroscopy techniques. A significant decrease of the metastable density is found for increasing nitrogen contents, more pronounced as the pressure is increased. As for the resonant atoms, their behaviour differs from that of metastable atoms, which results from the growing influence of radiation trapping with pressure. A simplified model accounting for several Ar metastable population/depopulation mechanisms (electron excitation/ionization, diffusion and excitation transfer from Ar metastable to nitrogen molecules) has been used to interpret these results. It shows that excitation transfer reactions from Ar metastable atoms to nitrogen become the main depopulation process, especially for large nitrogen contents and pressures above 10 mTorr.

SO2 degassing from Turrialba Volcano linked to seismic signatures during the period 2008–2012

In 1996, after 150 years of relative calm, Turrialba Volcano was reawakening. A visible plume and serious damage to surrounding vegetation due to acid rain are the most obvious signals. As part of the Network for Observation of Volcanic and Atmospheric Change project, four gas-monitoring stations were initially installed on the west flank of the volcano with the purpose of measuring sulphur dioxide emissions during this period of increased activity using the scanning-differential optical absorption spectroscopy technique. We present here the results of semicontinuous gas flux measurements over a period of 5 years (from 2008 to 2012), providing a novel data set that documents a relatively rapid increase in SO2 fluxes from around 350 t day−1 to around 4,000 t day−1 leading up to an eruptive period, followed by a gradual return to the former baseline values. Gas flux data were also compared with seismic data for selected periods of interest, providing insights into the link between degassing and seismicity. The most important result from this comparison is the identification of an inflexion point in the gas emissions followed by a clearly increasing trend in seismic activity, distinguishable 6 months prior to a phreatic eruptive event that occurred on 5 January 2010. This signal can be interpreted as a possible indicator of future eruptive events. Monitoring of SO2 thus complements seismic monitoring as a forecasting tool for eruptive events. Such monitoring is critical considering the proximity of Turrialba to the Central Valley, an area inhabited by more than 50 % of Costa Rica’s population.

Strong thermal optical nonlinearity caused by CdSe nanoparticles synthesised in smectic ionic liquid crystal

Spectral and nonlinear optical properties of cadmium octanoate composites containing CdSe nanoparticles (NPs) have been studied by using optical absorption spectroscopy and laser scanning technique (Z-scan). CdSe NPs are chemically synthesised in thermotropic ionic liquid crystal (ILC) phase of cadmium octanoate which is used as nanoreactor. Anisotropic glassy nanocomposites are obtained by the rapid cooling of the ILC phase of nanocomposites to room temperature. The sizes of the CdSe NPs are determined from the absorption spectra. The thermo-optical nonlinearity of the new nanocomposites is characterised by extremely large value of the nonlinear refractive index, n2, under relatively low-powered CW laser irradiation. This nonlinearity is caused by (1) the efficient light-induced heating due to the CdSe NPs strong exciton absorption, and (2) consequent thermal dissipation, which in turn, produces the photoelastic tensions in the glassy smectic matrix.

Electrical and optical properties of chalcedony and striped chalcedony

The electrical and optical properties of chalcedony (SiO2) and striped chalcedony are determined by the impedance and optical absorption spectroscopy techniques. The capacitance, impedance, dissipation factor and the complex dielectric constants are measured by the parallel plate technique in the voltage frequency range 100 to 10 MHz. The dissipation factor is measured as 1.2 and 0.7 for chalcedony and striped chalcedony respectively around 10 kHz. It is found that the striped chalcedony has a major complex broad band with two absorption bands that are centered at 225 and 275 nm. The chalcedony however, has a minor absorption band which is centered at 210 nm.

Principal Component Regression Applied in Differential Optical Absorption Spectroscopy Measurement

Differential optical absorption spectroscopy (DOAS) is a well-established and widely used technique for monitoring atmospheric pollution. The month performance of a DOAS system was assessed at a certain place in Tianjin University, China, where is farther away from the industrial pollution a source. Three methods were used to inverse the hourly concentrations of nitrogen dioxide (NO2), sulfur dioxide (SO2), ozone (O3). Principal component analysis (PCA) was performed to analyze the retrieving concentrations. Results were obtained for estimated temporal NO, NO2, SO2, O3 distributions over the urban atmosphere; demonstrating the capability of the principal component analysis applied in differential optical absorption spectroscopy (PCA-DOAS) technique.

The spring 2011 final stratospheric warming above Eureka: anomalous dynamics and chemistry

Abstract. In spring 2011, the Arctic polar vortex was stronger than in any other year on record. As the polar vortex started to break up in April, ozone and NO2 columns were measured with UV-visible spectrometers above the Polar Environment Atmospheric Research Laboratory (PEARL) in Eureka, Canada (80.05° N, 86.42° W) using the differential optical absorption spectroscopy (DOAS) technique. These ground-based column measurements were complemented by Ozone Monitoring Instrument (OMI) and Optical Spectrograph and Infra-Red Imager System (OSIRIS) satellite measurements, Global Modeling Initiative (GMI) simulations, and meteorological quantities. On 8 April 2011, NO2 columns above PEARL from the DOAS, OMI, and GMI datasets were approximately twice as large as in previous years. On this day, temperatures and ozone volume mixing ratios above Eureka were high, suggesting enhanced chemical production of NO2 from NO. Additionally, GMI NOx (NO + NO2) and N2O fields suggest that downward transport along the vortex edge and horizontal transport from lower latitudes also contributed to the enhanced NO2. The anticyclone that transported lower-latitude NOx above PEARL became frozen-in and persisted in dynamical and GMI N2O fields until the end of the measurement period on 31 May 2011. Ozone isolated within this frozen-in anticyclone (FrIAC) in the middle stratosphere was lost due to reactions with the enhanced NOx. Below the FrIAC (from the tropopause to 700 K), NOx driven ozone loss above Eureka was larger than in previous years, according to GMI monthly average ozone loss rates. Using the passive tracer technique, with passive ozone profiles from the Lagrangian Chemistry and Transport Model, ATLAS, ozone losses since 1 December 2010 were calculated at 600 K. In the air mass that was above Eureka on 20 May 2011, ozone losses reached 4.2 parts per million by volume (ppmv) (58%) and 4.4 ppmv (61%), when calculated using GMI and OSIRIS ozone profiles, respectively. This gas-phase ozone loss led to a more rapid decrease in ozone column amounts above Eureka in April/May 2011 compared with previous years. Ground-based, OMI, and GMI ozone total columns all decreased by more than 100 DU from 15 April to 20 May. Two lows in the ozone columns were also investigated and were attributed to a vortex remnant passing above Eureka at ~500 K on 12/13 May and an ozone mini-hole on 22/23 May.

Retrieval of surface NO2 mixing ratio from multi-axis differential optical absorption spectroscopy

The multi-axis differential optical absorption spectroscopy (MAX-DOAS) technique, in which solar scattered light beams of different elevation angles are used and the spatial distribution of various trace gases is derived, has been widely used for monitoring the NO2 slant column density. Due to the lack of information in a detectable horizontal range of the MAX-DOAS instrument, the concentration of trace gases including NO2 is unable to yield directly. In this work, the relationship between extinction coefficient and light path length of MAX-DOAS observation is analyzed, and a retrieval algorithm to convert the horizontal NO2 differential slant column density into the volume mixing ratio with the information of visibility is described. This algorithm has been used in the MAX-DOAS observation at Hefei, and volume NO2 mixing ratio is derived from MAX-DOAS measurement combining the data of visibility. The NO2 concentration measured with MAX-DOAS shows that it is in good agreement with the result obtained with long path differential optical absorption spectroscopy, proving the feasibility of the retrieval method. This research presents a simple and effective monitoring method of volume NO2 mixing ratio with MAX-DOAS, there by expanding the application scope of MAX-DOAS technique.

Improved Low-Temperature Aqueous Synthesis of ZnO Nanorods and Their Use in SERS Detection of 4-ABT and RDX

The growth-controlled synthesis of zinc oxide nanorods (ZnO NR) in the aqueous phase has been investigated. The rods were grown on ZnO films previously deposited onto Si(100) and indium tin oxide (ITO) substrates by RF magnetron sputtering. The formation of the rods took place in the presence of hexamethylenetetramine (HMT) as habit-control reagent. The grains in the base ZnO film acted as seeds that promoted the longitudinal growth of the oxide. As-synthesized base films and rods were characterized by X-ray diffraction, scanning electron microscopy (SEM), field emission SEM, optical absorption and photoluminescence spectroscopy techniques. Subsequently, a wet chemistry procedure was performed to achieve ZnO NR growth. This methodology was conducive to the formation of rods of a relatively narrow distribution of diameters (60 - 70 nm) with lengths in the 1 - 3 μm range. Photoluminescence spectra were characterized by a dominant near-band-edge (NBE) peak followed by a green luminescence (GL) broad band, indicative of higher oxygen vacancy concentration in the ZnO NR grown on ZnO/ITO in comparison with those grown on ZnO/Si(100). A UV process was used for coating the ZnO NR with gold (Au). Au coating on ZnO NR was used to evaluate the detection capability by SERS of different analytes such as: 4-aminobenzenethiol (4-ABT) and 1,3,5-trinitroperhydro-1,3,5- triazine (RDX) at low levels. A strong SERS Raman spectrum was observed for 4-ABT. A limit of detection (LOD) of 1 × 10-8M for 4-ABT was achieved corresponding to a minimum of 5.4 × 105molecules detected under the experimental conditions at excitation wavelength of 785 nm with a sensitivity of the ZnO NR in the range of 1.1 × 10-16g under the laser spot.

A convolution algorithm of differential coefficients of liquid water based on vibrational Raman scattering

Inelastic vibrational Raman scattering by liquid water is one significant limitation to the accuracy of the retrieval of trace gas constituents in atmosphere over waters, particularly over clear ocean waters, while using satellite data with differential optical absorption spectroscopy technique (DOAS). The effect which is similar to the Ring effect in atmosphere results in the filling-in of Fraunhofer lines, which is known as solar absorption lines. The inelastic component of the liquid water scattering causes a net increase of radiance in the line because more radiations shift to the wavelength of an absorption line than from this wavelength to other wavelengths. The solar spectrum transmitting atmosphere is convolved with vibrational Raman scattering coefficient of liquid water, divided by the original computed spectrum, with a cubic polynomial subtracted off, to create differential water Ring spectrum. This method is suggested in order to obtain an effective differential water Ring coeffient for the DOAS fitting process, which could be used to improve the accuracy of the retrieval of the trace gases concentration. The method does not rely on radiative transfer model of water, which would be time-consuming and depending on lot of parameters. Therefore, it is very fast and convenient.

DOAS measurements of formaldehyde and glyoxal above a south-east Asian tropical rainforest

Abstract. Tropical rainforests act as a huge contributor to the global emissions of biogenic volatile organic compounds (BVOCs). Measurements of their oxidation products, such as formaldehyde (HCHO) and glyoxal (CHOCHO), provide useful indicators of fast photochemistry occurring in the lower troposphere. However, measurements of these species in tropical forest locations are extremely limited. To redress this, HCHO and CHOCHO were measured using the long-path (LP) and multi-axis (MAX) differential optical absorption spectroscopy (DOAS) techniques above the rainforest canopy in Borneo during two campaigns in spring and summer 2008, as part of the Oxidant and Particle Photochemical Processes above a south-east Asian tropical rainforest (OP3) project. The results were compared with concurrent measurements of hydroxyl radical (OH), isoprene (C5H8) (which was the dominant organic species emitted in this forest environment), and various meteorological parameters. Formaldehyde was observed at a maximum concentration of 4.5 ppb and glyoxal at a maximum of 1.6 ppb, significantly higher than previous measurements in rural locations. A 1-D chemistry model was then used to assess the diurnal evolution of formaldehyde and glyoxal throughout the boundary layer. The results, which compare well with the LP-DOAS and MAX-DOAS observations, suggest that the majority of the glyoxal and formaldehyde is confined to the first 500 m of the boundary layer, and that the measured ratio of these species is reproduced using currently accepted product yields for the oxidation of isoprene by OH. An important conclusion is that the measured levels of glyoxal are consistent with the surprisingly high concentrations of OH measured in this environment.

Quantifying the relationship between the measurement precision and specifications of a UV/visible sensor on a geostationary satellite

To investigate the feasibility of new satellite observations, including air quality (AQ) observations from geostationary (GEO) orbit, it is essential to link the measurement precision (ε) with sensor specifications in advance. The present study attempts to formulate the linkage between ε and specifications of a UV/visible sensor (signal-to-noise ratio (SNR), full width at half maximum (FWHM) of the slit function, and sampling ratio (SR)) on a GEO satellite. A sophisticated radiative transfer model (JACOSPAR) is used to calculate synthetic radiance spectra that would be measured by a UV/visible sensor observing the atmosphere over Tokyo (35.7°N, 139.7°E) from GEO orbit at 120°E longitude. The spectra, modified according to given sensor specifications, are analyzed by the differential optical absorption spectroscopy technique to estimate the ε for slant column densities of O3 and NO2. We find clear relationships: for example, the ε of the O3 slant column density (molecules cm−2) and SNR at 330nm are linked by the equation log(ε)=−1.06·log(SNR)+20.71 in the UV region, and the ε of the NO2 slant column density and SNR at 450nm are linked by log(ε)=−0.98·log(SNR)+18.00, at a FWHM=0.6nm (for the Gaussian slit function) and SR=4. The relationships are mostly independent of other specifications (e.g., horizontal and temporal resolutions), as they affect ε primarily through SNR, providing constraints in determining the optimal SNR (and alternatively FWHM and SR) for similar UV/visible sensors dedicated for AQ studies.