A novel multiple species ringdown spectrometer for in situ measurements of methane,carbon dioxide,and carbon isotope

We have developed a standalone, user-friendly, multi-species ringdown spectrometer for in situ measurements of methane (CH₄), carbon dioxide (CO₂), and a carbon dioxide isotope (¹³CO₂). The instrument is based on near-infrared continuous-wave cavity ringdown spectroscopy (NIR cw-CRDS) and engineered to be of approximately 16 kg with dimensions of 50 cm × 40 cm × 15 cm. The instrument design, optical configuration, electronic control, and performance are described. CH₄, CO₂, and ¹³CO₂ are measured at different wavelengths that are obtained through multiplexing two distributed feedback laser diodes with central wavelengths at 1597 and 1650 nm. The spectrometer has low power consumption and runs for 4–6 h when powered by a standard car battery. The instrument is operated either locally by interacting with a 7-inch touch screen or remotely via an Internet connection. The 1-σ detection limits for CH₄ and CO₂ are 0.2 and 120 ppmv, respectively. The measurement uncertainty is better than ±4% of full-scale reading for CH₄ and CO₂ and ±1.5‰ for δ¹³C (part per thousand relative to the Pee Dee Belemnite scale). Measurement of each species is near real-time; switching from measuring one species to another takes less than one minute. This work demonstrates a novel multiple-species CRDS-instrumentation platform, which can be adopted for development of an array of ringdown spectrometers for portable, user-friendly, field analysis of a variety of gases in environmental and industrial applications. Discussion of a future version of the spectrometer with better detection sensitivity, higher accuracy, and a smaller geometry is also presented. PACS  42.62.Fi; 42.55.Px; 33.20.Ea; 07.88.+y; 07.57.Ty     

Thirteen years of atmospheric carbon dioxide measurements at Mt. Cimone station, Italy

Summary The atmospheric carbon dioxide concentration has been continuously measured at Mt. Cimone station from March 1979. In this paper a selection scheme is applied to the measured concentrations in order to obtain data representative of background conditions. Monthly averages, expressed in the WMO X-85 scale are calculated from the selected data and analysed by a technique of time series decomposition until december 1991. Monthly values exibit an increasing long-term trend, mainly due to the fossil fuel combustion: over the whole monitoring period the average CO₂ growth rate is 1.66 p.p.m.v./y. A seasonal cycle, largely due to the biospheric activity of the northern hemisphere is evident. The estimated average peak-to-peak amplitude is 11.32 p.p.m.v. with a maximum occurring in April and a minimum in August. The seasonal amplitude is found to be decreasing with time, by about 1.5 p.p.m.v. over the entire record: no conclusive interpretations are given about this experimental result. Besides the long-term trend and the seasonal cycle, CO₂ interannual variations are observed in the selected record; these correlate negatively with the Southern Oscillation Index (SOI) with a maximum correlation coefficient of 0.6 for a delay of about 7–8 months.     

Preliminary results of an aircraft system based on near-IR diode lasers for continuous measurements of the concentration of methane, carbon dioxide, water and its isotopes

The Federal Agency for Hydrometeorology of the Russian Federation created the flying laboratory on board the passenger airplane Yak-42D for geophysical monitoring of the environment, including aircraft measurements of vertical concentrations of greenhouse gases in the troposphere. Within the limits of this project, General Physics Institute of the Russian Academy of Science developed airborne tunable diode laser spectrometer (TDLS) on the basis of diode lasers of a near-IR range for measurement of the altitude profiles of CO₂, CH₄, H₂O and its isotopes. TDLS complex was integrated aboard in standard 19-in. rack. Air samples, taken over an aircraft on the pipeline, were injected into the optical cell. Using the system of inflow and heating, the air was set laminar with a flowrate of 0.2?l/s at a reduced pressure of 100?mbar for detecting narrow absorption lines of water vapor isotopes. For registration of the absorption spectra and for the measurement of greenhouse gas concentrations in online mode, modulation-correlation technique was used. Diode laser spectrometer output data were transferred to the airborne central computer. Sensitivity of TDLS measurements was 20?C30?ppm for water, 3?C4?ppm for CO₂ and 20?C25?ppb for CH₄. Time of one-unit measurement is about 30?ms.     

Frequency-stabilized cavity ring-down spectrometer for high-sensitivity measurements of water vapor concentration

We present a portable spectrometer that uses the frequency-stabilized cavity ring-down spectroscopy technique capable of high-precision measurements of trace water vapor concentration. Measuring one of the strongest rovibrational transitions in the ν₁+ν₃ water vapor combination band near ˜ν=7181.156 cm^-1, we compare spectroscopic and thermodynamic determinations of trace water vapor in N₂, and find systematic differences attributable to water vapor background effects and/or uncertainties in line intensities. We also compare the frequency-stabilized ring-down method with other cavity ring-down approaches that are based on unstabilized probe lasers and unstabilized ring-down cavities. We show that for the determination of water vapor concentration, the frequency-stabilized cavity ring-down method has the minimum measurement uncertainty of these techniques. The minimum noise-equivalent absorption coefficient of the spectrometer was 1.2×10^-10 cm^-1 Hz^-1/2, which further corresponds to a minimum detectable water vapor mole fraction equal to 0.7×10^-9 for an absorption spectrum of 10 minutes duration. PACS 33.20.-t; 33.70.Jg; 33.70.Fd; 42.62.Fi     

A cavity ring-down analyzer for measuring atmospheric levels of methane, carbon dioxide, and water vapor

Researchers investigating global climate change need measurements of greenhouse gases with extreme precision and accuracy to enable the development and benchmarking of better climate models. Existing atmospheric monitors based on non-dispersive infrared (NDIR) sensors have known problems – they are non-linear, sensitive to water vapor concentration, and susceptible to drift. Many cannot easily be simultaneously calibrated across different sites to the level of accuracy required for use in atmospheric studies. We present results from field trials by Pennsylvania State University and the National Oceanographic and Atmospheric Administration (NOAA) of a newly available analyzer, based on cavity ring-down spectroscopy (CRDS), capable of measuring the concentrations of carbon dioxide (CO₂) and water vapor (H₂O). In addition, we present data from a new analyzer which measures CO₂, methane (CH₄), and H₂O. PACS  07.88.+y     

非线性拉曼激光雷达系统检测CO2气体的受激拉曼过程

 利用气体的受激拉曼散射增益效应的非线性雷达技术是探测大气中的CO₂气体的重要方法，用Nd:YAG固体激光器（1 064 nm）的三倍频光（354.7 nm）注入装有CO₂和N₂高压气体的拉曼管中，气体的受激拉曼散射（SRS）过程产生两种气体的一阶斯托克斯光，用来作为拉曼雷达的发射种子光源。介绍了产生光源的实验装置，论述了SRS中气体气压变化与一阶斯托克斯光能量输出变化的定量关系，得到最佳能量输出的优化条件，并对SRS中一阶斯托克斯光产生过程的物理机制进行了讨论。并根据光源的试验结果，设计了非线性受激拉曼雷达系统，对前期的普通拉曼雷达进行了实验，得到了初步的实验结果。     

Photoacoustic measurements of ion-implanted semiconductors

Summary We have measured photoacoustic-signal amplitude and phase of ion-implanted semiconductors. The main factors which determine the photoacoustic behaviour of implanted samples are the opticalabsorption coefficient and the thermal conductivity of the implanted layer. For the thermal conductivity of such a layer a value has been found like that for vitreous materials. Experimental results are in agreement with theoretical models which describe the photoacoustic response of a two-layer sample.

---

Riassunto Sono state eseguite misure di segnale fotoacustico e di fase in semiconduttori impiantati. Le grandezze che caratterizzano il comportamento fotoacustico di tali sistemi sono il coefficiente di assorbimento ottico e la conducibilità termica dello strato impiantato. Si è trovato per lo strato impiantato una conducibilità termica simile a quella dei vetri. I risultati sperimentali sono in accordo con i modelli teorici che descrivono la risposta fotoacustica di campioni costituiti da due strati.

---

Резюме Измеряются фотоакустические ситналы и фазы в ионно-имплантированных полупроводниках. Основные величины, которые характеризуют фотоакустическое поведение имплантированных образцов, представляют коэффициент оптического поглощения и теплопроводность имплантированного слоя. Для теплопроводности имплантированного слоя получена беличина аналогичная для стеклообразных материалов. Экспериментальные результаты согласуются с теоретнческими моделями, которые описывают фотоакустический отклик для двухслойного образца.

---

---

To speed up publication, the authors of this paper have agreed to not receive the proofs for correction.     

Partitioning of atmospheric carbon dioxide over Central Europe: insights from combined measurements of CO2 mixing ratios and their carbon isotope composition

Regular measurements of atmospheric CO (2) mixing ratios and their carbon isotope composition ((13)C/(12)C and (14)C/(12)C ratios) performed between 2005 and 2009 at two sites of contrasting characteristics (Krakow and the remote mountain site Kasprowy Wierch) located in southern Poland were used to derive fossil fuel-related and biogenic contributions to the total CO (2) load measured at both sites. Carbon dioxide present in the atmosphere, not coming from fossil fuel and biogenic sources, was considered 'background' CO (2). In Krakow, the average contribution of fossil fuel CO (2) was approximately 3.4%. The biogenic component was of the same magnitude. Both components revealed a distinct seasonality, with the fossil fuel component reaching maximum values during winter months and the biogenic component shifted in phase by approximately 6 months. The partitioning of the local CO (2) budget for the Kasprowy Wierch site revealed large differences in the derived components: the fossil fuel component was approximately five times lower than that derived for Krakow, whereas the biogenic component was negative in summer, pointing to the importance of photosynthetic sink associated with extensive forests in the neighbourhood of the station. While the presented study has demonstrated the strength of combined measurements of CO (2) mixing ratios and their carbon isotope signature as efficient tools for elucidating the partitioning of local atmospheric CO (2) loads, it also showed the important role of the land cover and the presence of the soil in the footprint of the measurement location, which control the net biogenic surface CO (2) fluxes.     

Partitioning of atmospheric carbon dioxide over Central Europe: insights from combined measurements of CO 2 mixing ratios and their carbon isotope composition

Regular measurements of atmospheric CO ₂ mixing ratios and their carbon isotope composition (¹³C/¹²C and ¹⁴C/¹²C ratios) performed between 2005 and 2009 at two sites of contrasting characteristics (Krakow and the remote mountain site Kasprowy Wierch) located in southern Poland were used to derive fossil fuel-related and biogenic contributions to the total CO ₂ load measured at both sites. Carbon dioxide present in the atmosphere, not coming from fossil fuel and biogenic sources, was considered ‘background’ CO ₂. In Krakow, the average contribution of fossil fuel CO ₂ was approximately 3.4%. The biogenic component was of the same magnitude. Both components revealed a distinct seasonality, with the fossil fuel component reaching maximum values during winter months and the biogenic component shifted in phase by approximately 6 months. The partitioning of the local CO ₂ budget for the Kasprowy Wierch site revealed large differences in the derived components: the fossil fuel component was approximately five times lower than that derived for Krakow, whereas the biogenic component was negative in summer, pointing to the importance of photosynthetic sink associated with extensive forests in the neighbourhood of the station. While the presented study has demonstrated the strength of combined measurements of CO ₂ mixing ratios and their carbon isotope signature as efficient tools for elucidating the partitioning of local atmospheric CO ₂ loads, it also showed the important role of the land cover and the presence of the soil in the footprint of the measurement location, which control the net biogenic surface CO ₂ fluxes.     

Laboratory measurements of dry air atmospheric absorption with a millimeter wave cavity ringdown spectrometer

Fast scan submillimeter spectroscopy (FASSST) cavity ring down spectroscopy has been used to measure the dry air continuum, and separately its individual component parts, at ∼6000 frequencies in the spectral region between 170 and 260 GHz. These measurements have been made at pressures that range from 0 to 3 atmospheres and in the temperature range between 230 and 320 K. For several of the components these are the first measurements made at or near atmospheric conditions. These measurements contain all of the information necessary to parameterize the observed absorptions in terms of the fundamental line and continuum interactions without the need to import external parameters. The inversion of this analysis makes possible the calculation of atmospheric absorption with meaningful uncertainties over this spectral region for temperatures and pressures of atmospheric interest.     

Human population and atmospheric carbon dioxide growth dynamics: Diagnostics for the future

We analyze the growth rates of human population and of atmospheric carbon dioxide by comparing the relative merits of two benchmark models, the exponential law and the finite-time-singular (FTS) power law. The later results from positive feedbacks, either direct or mediated by other dynamical variables, as shown in our presentation of a simple endogenous macroeconomic dynamical growth model describing the growth dynamics of coupled processes involving human population (labor in economic terms), capital and technology (proxies by CO₂ emissions). Human population in the context of our energy intensive economies constitutes arguably the most important underlying driving variable of the content of carbon dioxide in the atmosphere. Using some of the best databases available, we perform empirical analyses confirming that the human population on Earth has been growing super-exponentially until the mid-1960s, followed by a decelerated sub-exponential growth, with a tendency to plateau at just an exponential growth in the last decade with an average growth rate of 1.0% per year. In contrast, we find that the content of carbon dioxide in the atmosphere has continued to accelerate super-exponentially until 1990, with a transition to a progressive deceleration since then, with an average growth rate of approximately 2% per year in the last decade. To go back to CO₂ atmosphere contents equal to or smaller than the level of 1990 as has been the broadly advertised goals of international treaties since 1990 requires herculean changes: from a dynamical point of view, the approximately exponential growth must not only turn to negative acceleration but also negative velocity to reverse the trend.     

Frequency-stabilized cavity ring-down spectroscopy measurements of carbon dioxide isotopic ratios

Carbon dioxide (CO₂) isotopic ratios on samples of pure CO₂ were measured in the 1.6 μm wavelength region using the frequency-stabilized cavity ring-down spectroscopy (FS-CRDS) technique. We present CO₂ absorption spectra with peak signal-to-noise ratios as high as 28,000:1. Measured single-spectrum signal-to-noise ratios were as high as 8900:1, 10,000:1, and 1700:1 for ¹³C/¹²C, ¹⁸O/¹⁶O, and ¹⁷O/¹⁶O, respectively. In addition, we demonstrate the importance of utilizing the Galatry line profile in the spectrum analysis. The use of the Voigt line profile, which neglects the observed collisional narrowing, leads to large systematic errors which are transition-dependent and vary with temperature and pressure. While the relatively low intensities of CO₂ transitions near λ=1.6 μm make this spectral region non-optimal, the sensitivity and stability of FS-CRDS enabled measurement precision of pure CO₂ samples which are comparable to those of other optical techniques which operate at far more propitious wavelengths. These results indicate that a FS-CRDS spectrometer designed to probe CO₂ bands near wavelengths of 2.0 μm or 4.3 μm could achieve significantly improved precision over the present instrument and likely be competitive with mass spectrometric methods.     

用发光二极管实现的双通道、双色红外CO_2分析仪

介绍了一种采用发光二极管InAsSbP作光源、以PbSe探测器作光电转换器件实现的红外CO2浓度分析仪。分析仪由探测器系统、信号放大与处理系统及显示输出系统三部分组成。探测器系统主要包括发光二极管InAsS bP、红外窗口、气路、取样泵、球面反射镜、带通滤光片及PbSe探测器等;信号放大与处理系统主要包括电压跟随放大电路、采样保持电路、多路模拟开关、模 数转换电路及8031单片机等;显示输出系统主要包括显示器、打印机及声报警器等。叙述了分析仪的工作原理、基本结构及主要技术指标,讨论了其中的技术难点及其相应的解决方法,并给出了其所能达到的技术指标。     

Continuous-wave far-infrared ESR spectrometer for high-pressure measurements

We present a newly-developed microwave probe for performing sensitive high-field/multi-frequency electron spin resonance (ESR) measurements under high hydrostatic pressures. The system consists of a BeCu-made pressure-resistant vessel, which accommodates the investigated sample and a diamond microwave coupling window. The probe’s interior is completely filled with a pressure-transmitting fluid. The setup operates in reflection mode and can easily be assembled with a standard oversized microwave circuitry. The probe-head withstands hydrostatic pressures up to 1.6 GPa and interfaces with our home-built quasi-optical high-field ESR facility, operating in a millimeter/submillimeter frequency range of 105–420 GHz and in magnetic fields up to 16 T. The overall performance of the probe was tested, while studying the pressure-induced changes in the spin-relaxation mechanisms of a quasi-1D conducting polymer, KC₆₀. The preliminary measurements revealed that the probe yields similar signal-to-noise ratio to that of commercially available low-frequency ESR spectrometers. Moreover, by observing the conduction electron spin resonance (CESR) linewidth broadening for KC₆₀ in an unprecedented microwave frequency range of 210–420 GHz and in the pressure range of up to 1.6 GPa, we demonstrate that a combination of high-pressure ESR probe and high-field/multi-frequency spectrometer allows us to measure the spin relaxation rates in conducting spin systems, like the quasi-1D conductor, KC₆₀.     

An acousto-optical imaging spectrometer for astrophysical measurements

An optical scheme of an acousto-optical imaging spectrometer for observing extended astrophysical objects with line emission spectra is proposed. The use of an additional prism with a specified angular dispersion makes it possible to separate images of an extended object at different emission lines and images generated by minor maxima of the acousto-optical filter transmission function. A prototype of the imaging spectrometer has been designed.     

Split-pulse spectrometer for absolute XUV frequency measurements

A split-pulse spectrometer based on pairs of time-delayed femtosecond pulses can give access to accurate frequency measurements in the extreme ultraviolet (XUV) spectral domain. We demonstrate this approach by measuring the absolute frequency of a single-XUV-photon transition to a bound state of atomic argon excited with the ninth harmonic of an amplified Ti:sapphire laser.     

Photoacoustic soot sensor for in-situ black carbon monitoring

The PhotoAcoustic Soot Sensor (PASS) for in situ black carbon mass monitoring is presented. The sensor combines a high-power laser diode ( = 802 nm;P = 450 mW) and a novel spectrophone setup to achieve a portable sensor system for black carbon measurements. The acoustic resonator with aQ-factor of 300 is operated in its 2nd azimuthal mode at 6670 Hz. To estimate the effects of the window position, laser beam collimation, and different loss mechanisms on spectrophone sensitivity a model treating these effects with respect to the signal strength of the azimuthal modes is described. It gives a cell constant of 5.8 V/(W m^–1) in good agreement with 5.9 V/(W m^–1) obtained from measurements with particulate carbon. Additionally, this model permits a method for an absolute calibration of the spectrophone. To improve the signal-to-noise ratio, the photoacoustic signal is estimated by a weighted least-squares fit to an averaged line profile of the excited normal mode instead of a direct measurement of peak height. Finally, the application of this data processing algorithm yields a detection limit of 1.5 × 10^–6 m^–1 or 0.5 g black carbon per m³     

Photoacoustic methodologies for thermal diffusivity measurements for highly opaque single-layered materials

The analytical solution for the one-dimensional heat diffusion problem, involving a harmonic heat source in a single layer, is used to provide of photoacoustic self-normalized methodologies for thermal diffusivity measurements for highly opaque materials. The self-normalized procedure involves the photoacoustic phase lag between the rear and front configurations. Three methodologies are described; two of them involving linear fits in the photoacoustic thermally thick and thermally thin regimes. Comparison between the theoretical normalized equations and the corresponding normalized experimental data allows for the development of criteria on the selection of an appropriate modulation frequency range where a reliable analysis can be done.