Cavity Ring-down Spectroscopy Research Articles

A Mid-Infrared Quantum Cascade Laser Ultra-Sensitive Trace Formaldehyde Detection System Based on Improved Dual-Incidence Multipass Gas Cell

Formaldehyde (HCHO) is a tracer of volatile organic compounds (VOCs), and its concentration has gradually decreased with the reduction in VOC emissions in recent years, which puts forward higher requirements for the detection of trace HCHO. Therefore, a quantum cascade laser (QCL) with a central excitation wavelength of 5.68 μm was applied to detect the trace HCHO under an effective absorption optical pathlength of 67 m. An improved, dual-incidence multi-pass cell, with a simple structure and easy adjustment, was designed to further improve the absorption optical pathlength of the gas. The instrument detection sensitivity of 28 pptv (1σ) was achieved within a 40 s response time. The experimental results show that the developed HCHO detection system is almost unaffected by the cross interference of common atmospheric gases and the change of ambient humidity. Additionally, the instrument was successfully deployed in a field campaign, and it delivered results that correlated well with those of a commercial instrument based on continuous wave cavity ring-down spectroscopy (R2 = 0.967), which indicates that the instrument has a good ability to monitor ambient trace HCHO in unattended continuous operation for long periods of time.

Trace Ammonia Equilibrium Pressure of Zirconium Phosphate in Moisture.

Zirconium phosphate-absorbed ammonia gas and the ammonia concentration (pressure) decreased to 2 ppm (ca. 20 Pa). However, it has not been clarified what the equilibrium pressure of zirconium phosphate is during ammonia gas ab/desorption. In this study, the equilibrium pressure of zirconium phosphate during ammonia ab/desorption was measured using cavity ring-down spectroscopy (CRDS). For ammonia-absorbed zirconium phosphate, a two-step equilibrium plateau pressure was observed during the ammonia desorption in gas. The value of the higher equilibrium plateau pressure at the desorption process was about 25 mPa at room temperature. If the standard entropy change (ΔS0) of the desorption process is assumed to be equal to the standard molar entropy of ammonia gas (192.77 J/mol(NH3)/K), the standard enthalpy change (ΔH0) is about -95 kJ/mol(NH3). In addition, we observed hysteresis in zirconium phosphate at different equilibrium pressures during ammonia desorption and absorption. Finally, the CRDS system allows the ammonia equilibrium pressure of a material in the presence of water vapor equilibrium pressure, which cannot be measured by the Sievert-type method.

Primary measurement standards for trace moisture in multiple gases: extension of gas species to He and O2

The National Metrology Institute of Japan developed a multi-gas trace-moisture generator which was designed for generating trace water vapor (trace moisture) in multiple gases. Using this system, we previously developed primary measurement standards for trace moisture in N2 (10 nmol mol−1–5 μmol mol−1) and Ar (10 nmol mol−1–1 μmol mol−1). In this study, we have extended the target gas species; trace-moisture standards in He and O2 in the rage of 10 nmol mol−1 − 1 μmol mol−1 were developed. The relative expanded uncertainty (k = 2) of the trace-moisture standard in He was 0.74 %–5.7 %, and that in O2 was 0.78 %–8.9 %. In addition, we have improved stability of the flow rate of the diluent gas by controlling the temperature around the flow measurement/control systems and re-evaluated the uncertainty of the trace-moisture standards in N2 and Ar. The updated relative expanded uncertainty (k = 2) of the trace-moisture standard in N2 and Ar is 0.41 %–2.6 % and 0.73 %–2.6 %, respectively. The uncertainty budgets of the standards in these four gases are presented. The trace-moisture standard in N2 developed using the multi-gas trace-moisture generator was confirmed to be consistent with the standards realized by other generators, whose international comparability were already ensured. A commercial moisture analyzer (MA) based on the cavity ring-down spectroscopy (CRDS) was connected to the multi-gas trace-moisture generator as a device under test, and its performance was evaluated by comparing the readings with the standard values. The MA showed lower accuracy and stability in the measurement of moisture in He when it was used in the default setting, whereas it performed well in N2. This performance difference is related to the pressure-broadening coefficient of water, which depends on the gas species. We estimated the pressure-broadening coefficients of water by N2, Ar, He and O2 and discuss the gas-type dependence of the performance of CRDS-based MAs.

Real-Time Probing of Melamine-Induced Gold Nanoparticle Aggregation Kinetics via Evanescent-Wave Coupled Cavity Ring-down Spectroscopy.

Insight into the aggregation kinetics of gold nanoparticles (GNPs) is critical for developing a colorimetric assay extensively used in chemical and biomolecular sensing. The aggregation of NPs plays a significant role in many natural and industrial processes, demanding comprehensive perceptions of the aggregation kinetics at a solid-liquid interface. However, the direct observation of the melamine-induced aggregation process of GNPs in the time-domain still remains a challenge. There is little to no information on the fundamental mechanisms of such kinetics using evanescent waves. Total internal reflection (TIR) has been applied to generate the evanescent field (EF), exploring aggregation kinetics near the solid-liquid interface. Here, we utilized a precise optical cavity-based method, an evanescent-wave coupled cavity ring-down spectroscopy (EW-CRDS), that can probe the melamine-induced aggregation kinetics of GNPs. The key feature of the present method is that the evanescent field generated by TIR illumination harnesses the power of CRDS to study 2D fractals via the collision and attachment of the GNPs and their melamine-induced aggregates at the interfacial region in real-time. This kinetic study reveals a critical point for diffusion-limited aggregation and provides insights into the design and optimization of colorimetric sensors that exploit the aggregation of GNPs. Furthermore, the EW-CRDS is a unique analytical approach that helps to deepen our understanding in probing the real-time aggregation process, detecting the presence of aggregator as compared to UV-vis and dynamic light scattering (DLS) spectroscopy.

Experiment on Recording Ozone Absorption Transitions to 3A2 Triplet Electronic State by High-Sensitivity Cavity Ring-Down Spectroscopy in the Range 9350–10 000 cm−1

Experiment on Recording Ozone Absorption Transitions to 3A2 Triplet Electronic State by High-Sensitivity Cavity Ring-Down Spectroscopy in the Range 9350–10 000 cm−1

Impact of breast density on classification of infrared spectroscopy for breath-based breast cancer screening.

e13558 Background: While mammography is currently the standard of care for breast cancer screening, dense breast tissue can significantly degrade results. Alternatively, infrared spectroscopy analysis of breath offers a highly sensitive method for identifying exhaled volatile organic compounds (VOCs), which may circumvent issues with breast density. Methods: Alveolar breath samples were collected onto Tenax TA sorbent tubes using a SohnoXB™ breath sampler. Using four desorb temperatures (75, 150, 225 and 300°C), absorption spectra were measured by infrared cavity ring-down spectroscopy (IR-CRDS), a technique for measuring absorption coefficients due to VOCs in exhaled breath. Missing values in the absorption spectra were backfilled using interpolation, and the spectrum was min-max normalized and quadratic detrended. First and second derivatives of the preprocessed absorption spectra were used as features for a support vector machine machine-learning model. Features were ranked based on minimum redundancy maximum relevance (mRMR). The top 20 ranked features were selected to limit the potential for overfitting and then optimized. Model performance was validated using non-nested leave-one-out cross-validation (LOOCV) and nested LOOCV to provide optimistic and pessimistic results, respectively. Results: Absorption spectra from 111 participants (71 positive, 40 control) were used. Of the positive subjects, 30 had low- and 31 had high-density breast tissue (measures missing for 10). Model performance is outlined. A subgroup analysis compared model performance for subjects with low- and high-density breast tissue for both non-nested and nested LOOCV models. Breast density data was not captured for control subjects thus they were not included in the subgroup analysis. Fisher’s exact test was performed to assess for significant difference between model performance for those with low- vs high-density breast tissue, resulting in a p-value of 1.00. Conclusions: Our results suggest that the classification of alveolar breath using IR-CRDS is a promising technique for the detection of breast cancer that is independent of breast density. Breath analysis may therefore become a new alternative or corroborative to mammography to support clinical decision-making. [Table: see text]

Novel gas exposure system for the controlled exposure of plants to gaseous hydrogen fluoride

Plants can serve as sensitive bioindicators of the presence of contaminant vapors in the atmosphere. This work describes a novel laboratory-based gas exposure system capable of calibrating plants as bioindicators for the detection and delineation of the atmospheric contaminant hydrogen fluoride (HF) as a preparatory step for monitoring release emissions. To evaluate changes in plant phenotype and stress-induced physiological effects attributed to HF alone, the gas exposure chamber must have additional controls to simulate otherwise optimal plant growth conditions including variables such as light intensity, photoperiod, temperature, and irrigation. The exposure system was designed to maintain constant growth conditions during a series of independent experiments that varied between optimal (control) and stressful (HF exposure) conditions. The system was also designed to ensure the safe handling and application of HF. An initial system calibration introduced HF gas into the exposure chamber and monitored HF concentrations by cavity ring-down spectroscopy for a 48-h period. Stable concentrations inside the exposure chamber were observed after approximately 15 h, and losses of HF to the system ranged from 88 to 91%. A model plant species (Festuca arundinacea) was then exposed to HF for 48 h. Visual phenotype stress-induced responses aligned with symptoms reported in the literature for fluoride exposure (tip dieback and discoloration along the dieback transition margin). Fluoride concentrations in exposed tissues compared to control tissues confirmed enhanced fluoride uptake due to HF exposure. The system described herein can be applied to other reactive atmospheric pollutants of interest in support of bioindicator research.

Elucidation of rotational-interaction coupling and collision-induced effects in rovibrational transitions of β-N2O isotopologue at 7.8 µm mid-infrared region by cavity ring-down spectroscopy

High-sensitive cavity ring-down spectroscopy (CRDS) coupled with a cw-quantum cascade laser operating at 7.8 μm mid-infrared (MIR) region has been employed to investigate the rovibrational interaction coupling for various MIR rotational transitions of the P-and R-branches in the ν1 fundamental vibrational band (1000 ← 0000) of the β-site-specific isotopologue of nitrous oxide (β-N2O) i.e., 15N14N16O. The coupled rotational interaction was experimentally quantified from the high-resolution CRDS data and a data-driven approach was taken for the approximation of the Herman-Wallis series. Moreover, J-dependent pressure-broadened absorptions and their collision lifetimes in response to foreign-perturbing gas molecules were investigated to understand the collision-induced rotational quantum effect in β-N2O molecule. This study reveals an experimental elucidation of the fundamental infrared physics underlying rovibrational interaction and its coupling to the vibrational and rotational degrees of freedom for a non-centrosymmetric linear polyatomic molecule possessing a permanent dipole moment. Moreover, the experimentally probed interference-free spectral lines of β-N2O molecule attributing different spectroscopic signatures in the MIR region may drive new applications in environmental monitoring, biological and biomedical diagnostics in the future.

Investigating the effect of nanolime treatment on the drying kinetics of Clipsham limestone

Climate change poses an ever-increasing risk to our stone built heritage. Among conservation actions, the use of consolidant products is considered a possible response to this challenge, and the adoption of nanolimes has been widely studied showing promising results. However, while the effectiveness and method of application has been assessed, few studies have probed the changes in drying kinetics following treatment. In fact, a drastic alteration of the water transport might lead to further anomalies. This study investigates the influence of nanolimes dispersed in ethanol on the drying kinetics of Clipsham limestone using cavity ring-down spectroscopy. The degree of treatment was assessed by gravimetry, Raman spectroscopy, optical microscopy, colorimetry, optical profilometry and thin section analysis. Results showed an increase in the dry mass, observable colour changes and decrease in surface roughness. Small but reproducible increases were observed in the evaporation flux for phase I behaviour following treatment, however, no changes were observed in the total mass of water released or the phase II diffusivity. Determination of the activation energy associated with phase II drying was unchanged following treatment . These results indicate that following treatment there has been little-to-no change in the internal surfaces and structure of the stone to affect vapour transport.

Calculated and Empirical Values of Vibronic Transition Dipole Moments of Reactive Chemical Intermediates for Determination of Concentrations.

Absorption spectroscopy has long been known as a technique for making molecular concentration measurements and has received enhanced visibility in recent years with the advent of new techniques, like cavity ring-down spectroscopy, that have increased its sensitivity. To apply the method, it is necessary to have a known molecular absorption cross section for the species of interest, which typically is obtained by measurements of a standard sample of known concentration. However, this method fails if the species is highly reactive, and indirect means for attaining the cross section must be employed. The HO2 and alkyl peroxy radicals are examples of reactive species for which absorption cross sections have been reported. This work explores and describes for these peroxy radicals the details of an alternative approach for obtaining these cross sections using quantum chemistry methods for the calculation of the transition dipole moment upon whose square the cross section depends. Likewise, details are given for obtaining the transition moment from the experimentally measured cross sections of individual rovibronic lines in the near-IR Ã-X̃ electronic spectrum of HO2 and the peaks of the rotational contours in the corresponding electronic transitions for the alkyl (methyl, ethyl, and acetyl) peroxy radicals. In the case of the alkyl peroxy radicals, good agreement for the transition moments, ≈20%, is found between the two methods. However, rather surprisingly, the agreement is significantly poorer, ≈40%, for the HO2 radical. Possible reasons for this disagreement are discussed.

Concurrent measurements of atmospheric ammonia concentrations in the megacities of Beijing and Shanghai by using cavity ring-down spectroscopy

Ammonia (NH3) is a vital precursor of secondary aerosols, which play an important role in urban air pollution. The passive observation of NH3 in the urban atmosphere showed higher concentrations than conventionally believed; however, the NH3 dynamics remain limited due to the paucity of active measurements with fast response instruments. In this study, intensive online measurements of ambient NH3 were conducted using cavity ring-down spectroscopy in late spring and early summer 2020 at the megacities of Beijing and Shanghai in northern and southern China. The results show that the average NH3 concentration in Beijing (23.1 ± 10.3 ppb) was nearly double that in Shanghai (12.0 ± 5.0 ppb). This spatial difference was confirmed by satellite column observations and bottom-up emission patterns. In addition, there was a significant increase in NH3 concentrations during the morning in our study. This special diurnal profile was a universal feature, with an occurrence frequency exceeding 50% in both cities. These frequent morning increases were mainly caused by motor vehicle emissions, with an additional contribution from the residual layer breakup for one-quarter of the days in the morning increase. On these days, the NH3 concentration increased by approximately 20% due to the downward mixing of the residual layer rupture. The unique data observed here could be used to validate the chemistry and transport models at a higher time resolution and improve the understanding of the current status of NH3 pollution in the urban atmosphere.

Material Circularity: A Novel Method for Biobased Carbon Quantification of Leather, Artificial Leather, and Trendy Alternatives

In the past, climate change led the United Nations to define the Sustainable Development Goals Statement “blueprint to achieve a better and more sustainable future” and the European Commission to promote the “bioeconomy” concept and to launch the Green Deal Policy. Accordingly, the COP26 conference proposed a drastic reduction of fossil-based fuels and materials, in favor of biobased materials which should ensure intrinsic carbon neutrality. Contextually, many startups and established materials suppliers proposed new, trendy materials claiming sustainability advantages but, in many cases, without robust scientific backing. The need for transparency in terms of circularity led us to exploit a fast, reliable and easily deployable analytical method for assessing the biogenic carbon fraction in a variety of industrial materials. Our research team identified a radiocarbon analysis based on Saturated-absorption CAvity Ring-down (SCAR) spectroscopy as a quick and effective method for such a scope. Here we demonstrate its use for the determination of biogenic/fossil carbon proportions of polymeric and coated materials such as leather, coated textiles and trendy alternatives used in the fashion industry, with the scope of defining their intrinsic renewable content. The reliability of the SCAR method is validated through a comparison with the results obtained by the benchmark technique.

Experimental determination of Rayleigh scattering cross-sections at 408 nm

Cavity ring-down spectroscopy (CRDS) has been applied to retrieve accurate Rayleigh scattering cross-sections, {upsigma }_{mathrm{Rayl}.} for a set of atmospheric gases at ~ 408 nm. Step pressure changes and pressure ramps were used in three different but similar optical cavities to measure light extinction by N2, O2, Ar, CO, CO2, N2O, CH4 and synthetic air (SA). The experimentally determined {upsigma }_{mathrm{Rayl}.} were compared with {upsigma }_{mathrm{Rayl}.} values calculated for these atmospheric gases using knowledge of extrapolated literature values of the refractive index (n) and King correction factors measured in different spectral regions.The difference between measured and calculated {upsigma }_{mathrm{Rayl}.} using the most recently published dispersion relationship for N2O and CH4 is ~ 0.6%. This confirms the improved accuracy of the new dispersion relationship. The calculated and measured {upsigma }_{mathrm{Rayl}.} agreed on average within 0.6%, 2.4%, 1.2%, 2.2%, and 1.5% for the gases CO2, N2 O2, SA, and Ar at ~ 408 nm. However, for CO, the difference is 4.1%, i.e. more than twice the error. This implies that improved knowledge of the dispersion relationship for CO, and thus the refractive index and King correction factors, would be of value to calculate {upsigma }_{mathrm{Rayl}.} in the blue spectral region.

Examining the variability of rock glacier meltwater in space and time in high-elevation environments of Utah, United States

Rock glaciers are common geomorphic features in alpine landscapes and comprise a potentially significant but poorly quantified water resource. This project focused on three complementary questions germane to rock glacier hydrology: 1) Does the composition of rock glacier meltwater vary from year to year? 2) How dependent is the composition of rock glacier meltwater on lithology? And 3) How does the presence of rock glaciers in a catchment change stream water chemistry? To address these questions, we deployed automated samplers to collect water from late June through mid-October 2022 in two rock-glacierized mountain ranges in Utah, United States characterized by different lithologies. In the Uinta Mountains of northern Utah, where bedrock is predominantly quartzite, water was collected at springs discharging from two rock glaciers previously shown to release water in late summer sourced from internal ice. In the La Sal Mountains of southeastern Utah, where trachyte bedrock is widespread, water was collected at a rock glacier spring, along the main stream in a watershed containing multiple rock glaciers, and from a stream in a watershed where rock glaciers are absent. Precipitation was also collected, and data loggers for water temperature and electric conductivity were deployed. Water samples were analyzed for stable isotopes with cavity ring-down spectroscopy and hydrochemistry with ICP-MS. Our data show that water discharging from rock glaciers in the Uinta Mountains exhibits a shift from a snowmelt source to an internal ice source over the course of the melt season that is consistent from year to year. We also found that the chemistry of rock glacier water in the two study areas is notably different in ways that can be linked back to their contrasting bedrock types. Finally, in the La Sal Mountains, the properties of water along the main stream in a rock-glacierized basin resemble the properties of water discharging from rock glaciers, and strongly contrast with the water in a catchment lacking rock glaciers. Collectively these results underscore the role of rock glaciers as an agent influencing the hydrochemistry of water in high-elevation stream systems.

Impactor collection efficiencies can modify the uncertainty of multiply charged particles in optical extinction measurements

The complex distribution of particle charge states resulting from neutralization processes by radioactive or soft X-ray charge neutralizers is a well-documented problem in aerosol science. Here, we demonstrate that non-idealities in the collection efficiency of an impactor allows for the transmission of an unexpected population of multiply charged particles by a differential mobility analyzer that can bias optical measurements. The extinction cross sections (Cext) of ammonium sulfate particles were quantified using cavity ring-down spectroscopy and particle counting. Particles were selected by electrical mobility (i.e., a metric of particle size) using a differential mobility analyzer (DMA) or electrical mobility and mass selected by a tandem DMA and aerosol particle mass analyzer (APM), respectively, to elucidate multiple charging artifacts. Measured Cext exhibited statistically significant differences at particle sizes near the impactor cut point implying that these multiply charged particles should not be present and could not be confirmed by parallel size distribution measurements. Additionally, comparison of Cext with Mie theory demonstrates that misclassification of the multiply charged particles can give rise to numerically accurate results. To understand these observations, the collection efficiency (CE) of four impactors from similar electrostatic classifiers was investigated. From these measurements, it was determined that the nominal and actual diameters of the impactors differed by −0.5% (457 μm vs. (455 ± 1) μm, respectively (uncertainty is 1σ standard deviation)) but the average Stk50 (the Stokes number at the cut-point, D50) values differed by ≈ 23% (0.23 vs. 0.18 ± 0.01, respectively). The measured CE as a function of √Stk (a metric of particle aerodynamic size) exhibits a long tail toward higher √Stk values, allowing for transmission of the larger and multiply charged particles observed in the optical measurements. These measurements highlight the utility of using orthogonal, spectroscopic methods to quantify the presence of multiply charged particles.

Effect of Non-Markovian Collisions on Measured Integrated Line Shapes of CO.

Using cavity ring-down spectroscopy to probe R-branch transitions of CO in N_{2}, we show that the spectral core of the line shapes associated with the first few rotational quantum numbers, J, can be accurately modeled using a sophisticated line profile, provided that a pressure-dependent line area is introduced. This correction vanishes as J increases and is always negligible in CO-He mixtures. The results are supported by molecular dynamics simulations attributing the effect to non-Markovian behavior of collisions at short times. This work has large implications because corrections must be considered for accurate determinations of integrated line intensities, and for spectroscopic databases and radiative transfer codes used for climate predictions and remote sensing.

Vacuum extraction of high-salinity water for the determination of oxygen and hydrogen isotopic compositions using cavity ring-down spectroscopy

Tracking the hydrogen and oxygen isotopic compositions of water samples can aid in understanding the water cycle. Compared to that of fresh water, analyzing the hydrogen and oxygen isotopic composition of high-salinity water is still a challenging task owing to the influence of dissolved salts. In this study, desalination was achieved by vacuum extraction, and the oxygen and hydrogen isotope ratios (δ18O and δ2H) were measured using cavity ring-down spectroscopy (CRDS). Different solutions of the individual salts (NaCl, KCl, MgCl2, and CaCl2) were prepared with deionized water (DI) having a known stable isotopic composition. After vacuum extraction, the maximum differences in isotopic composition was no more than 0.09‰ for δ18O and 0.30‰ for δ2H at 4 mol/L NaCl and KCl and 1 mol/L MgCl2 and CaCl2. The isotopic compositions of two high-salinity samples (IAPSO standard seawater and brine water) were determined by the proposed procedure as well as thermal conversion/elemental analyzer-isotope ratio mass spectrometry for comparison. The δ18O and δ2H results obtained using the two methods were consistent. The influence of isotope-salts was completely overcome by the proposed vacuum extraction desalination procedure. Thus, the method enables the rapid extraction of a large number of samples, regardless of the type and origin of the salt solutions, provided the concentrations of MgCl2 and CaCl2 are below 1.0 mol/L.

The Extreme Learning Machine for the Extraction of Mono-Exponential Decay Time

The mono-exponential decay has been used to describe various physical phenomena such as cavity ring-down signal, fluorescence decay, etc. In this paper, a neural network method of extreme learning machine (ELM) is adopted to efficiently extract decay time. The theoretical extraction precision, accuracy, and computation cost are all preliminarily analyzed and quantitatively compared with the traditional Levenberg-Marquardt (LM) algorithm. The training set and the testing set for the ELM are built based on our experimental system parameters. After dataset training, the ELM model for mono-exponential decay extraction is obtained. In the dataset testing, this model gives almost the same results with the LM algorithm. The relative deviation of precision is only about ±1 nanosecond. This ELM model can also be directly used in experimental cavity ring-down system. Comparing with the LM algorithm, the relative deviations are less than ±2 nanoseconds when the decay time is in the range of 0.98 μs∼2.20 μs. The ELM method for mono-exponential decay extraction has high efficiency and fine robustness. It has the potential for the applications in cavity ring-down spectroscopy, fluorescence decay analysis, and nuclear radioactive technique, etc.

Evaluating the accuracy of absorbing aerosol optical properties measured using single particle cavity ring-down spectroscopy

Single particle cavity ring-down spectroscopy (CRDS) allows direct and continuous measurements of the extinction cross-sections for levitated micron-scale aerosol particles of constant or evolving composition. Our recent interests have concerned single particle CRDS measurements for light-absorbing particles. These measurements are made on single, spherical particles evaporating over the radius range 1500–700 nm that are levitated within a 405-nm cavity ring-down spectrometer using a linear electrodynamic quadrupole trap. Here, we quantify the accuracy and precision of our cavity ring-down time measurements and the consequences of particle motion within our electrodynamic trap. Next, we estimate the uncertainty in our particle size retrievals from angularly resolved elastic light scattering measurements for particles with a range of absorption strengths. Finally, we assess the accuracy of complex refractive index values retrieved from simultaneous ring-down time and particle size measurements. The assessments account for the impacts of shot and detector noise in the measured ring-down times, the driven particle motion within the electrodynamic trap, and particle absorption strength (for imaginary refractive indices in the range ∼0.0–0.1). The real and imaginary refractive indices are retrieved to an accuracy better than 0.005 and 0.002, respectively, for almost all absorption strengths studied, and for particles of constant or evolving composition. Although particles confined in our electrodynamic quadrupole trap undergo considerable levels of driven motion (with oscillation amplitudes of several tens of micrometers), the contribution of this motion to uncertainty in retrieved refractive indices is negligible compared to contributions from particle sizing errors.

New methods for the calibration of optical resonators: integrated calibration by means of optical modulation (ICOM) and narrow-band cavity ring-down (NB-CRD)

Abstract. Optical resonators are used in spectroscopic measurements of atmospheric trace gases to establish long optical path lengths L with enhanced absorption in compact instruments. In cavity-enhanced broad-band methods, the exact knowledge of both the magnitude of L and its spectral dependency on the wavelength λ is fundamental for the correct retrieval of trace gas concentrations. L(λ) is connected to the spectral mirror reflectivity R(λ), which is often referred to instead. L(λ) is also influenced by other quantities like broad-band absorbers or alignment of the optical resonator. The established calibration techniques to determine L(λ), e.g. introducing gases with known optical properties or measuring the ring-down time, all have limitations: limited spectral resolution, insufficient absolute accuracy and precision, inconvenience for field deployment, or high cost of implementation. Here, we present two new methods that aim to overcome these limitations: (1) the narrow-band cavity ring-down (NB-CRD) method uses cavity ring-down spectroscopy and a tunable filter to retrieve spectrally resolved path lengths L(λ); (2) integrated calibration by means of optical modulation (ICOM) allows the determination of the optical path length at the spectrometer resolution with high accuracy in a relatively simple setup. In a prototype setup we demonstrate the high accuracy and precision of the new approaches. The methods facilitate and improve the determination of L(λ), thereby simplifying the use of cavity-enhanced absorption spectroscopy.