Determination of spectrometer-detector parameters from calibration spectra and the use of the parameters in spectrometer calibrations

The grating equation is used to generate quadratic calibration equations for multichannel detectors with perpendicular and tilted focal planes. The quadratic coefficients are not independent and contain terms that are used to solve for spectrometer-detector parameters. The parameters can be calculated from a quadratic fit at one spectrometer position, but more accurate values can be obtained from quadratic fits at two spectrometer positions. The calculations show that the detector focal plane is tilted by about two degrees. Once values for the spectrometer-detector parameters are obtained from calibrations using at least three lines at one or two spectrometer positions, only one calibration line at any spectrometer position is required to obtain accuracies on the order of 0.1 cm(-1) over a several thousand wavenumber range. The main cause of spectrometer drift is a change in the diffraction angle and/or the spectrometer included angle. This drift is almost totally compensated by the one-line calibration, which adjusts the diffraction angle. A neon pen lamp is used to generate the calibration spectra. Using standard air wavelengths compared to true wavelengths can produce calibration errors of 0.1 to 0.6 cm(-1); the magnitude depends on local conditions and how the laser wavelength is treated.     

Accurate and precise wavelength calibration for wide bandwidth array spectrometers

Calibrating the wavelength scale of an array spectrometer typically involves measurements of lines at well-known wavelengths from a calibration lamp such as a mercury-argon source. This process is relatively straightforward when the lines are well separated, relative to the bandwidth of the spectrometer. When the spectrometer's bandwidth is large, compared with the distance between calibration wavelengths, it becomes increasingly difficult to accurately locate lines in the calibration spectrum. Even calibrations for instruments with a modest bandwidth of 12 nm can be difficult. Here we present results from a simple approach to improve the accuracy of wavelength calibration for an instrument with a large bandwidth (12 nm, center-to-center pixel spacing 3.3 nm). A monochromator has been used to filter the source so that each calibration line can be measured separately. For ten spectrometers, we were able to achieve accuracy better than 0.12 nm, or 0.09 nm on average; this is less than 3% of the pixel spacing. We anticipate this approach will be useful for improving the accuracy of measurements on array spectrometers and particularly in transferring multivariate calibrations between instruments.     

Comparison of spectral irradiance standards used to calibrate shortwave radiometers and spectroradiometers

Absolute calibration of spectral shortwave radiometers is usually performed with National Institute of Standards and Technology (NIST) or NIST-traceable incandescent lamps. We compare 18 irradiance standards from NIST and three commercial vendors using the same spectrometer to assess their agreement with our working standard. The NIST procedure is followed for the 1000-W FEL lamps from NIST, Optronics, and EG&G. A modified calibration procedure developed by Li-Cor is followed for their 200-W tungsten-halogen lamps. Results are reproducible from one day to the next to approximately 0.1% using the same spectrometer. Measurements taken four months apart using two similar but different spectrometers were reproducible to 0.5%. The comparisons suggest that even NIST standards may disagree with each other beyond their stated accuracy. Some of the 1000-W commercial lamps agreed with the NIST lamps to within their stated accuracy, but not all. Surprisingly, the lowest-cost lamps from Li-Cor agreed much better with the NIST lamps than their stated accuracy of 4%, typically within 2%. An analysis of errors leads us to conclude that we can transfer the calibration from a standard lamp to a secondary standard lamp with approximately 1% added uncertainty. A field spectrometer was calibrated with a secondary standard, producing a responsivity for the spectrometer that was within 5% of the responsivity obtained by Langley calibration using routine field measurements.     

Comments on "Accuracy of Raman lidar water vapor calibration and its applicability to long-term measurements"

In a recent publication, Leblanc and McDermid [Appl. Opt., 47, 5592 (2008)]APOPAI0003-693510.1364/AO.47.005592 proposed a hybrid calibration technique for Raman water vapor lidar involving a tungsten lamp and radiosondes. Measurements made with the lidar telescope viewing the calibration lamp were used to stabilize the lidar calibration determined by comparison with radiosonde. The technique provided a significantly more stable calibration constant than radiosondes used alone. The technique involves the use of a calibration lamp in a fixed position in front of the lidar receiver aperture. We examine this configuration and find that such a configuration likely does not properly sample the full lidar system optical efficiency. While the technique is a useful addition to the use of radiosondes alone for lidar calibration, it is important to understand the scenarios under which it will not provide an accurate quantification of system optical efficiency changes. We offer examples of these scenarios. Scanning of the full telescope aperture with the calibration lamp can circumvent most of these limitations. Based on the work done to date, it seems likely that the use of multiple calibration lamps in different fixed positions in front of the telescope may provide sufficient redundancy for long-term calibration needs. Further full-aperture scanning experiments, performed over an extended period of time, are needed to determine a "best practice" for the use of multiple calibration lamps in the hybrid technique.     

Characteristics of an absolutely calibrated flat-field extreme ultraviolet spectrometer in the 10-130 A range for fusion plasma diagnostics

A flat-field extreme ultraviolet (EUV) spectrometer with a nominal 2400 grooves/mm aberration-corrected ruled grating has been developed to analyze the emission spectrum in the wavelength range of 10 to 130 A from large helical device (LHD) plasmas. Spectral properties such as resolution, sensitivity, contribution of higher-order light, and background stray light have been studied using emission spectra mainly from intrinsic impurities, e.g., C and Fe. It is found that the spectrometer well resolves closely existing spectral lines of highly ionized medium- and high-Z impurities even in a very short wavelength range such as 10 to 20 A. As a result, it allows one to study the charge state distribution of elements in high-temperature fusion plasma. The ruled grating was then replaced by a laminar type holographic grating for the comparative study. The spectral resolution for the ruled grating (Dlambda approximately 0.08 A at 33.73 A) is clearly better than the holographic grating (Dlambda approximately 0.13 A at 33.73 A). Both gratings well suppress the higher-order light, e.g., the second-order light is only less than 11% of the first-order light for C vi(33.73 A). Relative sensitivity calibration with the wavelength has been done using bremsstrahlung continuum from the LHD plasmas. Absolute intensity calibration has been done by comparing the spectral intensities directly with the absolutely calibrated 1200 grooves/mm EUV spectrometer in the overlapping range of 90-120 A due to the absence of a good branching pair in 10-130 A. As a typical result on the present spectrometer well-resolved n=2-3 full transition arrays from Ne- to Li-like ions are measured for Fe and Ti and wavelengths of the spectral array are tabulated for each charge state. Spectroscopic comparison is also made between the 1200 grooves/mm and 2400 grooves/mm gratings in a range of 50-130 A.     

Procedures for Wavelength Calibration and Spectral Response Correction of CCD Array Spectrometers

This work describes a procedure for acquiring a spectrum of an analyte over an extended range of wavelengths and validating the wavelength and intensity assignments. To acquire a spectrum over an extended range of wavelengths with a spectrometer with a charge coupled device (CCD) array detector, it is necessary to acquire many partial spectra, each at a different angular position of the grating, and splice the partial spectra into a single extended spectrum. The splicing procedure exposes instrument dependent artifacts. It is demonstrated that by taking a spectrum of a reference irradiance source and making spectral correction, the artifacts exposed by the splicing are removed from the analyte spectrum. This is because the irradiance reference spectrum contains the same artifacts as the analyte spectrum. The artifacts exposed by the splicing depend on the wavelength of the splice; therefore it is important to measure the irradiance reference spectrum for the same range of wavelengths used to measure the spectrum of the analyte solution. In other words, there is no general spectral correction factor which is applicable to spectra taken for different range of wavelengths. The wavelength calibration is also carried out by splicing many partial spectra from a source like a krypton lamp. However the wavelength assignments are not sensitive to the splicing procedure and the same wavelength calibration can be used for spectra acquired over different extended wavelength ranges. The wavelength calibration checks the validity of the setting of the grating angular position, and the assignment of wavelengths to individual pixels on the CCD array detector. The procedure is illustrated by measuring the spectrum of an orange glass and the spectrum of a suspension of microalgae.     

On-line near-infrared spectrometer to monitor urea removal in real time during hemodialysis

The ex vivo removal of urea during hemodialysis treatments is monitored in real time with a noninvasive near-infrared spectrometer. The spectrometer uses a temperature-controlled acousto optical tunable filter (AOFT) in conjunction with a thermoelectrically cooled extended wavelength InGaAs detector to provide spectra with a 20 cm(-1) resolution over the combination region (4000-5000 cm(-1)) of the near-infrared spectrum. Spectra are signal averaged over 15 seconds to provide root mean square noise levels of 24 micro-absorbance units for 100% lines generated over the 4600-4500 cm(-1) spectral range. Combination spectra of the spent dialysate stream are collected in real-time as a portion of this stream passes through a sample holder constructed from a 1.1 mm inner diameter tube of Teflon. Real-time spectra are collected during 17 individual dialysis sessions over a period of 10 days. Reference samples were extracted periodically during each session to generate 87 unique samples with corresponding reference concentrations for urea, glucose, lactate, and creatinine. A series of calibration models are generated for urea by using the partial least squares (PLS) algorithm and each model is optimized in terms of number of factors and spectral range. The best calibration model gives a standard error of prediction (SEP) of 0.30 mM based on a random splitting of spectra generated from all 87 reference samples collected across the 17 dialysis sessions. PLS models were also developed by using spectra collected in early sessions to predict urea concentrations from spectra collected in subsequent sessions. SEP values for these prospective models range from 0.37 mM to 0.52 mM. Although higher than when spectra are pooled from all 17 sessions, these prospective SEP values are acceptable for monitoring the hemodialysis process. Selectivity for urea is demonstrated and the selectivity properties of the PLS calibration models are characterized with a pure component selectivity analysis.     

Radiometric calibration of the telescope and ultraviolet spectrometer SUMER on SOHO

The prelaunch spectral-sensitivity calibration of the solar spectrometer SUMER (Solar Ultraviolet Measurements of Emitted Radiation) is described. SUMER is part of the payload of the Solar and Heliospheric Observatory (SOHO), which begins its scientific mission in 1996. The instrument consists of a telescope and a spectrometer capable of taking spatially and spectrally highly resolved images of the Sun in a spectral range from 50 to 161 nm. The pointing capabilities, the dynamic range, and the sensitivity of the instrument allow measurements both on the solar disk and above the limb as great as two solar radii. To determine plasma temperatures and densities in the solar atmosphere, the instrument needs an absolute spectral-sensitivity calibration. Here we describe the prelaunch calibration of the full instrument, which utilizes a radiometric transfer-standard source. The transfer standard was based on a high-current hollow-cathode discharge source. It had been calibrated in the laboratory for vacuum UV radiometry of the Physikalisch-Technische Bundesanstalt by use of the calculable spectral photon flux of the Berlin electron storage ring for synchrotron radiation (BESSY)-a primary radiometric source standard.     

Vicarious calibrations of HICO data acquired from the International Space Station

The Hyperspectral Imager for the Coastal Ocean (HICO) presently onboard the International Space Station (ISS) is an imaging spectrometer designed for remote sensing of coastal waters. The instrument is not equipped with any onboard spectral and radiometric calibration devices. Here we describe vicarious calibration techniques that have been used in converting the HICO raw digital numbers to calibrated radiances. The spectral calibration is based on matching atmospheric water vapor and oxygen absorption bands and extraterrestrial solar lines. The radiometric calibration is based on comparisons between HICO and the EOS/MODIS data measured over homogeneous desert areas and on spectral reflectance properties of coral reefs and water clouds. Improvements to the present vicarious calibration techniques are possible as we gain more in-depth understanding of the HICO laboratory calibration data and the ISS HICO data in the future.     

Near-infrared spectroscopic measurement of urea in dialysate samples collected during hemodialysis treatments

Single-beam spectra were collected over the combination region of the near-infrared spectrum for 80 samples collected from 15 people over a two-week period. Partial least-squares (PLS) regression was used to generate an optimized calibration model for urea. PLS calibration models accurately measure urea in the spent dialysate matrix. Prediction errors are on the order of 0.15 mM, which is sufficient for the clinical assessment of the dialysis process. In addition, the feasibility of a global calibration model is demonstrated by generating a calibration model from samples and spectra obtained from 12 people to predict the level of urea in samples collected from 3 different people. In this case, the standard error of prediction is 0.09 mM. Spectra were modified in order to systematically examine the impact of resolution and noise. Little impact is observed by altering the spectral resolution from 4 to 32 cm-1. Spectral noise, however, plays an important role in the accuracy of these calibration models. Increasing the magnitude of the spectral noise increases the prediction errors and increases the width of the spectral range necessary for extracting the analytical information. The utility of the method is demonstrated by analyzing dialysate samples collected during actual dialysis treatments. In addition, the necessary resolution and spectral quality necessary for reliable on-line urea monitoring is identified. These findings indicate that a dedicated, on-line urea spectrometer must posses a resolution of 16 cm-1 coupled with a sample thickness of 1.5 mm and spectral noise levels on the order of 25 micro-absorbance units when measured as the root-mean-square (RMS) noise of 100% lines.     

基于探测器的成象光谱仪绝对辐射定标方法

用一组窄带滤光片、简易辐亮度计和硅光二极管探测器设计了绝对型光谱辐亮度计。精确测量滤光片的光谱透过函数，计算辐亮度计的视场，标定探测器的绝对光谱响应度，成为绝对光谱辐亮度计，用来标定成象光谱和其它光学遥感器，并与基于光谱辐照度灯进行辐射定标的传统方法进行了比较。结果表明，基于探测器进行辐射定标的方法是一种提高光学遥感器定标精度的途径，而且是佐证其它定标方法可靠性的一种手段。     

High mass measurement accuracy determination for proteomics using multivariate regression fitting: application to electrospray ionization time-of-flight mass spectrometry

Important factors that limit the mass measurement accuracy from a mass spectrometer are related to (1) the type of mass analyzer used and (2) the data processing/calibration methods used to obtain mass values from the raw data. Here, two data processing methods are presented that correct for systematic deviations when the mass of ions is measured using a time-of-flight (TOF) mass spectrometer. The first fitting method is one where m/z values are obtained from fitting peak distributions using double Gaussian functions. A second calibration method takes into account the slight nonlinear response of the TOF analyzer in addition to the drift in the calibration over time. Using multivariate regression, both of these two effects can be corrected for using a single calibration formula. Achievable performance was evaluated with a trypsin digestion of serum albumin and proteins from the organism D. radiodurans that was analyzed using gradient reversed-phase liquid chromatography combined with an electrospray ionization orthogonal TOF mass spectrometer. The root-mean-square deviation between the theoretical and experimental m/z values for serum albumin tryptic peptides was found to be 8 ppm using the double Gaussian-multivariate method compared to 29 ppm determined using linear calibration and normal peak centroiding. An advantage of the methods presented here is that no calibrant compounds need to be added to the mobile phase, thereby avoiding interference effects and signal suppression of analytes.     

飞秒脉冲光谱测量对时域波形重建的影响

利用光谱相位还原直接电场重建法对飞秒脉冲激光时域波形进行重建,分析了光谱测量波长示值误差和光谱辐照度示值误差对于飞秒脉冲光谱测量的影响。使用低压汞灯对光谱仪波长校准,根据校准结果,对测量光谱蓝移和红移,通过数值模拟研究波长示值误差对重建脉冲波形的影响;利用光谱辐射照度标准装置对光谱仪光谱辐照度校准,通过增加白噪声模拟分析和各种常用反射片实验测量研究光谱辐照度示值误差对重建脉冲波形的影响。结果表明,光谱测量波长示值误差和光谱辐照度示值误差对于飞秒脉冲光谱测量的相对标准差在1%之内。     

High-energy neutron reference fields for the calibration of detectors used in neutron spectrometry

Quasi-monoenergetic reference neutron beams in the energy range between 20 and 100 MeV have been produced and characterized with a proton recoil telescope, a scintillation spectrometer, a ²³⁸U fission chamber and a Bonner sphere spectrometer. The beams are well suited for the calibration of detectors used in neutron spectrometry. A new method is described which reduces the correction for the contribution from low-energy neutrons present in the beams.     

Continuous calibration of a vacuum ultraviolet system from 65 to 125 nm by a cascade arc and comparison with the calibrated line radiation of a hollow cathode

A high-power stationary helium cascade arc has been developed as a standard source for continuum radiation in the VUV spectral range from 65 to 125 nm. The calibration of the VUV system response was based on the calculated and measured continuum radiation of a 2-mmphi pure He arc. Diagnostics of the arc plasma in partial thermal equilibrium yielded the electron density and the temperature that were inserted in the calculations of the continuous radiation. The results were compared with the helium, argon, and krypton radiation lines of a high-current hollow cathode lamp. This lamp was built according to the construction drawings of a hollow cathode, which was calibrated by means of the electron synchrotron radiation at the Physikalisch Technische Bundesanstalt Berlin.     

"日盲"紫外电晕探测系统定标

"日盲"紫外电晕探测是电力设备检修与维护的主要手段之一.为了提供更为准确和客观的评价依据,需要对"日盲"紫外电晕探测系统进行辐亮度定标,从而确定目标辐亮度与增益控制电压、系统输出灰度值之间的关系.为此构建了由高稳定氘灯光源、积分球、光纤光谱仪等组成的定标装置.采用可溯源美国NIST的紫外标准氘灯对光纤光谱仪进行光谱辐照度标定,并以光纤光谱仪作为标准探测器对电晕探测系统进行定标.通过实验拟合出ICCD增益控制电压与系统增益之间的关系曲线,并给出了系统的标定方程.随后进行了三组不同增益的验证实验,实验结果表明在线性区内辐亮度推算值与测量值之间的最大相对误差为6.11%,均方根为3.22%.经分析,文中所采用的系统定标方案的不确定度为9.1%,基本可以满足了"日盲"紫外电晕探测系统的需求.此外,不同增益条件下的系统响应特性可以为"电晕"探测过程中进行自动增益调整算法的设计提供参考依据.     

Determination of physiological levels of glucose in an aqueous matrix with digitally filtered Fourier transform near-infrared spectra

A procedure is described for the measurement of clinically relevant concentrations of glucose in aqueous solutions with near-infrared (NIR) absorbance spectroscopy. A glucose band centered at 4400 cm-1 is used for this analysis. NIR spectra are collected over the frequency range 5000-4000 cm-1 with a Fourier transform spectrometer. A narrow-band-pass optical interference filter is placed in the optical path of the spectrometer to eliminate light outside this restricted range. This configuration provides a 2.9-fold reduction in spectral noise by utilizing the dynamic range of the detector solely for light transmitted through the filter. In addition, a novel spectral processing scheme is described for extracting glucose concentration information from the resulting absorbance spectra. The key component of this scheme is a digital Fourier filter that removes both high-frequency noise and low-frequency base-line variations from the spectra. Numerical optimization procedures are used to identify the best location and width of a Gaussian-shaped frequency response function for this Fourier filter. A dynamic area calculation, coupled with a simple linear base-line correction, provides an integrated area from the processed spectra that is linearly related to glucose concentrations over the range 1-20 mM. The linear calibration model accurately predicted glucose levels in a series of test solutions with an overall mean percent error of 2.5%. Based on the uncertainty in the parameters defining the calibration model and the variability of the magnitudes of the integrated areas, an overall uncertainty of 7.8% was estimated for predicted glucose concentrations.     

Design and optimization of the calibration procedure for a miniaturized Fourier transform spectrometer

This paper presents a Fourier transform infrared (FT-IR) spectrometer calibration procedure based on an unusual source made from a spectrally selective surface. An alternative solution to the usual calibrators has been developed to cope with the tight mass budget of an instrument devoted to Mars surface exploration. The designed system has proved effective, in terms of achievable radiometric accuracy, despite the drawbacks due to the significant reflectivity of the sources. The proposed procedure is a standard "two-source" approach in which both cold and hot sources are thermally controlled surfaces, similar to an optical solar reflector, associated to a filament lamp. Such a system allows the required signal to be achieved in the 2-25 l m instrument wavelength range. Source optimization was performed using, as a cost function, the computed radiometric uncertainty, while the required absolute accuracy of the instrument was imposed as the optimization constraint.     

Systematic comparison of bias and precision data obtained with multiple-point and one-point calibration in six validated multianalyte assays for quantification of drugs in human plasma

One-point (linear through zero) calibration is often used as a compromise between necessary calibration, workload, and time. The aim of the present study was to systematically check the applicability of one-point calibration by comparing bias and precision data obtained with full and one-point calibration. Data from validation studies of six mass spectrometry-based multianalyte bioanalytical assays were used for this purpose. Bias and intermediate precision datasets of full multiple-point calibration were compared to six one-point calibration datasets (A-F in rising calibrator concentration order) calculated from the same raw data. The datasets were statistically compared using the Friedman test followed by Dunn's multiple comparison test. The results obtained with full calibration and the different one-point calibrations were found to differ significantly (P < 0.05) in all of the six studied methods. The best one-point calibration results were obtained with calibrator D, with which acceptance criteria for bias and precision were fulfilled for the majority of analytes. However, some extremely high bias and precision data were obtained for some analytes in the low-concentration range. In conclusion, one-point calibration with a calibrator close to the center of the full calibration range can be a feasible alternative to full calibration.