Measuring δ13C of atmospheric air with non-dispersive infrared spectroscopy

The potential use of non-dispersive infrared spectroscopy for measuring δ¹³C in air is demonstrated. This technique has already been successfully established for breath test analyses in medical diagnostics, where the CO₂ concentration ranges from 1 to 5 vol.% in the exhaled breath of vertebrates. For breath tests, the sensitivity and accuracy has been improved to reach a standard deviation of 0.2 ‰ (delta-value). Further adjustments were necessary to improve the sensitivity of the instrument at concentration levels typical of atmospheric air. The long-term stability is given by a standard deviation of 0.35 ‰ for CO₂ concentrations of about 400 ppm with signal averaging over 60 s.     

Applications of cavity ring-down spectroscopy to high precision isotope ratio measurement of 13C/12C in carbon dioxide

Recent measurements of carbon isotopes in carbon dioxide using near-infrared, diode-laser-based cavity ring-down spectroscopy (CRDS) are presented. The CRDS system achieved good precision, often better than 0.2 per thousand, for 4% CO2 concentrations, and also achieved 0.15-0.25 per thousand precision in a 78 min measurement time with cryotrap-based pre-concentration of ambient CO2 concentrations (360 ppmv). These results were obtained with a CRDS system possessing a data rate of 40 ring-downs per second and a loss measurement of 4.0 x 10(-11) cm(-1) Hz(-1/2). Subsequently, the measurement time has been reduced to under 10 min. This standard of performance would enable a variety of high concentration (3-10%) isotopic measurements, such as medical human breath analysis or animal breath experiments. The extension of this ring-down to the 2 microm region would enable isotopic analysis at ambient concentrations, which, combined with the small size, robust design, and potential for frequent measurements at a remote site, make CRDS technology attractive for remote atmospheric measurement applications.     

CO2 concentrations and delta13C (CO2) values in monthly sets of air samples from downtown Parma and the Parma and Taro river valleys, Emilia-Romagna, Italy

Monthly sets of discrete air samples were collected from September 2004 to June 2005 in the town of Parma, along North-South and East-West runs (8 plus 8 samples), using four-litre Pyrex flasks. The CO2 concentrations and delta13C values were determined on these samples with the aim of evaluating quantitatively the contribution of domestic heating to the winter atmospheric CO2 pollution in downtown Parma by comparing autumn and spring atmospheric values with winter values. After separation of CO2 from the other air gases in the laboratory, the CO2 concentrations were calculated from the intensity of the 12C16O2+ ion beam in the mass spectrometer, after calibration with artificial air samples whose CO2 concentration was very carefully determined by the Monte Cimone Observatory (Sestola, Modena, Italy). The reproducibility of these measurements was of approximately +/-0.4 % and, consequently, the most probable error is not higher than+/-2-3 ppmv and does not affect the magnitude of the gradients between different samples. The standard deviation of delta13C measurements ranges from+/-0.02 to +/-0.04 per thousand (1sigma). The results suggest that the contribution of domestic heating to atmospheric CO2 pollution is almost negligible in the case of ground level atmosphere, where the main CO2 pollution is essentially related to the heavy car traffic. This is probably because of the fact that the gases from the domestic heating systems are discharged tens of metres above ground level at a relatively high temperature so that they rise quickly to the upper atmospheric layers and are then displaced by air masses dynamics. Monthly sets of discrete air samples were also collected from October 2004 to June 2005 along North-South runs from the town of Parma to the Apennine ridge following the Parma and the Taro river valleys (8 samples and 7 samples per set, respectively) and measured using the same technique. The aim of this study was the comparison between the town samples, the plain country samples and the samples collected on the northern slope of the Apennines. The results reveal huge variations of both CO2 concentration and delta13C through space and time, some of which can be reasonably explained whereas others are rather difficult to understand. The sets of values are discussed and various hypotheses are suggested.     

Qualitative and quantitative determination of human biomarkers by laser photoacoustic spectroscopy methods

The hypothesis that blood, urine and other body fluids and tissues can be sampled and analyzed to produce clinical information for disease diagnosis or therapy monitoring is the basis of modern clinical diagnosis and medical practice. The analysis of breath air has major advantages because it is a non-invasive method, represents minimal risk to personnel collecting the samples and can be often sampled. Breath air samples from the human subjects were collected using aluminized bags from QuinTron and analyzed using the laser photoacoustic spectroscopy (LPAS) technique. LPAS is used to detect traces of ethylene in breath air resulting from lipid peroxidation in lung epithelium following the radiotherapy and also traces of ammonia from patients subjected to hemodialysis for treatment of renal failure. In the case of patients affected by cancer and treated by external radiotherapy, all measurements were done at 10P(14) CO₂ laser line, where the ethylene absorption coefficient has the largest value (30.4 cm⁻¹ atm⁻¹), whereas for patients affected by renal failure and treated by standard dialysis, all measurements were performed at 9R(30) CO₂ laser line, where the ammonia absorption coefficient has the maximum value of 57 cm⁻¹ atm⁻¹. The levels of ethylene and ammonia in exhaled air, from patients with cancer and renal failure, respectively, were measured and compared with breath air contents from healthy humans. Human gas biomarkers were measured at sub-ppb (parts per billion) concentration sensitivities. It has been demonstrated that LPAS technique will play an important role in the future of exhaled breath air analysis. The key attributes of this technique are sensitivity, selectivity, fast and real time response, as well as its simplicity.     

Measuring the 13C/12C isotope ratio in atmospheric CO2 by means of laser absorption spectrometry: a new perspective based on a 2.05-microm diode laser

The potential use of high sensitivity laser absorption spectroscopy for measuring the 13C/12C isotope ratio in atmospheric CO2 has been demonstrated, using a GaSb-based diode laser at 2.05 microm. In this spectral region, the overlapping between relatively strong 12CO2 and 13CO2 absorption features gives rise to several line pairs which are well suitable for a spectroscopic determination of the isotope ratio. Preliminary results have demonstrated that a short-term precision better than 1 per thousand can be easily obtained, for a CO2 concentration of 1000 ppm. We extensively discuss the influence of a possible non-linearity in the detectors' response on the delta-value and suggest an instrumental development that would allow to eliminate this effect.     

Use of the optogalvanic effect (OGE) for isotope ratio spectrometry of 13CO2 and 14CO2

The use of isotopic carbon dioxide lasers for determination of carbon (and oxygen) isotope ratios was first demonstrated in 1994. Since then a commercial device called LARA, has been manufactured and used for Helicobacter pylori breath tests using (13)C-labelled urea. The major advantages of the optogalvanic effect compared with other infrared absorption isotope ratio measurement techniques are its lack of optical background and its high sensitivity resulting from a signal gain proportional to laser power. Continuous normalisation using two cells, a standard and sample, lead to high accuracy as well as precision. Recent advances in continuous flow measurement of (13)C/(12)C ratios of CO(2) in air and extensions of the technique to (14)C, which can be analysed as a stable isotope, are described.     

Effects of natural environmental factors on delta13C of lichens

This preliminary study was designed to determine the extent to which the carbon isotope ratio in four species of lichens was influenced by such features as humidity, rainfall, radioactivity, and air quality. The sampling sites were selected to be at a great distance from any pollution. At the time of sampling, field data (temperature, relative humidity, average monthly precipitation, and radioactivity) were recorded. delta(13)C in whole lichen specimens were determined using standard mass spectrometric techniques with a standard deviation of+/-0.3 per thousand. We have found a weak but negative correlation between delta(13)C and relative humidity, and a positive correlation between delta(13)C and average monthly precipitation at the studied sites. The effects were minor, of the order of 1.5 per thousand for all the lichens. We have examined the correlation between (137)Cs activity concentration of the studied lichens and delta(13)C of these lichens, and we have suggested that fixation of radiocesium does not alter photosynthesis rate. There was a delta(13)C variation with the altitude gradient with less negative delta(13)C values at higher altitude. It is possible that this difference is caused by the ozone and occurred at the high elevations.     

Continuous field measurements of delta(13)C-CO(2) and trace gases by FTIR spectroscopy

Continuous analysis of the (13)C/(12)C ratio of atmospheric CO(2) (delta(13)C-CO(2)) is a powerful tool to quantify CO(2) flux strengths of the two major ecosystem processes assimilation and respiration. Traditional laboratory techniques such as isotope ratio mass spectrometry (IRMS) in combination with flask sampling are subject to technical limitations that do not allow to fully characterising variations of atmospheric delta(13)C-CO(2) at all relevant timescales. In our study, we demonstrate the strength of Fourier transform infrared (FTIR) spectroscopy in combination with a PLS-based calibration strategy for online analysis of delta(13)C-CO(2) in ambient air. The ability of the instrument to measure delta(13)C-CO(2) was tested on a grassland field-site and compared with standard laboratory-based IRMS measurements made on field-collected flask samples. Both methods were in excellent agreement, with an average difference of 0.4 per thousand (n=81). Simultaneously, other important trace gases such as CO, N(2)O and CH(4) were analysed by FTIR spectroscopy.     

Degradation pathways of dissolved carbon in landfill leachate traced with compound-specific (13)C analysis of DOC

The isotopic compositions of carbon compounds in landfill leachate provide insights into the biodegradation pathways that dominate the different stages of waste decomposition. In this study, the carbon geochemistry of different carbon pools, environmental stable isotopes and compound-specific isotope analysis (CSIA) of leachate dissolved organic carbon (DOC) fractions and gases show distinctions in leachate biogeochemistry and methane production between the young area of active waste emplacement and the old area of historical emplacement at the Trail Road Landfill (TRL). The active area leachate has low DOC concentrations (<200 mg l(-1)) dominated by fulvic acid (FA=160 mg l(-1)), and produces CH(4) dominantly by CO(2) reduction (D- excess=20.6 per thousand). Leachate generated in the area of older waste has high DOC (>4770 mg l(-1)) dominated by FA (4482 mg l(-1)) and simple fatty acids (acetic=1008 mg l(-1) and propionic=608 mg l(-1)), and produces CH(4) by the acetate fermentation pathway (D- excess=9.8 per thousand). CSIA shows an advanced degradation and a progressive accumulation of (13)C of fatty acids in leachate from the older area. The enriched (13)C value of FA (-20 and-26 per thousand for the older and active parts, respectively,) and of low molecular weight DOC (-8 and-27 per thousand) as well as of the bulk DOC (-21 and-25 per thousand) shows more advanced degradation in the older part of the landfill, which is consistent with the shift in the humic/FA ratios (0.05 and 0.18). The (13)C enrichment of acetate (-12 per thousand) above the (13)C of DOC (-21 per thousand) and of propionic acid (-19 per thousand), in older leachate, suggests that this acetate has not evolved from the simple degradation of larger organic molecules, but by homoacetogenesis from the enriched dissolved inorganic carbon (DIC) pool (8 per thousand) and H(2,) which produce a more enriched (13)C of acetate. In contrast, the (13)C of the minor acetate in the active area (-17 per thousand) indicates that CO(2)-reducing bacteria must be the primary consumers of H(2), which has resulted in enriched (13)C(DIC) (10 per thousand) and depleted (13)C(CH4) (-58 per thousand).     

减压氩气环境下激光显微光谱分析再现性和灵敏度的研究

以金属合金光谱分析标样为样品，采用激光显微发射光谱分析系统在减压氩气环境下，实验研究了光谱分析再现性和灵敏度。以原子线作为分析线的RSD减压氩气环境好于常压空气环境，以离子线作为分析线的RSD基本相同，样品的组成和元素的浓度对分析线的RSD有较大的影响。测定的铝合金样品Cu,Zn,Mg浓度曲线斜率是空气环境下的1．5－2倍，表明分析灵敏度得到明显改善，有利于激光显微光谱分析范围的扩展。     

On-line delta(18)O measurement of organic and inorganic substances

A method for the automated sample conversion and on-line oxygen isotope ratio (delta(18)O) determination for organic and inorganic substances is presented. The samples are pyrolytically decomposed at 1400 degrees C in the presence of nickelized graphite. With the system presented organic as well as inorganic samples such as nitrates, sulphates and phosphates of 50-100 &mgr;g O can be analyzed for their delta(18)O values with a standard deviation usually better than 0.5 per thousand. Additionally, carbon isotope ratios of organic substances and nitrogen isotope ratios of inorganic nitrogenous compounds are available in the same sample run. Data for international and some inter-laboratory reference materials are presented to show the accuracy and reliability of the method. The effect of some additives on the CO yield was checked for substances which do not pyrolyze completely. Copyright 1999 John Wiley & Sons, Ltd.     

Isotopic ((13)C) fractionation during plant residue decomposition and its implications for soil organic matter studies

Carbon isotopic fractionations in plant materials and those occurring during decomposition have direct implications in studies of short-and longer-term soil organic matter dynamics. Thus the products of decomposition, the evolved CO(2) and the newly formed soil organic matter, may vary in their (13)C signature from that of the original plant material. To evaluate the importance of such fractionation processes, the variations in (13)C signatures between and within plant parts of a tropical grass (Brachiaria humidicola) and tropical legume (Desmodium ovalifolium) were measured and the changes in (13)C content (signatures) during decomposition were monitored over a period of four months. As expected the grass materials were less depleted in (13)C (-11.4 to -11.9 per thousand) than those of the legume (-27.3 to -25.8 per thousand). Root materials of the legume were less (1.5 per thousand) depleted in (13)C compared with the leaves. Plant lignin-C was strongly depleted in (13)C compared with the bulk material by up to 2.5 per thousand in the legume and up to 4.7 per thousand in the grass. Plant materials were subsequently incubated in a sand/nutrient-solution/microbial inoculum mixture. The respiration product CO(2) was trapped in NaOH and precipitated as CaCO(3), suitable for analysis using an automated C/N analyser coupled to an isotope ratio mass spectrometer. Significant depletion in (13)C of the evolved CO(2) was observed during the initial stages of decomposition probably as a result of microbial fractionation as it was not associated with the (13)C signatures of the measured more decomposable fractions (non-acid detergent fibre and cellulose). While the cumulative CO(2)-(13)C signatures of legume materials became slightly enriched with ongoing decomposition, the CO(2)-C of the grass materials remained depleted in (13)C. Associated isotopic fractionation correction factors for source identification of CO(2-)C varied with time and suggested errors of 2-19% in the estimation of the plant-derived C at 119 days of incubation in a soil of an intermediate (-20.0 per thousand) (13)C signature. Analysis of the residual material after 119 days of incubation showed little or no change in the (13)C signature partly due to the incomplete decomposition at the time of harvesting. Copyright 1999 John Wiley & Sons, Ltd.     

一个简便快速测定CO的纳米金表面等离子体共振吸收光谱法

CO主要由火焰或烤炉等碳的不完全燃烧所产生,是一种常温下为无色、无臭的有毒气体,人们受一氧化碳的污染在慢性中毒时完全意识不到它,有时甚至有舒适的感觉,这些特性更增加了它的危害性。因此,探索简便快速灵敏的CO检测方法具有重要意义。研究表明,在pH 7.2 磷酸盐缓冲溶液中,一氧化碳还原HAuCl₄ 生成近似球形的金纳米粒子(NG),其平均粒径为45 nm,在1.70, 2.20和9.70 keV处产生3个金元素的能谱峰,在540 nm处产生一个表面等离子体共振(SPR) 吸收峰。采用分光光度法优化了分析条件,选择磷酸盐缓冲缓冲溶液的pH为7.2,磷酸盐缓冲浓度为40 mmoL·L-1,HAuCl₄浓度为40.0 μg·mL-1,反应时间为5 min。在选定条件下,CO浓度在0.2～8.75 μg·mL-1范围内与其SPR吸收峰峰值成线性关系,检出限为0.1 μg·mL-1 CO。考察了共存物质对测定1.0 μg·mL-1 CO的影响。结果表明, 当相对误差在±5%之内,200倍的SO2-₃, PO3-₄, SO2-₄、CO2-₃, NO-₃;100倍的Zn2+, K+, BrO-₃, Na₂S, 乙醇, 甲醇;80倍的Ni2+,Cr3+,Co2+,Ca2+, Mg2+, Fe3+, 葡萄糖, Pb2+, Al3+, SeO2-₃, Na₂S₂O₃,甲醛;50倍的Mn2+不干扰测定。这表明该SPR光度法具有较好的选择性。采用本法测定了空气样品中CO含量,结果与气相色谱法一致,相对误差在1.8%～4.2%之间。     

Mid-infrared cavity leak-out spectroscopy for ultrasensitive detection of carbonyl sulfide

We present a ringdown absorption spectrometer based on a continuous-wave CO laser in the mid-infrared spectral region near lambda = 5 microm. Using a linear ringdown cavity (length, 0.5 m) with R > = 99.99% mirrors, we observed a noise-equivalent absorption coefficient of 7 x 10(-11) cm(-1) Hz(-1/2). This is 2 orders of magnitude improved compared with previous values. With this setup we studied the spectroscopic detection of carbonyl sulfide (here abbreviated OCS) traces in ambient air and in exhaled breath. We achieved a detection limit of 7 parts in 10(12) (parts per trillion) OCS in ambient air, which is unprecedented and shows great promise for environmental and biomedical applications.     

Impact of water table depth on forest soil methane turnover in laboratory soil cores deduced from natural abundance and tracer 13C stable isotope experiments

We investigated turnover of methane (CH4) in soils from a poorly drained UK forest. In situ, this forest exhibited a negligible soil-atmosphere CH4 flux, whereas adjacent grassland plots were sources of CH4. We hypothesised that the forest plots exhibited reduced anaerobic CH4 production through water-table draw down. Consequently, we exposed soil cores from under oak to high and low water-table conditions in the laboratory. Methane fluxes increased significantly in the high water-table (1925+/-1702 mug CH4 m(-2) h(-1)) compared to the low one (-3.5+/-6.8 microg CH4 m(-2) h(-1)). Natural abundance delta13C values of CH4 showed a strong depletion in high water-table cores (-56.7+/-2.9 per thousand) compared to methane in ambient air (-46.0 per thousand) indicative of methanogenic processes. The delta13C values of CH4 from low water-table cores (delta13C-46.8+/-0.2 per thousand) was similar to ambient air and suggested little alteration of headspace CH4 by the soil microbial community. In order to assess the CH4 oxidizing activity of the two treatments conclusively, a 13CH4 spike was added to the cores and 13CO2 production was measured as the by-product of CH4 oxidation. 13CH4 oxidation rates were 57.5 (+/-12.7) and 0.5 (+/-0.1) microg CH4 m(-2) h(-1) for high and low water-tables, respectively. These data show that the lower water-table hydrology treatment impacted methanogenic processes without stimulating methanotrophy.     

Towards an inhalative 13C breath test method

Customary 13CO2 breath tests--and also 15N urine tests--always start with an oral administration of a test substrate. The test person swallows a stable isotope labelled diagnostic agent. This technique has been used to study several pathophysiological changes in gastrointestinal organs. However, to study pathophysiological changes of the bronchial and lung epithelium, the inhalative administration of a stable isotope labelled agent appeared more suitable to us. [1-13C]Hexadecanol and [1-13C]glucose were chosen. Inhaled [1-13C]hexadecanol did not yield 13CO2 in the exhaled air, but [1-13C]glucose did. To study the practicability of the [1-13C]glucose method and the reproducibility of the results, 18 inhalation tests were performed with healthy subjects. In 6 self-tests, the optimum inhalative dose of [13C]glucose was determined to be 205 mg. Using the APS aerosol provocation system with the nebulizer 'Medic Aid' (Erich Jaeger Würzburg), a 25% aqueous solution was inhaled. Then, breath samples were collected at 15 min. intervals and analysed for 13CO2. 75-120 min after the end of inhalation a well-reproducible maximum delta13C value of 6%o over baseline (DOB) was detected for 12 healthy probands. Speculating that the pulmonary resorption of the [13C]glucose is the rate-limiting step of elimination, decompensations in the epithelium ought to be reflected in changed [1-13C]glucose resorption rates and changed 13CO2 output. Therefore, we speculate that the inhalation of suitable 13C-labelled substrates will pave the way for a new group of 13CO2 breath tests aiding investigations of specific pathophysiological changes in the pulmonary tract, such as inflammations of certain sections and decompensations of cell functions.     

Isolation of NO(3)(-)-N as 1-phenylazo-2-naphthol (Sudan-1) for measurement of delta(15)N

The conversion of nitrate (NO(3)(-)) to 1-phenylazo-2-naphthol (Sudan-1) has been examined as a method for natural abundance measurement of delta(15)N of NO(3)(-). The reaction results in dilution of NO(3)(-)-N with only one reagent-derived N and the product is readily concentrated from dilute samples by reverse phase chromatography. There is systematic isotopic fractionation during the reaction, but this can be allowed for by analysing known NO(3)(-) standards along with each sample set. Sudan-1 prepared from surface water samples containing approximately 50 &mgr;g NO(3)(-)-N can be analysed by automated continuous flow isotope ratio mass spectrometry with a precision of 0.2 per thousand (one standard deviation) and the accuracy is not affected by interference from other nitrogenous species in the sample or reagents. Copyright 1999 John Wiley & Sons, Ltd.     

Exact profiles of (13)CO(2) recovery in breath air after per oral administration of [(13)C]methacetin in two groups of different ages

The aim of this study is to determine if age is a factor influencing the results of a [(13)C]methacetin breath test ((13)C-MBT). Two groups of healthy volunteers, each comprising six men and six women, but differing in average age (Y=young, 25.1+/-0.6 years, MA=middle-aged;, 46.0+/-2.1 years) orally took 75 mg [(13)C]methacetin. Samples of expiratory air for (13)CO(2) measurement were collected up to 48 h after intake of the substrate. A maximum momentary (13)CO(2) breath exhalation of 37.0+/-2.6%dose/h was observed at 18 min (median, range: 9-30 min) in the young subjects and of 38.4+/-2.5%dose/h at 18 min (median, range: 12-30 min) in the middle-age volunteers. The cumulative (13)C elimination in expiratory air was statistically significantly higher in the MA compared with the Y group as from 75 min up to 180 min, indicating a greater microsomal metabolic efficiency of the liver in the middle-aged healthy subjects. Gender, use of hormonal contraception, cigarette smoking, or body mass index did not modify the age-related effect on the cumulative (13)C elimination in breath air. The study results imply a necessity of composing control groups well matched with regard to the age structure for a proper interpretation of clinical (13)C-MBT results.     

Advances in Air Quality Monitoring via Nanotechnology

Urban air pollution has become an inescapable issue due to its serious consequences on public health and, therefore, needs more accurate tracking through denser networks of air quality monitoring (AQM) stations. A higher density of these networks can be afforded by cities only if the costs of future individual AQM stations decrease. We review here the outcome of two European projects where our objective was to provide an alternative approach consisting in the development of cost-effective mobile microstations based on semiconductor sensors and capable of complementing the expensive and bulky current AQM stations. Improvement of the sensor sensitivity to detect very low levels of pollutants (CO, NO, NO₂, O₃) in air was the major challenge to take up. This was achieved by using metal oxide nanosized particles with both controlled size and surface chemistry, and by adapting the screen-printing process to the nanometer size specificity. The detection thresholds for NO₂, NO and O₃ of our nanoparticles-based sensors have been decreased by a factor of 3–5 compared to currently commercialized sensors. The lowest detectable concentration of CO has been reduced from 5 to 3 ppm without affecting the selectivity. In terms of sensitivity performance, our sensor prototypes can now meet the criteria for outdoor AQM whereas the commercial semiconductor and electrochemical sensors still cannot. As for the implementation of the network as a whole, our technological approach is outlined.