Béla Tuzson

Isotope Signatures of N2O in a Mixed Microbial Population System: Constraints on N2O Producing Pathways in Wastewater Treatment

We present measurements of site preference (SP) and bulk (15)N/(14)N ratios (δ(15)N(bulk)(N2O)) of nitrous oxide (N(2)O) by quantum cascade laser absorption spectroscopy (QCLAS) as a powerful tool to investigate N(2)O production pathways in biological wastewater treatment. QCLAS enables high-precision N(2)O isotopomer analysis in real time. This allowed us to trace short-term fluctuations in SP and δ(15)N(bulk)(N2O) and, hence, microbial transformation pathways during individual batch experiments with activated sludge from a pilot-scale facility treating municipal wastewater. On the basis of previous work with microbial pure cultures, we demonstrate that N(2)O emitted during ammonia (NH(4)(+)) oxidation with a SP of -5.8 to 5.6 ‰ derives mostly from nitrite (NO(2)(-)) reduction (e.g., nitrifier denitrification), with a minor contribution from hydroxylamine (NH(2)OH) oxidation at the beginning of the experiments. SP of N(2)O produced under anoxic conditions was always positive (1.2 to 26.1 ‰), and SP values at the high end of this spectrum (24.9 to 26.1 ‰) are indicative of N(2)O reductase activity. The measured δ(15)N(bulk)(N2O) at the initiation of the NH(4)(+) oxidation experiments ranged between -42.3 and -57.6 ‰ (corresponding to a nitrogen isotope effect Δδ(15)N = δ(15)N(substrate) - δ(15)N(bulk)(N2O) of 43.5 to 58.8 ‰), which is considerably higher than under denitrifying conditions (δ(15)N(bulk)(N2O) 2.4 to -17 ‰; Δδ(15)N = 0.1 to 19.5 ‰). During the course of all NH(4)(+) oxidation and nitrate (NO(3)(-)) reduction experiments, δ(15)N(bulk)(N2O) increased significantly, indicating net (15)N enrichment in the dissolved inorganic nitrogen substrates (NH(4)(+), NO(3)(-)) and transfer into the N(2)O pool. The decrease in δ(15)N(bulk)(N2O) during NO(2)(-) and NH(2)OH oxidation experiments is best explained by inverse fractionation during the oxidation of NO(2)(-) to NO(3)(-).

Determination of N2O isotopomers with quantum cascade laser based absorption spectroscopy

We present an analytical technique based on direct absorption laser spectroscopy for high precision and simultaneous determination of the mixing ratios of the most abundant nitrous oxide isotopic species: (14)N(15)N(16)O, (15)N(14)N(16)O and (14)N(2) (16)O. A precision of 0.5 ??? was achieved for the site specific isotope ratios of N(2)O at 90 ppm using an averaging time of 300 s.

Novel laser spectroscopic technique for continuous analysis of N2O isotopomers--application and intercomparison with isotope ratio mass spectrometry.

RATIONALE Nitrous oxide (N(2)O), a highly climate-relevant trace gas, is mainly derived from microbial denitrification and nitrification processes in soils. Apportioning N(2)O to these source processes is a challenging task, but better understanding of the processes is required to improve mitigation strategies. The N(2)O site-specific (15)N signatures from denitrification and nitrification have been shown to be clearly different, making this signature a potential tool for N(2)O source identification. We have applied for the first time quantum cascade laser absorption spectroscopy (QCLAS) for the continuous analysis of the intramolecular (15)N distribution of soil-derived N(2)O and compared this with state-of-the-art isotope ratio mass spectrometry (IRMS). METHODS Soil was amended with nitrate and sucrose and incubated in a laboratory setup. The N(2)O release was quantified by FTIR spectroscopy, while the N(2)O intramolecular (15)N distribution was continuously analyzed by online QCLAS at 1 Hz resolution. The QCLAS results on time-integrating flask samples were compared with those from the IRMS analysis. RESULTS The analytical precision (2σ) of QCLAS was around 0.3‰ for the δ(15)N(bulk) and the (15)N site preference (SP) for 1-min average values. Comparing the two techniques on flask samples, excellent agreement (R(2)= 0.99; offset of 1.2‰) was observed for the δ(15)N(bulk) values while for the SP values the correlation was less good (R(2 )= 0.76; offset of 0.9‰), presumably due to the lower precision of the IRMS SP measurements. CONCLUSIONS These findings validate QCLAS as a viable alternative technique with even higher precision than state-of-the-art IRMS. Thus, laser spectroscopy has the potential to contribute significantly to a better understanding of N turnover in soils, which is crucial for advancing strategies to mitigate emissions of this efficient greenhouse gas.

Compact multipass optical cell for laser spectroscopy

A multipass cell (MPC) design for laser absorption spectroscopy is presented. The development of this new type of optical cell was driven by stringent criteria for compactness, robustness, low volume, and ease of use in optical systems. A single piece of reflective toroidal surface forms a near-concentric cavity with a volume of merely 40 cm(3). Contrary to traditional MPCs, this design allows for flexible path-length adjustments by simply changing the aiming angle of the laser beam at the entrance window. Two effective optical path lengths of 2.2 and 4.1 m were chosen to demonstrate the cells suitability for high-precision isotope ratio measurements of CO(2) at 1% and ambient mixing ratio levels.

Dual-wavelength quantum cascade laser for trace gas spectroscopy

We demonstrate a sequentially operating dual-wavelength quantum cascade laser with electrically separated laser sections, emitting single-mode at 5.25 and 6.25 μm. Based on a single waveguide ridge, this laser represents a considerable asset to optical sensing and trace gas spectroscopy, as it allows probing multiple gas species with spectrally distant absorption features using conventional optical setups without any beam combining optics. The laser capability was demonstrated in simultaneous NO and NO2 detection, reaching sub-ppb detection limits and selectivity comparable to conventional high-end spectroscopic systems.

Real-time analysis of δ13C- and δD-CH4 in ambient air with laser spectroscopy: method development and first intercomparison results

In situ and simultaneous measurement of the three most abundant isotopologues of methane using midinfrared laser absorption spectroscopy is demonstrated. A field-deployable, autonomous platform is realized by coupling a compact quantum cascade laser absorption spectrometer (QCLAS) to a preconcentration unit, called trace gas extractor (TREX). This unit enhances CH4 mole fractions by a factor of up to 500 above ambient levels and quantitatively separates interfering trace gases such as N2O and CO2. The analytical precision of the QCLAS isotope measurement on the preconcentrated (750 ppm, parts-per-million, μmole mole) methane is 0.1 and 0.5 ‰ for δCand δDCH4 at 10 min averaging time. Based on repeated measurements of compressed air during a 2-week intercomparison campaign, the repeatability of the TREX–QCLAS was determined to be 0.19 and 1.9 ‰ for δC and δD-CH4, respectively. In this intercomparison campaign the new in situ technique is compared to isotoperatio mass spectrometry (IRMS) based on glass flask and bag sampling and real time CH4 isotope analysis by two commercially available laser spectrometers. Both laser-based analyzers were limited to methane mole fraction and δC-CH4 analysis, and only one of them, a cavity ring down spectrometer, was capable to deliver meaningful data for the isotopic composition. After correcting for scale offsets, the average difference between TREX–QCLAS data and bag/flask sampling–IRMS values are within the extended WMO compatibility goals of 0.2 and 5 ‰ for δCand δD-CH4, respectively. This also displays the potential to improve the interlaboratory compatibility based on the analysis of a reference air sample with accurately determined isotopic composition.

Simultaneous measurement of NO and NO(2) by dual-wavelength quantum cascade laser spectroscopy.

The concept of a multi-wavelength quantum cascade laser emitting at two or more spectrally well-separated wavelengths is highly appealing for applied spectroscopy, as it allows detecting several species with compact and cost-efficient optical setups. Here we present a practical realization of such a dual-wavelength setup, which is based on a room-temperature quantum cascade laser emitting single-mode at 1600 cm-1 and 1900 cm-1 and is thus well-suited for simultaneous NO and NO2 detection. Operated in a time-division multiplexed mode, our spectrometer reaches detection limits of 0.5 and 1.5 ppb for NO2 and NO, respectively. The performance of the system is validated against the well-established chemiluminescence detection while measuring the NOx emissions on an automotive test-bench, as well as upon monitoring the pollution at a suburban site.

Intermittent operation of QC-lasers for mid-IR spectroscopy with low heat dissipation: tuning characteristics and driving electronics

Intermittent scanning for continuous-wave quantum cascade lasers is proposed along with a custom-built laser driver optimized for such operation. This approach lowers the overall heat dissipation of the laser by dropping its drive current to zero between individual scans and holding a longer pause between scans. This allows packaging cw-QCLs in TO–3 housings with built-in collimating optics, thus reducing cost and footprint of the device. The fully integrated, largely analog, yet flexible laser driver eliminates the need for any external electronics for current modulation, lowers the demands on power supply performance, and allows shaping of the tuning current in a wide range. Optimized ramp shape selection leads to large and nearly linear frequency tuning (>1.5 cm−1). Experimental characterization of the proposed scheme with a QCL emitting at 7.7 μm gave a frequency stability of 3.2×10−5 cm−1 for the laser emission, while a temperature dependence of 2.3×10−4 cm−1/K was observed when the driver electronics was exposed to sudden temperature changes. We show that these characteristics make the driver suitable for high precision trace gas measurements by analyzing methane absorption lines in the respective spectral region.

Highly sensitive and fast detection of propane–butane using a 3 μm quantum cascade laser

A mid-IR optical analyzer based on a 3 μm Fabry-Perot quantum cascade laser has been developed for ultrafast detection of aerosol propellants, such as propane and butane. Given the laser emission bandwidth of 35 cm(-1), the system is spectrally well-matched to the C-H vibrational band of hydrocarbons, it is insusceptible to water interference, and stable enough to operate without wavelength scanning. Thus, it offers both high sensitivity and speed, reaching 1 ppm precision within a measurement time of 10 ms. The performance of the instrument is evaluated with an industrial demonstrator for aerosol cans leak testing, confirming that, in compliance with international directives, it can detect leaks of 1.2×10(-4) slpm at a rate of 500 cans per minute.

Highly Selective Volatile Organic Compounds Breath Analysis Using a Broadly-Tunable Vertical-External-Cavity Surface-Emitting Laser

A broadly tunable mid-infrared vertical-external-cavity surface-emitting laser (VECSEL) is employed in a direct absorption laser spectroscopic setup to measure breath acetone. The large wavelength coverage of more than 30 cm-1 at 3.38 μm allows, in addition to acetone, the simultaneous measurement of isoprene, ethanol, methanol, methane, and water. Despite the severe spectral interferences from water and alcohols, an unambiguous determination of acetone is demonstrated with a precision of 13 ppbv that is achieved after 5 min averaging at typical breath mean acetone levels in synthetic gas samples mimicking human breath.