Reference-free dual-comb spectroscopy with inbuilt coherence.

We demonstrate a simple system for dual-comb spectroscopy based on two inherently coherent optical frequency combs generated via seeded parametric downconversion. The inbuilt coherence is established by making the two combs share a common comb line. We show that the inbuilt coherence makes it possible to use a simple numerical post-processing procedure to compensate for small drifts of the dual-comb interferogram arrival time and phase. This enables long-time coherent averaging of the interferograms.

Anaerobic Digestion of Solid Agricultural Biomass in Leach-Bed Reactors.

This study focuses on the feasibility of the dry anaerobic digestion of solid agricultural biomass for efficient renewable-energy production and nutrient recycling. Methane production and the amount of nitrogen in the digestates were measured in pilot- and farm-scale leach-bed reactors. In the pilot scale, with a digestion time of 133 days, the methane production of a mixture of whole crop fava bean and horse manure corresponded to 94% and 116%, respectively, of the methane potentials of the solid substrates. The mono-digestion of fava beans resulted in relatively low methane production (production/potential ratios of 59% and 57%). In two full-scale experiments, the methane production of mixtures of clover-grass silage, chicken manure, and horse manure corresponded to 108% and 100% of their respective methane potentials with digestion times of 117 and 185 days. In co-digestion, the production/potential ratios were similar in the pilot and farm experiments. High nitrogen loss was observed in the farm scale when the digestate was stored in a stack covered with a tarpaulin during summertime. Thus, although the technology seems promising, attention needs to be paid to management practices to minimise nitrogen losses and greenhouse gas emissions.

Terahertz radiation detection with a cantilever-based photoacoustic sensor.

We report the photoacoustic (PA) response in the terahertz (THz) range by employing a detection process actuated with a silicon cantilever pressure sensor and a carbon-based radiation absorber. The detection relies on the mechanical response of the cantilever, when the volume of the carrier gas inside the PA cell expands with the heat produced by the radiation absorber. The detector interferometrically monitors the movement of the cantilever sensor to generate the PA signal. We selected the absorber material with the highest THz responsivity for detailed studies at 1.4 THz (214 µm wavelength). The observed responsivities of two different radiation absorbers are nearly the same at 1.4 THz and agree within 10% with responsivity values at 0.633 µm wavelength. The results demonstrate the potential of covering with a single PA detector a broad spectral range with approximately constant responsivity, large dynamic range, and high damage threshold.

Versatile optical frequency combs based on multi-seeded femtosecond optical parametric generation.

This study proposes and demonstrates a versatile method for near- and mid-infrared optical frequency comb generation using multi-seeded femtosecond optical parametric generation. The method allows one to divide the repetition rate by an arbitrarily large integer factor, freely tune the offset frequency, and adjust the common phase offset of the comb modes. Since all possible degrees of freedom are adjustable, the proposed method manifests itself as versatile optical frequency synthesis.

Optical power detector with broad spectral coverage, high detectivity, and large dynamic range.

Optical power measurements are needed in practically all technologies based on light. Here, we report a general-purpose optical power detector based on the photoacoustic effect. Optical power incident on the detector's black absorber produces an acoustic signal, which is further converted into an electrical signal using a silicon-cantilever pressure transducer. We demonstrate an exceptionally large spectral coverage from ultraviolet to far infrared, with the possibility for further extension to the terahertz region. The linear dynamic range of the detector reaches 80 dB, ranging from a noise-equivalent power of 6 n W/H z to 600 mW (independent of signal averaging time).

LED-Based Photoacoustic NO2 Sensor with a Sub-ppb Detection Limit.

A high-sensitivity light-emitting diode (LED)-based photoacoustic NO2 sensor is demonstrated. Sensitive photoacoustic gas sensors based on incoherent light sources are typically limited by background noise and drifts due to a strong signal generated by light absorbed at the photoacoustic cell walls. Here, we reach a sub-ppb detection limit and excellent stability using cantilever-enhanced photoacoustic detection and perform a two-channel relative measurement. A white-light LED is used as a light source, and the spectrum is divided into two wavelength channels with a dichroic filter. The photoacoustic signals generated by the two wavelength channels are measured simultaneously and used to solve the NO2 concentration. The background signal is highly correlated between the two channels, and its variations are suppressed in the relative measurement. A noise level below 1 ppb is reached with an averaging time of 70 s. This is, to the best of our knowledge, the first time a sub-ppb detection limit is demonstrated with an LED-based photoacoustic NO2 sensor. As LEDs are available at a wide selection of emission wavelengths, the results show great potential for development of cost-effective and sensitive detectors for a variety of other trace gasses as well.

Mid-infrared frequency comb with 25 pJ threshold via CW-seeded optical parametric generation in nonlinear waveguide.

We demonstrate efficient generation of mid-infrared frequency combs based on continuous-wave-seeded femtosecond optical parametric generation in nonlinear waveguides. Conversion of the near-infrared pump to signal and idler light takes place with very high efficiency (74%), and the threshold (25 pJ for 100 fs pulses) is over 300 times lower than in bulk analogs. Relative intensity noise of the mid-infrared comb is exceptionally low, below 5×10-5 (integrated from 10 Hz to 2 MHz). Furthermore, the mid-infrared bandwidth can be increased by driving the process with a broadband pump obtained via supercontinuum generation.

Photoacoustic characteristics of carbon-based infrared absorbers.

We present an experimental comparison of photoacoustic responsivities of common highly absorbing carbon-based materials. The comparison was carried out with parameters relevant for photoacoustic power detectors and Fourier-transform infrared (FTIR) spectroscopy: we covered a broad wavelength range from the visible red to far infrared (633 nm to 25 µm) and the regime of low acoustic frequencies (< 1 kHz). The investigated materials include a candle soot-based coating, a black paint coating and two different carbon nanotube coatings. Of these, the low-cost soot absorber produced clearly the highest photoacoustic response over the entire measurement range.

Radiocarbon dioxide detection using cantilever-enhanced photoacoustic spectroscopy.

In this Letter, we report on the sub-parts-per-billion-level radiocarbon dioxide detection using cantilever-enhanced photoacoustic spectroscopy. The 14C/C ratio of samples is measured by targeting a 14CO2 absorption line with minimal interference from other CO2 isotopes. Using a quantum cascade laser as a light source allows for a compact experimental setup. In addition, measurements of sample gases with 14CO2 concentrations as low as 100 parts-per-trillion (ppt) are presented. The Allan deviation demonstrates a noise equivalent concentration of 30 ppt at an averaging time of 9 min. The achieved sensitivity validates this method as a suitable alternative to more complex optical detection methods for radiocarbon dioxide detection used so far, and it can be envisioned for future in situ radiocarbon detection.

Broadband Laser-Based Infrared Detector for Gas Chromatography.

Cantilever-enhanced photoacoustic spectroscopy coupled with gas chromatography is used to quantitatively analyze a mixture of alcohols in a quasi-online manner. A full identification and quantification of all analytes are achieved based on their spectral fingerprints using a widely tunable continuous-wave laser as a light source. This can be done even in the case of interfering column/septum bleed or simultaneously eluted peaks. The combination of photoacoustic spectroscopy and gas chromatography offers a viable solution for compact and portable instruments in applications that require straightforward analyses with no consumables.

Effect of Inoculum Pretreatment on the Composition of Microbial Communities in Anaerobic Digesters Producing Volatile Fatty Acids.

Volatile fatty acids (VFAs) are intermediates in the methane formation pathway of anaerobic digestion and can be produced through the fermentation of organic wastes. VFAs have become an anticipated resource- and cost-effective way to replace fossil resources with higher added value and more versatile fuels and chemicals. However, there are still challenges in the production of targeted compounds from diverse and complex biomasses, such as urban biowastes. In this study, the aim was to modulate the microbial communities through inoculum treatment to enhance the production of green chemicals. Thermal and freeze-thaw treatments were applied to the anaerobic digester inoculum to inhibit the growth of methanogens and to enhance the performance of acidogenic and acetogenic bacteria. VFA fermentation after different inoculum treatments was studied in batch scale using urban biowaste as the substrate and the process performance was assessed with chemical and microbial analyses. Inoculum treatments, especially thermal treatment, were shown to increase VFA yields, which were also correlating with the dynamics of the microbial communities and retention times of the test. There was a strong correlation between VFA production and the relative abundances of the microbial orders Clostridiales (families Ruminococcaceae, Lachnospiraceae and Clostridiaceae), and Lactobacillales. A syntrophic relationship of these taxa with members of the Methanobacteriales order was also presumed.

Cascade processing of softwood bark with hot water extraction, pyrolysis and anaerobic digestion.

A process model based on hot water extraction (HWE), slow pyrolysis and anaerobic digestion (AD) were used for pine and spruce bark utilisation. First tannins (32 mg/g and 11.8 mg/g, respectively) and polyphenols were recovered via HWE. Then, the residue was pyrolysed to produce biochar (marketable quality), gas (energy source) and liquid fractions. The liquid fraction was further separated into aqueous acidic fraction and to tar fraction. Bark, extracted bark residue and acidic liquid fraction from pyrolysis were treated in AD to produce biomethane and digestate. The methane yields from pine and spruce bark and extracted bark residue were low (from 42 to 96 mLCH4/gVSadded) and showed only small differences. In conclusion, cascade processing can improve the performance of subsequent single processes and utilise biomass sources with higher efficiency. The best processing chain may vary in different cases and the overall energy balance of processing needs further research.

Broadband photoacoustic spectroscopy of CH414 with a high-power mid-infrared optical frequency comb.

We report a photoacoustic spectroscopy setup with a high-power mid-infrared frequency comb as the light source. The setup is used in broadband spectroscopy of radiocarbon methane. Owing to the high sensitivity of a cantilever-enhanced photoacoustic cell and the high-power light source, we can reach a detection limit below 100 ppb in a broadband measurement with a sample volume of only a few milliliters. The first infrared spectrum of CH414 is reported and given a preliminary assignment. The results lay a foundation for the development of optical detection systems for radiocarbon methane.

Cavity-enhanced cantilever-enhanced photo-acoustic spectroscopy.

We have improved the sensitivity of a state-of-the-art cantilever-enhanced photo-acoustic trace gas sensor by combining it with an optical power build-up cavity. The build-up cavity enhances the photo-acoustic signal by a factor of ∼100, resulting in an exceptionally good normalised noise equivalent absorption (NNEA) value of 1.75 × 10-12 W cm-1 Hz-1/2. We demonstrate the sensor platform in the 1530 nm wavelength range with a simple distributed feedback diode laser, achieving 75 ppt sensitivity for C2H2 with a 10 s integration time.

Step-modulated decay cavity ring-down detection for double resonance spectroscopy.

A method of measuring double resonant two-photon signal and background from a single cavity ring-down decay is introduced. This is achieved by modulating the double resonance loss via one of the light sources exciting the transition. The noise performance of the method is characterized theoretically and experimentally. The addition of a new parameter to the fitting function introduces a minor noise increase due to parameter correlation. However, the concurrent recording of the background can extend the stable measurement time. Alternatively, the method allows a faster measurement speed, while still recording the background, which is often advantageous in double resonance measurements. Finally, the method is insensitive to changes in the cavity decay rate at short timescales and can lead to improved performance if they have significant contribution to the final noise level compared to the detector noise.

Optical frequency comb photoacoustic spectroscopy.

We report the first photoacoustic detection scheme using an optical frequency comb-optical frequency comb photoacoustic spectroscopy (OFC-PAS). OFC-PAS combines the broad spectral coverage and the high resolution of OFCs with the small sample volume of cantilever-enhanced PA detection. In OFC-PAS, a Fourier transform spectrometer (FTS) is used to modulate the intensity of the exciting comb source at a frequency determined by its scanning speed. One of the FTS outputs is directed to the PA cell and the other is measured simultaneously with a photodiode and used to normalize the PA signal. The cantilever-enhanced PA detector operates in a non-resonant mode, enabling detection of a broadband frequency response. The broadband and the high-resolution capabilities of OFC-PAS are demonstrated by measuring the rovibrational spectra of the fundamental C-H stretch band of CH4, with no instrumental line shape distortions, at total pressures of 1000 mbar, 650 mbar, and 400 mbar. In this first demonstration, a spectral resolution two orders of magnitude better than previously reported with broadband PAS is obtained, limited by the pressure broadening. A limit of detection of 0.8 ppm of methane in N2 is accomplished in a single interferogram measurement (200 s measurement time, 1000 MHz spectral resolution, 1000 mbar total pressure) for an exciting power spectral density of 42 µW/cm-1. A normalized noise equivalent absorption of 8 × 10-10 W cm-1 Hz-1/2 is obtained, which is only a factor of three higher than the best reported with PAS based on continuous wave lasers. A wide dynamic range of up to four orders of magnitude and a very good linearity (limited by the Beer-Lambert law) over two orders of magnitude are realized. OFC-PAS extends the capability of optical sensors for multispecies trace gas analysis in small sample volumes with high resolution and selectivity.

Sub-parts-per-trillion level sensitivity in trace gas detection by cantilever-enhanced photo-acoustic spectroscopy.

An exceptional property of photo-acoustic spectroscopy is the zero-background in wavelength modulation configuration while the signal varies linearly as a function of absorbed laser power. Here, we make use of this property by combining a highly sensitive cantilever-enhanced photo-acoustic detector, a particularly stable high-power narrow-linewidth mid-infrared continuous-wave optical parametric oscillator, and a strong absorption cross-section of hydrogen fluoride to demonstrate the ability of cantilever-enhanced photo-acoustic spectroscopy to reach sub-parts-per-trillion level sensitivity in trace gas detection. The high stability of the experimental setup allows long averaging times. A noise equivalent concentration of 650 parts-per-quadrillion is reached in 32 minutes.

Stabilization of femtosecond optical parametric oscillators for infrared frequency comb generation.

A synchronously pumped optical parametric oscillator (SP-OPO) is one of the most common techniques to generate femtosecond frequency combs in the mid-infrared region. Stable long-term operation of an SP-OPO requires active locking of the OPO resonator round-trip time to the pump pulse interval. A simple modulation-free locking method based on stabilization of narrow-band frequency-doubled power of the SP-OPO output comb is demonstrated in this Letter. The method relies on the strong dependency of frequency-doubled power on spectral shape of the comb, leading to better stability of the comb envelope spectrum than the commonly used dither-and-lock method.

Frequency comb assisted two-photon vibrational spectroscopy.

We report a setup for high-resolution two-photon spectroscopy using a mid-infrared continuous wave optical parametric oscillator (CW-OPO) and a near-infrared diode laser as the excitation sources, both of which are locked to fully stabilized optical frequency combs. The diode laser is directly locked to a commercial near-infrared optical frequency comb using an optical phase-locked loop. The near-infrared frequency comb is also used to synchronously pump a degenerate femtosecond optical parametric oscillator to produce a fully stabilized mid-infrared frequency comb. The beat frequency between the mid-infrared comb and the CW-OPO is then stabilized through frequency locking. We used the setup to measure a double resonant two-photon transition to a symmetric vibrational state of acetylene with a sub-Doppler resolution and high signal-to-noise ratio.

Fully stabilized mid-infrared frequency comb for high-precision molecular spectroscopy.

A fully stabilized mid-infrared optical frequency comb spanning from 2.9 to 3.4 µm is described in this article. The comb is based on half-harmonic generation in a femtosecond optical parametric oscillator, which transfers the high phase coherence of a fully stabilized near-infrared Er-doped fiber laser comb to the mid-infrared region. The method is simple, as no phase-locked loops or reference lasers are needed. Precise locking of optical frequencies of the mid-infrared comb to the pump comb is experimentally verified at sub-20 mHz level, which corresponds to a fractional statistical uncertainty of 2 × 10-16 at the center frequency of the mid-infrared comb. The fully stabilized mid-infrared comb is an ideal tool for high-precision molecular spectroscopy, as well as for optical frequency metrology in the mid-infrared region, which is difficult to access with other stabilized frequency comb techniques.