Laser-based Analysis Research Articles

Recent decline in carbon monoxide levels observed at an urban site in Ahmedabad, India.

Carbon monoxide (CO) is a prominent air pollutant in cities, with far-reaching implications for both local air quality and global atmospheric chemistry. The long-term change in atmospheric CO levels at a specific location is influenced by a complex interplay of local emissions, atmospheric transport, and photochemical processes, making it a subject of considerable interest. This study presents an 8-year analysis (2014-2021) of in situ CO observations using a cutting-edge laser-based analyzer at an urban site in Ahmedabad, western India. The long-term observations reveal a subtle trend in CO levels, masked by contrasting year-to-year variations, particular after 2018, across distinct diurnal time windows. Mid-afternoon (12:00-16:00h) CO levels, reflecting background and regional conditions, remained relatively stable over the study period. In contrast, evening (18:00-21:00h) CO levels, influenced by local emissions, exhibited substantial inter-annual variability without discernible trends from 2014 to 2018. However, post-2018, evening CO levels showed a consistent decline, predating COVID-19 lockdown measures. This decline coincided with the nationwide adoption of Bharat stage IV emission standards and other measures aimed at reducing vehicular emissions. The COVID-19 lockdown in 2020 further resulted in a noteworthy 29% reduction in evening CO levels compared to the pre-lockdown (2014-2019) period, highlighting the potential for substantial CO reduction through stringent vehicular emission controls. The observed long-term changes in CO levels do not align with the decreasing emission estimated by various inventories from 2014 to 2018, suggesting a need for improved emission statistics in Indian urban regions. This study underscores the importance of ongoing continuous CO measurements in urban areas to inform policy efforts aimed at controlling atmospheric pollutants.

Laser-irradiating infrared attenuated total reflection spectroscopy of articular cartilage: Potential and challenges for diagnosing osteoarthritis

ObjectiveA prototype infrared attenuated total reflection (IR-ATR) laser spectroscopic system designed for in vivo classification of human cartilage tissue according to its histological health status during arthroscopic surgery is presented. Prior to real-world in vivo applications, this so-called osteoarthritis (OA) scanner has been tested at in vitro conditions revealing the challenges associated with complex sample matrices and the accordingly obtained sparse spectral datasets. MethodsIn vitro studies on human knee cartilage samples at different contact pressures (i.e., 0.2–0.5 ​MPa) allowed recording cartilage degeneration characteristic IR signatures comparable to in vivo conditions with high temporal resolution. Afterwards, the cartilage samples were assessed based on the clinically acknowledged osteoarthritis cartilage histopathology assessment (OARSI) system and correlated with the obtained sparse IR data. ResultsAmide and carbohydrate signal behavior was observed to be almost identical between the obtained sparse IR data and previously measured FTIR data used for sparse partial least squares discriminant analysis (SPLSDA) to identify the spectral regions relevant to cartilage condition. Contact pressures between 0.3 and 0.4 ​MPa seem to provide the best sparse IR spectra for cylindrical (d ​= ​3 ​mm) probe tips. ConclusionLaser-irradiating IR-ATR spectroscopy is a promising analytical technique for future arthroscopic applications to differentiate healthy and osteoarthritic cartilage tissue. However, this study also revealed that the flexible connection between the laser-based analyzer and the arthroscopic ATR-probe via IR-transparent fiberoptic cables may affect the robustness of the obtained IR data and requires further improvements.

Technical note: Discrete in situ vapor sampling for subsequent lab-based water stable isotope analysis

Abstract. Methodological advancements have been made in in situ observations of water stable isotopes that have provided valuable insights into ecohydrological processes. The continuous measurement capabilities of laser-based analyzers allow for high temporal resolutions and non-destructive minimally invasive study designs of such in situ approaches. However, isotope analyzers are expensive, heavy, and require shelter and access to electrical power, which impedes many in situ assays. Therefore, we developed a new inexpensive technique to collect discrete water vapor samples in the field via diffusion-tight inflatable bags that can later be analyzed in the lab. In a series of structured experiments, we tested different procedural settings, bag materials, and closure types for diffusion tightness during storage as well as for practical handling during filling and extraction. To facilitate reuse of sampling bags, we present a conditioning procedure using ambient air as primer. In order to validate our method, direct measurements through hydrophobic in situ probes were compared to repeated measurements of vapor sampled with our bags from the same source. All steps are summarized in a detailed standard operating procedure (SOP). This procedure represents the preparation and measurement of calibration and validation vapor standards necessary for processing of unknown field-collected vapor samples in the foreseen application. By performing pertinent calibration procedures, accuracy was better than 0.4 ‰ for δ18O and 1.9 ‰ for δ2H after 1 d of storage. Our technique is particularly suitable when used in combination with minimally invasive water vapor sampling in situ probes that have already been employed for soils and tree xylem. It is an important step towards minimally invasive monitoring of stable isotope distributions and also time series in virtually undisturbed soils and trees without the need to have an analyzer in the field. It is therefore a promising tool for many applications in ecohydrology and meteorology.

Two species–one wavelength detection based on selective optical saturation spectroscopy

Cross-sensitivity limits accurate quantitative detection of species concentrations in all sensor technologies, including laser-based absorption techniques. Absorption sensors capture a signal that combines contributions from all interfering species at a given detection wavelength. Careful selection of the probed spectral line, broadband detection, or upstream separation can partially mitigate cross-sensitivity, however, weak or unidentified signal interference remains a challenge for accuracy. Here, we present a proof-of-principle study to overcome cross-sensitivity by taking advantage of the distinct optical saturation characteristics of different gas mixture components. By controlling the absorption contribution of a selected species by intentional optical saturation, simultaneous and quantitative detection of two interfering species becomes possible even without the need for spectral scanning, hence offering two species–one wavelength detection (2S1W) capability. Demonstrated with direct absorption and cavity-ringdown setups, the method offers a new, previously unexploited opportunity to further enhance laser-based analyzers for complex gas mixture analysis in environmental, medical, and technical applications.

Intercomparison of commercial analyzers for atmospheric ethane and methane observations

Abstract. Methane (CH4) is a strong greenhouse gas that has become the focus of climate mitigation policies in recent years. Ethane/methane ratios can be used to identify and partition the different sources of methane, especially in areas with natural gas mixed with biogenic methane emissions, such as cities. We assessed the precision, accuracy, and selectivity of three commercially available laser-based analyzers that have been marketed as measuring instantaneous dry-mole fractions of methane and ethane in ambient air. The Aerodyne SuperDUAL instrument performed the best out of the three instruments, but it is large and requires expertise to operate. The Aeris Mira Ultra LDS analyzer also performed well for the price point and small size, but it required characterization of the water vapor dependence of reported concentrations and careful set-up for use. The Picarro G2210-i precisely measured methane, but it did not detect the 10 ppbv (part-per-billion by volume) increases in ambient ethane detected by the other two instruments when sampling a plume of incompletely combusted natural gas. For long-term tower deployments or those with large mobile laboratories, the Aerodyne SuperDUAL provides the best precision for methane and ethane. The more compact Aeris MIRA can, with careful use, quantify thermogenic methane sources to sufficient precision for mobile and short-term deployments in urban or oil and gas areas. We weighed the advantages of each instrument, including size, power requirement, ease of use on mobile platforms, and expertise needed to operate the instrument. We recommend the Aerodyne SuperDUAL or the Aeris MIRA Ultra LDS depending on the situation.

Theoretical principles and application to measure the flux of carbon dioxide in the air of urban zones

Atmospheric carbon dioxide (CO2) concentrations increase due to volcanic emissions, diffuse degassing from fault zones, and various human-caused gas emissions, especially in densely populated urban zones, which play a pivotal role in the ongoing climate change. This study aims to examine changes in the concentration and stable isotopic composition of atmospheric CO2. A laser-based analyzer provided the δ13C and δ18O values based on concentration measurements for various CO2 isotopologues. Multiple linear regression (MLR) showed that almost 30% of the atmospheric CO2 changes are caused by weather variations, while ∼70% of the changes involve CO2 from various gas sources related to human activities. The Keeling plot approach was used to identify the isotopic signature of the extra CO2, which points to the gas produced by hydrocarbon combustion. An isotopic mass balance model was designed to show the relation between excess atmospheric CO2 and the flux of human-related gas emissions. Calculating the CO2 flux in the atmosphere based on this isotopic mass balance model showed that several tons of CO2 move daily between geospheres. This study shows that surveying atmospheric CO2 in urban zones allows quantifying the CO2 emissions from various sources.

Modeling the dynamic behavior of a droplet evaporation device for the delivery of isotopically calibrated low-humidity water vapor

Abstract. A model is presented that gives a quantitative description of the dynamic behavior of a low-humidity water vapor generator in terms of water vapor concentration (humidity) and isotope ratios. The generator is based on the evaporation of a nanoliter-sized droplet produced at the end of a syringe needle by balancing the inlet water flow and the evaporation of water from the droplet surface into a dry-air stream. The humidity level is adjusted by changing the speed of the high-precision syringe pump and, if needed, the dry-air flow. The generator was developed specifically for use with laser-based water isotope analyzers in Antarctica, and it was recently described in Leroy-Dos Santos et al. (2021). Apart from operating parameters such as temperature, pressure, and water and dry-air flows, the model has as “free” input parameters: water isotope fractionation factors and the evaporation rate. We show that the experimental data constrain these parameters to physically realistic values that are in reasonable to good agreement with available literature values. With the advent of new ultraprecise isotope ratio spectrometers, the approach used here may permit the measurement of not only the evaporation rate but also the effective fractionation factors and isotopologue-dependent diffusivity ratios, in the evaporation of small droplets.

An approach for calibrating laser-based N2 O isotopic analyzers for soil biogeochemistry research.

Technological advances have motivated researchers to transition from traditional gas chromatography/isotope ratio mass spectrometry to rapid, high-throughput, laser-based instrumentation for N2 O isotopic research. However, calibrating laser-based instruments to yield accurate and precise isotope ratios has been an ongoing challenge. To streamline the N2 O isotope research pipeline, we developed the calibration protocol for laser-based analyzers described here. While our approach is targeted at laboratory soil incubations, we anticipate that it will be broadly applicable for diverse types of stable isotope research. We prepared standards diluted from USGS52 and from a commercial cylinder to develop a calibration curve spanning from 0.3 to 300 ppm N2 O. To calibrate over this broad range, we binned each isotopocule (N2 O, N15 NO, 15 NNO, and NN18 O) into low, medium, and high concentration ranges and then used mathematically similar polynomial functions to calibrate the isotopocules within each concentration range. We also assessed the temporal stability of the instrument and the capacity for our calibration approach to work with isotopically enriched gas samples. Our calibration approach yielded generally accurate and precise data when isotopocules were calibrated in concentration ranges, and the measurements appeared to be temporally stable. For all isotopocules at natural abundance, the residual percentage error was smallest in the medium N2 O range. There was more noise in the corrected isotopomers and isotopologue at natural abundance in samples with the lowest and highest N2 O concentrations. Corrected isotopomer results from isotopically enriched samples were very precise. Developing our calibration strategy involved learning several key lessons: (1) calibrate isotopocules in distinct concentration ranges, (2) use mathematically similar models to calibrate the isotopocules in each range, (3) calibrated N2 O concentrations and δ values tend to be most accurate and precise in the medium N2 O range, and (4) we encourage users to take advantage of isotopic enrichment to capitalize on laser-based instrument strengths.

Analyses of deuterium retention in tungsten and graphite first wall materials by laser-induced ablation spectroscopy on EAST

• Combined LIBS and LIAS measurements were applied to determine the dynamic deuterium retention in C and W during EAST discharges. • LIAS measurements show more than three times higher deuterium retention in graphite than in tungsten during EAST discharges. • The deuterium retention on the graphite PFC is saturated within 0.2 s plasma exposure for limited magnetic configuration when the plasma actively touches the first wall. • The deuterium retention in the start-up phase is significantly larger than during the discharge for diverted magnetic configuration. Plasma-wall interactions at the first wall in fusion experimental devices are critical for the life time of plasma-facing components and tokamak operation. In-situ measurements of these plasma-wall interaction processes are required in long pulse devices in order to understand better the underlying mechanisms as well as monitoring of the tritium content of the first wall as an immediate safety application. In this work we present measurements of the deuterium retention in the first wall of EAST using laser-induced ablation spectroscopy. The diagnostic is applied during plasma operation and the dynamic retention for graphite and tungsten as plasma-facing materials are compared, showing more than three times higher short-term retention in graphite than in tungsten. Laser-based analysis is applied during a shift of the vertical positions of the plasma column in limited as well as in the start-up phase of discharges in diverted magnetic configuration. Plasma core densities of n e = (1.5–3.2) × 10 19 /m 3 are chosen to vary the ion flux to the first wall and study saturation effects of deuterium on the surface first wall materials during tokamak plasma operation. A linear dependence of the retention from ion fluence is observed for graphite as PFC up to 3 × 10 18 D + /cm 2 , followed by a constant retention up to fluences of 3.5 × 10 19 D + /cm 2 for nearby first wall temperatures of T PFC ≈ 350 K.

Blood Storage Conditions Affect Hematological Analysis in Samples From Healthy Donkeys and Donkeys With Experimentally-Induced Endotoxemia.

Preanalytical factors such as storage time and temperature are proved to induce marked artifactual changes in hematological parameters in horses, small animals and humans. These errors can mirror findings typical of endotoxemia, leading to dangerous misdiagnosis. Since donkeys are common in warm climates and remote regions, blood samples from this species can be subjected to long lasting travels from the farm to the nearest laboratory, frequently under suboptimal conditions. Moreover, as other equids, donkeys are prone to suffer endotoxemia. Nonetheless, stability has not been evaluated in samples for hematology in this species. The aim of this study was to characterize the effect of temperature and storage time in hematological parameters from healthy donkeys and donkeys with induced endotoxemia. Blood samples were collected from six healthy female Andalusian donkeys and stored for 6, 12, 24, and 48 h at several temperatures (4, 24, and 35°C). Endotoxemia was induced in the same animals by an intravenous LPS infusion and samples obtained 30 min post-infusion were handled similarly. Hematological analysis was performed using a laser-based analyzer and blood smear examination. Storage at 24°C caused significant neutropenia after 48 h as well as morphological changes typical of endotoxemia in blood from healthy donkeys as soon as 24 h post-storage. Samples kept at 35°C displayed more profound and earlier artifactual variations. Conservation at 4°C did not cause any significant change in blood parameters. Prolonged (48 h) storage of samples from animals with induced endotoxemia at 24 and 35°C accentuated pre-existing leukopenia and neutropenia. These findings highlight that donkey samples should be stored at 4°C, instead of 24°C as recommended for horses. Moreover, blood smear interpretation should be cautious in samples stored for longer than 24 h and could be misleading when blood is kept at 35°C.

Liquid Atmospheric Pressure Matrix-Assisted Laser Desorption/Ionization Mass Spectrometry Adds Enhanced Functionalities to MALDI MS Profiling for Disease Diagnostics.

A liquid matrix-assisted laser desorption/ionization (liquid MALDI) method has been developed for high-throughput atmospheric pressure (AP) mass spectrometry (MS) analysis of the molecular content of crude bioliquids for disease diagnostics. The presented method is rapid and highly robust, enabling its application in environments where speed and low-cost high-throughput analyses are required. Importantly, because of the creation of multiply charged analyte ions, it provides additional functionalities that conventional solid MALDI MS profiling is lacking, including the use of high-performance mass analyzers with limited m/z range. The concomitant superior MS/MS performance that is achieved similar to ESI MS/MS adds greater analytical power and specificity to MALDI MS profiling while retaining the advantages of a fast laser-based analysis system and off-line large-scale sample preparation. The potential of this MALDI MS profiling method is demonstrated on the detection of dairy cow mastitis, which is a substantial economic burden on the dairy industry with losses of hundreds of dollars per diseased cow per year, equating to a total annual loss of billions of dollars, as well as leading to the use of large quantities of antibiotics, adding to the proliferation of antimicrobial resistance. Only small amounts of aliquots obtained from the daily farm milking process were prepared for liquid MALDI MS profiling using a simple one-pot/two-step analyte extraction. Automated analysis was performed using a custom-built AP-MALDI ion source, enabling the simultaneous detection of lipids, peptides, and proteins. Diagnostic, multiply charged, proteinaceous ions were easily sequenced and identified by MS/MS experiments. Samples were classified according to mastitis status using multivariate analysis, achieving 98.5% accuracy (100% specificity) determined by “leave 20% out” cross-validation. The methodology is generally applicable to AP-MALDI MS profiling on most commercial high-resolution mass spectrometers, with the potential for expansion into hospitals for rapid assessment of human and other biofluids.

A cool-temperate young larch plantation as a net methane source - A 4-year continuous hyperbolic relaxed eddy accumulation and chamber measurements

Upland forests are thought to be methane (CH4) sinks due to oxidation by methanotrophs in aerobic soils. However, CH4 budget for upland forests are not well quantified at the ecosystem scale, when possible CH4 sources, such as small wet areas, exists in the ecosystem. Here, we quantified CH4 fluxes in a cool-temperate larch plantation based on four-year continuous measurements using the hyperbolic relaxed eddy accumulation (HREA) method and dynamic closed chambers with a laser-based analyzer. After filling data gaps for half-hourly data using machine-learning-based regressions, we found that the forest acted as a net CH4 source at the canopy scale: 30 ± 11 mg CH4 m−2 yr−1 in 2014, 56 ± 8 mg CH4 m−2 yr−1 in 2015, 154 ± 5 mg CH4 m−2 yr−1 in 2016, and 132 ± 6 mg CH4 m−2 yr−1 in 2017. Hotspot emissions from the edge of the pond could strongly contribute to the canopy-scale emissions. The magnitude of the hotspot emissions was 10–100 times greater than the order of the canopy-scale and chamber-based CH4 fluxes at the dry soils. The high temperatures with wet conditions stimulated the hotspot emissions, and thus induced canopy-scale CH4 emissions in the summer. Understanding and modeling the dynamics of hotspot emissions are important for quantifying CH4 budgets of upland forests. Micrometeorological measurements at various forests are required for revisiting CH4 budget of upland forests.

Tracing the fate and transport of secondary plant metabolites in a laboratory mesocosm experiment by employing mass spectrometric imaging

Mass spectrometric imaging (MSI) has received considerable attention in recent years, since it allows the molecular mapping of various compound classes, such as proteins, peptides, glycans, secondary metabolites, lipids, and drugs in animal, human, or plant tissue sections. In the present study, the application of laser-based MSI analysis of secondary plant metabolites to monitor their transport from the grass leaves of Dactylis glomerata, over the crop of the grasshopper Chorthippus dorsatus to its excrements, and finally in the soil solution is described. This plant-herbivore-soil pathway was investigated under controlled conditions by using laboratory mesocosms. From six targeted secondary plant metabolites (dehydroquinic acid, quinic acid, apigenin, luteolin, tricin, and rosmarinic acid), only quinic acid, and dehydroquinic acid, an in-source-decay (ISD) product of quinic acid, could be traced in nearly all compartments. The tentative identification of secondary plant metabolites was performed by MS/MS analysis of methanol extracts prepared from the investigated compartments, in both the positive and negative ion mode, and subsequently compared with the results generated from the reference standards. Except for tricin, all secondary metabolites could be tentatively identified by this approach. Additional liquid-chromatography mass spectrometry (LC-MS) experiments were carried out to verify the MSI results and revealed the presence of quinic acid only in grass and chewed grass, whereas apigenin-hexoside-pentoside and luteolin-hexoisde-pentoside could be traced in the grasshopper body and excrement extracts. In summary, the MSI technique shows a trade-off between sensitivity and spatial resolution.Graphical abstractMonitoring quinic acid in a mesocosm experiment by mass spectrometric imaging (MSI).

Real-time analysis of <i>δ</i><sup>13</sup>C- and <i>δ</i>D-CH<sub>4</sub> in ambient air with laser spectroscopy: method development and first intercomparison results

Abstract. In situ and simultaneous measurement of the three most abundant isotopologues of methane using mid-infrared 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−1) methane is 0.1 and 0.5 ‰ for δ13C- and δD-CH4 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 δ13C and δD-CH4, respectively. In this intercomparison campaign the new in situ technique is compared to isotope-ratio 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 δ13C-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 δ13C- and 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.

Time-Domain Optoelectronic Vector Network Analysis on Coplanar Waveguides

The development of a one-port laser-based vector network analyzer (VNA) is described. Measurements are carried out in the time domain using a femtosecond laser for the generation and detection of ultrashort voltage pulses on a coplanar waveguide (CPW). The accurate separation of voltage signals propagating in forward and backward directions, being one of the key tasks of vector network analysis, is achieved by measuring voltage pulses at different positions on the CPW. This separation technique even works in the case of temporally overlapping forward and backward propagating signals. With this laser-based VNA, a frequency spacing of 500 MHz, a measurement bandwidth of approximately 500 GHz, and a dynamic range of more than 40 dB are obtained. As an application example, the laser-based VNA is used to realize an ultra-broadband voltage pulse standard.

Methane uptake in a temperate forest soil using continuous closed-chamber measurements

Methane (CH4) fluxes were continuously measured in a temperate forest soil using six dynamic closed chambers with a laser-based analyzer. CH4 uptake increased with an increase in soil temperature and a decrease in volumetric water content, where multiple linear regressions using the two variables explained approximately 80% of the seasonal variations. Based on the measurements, our forest acted as an annual CH4 sink with a spatial variation of 25%. The calculated annual CH4 sink significantly decreased by increasing the chamber deployment period: 8–13mg CH4m−2yr−1min−1. The annual CH4 sink was significantly different using different calculation methods for the initial slope: 898±11mg CH4m−2yr−1 using a linear regression, 924±8mg CH4m−2yr−1 using a quadratic regression, and 975±10mg CH4m−2yr−1 using an exponential model. These results indicate that underestimations due to disturbing the CH4 gradient between chamber headspaces and soils were significant despite of the short deployment periods of 4–10min. Chamber-based fluxes were consistent with canopy-scale CH4 fluxes by the micrometeorological hyperbolic relaxed eddy accumulation method: sink of 731±38 to 888±87mg CH4m−2yr−1. Continuous dynamic closed chambers with laser-based analyzers are a powerful tool to understand CH4 fluxes in temperate forest soils, as long as a range of uncertainties are carefully evaluated.

Ultra-high-resolution paleoenvironmental records via direct laser-based analysis of lipid biomarkers in sediment core samples.

Marine microorganisms adapt to their habitat by structural modification of their membrane lipids. This concept is the basis of numerous molecular proxies used for paleoenvironmental reconstruction. Archaeal tetraether lipids from ubiquitous marine planktonic archaea are particularly abundant, well preserved in the sedimentary record and used in several molecular proxies. We here introduce the direct, extraction-free analysis of these compounds in intact sediment core sections using laser desorption ionization (LDI) coupled to Fourier transform ion cyclotron resonance mass spectrometry (FTICR-MS). LDI FTICR-MS can detect the target lipids in single submillimeter-sized spots on sediment sections, equivalent to a sample mass in the nanogram range, and could thus pave the way for biomarker-based reconstruction of past environments and ecosystems at subannual to decadal resolution. We demonstrate that ratios of selected archaeal tetraethers acquired by LDI FTICR-MS are highly correlated with values obtained by conventional liquid chromatography/MS protocols. The ratio of the major archaeal lipids, caldarchaeol and crenarchaeol, analyzed in a 6.2-cm intact section of Mediterranean sapropel S1 at 250-µm resolution (∼ 4-y temporal resolution), provides an unprecedented view of the fine-scale patchiness of sedimentary biomarker distributions and the processes involved in proxy signal formation. Temporal variations of this lipid ratio indicate a strong influence of the ∼ 200-y de Vries solar cycle on reconstructed sea surface temperatures with possible amplitudes of several degrees, and suggest signal amplification by a complex interplay of ecological and environmental factors. Laser-based biomarker analysis of geological samples has the potential to revolutionize molecular stratigraphic studies of paleoenvironments.

The Taihu Eddy Flux Network: An Observational Program on Energy, Water, and Greenhouse Gas Fluxes of a Large Freshwater Lake

Lakes are an important component of the climate system. They provide moisture for precipitation, buffer temperature variations, and contribute to regional atmospheric carbon budgets. This article describes an eddy covariance (EC) mesonet on Lake Taihu, a large (area 2400 km2) and shallow (depth 2 m) lake situated in the heavily populated Yangtze River Delta, China. The mesonet consists of five lake sites, representing different biological attributes and wind–wave patterns, and a land site near the lake shore. Common to all the sites are standard EC instruments for measurement of the momentum, sensible heat, water vapor, and CO2 flux. One site is also equipped with laser-based analyzers for precise measurement of the CO2, CH4, and H2O mixing ratios and their isotopic compositions. To the authors' best knowledge, this is the first lake eddy flux mesonet. Early results reveal evidence of biological and pollution controls on the surface–air fluxes of energy, momentum, and greenhouse gases across the lake. The...

Equilibrator-based measurements of dissolved nitrous oxide in the surface ocean using an integrated cavity output laser absorption spectrometer

Abstract. Dissolved nitrous oxide (N2O) concentrations are usually determined by gas chromatography (GC). Here we present laboratory tests and initial field measurements using a novel setup comprising a commercially available laser-based analyser for N2O, carbon monoxide and water vapour coupled to a glass-bed equilibrator. This approach is less labour-intensive and provides higher temporal and spatial resolution than the conventional GC technique. The standard deviation of continuous equilibrator or atmospheric air measurements was 0.2 nmol mol−1 (averaged over 5 min). The short-term repeatability for reference gas measurements within 1 h of each other was 0.2 nmol mol−1 or better. Another indicator of the long-term stability of the analyser is the standard deviation of the calibrated N2O mole fraction in marine air, which was between 0.5 and 0.7 nmol mol−1. The equilibrator measurements were compared with purge-and-trap gas chromatography–mass spectrometry (GC-MS) analyses of N2O concentrations in discrete samples from the Southern Ocean and showed agreement to within the 2% measurement uncertainty of the GC-MS method. The equilibrator response time to concentration changes in water was from 142 to 203 s, depending on the headspace flow rate. The system was tested at sea during a north-to-south transect of the Atlantic Ocean. While the subtropical gyres were slightly undersaturated, the equatorial region was a source of nitrous oxide to the atmosphere, confirming previous findings (Forster et al., 2009). The ability to measure at high temporal and spatial resolution revealed submesoscale variability in dissolved N2O concentrations. Mean sea-to-air fluxes in the tropical and subtropical Atlantic ranged between −1.6 and 0.11 μmol m−2 d−1 and confirm that the subtropical Atlantic is not an important source region for N2O to the atmosphere, compared to global average fluxes of 0.6–2.4 μmol m−2 d−1. The system can be easily modified for autonomous operation on voluntary observing ships (VOS). Future work should include an interlaboratory comparison exercise with other methods of dissolved N2O analyses.

Performance assessment of a cavity ring-down laser spectrometer: achieving better precision and accuracy in the measurement of δ18O and δ2H in liquid water samples

The development of new isotopic laser-based analyzers currently represents a clear alternative to conventional isotope ratio mass spectrometers. However, this analytical technique also suffers some disadvantages such as the memory effect, problems related to the overall stability of the equipment and other issues associated with the injection system, essentially regarding the syringe's longevity. This paper aims to minimize these disadvantages in order to increase the overall performance, in terms of precision and accuracy, of these kinds of analyzers. The main results of the experiments carried out in this paper have shown that: (i) the minimum number of discarded injections needed to eliminate the memory effect can be determined just considering the expected isotopic signature difference between two consecutive samples; (ii) both accuracy and precision of the isotopic measurements increase with increasing injection volume up to 2.1–2.2 µL; (iii) it is possible to extend the syringe lifetime by almost a factor of 6 by using n-methyl 2-pyrrolidone as a lubricant. Besides, it has been concluded that, by using the appropriate procedure, the main disadvantages associated with CRDS laser spectroscopy analyzers can be minimized, achieving measurement accuracy and precision of the order of ±0.05 ‰ for δ18O and ±0.3 ‰ for δ2H.