New methods for the calibration of optical resonators : integrated calibration by means of optical modulation (ICOM) and narrow-band cavity ring-down (NB-CRD)

Optical resonators are used in spectroscopic measurements of atmospheric trace gases to establish long optical path lengths L with enhanced absorption in compact in-struments. In cavity-enhanced broad-band methods, the ex-act knowledge of both the magnitude of L and its spectral dependency on the wavelength lambda is fundamental for the correct retrieval of trace gas concentrations. L(lambda) is connected to the spectral mirror reflectivity R (lambda), which is often referred to instead. L(lambda) is also influenced by other quantities like broad-band absorbers or alignment of the optical resonator. The established calibration techniques to determine L(lambda), e.g. introducing gases with known optical properties or measuring the ring-down time, all have limitations: limited spectral resolution, insufficient absolute accuracy and precision, inconvenience for field deployment, or high cost of implementation. Here, we present two new methods that aim to overcome these limitations: (1) the narrow-band cavity ring-down (NB-CRD) method uses cavity ring-down spectroscopy and a tunable filter to retrieve spectrally resolved path lengths L(lambda); (2) integrated calibration by means of op-tical modulation (ICOM) allows the determination of the op-tical path length at the spectrometer resolution with high ac-curacy in a relatively simple setup. In a prototype setup we demonstrate the high accuracy and precision of the new approaches. The methods facilitate and improve the determination of L(lambda), thereby simplifying the use of cavity-enhanced absorption spectroscopy.Peer reviewe

On the link between Earth tides and volcanic degassing

Long-term measurements of volcanic gas emissions conducted during the recent decade suggest that under certain conditions the magnitude or chemical composition of volcanic emissions exhibits periodic variations with a period of about two weeks. A possible cause of such a periodicity can be attributed to the Earth tidal potential. The phenomenology of such a link has been debated for long, but no quantitative model has yet been proposed. The aim of this paper is to elucidate whether a causal link from the tidal forcing to variation in the volcanic degassing can be traced analytically. We model the response of a simplified magmatic system to the local tidal gravity variations and derive a periodical vertical magma displacement in the conduit with an amplitude of 0.1–1 m, depending on geometry and physical state of the magmatic system. We find that while the tide-induced vertical magma displacement has presumably no significant direct effect on the volatile solubility, the differential magma flow across the radial conduit profile may result in a significant increase of the bubble coalescence rate in a depth of several kilometres by up to several ten percent. Because bubble coalescence facilitates separation of gas from magma and thus enhances volatile degassing, we argue that the derived tidal variation may propagate to a manifestation of varying volcanic degassing behaviour. The presented model provides a first basic framework which establishes an analytical understanding of the link between the Earth tides and volcanic degassing

First Results on the DOAS-Retrieval of OClO from SCIAMACHY Nadir Measurements

The Scanning Imaging Absorption Spectrometer for Atmospheric Chartography was launched successfully onboard ENVISAT on March 1, 2002. It observes solar radiation transmitted, backscattered from the atmosphere and reflected from the ground in nadir, limb and occultation viewing modes. Chlorinedioxide (OClO), an important indicator for stratospheric chlorine activation, can be measured in the UV spectral range by Differential Optical Absorption Spectroscopy (DOAS). First results of the DOAS retrieval of OClO slant column densities (SCDs) from the SCIAMACHY measurements are presented. The influence of several parameters like the wavelength range chosen as fitting window or the reference spectra included in the fit on the quality of the retrieval is examined. It is found that a proper correction of polarisation features in the spectra is essential for a good DOAS analysis of OClO. The OClO SCDs derived from SCIAMACHY are compared to measurements of the Global Ozone Monitoring Experiment (GOME) which has successfully measured OClO since 1995. SCIAMACHY flies in the same orbit, but measures approx. 30 minutes earlier than GOME. As OClO shows a strong diurnal variation, this leads to differences in the observed column densities, which may be useful to investigate the photochemistry of OClO and related compounds. Also, the spatial resolution of SCIAMACHY is higher (30*60 km^2 compared to 40*320 km^2 for GOME), which will allow a more detailed study of small scale effects like e.g. chlorine activation in mountain waves

Ground-Based Remote Sensing and Imaging of Volcanic Gases and Quantitative Determination of Multi-Species Emission Fluxes

The physical and chemical structure and the spatial evolution of volcanic plumes are of great interest since they influence the Earth's atmospheric composition and the climate. Equally important is the monitoring of the abundance and emission patterns of volcanic gases, which gives insight into processes in the Earth's interior that are difficult to access otherwise. Here, we review spectroscopic approaches (from ultra-violet to thermal infra-red) to determine multi-species emissions and to quantify gas fluxes. Particular attention is given to the emerging field of plume imaging and quantitative image interpretation. Here UV SO2 cameras paved the way but several other promising techniques are under study and development. We also give a brief summary of a series of initial applications of fast imaging techniques for volcanological research

Remote measurement of high preeruptive water vapor emissions at Sabancaya volcano by passive differential optical absorption spectroscopy

Water (H2O) is by far the most abundant volcanic volatile species and plays a predominant role in driving volcanic eruptions. However, numerous difficulties associated with making accurate measurements of water vapor in volcanic plumes have limited their use as a diagnostic tool. Here we present the first detection of water vapor in a volcanic plume using passive visible-light differential optical absorption spectroscopy (DOAS). Ultraviolet and visible-light DOAS measurements were made on 21 May 2016 at Sabancaya Volcano, Peru. We find that Sabancaya's plume contained an exceptionally high relative water vapor abundance 6 months prior to its November 2016 eruption. Our measurements yielded average sulfur dioxide (SO2) emission rates of 800–900 t/d, H2O emission rates of around 250,000 t/d, and an H2O/SO2 molecular ratio of 1000 which is about an order of magnitude larger than typically found in high-temperature volcanic gases. We attribute the high water vapor emissions to a boiling-off of Sabancaya's hydrothermal system caused by intrusion of magma to shallow depths. This hypothesis is supported by a significant increase in the thermal output of the volcanic edifice detected in infrared satellite imagery leading up to and after our measurements. Though the measurement conditions encountered at Sabancaya were very favorable for our experiment, we show that visible-light DOAS systems could be used to measure water vapor emissions at numerous other high-elevation volcanoes. Such measurements would provide observatories with additional information particularly useful for forecasting eruptions at volcanoes harboring significant hydrothermal systems

Active alkaline traps to determine acidic-gas ratios in volcanic plumes: Sampling techniques and analytical methods

In situ measurements have been the basis for monitoring volcanic gas emissions for many years and—being complemented by remote sensing techniques—still play an important role to date. Con- cerning in situ techniques for sampling a dilute plume, an increase in accuracy and a reduction of detection limits are still necessary for most gases (e.g., CO2, SO2, HCl, HF, HBr, HI). In this work, the Raschig-Tube tech- nique (RT) is modified and utilized for application on volcanic plumes. The theoretical and experimental absorption properties of the RT and the Drechsel bottle (DB) setups are characterized and both are applied simultaneously to the well-established Filter packs technique (FP) in the field (on Stromboli Island and Mount Etna). The comparison points out that FPs are the most practical to apply but the results are error- prone compared to RT and DB, whereas the RT results in up to 13 times higher analyte concentrations than the DB in the same sampling time. An optimization of the analytical procedure, including sample pretreat- ment and analysis by titration, Ion Chromatography, and Inductively Coupled Plasma Mass Spectrometry, led to a comprehensive data set covering a wide range of compounds. In particular, less abundant species were quantified more accurately and iodine was detected for the first time in Stromboli's plume. Simultane- ously applying Multiaxis Differential Optical Absorption Spectroscopy (MAX-DOAS) the chemical transforma- tion of emitted bromide into bromine monoxide (BrO) from Stromboli and Etna was determined to 3–6% and 7%, respectively, within less than 5 min after the gas release from the active vents

BrO/SO2 molar ratios from scanning DOAS measurements in the NOVAC network

The molar ratio of BrO to SO2 is, like other halogen/sulfur ratios, a possible precursor for dynamic changes in the shallow part of a volcanic system. While the predictive significance of the BrO/SO2 ratio has not been well constrained yet, it has the major advantage that this ratio can be readily measured using the remote-sensing technique differential optical absorption spectroscopy (DOAS) in the UV. While BrO/SO2 ratios have been measured during several short-term field campaigns, this article presents an algorithm that can be used to obtain long-term time series of BrO/SO2 ratios from the scanning DOAS instruments of the Network for Observation of Volcanic and Atmospheric Change (NOVAC) or comparable networks. Parameters of the DOAS retrieval of both trace gases are given. The influence of co-adding spectra on the retrieval error and influences of radiative transfer will be investigated. Difficulties in the evaluation of spectroscopic data from monitoring instruments in volcanic environments and possible solutions are discussed. The new algorithm is demonstrated by evaluating data from the NOVAC scanning DOAS systems at Nevado del Ruiz, Colombia, encompassing almost 4 years of measurements between November 2009 and end of June 2013. This data set shows variations of the BrO/SO2 ratio several weeks prior to the eruption on 30 June 2012

The sensitivity of murine spermiogenesis to miglustat is a quantitative trait: a pharmacogenetic study

BACKGROUND: A major event in the post-meiotic development of male germ cells is the formation of the acrosome. This process can be perturbed in C57BL/6 mice by administration of the small molecule miglustat (N-butyldeoxynojirimycin, NB-DNJ). The miglustat-treated mice produce morphologically abnormal spermatozoa that lack acrosomes and are poorly motile. In C57BL/6 mice, miglustat can be used to maintain long-term reversible infertility. In contrast, when miglustat was evaluated in normal men, it did not affect spermatogenesis. To gain more insight into this species difference we have now evaluated the reproductive effects of miglustat in rabbits, in multiple mouse strains and in interstrain hybrid mice. METHODS: Male mice of 18 inbred strains were administered miglustat orally or via miniosmotic pumps. Rabbits were given the compound in their food. Fourth-generation interstrain hybrid mice, bred from C57BL/6 and FVB/N mice (which differ in their response to miglustat), also received the drug. Data on fertility (natural mating), sperm motility and morphology, acrosome status, and serum drug levels were collected. RESULTS: In rabbits the drug did not induce aberrations of sperm shape or motility, although the serum level of miglustat in rabbits far exceeded the level in C57BL/6 mice (8.4 μM and 0.5 μM, respectively). In some strains of the Swiss and Castle lineages of inbred mice miglustat did not cause infertility, severe morphological sperm aberrations or reduced sperm motility. In these strains miglustat only had milder effects. However, miglustat strongly disturbed acrosome and sperm nucleus development in AKR/J and BALB/c mice and in a number of C57BL/6-related strains. The consequences of drug administration in the interstrain hybrid mice were highly variable. Judging by the number of grossly abnormal spermatozoa, these genetically heterogeneous mice displayed a continuous range of intermediate responses, distinct from either of their parental strains. CONCLUSION: The effects of miglustat on spermatogenesis in mice are strain-dependent, while in rabbits the drug is ineffective. Evaluation of interstrain hybrid mice indicated that the sensitivity of spermatogenesis to miglustat is a quantitative trait. These studies pave the way for identifying the genetic factors underlying the strain/species differences in the effect of miglustat