The Application of Laser-Ablation Split-Stream ICP Petrochronology to Metamorphic Studies

Discussion of a new, innovative method for dating rocks, called laser ablation split stream (LASS) petrochronology, which is an in situ method that couples geochronological and geochemical data of minerals that remain in the rock matrix. The talk focuses on the application of this technique with U-Th-Pb dating of the phosphate minerals monazite and xenotine in metamorphic rocks. Examples from the Ruby Range in southwestern Montana and metamorphic core complexes in the northern Idaho panhandle will be explored.

The influence of PVC wrapping on the performance of two laser fluorescence devices on occlusal surfaces in vitro

OBJECTIVE: The aim of this study was to determine the influence of polyvinyl chloride (PVC) wrapping on the performance of two laser fluorescence devices (LF and LFpen) by assessing tooth occlusal surfaces. BACKGROUND DATA: Protection of their tips may influence LF measurements. To date there are no studies evaluating the influence of this protection on the performance of the LFpen on permanent teeth, or comparing it to the original LF device. MATERIALS AND METHODS: One hundred nineteen permanent molars were assessed by two experienced dentists using the LF and the LFpen devices, both with and without PVC wrapping. The teeth were histologically prepared and assessed for caries extension. RESULTS: The LF values with and without PVC wrapping were significantly different. For both LF devices, the sensitivity and accuracy were lower when the PVC wrapping was used. The specificity was statistically significantly higher for the LFpen with PVC. No difference was found between the areas under the ROC curves with and without PVC wrapping. The ICC showed excellent interexaminer agreement. The Bland and Altman method showed a range between the upper and the lower limits of agreement of 63.4 and 57.8 units for the LF device, and 49.4 and 74.2 for the LFpen device, with and without PVC wrapping, respectively. CONCLUSIONS: We found an influence of the PVC wrapping on the performance of the LF and LFpen devices. However, since its influence on detection of occlusal caries lesions is considered for, the use of one PVC layer is suggested to avoid cross-contamination in clinical practice.

Highly accurate isotope composition measurements by a miniature laser ablation mass spectrometer designed for in situ investigations on planetary surface

An experimental procedure for precise and accurate measurements of isotope abundances by a miniature laser ablation mass spectrometer for space research is described. The measurements were conducted on different untreated NIST standards and galena samples by applying pulsed UV laser radiation (266 nm, 3 ns and 20 Hz) for ablation, atomisation, and ionisation of the sample material. Mass spectra of released ions are measured by a reflectron-type time-of-flight mass analyser. A computer controlled performance optimiser was used to operate the system at maximum ion transmission and mass resolution. At optimal experimental conditions, the best relative accuracy and precision achieved for Pb isotope compositions are at the per mill level and were obtained in a range of applied laser irradiances and a defined number of accumulated spectra. A similar relative accuracy and precision was achieved in the study of Pb isotope compositions in terrestrial galena samples. The results for the galena samples are similar to those obtained with a thermal ionisation mass spectrometer (TIMS). The studies of the isotope composition of other elements yielded relative accuracy and precision at the per mill level too, with characteristic instrument parameters for each element. The relative accuracy and precision of the measurements is degrading with lower element/isotope concentration in a sample. For the elements with abundances below 100 ppm these values drop to the percent level. Depending on the isotopic abundances of Pb in minerals, 207Pb/206Pb ages with accuracy in the range of tens of millions of years can be achieved.

Coupling of LMS with a fs-laser ablation ion source: elemental and isotope composition measurements

Mass spectrometric analysis of elemental and isotopic compositions of several NIST standards is performed by a miniature laser ablation/ionisation reflectron-type time-of-flight mass spectrometer (LMS) using a fs-laser ablation ion source (775 nm, 190 fs, 1 kHz). The results of the mass spectrometric studies indicate that in a defined range of laser irradiance (fluence) and for a certain number of accumulations of single laser shot spectra, the measurements of isotope abundances can be conducted with a measurement accuracy at the per mill level and at the per cent level for isotope concentrations higher and lower than 100 ppm, respectively. Also the elemental analysis can be performed with a good accuracy. The LMS instrument combined with a fs-laser ablation ion source exhibits similar detection efficiency for both metallic and non-metallic elements. Relative sensitivity coefficients were determined and found to be close to one, which is of considerable importance for the development of standard-less instruments. Negligible thermal effects, sample damage and excellent characteristics of the fs-laser beam are thought to be the main reason for substantial improvement of the instrumental performance compared to other laser ablation mass spectrometers.

Performance evaluation of a miniature laser ablation time-of-flight mass spectrometer designed for in situ investigations in planetary space research

Key performance features of a miniature laser ablation time-of-flight mass spectrometer designed for in situ investigations of the chemical composition of planetary surfaces are presented. This mass spectrometer is well suited for elemental and isotopic analysis of raw solid materials with high sensitivity and high spatial resolution. In this study, ultraviolet laser radiation with irradiances suitable for ablation (< 1 GW/cm2) is used to achieve stable ion formation and low sample consumption. In comparison to our previous laser ablation studies at infrared wavelengths, several improvements to the experimental setup have been made, which allow accurate control over the experimental conditions and good reproducibility of measurements. Current performance evaluations indicate significant improvements to several instrumental figures of merit. Calibration of the mass scale is performed within a mass accuracy (Δm/m) in the range of 100 ppm, and a typical mass resolution (m/Δm) ~600 is achieved at the lead mass peaks. At lower laser irradiances, the mass resolution is better, about (m/Δm) ~900 for lead, and limited by the laser pulse duration of 3 ns. The effective dynamic range of the instrument was enhanced from about 6 decades determined in previous study up to more than 8 decades at present. Current studies show high sensitivity in detection of both metallic and non-metallic elements. Their abundance down to tens of ppb can be measured together with their isotopic patterns. Due to strict control of the experimental parameters, e.g. laser characteristics, ion-optical parameters and sample position, by computer control, measurements can be performed with high reproducibility. Copyright © 2012 John Wiley & Sons, Ltd.

Protein quaternary structure determination using matrix-assisted laser desorption/ionization time-of-flight mass spectrometry and chemical crosslinking

A means of analyzing protein quaternary structure using matrix-assisted laser desorption ionization time-of-flight mass spectrometry (MALDI MS) and chemical crosslinking was evaluated. Proteins of known oligomeric structure, as well as monomeric proteins, were analyzed to evaluate the method. The quaternary structure of proteins of unknown or uncertain structure was investigated using this technique. The stoichiometry of recombinant E. coli carbamoyl phosphate synthetase and recombinant human farnesyl protein transferase were determined to be heterodimers using glutaraldehyde crosslinking, agreeing with the stoichiometry found for the wild type proteins. The stoichiometry of the gamma subunit of E. coli DNA polymerase III holoenzyme was determined in solution without the presence of other subunits to be a homotetramer using glutaraldehyde crosslinking and MALDI MS analysis. Chi and psi subunits of E. coli DNA polymerase III subunits appeared to form a heterodimer when crosslinked with heterobifunctional photoreactive crosslinkers.^ Comparison of relative % peak areas obtained from MALDI MS analysis of crosslinked proteins and densitometric scanning of silver stained sodium dodecyl sulfate polyacrylamide gel electrophoresis (SDS-PAGE) gels showed excellent qualitative agreement for the two techniques, but the quantitative analyses differed, sometimes significantly. This difference in quantitation could be due to SDS-PAGE conditions (differential staining, loss of sample) or to MALDI MS conditions (differences in ionization and/or detection). Investigation of pre-purified crosslinked monomers and dimers recombined in a specific ratio revealed the presence of mass discrimination in the MALDI MS process. The calculation of mass discrimination for two different MALDI time-of-flight instruments showed the loss of a factor of approximately 2.6 in relative peak area as the m/z value doubles over the m/z range from 30,000 to 145,000 daltons.^ Indirect symmetry was determined for tetramers using glutaraldehyde crosslinking with MALDI MS analysis. Mathematical modelling and simple graphing allowed the determination of the symmetry for several tetramers known to possess isologous D2 symmetry. These methods also distinguished tetramers that did not fit D2 symmetry such as apo-avidin. The gamma tetramer of E. coli DNA polymerase III appears to have isologous D2 symmetry. ^

New online method for water isotope analysis of speleothem fluid inclusions using laser absorption spectroscopy (WS-CRDS)

A new online method to analyse water isotopes of speleothem fluid inclusions using a wavelength scanned cavity ring down spectroscopy (WS-CRDS) instrument is presented. This novel technique allows us simultaneously to measure hydrogen and oxygen isotopes for a released aliquot of water. To do so, we designed a new simple line that allows the online water extraction and isotope analysis of speleothem samples. The specificity of the method lies in the fact that fluid inclusions release is made on a standard water background, which mainly improves the δ D robustness. To saturate the line, a peristaltic pump continuously injects standard water into the line that is permanently heated to 140 °C and flushed with dry nitrogen gas. This permits instantaneous and complete vaporisation of the standard water, resulting in an artificial water background with well-known δ D and δ18O values. The speleothem sample is placed in a copper tube, attached to the line, and after system stabilisation it is crushed using a simple hydraulic device to liberate speleothem fluid inclusions water. The released water is carried by the nitrogen/standard water gas stream directly to a Picarro L1102-i for isotope determination. To test the accuracy and reproducibility of the line and to measure standard water during speleothem measurements, a syringe injection unit was added to the line. Peak evaluation is done similarly as in gas chromatography to obtain &delta D; and δ18O isotopic compositions of measured water aliquots. Precision is better than 1.5 ‰ for δ D and 0.4 ‰ for δ18O for water measurements for an extended range (−210 to 0 ‰ for δ D and −27 to 0 ‰ for δ18O) primarily dependent on the amount of water released from speleothem fluid inclusions and secondarily on the isotopic composition of the sample. The results show that WS-CRDS technology is suitable for speleothem fluid inclusion measurements and gives results that are comparable to the isotope ratio mass spectrometry (IRMS) technique.

High-Resolution Chemical Depth Profiling of Solid Material Using a Miniature Laser Ablation/Ionization Mass Spectrometer

High-resolution chemical depth profiling measurements of copper films are presented. The 10 μm thick copper test samples were electrodeposited on a Si-supported Cu seed under galvanostatic conditions in the presence of particular plating additives (SPS, Imep, PEI, and PAG) used in the semiconductor industry for the on-chip metallization of interconnects. To probe the trend of these plating additives toward inclusion into the deposit upon growth, quantitative elemental mass spectrometric measurements at trace level concentration were conducted by using a sensitive miniature laser ablation ionization mass spectrometer (LIMS), originally designed and developed for in situ space exploration. An ultrashort pulsed laser system (τ ∼ 190 fs, λ = 775 nm) was used for ablation and ionization of sample material. We show that with our LIMS system, quantitative chemical mass spectrometric analysis with an ablation rate at the subnanometer level per single laser shot can be conducted. The measurement capabilities of our instrument, including the high vertical depth resolution coupled with high detection sensitivity of ∼10 ppb, high dynamic range ≥10(8), measurement accuracy and precision, is of considerable interest in various fields of application, where investigations with high lateral and vertical resolution of the chemical composition of solid materials are required, these include, e.g., wafers from semiconductor industry or studies on space weathered samples in space research.

Satellite laser ranging to GPS and GLONASS

Satellite laser ranging (SLR) to the satellites of the global navigation satellite systems (GNSS) provides substantial and valuable information about the accuracy and quality of GNSS orbits and allows for the SLR-GNSS co-location in space. In the framework of the NAVSTAR-SLR experiment two GPS satellites of Block-IIA were equipped with laser retroreflector arrays (LRAs), whereas all satellites of the GLONASS system are equipped with LRAs in an operational mode. We summarize the outcome of the NAVSTAR-SLR experiment by processing 20 years of SLR observations to GPS and 12 years of SLR observations to GLONASS satellites using the reprocessed microwave orbits provided by the center for orbit determination in Europe (CODE). The dependency of the SLR residuals on the size, shape, and number of corner cubes in LRAs is studied. We show that the mean SLR residuals and the RMS of residuals depend on the coating of the LRAs and the block or type of GNSS satellites. The SLR mean residuals are also a function of the equipment used at SLR stations including the single-photon and multi-photon detection modes. We also show that the SLR observations to GNSS satellites are important to validate GNSS orbits and to assess deficiencies in the solar radiation pressure models. We found that the satellite signature effect, which is defined as a spread of optical pulse signals due to reflection from multiple reflectors, causes the variations of mean SLR residuals of up to 15 mm between the observations at nadir angles of 0∘ and 14∘. in case of multi-photon SLR stations. For single-photon SLR stations this effect does not exceed 1 mm. When using the new empirical CODE orbit model (ECOM), the SLR mean residual falls into the range 0.1–1.8 mm for high-performing single-photon SLR stations observing GLONASS-M satellites with uncoated corner cubes. For best-performing multi-photon stations the mean SLR residuals are between −12.2 and −25.6 mm due to the satellite signature effect.

Higher order parametric excitation modes for spaceborne quadrupole mass spectrometers

This paper describes a technique to significantly improve upon the mass peak shape and mass resolution of spaceborne quadrupolemass spectrometers (QMSs) through higher order auxiliary excitation of the quadrupole field. Using a novel multiresonant tank circuit, additional frequency components can be used to drive modulating voltages on the quadrupole rods in a practical manner, suitable for both improved commercial applications and spaceflight instruments. Auxiliary excitation at frequencies near twice that of the fundamental quadrupole RF frequency provides the advantages of previously studied parametric excitation techniques, but with the added benefit of increased sensed excitation amplitude dynamic range and the ability to operate voltage scan lines through the center of upper stability islands. Using a field programmable gate array, the amplitudes and frequencies of all QMS signals are digitally generated and managed, providing a robust and stable voltage control system. These techniques are experimentally verified through an interface with a commercial Pfeiffer QMG422 quadrupole rod system. When operating through the center of a stability island formed from higher order auxiliary excitation, approximately 50% and 400% improvements in 1% mass resolution and peak stability were measured, respectively, when compared with traditional QMS operation. Although tested with a circular rod system, the presented techniques have the potential to improve the performance of both circular and hyperbolic rod geometry QMS sensors.

Enabling the Next Generation of Spaceborne Quadrupole Mass Spectrometers

The quadrupole mass spectrometer (QMS) has over 30 years of spaceflight heritage in making important neutral gas and low energy ion observations. Given their geometrical constraints, these instruments are currently operated at the extreme limit of their capabilities. However, a technique called higher order auxiliary excitation provides a set of novel, robust, electronics-based solutions for improving the performance of these sensors. By driving the quadrupole rods with an additional frequency nearly twice that of the normal RF operating frequency, substantially increased abundance sensitivity, maximum attainable mass resolution, and peak stability can be achieved through operation of voltage scan lines through the center of formed upper stability islands. Such improvements are modeled using numerical simulations of ion trajectories in a quadrupole field with and without applied higher order auxiliary excitation. When compared to a traditional QMS with a mass range up to 500Da, sensors can be designed with the same precision electronics to have expected mass ranges beyond 1500Da with a power increase of less than twice that of its heritage implementations.

Lithogeochemical and isotope (Rb-Sr, Sm-Nd, Pb-Pb whole rock and Lu-Hf zircon) composition of samples from the Shackleton Range, East Antarctica

Three distinct, spatially separated crustal terranes have been recognised in the Shackleton Range, East Antarctica: the Southern, Eastern and Northern Terranes. Mafic gneisses from the Southern Terrane provide geochemical evidence for a within-plate, probably back-arc origin of their protoliths. A plume-distal ridge origin in an incipient ocean basin is the favoured interpretation for the emplacement site of these rocks at c. 1850 Ma, which, together with a few ocean island basalts, were subsequently incorporated into an accretionary continental arc/supra-subduction zone tectonic setting. Magmatic underplating resulted in partial melting of the lower crust, which caused high-temperature granulite-facies metamorphism in the Southern Terrane at c. 1710-1680 Ma. Mafic and felsic gneisses there are characterised by isotopically depleted, positive Nd and Hf initials and model ages between 2100 and 2000 Ma. They may be explained as juvenile additions to the crust towards the end of the Palaeoproterozoic. These juvenile rocks occur in a narrow, c. 150 km long E-W trending belt, inferred to trace a suture that is associated with a large Palaeoproterozoic accretionary orogenic system. The Southern Terrane contains many features that are similar to the Australo-Antarctic Mawson Continent and may be its furthermost extension into East Antarctica. The Eastern Terrane is characterised by metagranitoids that formed in a continental volcanic arc setting during a late Mesoproterozoic orogeny at c. 1060 Ma. Subsequently, the rocks experienced high-temperature metamorphism during Pan-African collisional tectonics at 600 Ma. Isotopically depleted zircon grains yielded Hf model ages of 1600-1400 Ma, which are identical to Nd model ages obtained from juvenile metagranitoids. Most likely, these rocks trace the suture related to the amalgamation of the Indo-Antarctic and West Gondwana continental blocks at ~600 Ma. The Eastern Terrane is interpreted as the southernmost extension of the Pan-African Mozambique/Maud Belt in East Antarctica and, based on Hf isotope data, may also represent a link to the Ellsworth-Whitmore Mountains block in West Antarctica and the Namaqua-Natal Province of southern Africa. Geochemical evidence indicates that the majority of the protoliths of the mafic gneisses in the Northern Terrane formed as oceanic island basalts in a within-plate setting. Subsequently the rocks were incorporated into a subduction zone environment and, finally, accreted to a continental margin during Pan-African collisional tectonics. Felsic gneisses there provide evidence for a within-plate and volcanic arc/collisional origin. Emplacement of granitoids occurred at c. 530 Ma and high-temperature, high-pressure metamorphism took place at 510-500 Ma. Enriched Hf and Nd initials and Palaeoproterozoic model ages for most samples indicate that no juvenile material was added to the crust of the Northern Terrane during the Pan-African Orogeny but recycling of older crust or mixing of crustal components of different age must have occurred. Isotopically depleted mafic gneisses, which are spatially associated with eclogite-facies pyroxenites, yielded late Mesoproterozoic Nd model ages. These rocks occur in a narrow, at least 100 km long, E-W trending belt that separates alkaline ocean island metabasalts and within-plate metagranitoids from volcanic arc metabasalts and volcanic arc/syn-collisional metagranitoids in the Northern Terrane. This belt is interpreted to trace the late Neoproterozoic/early Cambrian Pan-African collisional suture between the Australo-Antarctic and the combined Indo-Antarctic/West Gondwana continental blocks that formed during the final amalgamation of Gondwana.

Glacier mass balances of Stubacher Sonnblickkees, Hohe Tauern Range, Eastern Alps, Austria, 1958/1959 to 2012/2013

Stubacher Sonnblickkees (SSK) is located in the Hohe Tauern Range (Eastern Alps) in the south of Salzburg Province (Austria) in the region of Oberpinzgau in the upper Stubach Valley. The glacier is situated at the main Alpine crest and faces east, starting at elevations close to 3050 m and in the 1980s terminated at 2500 m a.s.l. It had an area of 1.7 km² at that time, compared with 1 km² in 2013. The glacier type can be classified as a slope glacier, i.e. the relief is covered by a relatively thin ice sheet and there is no regular glacier tongue. The rough subglacial topography makes for a complex shape in the surface topography, with various concave and convex patterns. The main reason for selecting this glacier for mass balance observations (as early as 1963) was to verify on a complex glacier how the mass balance methods and the conclusions - derived during the more or less pioneer phase of glaciological investigations in the 1950s and 1960s - could be applied to the SSK glacier. The decision was influenced by the fact that close to the SSK there was the Rudolfshütte, a hostel of the Austrian Alpine Club (OeAV), newly constructed in the 1950s to replace the old hut dating from 1874. The new Alpenhotel Rudolfshütte, which was run by the Slupetzky family from 1958 to 1970, was the base station for the long-term observation; the cable car to Rudolfshütte, operated by the Austrian Federal Railways (ÖBB), was a logistic advantage. Another factor for choosing SSK as a glaciological research site was the availability of discharge records of the catchment area from the Austrian Federal Railways who had turned the nearby lake Weißsee ('White Lake') - a former natural lake - into a reservoir for their hydroelectric power plants. In terms of regional climatic differences between the Central Alps in Tyrol and those of the Hohe Tauern, the latter experienced significantly higher precipitation , so one could expect new insights in the different response of the two glaciers SSK and Hintereisferner (Ötztal Alps) - where a mass balance series went back to 1952. In 1966 another mass balance series with an additional focus on runoff recordings was initiated at Vernagtfener, near Hintereisferner, by the Commission of the Bavarian Academy of Sciences in Munich. The usual and necessary link to climate and climate change was given by a newly founded weather station (by Heinz and Werner Slupetzky) at the Rudolfshütte in 1961, which ran until 1967. Along with an extension and enlargement to the so-called Alpine Center Rudolfshütte of the OeAV, a climate observatory (suggested by Heinz Slupetzky) has been operating without interruption since 1980 under the responsibility of ZAMG and the Hydrological Service of Salzburg, providing long-term met observations. The weather station is supported by the Berghotel Rudolfshütte (in 2004 the OeAV sold the hotel to a private owner) with accommodation and facilities. Direct yearly mass balance measurements were started in 1963, first for 3 years as part of a thesis project. In 1965 the project was incorporated into the Austrian glacier measurement sites within the International Hydrological Decade (IHD) 1965 - 1974 and was afterwards extended via the International Hydrological Program (IHP) 1975 - 1981. During both periods the main financial support came from the Hydrological Survey of Austria. After 1981 funds were provided by the Hydrological Service of the Federal Government of Salzburg. The research was conducted from 1965 onwards by Heinz Slupetzky from the (former) Department of Geography of the University of Salzburg. These activities received better recognition when the High Alpine Research Station of the University of Salzburg was founded in 1982 and brought in additional funding from the University. With recent changes concerning Rudolfshütte, however, it became unfeasible to keep the research station going. Fortunately, at least the weather station at Rudolfshütte is still operating. In the pioneer years of the mass balance recordings at SSK, the main goal was to understand the influence of the complicated topography on the ablation and accumulation processes. With frequent strong southerly winds (foehn) on the one hand, and precipitation coming in with storms from the north to northwest, the snow drift is an important factor on the undulating glacier surface. This results in less snow cover in convex zones and in more or a maximum accumulation in concave or flat areas. As a consequence of the accentuated topography, certain characteristic ablation and accumulation patterns can be observed during the summer season every year, which have been regularly observed for many decades . The process of snow depletion (Ausaperung) runs through a series of stages (described by the AAR) every year. The sequence of stages until the end of the ablation season depends on the weather conditions in a balance year. One needs a strong negative mass balance year at the beginning of glacier measurements to find out the regularities; 1965, the second year of observation resulted in a very positive mass balance with very little ablation but heavy accumulation. To date it is the year with the absolute maximum positive balance in the entire mass balance series since 1959, probably since 1950. The highly complex ablation patterns required a high number of ablation stakes at the beginning of the research and it took several years to develop a clearer idea of the necessary density of measurement points to ensure high accuracy. A great number of snow pits and probing profiles (and additional measurements at crevasses) were necessary to map the accumulation area/patterns. Mapping the snow depletion, especially at the end of the ablation season, which coincides with the equilibrium line, is one of the main basic data for drawing contour lines of mass balance and to calculate the total mass balance (on a regular-shaped valley glacier there might be an equilibrium line following a contour line of elevation separating the accumulation area and the ablation area, but not at SSK). - An example: in 1969/70, 54 ablation stakes and 22 snow pits were used on the 1.77 km² glacier surface. In the course of the study the consistency of the accumulation and ablation patterns could be used to reduce the number of measurement points. - At the SSK the stratigraphic system, i.e. the natural balance year, is used instead the usual hydrological year. From 1964 to 1981, the yearly mass balance was calculated by direct measurements. Based on these records of 17 years, a regression analysis between the specific net mass balance and the ratio of ablation area to total area (AAR) has been used since then. The basic requirement was mapping the maximum snow depletion at the end of each balance year. There was the advantage of Heinz Slupetzky's detailed local and long-term experience, which ensured homogeneity of the series on individual influences of the mass balance calculations. Verifications took place as often as possible by means of independent geodetic methods, i.e. monoplotting , aerial and terrestrial photogrammetry, more recently also the application of PHOTOMODELLER and laser scans. The semi-direct mass balance determinations used at SSK were tentatively compared with data from periods of mass/volume change, resulting in promising first results on the reliability of the method. In recent years re-analyses of the mass balance series have been conducted by the World Glacier Monitoring Service and will be done at SSK too. - The methods developed at SSK also add to another objective, much discussed in the 1960s within the community, namely to achieve time- and labour-saving methods to ensure continuation of long-term mass balance series. The regression relations were used to extrapolate the mass balance series back to 1959, the maximum depletion could be reconstructed by means of photographs for those years. R. Günther (1982) calculated the mass balance series of SSK back to 1950 by analysing the correlation between meteorological data and the mass balance; he found a high statistical relation between measured and determined mass balance figures for SSK. In spite of the complex glacier topography, interesting empirical experiences were gained from the mass balance data sets, giving a better understanding of the characteristics of the glacier type, mass balance and mass exchange. It turned out that there are distinct relations between the specific net balance, net accumulation (defined as Bc/S) and net ablation (Ba/S) to the AAR, resulting in characteristic so-called 'turnover curves'. The diagram of SSK represents the type of a glacier without a glacier tongue. Between 1964 and 1966, a basic method was developed, starting from the idea that instead of measuring years to cover the range between extreme positive and extreme negative yearly balances one could record the AAR/snow depletion/Ausaperung during one or two summers. The new method was applied on Cathedral Massif Glacier, a cirque glacier with the same area as the Stubacher Sonnblickkees, in British Columbia, Canada. during the summers of 1977 and 1978. It returned exactly the expected relations, e.g. mass turnover curves, as found on SSK. The SSK was mapped several times on a scale of 1:5000 to 1:10000. Length variations have been measured since 1960 within the OeAV glacier length measurement programme. Between 1965 and 1981, there was a mass gain of 10 million cubic metres. With a time lag of 10 years, this resulted in an advance until the mid-1980s. Since 1982 there has been a distinct mass loss of 35 million cubic metres by 2013. In recent years, the glacier has disintegrated faster, forced by the formation of a periglacial lake at the glacier terminus and also by the outcrops of rocks (typical for the slope glacier type), which have accelerated the meltdown. The formation of this lake is well documented. The glacier has retreated by some 600 m since 1981. - Since August 2002, a runoff gauge installed by the Hydrographical Service of Salzburg has recorded the discharge of the main part of SSK at the outlet of the new Unterer Eisboden See. The annual reports - submitted from 1982 on as a contractual obligation to the Hydrological Service of Salzburg - document the ongoing processes on the one hand, and emphasize the mass balance of SSK and outline the climatological reasons, mainly based on the met-data of the observatory Rudolfshütte, on the other. There is an additional focus on estimating the annual water balance in the catchment area of the lake. There are certain preconditions for the water balance equation in the area. Runoff is recorded by the ÖBB power stations, the mass balance of the now approx. 20% glaciated area (mainly the Sonnblickkees) is measured andthe change of the snow and firn patches/the water content is estimated as well as possible. (Nowadays laserscanning and ground radar are available to measure the snow pack). There is a net of three precipitation gauges plus the recordings at Rudolfshütte. The evaporation is of minor importance. The long-term annual mean runoff depth in the catchment area is around 3.000 mm/year. The precipitation gauges have measured deficits between 10% and 35%, on average probably 25% to 30%. That means that the real precipitation in the catchment area Weißsee (at elevations between 2,250 and 3,000 m) is in an order of 3,200 to 3,400 mm a year. The mass balance record of SSK was the first one established in the Hohe Tauern region (and now since the Hohe Tauern National Park was founded in 1983 in Salzburg) and is one of the longest measurement series worldwide. Great efforts are under way to continue the series, to safeguard against interruption and to guarantee a long-term monitoring of the mass balance and volume change of SSK (until the glacier is completely gone, which seems to be realistic in the near future as a result of the ongoing global warming). Heinz Slupetzky, March 2014