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KEY COMPARISON
Under the auspices of the Organic Analysis Working Group (OAWG) of the Comité Consultatif pour la Quantité de Matière (CCQM) a key comparison, CCQM K55.c, was coordinated by the Bureau International des Poids et Mesures (BIPM) in 2012. Twenty National Measurement Institutes or Designated Institutes and the BIPM participated. Participants were required to assign the mass fraction of valine present as the main component in the comparison sample for CCQM-K55.c. The comparison samples were prepared from analytical grade L-valine purchased from a commercial supplier and used as provided without further treatment or purification.
Valine was selected to be representative of the performance of a laboratory's measurement capability for the purity assignment of organic compounds of low structural complexity [molecular weight range 100300] and high polarity (pKOW > –2).
The KCRV for the valine content of the material was 992.0 mg/g with a combined standard uncertainty of 0.3 mg/g. The key comparison reference value (KCRV) was assigned by combination of KCRVs assigned from participant results for each orthogonal impurity class. The relative expanded uncertainties reported by laboratories having results consistent with the KCRV ranged from 1 mg/g to 6 mg/g when using mass balance based approaches alone, 2 mg/g to 7 mg/g using quantitative 1H NMR (qNMR) based approaches and from 1 mg/g to 2.5 mg/g when a result obtained by a mass balance method was combined with a separate qNMR result.
The material provided several analytical challenges. In addition to the need to identify and quantify various related amino acid impurities including leucine, isoleucine, alanine and a-amino butyrate, care was required to select appropriate conditions for performing Karl Fischer titration assay for water content to avoid bias due to in situ formation of water by self-condensation under the assay conditions. It also proved to be a challenging compound for purity assignment by qNMR techniques.
There was overall excellent agreement between participants in the identification and the quantification of the total and individual related structure impurities, water content, residual solvent and total non-volatile content of the sample. Appropriate technical justifications were developed to rationalise observed discrepancies in the limited cases where methodology differences led to inconsistent results.
The comparison demonstrated that to perform a qNMR purity assignment the selection of appropriate parameters and an understanding of their potential influence on the assigned value is critical for reliable implementation of the method, particularly when one or more of the peaks to be quantified consist of complex multiplet signals.
Under the auspices of the Organic Analysis Working Group (OAWG) of the Comité Consultatif pour la Quantité de Matière (CCQM) a key comparison, CCQM K55.b, was coordinated by the Bureau International des Poids et Mesures (BIPM) in 2010/2011. Nineteen national measurement institutes and the BIPM participated. Participants were required to assign the mass fraction of aldrin present as the main component in the comparison sample for CCQM-K55.b which consisted of technical grade aldrin obtained from the National Measurement Institute Australia that had been subject to serial recrystallization and drying prior to sub-division into the units supplied for the comparison.
Aldrin was selected to be representative of the performance of a laboratory's measurement capability for the purity assignment of organic compounds of medium structural complexity [molar mass range 300 Da to 500 Da] and low polarity (pKOW < -2) for which related structure impurities can be quantified by capillary gas phase chromatography (GC).
The key comparison reference value (KCRV) for the aldrin content of the material was 950.8 mg/g with a combined standard uncertainty of 0.85 mg/g. The KCRV was assigned by combination of KCRVs assigned by consensus from participant results for each orthogonal impurity class. The relative expanded uncertainties reported by laboratories having results consistent with the KCRV ranged from 0.3% to 0.6% using a mass balance approach and 0.5% to 1% using a qNMR method.
The major analytical challenge posed by the material proved to be the detection and quantification of a significant amount of oligomeric organic material within the sample and most participants relying on a mass balance approach displayed a positive bias relative to the KCRV (overestimation of aldrin content) in excess of 10 mg/g due to not having adequate procedures in place to detect and quantify the non-volatile content–specifically the non-volatile organics content–of the comparison sample.
There was in general excellent agreement between participants in the identification and the quantification of the total and individual related structure impurities, water content and the residual solvent content of the sample.
The comparison demonstrated the utility of 1H NMR as an independent method for quantitative analysis of high purity compounds. In discussion of the participant results it was noted that while several had access to qNMR estimates for the aldrin content that were inconsistent with their mass balance determination they decided to accept the mass balance result and assumed a hidden bias in their NMR data. By contrast, laboratories that placed greater confidence in their qNMR result were able to resolve the discrepancy through additional studies that provided evidence of the presence of non-volatile organic impurity at the requisite level to bring their mass balance and qNMR estimates into agreement.
The CCQM-K148.a comparison was coordinated by the BIPM on behalf of the CCQM Organic Analysis Working Group for NMIs and DIs which provide measurement services in organic analysis under the CIPM MRA. It was undertaken as a "Track A" comparison within the OAWG strategic plan. CCQM-K148.a demonstrates capabilities for assigning the mass fraction content of a solid organic compound having moderate molecular complexity, where the compound has a molar mass in the range (75 - 500) g/mol and is non-polar (pKow < −2), when present as the primary organic component in a neat organic solid and where the mass fraction content of the primary component in the material is in excess of 950 mg/g.
Participants were required to report the mass fraction of Bisphenol A present in one supplied unit of the comparison material. Participants using a mass balance method for the assignment were also required to report their assignments of the impurity components present in the material. Methods used by the seventeen participating NMIs or DIs were predominantly based on either stand-alone mass balance (summation of impurities) or qNMR approaches, or the combination of data obtained using both methods. The results obtained using thermal methods based on freezing-point depression methods were also reported by a limited number of participants. There was excellent agreement between assignments obtained using all three approaches to assign the BPA content.
The assignment of the values for the mass fraction content of BPA consistent with the KCRV was achieved by most of the comparison participants with an associated relative standard uncertainty in the assigned value in the range (0.1 - 0.5)%.
The comparison required the assignment of the mass fraction of folic acid present as the main component in the comparison sample. Performance in the comparison is representative of a laboratory's measurement capability for the purity assignment of organic compounds of medium structural complexity [molecular weight range 300–500] and high polarity (pKOW < −2).
Methods used by the eighteen participating NMIs or DIs were based on a mass balance (summation of impurities) or qNMR approach, or the combination of data obtained using both methods. The qNMR results tended to give slightly lower values for the content of folic acid, albeit with larger associated uncertainties, compared with the results obtained by mass balance procedures. Possible reasons for this divergence are discussed in the report, without reaching a definitive conclusion as to their origin.
The comparison demonstrates that for a structurally complex polar organic compound containing a high water content and presenting a number of additional analytical challenges, the assignment of the mass fraction content property value of the main component can reasonably be achieved with an associated relative standard uncertainty in the assigned value of 0.5%
Under the auspices of the Organic Analysis Working Group (OAWG) of the Comité Consultatif pour la Quantité de Matière (CCQM) a key comparison, CCQM K55.a, was coordinated by the Bureau International des Poids et Mesures (BIPM) in 2009/2010. Eleven national measurement institutes and the BIPM participated. Participants were required to assign the mass fraction of estradiol present as the main component in the comparison sample (CCQM-K55.a) which consisted of a bulk estradiol hemihydrate material obtained from a commercial supplier that had been extensively but not exhaustively dried prior to sub-division into the units supplied for the comparison.
Estradiol was selected to be representative of the performance of a laboratory's measurement capability for the purity assignment of organic compounds of medium structural complexity [molar mass range 300500 Da] and low polarity (pKOW < -2) for which related structure impurities can be quantified by capillary gas phase chromatography (GC) or by high performance liquid chromatography (LC).
The majority of participants used a mass balance approach to determine the estradiol content. The key comparison reference value (KCRV) for estradiol in CCQM-K55.a was assigned by combination of KCRVs assigned by consensus from participant results for each orthogonal impurity class. This allowed participants to demonstrate the efficacy (or otherwise) of their implementation of the mass balance approach and to demonstrate that their assigned value for the main component agreed with the KCRV through use of internally consistent contributing methods.
The KCRV for the estradiol content of the material was 984.3 mg/g with a combined standard uncertainty of 0.42 mg/g. The individual participant results showed that a relative expanded uncertainty for the purity assignment of 0.2% is a reasonable estimate of the best achievable result by an individual laboratory for a material of this complexity available in this amount at this level of purity. The relative expanded uncertainties reported by laboratories having results consistent with the KCRV ranged from 0.2% to 0.8%.
The review of results that were biased from the KCRV showed that two major analytical challenges are posed by the material: the measurement of its water content and controlling for related substance artefact formation during the analysis process. The results displaying a positive bias relative to the KCRV (overestimation of estradiol content) were due to underestimation of the water content of the material, while those with a negative bias (underestimation of estradiol) overestimated the total related substance impurities through a failure to detect and control for artefact formation arising from in situ oxidative dimerization of estradiol in neutral solution prior to analysis. There was however good agreement between all participants in the identification and the quantification of the individual related structure impurities actually present in the sample.
The comparison also demonstrated the utility of high-field 1H NMR for both quantitative and qualitative analysis of high purity compounds. It is noted that all the participants who used qNMR as a major or contributing technique and included it as part of, combined it or confirmed it with a conventional 'mass balance' data estimate, obtained results consistent with the KCRV.
Supplementary comparison study - measurement capabilities for the quantification of ethanol in water
(2022)
The accurate quantification of ethanol in water is essential for forensic applications such as blood and breath alcohol testing and for commercial applications such as the assessment of alcoholic beverages.
The intercomparison EURAMET.QM-S14 is part of a capacity building project named ALCOREF “Certified forensic alcohol reference materials”
that is running within the European Metrology Programme for Innovation and Research (EMPIR). The intercomparison should allow project partners and other interested National Metrology Institutes (NMIs) and Designated Institutes (DIs) to benchmark their analytical methods for the quantification of ethanol in water. The study plan was agreed by the European Association of National Metrology Institutes (EURAMET) Subcommittee Bio- and Organic Analysis (SCBOA) and the Organic Analysis Working Group (OAWG) of the Comité Consultatif pour la Quantité de Matière (CCQM) in February and April 2019, respectively. The intercomparison was coordinated by BAM. Two concentration levels relevant for the calibration and verification of evidential breath alcohol analysers were distributed to study participants. Fifteen institutes from 15 countries registered for the intercomparison and returned results. Participants mostly applied gas chromatography with flame ionisation detection (GC-FID) or mass spectroscopy (GC-MS), one participant used titrimetry and one participant employed a test bench for breath analyser calibration (“bubble train”). Participants did either in-house purity assessment of their commercial ethanol calibrants by Karl-Fischer titration, chromatographic methods, quantitative nuclear magnetic resonance spectroscopy (qNMR) and/or density measurements; or they used ethanol/water Certified Reference Materials (CRMs) from NMIs/DIs for calibration.
CCQM OAWG agreed to use a consensus value from participants results that utilizes the reported uncertainties as Key Comparison Reference Value (KCRV). The Gaussian Random effects model with Hierarchical Bayesian solution (HB-REM) is a reasonable approach in this case. The KCRVs and Degrees of Equivalence (DoEs) were calculated with the NIST consensus builder version 1.2 Hierarchical Bayes procedure.
Successful participation in the interlaboratory comparison has demonstrated the capabilities in determining the mass fraction of ethanol in aqueous matrices in the range 0.1 mg/g to 8 mg/g. Fourteen out of 15 participants have successfully quantified both samples, one participant successfully quantified only the lower-level (0.6 mg/g) sample.
The 2010 CCQM-K79 'Comparison of value-assigned CRMs and PT materials: Ethanol in aqueous media' is the second key comparison directly testing the chemical measurement services provided to customers by National Metrology Institutes (NMIs) and Designated Institutes (DIs). CCQM-K79 compared the assigned ethanol values of proficiency test (PT) and certified reference materials (CRMs) using measurements made on these materials under repeatability conditions. Nine NMIs submitted 27 CRM or value-assigned PT materials for evaluation. These materials represent many of the higher-order reference materials then available for this commercially and forensically important measurand.
The assigned ethanol mass fraction in the materials ranged from 0.1 mg/kg to 334 mg/kg. All materials were stored and prepared according the specifications provided by each NMI. Samples were processed and analyzed under repeatability conditions by one analytical team using a gas chromatography with flame ionization detection (GC-FID) method of demonstrated trueness and precision.
Given the number of materials and the time required for each analysis, the majority of the measurements were made in two measurement campaigns ('runs'). Due to a shipping delay from one NMI, an unanticipated third campaign was required. In all three campaigns, replicate analyses (three injections of one preparation separated in time) were made for one randomly selected unit of each of the 27 materials. Nine of the 27 materials were gravimetrically diluted before measurement to provide solutions with ethanol mass fraction in the established linear range of the GC-FID method. The repeatability measurement value for each analyzed solution was estimated as the mean of all replicate values. The within- and between-campaign variance components were estimated using one-way ANOVA. Markov Chain Monte Carlo Bayesian analysis was used to estimate 95% level-of-confidence coverage intervals for the mean values.
Uncertainty-weighted generalized distance regression was used to establish the key comparison reference function (KCRF) relating the assigned values to the repeatability measurements. On the basis of leave-one-out cross-validation, all of the assigned values for all 27 materials were deemed equivalent at the 95% level of confidence. These materials were used to define the KCRF.
Parametric bootstrap Monte Carlo was used to estimate 95% level-of-confidence coverage intervals for the degrees of equivalence of materials, d ± U95(d), and of the participating NMIs, D ± U95(D). Because of the very wide range of ethanol mass fraction in the materials, these degrees of equivalence are expressed in percent relative form: %d ± U95(%d) and %D ± U95(%D). The median of the absolute values of the %D for the participating NMIs is less than 0.05% with a median U95(%D) of less than 1%. These results demonstrate that the participating NMIs have the ability to correctly value-assign CRMs and proficiency test materials for ethanol in aqueous media and similar measurands.
Solutions of organic analytes of known mass fraction are typically used to calibrate the measurement processes used to determine these compounds in matrix samples. Appropriate value assignments and uncertainty calculations for calibration solutions are critical for accurate measurements. Evidence of successful participation in formal, relevant international comparisons is needed to document measurement capability claims (CMCs) made by national metrology institutes (NMIs) and designated institutes (DIs). To enable NMIs and DIs to update or establish their claims, in 2015 the Organic Analysis Working Group (OAWG) sponsored CCQM-K131 "Low-Polarity Analytes in a Multicomponent Organic Solution: Polycyclic Aromatic Hydrocarbons (PAHs) in Acetonitrile".
Polycyclic aromatic hydrocarbons (PAHs) result from combustion sources and are ubiquitous in environmental samples. The PAH congeners, benz[a]anthracene (BaA), benzo[a]pyrene (BaP), and naphthalene (Nap) were selected as the target analytes for CCQM-K131. These targets span the volatility range of PAHs found in environmental samples and include potentially problematic chromatographic separations. Nineteen NMIs participated in CCQM-K131. The consensus summary mass fractions for the three PAHs are in the range of (5 to 25) μg/g with relative standard deviations of (2.5 to 3.5) %.
Successful participation in CCQM-K131 demonstrates the following measurement capabilities in determining mass fraction of organic compounds of moderate to insignificant volatility, molar mass of 100 g/mol up to 500 g/mol, and polarity pKow < −2 in a multicomponent organic solution ranging in mass fraction from 100 ng/g to 100 μg/g: (1) value assignment of primary reference standards (if in-house purity assessment carried out), (2) value assignment of single and/or multi-component organic solutions, and (3) separation and quantification using gas chromatography or liquid chromatography.
KEY COMPARISON
At the October 2005 CCQM Organic Analysis Working Group Meeting (IRMM, Belgium), the decision was made to proceed with a Key Comparison study (CCQM-K47) addressing the calibration function for the determination of volatile organic compounds (VOCs) used for water quality monitoring. This was coordinated by CENAM and NIST. Benzene, o-xylene, m-xylene and p-xylene were chosen as representative VOCs. The solvent of choice was methanol.
Key Comparison CCQM-K47 demonstrated the capabilities of participating NMIs to identify and measure the four target VOCs in a calibration solution using GC-based methods. The measurement challenges in CCQM-K47, such as avoiding volatility loss, achieving adequate chromatographic resolution and isolating potential interferences, are typical of those required for value-assigning volatile reference materials. Participants achieving comparable measurements for all four VOCs in this Key Comparison should be capable of providing reference materials and measurements for VOCs in solutions when present at concentration levels greater than 10 µg/g.
The European Water Framework Directive 2000/60/EC requires monitoring of organic priority pollutants in so-called whole water samples, i.e. in aqueous nonfiltered samples that contain natural colloidal and suspended particulate matter. Colloids and suspended particles in the liquid phase constitute a challenge for sample homogeneity and stability. Within the joint research project ENV08 ‘‘Traceable measurements for monitoring critical pollutants under the European Water Framework Directive 2000/60/EC’’, whole water test materials were developed by spiking defined amounts of aqueous slurries of ultrafinely milled contaminated soil or sediment and aqueous solutions of humic acid into a natural mineral water matrix. This paper presents the results of an European-wide interlaboratory comparison (ILC) using this type of test materials. Target analytes were tributyltin, polybrominated diphenyl ethers and polycyclic aromatic hydrocarbons in the ng/L concentration range. Results of the ILC indicate that the produced materials are sufficiently homogeneous and stable to serve as samples for, e.g. proficiency testing or method validation. To our knowledge, this is the first time that ready-to-use water materials with a defined amount of suspended particulate and colloidal matter have been applied as test samples in an interlaboratory exercise. These samples meet the requirements of the European Water Framework Directive. Previous proficiency testing schemes mainly employed filtered water samples fortified with a spike of the target analyte in a water-miscible organic solvent.
Extraction, chromatographic separation, and quantification of low-concentration organic compounds in complex matrices are core challenges for reference material producers and providers of calibration services. Evidence of successful participation in formal, relevant international comparisons is needed to document measurement capability claims made by national metrology institutes (NMIs) and designated institutes (DIs). To enable NMIs and DIs to update or establish their claims, in 2014 the Organic Analysis Working Group (OAWG) initiated CCQM-K95.1 "Low-Polarity Analytes in a Botanical Matrix: Polycyclic Aromatic Hydrocarbons (PAHs) in Tea". This was a follow-on comparison from CCQM-K95 which was completed in 2014.
The polycyclic aromatic hydrocarbons (PAHs) benz[a]anthracene (BaA) and benzo[a]pyrene (BaP) are considered priority pollutants by U.S. Environmental Protection Agency and are regulated contaminants in food, pose chromatographic separation challenges, and for which exist well-characterized measurement procedures and standard materials. BaA and BaP in a smoked tea were therefore selected as representative target measurands for CCQM-K95.1. Ten NMIs participated in CCQM-K95.1. The consensus summary mass fractions for the two PAHs are in the range of (50 to 70) ng/g with relative standard deviations of (6 to 10) %.
Successful participation in CCQM K95.1 demonstrates the following measurement capabilities in determining mass fraction of organic compounds, with molar mass of 100 g/mol to 500 g/mol and having polarity pKow −2, in a botanical matrix ranging in mass fraction from 10 ng/g to 1000 ng/g: (1) value assignment of primary reference standards (if in-house purity assessment carried out), (2) value assignment of single and/or multi-component organic solutions, (3) extraction of analytes of interest from the matrix, (4) cleanup and separation of analytes of interest from interfering matrix or extract components, and (5) separation and quantification using gas chromatography or liquid chromatography.
Aktive Thermografie mit Lockin-Anregung ist ein zerstörungsfreies Prüfverfahren, das insbesondere auch die Prüfung von kohlenstofffaserverstärkten Kunststoffen ermöglicht. Um eine Standardisierung dieses Verfahrens voranzubringen, wurden im Rahmen eines Forschungsprojektes umfangreiche Untersuchungen zur Validierung des Verfahrens durchgeführt. Für die Anregungsmethoden optisch und Ultraschall wurden die wichtigsten Parameter systematisch untersucht. Auf der Auswertungsseite ist dies z.B. der Einfluss der spektralen Empfindlichkeit verschiedener Kamerasysteme. Für die Anregungen sind unter anderem die Einflüsse von Anregungsenergie und Ultraschallfrequenz untersucht worden. Auch Materialparameter, wie der Lagenaufbau bei CFK-Probekörpern, beeinflussen die Ergebnisse stark.
The European Union (EU) has included tributyltin (TBT) and its compounds in the list of priority water pollutants. Quality standards demanded by the EU Water Framework Directive (WFD) require determination of TBT at so low concentration level that chemical analysis is still difficult and further research is needed to improve the sensitivity, the accuracy and the precision of existing methodologies. Within the frame of a joint research project “Traceable measurements for monitoring critical pollutants under the European Water Framework Directive” in the European Metrology Research Programme (EMRP), four metrological and designated institutes have developed a primary method to quantify TBT in natural water using liquid–liquid extraction (LLE) and species-specific isotope dilution mass spectrometry (SSIDMS). The procedure has been validated at the Environmental Quality Standard (EQS) level (0.2 ng L−1 as cation) and at the WFD-required limit of quantification (LOQ) (0.06 ng L−1 as cation). The LOQ of the methodology was 0.06 ng L−1 and the average measurement uncertainty at the LOQ was 36%, which agreed with WFD requirements. The analytical difficulties of the method, namely the presence of TBT in blanks and the sources of measurement uncertainties, as well as the interlaboratory comparison results are discussed in detail.
The irradiation of ~0.9-µm-thick hydrogenated amorphous carbon (a-C:H) layers deposited on silicon substrates with single femtosecond (fs) laser pulses (35 fs pulse duration, 790 nm centre wavelength) in air is studied experimentally. Irradiation spots have been generated with different peak fluences and subsequently investigated by optical topometry, micro Raman spectroscopy and microscale mechanical indentation in order to evaluate their microscopic, topographical, structural and mechanical properties (e.g. elastic modulus). By this multi-method approach, a clear separation of different effects (delamination and graphitisation) becomes possible. The joint application of mechanical and spectroscopic techniques provides unique insights into the effects of the fs-laser radiation on the carbon layer.
Fiber optic sensors based on polymer optical fibers (POF) have the advantage of being very elastic and robust at the same time. Unlike silica fibers, standard PMMA POF fibers can be strained to more than 40% while fully maintaining their light guiding properties. We investigated POF as a distributed strain sensor by analysing the backscatter increase at the strained section using the optical time domain reflectometry (OTDR) technique. This sensing ability together with its high robustness and break-down strain makes POF well-suited for integration into technical textiles for structural health monitoring purposes. Within the European research project POLYTECT (Polyfunctional textiles against natural hazards) technical textiles with integrated POF sensors, among others sensors are being developed for online structural health monitoring of geotechnical structures. Mechanical deformation in slopes, dams, dikes, embankments and retrofitted masonry structures is to be detected before critical damage occurs. In this paper we present the POF strain sensor properties, reactions to disturbing influences as temperature and bends as well as the results of the different model tests we conducted within POLYTECT. We further show the potential of perfluorinated graded-index POF for distributed strain sensing with increased spatial resolution and measurement lengths.
The capabilities of National Metrology Institutes (NMIsthose which are members of the Comité Consultatif pour la Quantité de Matière (CCQM)of the CIPM) and selected outside "expert" laboratories to quantitate (C4H9)3Sn+ (TBT) in a prepared marine sediment were assessed. This exercise was sanctioned by the 7th CCQM meeting, April 46, 2001, as an activity of the Inorganic Analysis Working Group and was jointly piloted by the Institute for National Measurement Standards of the National Research Council of Canada (NRC) and the Laboratory of the Government Chemist (LGC), UK. A total of 11 laboratories submitted results (7 NMIs, and 4 external labs). Two external laboratories utilized a standard calibration approach based on a natural abundance TBT standard, whereas all NMIs relied upon isotope dilution mass spectrometry for quantitation. For this purpose, a species specific 117Sn-enriched TBT standard was supplied by the LGC. No sample preparation methodology was prescribed by the piloting laboratories and, by consequence, a variety of approaches was adopted by the participants, including mechanical shaking, sonication, accelerated solvent extraction, microwave assisted extraction and heating in combination with Grignard derivatization, ethylation and direct sampling. Detection techniques included ICPMS (with GC and HPLC sample introduction), GCMS, GCAED and GCFPD. Recovery of TBT from a control standard (NRCC CRM PACS-2 marine sediment) averaged 93.5±2.4% (n=14). Results for the pilot material averaged 0.680±0.015 µmol kg1 (n=14; 80.7±1.8 µg kg1) with a median value of 0.676 µmol kg1. Overall, performance was substantially better than state-of-the-art expectations and the satisfactory agreement amongst participants permitted scheduling of a follow-up Key comparison for TBT (K-28), a Pilot intercomparison for DBT (P-43), and certification of the test sediment for TBT content and its release as a new Certified Reference Material (HIPA-1) with a TBT content of 0.679±0.089 µmol kg1 (expanded uncertainty, k=2, as Sn) (80.5±10.6 µg kg1). Electronic Supplementary Material Supplementary material is available in the online version of this article at http://dx.doi.org/10.1007/s00216-003-2016-9.
Sensing characteristics of polymer optical fibers (POF) are studied using the optical
time-domain reflectometry technique. For the first time to our knowledge, investigations are
carried out with respect to integration of POF in technical textiles for distributed measurement
of mechanical deformation. The research on this new sensor type focuses on its application in
monitoring of geotechnical structures such as railway embankments, dikes, slopes and dams.
We report on a distributed sensor system using POF integrated in technical textiles as sensing
elements for measurement of displacement of soil. This sensor system is very robust it
withstands the integration under rough condition at a construction site and can detect strain
of more than 40 % over distances of more than 100 meters.
Carbon fiber reinforced polymer (CFRP) specimens with artificial delaminations and with impact damage have been characterized using active thermography with flash excitation. Systematic investigations have been performed in four different experimental configurations of flash lamps and infrared (IR) camera in transmission as well as in reflection alignment. It is shown here that the diffusivities determined for the sound and for the damaged areas give a good measure for damage characterization. Although reflection measurements also give information about defect depth, reflection measurements from only one side are not sufficient for assessing the whole cross section of the specimens. Thus, depending on sample thickness the lateral size of damage could only be determined from reflections measurements from both sides or from transmission measurements. In this paper, measurement accuracy and limits of flash thermography for the investigation of CFRP specimens are presented in detail together with quantitative data concerning the defects.
Eines der bedeutendsten Kunstwerke des Magdeburger Doms sind die Putzritzungen am Ostflügel des Kreuzgangs aus dem 13. Jahrhundert. Der größte Teil der einzelnen Putzoberflächen sind Ausbesserungen oder Neuverputzungen aus verschiedenen Restaurierungs- oder Reparaturphasen. In dem von der Forschungsinitiative Zukunft Bau geförderten Projekt zur 3D-Kartierung von Bauwerksoberflächen wurden Untersuchungen zur Erfassung der Schäden an diesen Putzritzungen mit optischen 3D-Messverfahren und der aktiven Thermografie durchgeführt. Dabei wurden bei den optischen Verfahren hochauflösende Techniken zur Erfassung der Oberflächentopologie (Stereophotogrammmetrie) und zur Vermessung der Rissstrukturen und Ausbeulungen (3D-Trackingverfahren) eingesetzt. Die Zuordnung der Signaturen in den Thermogrammen zu Hohlstellen sowie Materialergänzungen und -ersatz wird diskutiert. Weiterhin erfolgt ein Vergleich der Ergebnisse mit Messungen an neu freigelegten Putzbereichen.
block and mortar types is analysed with particular regard to the influence of varying relative humidity. The uniaxial compressive strength and deformation characteristics of unstabilised earth blocks and mortars as well as of unstabilised earth block masonry are studied in detail and compared to conventional masonry to evaluate whether the structural design can be made accordingly. An increase of 30 % points in relative humidity leads to a reduction of the masonry´s compressive strength between 33 % and 35 % whereas the Young´s modulus is reduced by 24–29 %. However, the ratio between the Young´s modulus and the characteristic compressive strength of earth block masonry ranges between E33/fk = 283–583 but is largely independent of the relative humidity. The results show that the mechanical properties of the investigated unstabilised earth block masonry are sufficient for load-bearing structures, yielding a masonry compressive strength between 2.3 MPa and 3.7 MPa throughout the range of moisture contents
investigated. In general, the design concept of conventional masonry can be adapted for unstabilised earth masonry provided that the rather low Young´s modulus as well as the moisture dependence of both, compressive strength and Young´s modulus, are sufficiently taken into
account.
Die Bemessung von tragendem Lehmmauerwerk erfolgt in Deutschland auf Basis der Lehmbau Regeln. Das dort verankerte Nachweisverfahren beruht auf einem globalen Sicherheitskonzept, welches aus zuverlässigkeitstheoretischer Sicht nicht mehr dem Stand der Technik entspricht. Auf Grund dessen wird das Bemessungskonzept für Lehmmauerwerk vom Deutschen Institut für Bautechnik (DIBt) voraussichtlich 2023 außer Kraft gesetzt. Ein statischer Nachweis von tragenden Lehmbauten wäre in Deutschland dann ausschließlich mit einer Zustimmung im Einzelfall (ZiE) oder vorhabenbezogener Bauartgenehmigung (vBg) möglich. Beides ist mit erheblichem Mehraufwand und höheren Kosten verbunden, was für den Lehmmauerwerksbau einen entscheidenden Nachteil im Vergleich zum konventionellen Mauerwerksbau darstellt. Um eine unkomplizierte Praxisanwendung von Lehmmauerwerk zu ermöglichen, werden innerhalb eines Forschungsvorhabens, welches von der Bundesanstalt für Materialforschung und -prüfung (BAM), dem Institut für Massivbau der Technischen Universität Darmstadt sowie dem Ingenieurbüro ZRS durchgeführt wird, auf Basis der Produktnormen für Lehmsteine und Lehmmauermörtel Grundlagen für ein aktualisiertes Bemessungskonzept entwickelt. Im Rahmen des Projekts wird ebenfalls untersucht, inwiefern die Bemessungsregeln nach den vereinfachten Berechnungsmethoden für unbewehrtes Mauerwerk gemäß DIN EN 1996-3 / NA auf den Lehmmauerwerksbau übertragbar sind. Falls eine Anwendung des normativen Nachweisverfahrens bei Lehmmauerwerk möglich ist, wäre zukünftig eine Aufnahme von Lehmsteinen und Lehmmauermörtel in den nationalen Anhang des Eurocode 6 denkbar, was eine bedeutsame Erweiterung des Anwendungsbereichs von Lehmmauerwerk zur Folge hätte.
Diverse wissenschaftliche Untersuchungen konnten zeigen, dass bemessungsrelevante Festigkeits- und Verformungseigenschaften von Lehmmauerwerksbaustoffen stark von der vorherrschenden Materialfeuchte abhängen, welche im hygroskopischen Wassergehaltsbereich im Wesentlichen von der relativen Luftfeuchte (RLF) bestimmt wird. Auch die Zwischenergebnisse des laufenden Forschungsvorhabens zur Entwicklung eines Bemessungskonzepts für Lehmmauerwerk ergaben eine deutlich erkennbare Abhängigkeit zwischen der Materialfeuchte und den relevanten Festigkeits- und Verformungseigenschaften. Eine detaillierte Kenntnis des feuchteabhängigen Materialverhaltens von Lehmsteinen, -mörtel und -mauerwerk ist zwingend erforderlich, um ein konsistentes und zuverlässiges Bemessungskonzept für Lehmmauerwerk zu entwickeln. Im Rahmen des laufenden Forschungsprojektes werden deshalb umfangreiche Versuche zum Drucktragverhalten von Lehmsteinen und -mörtel sowie Lehmmauerwerk nach Konditionierung bei unterschiedlichen RLF durchgeführt und analysiert. Weiterhin werden auf Basis der experimentellen Ergebnisse numerische Modelle kalibriert, welche die detaillierte Analyse der Biegedrucktragfähigkeit von Lehmmauerwerk ermöglichen.
In diesem Beitrag werden zunächst die bisherigen Zwischenergebnisse bezüglich der experimentell ermittelten feuchteabhängigen Materialkennwerte von Lehmsteinen, -mörtel und -mauerwerk dargelegt. Darauf aufbauend werden numerische Untersuchungen zur Bestimmung der Systemtragfähigkeit von Lehmmauerwerk unter Feuchteeinflusses durchgeführt und erläutert.
In dem von der Forschungsinitiative Zukunft Bau geförderten Projekt
zur „3D Kartierung von Bauwerksoberflächen“ wurden Verfahren zur Ortung von Rissen und Rissverläufen an historischen Gebäuden und Skulpturen weiterentwickelt und optimiert. Diese neuen Entwicklungen zur effizienten 3D Erfassung, Darstellung und zum Monitoring von Rissen basieren auf der aktiven Thermografie, einem Trackingsystem und Ultraschall.
Systematische Untersuchungen zur Zuverlässigkeit und zu Messgenauigkeiten der Messverfahren im Labor wurden durch den kombinierten Einsatz der Verfahren an Skulpturen aus historischem Beton an der Giebichensteinbrücke in Halle ergänzt.
Untersuchung der Auflösungsgrenzen der Lockin-Thermografie zur Prüfung von Faserverbundwerkstoffen
(2014)
Aktive Thermografie mit Lockin-Anregung stellt ein berührungsfreies und zerstörungsfreies Prüfverfahren dar, welches insbesondere auch die Prüfung von kohlenstofffaserverstärkten Kunststoffen ermöglicht. Um eine Standardisierung dieses Verfahrens voranzubringen, wurden im Rahmen eines Forschungsprojektes umfangreiche Untersuchungen zur Validierung des Verfahrens durchgeführt.
Dabei wurden unter anderem der Einfluss der spektralen Empfindlichkeit verschiedener Kamerasysteme, unterschiedlicher Lagenaufbauten bei CFK-Probekörpern und der Einfluss einer Phasenverschiebung zwischen dem Anregungssignal und der Detektion der Thermografiebilder untersucht.
Polymer optical fiber (POF) sensors have the unique ability to measure high strain distributed along the fiber up to 40% using the optical time-domain reflectometry (OTDR) technique. Both, standard PMMA fibers and perfluorinated (PF) graded-index (GI) POF are introduced and evaluated in potential use and applicability. Further, distributed length change measurement based on cross-correlation analysis of the characteristic fiber signature of PF POF is introduced. We conclude the advances in distributed POF strain sensors technology with respect to application in structural health monitoring. Special focus is on the sensor integration into technical textiles for health monitoring of geotechnical structures and masonry structures. Measurement results of sensor-equipped textiles in different model tests are presented, displacement of soil and cracks in retrofitted masonry structures are detected and evaluated.
Die messtechnische Erfassung von Bauwerkschäden ist eine wichtige Voraussetzung für die dreidimensionale und zeitaufgelöste Darstellung von möglicherweise sicherheitsrelevanten Veränderungen an Bauwerken, wie z. B. Verformungen, Verwindungen und Risswachstum. Ziel des vorgestellten Projektes war die Entwicklung eines Verfahrens zur effizienten und wiederholbaren 3D-Schadenkartierung an zum Teil empfindlichen Bauteiloberflächen.
Monitoring of cracks in historic concrete structures using optical, thermal and acoustical methods
(2015)
Cracks are a major issue in the field of cultural heritage. In order to evaluate the significance of a crack, a long term monitoring of the damaged region is required. However, there is a lack of easy to operate tools for such monitoring measures. Therefore, new or existing methods for other applications have to be optimised for cultural heritage investigation. The paper describes the application of such crack observation methods on a historic concrete sculpture. Beside conventional methods, like mapping by hand and ultrasonic depth profiling, a novel tracking system is presented. Furthermore, the suitability of active thermography for the investigation of cracks was investigated. The results show promising prospects for these non-destructive techniques.
Standardisierung der Lockin-Thermografie: Vorstellung des TNS-Projektes und Auswahl der Probekörper
(2013)
Ziel des Verbundprojektes zwischen der BAM und dem IKT der Universität Stuttgart ist die Festlegung einer einheitlichen Vorgehensweise für die Auswahl der Gerätekomponenten und für die Durchführung von Prüfungen mit der Lockin-Thermografie. Daraus soll ein Standard abgeleitet werden, der die Prüfung
unterschiedlicher Materialsysteme auf Fehlstellen mittels Lockin-Thermografie unter Berücksichtigung verschiedener Anregungsquellen ermöglicht. In diesem Beitrag wird die Entwicklung der Probekörper vorgestellt, die in diesem Projekt untersucht und später als Referenzprobekörper verwendet werden können.
In diesem Beitrag werden Verfahren und Strategien basierend auf optischen und thermografischen Methoden zur Lokalisierung, Erfassung und Bewertung von Putzablösungen, Ablösungen von Fassadenelementen und Rissen vorgestellt. Abgelöste Fassadenbereiche und Risse zeigen dabei sowohl geometrische als auch thermische Auffälligkeiten, die im Rahmen eines Monitoring auch über größere Zeiträume verfolgt werden können. Als optische Verfahren werden die trackingbasierte taktile 3D‐Erfassung von Oberflächenmerkmalen und die Stereophotogrammetrie eingesetzt. Zur Charakterisierung verdeckter Ablösungen und Bauteile wird die aktive Thermografie mit natürlicher und künstlicher Erwärmung der Bauteiloberfläche verwendet. Systematische Untersuchungen an Probekörpern und Fallstudien (Magdeburger Dom, Wandbild in Cobbelsdorf, Giebichensteinbrücke) zeigen, wie u. a. mit der Verfahrenskombination die Schäden charakterisiert werden können.
Active thermography with lock-in excitation is a non-destructive testing method that is also feasible for testing of carbon fiber reinforced polymers (CFRP). For validating the method extensive investigations were done during a research project in order to advance a standardization process.
The most important parameters of optical and ultrasonic excitation thermography were investigated. For example, the appropriate selection of spectral sensitivity of the used infrared camera systems is important for recording undisturbed thermal signals. Regarding excitation,
influences of excitation power and ultrasonic frequency were studied. Furthermore, material parameters such as CFRP layup are known for strongly affecting the results of
measurement.
In the field of computational science and engineering, workflows often entail the application of various software, for instance, for simulation or pre- and postprocessing. Typically, these components have to be combined in arbitrarily complex workflows to address a specific research question. In order for peer researchers to understand, reproduce and (re)use the findings of a scientific publication, several challenges have to be addressed. For instance, the employed workflow has to be automated and information on all used software must be available for a reproduction of the results. Moreover, the results must be traceable and the workflow documented and readable to allow for external verification and greater trust. In this paper, existing workflow management systems (WfMSs) are discussed regarding their suitability for describing, reproducing and reusing scientific workflows. To this end, a set of general requirements for WfMSswere deduced from user stories that we deem relevant in the domain of computational science and engineering. On the basis of an exemplary workflow implementation, publicly hosted at GitHub (https:// this http URL), a selection of different WfMSs is compared with respect to these requirements, to support fellow scientists in identifying the WfMSs that best suit their requirements.
Software-driven scientific workflows are often characterized by a complex interplay of various pieces of software executed in a particular order. The output of a computational step may serve as input to a subsequent computation, which requires them to be processed sequentially with a proper mapping of outputs to inputs. Other computations are independent of each other and can be executed in parallel. Thus, one of the main tasks of a workflow tool is a proper and efficient scheduling of the individual processing steps.
Each processing step, just as the workflow itself, typically processes some input and produces output data. Apart from changing the input data to operate on, processing steps can usually be configured by a set of parameters to change their behavior. Moreover, the behavior of a processing step is determined by its source code and/or executable binaries/packages that are called within it. Beyond this, the computation environment not only has a significant influence on its behavior, but is also crucial in order for the processing step to work at all. The environment includes the versions of the interpreters or compilers, as well as all third-party libraries and packages that contribute to the computations carried out in a processing step.
The mechanical properties of unstabilised earthen building materials are distinctively influenced by changes in material moisture content. However, this moisture-dependency often remains unconsidered in the calculation of the load-bearing capacity of earth constructions. This paper aims to derive a convenient way to sufficiently consider the impact of different material moisture contents on the mechanical properties of unstabilised earth masonry. Therefore, the influence of relative humidity and temperature on the strength and deformation characteristics of unstabilised earth blocks, earth mortar and earth masonry is evaluated by conducting compression tests under various climate conditions. The results show that the compressive strength and the modulus of elasticity are linearly correlated with the relative humidity, whereas changes in temperature at constant relative humidity have no significant influence. To account the distinct moisture-dependency, a general applicable modification factor for unstabilised earthen materials is provided, which enables the adjustment of the compressive strength and the modulus of elasticity in dependency of arbitrary hygroscopic material moisture contents.
Research on per- and polyfluoroalkyl substances (PFAS) frequently incorporates organofluorine measurements, particularly because they could support a class-based approach to regulation. However, standardized methods for organofluorine analysis in a broad suite of matrices are currently unavailable, including a method for extractable organofluorine (EOF) measured using combustion ion chromatography (CIC). Here, we report the results of an international interlaboratory comparison. Seven laboratories representing academia, government, and the private sector measured paired EOF and PFAS concentrations in groundwater and eel (Anguilla rostrata) from a site contaminated by aqueous film-forming foam. Among all laboratories, targeted PFAS could not explain all EOF in groundwater but accounted for most EOF in eel. EOF results from all laboratories for at least one replicate extract fell within one standard deviation of the interlaboratory mean for groundwater and five out of seven laboratories for eel. PFAS spike mixture recoveries for EOF measurements in groundwater and eel were close to the criterion (±30%) for standardized targeted PFAS methods. Instrumental operation of the CIC such as replicate sample injections was a major source of measurement uncertainty. Blank contamination and incomplete inorganic fluorine removal may introduce additional uncertainties. To elucidate the presence of unknown organofluorine using paired EOF and PFAS measurements, we recommend that analysts carefully consider confounding methodological uncertainties such as differences in precision between measurements, data processing steps such as blank subtraction and replicate analyses, and the relative recoveries of PFAS and other fluorine compounds.
Lehmmauerwerk bietet sich aufgrund seiner zahlreichen ökologischen Vorteile für die Errichtung klimafreundlicher und ressourcenschonender Gebäude an. Um den Anwendungsbereich tragenden Lehmmauerwerks durch eine zeitgemäße Nachweisführung zu erweitern, werden in diesem Beitrag Grundlagen für die Entwicklung eines eurocodekonformen Bemessungskonzepts erarbeitet. Hierzu werden die Ergebnisse umfangreicher experimenteller Untersuchungen an Lehmmauerwerk sowie Lehmsteinen und -mörteln nach Konditionierung bei unterschiedlichen Klimata vorgestellt. Darauf aufbauend erfolgt eine Traglastanalyse druckbeanspruchter Lehmmauerwerkswände mittels numerischer und analytischer Methoden. Die daraus gewonnenen Erkenntnisse werden abschließend in einen an DIN~EN~1996-3/NA angelehnten Bemessungsvorschlag überführt, welcher die materialspezifischen Besonderheiten von Lehmmauerwerk berücksichtigt und eine fundierte Grundlage für eine wirtschaftliche und zuverlässige Nachweisführung darstellt.
Für die Sicherheit von Spannbetonbauwerken ist eine Empfindlichkeitsprüfung von Spannstahlprodukten gegenüber der wasserstoffinduzierten Spannungsrisskorrosion zwingend erforderlich. Die derzeitig normativ festgelegten Prüfmethoden nach DIN EN ISO 15630-3 zeigen nachweislich Schwächen hinsichtlich der Reproduzierbarkeit der Ergebnisse und erschweren damit die eindeutige Bewertung der Empfindlichkeit. Ziel des Forschungsvorhabens der Förderinitiative WIPANO des BMWK war es, die Prüfmethode hinsichtlich der Reproduzierbarkeit und Aussagesicherheit zu verbessern. Im Projekt wurden durch materialseitige, elektrolytische und verfahrenstechnische Parameteränderungen konstante und reproduzierbare Prüfbedingungen geschaffen. Dies ermöglichte eine eindeutige Differenzierung zwischen Gut- und Schlechtprodukten. Innerhalb des Projekts wurde ein Ringversuch initiiert, welcher die Anwendbarkeit und Reproduzierbarkeit der neuen Prüfmethode bestätigte. Das neue Prüfverfahren wurde hinsichtlich der Anwendbarkeit für das Spannstahlerzeugnis Draht evaluiert. Ein entsprechender Normentwurf mit einem Vorschlag für ein Konformitätskriterium dieser Erzeugnisse wurde dem zuständigen ISO-Gremium präsentiert und zur Abstimmung überlassen. Nach aktueller Rückmeldung seitens des Gremiums wird der Normentwurf den Eingang in den informativen Anhang der Prüfnorm finden, dies könnte den Weg für eine Spiegelung auf europäischer und nationaler Normungsebene ebnen.
The occurrence of solidification cracking during welding remains a little understood phenomenon, in spite of extensive studies and tests performed to evaluate and compare the relative weldability of many different alloys. From an approach often adopted in the welding community attributed to Prokhorov, solidification cracks are believed to form when a critical tensile strain is exceeded, specific to the alloy, assuming that the mushy-zone has limited ductility. Tensile stresses and strains normally form behind a moving weld pool as a result of solidification shrinkage and thermal contraction, as influenced by welding parameters and the degree of restraint.
In Europe the maximum allowable concentration for tributyltin (TBT) compounds in surface water has been regulated by the water framework directive (WFD) and daughter directive that impose a limit of 0.2 ng L-1 in whole water (as tributyltin cation). Despite the large number of different methodologies for the quantification of organotin species developed in the last two decades, standardised analytical methods at required concentration level do not exist. TBT quantification at picogram level requires efficient and accurate sample preparation and preconcentration, and maximum care to avoid blank contamination. To meet the WFD requirement, a method for the quantification of TBT in mineral water at environmental quality standard (EQS) level, based on solid phase extraction (SPE), was developed and optimised. The quantification was done using species-specific isotope dilution (SSID) followed by gas chromatography (GC) coupled to inductively coupled plasma mass spectrometry (ICP–MS). The analytical process was optimised using a design of experiment (DOE) based on a factorial fractionary plan. The DOE allowed to evaluate 3 qualitative factors (type of stationary phase and eluent, phase mass and eluent volume, pH and analyte ethylation procedure) for a total of 13 levels studied, and a sample volume in the range of 250–1000 mL. Four different models fitting the results were defined and evaluated with statistic tools: one of them was selected and optimised to find the best procedural conditions. C18 phase was found to be the best stationary phase for SPE experiments. The 4 solvents tested with C18, the pH and ethylation conditions, the mass of the phases, the volume of the eluents and the sample volume can all be optimal, but depending on their respective combination. For that reason, the equation of the model conceived in this work is a useful decisional tool for the planning of experiments, because it can be applied to predict the TBT mass fraction recovery when the experimental conditions are drawn. This work shows that SPE is a convenient technique for TBT pre-concentration at pico-trace levels and a robust approach: in fact (i) number of different experimental conditions led to satisfactory results and (ii) the participation of two institutes to the experimental work did not impact the developed model.
With the aim of improving limits of detection (LOD) of trace elements in a matrix with adjacent fluorescence energies, a simple double dispersive X-ray fluorescence detection system (D2XRF) was constructed to operate at the beamlines BAMline and the mySpot @ BESSY II. This system is based on the combination of a crystal analyzer with an energy resolving single photon counting pnCCD. Without further collimators, the efficient suppression of the background by the pnCCD and the good energy resolution of the crystal results in improved LOD. In first order reflections, an energy resolution of 13 eV for Cu Kα was reached, and an energy range of 1 keV was covered in one shot.
This new system was applied to the detection of platinum (Pt) in gold leaves with a LOD of 0.9 mg/kg, which is the lowest attained by totally non-destructive methods nowadays. The presence of Pt in gilded objects from Abydos and Byzantine mosaics provides vital information, as it indicates the alluvial origin of the gold for these examples.