Fluorescence Instrument Research Articles

Geological sources and chronological change in ground-edged artefacts of the Hawkesbury region, the Sydney Basin: A Macdonald River case study

Evaluating temporal changes in exchange systems and social networks in pre-contact Aboriginal societies remains a major challenge for Australian archaeology. As part of a larger research program identifying exchange systems and social networks in the Sydney Basin, several excavated sites were selected to identify changes over time in the relationship between ground-edged artefacts and sources of rock used. Portable X-Ray Fluorescence (pXRF) instrumentation was used to non-destructively elementally characterise and compare excavated stone artefacts and source rocks in a geological reference collection.For one of the sites on the NSW Central Coast – Macdonald River rockshelter (MR/1), in the lower reaches of the Macdonald River close to its junction with the Hawkesbury River – 86 stone artefacts derive from the production and/or repair of ground-edged artefacts. A large proportion of these artefacts match basalts from a local source at Peats Ridge–Popran Creek in the adjacent Mangrove Creek Valley. Other artefacts match hornfels and quartzite cobbles from the Nepean–Hawkesbury or Hunter Rivers. Peats Ridge–Popran Creek basalt was present throughout the final 3000 years of the MR/1 archaeological record, though it decreased relative to hornfels from between 1700 and 1150 years ago until contact. The sequence at MR/1 shows historically-reported exchange routes may have a time-depth of at least 3000 years.

Qualitative and quantitative characterization of sialylated N-glycans using three fluorophores, two columns, and two instrumentations

Sialylation can influence the stability, half-life, and immunogenicity of glycoproteins, but sialylated N-glycans are known to be difficult to analyze. Human alpha1-acid glycoprotein (AGP) is reported to have glycans that consist of sialylated N-glycans. The N-glycan profiling of AGP is qualitatively and quantitatively investigated here by UPLC and LC-ESI-MS/MS. Three fluorescent tags (AB, AA, and ProA) and two separation columns (HILIC and AEX-HILIC) were adopted to confirm and compare each analytical characteristic. The results of AA were comparable to those of the well-established AB. The qualification of ProA was notable due to its superior fluorescence intensity and ionization efficiency, and ProA showed smaller quantitative or larger-sized fragments in LC-ESI-MS/MS compared to AB and AA. However, the MS quantification of ProA was distorted because the increased sialylation level decreased the LC-ESI-MS/MS ionization efficiency. HILIC had better peak separability, AEX-HILIC had an advantage in UPLC sialylation profiling, and each isomeric glycan could be identified by both columns in LC-ESI-MS/MS. In conclusion, ProA is favored for UPLC and LC-ESI-MS/MS detection but not reliable for MS quantification. This study firstly demonstrates the qualification and quantification of sialylated N-glycans by comparing the commonly used analytical conditions with different fluorescent tags, columns, and instruments.

Lidar Monitoring of Chlorophyll a During the XXIX and XXXI Italian Antarctic Expeditions

Although it is known that the Ross Sea is responsible for more than a quarter of CO2 absorption of the Southern Ocean, more information is needed to model the primary production of this key area. In particular, it is necessary to improve the characterization of the size class distribution, biomass and taxonomic composition of phytoplankton in the Ross Sea. Recently, an innovative compact lidar fluorosensor was deployed for real-time sensing of chlorophyll a, during the Ross Sea Mesoscale Experiment (RoME), conducted in the XXIX (2014) and XXXI (2016) Italian Antarctic expeditions. Furthermore, high-performance liquid chromatography (HPLC) was also performed to provide pigment analysis of in situ samples. Lidar fluorosensors are laser-induced fluorescence (LIF) instruments and have been extensively operated by the Italian National Agency for New Technologies, Energy and Sustainable Economic Development (ENEA) since the 1990s to monitor water bodies. Spectra obtained with LIF contain signatures of phytoplankton pigments, chromophoric dissolved organic matter and dispersed impurities, such as crude oils. The study of algal pigments provides not only the phytoplankton biomass—directly linked to chlorophyll a—but also its taxonomic composition through detection of several accessory pigments. Moreover, some models allow the identification of phytoplankton size classes. Lidar and HPLC mapped the spatiotemporal distribution of algal biomass and showed that during RoME, the phytoplankton assemblage structure was dominated by large-size cells (micro-phytoplankton) and the prevailing algal groups were diatoms.

Characterisation and source identification of biofluorescent aerosol emissions over winter and summer periods in the United Kingdom

Abstract. Primary biological aerosol particles (PBAPs) are an abundant subset of atmospheric aerosol particles which comprise viruses, bacteria, fungal spores, pollen, and fragments such as plant and animal debris. The abundance and diversity of these particles remain poorly constrained, causing significant uncertainties for modelling scenarios and for understanding the potential implications of these particles in different environments. PBAP concentrations were studied at four different sites in the United Kingdom (Weybourne, Davidstow, Capel Dewi, and Chilbolton) using an ultraviolet light-induced fluorescence (UV-LIF) instrument, the Wideband Integrated Bioaerosol Spectrometer (WIBS), versions 3 and 4. Using hierarchical agglomerative cluster (HAC) analysis, particles were statistically discriminated. Fluorescent particles and clusters were then analysed by comparing to laboratory data of known particle types, assessing their diurnal variation and examining their relationship to the meteorological variables temperature, relative humidity, wind speed, and wind direction. Using local land cover types, sources of the suspected fluorescent particles and clusters were then identified. Most sites exhibited a wet discharged fungal spore dominance, with the exception of one site, Davidstow, which had higher concentrations of bacteria, suggested to result from the presence of a local dairy factory and farm. Differences were identified as to the sources of wet discharged fungal spores, with particles originating from arable and horticultural land at Chilbolton, and improved grassland areas at Weybourne. Total fluorescent particles at Capel Dewi were inferred to comprise two sources, with bacteria originating from the broadleaf and coniferous woodland and wet discharged fungal spores from nearby improved grassland areas, similar to Weybourne. The use of the HAC method and a higher fluorescence threshold (9 standard deviations instead of 3) produced clusters which were considered to be biological following the complete analysis. More published data and information on the reaction of different speciated biological particle types to fluctuations in meteorological conditions, such as relative humidity and temperature, would aid particle type characterisation in studies such as this.

Heavy metals in the near-road environment: Results of semi-continuous monitoring of ambient particulate matter in the greater Toronto and Hamilton area

Abstract Six heavy metals - Mn, Fe, Cu, Zn, Se, and Pb among other elemental species were monitored in ambient PM2.5 at three near-road ambient air monitoring locations in the Greater Toronto and Hamilton Area (GTHA) with semi-continuous X-ray fluorescence (XRF) instrumentation over a period spanning January 1st, 2014 to June 30th, 2017. Land use in these air monitoring locations includes residential, institutional and industrial, thus, air monitoring is representative of typical urban areas. Ambient metal concentrations were found below Ontario's ambient air quality criteria. Temporal trends however indicated that high concentrations of Fe and Cu correlated with peak commuting and working hours on weekdays. To further understand the potential sources of these metals, scatterplots of metal concentrations and criteria pollutant gases were made on weekdays and weekends. These scatterplots reveal edges that are due to multiple sources of these metals. When these scatterplots are colour-coded by the hour of day, edges associated with the morning rush hour on weekdays for Fe and Cu (also Mn and Zn to a lesser extent) likely due to traffic-related emissions are more clearly-delineated from other edges arising from industrial or regional sources that were prevalent during other times of the day. Finally, an auxiliary receptor model was used to explore the potential source regions of these metals. It was observed that Mn, Fe and Cu had intense potential source regions within the GTHA on weekdays that diminished on the weekends, and in the case of Fe, the potential source regions in the GTHA were sensitive to the morning rush hour period, indicating that traffic-related emissions are a major source of Fe. Other metals, especially Zn, Se and Pb have source regions that are less sensitive to the morning rush hour period and are usually situated outside the GTHA.

Hand-held X-ray fluorescence spectrometry

This Technical Brief describes the evolution of hand-held X-ray fluorescence instrumentation designed for inorganic elemental analysis outside the confines of a laboratory, thereby offering the capability for in situ analysis. As well as providing an overview of the instrumentation, it aims to inform both analysts and less-technically aware users how the technique may be used for a comprehensive assessment of a complex measurement problem and enable on-site decision making.

Stain-free LED scanning lifetime imaging system for diabetes modified tissue matrices.

In contrast to labor intensive and destructive histological techniques, intrinsic autofluorescence lifetimes of extra cellular matrix proteins can provide label-free imaging of tissue modifications in diseases, including the diabetic ulcers. However, decoupling the complex mixture of tissue fluorophores requires costly and complicated fluorescent lifetime instrumentation. Furthermore, a list of autofluorescent and fluorogenic proteins must be characterized to profile their changes during disease progression. Towards these goals, an imaging system based on frequency domain light-emitting diode (LED) modulation was designed and demonstrated, using off-the-shelf components in a low complexity design. The system was operated by coupling and imaging fluorescence intensities using a pair of objectives. The system's scanning and signal acquisition performances were optimized with respect to etendues. To study fluorescent proteins in diabetic ulcers, lifetimes from purified and pentosidine modified collagen I, collagen III, and elastin were measured. Pentosidine measurements showed a decrease in autofluorescent lifetimes while elevated collagen III in diabetic ulcers showed increased lifetimes. These lifetimes, plus future protein measurements enabled by our system, can serve as standards for developing a biophotonic model of diabetic ulcers. As a proof-of-concept, a 3 cm × 3 cm diabetic foot ulcer was imaged using the developed system. Phasor analysis was applied to aid the interpretation of lifetime images. As a result, a compact biophotonic imaging system targeting diabetic tissue was achieved, towards making the technique accessible for clinical histology.

Machine learning for improved data analysis of biological aerosol using the WIBS

Abstract. Primary biological aerosol including bacteria, fungal spores and pollen have important implications for public health and the environment. Such particles may have different concentrations of chemical fluorophores and will respond differently in the presence of ultraviolet light, potentially allowing for different types of biological aerosol to be discriminated. Development of ultraviolet light induced fluorescence (UV-LIF) instruments such as the Wideband Integrated Bioaerosol Sensor (WIBS) has allowed for size, morphology and fluorescence measurements to be collected in real-time. However, it is unclear without studying instrument responses in the laboratory, the extent to which different types of particles can be discriminated. Collection of laboratory data is vital to validate any approach used to analyse data and ensure that the data available is utilized as effectively as possible. In this paper a variety of methodologies are tested on a range of particles collected in the laboratory. Hierarchical agglomerative clustering (HAC) has been previously applied to UV-LIF data in a number of studies and is tested alongside other algorithms that could be used to solve the classification problem: Density Based Spectral Clustering and Noise (DBSCAN), k-means and gradient boosting. Whilst HAC was able to effectively discriminate between reference narrow-size distribution PSL particles, yielding a classification error of only 1.8 %, similar results were not obtained when testing on laboratory generated aerosol where the classification error was found to be between 11.5 % and 24.2 %. Furthermore, there is a large uncertainty in this approach in terms of the data preparation and the cluster index used, and we were unable to attain consistent results across the different sets of laboratory generated aerosol tested. The lowest classification errors were obtained using gradient boosting, where the misclassification rate was between 4.38 % and 5.42 %. The largest contribution to the error, in the case of the higher misclassification rate, was the pollen samples where 28.5 % of the samples were incorrectly classified as fungal spores. The technique was robust to changes in data preparation provided a fluorescent threshold was applied to the data. In the event that laboratory training data are unavailable, DBSCAN was found to be a potential alternative to HAC. In the case of one of the data sets where 22.9 % of the data were left unclassified we were able to produce three distinct clusters obtaining a classification error of only 1.42 % on the classified data. These results could not be replicated for the other data set where 26.8 % of the data were not classified and a classification error of 13.8 % was obtained. This method, like HAC, also appeared to be heavily dependent on data preparation, requiring a different selection of parameters depending on the preparation used. Further analysis will also be required to confirm our selection of the parameters when using this method on ambient data. There is a clear need for the collection of additional laboratory generated aerosol to improve interpretation of current databases and to aid in the analysis of data collected from an ambient environment. New instruments with a greater resolution are likely to improve on current discrimination between pollen, bacteria and fungal spores and even between different species, however the need for extensive laboratory data sets will grow as a result.

The associations between lead exposure at multiple sensitive life periods and dental caries risks in permanent teeth

BackgroundDental caries is an important public health problem in Mexico, a country also faced with high exposure to toxicants including lead (Pb). MethodsParticipants were 386 children living in Mexico City. Prenatal (trimester 1–3), early-childhood (12, 24, 36, and 48 months of age) and peri-pubertal (10–18 years of age) blood Pb levels were quantified using graphite-furnace atomic-absorption spectroscopy. Maternal patella and tibia bone Pb at 1 month postpartum were quantified with K X-ray fluorescence instrument. Dental caries presence was evaluated using decayed, missing, and filled teeth (DMFT) scores. Peri-pubertal sugar sweetened beverage (SSB) intake was estimated using a 116-item, interview-administered semi-quantitative food frequency questionnaire (FFQ). Total energy adjusted daily SSB intake was generated using the residual approach. Zero inflated negative binomial (ZINB) Poisson regression models were used to examine the associations between Pb with D1MFT and D4MFT at adolescence. ResultsMaternal second and third trimester and cumulative early childhood Pb exposure were positively associated with peri-pubertal D1MFT scores in unadjusted ZINB models (2nd trimester: RR = 1.17 (1.00, 1.37); 3rd trimester: RR = 1.20 (1.03, 1.40); early childhood: RR = 1.22 (1.02, 1.48)). These effect sizes were attenuated and no longer statistically significant after adjusting for covariates. When stratified by high/low SSB intake, a one unit increase of log-transformed 2nd trimester Pb exposure was associated with a 1.41 times (1.06, 1.86) higher D1MFT count, and 3rd trimester Pb exposure was associated with a 1.50 times (1.18, 1.90) higher D1MFT count among those with higher than median peri-pubertal SSB. Associations among those with lower SSB intake were roughly half those of the higher group and not statistically significant. ConclusionsPb exposure during sensitive developmental periods was not statistically significantly associated with caries risk after accounting for confounders among our cohort. However, evidence from stratified analysis suggested a Pb-caries association among children with high SSB intake.

A prototype handheld X-ray diffraction instrument.

A conceptual design for a handheld X-ray diffraction (HHXRD) instrument is proposed. Central to the design is the application of energy-dispersive XRD (EDXRD) in a back-reflection geometry. This technique brings unique advantages which enable a handheld instrument format, most notably, insensitivity to sample morphology and to the precise sample position relative to the instrument. For fine-grained samples, including many geological specimens and the majority of common alloys, these characteristics negate sample preparation requirements. A prototype HHXRD device has been developed by minor modification of a handheld X-ray fluorescence instrument, and the performance of the prototype has been tested with samples relevant to mining/quarrying and with an extensive range of metal samples. It is shown, for example, that the mineralogical composition of iron-ore samples can be approximately quantified. In metals analysis, identification and quantification of the major phases have been demonstrated, along with extraction of lattice parameters. Texture analysis is also possible and a simple example for a phosphor bronze sample is presented. Instrument formats other than handheld are possible and online process control in metals production is a promising area. The prototype instrument requires extended measurement times but it is argued that a purpose-designed instrument can achieve data-acquisition times below one minute. HHXRD based on back-reflection EDXRD is limited by the low resolution of diffraction peaks and interference by overlapping fluorescence peaks and, for these reasons, cannot serve as a general-purpose XRD tool. However, the advantages of in situ, nondestructive and rapid measurement, tolerance of irregular surfaces, and no sample preparation requirement in many cases are potentially transformative. For targeted applications in which the analysis meets commercially relevant performance criteria, HHXRD could become the method of choice through sheer speed and convenience.

Optimized Compton fitting and modeling for light element determination in micro-X-ray fluorescence map datasets

The Planetary Instrument for X-ray Lithochemistry (PIXL) is an X-ray fluorescence instrument scheduled to fly to Mars on NASA’s 2020 rover (Allwood et al., 2015). It will be capable of quantifying elements with atomic number of at least 11 using X-ray fluorescence (XRF), but the detector window blocks fluorescence from lighter elements. Important elements otherwise invisible include carbon, oxygen, and nitrogen, which can make up anions in minerals of scientific interest. X-rays scattered by all elements can be detected, so the ratio of Compton to Rayleigh scatter may be measured and used to infer the presence of elements for which there is no detectable fluorescence. We have refined a fundamental parameters model to predict the Compton/Rayleigh ratio for any given composition that can be compared to an experimentally measured ratio. We compare with a published Monte Carlo model (Schoonjans et al., 2012) and to experimental values for a set of seven materials. Compton/Rayleigh ratios predicted by the model are in good, though imperfect, agreement with experimental measurements. A procedure for consistently computing the Compton/Rayleigh ratio from a noisy spectrum has also been developed using a variation on a common background removal method and peak fitting.

Evaluation of a hierarchical agglomerative clustering method applied to WIBS laboratory data for improved discrimination of biological particles by comparing data preparation techniques

Abstract. Hierarchical agglomerative clustering (HAC) analysis has been successfully applied to several sets of ambient data (e.g., Crawford et al., 2015; Robinson et al., 2013) and with respect to standardized particles in the laboratory environment (Ruske et al., 2017, 2018). Here we show for the first time a systematic application of HAC to a comprehensive set of laboratory data collected for many individual particle types using the wideband integrated bioaerosol sensor (WIBS-4A) (Savage et al., 2017). The impact of the ratio of particle concentrations on HAC results was investigated, showing that clustering quality can vary dramatically as a function of ratio. Six strategies for particle preprocessing were also compared, concluding that using raw fluorescence intensity (without normalizing to particle size) and logarithmically transforming data values (scenario B) consistently produced the highest-quality results for the particle types analyzed. A total of 23 one-to-one matchups of individual particles types was investigated. Results showed a cluster misclassification of < 15 % for 12 of 17 numerical experiments using one biological and one nonbiological particle type each. Inputting fluorescence data using a baseline +3σ threshold produced a lower degree of misclassification than when inputting either all particles (without a fluorescence threshold) or a baseline +9σ threshold. Lastly, six numerical simulations of mixtures of four to seven components were analyzed using HAC. These results show that a range of 12 %–24 % of fungal clusters was consistently misclassified by inclusion of a mixture of nonbiological materials, whereas bacteria and diesel soot were each able to be separated with nearly 100 % efficiency. The study gives significant support to clustering analysis commonly being applied to data from commercial ultraviolet laser/light-induced fluorescence (UV-LIF) instruments used for bioaerosol research across the globe and provides practical tools that will improve clustering results within scientific studies as a part of diverse research disciplines.

Determining re-refined engine oil bottom content in asphalt binders using a handheld X-ray fluorescence instrument

Re-refined engine oil bottoms (REOB) are major modifiers used to produce softer binders from stiffer binders. Studies have revealed that pavements constructed with REOB-modified binders experience premature cracking and ravelling problems much sooner than usual. Therefore, some state agencies in the US have enacted regulatory measures on the use of REOB-modified binders in their contracts. To implement these measures, there is a need of a well-verified, cost friendly test method that can accurately estimate REOB contents in binders used in these contracts on site. This paper presents a simple method that fulfils this objective. The method involves the measurement of element concentrations in an unknown sample using a portable X-ray fluorescence (XRF) instrument, the identification of the most likely sources of this sample using normalised sulphur-versus-vanadium concentration plot, and the estimation of REOB content in the sample using the calibration curves of zinc, calcium and molybdenum elements. Researchers developed and verified this method using 384 calibration and 24 verification samples. Test results show the proposed method can quantify REOB content in binders with reasonable accuracy. Test results also show that this portable XRF-based REOB estimation method is as effective as a previous benchtop instrument-based REOB estimation method.

Lead poisoning

Lead is not known to have any physiological role in the body but is ubiquitous in nature. In our country there are many sources of lead exposure, in particular paints and recycling of batteries. Lead is a persistent metal and is present in water, soil and dust. After being absorbed through the gastrointestinal tract (GIT) or respiratory system, it is stored in soft tissues as well as bones. Lead tends to affect many organ systems in the body particularly the nervous system and kidneys. There are no safe levels and data suggests that low level exposure to lead may also affect health of individuals. The diagnosis of lead toxicity can be done by measuring blood lead levels and K x ray fluorescence (KXRF) instruments which measure lead levels in bone. The treatment consists of chelating agents like BAL, EDTA & DMSA. Eliminating lead from potential sources of exposure would go a long way in preventing effects of lead toxicity.

Field and laboratory evaluation of a high time resolution x-ray fluorescence instrument for determining the elemental composition of ambient aerosols

Abstract. Measuring the chemical composition of airborne particulate matter (PM) can provide valuable information on the concentration of regulated toxic metals, support modelling approaches for source detection and assist in the identification and validation of abatement techniques. Undertaking these at a high time resolution (1 h or less) enables receptor modelling techniques to be more robustly linked to emission processes. This study describes a comprehensive laboratory and field evaluation of a high time resolution x-ray fluorescence (XRF) instrument (CES XACT 625) for a range of elements (As, Ba, Ca, Cd, Ce, Cl, Cr, Cu, Fe, K, Mn, Mo, Ni, Pb, Pt, S, Sb, Se, Si, Sr, Ti, V and Zn) against alternative techniques: high time resolution mass measurements, high time resolution ion chromatography, aerosol mass spectrometry, and established filter-based, laboratory analysis using inductively coupled plasma mass spectrometry (ICP-MS). Laboratory evaluation was carried out using a novel mass-based calibration technique to independently assess the accuracy of the XRF against laboratory generated aerosols, which resulted in slopes that were not significantly different from unity. This demonstrated that generated particles can serve as an alternative calibration method for this instrument.The XACT was evaluated in three contrasting field deployments; a heavily trafficked roadside site (PM10 and PM2.5), an industrial location downwind of a nickel refinery (PM10) and an urban background location influenced by nearby industries and motorways (PM10). The XRF technique agreed well with the ICP-MS measurements of daily filter samples in all cases with a median R2 of 0.93 and a median slope of 1.07 for the elements As, Ba, Ca, Cr, Cu, Fe, K, Mn, Ni, Pb, Se, Sr, Ti, V and Zn. Differences in the results were attributed to a combination of inlet location and sampling temperature, variable blank levels in filter paper and recovery rates from acid digestion. The XRF technique also agreed well with the other high time resolution measurements but showed a clear positive difference (slopes between 1.41 and 4.6), probably due to differences in the size selection methodology, volatility and water solubility of the PM in aerosol mass spectrometry (SO4) and ion chromatography (Ca, Cl, K and SO4), respectively.A novel filter analysis technique using the XACT showed promising initial results: filters analysed off-line with the XACT compared well to in situ XACT measurements with a median R2 of 0.96 and median slope of 1.07. The resulting range of slopes was comparable to slopes produced in the ICP-MS comparison. This technique provides an opportunity to use the XACT when it is not deployed in the field; thus expanding the potential use of this instrument in future studies.

A dual geochemical‐phytolith methodology for studying activity areas in ephemeral sites: Insights from an ethnographic case study from Jordan

AbstractThis study aims to contribute to the interpretation of ephemeral sites by exploring the efficacy of geochemistry and phytolith analysis to identify activity areas in seasonally occupied ethnographic sites. The application of a portable X‐ray fluorescence (XRF) instrument and phytolith analysis to soil samples from six Bedouin campsites at Wadi Faynan, Jordan, provided insights about anthropogenic enrichment patterns and the effects of short periods of abandonment on these. The compatibility of the two analysis techniques and means to combine the results of both are addressed. The results of this study suggest that soil signatures can be found in ephemeral sites following abandonment, even in dynamic and harsh environments. The efficacy of the geochemical analysis to indicate variance within the data was found to be greater than that of the phytolith analysis in these case studies, while certain trends within the phytolith results were more useful in identifying specific activities. Due to the compatibility of the geochemical and phytolith data, it is proposed that a serial or parallel approach should be taken for their statistical analysis.

Portable X-ray fluorescence for the detection of POP-BFRs in waste plastics

The purpose of this study was to establish the efficacy of portable X-ray fluorescence (XRF) instrumentation as a screening tool for a variety of end of life plastics which may contain excess amounts of brominated flame retardants (BFRs), in compliance with European Union (EU) and United Nations Environment Programme (UNEP) legislative limits (low POP concentration limits – LPCLs). 555 samples of waste plastics were collected from eight waste and recycling sites in Ireland, including waste electrical and electronic equipment (WEEE), textiles, polyurethane foams (PUFs), and expanded polystyrene foams. Samples were screened for bromine content, in situ using a Niton™ XL3T GOLDD XRF analyser, the results of which were statistically compared to mass spectrometry (MS)-based measurements of polybrominated diphenyl ethers (PBDEs), hexabromocyclododecane (HBCDD) and tetrabromobisphenol-A (TBBP-A) concentrations in the same samples.Regression between XRF and MS for WEEE samples shows that, despite an overall favourable trend, large deviations occur for a cluster of samples indicative of other bromine-based compounds in some samples; even compensating for false-positives due to background interference from electronic components, XRF tends to over-estimate MS-determined BFR concentrations in the 100 to 10,000 mg kg−1 range. Substantial deviations were additionally found between results for PUFs, textiles and polystyrene samples, with the XRF over-estimating BFR concentrations by a factor of up to 1.9; this is likely due to matrix effects influencing XRF measurements. However, expanded (EPS) and extruded polystyrene (XPS) yielded much more reliable estimations of BFR-content due to a dominance of HBCDD in these materials.XRF proved much more reliable as a “pass/fail” screening tool for LPCL compliance (including a prospective LPCL on Deca-BDE based on REACH). Using a conservative threshold of BFR content exceeding legislative limits (710 mg kg−1 bromine attributed to Penta-BDE), XRF mistakenly identifies only 6 % of samples (34/555) as exceeding legislative limits.

Evaluation of high resolution X-ray monochromatic wavelength dispersive X-ray fluorescence instrument for determining Pu and U in nuclear reprocessing streams

An alpha-prototype benchtop instrument was developed and tested for measuring Pu and U in spent fuel dissolver tanks in a nuclear fuel reprocessing plant. The high resolution X-ray (hiRX) instrument was designed with the aim of providing a new capability to measure samples with high radiation background with selectivity, accuracy, and precision using ultra-low volumes (7 μL) of liquid. The instrument was tested with specimens from the operational reprocessing facility at Savannah River National Laboratory. The results showed that bias was <6% for Pu nitrate process solution and < 18% for Pu in U/HNO3 matrix. Instrumental precision was <1% RSD while between microcell repeatability was <6% RSD. The limit of detection for Pu in HNO3 matrix was 3 × 10−5 g/L (100 s, 35 W). This study demonstrates that hiRX technology has the potential to provide rapid and simultaneous quantification of Pu and U without sample preparation, making it suitable for process monitoring and materials control and accountability applications.

Accurate experimental determination of gallium K- and L3-shell XRF fundamental parameters

The fluorescence yield of the K- and L3-shell of gallium was determined using the radiometrically calibrated (reference-free) X-ray fluorescence instrumentation at the BESSY II synchrotron radiation facility.

Identification of Uranium Minerals in Natural U-Bearing Rocks Using Infrared Reflectance Spectroscopy

The identification of minerals, including uranium-bearing species, is often a labor-intensive process using X-ray diffraction (XRD), fluorescence, or other solid-phase or wet chemical techniques. While handheld XRD and fluorescence instruments can aid in field applications, handheld infrared (IR) reflectance spectrometers can now also be used in industrial or field environments, with rapid, nondestructive identification possible via analysis of the solid's reflectance spectrum providing information not found in other techniques. In this paper, we report the use of laboratory methods that measure the IR hemispherical reflectance of solids using an integrating sphere and have applied it to the identification of mineral mixtures (i.e., rocks), with widely varying percentages of uranium mineral content. We then apply classical least squares (CLS) and multivariate curve resolution (MCR) methods to better discriminate the minerals (along with two pure uranium chemicals U3O8 and UO2) against many common natural and anthropogenic background materials (e.g., silica sand, asphalt, calcite, K-feldspar) with good success. Ground truth as to mineral content was attained primarily by XRD. Identification is facile and specific, both for samples that are pure or are partially composed of uranium (e.g., boltwoodite, tyuyamunite, etc.) or non-uranium minerals. The characteristic IR bands generate unique (or class-specific) bands, typically arising from similar chemical moieties or functional groups in the minerals: uranyls, phosphates, silicates, etc. In some cases, the chemical groups that provide spectral discrimination in the longwave IR reflectance by generating upward-going (reststrahlen) bands can provide discrimination in the midwave and shortwave IR via downward-going absorption features, i.e., weaker overtone or combination bands arising from the same chemical moieties.