X-ray fluorescence (XRF) detection of heavy metals is a cost- and time-effective method for investigation of polluted areas. Compared to laboratory analysis, XRF analysis is limited by high detection limits and uncertainties in some situations. Preparation of samples is known to affect the results of measurements. The purpose of this thesis is to bring a deeper understanding of how different factors affect the results of XRF-analysis. A large number of measurements have been made with the instruments Niton XLt 700 and Niton Xli 700. Results from measurements of lead, zinc and copper have been analysed. This study has shown that a greater moisture content will give a lower measured concentration for the same sample. If the moisture content is known, it is possible to make good approximations of concentrations in dry samples. No obvious differences were found between different metals. Proper homogenisation of samples was found to be one of the most critical issues. It should be noted that laboratories do not usually homogenise samples prior to analysis, so samples sent for laboratory verification should therefore be homogenised before sending. Sample preparation, including drying, sieving to finer grain-sizes and analysing in a special sample cup was found to increase the measured concentrations and decrease the variation between measurements. The concentrations differed with different sample matrices and with sample preparation. Because of the differences, measurements should always be correlated with laboratory analysis before any conclusions can be made. In situations when metals are well within detection range of the XRF instrument, the only preparation needed is in most cases homogenisation. If metal levels are just at the limit, or just below the detection limit, further preparations of samples should be made. When drying samples makes detection possible, more preparation is usually not worth the effort. If detection limits still are a problem after drying, the samples should be sieved and analysed in sample cups. In situations where concentrations still are below the detection limit when analysing in sample cups, or if the measurements are disturbed for other reasons, another method than XRF-analysis must be used. When XRF analysis is possible, the method is preferable compared to only laboratory analysis. This cost- and time effective method makes a larger number of measurements possible, and gives a more complete overview of a polluted area. / Analys med röntgenfluorescensdetektor (XRF) är en snabb och kostnadseffektiv fältmetod för detektion av tungmetaller i mark. Nackdelen är att mätningarna inte är tillförlitliga i alla sammanhang och att detektionsgränsen för många ämnen är förhållandevis hög. Det är sedan tidigare känt att olika former av provbearbetning påverkar mätresultaten. I detta examensarbete har undersökts hur olika faktorer påverkar mätresultaten vid analys av jordprover med XRF instrument. Faktorerna som undersökts är inverkan av vattenkvot, kornstorlek, provpåsar och olika provbearbetningsmetoder. Vid provbearbetningsförsöken skickades prover även in till externt laboratorium för jämförande analys. Metaller som undersökts är bly, zink och koppar. Vid undersökningen konstaterades att en ökad vattenkvot ger upphov till lägre mätvärden. Vid kännedom om vattenkvot kan halt per torrsubstans med god överensstämmelse uppskattas utifrån mätningar på fuktiga prov. Är precisionskraven stora och vattenkvoten varierande och okänd bör dock proverna torkas innan mätningar görs. Ingen avsevärd skillnad sågs mellan de olika metaller som undersöktes. Vid undersökningen om provbearbetningens betydelse visade det sig att homogeniseringen av proverna är mycket viktig, inte minst av prover som skickas till laboratorieanalys. Ökad provbearbetning med torkning och siktning till mindre kornstorlek tenderar att ge högre mätvärden med XRF instrument. Storleksmässigt är mätvärden vid obearbetade prov mest överensstämmande med laboratorieanalys. Mest skiljer sig analys på finsiktade prover i provkopp. Korrelationsmässigt finns i en del fall en tendens till bättre överensstämmelse med mer bearbetade prov. Den största vinsten med ökad bearbetning av prover konstaterades i detta arbete vara att mark med lägre metallkoncentrationer då kan analyseras. I de fall där halterna av metaller ligger väl inom XRF instrumentets detektionsområde visade det sig att det oftast är tillräckligt att endast homogenisera proverna innan analys görs. I de fall där koncentrationen av metaller är på gränsen till vad XRF instrumentet kan detektera rekommenderas att proverna torkas, eller om nödvändigt torkas, siktas och analyseras i provkopp. Där nivåerna av metaller ligger under detektionsgränsen för XRF instrument trots provbearbetning, eller där andra ämnen till exempel järn stör mätningarna, måste en annan analysmetod väljas.

The purpose of this research is to develop a rapid determination method for heavy metals in soil. Using X-ray fluorescence to obtain soil metals decision limit (CC£\) and detection capability (CC£]), to establish the scope of soil metal concentration selection. Then aqua regia digestion digestion and ICP-OES analysis of Pb, Cd, Zn, Ni, Cr, Cu area to check the accuracy of screening. Operating conditions; First, the soil standard samples for the Establishment and assessment of the applicability of the standard. Finally,using of the soil near the control standard establish methods and explore ways to establish the applicability and potential impact. I hope this research can provide a fast, accurate, and sensitivity of soil heavy metal screening, to achieve savings of cost. The results show that the standard reference soil Cu: screening rate was 79.7%, sensitivity was 43.6% and an specificity of 87.7%; reference standard soil Pb: screening rate was 91.5%, a sensitivity of 8.3% specificity 91.5%;reference standard soil Cr:screening rate was 100%, sensitivity was 0%, 100% specificity; reference standard soil Ni: screening rate was 96.1%, sensitivity was 0%, specificity 92.4%; reference standard soil Zn: screening rate was 82.4%, sensitivity was 69.2%, specificity 87.1%; reaching control values of soil Cu: screening rate was 83.0%, sensitivity was 30.8%, specificity of 84.3%. Screening rate and specificity with 80%, the sensitivity poor areas, water was the major disturbance factor.

This research developed an on-line measurement systemfor determining the amount of fluorochemicals on carpet fibers using energy-dispersive X-ray fluorescence (EDXRF).This system is designed as a complementary tool to an existingchemical burn test certified by the American Association ofTextile Chemists and Colorists (AATCC), which is performed off-line on randomly selected carpet samples and time consuming.This research reviewed XRF principles and determined parameters that affect XRF spectra such as measurement time, measurement number, X-ray tube voltage, X-ray tube current, primary beam filter, and carpet characteristics. For this application, XRF calibrations must be performed for carpets of all styles and types. However, preparing actual carpet calibration samples is expensive. This research introduced a methodology to synthetically generate reference spectra using XRF spectra from standard fluorochemical stock solution samples and from base carpet samples for each carpet type to be tested. Thus, actual, physical standards are not required for each carpet type or style. This study showed that the synthetically generated XRF spectra alone were not always sufficient to guarantee the confidence interval required by the certified AATCC test. Thus, it is recommended that for on-line implementation, burn test results should be used to create a historical data base for each carpet type to reduce margin of error for calibrations generated from the synthetic spectra.

In the north of Sweden lots of the soil is naturally contaminated by acid sulfate. When soil gets in contact with oxygen an oxidation process begins which releases elements that may be harmful to the surroundings. When the Botniabanan was built, soil had to be transported from the railroad area to deposit sites. This study was made to investigate the suspicions a landowner had regarding if his estate had been contaminated sulphide soil soil during the building of the Botniabanan. To do that four pits were dug in the area where the soil had been deposited. Then the soil was analyzed to see the content of sulfate, iron, organic matters and water. When the results was compared to other studies it showed that the content of sulfate and organic matters was to low to classify the soil as an acid sulfate soil.

The objective of this thesis is to categorize carpet types according to their XRF spectra and verify if further classification of carpets is possible for use of an XRF analysis system in the carpet manufacturing line. This thesis consists of (1) implementing and studying effective algorithms for automated analysis of X-ray spectra, (2) comparing known algorithms for X-ray spectra analysis, and (3) implementing our own algorithm for classification of carpets spectra obtained for further fluorine online analysis of XRF inspected carpets. This research is intended for quick and accurate automated analysis of raw XRF spectra and matching analysis results to a database of XRF spectra of raw carpets. The research uses spectrum signal processing and spectrum analysis regarding efficacy of combined methods for XRF inspected carpets. X-Ray Fluorescence is a key technology for detection of chemical elements. Fluorine is a key element for carpet's quality. XRF has been chosen to be a potential candidate to measure fluorine since it is a versatile tool for low concentration element detection. Due to specific XRF background spectrum for each different carpet type, carpet samples may need specific calibrations for further computation of carpet fluorine concentration. Automating the detection of the carpet type is intended to help in automating the XRF calibration.

71f. / Submitted by Ana Hilda Fonseca (anahilda@ufba.br) on 2013-04-09T13:15:43Z No. of bitstreams: 1 dissertação ALETE_definitiva_110330.pdf: 1412727 bytes, checksum: c409be4d388a7ed5944c1d0866387a9d (MD5) / Approved for entry into archive by Ana Hilda Fonseca(anahilda@ufba.br) on 2013-04-19T14:50:36Z (GMT) No. of bitstreams: 1 dissertação ALETE_definitiva_110330.pdf: 1412727 bytes, checksum: c409be4d388a7ed5944c1d0866387a9d (MD5) / Made available in DSpace on 2013-04-19T14:50:36Z (GMT). No. of bitstreams: 1 dissertação ALETE_definitiva_110330.pdf: 1412727 bytes, checksum: c409be4d388a7ed5944c1d0866387a9d (MD5) Previous issue date: 2010 / CAPES / O objetivo principal do trabalho foi à utilização da espectrometria de fluorescência de raios X com energia dispersiva (EDXRF) para determinação de elementos essenciais, tais como P, Cu, Fe, Mn e Zn em amostras de arroz na forma de pastilhas como método alternativo, obtendo resultados com precisão e exatidão aceitáveis no controle de qualidade dos alimentos. A validação foi feita comparando os resultados obtidos pelo método proposto com valores certificados e com aqueles obtidos utilizando decomposição das amostras em forno de micro-ondas com cavidade e os digeridos foram usados para determinação dos analitos por espectrometria de emissão óptica com plasma indutivamente acoplado (ICP OES) e espectrometria de massas com plasma indutivamente acoplado (ICP-MS). A precisão foi avaliada em termos da repetibilidade, sendo que foram preparadas onze pastilhas do material de referência certificado de farinha de arroz 1568a NIST e efetuadas três medições em cada pastilha obtendo-se estimativas do desvio padrão relativo inferiores a 5%. A exatidão foi verificada com o material de referência certificado (farinha de arroz 1568a NIST) e o t-teste pareado revelou que não havia diferença significativa entre os valores certificados e obtidos ao nível de confiança de 95%. Foram obtidos os seguintes limites de detecção (LODs): 0,037 g 100g-1 para P e 1,2; 3,9; 5,1 e 2,2 mg Kg-1 para Cu, Fe, Mn e Zn, respectivamente. O procedimento proposto foi aplicado para P, Mn e Zn e apresenta vantagens tais como a redução do tempo de análise e a eliminação da etapa de decomposição da amostra, porém apresenta a desvantagem dos maiores LODs. De modo geral, os resultados são novas informações sobre a composição mineral do arroz consumido na cidade de Salvador, Bahia, sendo úteis para formação de base de dados. / Salvador

abstract: It is well known that the overall performance of a solar cell is limited by the worst performing areas of the device. These areas are usually micro and nano-scale defects inhomogenously distributed throughout the material. Mitigating and/or engineering these effects is necessary to provide a path towards increasing the efficiency of state-of-the-art solar cells. The first big challenge is to identify the nature, origin and impact of such defects across length scales that span multiple orders of magnitude, and dimensions (time, temperature etc.). In this work, I present a framework based on correlative X-ray microscopy and big data analytics to identify micro and nanoscale defects and their impact on material properties in CuIn1-xGaxSe2 (CIGS) solar cells. Synchrotron based X-ray Fluorescence (XRF) and X-ray Beam Induced Current (XBIC) are used to study the effect that compositional variations, between grains and at grain boundaries, have on CIGS device properties. An experimental approach is presented to correcting XRF and XBIC quantification of CIGS thin film solar cells. When applying XRF and XBIC to study low and high gallium CIGS devices, it was determined that increased copper and gallium at grain boundaries leads to increased collection efficiency at grain boundaries in low gallium absorbers. However, composition variations were not correlated with changes in collection efficiency in high gallium absorbers, despite the decreased collection efficiency observed at grain boundaries. Understanding the nature and impact of these defects is only half the battle; controlling or mitigating their impact is the next challenge. This requires a thorough understanding of the origin of these defects and their kinetics. For such a study, a temperature and atmosphere controlled in situ stage was developed. The stage was utilized to study CIGS films during a rapid thermal growth process. Comparing composition variations across different acquisition times and growth temperatures required the implementation of machine learning techniques, including clustering and classification algorithms. From the analysis, copper was determined to segregate the faster than indium and gallium, and clustering techniques showed consistent elemental segregation into copper rich and copper poor regions. Ways to improve the current framework and new applications are also discussed. / Dissertation/Thesis / Doctoral Dissertation Electrical Engineering 2018

The focus of this study is to detect any similarities – or lack thereof – between the alloys of different types of oval brooches from the later Iron Age in Scandinavia. The study is furthermore concerned with how the alloys and the typologies can be mutually complimentary to one another in regards to dating or determining the age of specific oval brooches. For this purpose X-ray fluorescence (pXRF) was used on five different items deriving from Birka, Vendel and one of unknown context. The results indicate continuity with earlier studies regarding copper alloys with contents of zinc, and that this study’s brass brooches may have been produced in this alloy for its gold-like appearance. A higher level of lead can be found in the younger brooches, therefore indicating that tortoise brooches of a later date may contain more lead than their earlier counterparts. Furthermore, the study shows that brass may be mistaken for gold, and it raises questions about the use of metal originating from native copper sources. This study is a part of the Birka Black Earth Harbour project. / The Birka Black Earth Harbour project

Si bien podemos creer que el estudio de objetos arqueológicos y artísticos es de carácter netamente estilístico o histórico, en realidad, una aproximación a ellos a través de la química puede brindar información importante también.  En un país como el nuestro, con un amplio patrimonio cultural, es mucho lo que un químico puede hacer para ayudar a conocer mejor estos objetos y a saber conservarlos. / Although we may think that studies of archaeological and artistic objects are mainly historical or stylistic, a chemical approach can also provide important information about them.  In a country like ours, with a vast cultural heritage, a chemist can do a lot to further our knowledge of these objects and to help in their conservation.

Geochemistry has been used to determine the provenance and diagenetic history of eolian sandstone deposits. However, the grain size, sorting, cementation, and detrital composition of eolian units can change along dune foreset laminae. The purpose of this study was to test for consistent trends of compositional change along dune foresets. Such trends could increase the quality of geochemical sampling of eolian sandstones and possibly aid in estimating the original height of ancient sand dunes. XRF data was gathered for both major and trace elements from the Pennsylvanian to Permian Weber Sandstone, Early Jurassic Navajo Sandstone, and modern Coral Pink Sand Dunes of southern Utah. Data was plotted using both 2-dimensional scatter plots and 3-dimensional principal components analysis (PCA) plots. The PCA plots proved to be the most informative and suggest that there are no consistent, statistically significant geochemical trends within or between the three units sampled. However, this study found that PCA was able to show significant geochemical differences between the three units sampled, even when they are all dominated by a single mineral (>90% quartz). The Weber Sandstone had the most varied composition, and dunes within the unit could be highly dissimilar to each other. The Navajo Sandstone had less overall geochemical variability than the Weber Sandstone, and individual dunes were similar to each other. The modern Coral Pink Sand Dunes had much less compositional variation than either of the other two units, and dunes in this unit were very similar to each other.