@phdthesis{Brinkmann2022,
  author    = {Brinkmann, Pia},
  title     = {Laserinduzierte Breakdownspektroskopie zur qualitativen und quantitativen Bestimmung von Elementgehalten in geologischen Proben mittels multivariater Analysemethoden am Beispiel von Kupfer und ausgew{\"a}hlten Seltenen Erden},
  doi       = {10.25932/publishup-57212},
  url       = {http://nbn-resolving.de/urn:nbn:de:kobv:517-opus4-572128},
  school      = {Universit{\"a}t Potsdam},
  pages     = {148},
  year      = {2022},
  abstract  = {Ein schonender Umgang mit den Ressourcen und der Umwelt ist wesentlicher Bestandteil des modernen Bergbaus sowie der zuk{\"u}nftigen Versorgung unserer Gesellschaft mit essentiellen Rohstoffen. Die vorliegende Arbeit besch{\"a}ftigt sich mit der Entwicklung analytischer Strategien, die durch eine exakte und schnelle Vor-Ort-Analyse den technisch-praktischen Anforderungen des Bergbauprozesses gerecht werden und somit zu einer gezielten und nachhaltigen Nutzung von Rohstofflagerst{\"a}tten beitragen. Die Analysen basieren auf den spektroskopischen Daten, die mittels der laserinduzierten Breakdownspektroskopie (LIBS) erhalten und mittels multivariater Datenanalyse ausgewertet werden. Die LIB-Spektroskopie ist eine vielversprechende Technik f{\"u}r diese Aufgabe. Ihre Attraktivit{\"a}t machen insbesondere die M{\"o}glichkeiten aus, Feldproben vor Ort ohne Probennahme oder ‑vorbereitung messen zu k{\"o}nnen, aber auch die Detektierbarkeit s{\"a}mtlicher Elemente des Periodensystems und die Unabh{\"a}ngigkeit vom Aggregatzustand. In Kombination mit multivariater Datenanalyse kann eine schnelle Datenverarbeitung erfolgen, die Aussagen zur qualitativen Elementzusammensetzung der untersuchten Proben erlaubt. Mit dem Ziel die Verteilung der Elementgehalte in einer Lagerst{\"a}tte zu ermitteln, werden in dieser Arbeit Kalibrierungs- und Quantifizierungsstrategien evaluiert. F{\"u}r die Charakterisierung von Matrixeffekten und zur Klassifizierung von Mineralen werden explorative Datenanalysemethoden angewendet. Die spektroskopischen Untersuchungen erfolgen an B{\"o}den und Gesteinen sowie an Mineralen, die Kupfer oder Seltene Erdelemente beinhalten und aus verschiedenen Lagerst{\"a}tten bzw. von unterschiedlichen Agrarfl{\"a}chen stammen. F{\"u}r die Entwicklung einer Kalibrierungsstrategie wurden sowohl synthetische als auch Feldproben von zwei verschiedenen Agrarfl{\"a}chen mittels LIBS analysiert. Anhand der Beispielanalyten Calcium, Eisen und Magnesium erfolgte die auf uni- und multivariaten Methoden beruhende Evaluierung verschiedener Kalibrierungsmethoden. Grundlagen der Quantifizierungsstrategien sind die multivariaten Analysemethoden der partiellen Regression der kleinsten Quadrate (PLSR, von engl.: partial least squares regression) und der Intervall PLSR (iPLSR, von engl.: interval PLSR), die das gesamte detektierte Spektrum oder Teilspektren in der Analyse ber{\"u}cksichtigen. Der Untersuchung liegen synthetische sowie Feldproben von Kupfermineralen zugrunde als auch solche die Seltene Erdelemente beinhalten. Die Proben stammen aus verschiedenen Lagerst{\"a}tten und weisen unterschiedliche Begleitmatrices auf. Mittels der explorativen Datenanalyse erfolgte die Charakterisierung dieser Begleitmatrices. Die daf{\"u}r angewendete Hauptkomponentenanalyse gruppiert Daten anhand von Unterschieden und Regelm{\"a}ßigkeiten. Dies erlaubt Aussagen {\"u}ber Gemeinsamkeiten und Unterschiede der untersuchten Proben im Bezug auf ihre Herkunft, chemische Zusammensetzung oder lokal bedingte Auspr{\"a}gungen. Abschließend erfolgte die Klassifizierung kupferhaltiger Minerale auf Basis der nicht-negativen Tensorfaktorisierung. Diese Methode wurde mit dem Ziel verwendet, unbekannte Proben aufgrund ihrer Eigenschaften in Klassen einzuteilen. Die Verkn{\"u}pfung von LIBS und multivariater Datenanalyse bietet die M{\"o}glichkeit durch eine Analyse vor Ort auf eine Probennahme und die entsprechende Laboranalytik weitestgehend zu verzichten und kann somit zum Umweltschutz sowie einer Schonung der nat{\"u}rlichen Ressourcen bei der Prospektion und Exploration von neuen Erzg{\"a}ngen und Lagerst{\"a}tten beitragen. Die Verteilung von Elementgehalten der untersuchten Gebiete erm{\"o}glicht zudem einen gezielten Abbau und damit eine effiziente Nutzung der mineralischen Rohstoffe.},
  language  = {de}
}
@misc{BoescheRogassLubitzetal.2017,
  author    = {B{\"o}sche, Nina Kristine and Rogass, Christian and Lubitz, Christin and Brell, Maximilian and Herrmann, Sabrina and Mielke, Christian and Tonn, Sabine and Appelt, Oona and Altenberger, Uwe and Kaufmann, Hermann},
  title     = {Hyperspectral REE (Rare Earth Element) mapping of outcrops},
  url       = {http://nbn-resolving.de/urn:nbn:de:kobv:517-opus4-400171},
  pages     = {27},
  year      = {2017},
  abstract  = {In this study, an in situ application for identifying neodymium (Nd) enriched surface materials that uses multitemporal hyperspectral images is presented (HySpex sensor). Because of the narrow shape and shallow absorption depth of the neodymium absorption feature, a method was developed for enhancing and extracting the necessary information for neodymium from image spectra, even under illumination conditions that are not optimal. For this purpose, the two following approaches were developed: (1) reducing noise and analyzing changing illumination conditions by averaging multitemporal image scenes and (2) enhancing the depth of the desired absorption band by deconvolving every image spectrum with a Gaussian curve while the rest of the spectrum remains unchanged (Richardson-Lucy deconvolution). To evaluate these findings, nine field samples from the Fen complex in Norway were analyzed using handheld X-ray fluorescence devices and by conducting detailed laboratory-based geochemical rare earth element determinations. The result is a qualitative outcrop map that highlights zones that are enriched in neodymium. To reduce the influences of non-optimal illumination, particularly at the studied site, a minimum of seven single acquisitions is required. Sharpening the neodymium absorption band allows for robust mapping, even at the outer zones of enrichment. From the geochemical investigations, we found that iron oxides decrease the applicability of the method. However, iron-related absorption bands can be used as secondary indicators for sulfidic ore zones that are mainly enriched with rare earth elements. In summary, we found that hyperspectral spectroscopy is a noninvasive, fast and cost-saving method for determining neodymium at outcrop surfaces},
  language  = {en}
}
@article{RethfeldtBrinkmannRiebeetal.2021,
  author    = {Rethfeldt, Nina and Brinkmann, Pia and Riebe, Daniel and Beitz, Toralf and K{\"o}llner, Nicole and Altenberger, Uwe and L{\"o}hmannsr{\"o}ben, Hans-Gerd},
  title     = {Detection of Rare Earth Elements in Minerals and Soils by Laser-Induced Breakdown Spectroscopy (LIBS) Using Interval PLS},
  series = {Minerals},
  volume    = {11},
  journal   = {Minerals},
  publisher = {MDPI},
  address   = {Basel, Schweiz},
  issn      = {2075-163X},
  doi       = {10.3390/min11121379},
  pages     = {1 -- 17},
  year      = {2021},
  abstract  = {The numerous applications of rare earth elements (REE) has lead to a growing global demand and to the search for new REE deposits. One promising technique for exploration of these deposits is laser-induced breakdown spectroscopy (LIBS). Among a number of advantages of the technique is the possibility to perform on-site measurements without sample preparation. Since the exploration of a deposit is based on the analysis of various geological compartments of the surrounding area, REE-bearing rock and soil samples were analyzed in this work. The field samples are from three European REE deposits in Sweden and Norway. The focus is on the REE cerium, lanthanum, neodymium and yttrium. Two different approaches of data analysis were used for the evaluation. The first approach is univariate regression (UVR). While this approach was successful for the analysis of synthetic REE samples, the quantitative analysis of field samples from different sites was influenced by matrix effects. Principal component analysis (PCA) can be used to determine the origin of the samples from the three deposits. The second approach is based on multivariate regression methods, in particular interval PLS (iPLS) regression. In comparison to UVR, this method is better suited for the determination of REE contents in heterogeneous field samples. View Full-Text},
  language  = {en}
}
@misc{RethfeldtBrinkmannRiebeetal.2021,
  author    = {Rethfeldt, Nina and Brinkmann, Pia and Riebe, Daniel and Beitz, Toralf and K{\"o}llner, Nicole and Altenberger, Uwe and L{\"o}hmannsr{\"o}ben, Hans-Gerd},
  title     = {Detection of Rare Earth Elements in Minerals and Soils by Laser-Induced Breakdown Spectroscopy (LIBS) Using Interval PLS},
  series = {Zweitver{\"o}ffentlichungen der Universit{\"a}t Potsdam : Mathematisch-Naturwissenschaftliche Reihe},
  journal   = {Zweitver{\"o}ffentlichungen der Universit{\"a}t Potsdam : Mathematisch-Naturwissenschaftliche Reihe},
  publisher = {Universit{\"a}tsverlag Potsdam},
  address   = {Potsdam},
  issn      = {1866-8372},
  doi       = {10.25932/publishup-55746},
  url       = {http://nbn-resolving.de/urn:nbn:de:kobv:517-opus4-557469},
  pages     = {1 -- 17},
  year      = {2021},
  abstract  = {The numerous applications of rare earth elements (REE) has lead to a growing global demand and to the search for new REE deposits. One promising technique for exploration of these deposits is laser-induced breakdown spectroscopy (LIBS). Among a number of advantages of the technique is the possibility to perform on-site measurements without sample preparation. Since the exploration of a deposit is based on the analysis of various geological compartments of the surrounding area, REE-bearing rock and soil samples were analyzed in this work. The field samples are from three European REE deposits in Sweden and Norway. The focus is on the REE cerium, lanthanum, neodymium and yttrium. Two different approaches of data analysis were used for the evaluation. The first approach is univariate regression (UVR). While this approach was successful for the analysis of synthetic REE samples, the quantitative analysis of field samples from different sites was influenced by matrix effects. Principal component analysis (PCA) can be used to determine the origin of the samples from the three deposits. The second approach is based on multivariate regression methods, in particular interval PLS (iPLS) regression. In comparison to UVR, this method is better suited for the determination of REE contents in heterogeneous field samples. View Full-Text},
  language  = {en}
}
@phdthesis{Boesche2015,
  author    = {B{\"o}sche, Nina Kristine},
  title     = {Detection of rare earth elements and rare earth oxides with hyperspectral spectroscopy},
  url       = {http://nbn-resolving.de/urn:nbn:de:kobv:517-opus4-85363},
  school      = {Universit{\"a}t Potsdam},
  pages     = {147},
  year      = {2015},
  abstract  = {The continuously increasing demand for rare earth elements in technical components of modern technologies, brings the detection of new deposits closer into the focus of global exploration. One promising method to globally map important deposits might be remote sensing, since it has been used for a wide range of mineral mapping in the past. This doctoral thesis investigates the capacity of hyperspectral remote sensing for the detection of rare earth element deposits. The definition and the realization of a fundamental database on the spectral characteristics of rare earth oxides, rare earth metals and rare earth element bearing materials formed the basis of this thesis. To investigate these characteristics in the field, hyperspectral images of four outcrops in Fen Complex, Norway, were collected in the near-field. A new methodology (named REEMAP) was developed to delineate rare earth element enriched zones. The main steps of REEMAP are: 1) multitemporal weighted averaging of multiple images covering the sample area; 2) sharpening the rare earth related signals using a Gaussian high pass deconvolution technique that is calibrated on the standard deviation of a Gaussian-bell shaped curve that represents by the full width of half maxima of the target absorption band; 3) mathematical modeling of the target absorption band and highlighting of rare earth elements. REEMAP was further adapted to different hyperspectral sensors (EO-1 Hyperion and EnMAP) and a new test site (Lofdal, Namibia). Additionally, the hyperspectral signatures of associated minerals were investigated to serve as proxy for the host rocks. Finally, the capacity and limitations of spectroscopic rare earth element detection approaches in general and of the REEMAP approach specifically were investigated and discussed. One result of this doctoral thesis is that eight rare earth oxides show robust absorption bands and, therefore, can be used for hyperspectral detection methods. Additionally, the spectral signatures of iron oxides, iron-bearing sulfates, calcite and kaolinite can be used to detect metasomatic alteration zones and highlight the ore zone. One of the key results of this doctoral work is the developed REEMAP approach, which can be applied from near-field to space. The REEMAP approach enables rare earth element mapping especially for noisy images. Limiting factors are a low signal to noise ratio, a reduced spectral resolution, overlaying materials, atmospheric absorption residuals and non-optimal illumination conditions. Another key result of this doctoral thesis is the finding that the future hyperspectral EnMAP satellite (with its currently published specifications, June 2015) will be theoretically capable to detect absorption bands of erbium, dysprosium, holmium, neodymium and europium, thulium and samarium. This thesis presents a new methodology REEMAP that enables a spatially wide and rapid hyperspectral detection of rare earth elements in order to meet the demand for fast, extensive and efficient rare earth exploration (from near-field to space).},
  language  = {en}
}