Handheld X-ray Fluorescence Spectrometer Research Articles

Long‐term stability of invisible X‐ray fluorescence identification tags

AbstractThe traditional labelling of archive documents (e.g., hand stamping) entails several limitations. It could affect the aesthetic value of the archive document and is easy to find and remove in case of the theft of the document. The use of a label that would not be easily visible by the naked eye would resolve both of these problems. One possibility in designing such label is the use of the elements that have a good response in X‐ray fluorescence (XRF) spectrum, are not disturbing in colour, and are not usually present in the archive materials themselves. This study focuses on such type of labelling, specifically, the tags based on the oxides of lanthanum, dysprosium, samarium, gadolinium, and niobium. For the material to be taken into account by the community, it has to fulfil several important characteristics, such as harmlessness to the archival documents, non‐toxicity, or long‐term stability. In the study, the long‐term stability of these tags was studied on model samples of lignocellulose materials subjected to several types of artificial ageing. The colour changes and changes in the intensity of the responses of the individual elements in the XRF spectra were evaluated. To simulate the practical use, the tags of minimal visibility to the naked eye were printed on samples of real archive materials, and their potential for detection using a handheld XRF spectrometer was studied. Both of the research parts should help bring this type of labelling closer to the field application.

Sedimentary environment and facies of the Huagang Formation in the northern central Xihu Depression, East China Sea Basin, China

The sedimentary facies of the Huagang Formation, the major petroleum exploration horizon in the Xihu Depression in the East China Sea Basin, have not been well constrained, owing to limited drilling and core recovery. Interpretations are vague and vary from beach bar, braided river and braided-river delta front sediments. In this paper, the paleosedimentary environments of the Huagang Formation are discussed based on detailed organic and inorganic geochemical analysis and proxies used to interpret the sedimentary facies. Kerogen, dominated by sapropelinite, is mainly of Type I and Type II, and n-Paraffins are dominated by short-chain and medium-chain, with no obvious odd-over-even advantages. The distribution of isoprenoid alkanes and steroids indicates that the organic matter in mudstones is mainly of lacustrine and mixed origins. Elemental ratios of Th/U (4–6), V/Cr (1–4), Ni/Co (3–11) and V/(V + Ni) (0.5–0.75) indicate that in the area studied, the Huagang Formation was deposited under anoxic to reduced conditions with some oxygen-enriched horizons. Both inorganic and organic geochemical signatures show that the Huagang Formation was mainly deposited in an aquatic environment but with some minor periods of subaerial exposure. The sequence of the Huagang Formation is characterised by interbedded grey-white thick sandstones and grey-black thin mudstones. Normally graded cycles are widely developed, with rare mudstone in the upper part and scoured surfaces at the base. The cumulative grainsize distribution curve is mainly a two-stage type. The sedimentary facies indicative markers are dominated by braided-river channel deposits and combined with the paleosedimentary environments it is inferred that the sedimentary system in the study area was typical of a braided-river delta front. The cores available were intensively analysed using a hand-held X-ray fluorescence spectrometer to probe the variations in the paleoclimate and show that the braided-river channels were controlled by paleoclimate. During arid climatic settings, the sediments within individual channels were thin, and grainsizes varied significantly; at the base of each channel, basal conglomerates were common. In contrast, under humid climatic settings, thin multi-stage channels were superimposed, and the bottom often developed erosion surface.KEY POINTSThe paleosedimentary environments are discussed based on detailed organic and inorganic geochemical analysis.The Huagang Formation was deposited in a freshwater lacustrine basin under warm and humid climatic settings.The Huagang Formation is characterised by braided-river delta front facies.The development of braided-river channels was controlled by paleoclimate.

On-site Analysis and Identification of Aluminum Alloys with a Handheld X-ray Fluorescence Spectrometer for Closed-loop Recycling

On-site Analysis and Identification of Aluminum Alloys with a Handheld X-ray Fluorescence Spectrometer for Closed-loop Recycling

In-situ versus laboratory characterization of historical site in marine environment using X-ray fluorescence and Raman spectroscopy

Raman spectroscopy and X-ray fluorescence spectrometry are powerful analytical techniques that allow for molecular and elemental analysis, respectively. Recent developments allowed for the miniaturization of equipment to an extent that in-situ experiments become available. There are many advantages in using portable instruments, but this requires sacrifices regarding the acquisition of the spectra and the quality of the analysis. How much information is lost with this exchange is not clear, neither how important this is for the use of these techniques as forensic tools. In this work, the damage of a façade of Villa Belza, a historic building in Biarritz, France, was evaluated using both portable and benchtop versions of X-ray fluorescence (XRF) and Raman spectroscopy and the approaches were compared. As the comparison of instruments designed for different conditions is not straightforward, the authors use a number of settings to discuss what would be a realistic juxtaposition of results and how this affects the diagnosis of the structure. Furthermore, some hand-held XRF spectrometers are not connected to appropriate software to proceed with the data treatment and the processing of such signals can be tedious or too time consuming. Thus this work also proposes an algorithm for the automatic identification and comparison of elements in the XRF spectra acquired on site. After discussing the trade-off involved with each technique and the respective effect in the limit of detection, the authors conclude that the extra information from benchtop instruments was negligible for this case study.

Geochemistry and Mineralogy of the Upper Cretaceous-Paleocene Marine Series, Iullemmeden Basin, Niger Republic

Major and trace elements, mineralogy as well as the total organic content of the Upper Cretaceous-Paleocene Marine Series of the Iullemmeden basin in Niger were determined in order to assess their composition, the chemistry of the paleoenvironment and the nature of the parent crystalline rocks that they evolved from. The major and trace elements were analyzed using a Bruker Tracer IV energy-dispersive hand held X-ray fluorescence spectrometer, the mineralogical analyses were done using a Bruker AXS D8 Discover, while the total organic carbon was calculated by subtraction of inorganic carbon from the total carbon, determined using a CM5014 coulometer (UIC, Joliet, IL, USA) and a LECO SC-144DR instrument. Geochemical indices calculated from major oxides such as CIA, PIA, ICV and CIW have been computed and the results show that the Marine Series are made essentially of clay minerals of the smectite group (montmorillonite), quartz and other accessory minerals like rutile and calcite. Computed ratios of some trace elements such as V/(V + Ni) and V/(V + Cr) showed that the paleoenvironment was dysoxic-oxic and the low values (2O3/TiO2 ratios, the sediments were derived from intermediate to acidic igneous rocks surrounding the basin.

Diagnostic Value of Energy Dispersive Hand-Held X-ray Fluorescence Spectrometry in Determining Trace Element Concentrations in Ovine Liver

There are no data available on the use of hand-held X-ray fluorescence (XRF) spectrometry to determine trace element concentrations in veterinary diagnostics. The hand-held XRF spectrometer is easy to use and does not require extensive training for the operator. In Sub-Saharan Africa with few centralised analytical laboratories equipped with expensive apparatus or mass spectrometry capabilities, trace element analysis using the hand-held XRF spectrometer provides an alternative. The objective of this study was to compare ovine hepatic copper (Cu), iron (Fe), manganese (Mn), molybdenum (Mo), selenium (Se) and zinc (Zn) concentrations as obtained with the hand-held XRF spectrometer to those of a reference laboratory using inductively coupled plasma mass spectrometry (ICP-MS). Thirty ovine livers were obtained from an abattoir; prepared as wet blended and oven-dried samples and analysed. Bayesian correlation was used to assess the correspondence between results from the XRF and ICP-MS analyses. The oven-dried preparation procedure for XRF provided the best correlation with the ICP-MS data. The correlations for Cu and Zn were strong and the XRF method may represent a suitable substitute for ICP-MS analysis. For Mn and Fe the correlations were moderately strong and the XRF method may be suitable. For Mo, the correlation was weak and XRF cannot be recommended. Selenium could not be detected in samples prepared by either method. Hand-held XRF spectrometry was a practical method to determine liver concentrations of specific trace elements under African conditions and may significantly reduce the turn-around time of analysis, but unfortunately the apparatus is expensive.

Calibration of handheld X-ray fluorescence spectrometer for identification and semi-quantitative analysis of objects with stratified structure

The aim of this paper is to introduce an easily feasible procedure for data evaluation in X-ray fluorescence analysis that enables to identify stratified structure of an investigated object and to determine the approximate amount of an element and its mean depth under the surface. This technique is based on a Kα/Kβ diagram describing the relation of Kα/Kβ ratio versus Kα count rate for various depth distributions of a certain element. Such calibration was performed for NITON XL3t GOLDD Plus analyzer as a typical example of nowadays very popular handheld analyzers that enable in-situ measurements and have many users worldwide. Kα/Kβ diagrams for iron, copper, nickel and titanium were drawn by means of combination of measurements and Monte Carlo simulations and then applied to the determination of approximate structures of several objects. The advantages and also some disadvantages of this technique in connection with the handheld analyzers are summarized in this article.

Depth-resolved analysis of historical painting model samples by means of laser-induced breakdown spectroscopy and handheld X-ray fluorescence

Paintings represent composed materials arranged in successive layers. Development of a suitable method for a depth-profiling analysis is essential for acquiring the information on the stratigraphy as well as on the chemical composition of individual layers, revealing the pigments which had been used. In this study, a depth-resolved analysis of multi-layered model samples of historical easel paintings was performed by means of laser-induced breakdown spectroscopy (LIBS) in combination with non-invasive X-ray fluorescence (XRF). The LIBS analysis was carried out using modified laser ablation system, UP-266 MACRO, equipped with a Czerny-Turner spectrometer. The XRF analysis was performed by handheld spectrometer, Delta Premium. In LIBS experiments, a set of six spots was examined with 5, 10, 15, 20, 25 and 30 pulses respectively, for each of the studied paint samples. Digital and 3D optical microscopy was employed to measure individual layer thickness and to obtain the information on average ablation rates of each sample. The chemical composition of the model samples with each layer partly uncovered was known, and this enabled to directly compare the results obtained by LIBS depth profiling with a fast analysis carried out with the handheld XRF spectrometer. The LIBS depth profiling proved to be a suitable method to distinguish layers of a different material composition and estimate their thickness. The combined use of LIBS and XRF analyses offered essential complementary information on the elemental composition of analysed multi-layered samples.

Investigation of the Presence of Heavy Metals in Plastic Toys Available in Sri Lankan Market

Many toys for children are partly or totally made of plastic. In these plastics, additives such as lead (Pb), cadmium (Cd), arsenic (As), chromium (Cr) and mercury (Hg) are added as pigments, fillers, UV stabilisers and plasticisers which are used to alter the properties of the material or to improve the production process. These additives, unreacted starting substances and impurities, can migrate from the plastic. As young children chew, lick and suck frequently on their toys, they can ingest certain amount of these compounds. The aim of this study was to identify the presence of heavy metals in plastic toy samples collected from market. Total of 145 plastic toys were screened on-site using handheld X-ray Fluorescence spectrometer (Skyray instrument-Genius 3000XRF) in Colombo Fort and Pettah area. The XRF device equipped with beryllium-window Silicon Drift Detector and 139 eV resolution was held on to the surface of the product and measurement was triggered for 45s in Plastics Mode. To eliminate the possibility of contamination, dust was removed prior to the XRF measurement. The built-in intensity correction method of the device corrects all deviations from samples of irregular geometric shape and uneven structure and density. The imported plastic toys were randomly selected from wholesale shops, retail shops and road side stalls considering accessibility to middle and low-income families. Results of the study revealed that the plastic toys contain heavy metals; Pb from 30.34 to 4,469.09 mg/kg, Cd from 15.09 to 1,140.73 mg/kg, As from 15.53 to 46.02 mg/kg, Cr from 15.21 to 247.78 mg/kg and Hg from 28.12 to 94.92 mg/kg respectively. Out of these 8.97% show high level of Cd and 1.38% show high level of Pb. However, the concentrations of Cr, As and Hg are under the permissible limits as per the testing standards by Restriction of Hazardous Substances (RoHS) directive. The permissible limits as per the testing standards by RoHS directive are 100 mg/kg for Cd and 1,000 mg/kg for Pb, Hg, and Cr and As. These results of the present study revealed that some toys are potential sources of heavy metals. Keywords: Plastic toys, Heavy metals, XRF, Chemical screening

Mapping elemental contamination on Palmyra Atoll National Wildlife Refuge

Palmyra Atoll, once a WWII U.S. Navy air station, is now a U.S. National Wildlife Refuge with nearly 50km2 of coral reef and 275ha of emergent lands with forests of Pisonia grandis trees and colonies of several bird species. Due to the known elemental and organic contamination from chemicals associated with aviation, power generation and transmission, waste management, and other air station activities, a screening survey to map elemental concentrations was conducted. A map of 1944 Navy facilities was georeferenced and identifiable features were digitized. These data informed a targeted survey of 25 elements in soils and sediment at locations known or suspected to be contaminated, using a hand-held X-ray fluorescence spectrometer. At dozens of locations, concentrations of elements exceeded established soil and marine sediment thresholds for adverse ecological effects. Results were compiled into a publically available geospatial dataset to inform potential remediation and habitat restoration activities.

Conditions affecting oxide quantification in unknown tropical soils via handheld X-ray fluorescence spectrometer

Soil chemical characterisation has been accurately performed worldwide using portable X-ray fluorescence (pXRF), contributing to fast, low-cost and environmentally-friendly soil analyses. However, many factors can influence the pXRF performance. Thus, this work was carried out to assess the oxides (SiO2, Al2O3, Fe2O3, TiO2 and P2O5) in tropical soils via pXRF, evaluating the effects of soil packing prior to analysis and the soil matrix. The packing of soil samples was performed using X-ray thin-film and common, low-cost plastic bags. Different soil matrices were obtained by grouping of samples according to the Munsell colour system. The obtained results were compared with a conventional method employed for the determination of soil oxides. In addition, the pXRF measurements made on either sieved soil samples or directly on the soil profile were compared. The P2O5 content was below the detection limit of pXRF (0.05 g kg−1). The Fe2O3 and TiO2 contents of several tropical soils were accurately determined via pXRF using air-dried and sieved samples. This result was not observed for SiO2 and Al2O3. For Fe2O3, a good correlation (R2 = 0.91) was obtained between pXRF measurements made on sieved soil samples and directly on the soil profile. The packing of soil samples using plastic bags did not negatively influence the pXRF performance.

Brominated flame retardants in black plastic kitchen utensils: Concentrations and human exposure implications

Concerns exist that restricted brominated flame retardants (BFRs) present in waste polymers may have, as a result of recycling, inadvertently contaminated items not required to meet flame retardancy regulations (e.g. plastic kitchen utensils). To investigate the extent to which kitchen utensils are contaminated with BFRs and the potential for resultant human exposure, we collected 96 plastic kitchen utensils and screened for Br content using a hand-held X-ray fluorescence (XRF) spectrometer. Only 3 out of 27 utensils purchased after 2011 contained detectable concentrations of Br (≥3μg/g). In contrast, Br was detected in 31 out of the 69 utensils purchased before 2011. Eighteen utensils with Br content higher than 100μg/g, and 12 new utensils were selected for GC–MS analysis of BFRs. BFRs targeted were polybrominated diphenyl ethers (PBDEs) BDE-28, 47, 99, 100, 153, 154, 183 and 209, and novel BFRs (NBFRs) pentabromoethylbenzene (PBEB), 2-ethylhexyl-2,3,4,5-tetrabromobenzoate (EH-TBB), 1,2-bis(2,4,6-tribromophenoxy)ethane (BTBPE), bis(2-ethylhexyl)-3,4,5,6-tetrabromo-phthalate (BEH-TEBP) and decabromodiphenyl ethane (DBDPE). The ability of XRF to act as a surrogate metric of BFR concentration was indicated by a significant (Spearman coefficient=0.493; p=0.006) positive relationship between Br and ΣBFR concentration. Measurements of ΣBFRs were always exceeded by those of Br. This may be due partly to the presence of BFRs not targeted in our study and also to reduced extraction efficiency of BFRs from utensils. Of our target BFRs, BDE-209 was the most abundant one in most samples, but an extremely high concentration (1000μg/g) of BTBPE was found in one utensil. Simulated cooking experiments were conducted to investigate BFR transfer from selected utensils (n=10) to hot cooking oil, with considerable transfer (20% on average) observed. Estimated median exposure via cooking with BFR contaminated utensils was 60ng/day for total BFRs. In contrast, estimated exposure via dermal contact with BFR-containing kitchen utensils was minimal.

A novel XRF method to measure environmental release of copper and zinc from antifouling paints

The release of copper (Cu) and zinc (Zn) from vessels and leisure crafts coated with antifouling paints can pose a threat to water quality in semi-enclosed areas such as harbors and marinas as well as to coastal archipelagos. However, no reliable, practical and low-cost method exists to measure the direct release of metals from antifouling paints. Therefore, the paint industry and regulatory authorities are obliged to use release rate measurements derived from either mathematical models or from laboratory studies. To bridge this gap, we have developed a novel method using a handheld X-Ray Fluorescence spectrometer (XRF) to determine the cumulative release of Cu and Zn from antifouling paints. The results showed a strong linear relationship between XRF Kα net intensities and metal concentrations, as determined by ICP-MS. The release of Cu and Zn were determined for coated panels exposed in harbors located in the Baltic Sea and in Kattegat. The field study showed salinity to have a strong impact on the release of Cu, i.e. the release increased with salinity. Contrary, the effect of salinity on Zn was not as evident. As exemplified in this work, the XRF method also makes it possible to identify the governing parameters to the release of Cu and Zn, e.g. salinity and type of paint formulation. Thus, the XRF method can be used to measure environmentally relevant releases of metallic compounds to design more efficient and optimized antifouling coatings.

A fast in situ non-invasive approach to classify mortars from a construction of high historical value

The use of hand-held X-ray fluorescence (HH-XRF) spectrometers has increased in the last years due to its easily portable capacity and its rapid and non-destructive analysis. In this work, HH-XRF is proposed as a fast in situ non-invasive technique to classify mortars from a construction of high historical value. The current HH-XRF devices are able to provide large amounts of information almost instantaneously based on Fundamental Parameters quantification methodology that especially for the analyses of samples with very complex matrixes such as building materials is not very reliable. The accuracy of the semi-quantitative information provided by the HH-XRF spectrometer was compared with a previously optimized WD-XRF quantification method and a complete spectral data treatment followed by Principal Component Analysis is also proposed to classify easily and quickly the mortars used in this construction, without a previous sampling procedure, according to the similarities/differences in their elemental composition.

Performance comparison of two Olympus InnovX handheld x-ray analyzers for feasibility of measuring arsenic in skin in vivo – Alpha and Delta models

The Figure-Of-Merit (FOM) performance, a combination of detection limit and dose, is compared between two generations of handheld X-Ray Fluorescence (XRF) spectrometers for the feasibility of in vivo XRF measurement of arsenic (As) in skin. The Olympus InnovX Delta model analyzer (40 kVp using either 37 or 17μA) was found to show improvements in Minimum Detection Limit (MDL) using arsenic As-doped skin calibration phantoms with bulk tissue backing, when compared to the first generation InnovX Alpha model (40kVp, 20μA) in 120s measurements. Differences between two different definitions of MDL are discussed. On the Delta system, an MDL of (0.462±0.002) μg/g As was found in phantoms, with a nylon backing behind to mimic bulk tissue behind skin. The equivalent and effective doses were found to be (10±2) mSv and ~7×10−3μSv respectively for the Alpha and (15±4) mSv and ~8×10−3μSv respectively for the Delta system in 120s exposures. Combining MDL and effective dose, a lower (better) FOM was found for the Delta, (1.7±0.4) ppm mSv1/2, compared to (4.4±0.5) ppm mSv1/2 for the Alpha model system. The Delta analyzer demonstrates improved overall system performance for a rapid 2-min measurement in As skin phantoms, such that it can be considered for use in populations exposed to arsenic.

A Decade of Portable (Hand-Held) X-Ray Fluorescence Spectrometer Analysis of Obsidian in the Mediterranean: Many Advantages and Few Limitations

ABSTRACTStarting in 2007, a portable, hand-held X-ray fluorescence spectrometer was used to elementally analyze and determine the geological source of obsidian artifacts in the Mediterranean, effectively replacing the instruments used in my previous research studies - INAA, LA-ICP-MS, ED-XRF and an electron microprobe with WDS. Approximately 400 geological obsidian samples from the Mediterranean area, and 8500 obsidian artifacts from prehistoric sites in Italy, France, Croatia, Malta, Tunisia, Greece, Cyprus, Turkey, Israel, and Egypt have been analyzed non-destructively by pXRF. Overall, the pXRF can distinguish all of the individual sources, based on the composition of Fe and trace elements Rb, Sr, Y, Zr, and Nb, as well as assign most artifacts to specific subsources and thus addressing archaeological research hypotheses about trade and exchange in many different time periods.

Application of a handheld X-ray fluorescence spectrometer for real-time, high-density quantitative analysis of drilled igneous rocks and sediments during IODP Expedition 352

Handheld energy dispersive portable X-ray spectrometers (pXRF) are generally designed and used for qualitative survey applications. We developed shipboard quantitative analysis protocols for pXRF and employed the instrument to make over 2000 individual abundance measurements for a selection of major and trace elements on over 1200m of recovered core during the eight weeks of the International Ocean Discovery Program (IODP) Expedition 352 to the Izu-Bonin forearc. pXRF analytical performance, accuracy and precision were found to be the same on powdered rock samples and on freshly cut rock surfaces, and sample results were similar within error to measurements made via shipboard ICP-OES analysis save at low abundance levels for a few elements. Instrument performance was optimal for elements between Z=19 and Z=40, and the system yielded reproducible data for K, Ca, Ti, V, Cr, Mn, Fe, Cu, Zn, Rb, Sr, and Zr on both powdered samples and rock surfaces. Working curves developed via pXRF measurement of a suite of geologic standard reference materials and well-characterized lavas permitted accurate quantitative measurements for many of the examined elements on both sample powders and rock surfaces. Although pXRF has been sporadically employed on previous cruises, Expedition 352 is the first time a detailed, high-density chemostratigraphy of recovered core samples was collected using pXRF measurements of rock core surfaces. These high-resolution data allowed the recognition of chemically distinct eruptive units in near real-time. The rapid identification of geochemical trends vastly improved our selection of samples for shipboard and shore-based analysis, permitted a more comprehensive interpretation of our Expedition results, and provided key decision-making information for drilling operations.

Innovative Strategy for Counterfeit Analysis

Currently, counterfeit medicine is a significant issue for the pharmaceutical world, and it targets all types of therapeutic areas. The health consequences are appalling, since counterfeit medicines can contain impurities and the wrong chemical composition, and can be manufactured and/or stored in dreadful conditions. The provision of fast and reliable analytical tools can contribute to an efficient fight against this phenomenon. In this paper, an analytical strategy based on mobile and forensic laboratories is presented. The mobile equipment, composed of handheld x-ray fluorescence, Raman, infrared, and near-infrared spectrometers, and a handheld microscope, can be used as a first screening tool to detect counterfeits. The counterfeits can then be confirmed in a forensic-dedicated lab in which the chemical composition of the counterfeits is determined to evaluate the danger encountered by the patients. Relevant links with former counterfeit cases then can be revealed based on the analytical data, and can be interpreted from a forensic intelligence perspective in order to provide additional information for law enforcement.

Calibration of handheld X-ray fluorescence (XRF) equipment for optimum determination of elemental concentrations in sediment samples

Handheld X-ray fluorescence spectrometers (XRFs) represent a more practical, efficient and economic tool to determine the elemental composition of solid inorganic and organic samples than conventional analytical techniques. The objective of this work was to demonstrate that handheld XRFs could be a precise, accurate and reliable tool to analyze up to 27 different elements. This objective was accomplished through the optimization of an empirical calibration curve that, in addition to include certified reference materials (CRM), it also introduced new approaches, such as the use of solid CRM mixtures and combinations of organic and inorganic matrices. These approaches significantly increased the number of calibration points and eliminated hiatuses in the calibration curve. Several factors were evaluated before construction of the calibration curve: incidence time of the X-ray beam, type of film through which the X-ray beams reach the samples, container type, minimum sample volume and sample moisture content. Results show that single elements can be analyzed with variable exposure times or, alternatively, multielemental analyses can be carried out with a constant exposure time (180s). Costs can be reduced by using Ziploc® bags as sample containers, but the number of measurable elements drops from 27 to 21, while the possibility of contamination increases.

Characterization of archaeometallurgical artefacts by means of portable Raman systems: corrosion mechanisms influenced by marine aerosol

This work focuses on the analytical study of eight medieval metallic artefacts discovered during the archaeological excavations of the Erenozar necropolis (13th century, Basque Country, Spain). As the conservation state of archaeological objects is closely related to the characteristics of the burial environment, chromatographic analysis was performed with the aim of quantifying the soluble salt content of the burial ground. Moreover, portable systems were used for the elemental and molecular characterization of the artefact collection. A hand-held X-ray fluorescence spectrometer was used to analyse the alloys constituting the objects. Then, the characterization of the main corrosion phases affecting the artefacts was carried out using two portable Raman systems. Both tools, equipped with different excitation lasers (785 and 532 nm respectively), were used in a complementary way by coupling them with the BAC151B video microscope. Thanks to its dual laser wavelength port, it was possible to sequentially focus with both lasers on the same selected spot. In this way, the sensitivity of each system for the characterization of Fe-based and Cu-based corrosion phases was also compared. Furthermore, the information obtained from both chromatographic and spectroscopic techniques allows the modelling of the chemical reactions that led to the formation of the identified degradation products. Copyright © 2016 John Wiley & Sons, Ltd.