Use Of Portable X-ray Fluorescence Research Articles

Clean and accurate soil quality monitoring in mining areas under environmental rehabilitation in the Eastern Brazilian Amazon.

Soil quality monitoring in mining rehabilitation areas is a crucial step to validate the effectiveness of the adopted recovery strategy, especially in critical areas for environmental conservation, such as the Brazilian Amazon. The use of portable X-ray fluorescence (pXRF) spectrometry allows a rapid quantification of several soil chemical elements, with low cost and without residue generation, being an alternative for clean and accurate environmental monitoring. Thus, this work aimed to assess soil quality in mining areas with different stages of environmental rehabilitation based on predictions of soil fertility properties through pXRF along with four machine learning algorithms (projection pursuit regression, PPR; support vector machine, SVM; cubist regression, CR; and random forest, RF) in the Eastern Brazilian Amazon. Sandstone and iron mines in different chronological stages of rehabilitation (initial, intermediate, and advanced) were evaluated, in addition to non-rehabilitated and native forest areas. A total of 81 soil samples (26 from sandstone mine and 55 from iron mine) were analyzed by both traditional wet-chemistry methods and pXRF. The available/exchangeable contents of K, Ca, B, Fe, and Al, in addition to H+Al, cation exchange capacity at pH = 7, Al saturation, soil organic matter, pH, sum of bases, base saturation, clay, and sand were accurately predicted (R2 > 0.70) using pXRF data, with emphasis on the prediction of Fe (R2 = 0.93), clay content (R2 = 0.81), H+Al (R2 = 0.81), and K+ (R2 = 0.85). The best predictive models were developed by RF and CR (86%) and when considering pXRF data + mining area + stage of rehabilitation (73%). The results highlight the potential of pXRF to accurately assess soil properties in environmental rehabilitation areas in the Amazon region (yet scarcely evaluated under this approach), promoting a more agile and cheaper preliminary diagnosis compared to traditional methods.

Proximal sensing provides clean, fast, and accurate quality control of organic and mineral fertilizers

Farms use large quantities of fertilizers from many sources, making quality control a challenging task, as the traditional wet-chemistry analyses are expensive, time consuming and not environmentally-friendly. As an alternative, this work proposes the use of portable X-ray fluorescence (pXRF) spectrometry and machine learning algorithms for rapid and low-cost estimation of macro and micronutrient contents in mineral and organic fertilizers. Four machine learning algorithms were tested. Whole (i.e., as delivered by the manufacturer) (CP) and ground (AQ) samples (429 in total) were analyzed to test the effect of fertilizer granulometry in prediction performance. Model validation indicated highly accurate predictions of macro (N: R2 = 0.92; P: 0.97; K: 0.99; Ca: 0.94, Mg: 0.98; S: 0.96) and micronutrients (B: 0.99; Cu: 0.99; Fe: 0.98; Mn: 0.91; Zn: 0.94) for both organic and mineral fertilizers. RPD values ranged from 2.31 to 9.23 for AQ samples, and Random Forest and Cubist Regression were the algorithms with the best performances. Even samples analyzed as they were received from the manufacturer (i.e., no grinding) provided accurate predictions, which accelerate the confirmation of nutrient contents contained in fertilizers. Results demonstrated the potential of pXRF data coupled with machine learning algorithms to assess nutrient composition in both mineral and organic fertilizers with high accuracy, allowing for clean, fast and accurate quality control. Sensor-driven quality assessment of fertilizers improves soil and plant health, crop management efficiency and food security with a reduced environmental footprint.

Expanding the use of portable XRF to monitor lead exposure in an Australian duck species two decades after a ban on lead shot

There is growing worldwide recognition of the threat posed by toxic lead for wildlife and humans. Lead toxicity from ammunition has been shown to be a threat to waterbirds across the globe. Lead shot was banned for all waterfowl hunting in Victoria, Australia, in 2002. However, no assessments of lead exposure in Australian waterfowl have been published since the 1990s. Our aim was to estimate contemporary lead exposure via measuring bone lead concentrations in a harvested dabbling duck, the Pacific black duck (Anas superciliosa). We collected wings from 77 Pacific black ducks, spanning 2018 (n = 30) and 2021 (n = 47), from nine sites with long-term histories of regular waterfowl hunting. We sought to validate portable X-ray fluorescence (XRF) for this purpose by taking a piece of humerus bone from each bird, and measuring lead concentration (mg/kg), first via non-destructive XRF and then via destructive inductively coupled plasma mass spectrometry (ICP-MS) and validated the relationship via regression analysis. Portable XRF bone lead measurement demonstrated a strong correlation with ICP-MS results using root-transformed regression (R2 = 0.85). Greater than 92 % of ducks had only background lead exposure (<10 mg/kg). When compared to historical studies in the same species at similar field sites from the 1990s, lead exposure levels were considerably lower, with mean lead concentrations ∼2-fold lower (3.7 c.f. 7.7 mg/kg), and the frequency of birds with severe lead exposure (>20 mg/kg) ∼3-fold lower (2.6 c.f. 7.5 %). Our results confirm that portable XRF is a useful option for measurement of bone lead in Australasian waterbird species. Our findings also demonstrate that a ban on the use of lead shot around 20 years ago has been associated with a substantial reduction in lead exposure in at least one species of waterfowl.

Assessment of X-ray fluorescence capabilities for nail and hair matrices through zinc measurement in keratin reference materials

BackgroundNovel and emerging biomarkers of zinc status are being developed to help study and address zinc deficiency around the world. Two potential biomarkers, nail and hair, involve the measurement of zinc from easily accessible keratin-based components of the body. Portable X-ray fluorescence (XRF) is a relatively new approach to the assessment of zinc in nail or hair, and has a number of compelling advantages compared with other techniques. The aim of the current study was to test the ability of XRF to measure zinc in keratinized reference materials (RMs) designed to simulate nail and hair. MethodsFour Keratin Matrix RMs were prepared and characterized for numerous trace elements by the New York State Department of Health’s Wadsworth Center. The Keratin Matrix RMs consisted of powdered samples of caprine (goat) horns pooled from several animals. Concentrations of zinc, as assessed by inductively coupled plasma mass spectrometry (ICP-MS), were similar to what would be expected from human nail or hair tissues. Repeat measurements of the RMs were made using a portable XRF system. The XRF zinc results were compared with the ICP-MS zinc concentrations. Three different approaches to quantifying the zinc content by XRF were performed: (1) zinc signal to total signal ratio, (2) zinc signal to sulfur signal ratio, and (3) system output zinc concentration. ResultsThe portable XRF results from a given RM were found to be consistent across repeat trials under all three approaches to XRF quantitation. Precision, calculated as the relative standard deviation of repeat measurements ranged from an average result of 0.8 % (using the system output zinc concentration method) to 6.1 % (using the zinc signal to sulfur signal ratio method). Measurement of the RMs provided XRF zinc results which scaled well with ICP-MS zinc concentration, particularly when using the XRF zinc to total and system zinc concentration methods. A Bland-Altman plot showed that the XRF system zinc concentration output exceeded the ICP-MS zinc concentration by, on average, 10.2 % ± 1.2 %. ConclusionOverall, both accuracy and precision of measurement were found to be promising for portable XRF, provided appropriate conversions to concentration are introduced. The results of this study indicate that portable XRF is an effective and dependable method of assessing zinc concentration in keratinized tissue RMs. This will have implications for the future use of portable XRF to monitor zinc status in humans through measurements of nail and hair.

Clean quality control of agricultural and non-agricultural lime by rapid and accurate assessment of calcium and magnesium contents via proximal sensors

Ca and Mg are the most important chemical elements in lime. Properly measuring Ca and Mg contents is essential to assess the quality of lime products. Quality control guarantees the adequate use of lime in industrial processes, in soils, and helps avoiding adulteration. Proximal sensors can aid in this process by determining Ca and Mg contents easily, rapidly and without producing chemical waste. The objective of this study was to evaluate the use an environmentally-friendly method of analyzing the quality of lime. We studied 1) the use of portable X-ray fluorescence (pXRF) to predict concentrations of Ca and Mg in lime, 2) tested if NixPro™ sensor can improve prediction accuracy and 3) tested if sample preparation methods (grinding) affect analyses. 74 samples of lime were analyzed by two different laboratories (lab. 1 = 38, lab. 2 = 36). All samples submitted to pXRF and NixPro™ analyses. Sensor analyses were done in whole (CP) and ground (AQ) samples to test the effect of sample preparation in prediction performance. High correlation was found between Ca and Mg contents measured via pXRF and laboratory analyses. Mg-CP presented the highest correlation coefficient (r = 0.81); Mg-AQ, the lowest (0.57). Predictions presented good performance (R2 > 0.68); Mg had the best results (0.86). Separating models per laboratory showed that some datasets are harder to model, probably due to variability in the source material (limestone). The addition of NixPro™ data contributed to improve prediction accuracy, although slightly. Predictions using CP samples presented the best results, especially for Mg, indicating that grinding is not necessary. This pioneer study demonstrated that fused proximal sensors can be used to rapidly and easily determine contents of Ca and Mg in soil amendments without producing chemical waste.

On the Influence and Correction of Water Content on pXRF Analysis of Lateritic Nickel Ore Deposits in the Context of Open Pit Mines of New-Caledonia

In a number of applications, the use of portable X-ray fluorescence (pXRF) instruments offers a time and cost-saving alternative to standard laboratory instruments. This is particularly true in a mining context where decisions must be taken quickly in the field. However, pXRF is a technique known to be efficient, provided that samples are well prepared, i.e., dried and finely ground. On the mine face, little-to-no sample preparation is conceivable as mining vehicles must be able to operate continuously. Therefore, solutions have to be found even for raw materials and one of the most critical problems is the sample water content, in particular in the context of open pit mines in a tropical area. A large number of analysis shows that knowledge of humidity enables the measured concentration to be effectively corrected for the three instruments used (Niton, X-met, Titan). It is possible to overcome the difficulty of measuring water content in the field by fixing it to its maximum value (saturation). The results show that the saturation method is reliable, or at least, promising.

Data fusion for the measurement of potentially toxic elements in soil using portable spectrometers

Soil contamination posed by potentially toxic elements is becoming more serious under continuously development of industrialization and the abuse of fertilizers and pesticides. The investigation of soil potentially toxic elements is therefore urgently needed to ensure human and other organisms’ health. In this study, we investigated the feasibility of the separate and combined use of portable X-ray fluorescence (pXRF) and visible near-infrared reflectance (vis-NIR) sensors for measuring eight potentially toxic elements in soil. Low-level fusion was achieved by the direct combination of the pXRF and vis-NIR spectra; middle-level fusion was achieved by the combination of selected bands of the pXRF and vis-NIR spectra using the Boruta feature selection algorithm; and high-level fusion was conducted by outer-product analysis (OPA) and Granger–Ramanathan averaging (GRA). The estimation accuracy for the eight considered elements were in the following order: Zn > Cu > Ni > Cr > As > Cd > Pb > Hg. The measurement for Cu and Zn could be achieved by pXRF spectra alone with Lin’s concordance correlation coefficient (LCCC) values of 0.96 and 0.98, and ratio of performance to interquartile distance (RPIQ) values of 2.36 and 2.69, respectively. The measurement of Ni had the highest model performance for high-level fusion GRA with LCCC of 0.89 and RPIQ of 3.42. The measurements of Cr using middle- and high-level fusion were similar, with LCCC of 0.86 and RPIQ of 2.97. The best estimation accuracy for As, Cd, and Pb were obtained by high-level fusion using OPA, with LCCC >0.72 and RPIQ >1.2. However, Hg measurement by these techniques failed, having an unacceptable performance of LCCC <0.20 and RPIQ <0.75. These results confirm the effectiveness of using portable spectrometers to determine the contents of several potentially toxic elements in soils.

Archaeometrical studies of prehistoric pottery using portable ED-XRF

This article presents the studies of archaeological ceramic materials from two sites located in Poland within the region called Kuyavia: Grabkowo no.7 and no. 8 yielded pottery dated to the younger pre-Roman Iron-Age and they represent two cultures and different traditions in the pottery production. This case allows to follow and analyse the differences and similarities between these materials chemical composition with the use of portable X-ray fluorescence (XRF) spectrometer. The knowledge of elemental composition of pottery samples have been applied in the archaeometric studies of ceramic differentiation. The methodology points to the possibility of identifying different pottery traditions in the production of mass archaeological material.

The use of portable X-ray fluorescence spectrometry to measure apparent total tract digestibility in beef cattle and sheep.

The use of portable X-ray fluorescence (PXRF) spectrometry to detect external markers on processed or unprocessed cattle and sheep fecal specimens to estimate apparent total tract digestibility (ATTD) was evaluated. Exp. 1: ruminally cannulated Angus-crossbred steers (n = 7; BW = 520 ± 30 kg) were individually fed ad libitum for 21 d in a completely randomized design (CRD). Markers (Cr2O3 and TiO2) were placed inside the rumen twice daily (7.5 g of each marker). Fecal samples were collected twice daily from day 14 to 21. Exp. 2: crossbred wethers (n = 8; BW = 68 ± 3 kg) were individually fed ad libitum for 21 d in a CRD. During this period, 2 g of Cr2O3 and TiO2 were top-dressed onto the feed twice daily. Sheep were housed in metabolism crates for 5 d for total fecal collection. Concentration of markers was determined on diets, refusals, and fecal specimens (fresh, dry-only, and dried/ground) using atomic absorption to detect Cr and spectrophotometry for Ti. Concentration of both markers was also determined via the PXRF spectrometer. Delta between ATTD estimated by wet chemistry and PXRF was not different from zero (P ≥ 0.14) when using cattle fresh fecal specimens for both markers, whereas ATTD estimated by PXRF with dry-only and dried/ground fecal specimens were 3.6 and 1.1 percent units lower (P ≤ 0.04), respectively, than ATTD estimated by wet chemistry for Cr and Ti, respectively. Regardless of the fecal sample preparation method on cattle specimens, Ti concentration was similar (P = 0.39) among methodologies, while Cr was underestimated (P < 0.01) by 13% when PXRF was used in dry-only or dried/ground samples. The ATTD of sheep was underestimated (P < 0.01) by 2.4 percent units compared with control when Cr was measured by PXRF in dry-only samples. The Cr concentration in dry-only fecal specimens of sheep tended (P = 0.09) to be lower compared with wet chemistry analysis. Fresh and dry/ground sheep fecal samples assessed for Cr, and dry-only assessed for Ti were not (P ≥ 0.49) affected by detection method. The Cr fecal recovery tended (P = 0.10) to be the lowest for dry-only, the greatest for wet chemistry, intermediate for fresh and dry/ground sheep-fecal specimens; while not affected (P = 0.40) for Ti. The PXRF is an accurate technology to detect Cr and Ti in fresh cattle fecal samples to estimate ATTD. For fresh and dry/ground, the technology was effective for determining the concentration of Cr, or dry-only fecal specimens when detecting Ti in sheep specimens.

Assessing soil contamination in automobile scrap yards by portable X-ray fluorescence spectrometry and magnetic susceptibility.

A by-product of industrialization and population growth, automobile scrap yards are a potential source of metal contamination in soil. This study evaluated the use of portable X-ray fluorescence (pXRF) spectrometry and magnetic susceptibility (χ) analysis in assessing metal soil contamination in scrap yards located in Brazil. Five automobile scrap yards were selected in Curitiba, Paraná State (CB1, CB2, and CB3) and Lavras, Minas Gerais State (LV1 and LV2). By evaluating metal concentrations and geoaccumulation index values, we verified moderate Cu, Pb, and Zr contamination and moderate to high Zn contamination, primarily in the topsoil (0-10cm). Soil Zn concentrations in automobile scrap yards were on average four times higher than in reference soils, suggesting that galvanized automobile parts may be the primary source of this soil contaminant. Although other elements (i.e., As, Cr, Fe, Nb, Ni, and Y) were slightly increased compared to reference values in one or more soils, concentrations did not constitute contamination. Automobile scrap yard topsoil had higher χ values (5.8 to 52.9 × 10-7m3kg-1) at low frequency (χlf) compared to reference soil (3.6 to 7.5 × 10-7m3kg-1). The highest values of χlf occurred in LV soils, which also represented the highest Zn contamination. Magnetic multidomain characteristics (percent frequency-dependent susceptibility between 2 and 10) indicated magnetic particle contributions of anthropogenic origin. The use of pXRF and χlf as non-destructive techniques displays potential for identifying soil contamination in automobile scrap yards.

PSIV-B-23 Late-Breaking: Detection of dietary external markers using portable X-ray fluorescence spectrometry for estimation of digestibility in beef cattle

Abstract The use of portable X-ray fluorescence (PXRF) spectrometry to detect dietary external markers on processed or unprocessed bovine fecal specimens to estimate apparent total tract digestibility (ATTD) was evaluated. Seven beef crossbred, ruminally-cannulated steers (BW = 520 ± 30 kg) were used in a completely randomized design. Steers were individually fed a steam-flaked corn-based finishing diet ad libitum for 21-d. Degradable gel capsules containing 7.5 g of titanium dioxide and chromic oxide were placed inside the rumen through the ruminal-cannulae twice daily, throughout the experiment. Fecal samples were collected twice daily from d 14–21, stored frozen (-20oC), and thawed on d-21 to make a composite sample per steer/day. Wet chemistry analyses of fecal samples included atomic absorption for Cr and spectrophotometry for TiO2 and were compared with PXRF to determine the concentration of these markers on three types of fecal specimens: fresh (average 22.5 % DM), dried (60oC, 72 h), or dried/ground (1 mm). Data were analyzed using the GLIMMIX procedures of SAS with collection day as a repeated measure. Delta between ATTD estimated by wet chemistry and PXRF was not different from zero when using fresh fecal specimens analyzed for Cr (P = 0.40) or Ti (P = 0.14), while for dried or dried/ground specimens it differed (P ≤ 0.04), in which ATTD was underestimated by 3.6 and 1.1 percent units for Cr and Ti, respectively, when using PXRF. Concentration of Ti in fecal specimens was similar (P = 0.39) between analytical methodologies regardless of sample preparation. However, concentration of Cr was underestimated (P &amp;lt; 0.01) by 13% when PXRF was used in dried or dried/ground fecal samples compared to wet chemistry. Detection of Cr and Ti in fresh fecal samples with PXRF spectrometry seems to be a viable alternative to wet chemistry for estimating ATTD for finishing steers.

Portable X-ray fluorescence of Lower Pecos painted pebbles: New insights regarding pigment choice and chronology

Painted pebbles are the primary mobiliary art found in the Lower Pecos Canyonlands of southwest Texas and northern Mexico. Previous studies of these artifacts have focused on stylistic variation of the imagery and interpretation of the role these artifacts played within Lower Pecos societies. The focus of this study is the use of portable X-ray fluorescence on Lower Pecos painted pebbles to conduct elemental analyses to identify the pigment used by ancient artists in the paint recipe for painted pebble production. Using a sample of recently excavated painted pebbles, as well as a sample from a private collection, a total of 254 pXRF measurements were collected on 70 pebbles. We determined that charcoal was used as a pigment for black paintings and that iron-based mineral pigments were used for red paintings. The newly excavated pebbles range in age from 6500 to 700 RCYBP, and the stratigraphic and chronologic context of these pebbles provides a dataset for analyzing not only pigment selection, but allows us to also address changes in painted pebble production through time. This paper summarizes the results from the pXRF analysis, and discusses the larger archaeological implications for Lower Pecos painted pebbles.

Sourcing qingbai porcelains from the Java Sea Shipwreck: Compositional analysis using portable XRF

This paper evaluates the use of portable x-ray fluorescence (pXRF) on glazes and pastes for sourcing Chinese porcelains from the 12th-13th century Java Sea Shipwreck (JSW) collection at the Field Museum. Three types of qingbai (bluish-white) wares from the JSW collection were chosen for pXRF analysis. Samples from four kiln complexes in China—Jingdezhen, Dehua, Huajiashan, and Minqing, hypothesized to be potential sources of the shipwreck’s qingbai ceramics based on visual inspection—were also analyzed to establish reference groups. Results from kiln samples show that different kiln complexes can be clearly differentiated by pXRF analysis of glazes. Based on pXRF analysis of ceramic samples from the JSW, there appear to be four compositional groups, and each group closely matches one of the four kiln reference groups. These findings support the use of pXRF on glazes, especially when pastes are difficult to access, as a method for identifying the potential sources for overseas cargos found distant from production contexts for Chinese porcelains.

Decoration composition of Iberian Iron Age ivory artifacts identified by no-destructive chemical analyses

In this work, five unique Iberian Iron Age handles have been studied. The use of portable X-ray fluorescence (pXRF) and Fourier transform near–infrared (FT-NIR) spectroscopy no-destructive techniques has allowed us to identify two raw materials (amber and tin) used to decorate the ivory handles. Due to the finesse of their inlaid decoration and the value and exoticism of the material employed for their manufacture, these ivory objects are really exceptional Iberian archaeology findings. Interestingly, it has been possible to determine that tin was used as an adherent material to fix the inlaid small pieces of amber in the handles. The obtained results allow the better understanding of the manufacturing processes, areas of production, and accessibility to exotic materials of valuable objects during the Iberian period.

Dating South Island Māori rock art: Pigment and pitfalls

New Zealand was first settled by Māori soon after 1200 CE, however the age, and so the social and environmental contexts of the rock art they made remains uncertain. We report the first attempts at the direct dating of New Zealand rock art through radiocarbon analysis focusing on the return of an unexpectedly early date. Historical information and pigment testing indicates that the particular figures that returned the early date were retouched with modern crayons. We report the use of portable X-ray fluorescence to identify rock art figures that have been retouched in this way. Results emphasise the need to consider historical information in future assessments of material for dating Māori rock art.

Use of portable XRF: Effect of thickness and antecedent moisture of soils on measured concentration of trace elements

The use of portable X-ray fluorescence (PXRF) for rapid measurements of concentrations of trace elements in soils is increasing. The purpose of this study was to assess in a systematic way the influence of soil moisture and sample thickness on concentrations of Ni, Zn, Cd, and Pb in a mixture of glass beads as well as Windsor loamy sand and Webster loam soils. The Windsor soil was collected from near Lebanon, NH, and the Webster soil was sampled from Story County, IA. In this context, the efficacy of the Compton Normalization (CN) calibration method to correct for changes in soil moisture was determined. Despite CN calibration, an inverse correlation between PXRF measured concentrations and soil moisture was observed. The magnitude of this effect depends upon the energy of the characteristic X-ray fluorescence of each element, with those emitting lower energy X-ray fluorescence being more greatly influenced. Moisture contents ranging from 0.09 to 0.26 cm3 cm−3 were found to generate trace element concentrations with no statistical difference, with significantly lower concentrations reported at greater moisture contents. In addition, measured concentrations of each trace element increased with increasing sample thickness until a constant measured concentration was attained, which was also correlated with the energy of the characteristic X-ray fluorescence of the corresponding trace element. Ni, with the lowest energy fluorescence, obtained constant measured concentration at 3 mm for all matrices, whereas a sample thickness of up to 10 mm was needed for Cd. In order to account for energy differences across a range of trace elements and matrices, the use of PXRF should be limited to soil samples having a thickness of at least 10 mm.

Compost salinity assessment via portable X-ray fluorescence (PXRF) spectrometry

Compost salinity is an ongoing concern for compost producers, especially with certain feedstocks and in arid or semiarid regions. Current testing protocols call for sampling and testing ex-situ via 1:5 (w/v) slurries via electrical conductance. For this research an alternate approach has been proposed, the use of portable X-ray fluorescence (PXRF) spectrometry. Adapting methods developed for soil and water salinity analysis via PXRF, elemental data was used as a proxy for the prediction of compost salinity. In total, 74 compost samples were scanned with PXRF followed by traditional laboratory analysis. Results indicated a strong correlation between the datasets (R2 0.80; RMSE 1.04 dS m−1), similar to findings for soil and water salinity. Furthermore, using the same elemental dataset, compost pH was reasonably predicted (R2 0.63; RMSE 0.35). PXRF has the benefit of being able to be conducted in-situ or in the laboratory. And, multiple chemical parameters of interest can potentially be predicted from the same dataset. In conclusion, PXRF shows promise for rapid, in-situ salinity determination of composted products.

An integrated pelagic carbonate multi-proxy study using portable X-ray fluorescence (pXRF): Maastrichtian strata from the Bottaccione Gorge, Gubbio, Italy

Pelagic carbonate sections constitute common archives for paleoclimatological and stratigraphical research. This study evaluates the use of portable X-ray fluorescence (pXRF) measurements on pelagic carbonates and applies the method to the well-studied latest Maastrichtian in the Bottaccione Gorge section from Gubbio, Italy. A calibration with carbonate reference materials makes it possible to acquire absolute elemental concentrations, and allows for comparison with results from previous geochemical studies, which used more expensive and time consuming conventional techniques, such as neutron activation or Inductively Coupled Plasma Mass Spectrometry (ICP-MS). With adequate measurement strategies and careful calibration, pXRF measurements can be a reliable, non-destructive, cheap, fast and easy to use alternative to acquire multi-elemental concentration data (Ca, Fe, Mn, Sr) in pelagic carbonates. These pXRF elemental concentration data represent valuable additions to classical proxies such as magnetic susceptibility and calcium carbonate content used in the study of pelagic carbonates. Furthermore, the potential of the portable pXRF method for applications in cyclostratigraphical (e.g. using Fe-concentrations) and chemostratigraphical (e.g. using Mn and Sr concentrations) investigations is demonstrated. A strong covariation between the measured Sr concentration profile obtained by pXRF and the existing δ18O record, in combination with micro-XRF mapping, demonstrated the sampling of calcite veins in some of the samples. The first 87Sr/86Sr isotope measurements for the latest Maastrichtian in the Bottaccione Gorge section seem to be little affected by this sampling effect.

Forensic identification of pharmaceuticals via portable X-ray fluorescence and diffuse reflectance spectroscopy

The importance of unknown substance identification in forensic science is vital to implementation or exclusion of criminal charges against an offender. While traditional laboratory measures include the use of gas chromatography/mass spectroscopy, an alternate method has been proposed to efficiently perform presumptive analyses of unknown substances at a crime scene or at airport security points. The use of portable X-ray fluorescence (PXRF) and visible near infrared diffuse reflectance spectroscopy (DRS) to determine elemental composition was applied to pharmaceutical medications (n=83), which were then categorized into 21 classifications based on their active ingredients. Each pharmaceutical was processed by standard laboratory procedures and scanned with both PXRF and DRS. Lastly, the datasets obtained were compared using multivariate statistical analyses. The aforementioned devices indicate that differentiation of unknown substances is clearly demonstrated among the samples with 73.49% DRS classification accuracy. Thus, the approach shows promise for future development as a rapid analytical technique for unknown pharmaceutical substances and/or illicit narcotics.

Use of portable X-ray fluorescence in the analysis of surficial sediments in the exploration of hydrothermal vents on the Southwest Indian Ridge

Hydrothermal plumes released from the eruption of sea floor hydrothermal fluids contain large amounts of oreforming materials. They precipitate within certain distances from the hydrothermal vent. Six surficial sediment samples from the Southwest Indian Ridge (SWIR) were analyzed by a portable X-ray fluorescence (PXRF) analyzer on board to find a favorable method fast and efficient enough for sea floor sulfide sediment geochemical exploration. These sediments were sampled near, at a moderate distance from, or far away from hydrothermal vents. The results demonstrate that the PXRF is effective in determining the enrichment characteristics of the oreforming elements in the calcareous sediments from the mid-ocean ridge. Sediment samples (>40 mesh) have high levels of elemental copper, zinc, iron, and manganese, and levels of these elements in sediments finer than 40 mesh are lower and relatively stable. This may be due to relatively high levels of basalt debris/glass in the coarse sediments, which are consistent with the results obtained by microscopic observation. The results also show clear zoning of elements copper, zinc, arsenic, iron, and manganese in the surficial sediments around the hydrothermal vent. Sediments near the vent show relatively high content of the ore-forming elements and either high ratios of copper to iron content and zinc to iron content or high ratios of copper to manganese content and zinc to manganese content. These findings show that the content of the ore-forming elements in the sediments around hydrothermal vents are mainly influenced by the distance of sediments to the vent, rather than grain size. In this way, the PXRF analysis of surface sediment geochemistry is found to satisfy the requirements of recognition geochemical anomaly in mid-ocean ridge sediments. Sediments with diameters finer than 40 mesh should be used as analytical samples in the geochemical exploration for hydrothermal vents on mid-oceanic ridges. The results concerning copper, zinc, arsenic, iron, and manganese and their ratio features can be used as indicators in sediment geochemical exploration of seafloor sulfides.