Measurement Of Trace Elements Research Articles

Timescales of storage and recycling of crystal mush at Krafla Volcano, Iceland

Processes in upper-crustal magma reservoirs such as recharge, magma mixing, recycling of previously crystallized material, and eruption affect both the physical state and the chemical composition of magmas. A growing body of evidence shows that crystals in intermediate or silicic volcanic rocks preserve records of these processes that may be obscured due to mixing in the liquid fraction of magmas. Fewer studies have focused on crystals in basaltic lavas, but these show evidence for a more subtle, but still rich record of magmatic processes. We present new 238U–230Th–226Ra data for plagioclase, combined with δ18O and trace-element measurements of the same crystal populations, from basalts erupted at Krafla Volcanic Center, Iceland. These data document the presence of multiple crystal populations within each sample, with chemical and oxygen isotope heterogeneity at a variety of scales: within individual crystals, between crystals in a given population, between crystal populations within the same sample, and between crystals in lavas erupted from different vents during the same eruption. Comparison to whole-rock or groundmass data shows that the majority of macroscopic crystals are not in trace-element or oxygen isotope equilibrium with their host liquids. The most likely explanation for these data is that the macroscopic crystals originated within a highly heterogeneous crystal mush in the shallow magma reservoir system. U-series and diffusion data indicate that the crystals (and therefore the mush) formed recently (likely within a few thousand years of eruption, and with a maximum age of 8–9 ka), and that the crystals resided in their host magma prior to eruption for decades to a few centuries at most. These data, in conjunction with other recent studies, suggest a model where erupted Icelandic magmas are the result of diverse magmas entering the crust, followed by complex interactions between melts and previously crystallized material at all crustal levels.

Geophysical, isotopic, and hydrogeochemical tools to identify potential impacts on coastal groundwater resources from Urmia hypersaline Lake, NW Iran.

Measurements of major ions, trace elements, water-stable isotopes, and geophysical soundings were made to examine the interaction between Urmia Aquifer (UA) and Urmia Lake (UL), northwest Iran. The poor correlation between sampling depth and Cl(-) concentrations indicated that the position of freshwater-saltwater interface is not uniformly distributed in the study area, and this was attributed to aquifer heterogeneities. The targeted coastal wells showed B/Cl and Br/Cl molar ratios in the range of 0.0022-2.43 and 0.00032-0.28, respectively. The base-exchange index (BEI) and saturation index (SI) calculations showed that the salinization process followed by cation-exchange reactions mainly controls changes in the chemical composition of groundwater. All groundwater samples are depleted with respect to δ(18)O (-11.71 to -9.4 ‰) and δD (-66.26 to -48.41 ‰). The δ(18)O and δD isotope ratios for surface and groundwater had a similar range and showed high deuterium excess (d-excess) (21.11 to 31.16 ‰). The high d-excess in water samples is because of incoming vapors from the UL mixed with an evaporated moisture flux from the Urmia mainland and incoming vapors from the west (i.e., Mediterranean Sea). Some saline samples with low B/Cl and Br/Cl ratios had depleted δ(18)O and δD. In this case, due to freshwater flushing, the drilled wells in the coastal playas and salty sediments could have more depleted isotopes, more Cl(-), and consequently smaller B/Cl and Br/Cl ratios. Moreover, the results of hydrochemical facies evolution (HFE) diagram showed that because of the existence fine-grained sediments saturated with high density saltwater in the coastal areas that act as a natural barrier, increasing the groundwater exploitation leads to movement of freshwaters from recharge zones in the western mountains not saltwater from UL. The highly permeable sediments at the junction of the rivers to the lake are characterized by low hydraulic gradient and high hydraulic conductivity. These properties enhance the salinization of groundwater observed in the study area. The main factors influencing the salinity are base-exchange reactions, invasion of highly diluted saltwater, dissolution of salty pans, and water chemistry evolution along flow paths.

Study of Trace Element Levels in Sudanese Moringa Olivera Leaves Using XRF Technique

Moringa Olivera is one of the most important plants in earth in fields of nutrition and medicines, and has economic value. The main objectives of this study were to measure trace elements concentrations and calculate co-factor of some elements K, Ca, Fe, Cu and Zn. Five samples were taken from soil and leaves of Moringa Olivera from Alsamrab area, analyzed by X- ray florescence (XRF) to measure concentrations of trace elements, which are K, Ca, Mn, Fe, Cu, Zn, Pb, Br, Rb, Y,± Zr and Nb which has concentrations of (6786 1650, 26920 ± 1209, 1051.2 ± 902.57, 41800 ± 3994.997, 13.04 ± 1.890, 65.68 ± 11.932, 22.48 ± 5.266, 6.2 ± 1.235, 48.14 ± 7.87, 18.66 ± 1.088, 307.8 ± 55.91 and 19.54 ± 3.95 ppm), respectively. Comparison between Sudanese Moringa Olivera and African studies (Nigeria, Burkina Faso and Ghana) concentrate in Ca, K, Cu, Zn and Fe elements. Nigerian Moringa (303, 1.65, N.F., 3.33 and 13.85 ppm), respectively. Burkina Faso Moringa (2098, 1922, N.F., 5.4 and 28.3 ppm), respectively. Ghanaian Moringa (26.4, 21.7, 7.1, 13.7 and 175 ppm). The results showed significantly cofactor of K and Ca (5.6% and 2.9%). Moringa has a competitive characteristic with other Sudanese food (Mango, Baobab and Pumpkin).

Detection of trace elements in children and its clinical value

While only in minute quantities in the body, trace elements are crucial co-factors and regulators of normal metabolism. Commonly tested elements include calcium, magnesium, iron, zinc, and copper. Imbalance or deficiencies in trace elements can cause growth retardation, malnutrition, immune malfunction and other abnormalities in children. Because these elements are in trace amounts, sensitivity and reproducibility of detection methods are of paramount importance. Different methods for the same element can yield different reference intervals, which, in order to be applied in the clinic, would have to be independently established by individual laboratories. Clearly defined indications and good quality control to ensure accuracy and sensitivity are necessary for the measurement of trace elements to provide objective reference for clinical diagnosis.(Chin J Lab Med, 2016, 39: 240-242) Key words: Trace elments; Reference values; Child

Particle induced X-ray emission study of blood samples of Indian Kala-azar patients.

Visceral leishmaniasis (VL) or Kala-azar (KA) is a neglected tropical disease caused by protozoan parasite, Leishmania sp. and is fatal, if left untreated. In this study, we measured trace elements (K, Fe, Cu, Zn, Br, Cl, S, Ca, Mn, Cr, Ni, As, Se, Rb and Sr) in the blood of Indian VL patients (32) by particle-induced X-ray emission (PIXE) study. Blood was collected from 36 subjects including healthy controls from Rambagh Kala-azar Hospital, Muzaffarpur, Bihar, India. PIXE experiment was carried out at the Institute of Physics, Bhubaneswar, India and data were analyzed by GUPIXWIN software. We observed first time the association of bromine with the disease. The results showed 48.47% decrease in Br, 35.16% decrease in Zn and 29.05% decrease in Fe in untreated state of the KA patients. In the same group, Cu has been increased by 16.73%. Cu/Zn ratio has been altered in diseased state. The association of bromine with the disease is reported for the first time and altered levels of trace elements (Br, Cu, Fe and Zn) may come back to normal after completion of the treatment regimen with Amphotericin B.

Ni/S/Cl systematics and the origin of impact‐melt glasses in Martian meteorite Elephant Moraine 79001

AbstractMartian meteorite Elephant Moraine A79001 (EET 79001) has received considerable attention for the unusual composition of its shock melt glass, particularly its enrichment in sulfur relative to the host shergottite. It has been hypothesized that Martian regolith was incorporated into the melt or, conversely, that the S‐enrichment stems from preferential melting of sulfide minerals in the host rock during shock. We present results from an electron microprobe study of EET 79001 including robust measurements of major and trace elements in the shock melt glass (S, Cl, Ni, Co, V, and Sc) and minerals in the host rock (Ni, Co, and V). We find that both S and major element abundances can be reconciled with previous hypotheses of regolith incorporation and/or excess sulfide melt. However, trace element characteristics of the shock melt glass, particularly Ni and Cl abundances relative to S, cannot be explained either by the incorporation of regolith or sulfide minerals. We therefore propose an alternative hypothesis whereby, prior to shock melting, portions of EET 79001 experienced acid‐sulfate leaching of the mesostasis, possibly groundmass feldspar, and olivine, producing Al‐sulfates that were later incorporated into the shock melt, which then quenched to glass. Such activity in the Martian near‐surface is supported by observations from the Mars Exploration Rovers and laboratory experiments. Our preimpact alteration model, accompanied by the preferential survival of olivine and excess melting of feldspar during impact, explains the measured trace element abundances better than either the regolith incorporation or excess sulfide melting hypothesis does.

Heavy metals in agricultural soils of the European Union with implications for food safety

Soil plays a central role in food safety as it determines the possible composition of food and feed at the root of the food chain. However, the quality of soil resources as defined by their potential impact on human health by propagation of harmful elements through the food chain has been poorly studied in Europe due to the lack of data of adequate detail and reliability. The European Union's first harmonized topsoil sampling and coherent analytical procedure produced trace element measurements from approximately 22,000 locations. This unique collection of information enables a reliable overview of the concentration of heavy metals, also referred to as metal(loid)s including As, Cd, Cr, Cu, Hg, Pb, Zn, Sb. Co, and Ni. In this article we propose that in some cases (e.g. Hg and Cd) the high concentrations of soil heavy metal attributed to human activity can be detected at a regional level. While the immense majority of European agricultural land can be considered adequately safe for food production, an estimated 6.24% or 137,000km2 needs local assessment and eventual remediation action.

Interlaboratory evaluation of cellulosic acid-soluble internal air sampling capsules for multi-element analysis

ABSTRACTAn interlaboratory study was carried out to evaluate the use of acid-soluble cellulosic air sampling capsules for their suitability in the measurement of trace elements in workplace atmospheric samples. These capsules are used as inserts to perform closed-face cassette sample collection for occupational exposure monitoring. The interlaboratory study was performed in accordance with NIOSH guidelines that describe statistical procedures for evaluating measurement accuracy of air monitoring methods. The performance evaluation materials used consisted of cellulose acetate capsules melded to mixed-cellulose ester filters that were dosed with multiple elements from commercial standard aqueous solutions. The cellulosic capsules were spiked with the following 33 elements of interest in workplace air monitoring: Ag, Al, As, Ba, Be, Ca, Cd, Co, Cr, Cu, Fe, In, K, La, Li, Mg, Mn, Mo, Ni, P, Pb, Sb, Se, Sn, Sr, Te, Ti, Tl, V, W, Y, Zn, Zr. The elemental loading levels were certified by an accredited provider of certified reference materials. Triplicates of media blanks and multielement-spiked capsules at three different elemental loadings were sent to each participating laboratory; the elemental loading levels were not revealed to the laboratories. The volunteer participating laboratories were asked to prepare the samples by acid dissolution and to analyze aliquots of extracted samples by inductively coupled plasma atomic emission spectrometry in accordance with NIOSH methods. It was requested that the study participants report their analytical results in units of μg of each target element per internal capsule sample. For the majority of the elements investigated (30 out of 33), the study accuracy estimates obtained satisfied the NIOSH accuracy criterion (A < 25%). This investigation demonstrates the utility of acid-soluble internal sampling capsules for multielement analysis by atomic spectrometry.

NanoSIMS measurements of trace elements at the micron scale interface between zircon and silicate glass

We present a new method to measure trace element variation at the micron scale interface between zircon and melt. Two analytical modes (“grain mode” and “image mode”) were applied and shown as below.

Paleoclimatic and paleoenvironmental fluctuations inferred for the Middle and Late Pleniglacial transition and Late Pleniglacial (MIS3/MIS2 and MIS2) based on high-resolution (ca. 35 and 70 years) complex sedimentological and paleoecological data from the

The Katymar brickyard profile, found at the northernmost fringe of the Backa loess plateau, is one of the thickest and best developed last glacial loess sequences of Central Europe. In the present work high resolution (at 2 cm and 4 cm intervals representing ca. 35 and 70 years) magnetic susceptibility, grain-size, LOI, water-solution trace elements measurements and pollen, phytholithic, anthracological and malacological analyses were implemented on samples derived from the 11,5 m profile corresponding to a period between 35,000 and 13,000 cal BP years (from the terminal phase of MIS3 to the end of MIS2).

Effects of sample storage and shell orientation on LA-ICPMS trace element measurements on deep-sea mussels

Geochemical markers are being increasingly applied to fundamental questions in population and community ecology in marine habitats because they allow inferences on individuals dispersal, but vital effects, small sample size and instrumental limitation are still challenging particularly in deep-sea studies. Here we use shells of the deep-sea bivalve Idas modiolaeformis to assess potential effects of sample storage, mineralogy, and valve orientation on LA-ICPMS measurements. Trace element concentrations of 24Mg, 43Ca, 88Sr, 137Ba, 208Pb, and 238U are not affected by the two most commonly used storage methods of biologic deep-sea samples (frozen at –20°C and fixed in 95% ethanol); thus combined analysis of differently preserved specimens is possible when the number of individuals is insufficient and distinct sample fixation is needed for multiple purposes. Valve orientation had a strong impact on quantification of trace elements in the calcitic but not in the aragonitic layer of adult shells. Hence, to enable comparisons between adult shells and entirely aragonitic embryonic shells, a reference map of site-specific signatures can potentially be generated using the aragonitic layer of the adult shells. Understanding ontogenetic changes and environmental effects in trace element incorporation is critical before geochemical fingerprinting can be used as a tool for larval dispersal studies in the deep-sea.

On-Line Analysis and Kinetic Behavior of Arsenic Release during Coal Combustion and Pyrolysis.

The kinetic behavior of arsenic (As) release during coal combustion and pyrolysis in a fluidized bed was investigated by applying an on-line analysis system of trace elements in flue gas. This system, based on inductively coupled plasma optical emission spectroscopy (ICP-OES), was developed to measure trace elements concentrations in flue gas quantitatively and continuously. Obvious variations of arsenic concentration in flue gas were observed during coal combustion and pyrolysis, indicating strong influences of atmosphere and temperature on arsenic release behavior. Kinetic laws governing the arsenic release during coal combustion and pyrolysis were determined based on the results of instantaneous arsenic concentration in flue gas. A second-order kinetic law was determined for arsenic release during coal combustion, and the arsenic release during coal pyrolysis followed a fourth-order kinetic law. The results showed that the arsenic release rate during coal pyrolysis was faster than that during coal combustion. Thermodynamic calculations were carried out to identify the forms of arsenic in vapor and solid phases during coal combustion and pyrolysis, respectively. Ca3(AsO4)2 and Ca(AsO2)2 are the possible species resulting from As-Ca interaction during coal combustion. Ca(AsO2)2 is the most probable species during coal pyrolysis.

NanoSIMS mapping and LA-ICP-MS chemical and U–Th–Pb data in monazite from a xenolith enclosed in andesite (Central Slovakia Volcanic Field)

In this study, we use NanoSIMS element and isotope ratio mapping and LA-ICP-MS trace element measurements to elucidate the origins of monazites from a restitic xenolith enclosed in a 13.5 ± 0.3 Ma andesitic lava (Slovakia). The xenolith/lava interaction is mainly characterized by the growth of a plagioclase-bearing corona around the xenolith and magmatic garnet overgrowths on primary metamorphic garnets within the xenolith. NanoSIMS images (89Y, 139La, 208Pb, 232Th and 238U) and trace element analyses indicate that variations of HREE, Y and Eu contents in the monazite are correlated with the resorption and the following overgrowth of garnet and plagioclase in the xenolith. Three domains are distinguished in the monazite grains: the inherited Variscan core at ca. 310 Ma (M1 domain) characterized by low Y and HREE contents and a weak negative Eu anomaly; the inner rim (M2 domain) crystallized during the growth of the plagioclase magmatic corona (large negative Eu anomaly) and the resorption of metamorphic garnet (high HREE and Y contents); and the external rim (M3 domain) crystallized during the growth of the plagioclase corona (large negative Eu anomaly) and during the crystallization of magmatic garnet (low Y, HREE contents) at ~13 Ma, i.e. the age of the andesitic lava. The age and chemical zonation of the monazites attest to the preservation of primary monazite in the xenolith despite the interaction with the andesite lava. NanoSIMS imaging provides high-quality sub-µm scale images of the monazite that reveals chemical domains that were not distinguishable on WDS X-ray maps, especially for depleted elements such as U and Pb. Owing to its small size, the M2 domain could not be accurately dated by the LA-ICP-MS method. However, NanoSIMS isotopic maps reveal that the M2 domain has similar 208Pb/232Th isotope ratios to the M3 domain and thus similar ages. These results support the hypothesis that melt-assisted partial dissolution–precipitation in monazite efficiently records chemical and mineralogical changes during xenolith/lava interaction.

Advanced source apportionment of size-resolved trace elements at multiple sites in London during winter

Abstract. Trace element measurements in PM10–2.5, PM2.5–1.0 and PM1.0–0.3 aerosol were performed with 2 h time resolution at kerbside, urban background and rural sites during the ClearfLo winter 2012 campaign in London. The environment-dependent variability of emissions was characterized using the Multilinear Engine implementation of the positive matrix factorization model, conducted on data sets comprising all three sites but segregated by size. Combining the sites enabled separation of sources with high temporal covariance but significant spatial variability. Separation of sizes improved source resolution by preventing sources occurring in only a single size fraction from having too small a contribution for the model to resolve. Anchor profiles were retrieved internally by analysing data subsets, and these profiles were used in the analyses of the complete data sets of all sites for enhanced source apportionment. A total of nine different factors were resolved (notable elements in brackets): in PM10–2.5, brake wear (Cu, Zr, Sb, Ba), other traffic-related (Fe), resuspended dust (Si, Ca), sea/road salt (Cl), aged sea salt (Na, Mg) and industrial (Cr, Ni); in PM2.5–1.0, brake wear, other traffic-related, resuspended dust, sea/road salt, aged sea salt and S-rich (S); and in PM1.0–0.3, traffic-related (Fe, Cu, Zr, Sb, Ba), resuspended dust, sea/road salt, aged sea salt, reacted Cl (Cl), S-rich and solid fuel (K, Pb). Human activities enhance the kerb-to-rural concentration gradients of coarse aged sea salt, typically considered to have a natural source, by 1.7–2.2. These site-dependent concentration differences reflect the effect of local resuspension processes in London. The anthropogenically influenced factors traffic (brake wear and other traffic-related processes), dust and sea/road salt provide further kerb-to-rural concentration enhancements by direct source emissions by a factor of 3.5–12.7. The traffic and dust factors are mainly emitted in PM10–2.5 and show strong diurnal variations with concentrations up to 4 times higher during rush hour than during night-time. Regionally influenced S-rich and solid fuel factors, occurring primarily in PM1.0–0.3, have negligible resuspension influences, and concentrations are similar throughout the day and across the regions.

Trace Element Concentrations in Liver of 16 Species of Cetaceans Stranded on Pacific Islands from 1997 through 2013.

The impacts of anthropogenic contaminants on marine ecosystems are a concern worldwide. Anthropogenic activities can enrich trace elements in marine biota to concentrations that may negatively impact organism health. Exposure to elevated concentrations of trace elements is considered a contributing factor in marine mammal population declines. Hawai'i is an increasingly important geographic location for global monitoring, yet trace element concentrations have not been quantified in Hawaiian cetaceans, and there is little trace element data for Pacific cetaceans. This study measured trace elements (Cr, Mn, Cu, Zn, As, Se, Sr, Cd, Sn, Hg, and Pb) in liver of 16 species of cetaceans that stranded on U.S. Pacific Islands from 1997 to 2013, using high resolution inductively coupled plasma mass spectrometry (HR-ICP-MS) (n = 31), and direct mercury analysis atomic absorption spectrometry (DMA-AAS) (n = 43). Concentration ranges (μg/g wet mass fraction) for non-essential trace elements, such as Cd (0.0031-58.93) and Hg (0.0062-1571.75) were much greater than essential trace elements, such as Mn (0.590-17.31) and Zn (14.72-245.38). Differences were found among age classes in Cu, Zn, Hg, and Se concentrations. The highest concentrations of Se, Cd, Sn, Hg, and Pb were found in one adult female false killer whale (Pseudorca crassidens) at concentrations that are known to affect health in marine mammals. The results of this study establish initial trace element concentration ranges for Pacific cetaceans in the Hawaiian Islands region, provide insights into contaminant exposure of these marine mammals, and contribute to a greater understanding of anthropogenic impacts in the Pacific Ocean.

Development of Desolvation System for Single-cell Analysis Using Droplet Injection Inductively Coupled Plasma Atomic Emission Spectroscopy.

With a view to enhance the sensitivity of analytical instruments used in the measurement of trace elements contained in a single cell, we have now equipped the previously reported micro-droplet injection system (M-DIS) with a desolvation system. This modified M-DIS was coupled to inductively coupled plasma atomic emission spectroscopy (ICP-AES) and evaluated for its ability to measure trace elements. A flow rate of 100 mL/min for the additional gas and a measurement point -7.5 mm above the load coil (ALC) have been determined to be the optimal parameters for recording the emission intensity of the Ca(II) spectral lines. To evaluate the influence of the desolvation system, we recorded the emission intensities of the Ca(I), Ca(II), and H-β spectral lines with and without inclusion of the desolvation system. The emission intensity of the H-β spectral line reduces and the magnitude of the Ca(II)/Ca(I) emission intensity ratio increases four-fold with inclusion of the desolvation system. Finally, the elements Ca, Mg, and Fe present in a single cell of Pseudococcomyxa simplex are simultaneously determined by coupling the M-DIS equipped with the desolvation system to ICP-AES.

PTH-216 Trace element measurement in hospitalised children on parenteral nutrition: Abstract PTH-216 Table 1

<h3>Introduction</h3> The aim of parenteral nutrition (PN) is to meet the body’s needs while avoiding complications of deficiency and toxicity.¹Trace elements (Cu, Zn, Se) play an important role in many of the body’s functions including metabolism, immunity and enzymes.¹ESPGHAN/ ESPEN guidelines recommended that levels of trace elements should be checked at the commencement and frequently after starting PN.¹Our aim was to review the current practice in our tertiary paediatric hospital. <h3>Method</h3> In-patients receiving PN were identified from the pharmacy database. All records from patients receiving PN on two randomly allocated days in December and January were analysed for demographic data and diagnosis. From the laboratory database we looked for Zinc (Zn), Copper (Cu) and Selenium (Se) levels at the commencement and 4–8 weeks after starting PN. We excluded patients with no available data on the start of PN. <h3>Results</h3> 72 patients receiving PN were identified on the two days. Data were available for 63 patients and 9 others were excluded as data was not available on starting PN. The 63 patients with available results were aged 1–16 years, median age of 4.5 years. 36 were males. Overall; Trace Elements (TE) were checked in 26/63 (41.2%) (Table1). TE results were available before or within one week of starting PN in 18/63 (28.5%). Thirteen had TE follow up. Table 3 shows the levels of TE within one week of starting PN and the follow up results. 5 patients had low initial Zn, Cu and Se. These were patients with Tufting enteropathy, early onset inflammatory bowel disease (IBD), one patient with IPEX, one patient with Intestinal obstruction and one with missing records. The latter two in addition to another patient with HLH also had low levels on follow up. Out of the whole cohort of 63, 27 (43%) patients have an underlying gastrointestinal disorder, 20 (74%) of whom had levels checked initially and 9 (33%) had levels done on follow up. <h3>Conclusion</h3> Unfortunately determination of TE level is frequently missed in our institution. Although figures from the gastroenterology department were better than other departments, we recommended use of a proforma to be filled by the clinician before starting PN. We recommend TE to be checked at least once every 3 months for those with normal levels and once a month for those with low levels. A re-audit is planned later in the year. <h3>Disclosure of interest</h3> None Declared. <h3>Reference</h3> Koletzko B, <i>et al</i>. J Pediatr Gastroenterol Nutr. 2005;41(Suppl 2)

Metals content in otoliths of Dicentrarchus labrax from two fish farms of Sicily.

Otoliths of cultured sea bass (Dicentrarchus labrax) from two different fish farms of Sicily were collected and analyzed by using inductively coupled plasma optical emission spectroscopy. Metal content (Ba, Cd, Fe, Mg, Mn, Sr, and Zn) was measured in order to test the potential use of biogenic carbonates as proxies of dissimilar environmental conditions since the fish farms are implanted in opposite coastal marine areas (Gulf of Castellammare and Gulf of Gela) characterized by different oceanographic features and human activities. Cluster analysis discriminates samples as different groups on the basis of metal content. Results show that concentrations of Sr in the otoliths have a similar range of distribution and not significantly different between the two farms. Otherwise, Fe, Mg, Mn, and Cd show higher concentrations in otoliths collected from fish reared in the farm in the southern coast (Gulf of Gela), an area subject to a great anthropogenic pressure. Zn is the only element with higher values in the otoliths from the farm in the northern coast (Gulf of Trappeto) probably due to industrial effluent. In this work, obtained data confirm the high potential of trace elements measurements in these biogenic carbonates as proxies of different environmental conditions.

Design of a Proton-induced Quasimonochromatic Micro-XRF Setup for Wet Biological Samples

Abstract We designed and constructed a proton-induced quasimonochromatic micro-XRF system for wet biological samples. A horizontal beam of MeV protons delivered by a 1.6 MV tandem accelerator was bent downward by 45° using a dipole magnet. A copper (Cu) foil target was placed perpendicular to the incident proton beam. The thickness of the foil was 30 μm, which is slightly larger the proton range. This Cu foil was used also as a vacuum window for the X-rays. The proton-induced quasimonochromatic X-rays (QMXRs) emitted to the atmosphere through the foil were focused by a polycapillary X-ray half lens. The monochromaticity and intensity of the QMXR microbeam as a function of the incident proton energy were investigated. The QMXR microbeam impinged on the horizontal sample surface with an incident angle of 45°, and emitted fluorescent X-rays from the sample were collected by a Si-PIN X-ray detector positioned at 90° with respect to the incident microbeam. The size of the X-ray beam was 250 μm × 350 μm. To demonstrate the capability of the micro-XRF setup for in-vivo measurement of trace elements in biological samples, we measured cobalt (Co) accumulated in leaves of duckweed floating on a Co solution surface. By using standard samples which simulated the duckweed leaf, the Co concentration in the leaf in the order of 100 ppm could be quantitatively determined.

Frozen melt–rock reaction in a peridotite xenolith from sub-arc mantle recorded by diffusion of trace elements and water in olivine

Inferring the ambient state of the lithospheric mantle from xenoliths may be misleading if the magmatic activity responsible for the exhumation has modified the xenolith. Changes due to melt–xenolith interactions during exhumation are usually identifiable because of the short timescales involved, but changes due to earlier pulses of magma passing through the lithosphere may be more insidious because the longer timescales allow extensive overprinting of the ambient petrography. Here we describe an intermediate stage of melt–rock reaction recorded in a porphyroclastic peridotite xenolith from the upper mantle wedge adjacent to the West Bismarck Island Arc. The texture and chemistry, frozen during rapid exhumation, reflects the progressive change from harzburgite to clinopyroxene-bearing dunite caused by the infiltration of hydrous basaltic melt into the xenolith. The unusually low equilibration temperature of the xenolith (∼650 °C) prior to this event is reflected in very low concentrations of incompatible elements in the olivine, enhancing the diffusion profiles of these elements into the olivine from the interaction with the melt. The Ca concentration profiles correspond to a timescale of approximately three months, which we interpret as the time between the first infiltration of melt into the lithospheric mantle at this locality and the subsequent exhumation of the xenolith by a second pulse of magma. The diffusion profiles of other trace elements (Li, Na, Sc, Ti, V, Cr, Mn, Ni, Cu, Y) and major elements (Fe–Mg) confirm that all these elements diffuse through olivine at rates that differ from each other by less than one order of magnitude. Infrared spectroscopy reveals OH− (“water”) contents and incorporation mechanisms typical of other arc mantle peridotites in the olivine cores. Water contents increase towards the crystal rims, similarly to the profiles of other measured trace elements. The increase in water concentration is accompanied by subtle changes in the infrared bands, caused by an increasing proportion of the OH− being bonded to Cr3+ towards the rim. The OH− coupled with Cr3+ follows the zoning pattern of Cr, except at the crystal rim, where it decreases due to late-stage degassing during eruption. This relationship shows that water incorporation in olivine was a metastable process controlled by the availability of suitable sites. In general, the amount of water incorporated into mantle olivine may be expected to depend not only on the intensive variables of H2O fugacity, temperature and pressure, but also on the concentrations of enabling trace components like Cr3+ and Fe3+ in the olivines. The water in the olivine core is associated with Cr3+ and Fe3+ in approximately equal proportions.