One-point calibration and matrix-matching concept for quantification of potentially toxic elements in wood by LA-ICP-MS.

The aim of this work is to evaluate two quantitative methods, based on the external calibration applied in laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) analysis, known as (i) analytical curve and (ii) one-point calibration, using the concept of matrix matching to quantify three potentially toxic elements (PTEs) in wood samples. These can biologically register changes in the abiotic environment and be applied to monitoring climate change or environmental toxicity. In this case, standard sample preparation was evaluated to prepare the standard pellets using Pinus taeda species as a matrix-matching concept. Six pellets of P. taeda, with different Pb, Cd, and Ba concentrations, were prepared to build the analytical curve and one-point calibration strategies. The LA-ICP-MS parameters were optimised for 206Pb, 208Pb, 112Cd, 114Cd, 137Ba, and 138Ba isotope analysis in wood samples. The two calibration strategies provided 74-110% analytical recovery from certified reference materials and similar results to those obtained by ICP-MS through the acid digestion of environmental wood samples from São Paulo City (Brazil). This demonstrated the applicability of the one-point calibration strategy in quantifying PTEs in wood samples, which could be used with environmental analyses. Differences observed between the Ba isotope results obtained via LA-ICP-MS and ICP-MS quantification were related to sampling by LA-ICP-MS and the ICP-MS sample introduction, as well as to laser matrix and transport effects because of the difference between the wood species evaluated.

The role of silver nanoparticles effects in the homeostasis of metals in soybean cultivation through qualitative and quantitative laser ablation bioimaging.

BACKGROUND: Nanoparticles (NPs) are currently found in the world in the form of natural colloids and volcanic ash, as well as in anthropogenic sources, such as nanofertilizers; however, in the literature, there is still a lack of toxicological evidence, risk assessment, and regulations about the use and environmental impact of NPs in the agroindustrial system. Therefore, the aim of this work was to evaluate alterations caused by the presence of AgNPs during the development of soybean plants. METHODS: The BRS232 non-transgenic (NT) soybean plant and 8473RR (TRR) and INTACTA RR2 PRO (TIntacta) transgenic soybean plants were irrigated for 18 days under controlled conditions with deionized water (control), AgNPs, and AgNO3. The isotopes 107Ag+, 55Mn+, 57Fe+, 63Cu+, and 64Zn+ were mapped in leaves, using 13C+ as an internal standard (IS), and carried out using a laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) technique with a Nd:YAG (213 nm) laser source in the imagagin mode using the LA-iMageS software and also Mathlab. RESULTS: Leaf images showed a low Ag translocation, indicated by the basal signal of this ion. Additionally, the presence of Ag in the ionic form and as NPs altered the homeostasis of 112Cd+, 64Zn+, 55Mn+, 63Cu+, and 57Fe+ in different ways. Quantitative image analysis was performed for Cu. CONCLUSION: The behavior of TRR and TIntacta plants was different in the presence of ionic silver or AgNPs, confirming that the metabolism of these two plants, despite both being transgenic, are different. Through the images, it was observed that the response of plants was different in the face of the same stress conditions during their development.

Comparative Analysis of Guatemalan and Qing Dynasty Jadeite Elemental Signs.

Different jadeites have different characteristics. In this paper, the La-ICP-MS test is used to compare and analyze the elemental characteristics of jadeite in Guatemala and the Qing dynasty. The test results show that the highest value of Guatemalan jadeite Ca can reach 2.5 apfu, while the highest value of Qing dynasty jadeite is 0.73 apfu. The highest value of Na is the same for both. The concentration distribution range and highest value of Guatemalan jadeite and Qing dynasty jadeite Mg/(Mg + Fe) are the same. Guatemalan jadeite and Qing dynasty jadeite have a very wide content of trace elements. Qing dynasty Ca/(Mg + Fe) distribution is wider. Concentrations of Guatemalan and Qing dynasty jadeite Sr/Ba, which is a marine sediment, are greater than 1. The Ba in the Qing dynasty jadeite sediments contains a large amount of clay, resulting in higher levels than the average amount in Guatemalan jadeite Ba. The standard distribution map is similar, showing a "horn" shape. The Sr distribution is uneven. Guatemalan jadeite is heavily enriched in rare earths. Eu shows positive and negative abnormalities. The total rare earth value is 8.15 ppm. Qing Dynasty jadeite shows light rare earth enrichment, and Eu is a positive anomaly. The total rare earth value is 7.07 ppm. The characteristics of the two elements are somewhat similar, but different, which does not rule out the possibility that Qing dynasty jadeite came from Guatemala.

Coral growth bands recorded trace elements associated with the Fundão dam collapse.

In November 2015, the collapse of the Fundão dam (Minas Gerais, Brazil) carried over 40 × 106 m3 of iron ore tailings into the Doce river and caused massive environmental and socioeconomic impacts across the watershed. The downstream mudslide scavenged contaminants deposited in the riverbed, and several potentially toxic elements were further released through reduction and solubilization of Fe oxy-hydroxides under estuarine conditions. A turbidity plume was formed off the river mouth, but the detection of contaminants' dispersion in the ocean remains poorly assessed. This situation is specially concerning because Southwestern Atlantic's largest and richest reefs are located 70-250 km to the north of the Doce river mouth, and the legal dispute over the extent of monitoring, compensation and restoration measures are based either on indirect evidence from modeling or on direct evidence from remote sensing and contaminated organisms. Coral skeletons can incorporate trace elements and are considered good monitors of marine pollution, including inputs from open cut mining. Here, we studied a Montastraea cavernosa (Linnaeus 1767) coral colony collected 220 km northward to the river mouth, using X-rays for assessing growth bands and Laser Ablation Inductively Coupled Plasma Mass Spectrometry to recover trace elements incorporated in growth bands formed between 2014 and 2018. A threefold positive Fe anomaly was identified in early 2016, associated with negative anomalies in several elements. Variation in Ba and Y was coherent with the region's sedimentation dynamics, but also increased after 2016, akin to Pb, V and Zn. Coral growth rates decreased after the disaster. Besides validating M. cavernosa as a reliable archive of ocean chemistry, our results evidence wide-reaching sub-lethal coral contamination in the Abrolhos reefs, as well as different incorporation mechanisms into corals' skeletons.

Five thousand years of bellyaches: Exploring boron concentration in ancient populations of the Atacama Desert.

OBJECTIVES: This study explores whether ancient Atacama Desert populations in northern Chile were exposed to endemic boron contamination. MATERIALS AND METHODS: Using Laser Ablation-Inductively Coupled Plasma-Mass Spectrometry (LA-ICP-MS), we studied 144 strands of ancient mummy hair, ranging from 3000 B.C. to 1500 A.D., excavated from the Lluta, Azapa, and Camarones valleys in northern Chile. We tested whether these ancient populations showed signs of significant boron concentration in hair tissue. RESULTS: On average, all individuals from these valleys showed high boron concentrations, ranging from 1.5 to 4 times above the average boron concentration in contemporary hair (baseline <0.85 µg/g). The boron concentration in mummy hair varied according to the main geographic areas mentioned above. CONCLUSIONS: The rivers of northern Chile have high geogenic boron concentrations. They contain 38 times above the recommended limit for human consumption. Geogenic boron contamination likely played a role in population morbidity and the types of crops that were cultivated in antiquity. The ancient populations were chronically affected by boron overexposure, suggesting that ancient geogenic water contamination should be considered when discussing the biocultural trajectories of ancient populations.

Determination of rare earth elements in Fe-minerals using external calibration by LA-ICP-MS and application on Cauê Iron Formation (Brazil).

The rare earth elements (REE) composition in Fe-mineral phases is an important tool in iron formation studies to obtain information about parent rocks and environmental and paragenetic processes. However, the determination of REE presents some difficulties, such as the low concentration of these elements, matrix complexity and lack of iron matrix certified reference materials. The aim of the present work is to propose an analytical method to determine the REE plus Y (REE + Y) contents at trace levels in Fe-(hydr)oxides by the laser ablation ICP-quadrupoleMS technique, using external calibration. The calibration curves were obtained from analyses of reference materials with different matrices, and the analytical conditions were checked on the NIST 614 glass. The linearity (R2 ≥ 0.98), limit of detection (0.002-0.044 µg g-1), limit of quantification (0.008-0.146 µg g-1), recovery (88.4-112.4%), and intraday (0.1-14.1%) and interday (1.6-17.8%) precision were systematically assessed. The results obtained showed that the method is fit for the purpose and showed evidence of a nonsignificant interference of the matrix. Thus, the developed procedure was applied in the analyses of magnetite, martite, hematite, and goethite grains from Cauê Iron Formation (Brazil). The REE + Y patterns of the minerals are consistent with the previous study of bulk analyses on whole rocks and highlight the postdepositional signature of these elements in banded iron formations.

White mullet Mugil curema population structure from Mexico and Brazil revealed by otolith chemistry.

The white mullet Mugil curema supports several fisheries in the neotropical region; nevertheless, the population structure is still elusive. The aim of this study was to assess the presence of adult management units and nursery areas from five sampling sites throughout the Gulf of Mexico and northern Brazil using otolith microchemistry. The Li/Ca, Na/Ca, Mn/Ca, Sr/Ca, Ba/Ca and Pb/Ca ratios were measured in otolith core (juvenile stage) and edge (adult stage) (N = 131) using laser ablation-inductively coupled plasma-mass spectrometry. Several ratios were significantly different between sampling sites for core and edge (P < 0.05). For otolith edge, permutational multivariate analysis of variance showed significant differences (P < 0.05) between all sampling sites from Mexico (except between Mecoacán and Tamiahua, P > 0.05) and between Mexico (pooled samples) and Brazil. Quadratic discriminant analyses showed jackknifed classification higher in the edge (66.6% and 99.5% for Mexico and Brazil plus Mexico, respectively) than in the core (46.3% and 76.5% Mexico and Brazil plus Mexico, respectively). The two cluster analyses based on the core microchemistry (Mexico and Brazil plus Mexico) produced three main clusters, which did not coincide with catchment areas. These results support the segregation of the M. curema adult life stages among several sampling sites from Mexico and Brazil; moreover, core analysis suggested that the nursery areas did not correspond to the capture sites or adults stocks.

Investigative Analysis of Lanthanum Oxide Nanoparticles on Elements in Bone of Wistar Rats After 30 Days of Repeated Oral Administration.

Accumulation of lanthanum oxide nanoparticles (La2O3NPs) in the femur bone of rats after 30 days of oral administration was explored. Also, the influence of La2O3NPs on macro and trace elements in the rats' femur bone was assessed. Inductively coupled plasma mass spectrometry (ICP-MS) and inductively coupled plasma optical spectrometry (ICP OES) were used for total element determination in the bone after decomposition while laser ablation-ICP-MS (LA-ICP-MS) was used to investigate element distribution (bio-imaging) in the bone. Some differences in element concentrations in the bone between the rats treated with La2O3NPs at 1.0 mg kg-1 (T1), 10.0 mg kg-1 (T2), and 100 mg kg-1 (T3) body weight (bw) and the control rats (CTR) were observed. More differences were observed in the bone of rat treated with 10.0 mg kg-1 La2O3NPs bw. However, the highest change observed was for Mg, which concentration ranged from 5230 ± 12 µg kg-1 for the CTR group to 4130 ± 138 µg kg-1 for the T3 group. Minor changes were observed for Ba, Ca, Cr, Cu, Fe, Mg, Na, Pb, Sr, and Zn between CTR and animals treated with La2O3NPs at the different levels of concentration. It was possible to observe from LA-ICP-MS analysis that La2O3NPs were accumulated only on the surface of the bone, not deeper than about 5 µm. LA-ICP-MS allowed also to investigate the distribution of La and the other elements in a cross section of the femur bone head, where higher amounts of the elements are present at the external part of the bone. Therefore, it was demonstrated that La2O3NPs are incorporated on the surface of the bone and it has a small influence on some of the other elements evaluated.

Otolith microchemistry and diadromy in Patagonian river fishes.

Coastal habitats in Chile are hypothesized to support a number of diadromous fish species. The objective of this study was to document migratory life histories of native galaxiids and introduced salmonids from a wide latitudinal range in Chilean Patagonia (39-48°S). Otolith microchemistry data were analysed using a recursive partitioning approach to test for diadromy. Based on annular analysis of Sr:Ca ratios, a diadromous life history was suggested for populations of native Aplochiton taeniatus, A. marinus, and Galaxias maculatus. Lifetime residency in freshwater was suggested for populations of A. zebra and G. platei. Among introduced salmonids, populations of Oncorhynchus tshawytscha and O. kisutch exhibited patterns consistent with anadromy, whereas the screened population of O. mykiss appeared restricted to freshwater. Salmo trutta exhibited variable patterns suggesting freshwater residency and possibly anadromy in one case. The capacity and geographic scope of hydropower development is increasing and may disrupt migratory routes of diadromous fishes. Identification of diadromous species is a critical first step for preventing their loss due to hydropower development.

Bioimaging Metallomics.

This chapter focuses on bioimaging in metallomics, which involves metal and metalloids distribution in animal tissues. It starts with laser ablation-inductively coupled plasma-mass spectrometry followed by secondary ion mass spectrometry, synchrotron-based X-ray fluorescence, and electron microscopy, including transmission electron microscopy, scanning electron microscopy, and energy-dispersive X-ray spectroscopy. The basic principles of these techniques and their application for qualitative and quantitative imaging of elements are presented. Sample preparation for bioimaging is briefly discussed. The usefulness of element bioimaging is demonstrated for cells and several animal tissues, including the brain, liver, hair, eye, teeth, and bone. As such, this chapter addresses the state of the art in bioimaging metallomics.

Rare earth elements profile in a cultivated and non-cultivated soil determined by laser ablation-inductively coupled plasma mass spectrometry.

Rare earth elements (REEs) have several applications but the effects on environment are not well known. Therefore, the aim of this work is to establish a method for direct solid sample analysis by laser ablation-inductively coupled plasma mass spectrometry (LA-ICP-MS) to evaluate the concentration and distribution of REEs in cultivated and non-cultivated soil. Samples were collected in two areas to 40 cm of depth. The LA-ICP-MS method is easy to be implemented and the sample treatment is very fast comprising only its drying, grounding and pressing as a pellet. The accuracy of the method was evaluated by using a certified reference material (BCR 667 - Estuarine Sediment, Institute for Reference Materials and Measurements (IRMM)) where good agreement with the certified values was obtained. Analyte recovery at two levels of concentration (2.5 and 15.0 µg g-1) was also performed and recoveries in the range of 85%-120% were achieved, values that are acceptable for LA-ICP-MS analysis. In general, the concentration of the REEs is higher in the cultivated soil and increased from the surface to deeper layers, which can be a consequence of fertilizer application.

Imaging of Selenium by Laser Ablation Inductively Coupled Plasma Mass Spectrometry (LA-ICP-MS) in 2-D Electrophoresis Gels and Biological Tissues.

Selenium and selenoproteins are important components of living organisms that play a role in different biological processes. Laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) is a powerful analytical technique that has been employed to obtain distribution maps of selenium in biological tissues in a direct manner, as well as in selenoproteins, previously separated by their molecular masses and isoelectric points using two-dimensional polyacrylamide gel electrophoresis (2-D PAGE). In this chapter, we present the protocols to perform LA-ICP-MS imaging experiments, allowing the distribution visualization and determination of selenium and/or selenoproteins in biological systems.

A quantitative approach for Cd, Cu, Fe and Mn through laser ablation imaging for evaluating the translocation and accumulation of metals in sunflower seeds.

The uptake and accumulation of Cd in sunflower seeds represents an important pathway for imputing potentially toxic metals into human and animal food. In this way, bioimaging of Cd and micronutrients (Cu, Fe and Mn) in the seeds of sunflower grown in soil contaminated with Cd are performed. For this task, laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) is used in quantitative approach, considering four groups: precursor, control, Cd-low (50mg) and Cd-high (700mg). For attaining our proposals, ICP-MS (nebulizer and auxiliary flow rates and radiofrequency power) and LA (laser intensity, frequency and spot size) parameters were optimized, and the analytical signal improved to 197%, 217%, 232%, and 283%, for 57Fe, 112Cd, 55Mn and 63Cu, respectively. The accuracy of proposed method using LA-ICP-MS is evaluated comparing the CRM results (Tomato leaves, NIST SRM 1573a). No difference is found at 95% confidence level. Regarding Cd accumulation in sunflower seeds, the results indicated that cadmium is translocated to seeds, and the cotyledons showed the highest concentration (Cd-high group), ranging from 10 to 20µgg-1. Considering both total concentration and the distribution in the seeds, Cd uptake is responsible to the homeostasis misbalance of micronutrients, which play an essential role in the sunflower metabolism. Such results highlight the importance of bioimaging evaluation, in the translocation and accumulation of metals, contributing to expand the information available of this culture.

Variation in habitat use along the freshwater-marine continuum by grey mullet Mugil cephalus at the southern limits of its distribution.

In this study, habitat use by Mugil cephalus was investigated in the waters of the west coast of the North Island of New Zealand by analysing microchemical composition of otoliths (laser-ablation inductively coupled plasma mass spectrometry) obtained from individuals from commercial fish stocks and research surveys. Results of this study show that M. cephalus at the southern limits of its distribution display highly flexible migratory behaviour with extensive use of freshwater and brackish habitats, potentially enabling them to maximize foraging opportunities. Mugil cephalus can tolerate a wide range of salinities and can therefore utilize higher productivity areas, such as estuaries and eutrophic riverine lakes. Finally, M. cephalus populations across a range of climates and latitudes appear to differ in the extent to which they utilize freshwater and brackish habitats, possibly with increasing penetration of fresh waters with increasing latitude.