High-quality identification of volatile organic compounds (VOCs) originating from breath.

INTRODUCTION: Volatile organic compounds (VOCs) can arise from underlying metabolism and are detectable in exhaled breath, therefore offer a promising route to non-invasive diagnostics. Robust, precise, and repeatable breath measurement platforms able to identify VOCs in breath distinguishable from background contaminants are needed for the confident discovery of breath-based biomarkers. OBJECTIVES: To build a reliable breath collection and analysis method that can produce a comprehensive list of known VOCs in the breath of a heterogeneous human population. METHODS: The analysis cohort consisted of 90 pairs of breath and background samples collected from a heterogenous population. Owlstone Medical's Breath Biopsy® OMNI® platform, consisting of sample collection, TD-GC-MS analysis and feature extraction was utilized. VOCs were determined to be "on-breath" if they met at least one of three pre-defined metrics compared to paired background samples. On-breath VOCs were identified via comparison against purified chemical standards, using retention indexing and high-resolution accurate mass spectral matching. RESULTS: 1471 VOCs were present in > 80% of samples (breath and background), and 585 were on-breath by at least one metric. Of these, 148 have been identified covering a broad range of chemical classes. CONCLUSIONS: A robust breath collection and relative-quantitative analysis method has been developed, producing a list of 148 on-breath VOCs, identified using purified chemical standards in a heterogenous population. Providing confirmed VOC identities that are genuinely breath-borne will facilitate future biomarker discovery and subsequent biomarker validation in clinical studies. Additionally, this list of VOCs can be used to facilitate cross-study data comparisons for improved standardization.

The scientific landscape of phytoremediation of tailings: a bibliometric and scientometric analysis.

This article seeks to evaluate the scientific landscape of the phytoremediation of mine tailings through a series of bibliometric and scientometric techniques. Phytoremediation has emerged as a sustainable approach to remediate metal-contaminated mine waste areas. A scientometric analysis of 913 publications indexed in Web of Science from 1999 to 2023 was conducted using CiteSpace. The results reveal an expanding, interdisciplinary field with environmental sciences as the core category. Keyword analysis of 561 nodes and 2,825 links shows a focus on plant-metal interactions, microbial partnerships, bioavailability, and field validation. Co-citation analysis of 1,032 nodes and 2,944 links identifies seminal works on native species, plant-microbe interactions, and amendments. Temporal mapping of 15 co-citation clusters indicates a progression from early risk assessments and native plant inquiries to integrated biological systems, economic feasibility, and sustainability considerations. Recent trends emphasize multidimensional factors influencing adoption, such as plant-soil-microbe interactions, organic amendments, and field-scale performance evaluation. The findings demonstrate an intensifying translation of phytoremediation from scientific novelty to engineering practice. This quantitative and qualitative analysis of research trends aids in understanding the development of phytoremediation for mine tailings. The results provide valuable insights for researchers and practitioners in this evolving field.

An extension of the characteristic curve model of plant species behavior in heavy metal soils.

This article proposes a mathematical model to characterize phytoremediation processes in soils contaminated with heavy metals. In particular, the proposed model constructs characteristic curves for the concentrations of several metals (As, Cd, Cu, Fe, Pb, Sb, and Zn) in soils and plants based on the experimental data retrieved from several bibliographical sources comprising 305 vegetal species. The proposed model is an extension of previous models of characteristic curves in phytoremediation processes developed by Lam et al. for root measurements using the bioconcentration factor. However, the proposed model extends this approach to consider roots, as well as aerial parts and shoots of the plant, while at the same time providing a less complex mathematical formula compared to the original. The final model shows an adjusted R2 of 0.712, and all its parameters are considered statistically significant. The model may be used to assess samples from a given plant species to identify its potential as an accumulator in the context of soil phytoremediation processes. Furthermore, a simplified version of the model was constructed using an approximation to provide an easy-to-compute alternative that is valid for concentrations below 37,000 mg/kg. This simplified model shows results similar to the original model for concentrations below this threshold and it uses an adjusted factor defined as [Formula: see text] that must be compared with a threshold depending on the metal, type of measurement, and target (e.g., accumulator or hyperaccumulator). The full model construction shows that 90 out of the 305 species assessed have a potential behavior as accumulators and 10 of them as hyperaccumulators. Finally, out of the 1405 experimental measurements, 1177 were shown to be accumulators or hyperaccumulators. In particular, 85% of the results coincide with the reported values, thus validating the proposed model.

Heavy metal pollution index calculation in geochemistry assessment: a case study on Playa Las Petroleras.

This work is aimed to assess potential risk associated with the presence of metals and metalloids in soil at "Playa Las Petroleras" sector, located in Antofagasta (Chile). The zone under study has been affected by four oil spill events. This sector is located in an urban area by the sea. So, it has a great social and environmental relevance. The concentrations of 15 elements in soil samples were assessed, four of them presenting potential ecological risk: As, Co, Cu, and Pb. Nine pollution indices were applied to data: four single pollution indices and five integrated pollution indices to assess soil pollution. The single pollution indices show that the site bears potential ecological and environmental risk due to the presence of Cu, the site being classified as highly contaminated owing to a severe enrichment of this metal. For Co, all the indices allow classifying the site as little or uncontaminated, while the level of As and Pb pollution could be considered as ranging from uncontaminated to moderately contaminated. The integrated pollution indices show that average concentrations are highly contaminated mainly owing to the presence of Cu.

Characteristic curve modeling of plant species behavior in soils with heavy metals.

Many vegetal species can accumulate great amounts of metallic elements in their tissues. For this reason, they are called metal hyperaccumulators. An indicator of great interest in environmental sciences is the bioconcentration factor because it is recognized for establishing the potential accumulation of chemicals in organisms. Particularly in soil phytoremediation processes, it measures the capacity of a certain plant to capture metals, in terms of soil concentration. According to their behavior, four types of plants can be distinguished regarding soil concentration increase: indicator, excluder, accumulator, and hyperaccumulator. This study proposes a new model to categorize plants according to their behavior related to soil concentration increase, using several characteristic curves obtained from 1288 experimental measurements collected from different bibliographic sources. The metals analyzed were Cu, Fe, Pb, and Zn. The proposed model is obtained through linear regression and nonlinear transformations to model the expected behavior of plants in high concentration conditions. In particular, the basic equation of the model has three key components to represent the expected concentration in the plant root given the final soil concentration level, the type of species, and specific metal: a linear factor that determines the growth for low concentration values, an exponential factor that determines its decrease for high concentration values, and a logarithmic factor that limits the maximum value that can be reached in practice and influences the decay for high concentration values. After fitting the experimental data using linear regression, the proposed model has a 0.084 R2 determination coefficient and all of its parameters are considered significant. Furthermore, it shows that 60 of the 257 species assessed behave as accumulators and 10 of them as hyperaccumulators. The main contribution of this model is its ability to handle soils with high concentrations, where it would be hard for plants to achieve concentrations similar to or higher than the substrate containing them. Thus, the conventional criterion of the bioconcentration factor would incorrectly categorize a plant as an excluder. In contrast, this new model allows assessing plant effectiveness in a phytoremediation process of highly concentrated affected sites, such as mine tailings.

Hydrochemical evolution of the Reocín mine filling water (Spain).

The Reocín mine is located in Cantabrian region, in northern Spain. Its exploitation ended in 2003 due to the exhaustion of its reserves. In November 2004, the controlled flooding of the openpit began. During this process, both the qualities of stored water and piezometric levels have been monitored to control the possible water detraction from the Saja-Besaya hydrographic system. This paper deals with the water chemistry analysis of the pit lake surface, as well as the different conditions of the area. Geological and hydrogeological contexts play an important role in the lake water chemistry. The lake water quality continues improving. The sulphate content and zinc concentrations are already below the permitted pouring limits. Three factors are distinguished: the washing of the mine shafts is completed; the water supply from the aquifer contributes to the dissolution of the salt content and the bedrock, and dolomite, which neutralizes acid waters and improves the water quality during the flooding process with a pH value of 8. Owing to these conditions, the stored water meets the necessary conditions for discharge and provides the opportunities to use it.

Evaluation of copper tailing amendments through poultry waste and ammonium nitrate.

In this study, two amendments, poultry waste and ammonium nitrate, were evaluated to condition and stabilize a mine tailing and thus help the vegetation cover settle. Individually, ammonium nitrate was tested as a nitrogen source and chicken bone ash as a phosphate source. For this, laboratory tests were made on soil columns from the area to be remediated. The mobility and availability of metals and nutrients were determined by analyzing their leachates chemically. The results showed that the use of chicken bone ash decreases soluble metal concentrations, particularly in Fe and soluble Mn. On the other hand, experimental conditions proved that the acidification produced by ammonium nitrate nitrification does not significantly increase the lechate metal content. Therefore, its use for fertilization does not involve phytotoxicity risks. Regarding the availability of macronutrients as well as trace elements, the results showed that the concentrations lie within the ranges suitable for plant nutrition. So, the treatments are effective both for fertilization and phytoremediation.

Systematic Review of Curriculum-Based Measurement with Students Who Are Deaf.

This review systematically identified and compared the technical adequacy (reliability and validity evidence) of reading curriculum-based measurement (CBM) tasks administered to students who are deaf and hard of hearing (DHH). This review included all available literature written in English. The nine studies identified used four CBM tasks: signed reading fluency, silent reading fluency, cloze (write in missing words given blank lines within a passage), and maze (circle the target word given multiple choice options within a passage). Data obtained from these measures were generally found to be internally consistent and stable with validity evidence varying across measures. Emerging evidence supports the utility of CBM for students who are DHH. Further empirical evidence is needed to continue to explore technical properties, identify if student scores are sensitive to growth over short periods of time, and examine whether CBM data can be used to inform instructional decision-making to improve student outcomes.

Methodology to Prioritize Chilean Tailings Selection, According to Their Potential Risks.

For centuries, Chile has been a territory with significant mining activity, resulting in associated social benefits and impacts. One of the main challenges the country faces today is the presence of a great number of mine tailings containing heavy metals, such as Cu, Cr, Ni, Zn, Pb, As, Cd, and Fe, which make up a potential risk for the population. This study is intended to develop a methodology for determining tailings requiring urgent treatment in Chile, based on risks associated with heavy metals. Geochemical data from 530 Chilean tailings were compared to the Dutch norm and the Canadian and Australian soil quality guidelines for residential use. Additionally, criteria about residents and water bodies were used, considering a 2-km area of influence around tailings. To do this, QGIS (Böschacherstrasse 10a CH-8624 Grüt (Gossau ZH),Zurich, Switzerland), a geospatial tool, was used to geolocate each deposit, considering regions, communes, rivers, lakes, and populated areas. To evaluate potential ecological contamination risks, Hakanson's methodology was used. Results revealed the presence of 12 critical tailings in Chile that require urgent treatment. From the 530 tailings evaluated, 195 are located at less than 2 km from a populated area and 154 at less than 2 km from a water body. In addition, 347 deposits require intervention: 30 on Cu, 30 on Cr, 13 on Zn, 69 on Pb, 138 on As, 1 on Cd, and 5 on Hg.

Technical Characteristics of Curriculum-Based Measurement With Students Who Are Deaf.

This study compared the reliability and validity of student scores from paper-pencil and e-based assessments using the "maze" and "silent reading fluency" (SRF) tasks. Forty students who were deaf and hard of hearing and reading between the second and fifth grade reading levels and their teachers (n = 21) participated. For maze, alternate form reliability coefficients obtained from correct scores and correct scores adjusted for guessing ranged from r = .61 to .84 (ps < .01); criterion-related validity coefficients ranged from r = .33 to .67 (most ps < .01). For SRF, reliability coefficients obtained from correct scores ranged from r = .50 to .75 (ps < .01); validity ranged from r = .25 to .72. Differences between student performance on paper-pencil and e-based conditions were generally non-significant for maze; significant differences between conditions for SRF favored the paper-pencil condition. Findings suggest that maze holds promise, with inconclusive results for SRF.

Making Paving Stones from Copper Mine Tailings as Aggregates.

Copper mining, the central axis of Chile's economic development, produces a large number of tailings, which become a potential environmental risk. This study aims to evaluate the mechanical properties resulting from the making of Portland cement mixtures with tailings as aggregates so that they can be eventually used in paving stones for building inactive tailings dams. Tailings coming from two dams at a concentration plant located in Taltal (Chile) were used. Currently, Dam 1 is inactive, while Dam 2 is active. The tailings samples obtained from both dams were granulometrically characterized by sieving. In addition, pH, humidity, Eh, and mineralogical assays (sulfides, oxides, sulfates, carbonates, phosphates, and silicates) were measured. The fines content of the tailings from Dams 1 and 2 with a sieve size of N°200 ASTM were 76.2% and 29.6%, respectively. Therefore, owing to their high percentage of fines, they cannot be as used as concrete aggregates. Aggregates must contain a maximum percentage of fines so that mortars and concrete can meet Chilean standards. In this paper, to comply with a 7% and 15% fines content lower than 0.075 mm, tailings materials were mixed with conventional aggregates containing very little fines. In addition, a reference mixture was made with only tailings aggregates with and without a superplasticizer additive. To measure the mixtures of cement, aggregates, and tailings, bending and compression strength assays were made of the specimens after a 28-day curing, according to the Chilean standard. The results of the study show that the addition of only part of the tailings to the mixture increases bending strength by 26% and compression strength by 180% compared with the reference mortar, with a fines content lower than 0.075 mm in the 7% mixture, thus allowing paving stone manufacture with tailings materials. In addition, it was possible to increase the workability of the reference mixture by using superplasticizers as additives.

Evaluation of metal mobility from copper mine tailings in northern Chile.

This work shows the results obtained on a copper mine tailing in the Antofagasta Region, Chile. The tailing was classified as saline-sodic with high concentrations of metals, especially Cu and Fe, with pH 8.4. Our objectives were to (1) compare the physicochemical properties of the tailing with surrounding soils of the mine under study, and (2) evaluate the effect of two amendments (CaCO3 and compost) and their mixtures on Cu(2+), Mn, Fe, Zn, Mg(2+), and K(+) and Ca(2+), SO4 (2-), NO3 (-), and PO4 (3-) leaching. The data obtained were submitted to variance and covariance analysis. The results from the comparison between both substrates showed that in general, the tailing presented greater content of metals. Regarding tailing leaching, pH, electrical conductivity (EC), and concentration of the elements of interest were measured. The statistical analysis showed that Cu(2+) leaching and immobilization of Fe occurred to the greatest extent with compost. The EC decreased throughout the experiment with irrigation and increased upon treatment with compost. The major interactions found among the chemical parameters were (1) tailings without treatment, Cu(2+)/Fe and NO3 (-)/SO4 (2-); (2) tailings treated with CaCO3, Cu(2+)/K(+); (3) tailings treated with compost, NO3 (-)/SO4 (-2) and EC/Cu(2+); and (4) tailings treated with both amendments, EC/Fe and Cu(2+)/Fe. The ANOVA showed that the number of irrigations and the amendments statistically significantly affected the copper mobility and the organic amendment significantly influenced the iron mobility.

A study on the effect of dianionic tridentate ligands on the radiative and nonradiative processes for gold(III) alkynyl systems by a computational approach.

Gold(III) alkynyl complexes with dianionic tridentate pincer ligands have received growing attention recently because of their rich luminescence behavior and their potential applications in areas such as optoelectronics and sensors. In this study, density functional theory (DFT) and time-dependent DFT (TDDFT) calculations have been performed to investigate the radiative and nonradiative processes for the gold(III) alkynyl complexes with different dianionic tridentate ligands, [Au(C^N^C)(C≡CC6H5)] (1; C^N^C = 2,6-diphenylpyridine), [Au(C(Np)^N^C(Np))(C≡CC6H5)] [2; C(Np)^N^C(Np) = 2,6-di(2-naphthyl)pyridine], [Au(N^N^N)(C≡CC6H5)] [3; N^N^N = 2,6-bis(benzimidazol-2'-yl)pyridine], and [Au(C^C^N)(C≡CC6H5)] [4; C^C^N = 3-(2-pyridyl)biphenyl]. It has been found that the electronic properties of the tridentate ligand could have a significant impact on the radiative and nonradiative processes. This study provides an in-depth understanding on the effect of the dianionic pincer ligands on the different photophysical behaviors among the gold(III) alkynyl complexes and crucial information for the future design of gold(III) complexes in various applications.

Synthesis, characterization, self-assembly, gelation, morphology and computational studies of alkynylgold(III) complexes of 2,6-bis(benzimidazol-2'-yl)pyridine derivatives.

A novel class of alkynylgold(III) complexes of the dianionic ligands derived from 2,6-bis(benzimidazol-2'-yl)pyridine (H2bzimpy) derivatives has been synthesized and characterized. The structure of one of the complexes has also been determined by X-ray crystallography. Electronic absorption studies showed low-energy absorption bands at 378-466 nm, which are tentatively assigned as metal-perturbed π-π* intraligand transitions of the bzimpy(2-) ligands. A computational study has been performed to provide further insights into the nature of the electronic transitions for this class of complexes. One of the complexes has been found to show gelation properties, driven by π-π and hydrophobic-hydrophobic interactions. This complex exhibited concentration- and temperature-dependent (1)H NMR spectra. The morphology of the gel has been characterized by transmission electron microscopy (TEM) and scanning electron microscopy (SEM).

Computational studies on the excited states of luminescent platinum(II) alkynyl systems of tridentate pincer ligands in radiative and nonradiative processes.

Platinum(II) alkynyl complexes of various tridentate pincer ligands, [Pt(trpy)(C≡CR)](+) (trpy = 2,2':6',2″-terpyridine), [Pt(R'-bzimpy)(C≡CR)](+) (R'-bzimpy = 2,6-bis(N-alkylbenzimidazol-2'-yl)pyridine and R' = alkyl), [Pt(R'-bzimb)(C≡CR)] (R'-bzimb = 1,3-bis(N-alkylbenzimidazol-2'-yl)benzene and R' = C4H9), have been found to possess rich photophysical properties. The emission in dilute solutions of [Pt(trpy)(C≡CR)](+) originated from a triplet alkynyl-to-tridentate pincer ligand-to-ligand charge transfer (LLCT) excited state, with mixing of a platinum-to-tridentate pincer ligand metal-to-ligand charge transfer (MLCT) excited state, while that of [Pt(R'-bzimb)(C≡CR)] originated from a triplet excited state of intraligand (IL) character of the tridentate ligand mixed with a platinum-to-tridentate ligand MLCT character. Interestingly, both emissions were observed in [Pt(R'-bzimpy)(C≡CR)](+) in some cases. In addition, [Pt(R'-bzimb)(C≡CR)] displayed a photoluminescence quantum yield higher than that of [Pt(R'-bzimpy)(C≡CR)](+). Computational studies have been performed on the representative complexes [Pt(trpy)(C≡CPh)](+) (1), [Pt(R'-bzimpy)(C≡CPh)](+) (2), and [Pt(R'-bzimb)(C≡CPh)] (3), where R' = CH3 and Ph = C6H5, to provide an in-depth understanding of the nature of their emissive origin as well as the radiative and nonradiative processes. In particular, the factors governing the ordering of the triplet excited states and radiative decay rate constants of the emissive state ((3)ES) have been examined. The potential energy profiles for the deactivation process from the (3)ES via triplet metal-centered ((3)MC) states have also been explored. This work reveals for the first time the potential energy profiles for the thermal deactivation pathway of square planar platinum(II) complexes.

Synthesis and characterization of luminescent cyclometalated platinum(II) complexes of 1,3-bis-hetero-azolylbenzenes with tunable color for applications in organic light-emitting devices through extension of π conjugation by variation of the heteroatom.

A series of luminescent cyclometalated platinum(II) complexes of N^C^N ligands [N^C^N=2,6-bis(benzoxazol-2'-yl)benzene (bzoxb), 2,6-bis(benzothiazol-2'-yl)benzene (bzthb), and 2,6-bis(N-alkylnaphthoimidazol-2'-yl)benzene (naphimb)] has been synthesized and characterized. Two of the platinum(II) complexes have been structurally characterized by X-ray crystallography. Their electrochemical, electronic absorption, and luminescence properties have been investigated. In dichloromethane solution at room temperature, the cyclometalated N^C^N platinum(II) complexes exhibited rich luminescence with well-resolved vibronic-structured emission bands. The emission energies of the complexes are found to be closely related to the electronic properties of the N^C^N ligands. By varying the electronic properties of the cyclometalated ligands, a fine-tuning of the emission energies can be achieved, as supported by computational studies. Multilayer organic light-emitting devices have been prepared by utilizing two of these platinum(II) complexes as phosphorescent dopants, in which a saturated yellow emission with Commission International de I'Eclairage coordinates of (0.50, 0.49) was achieved.

Cholesterol-/estradiol-appended alkynylplatinum(II) complexes as supramolecular gelators: synthesis, characterization, photophysical and gelation studies.

A series of cholesterol-/estradiol-appended alkynylplatinum(II) complexes with tridentate N-donor ligands, based on 2,6-bis(1-alkylpyrazol-3-yl)pyridine, has been synthesized and characterized by (1)H NMR spectroscopy, FAB-mass spectrometry, and elemental analysis. Their photophysical properties have also been investigated. Computational studies have been performed to provide insights into the nature of the electronic transitions. Some of the complexes have been found to form stable thermo- and mechanoresponsive supramolecular gels.

Luminescent cyclometalated alkynylplatinum(II) complexes with a tridentate pyridine-based N-heterocyclic carbene ligand: synthesis, characterization, electrochemistry, photophysics, and computational studies.

A new class of luminescent alkynylplatinum(II) complexes with a tridentate pyridine-based N-heterocyclic carbene (2,6-bis(1-butylimidazol-2-ylidenyl)pyridine) ligand, [Pt(II)(C^N^C)(C≡CR)][PF6], and their chloroplatinum(II) precursor complex, [Pt(II)(C^N^C)Cl][PF6], have been synthesized and characterized. One of the alkynylplatinum(II) complexes has also been structurally characterized by X-ray crystallography. The electrochemistry, electronic absorption and luminescence properties of the complexes have been studied. Nanosecond transient absorption (TA) spectroscopy has also been performed to probe the nature of the excited state. The origin of the absorption and emission properties has been supported by computational studies.

Luminescent platinum(II) complexes of 1,3-bis(N-alkylbenzimidazol- 2'-yl)benzene-type ligands with potential applications in efficient organic light-emitting diodes.

A series of luminescent platinum(II) complexes of tridentate 1,3-bis(N-alkylbenzimidazol-2'-yl)benzene (bzimb) ligands has been synthesized and characterized. One of these platinum(II) complexes has been structurally characterized by X-ray crystallography. Their electrochemical, electronic absorption, and luminescence properties have been investigated. Computational studies have been performed on this class of complexes to elucidate the origin of their photophysical properties. Some of these complexes have been utilized in the fabrication of organic light-emitting diodes (OLEDs) by using either vapor deposition or spin-coating techniques. Chloroplatinum(II)-bzimb complexes that are functionalized at the 5-position of the aryl ring, [Pt(R-bzimb)Cl], not only show tunable emission color but also exhibit high current and external quantum efficiencies in OLEDs. Concentration-dependent dual-emissive behavior was observed in multilayer OLEDs upon the incorporation of pyrenyl ligand into the Pt(bzimb) system. Devices doped with low concentrations of the complexes gave rise to white-light emission, thereby representing a unique class of small-molecule, platinum(II)-based white OLEDs.

Structure, photophysical properties and computational study of a highly luminescent mixed-metal platinum(II)-silver(I) system. Potential building blocks for emissive supramolecular structures.

A luminescent cyclometalated platinum(II) complex has been shown to sandwich a silver ion, which demonstrates intense luminescence with appreciable photoluminescence quantum yield. Computational studies have been performed to provide insights into the nature of the photophysical properties.