Halomethanes (HMs) are key contributors to ozone depletion and climate forcing, yet their natural sources remain undercharacterized. This study examines bioweathered Lopingian Kupferschiefer black shale in SW Poland as a potential source of HM emissions. Rich in fossil organic matter (FOM) and iron-bearing minerals, the shale was found to emit various chlorinated and brominated mono- to tetrahalomethanes.Using gas chromatography, the researchers propose a mechanism involving Fe³⁺-catalyzed abiotic reactions with organic precursors and halides. The findings identify a previously unrecognized deep subsurface source of halomethanes and report, for the first time, natural emission of tetrachloromethane.<blockquote><h4>The original article</h4><h4><a target="_blank" rel="noopener noreferrer" href="https://pubs.acs.org/doi/10.1021/acs.estlett.5c00593">Emissions of Halomethanes from Bioweathered Lopingian Kupferschiefer Black Shale (Fore-Sudetic Monocline, SW Poland)</a></h4>Michał Zalesko*, Robert Stasiuk, Renata MatlakowskaEnviron. Sci. Technol. Lett. 2025, XXXX, XXX, XXX-XXX<a target="_blank" rel="noopener noreferrer" href="https://doi.org/10.1021/acs.estlett.5c00593">https://doi.org/10.1021/acs.estlett.5c00593</a><h6>licensed under <a target="_blank" rel="noopener noreferrer" href="https://creativecommons.org/licenses/by/4.0/">CC-BY 4.0</a></h6></blockquote>Selected sections from the article follow. Formats and hyperlinks were adapted from the original.Halogenated methane derivatives (halomethanes, HMs) are significant sources of atmospheric halogens, which play an important role in ozone depletion and contribute to radiative forcing. <a href="javascript:void(0);">(1,2)</a> The most abundant HM in the atmosphere is chloromethane, which is responsible for 16.9% of tropospheric chlorine. <a href="javascript:void(0);">(2)</a> In addition to anthropogenic sources, several natural sources of HMs have been described. <a href="javascript:void(0);">(3,4)</a> However, the amount of naturally produced HMs appears to be underestimated. <a href="javascript:void(0);">(2)</a> Bahlmann et al. (2019) suggest the existence of a major missing source of atmospheric chloromethane. <a href="javascript:void(0);">(5)</a>Therefore, it is worth considering what other natural sources exist. Studies by Keppler et al. (2000) indicate that HMs were formed from natural organic matter through abiotic processes that were catalyzed by Fe3+. <a href="javascript:void(0);">(6,7)</a> In 2009, Huber et al. presented the mechanism of trihalomethane formation from dihydroxylated monocyclic aromatic hydrocarbons (DMAHs) in the presence of Fe3+ and (H2O2). The organic compound is oxidized and simultaneously halogenated by halide radicals in the presence of reactive oxygen species (ROS), both arising from a Fenton-like reaction between H2O2, Fe3+, and halides. <a href="javascript:void(0);">(8−10)</a>In our studies, we consider whether iron-catalyzed HM formation processes can occur in highly mineralized deposits of fossil organic matter (FOM). It is worth noting that FOM, in the form of kerogen, is considered to be the largest reservoir of organic carbon on Earth. It is estimated that kerogen contains ∼15,000,000 Gt of fossil organic carbon, an amount that significantly exceeds the amount (∼4,130 Gt) found in fossil fuels (such as gas, oil and coal). <a href="javascript:void(0);">(11)</a>This study focuses on the organic-rich deep black shale environment, represented by the Kupferschiefer black shale (BS), which contains both FOM (1–30 wt %, average 6 wt %, corresponding to type II kerogen) and Fe-containing minerals. <a href="javascript:void(0);">(12−14)</a> The extractable fraction of FOM consists of long-chain saturated and unsaturated hydrocarbons, polycyclic aromatic hydrocarbons (PAHs), and acid esters. <a href="javascript:void(0);">(15)</a> The ore minerals in BS are mainly represented by bornite [Cu5FeS4], chalcocite [Cu2S], digenite [Cu9S5], chalcopyrite [CuFeS2], pyrite [FeS2], sphalerite [ZnS], galena [PbS], covellite [CuS], and minerals from the tennantite–tetrahedrite series [(Cu, Fe)12As4S13–(Cu, Fe)12Sb4S13]. <a href="javascript:void(0);">(16)</a>Previous studies indicate colonization by microorganisms and the bioweathering of outcropped Kupferschiefer BS profiles. <a href="javascript:void(0);">(15)</a> This study confirmed that FOM underwent enzymatic oxidation, mediated primarily by chemoorganoheterotrophic bacteria. Furthermore, the dissimilative enzymatic oxidation of primary sulfidic minerals by chemolithotrophic bacteria was detected.This study aims to investigate whether bioweathered BS can be a source of HM emissions. In addition, we attempted to predict potential substrates and factors of HM formation. As sources of these substrates and factors, we considered BS bioweathering products and mine water (MW) (<a target="_blank" rel="noopener noreferrer" href="https://pubs.acs.org/doi/suppl/10.1021/acs.estlett.5c00593/suppl_file/ez5c00593_si_001.pdf">Figure SI1/1</a>): (1) as potential substrates, we indicated monocyclic aromatic hydrocarbons (MAHs) formed by FOM bioweathering; (2) as a halogenation factor, we indicated Fe3+ arising from the oxidation of primary Fe2+-containing minerals; (3) as a source of halides, we indicated high saline MW and secondary minerals on the surface of weathered BS.In order to achieve these objectives, we studied bioweathered BS covered by secondary minerals and MW. The following studies were conducted: (1) detection and identification of HMs; (2) prediction of MAHs in FOM extracted from bioweathered BS and MW; (3) detection of Fe and halides in bioweathered BS and MW; and (4) Fe3+ and halide detection in secondary minerals present on the surface of bioweathered BS.This experimental approach has enabled us to propose a hypothetical mechanism of HM formation in deep underground environments and reveal a previously unknown natural source of HMs.<h4>Methods and Materials</h4><h5>Extraction of Volatile Organic Compounds</h5>Volatile organic compounds were extracted using a modified EPA Method 5021A (2014). <a href="javascript:void(0);">(17)</a> A hundred grams of BS were placed in 100 mL bottles with septa, and 50 mL of methanol was added. The mixture was incubated at 50 °C for 72 h. For analysis, gas samples were collected using a gastight syringe (Hamilton Company, USA), or solid-phase microextraction (SPME, 65 μm, PDMS/DVB, Supelco, USA) was used. <a href="javascript:void(0);">(18)</a> More detailed information is provided in <a target="_blank" rel="noopener noreferrer" href="https://pubs.acs.org/doi/suppl/10.1021/acs.estlett.5c00593/suppl_file/ez5c00593_si_001.pdf">SI1</a>.<h5>Extraction of Bituminous and Dissolved Organic Compounds</h5>Organic compounds were extracted from BS and MW using a mixture of dichloromethane/methanol with an automatic Soxhlet apparatus (SER 158, Velp, Italy) and chloroform in a separatory funnel, respectively. More detailed information is provided in <a target="_blank" rel="noopener noreferrer" href="https://pubs.acs.org/doi/suppl/10.1021/acs.estlett.5c00593/suppl_file/ez5c00593_si_001.pdf">SI1</a>.<h5>Gas Chromatography with Mass Spectrometry (GC-MS) and Electron Capture Detector (GC-ECD)</h5>Volatile compounds were analyzed using GC-MS (Agilent GC <a target="_blank" rel="noopener noreferrer" href="https://gcms.labrulez.com/library?mainauthorItems=10&amp;search=7890A">7890A</a>, MS <a target="_blank" rel="noopener noreferrer" href="https://gcms.labrulez.com/library?mainauthorItems=10&amp;search=5975c">5975c</a>, Agilent Technologies, USA) and<a target="_blank" rel="noopener noreferrer" href="https://gcms.labrulez.com/library?mainauthorItems=10&amp;search=+GC-ECD"> GC-ECD </a>(GC 7890A, μECD, Agilent Technologies, USA), both equipped with a FS CAP VOCOL column (60 m × 0.25 mm I.D., 1.5 μm film thickness, Supelco, USA) according to modified EPA Method 8260(1986). <a href="javascript:void(0);">(19)</a> Commercial solutions of CH3Cl (Restek, Germany), CHCl2, and CHCl3 (VWR Chemicals, USA), as well as the VOA Stock Mix 8260B MegaMix Calibration Mix (Restek, Germany), were used as external standards.Compounds extracted from BS and MW were analyzed by GC-MS (Agilent GC 7890A, MS 5975c) using an HP5-MS column (30 m × 0.25 mm I.D., 0.25 μm film thickness, Agilent Technologies, USA). The obtained mass spectra were compared with the <a target="_blank" rel="noopener noreferrer" href="https://gcms.labrulez.com/products/887">Wiley 3.2 database</a> (The Wiley Registry of Mass Spectral Data, eighth edition). More details are provided in <a target="_blank" rel="noopener noreferrer" href="https://pubs.acs.org/doi/suppl/10.1021/acs.estlett.5c00593/suppl_file/ez5c00593_si_001.pdf">SI1</a>.<h5>Inductively Coupled Plasma with Mass Spectrometry (ICP-MS)</h5>The elemental analysis of the weathered BS and MW was determined by ACME Analytical Laboratories Ltd. (Vancouver, BC, Canada). LF202 Total Whole Rock Characterization with AQ200 add-on (LF302 + LF100-EXT) and SO200 – ICP-MS Analysis of Natural Waters were conducted on BS and MW samples, respectively.<h5>X-ray Fluorescence (XRF)</h5>Detection of Fe, Cl, and Br in BS was performed by using a Bruker S1 Titan Hand-held ED-XRF Analyzer.<h5>Scanning Electron Microscopy (SEM) with Energy Dispersive X-ray Spectroscopy (EDS)</h5>Analysis was performed using backscattered and secondary electron techniques with a JEOL JSM-6380LA SEM instrument (JEOL Co., Japan). The chemical composition was determined by using a CAMECA SX100 microprobe (CAMECA, France). More details are provided in <a target="_blank" rel="noopener noreferrer" href="https://pubs.acs.org/doi/suppl/10.1021/acs.estlett.5c00593/suppl_file/ez5c00593_si_001.pdf">SI1</a>.<h5>X-ray Powder Diffraction (XRD) Analyses</h5>XRD analyses of powdered samples were conducted using a PHILIPS X’PERT PRO diffractometer (PANalytical B.V., The Netherlands). The samples were manually ground in an agate mortar, mounted on a standard metal holder, and irradiated with CoKα radiation. Data was collected over a 2Θ range of 2.505° to 95.996° in step-scan mode, with a step size of 0.001° 2Θ and a count time of 1 s per step.<h4>Results and Discussion</h4><h5>Identification of HM Emitted from the Weathered BS</h5>Using GC-MS with the headspace extraction method, chloromethane and dichloromethane were identified in all BS samples analyzed with high probability (86–94%) (<a target="_blank" rel="noopener noreferrer" href="https://pubs.acs.org/doi/10.1021/acs.estlett.5c00593#fig1">Figure 1</a>; <a target="_blank" rel="noopener noreferrer" href="https://pubs.acs.org/doi/suppl/10.1021/acs.estlett.5c00593/suppl_file/ez5c00593_si_001.pdf">Figure SI2/1</a>). HMs were identified in all GC-ECD analyses. Using SPME, bromodichloromethane, dibromochloromethane, dichloromethane, tetrachloromethane, and trichloromethane were identified in all BS samples. Chloromethane was detected in all BS samples, except BS2, while dibromomethane was present exclusively in BS2. Relative abundance (z-score) analyses indicate higher emissions of HM from samples collected at site TS2 (<a target="_blank" rel="noopener noreferrer" href="https://pubs.acs.org/doi/10.1021/acs.estlett.5c00593#fig1">Figure 1</a>).<img src="https://storage.googleapis.com/labrulez-bucket-strapi-h3hsga3/Environ_Sci_Technol_Lett_2025_Figure_1_A_relative_abundance_of_H_Ms_found_in_B_Ss_through_SPME_extraction_and_GC_ECD_analysis_5332017a52.jpg" alt="Environ. Sci. Technol. Lett. 2025: Figure 1. A relative abundance of HMs found in BSs through SPME extraction and GC-ECD analysis. An asterisk indicates compounds identified by GC-MS. GC-ECD chromatograms, a detailed list, and mass spectra of the identified HMs can be found in SI2 (Table SI2/1–2; Figures SI2/1–8). GC-ECD chromatograms of standards and controls can be found in SI2 (Figures SI2/9–11)." srcset="https://storage.googleapis.com/labrulez-bucket-strapi-h3hsga3/thumbnail_Environ_Sci_Technol_Lett_2025_Figure_1_A_relative_abundance_of_H_Ms_found_in_B_Ss_through_SPME_extraction_and_GC_ECD_analysis_5332017a52.jpg 245w," sizes="100vw" width="1750" height="477"><img src="https://storage.googleapis.com/labrulez-bucket-strapi-h3hsga3/Environ_Sci_Technol_Lett_2025_Figure_SI_2_7_Chromatograms_of_the_volatile_phase_obtained_from_methanol_extracts_of_TS_1_GC_ECD_SPME_43d9f8c91d.jpg" alt="Environ. Sci. Technol. Lett. 2025: Figure SI2/7. Chromatograms of the volatile phase obtained from methanol extracts of TS1 (GC-ECD, SPME)." srcset="https://storage.googleapis.com/labrulez-bucket-strapi-h3hsga3/thumbnail_Environ_Sci_Technol_Lett_2025_Figure_SI_2_7_Chromatograms_of_the_volatile_phase_obtained_from_methanol_extracts_of_TS_1_GC_ECD_SPME_43d9f8c91d.jpg 80w," sizes="100vw" width="563" height="1090"><h5>Prediction of Potential Organic Substrates for HM Formation in Bioweathered BS and MW</h5>Potential organic substrates were predicted with Level 2 confidence according to Koelmel et al. 2022. <a href="javascript:void(0);">(20)</a> In the extractable fraction of BSs several MAHs are present: benzoic acid and 1,2-dicarboxybenzene derivatives (<a target="_blank" rel="noopener noreferrer" href="https://pubs.acs.org/doi/10.1021/acs.estlett.5c00593#fig2">Figure 2</a>). The MAH compounds may undergo enzymatic oxidation through microbial dioxygenases and monooxygenases to DMAHs, such as protocatechuate and catechol. <a href="javascript:void(0);">(15)</a> Esters of 1,2-dicarboxybenzene acids can be deesterified by bacterial esterases. <a href="javascript:void(0);">(21)</a> In MWs, the diversity of 1,2-dicarboxybenzene derivatives is higher, which may indicate the ongoing degradation and transformation of organic matter (<a target="_blank" rel="noopener noreferrer" href="https://pubs.acs.org/doi/10.1021/acs.estlett.5c00593#fig2">Figure 2</a>). The presence of dioxygenases, monooxygenases and esterases was previously confirmed in a metagenome and metaproteome of microbiocenoses that inhabit the bioweathered BS. <a href="javascript:void(0);">(15)</a><img src="https://storage.googleapis.com/labrulez-bucket-strapi-h3hsga3/ENVIRO_3_7fd06dfb40.jpg" alt="Environ. Sci. Technol. Lett. 2025: Figure 2. The abundance of benzoic acid and 1,2-dicarboxylic acid derivatives predicted with Level 2 confidence in BSs and MWs. Mass spectra of the predicted organic compounds are provided in SI3." srcset="https://storage.googleapis.com/labrulez-bucket-strapi-h3hsga3/thumbnail_ENVIRO_3_7fd06dfb40.jpg 245w," sizes="100vw" width="2100" height="500">

Emissions of Halomethanes from Bioweathered Lopingian Kupferschiefer Black Shale (Fore-Sudetic Monocline, SW Poland)

Wiley, one of the world's largest publishers and a trusted leader in research and learning, today announced the addition of over 17,500 spectra to its <a target="_blank" rel="noopener noreferrer" href="https://gcms.labrulez.com/products/887">Wiley Registry of Mass Spectral Data</a> subscription, bringing the collection to over 913,000 spectra.The renowned Wiley Registry is one of the largest high quality mass spectral libraries available. It serves as a lab standard and is an essential resource for GC-MS analysis across diverse fields, including environmental science, forensics, toxicology, pharmaceuticals, biotech, metabolomics, and other important sectors.This release includes significant contributions across multiple compound classes, with notable additions of new and emerging drugs of abuse, insect pheromones, and per- and polyfluoroalkyl substances (PFAS). The comprehensive update also features additions of fatty acids and fatty acid methyl esters, hydrocarbons, terpenes, alcohols and phenols, alkaloids, and sulfur, halogenated, organophosphorus, and carbonyl compounds, among many other compound classes.The newly added data is from multiple high-quality sources, including Cayman Chemical, research laboratories, literature abstraction from Wiley journals, and world patents, ensuring comprehensive coverage and reliability.Graeme Whitley, director, data science solutions at Wiley, emphasizes the value: “With a Wiley Registry subscription, your lab gains access to new data as it's added to the collection. No need to wait for the next major release of the Wiley Registry database every three years—your lab can benefit right away from up-to-date data that can make an impact on your analyses.”Including this most recent update, subscribers currently can access over 40,000 spectra more than those with the Wiley Registry 2023 edition.Wiley's comprehensive spectral database collections provide access to millions of high-quality spectra across a range of techniques, including IR, MS, NMR, Raman, and UV-Vis. These resources play a vital role in the interpretation, identification, verification, and classification of spectra.<ul><li><a target="_blank" rel="noopener noreferrer" href="https://www.sciencesolutions.wiley.com/spectral-databases">Learn more about Wiley's spectral data collections at Wiley Science Solutions</a></li><li><a target="_blank" rel="noopener noreferrer" href="https://sciencesolutions.wiley.com/how-to-update-knowitall-databases">Current subscribers can learn how to update their databases</a></li></ul><blockquote>* Exclusive access to these data updates is only available through the following KnowItAll data subscriptions: Wiley Registry, KnowItAll GC-MS Library, KnowItAll GC-MS Identification Pro, and KnowItAll MS Identification Pro subscriptions.</blockquote><h4>About Wiley</h4>Wiley (NYSE: WLY) is one of the world’s largest publishers and a trusted leader in research and learning. Our industry-leading content, services, platforms, and knowledge networks are tailored to meet the evolving needs of our customers and partners, including researchers, students, instructors, professionals, institutions, and corporations. We empower knowledge-seekers to transform today’s biggest obstacles into tomorrow’s brightest opportunities. For more than two centuries, Wiley has been delivering on its timeless mission to unlock human potential. Visit us at <a target="_blank" rel="noopener noreferrer" href="https://www.wiley.com/en-ie">Wiley.com</a>.

Wiley empowers its Wiley Registry of Mass Spectral Database KnowItAll subscribers with immediate access to over 17,500 additional spectra

New edition of the Wiley Registry of Mass Spectral Data expands compound coverage to over 915,500 reference spectra, strengthening a foundational layer of Wiley’s scientific data and research intelligence portfolio.Wiley, a global leader in authoritative content and research intelligence for the advancement of scientific discovery, innovation and learning, today released the <a target="_blank" rel="noopener noreferrer" href="https://gcms.labrulez.com/products/887">Wiley Registry of Mass Spectral Data 2026</a>.<img src="https://storage.googleapis.com/labrulez-bucket-strapi-h3hsga3/Wiley_Registry_of_Mass_Spectral_Data_2026_bc408d8245.jpg" alt="Wiley: Registry of Mass Spectral Data 2026" srcset="https://storage.googleapis.com/labrulez-bucket-strapi-h3hsga3/thumbnail_Wiley_Registry_of_Mass_Spectral_Data_2026_bc408d8245.jpg 110w," sizes="100vw" width="1527" height="2162">As AI-driven research pipelines become standard practice across pharmaceuticals, materials science and forensic investigation, the quality of reference data underpinning those pipelines determines whether results are trusted—or stall at the verification stage.The Wiley Registry of Mass Spectral Data 2026 addresses this issue directly: One of the world’s largest and most trusted mass spectral reference databases for identifying unknown chemical compounds, it is now expanded and validated to meet the analytical demands of modern, AI-assisted laboratory workflows.Laboratories face increasingly complex analytical challenges—from detecting emerging environmental contaminants to identifying novel substances in forensic investigations. As a result, having access to a comprehensive, rigorously validated spectral database has become foundational to getting results right. It is also a critical validation layer for AI-driven workflows.The Wiley Registry database helps scientists and researchers around the world with environmental testing, forensic investigation, food safety research, drug analysis, defense research, homeland security, and more, providing critical reference data for identifying and analyzing chemical compounds and materials.The new edition represents a significant expansion of the collection, which now contains more than 915,500 reference spectra—the unique chemical “signatures” used to identify substances—making it among the most comprehensive databases of its kind. More than 42,000 new GC-MS spectra representing 34,100 compounds have been added, with data from laboratories, world patents and peer-reviewed scientific literature. Each spectrum is validated to the same rigorous standard, ensuring that the data perform reliably whether a researcher is running a manual comparison or feeding it into an automated identification pipeline.The Wiley Registry is part of Wiley’s growing portfolio of scientific data and research intelligence solutions, which includes spectral databases, chemistry and materials literature, and analytical tools designed to support researchers and organizations from discovery through to applied outcomes. Wiley spectral database solutions are trusted by the world’s top pharmaceutical companies and many Fortune 500 organizations—reflecting Wiley’s mission to transform knowledge into actionable intelligence, equipping researchers with the rigorous reference data that drives real-world scientific discovery.Updated every three years, the Wiley Registry is among the company’s longest-standing data products, with a history spanning decades of continuous development.“The Wiley Registry is a foundational layer of intelligence for any laboratory conducting GC-MS analysis—and increasingly, for the AI-assisted workflows being built around that analysis,” said Armughan Rafat, Wiley senior vice president and chief AI &amp; data analytics officer. “By expanding compound coverage and applying consistent quality measures across the collection, we help analysts provide a deterministic layer to move from unknown to identified faster.”Available in the most common instrumentation manufacturer formats, the Wiley Registry of Mass Spectral Data 2026 also offers bundled options to access even more data with its <a target="_blank" rel="noopener noreferrer" href="https://gcms.labrulez.com/products/885">Wiley Registry/NIST</a> and the KnowItAll GC-MS Library collection for labs seeking the most comprehensive coverage and workflow integration. The Wiley Registry is also available as a KnowItAll subscription for continued access to new data as they are added to the collection.Spectral databases contain detailed “fingerprints” of substances captured through analytical techniques such as <a target="_blank" rel="noopener noreferrer" href="https://gcms.labrulez.com/products/934">mass spectrometry (MS)</a> or <a target="_blank" rel="noopener noreferrer" href="https://gcms.labrulez.com/products/1271">Raman spectroscopy</a>, enabling researchers to identify unknown materials by comparing their spectral signatures against validated reference spectra. This data is essential for quality control, research verification and discovery across industries from pharmaceuticals to materials science.<blockquote>For more information about the Wiley Registry of Mass Spectral Data 2026, please <a target="_blank" rel="noopener noreferrer" href="https://sciencesolutions.wiley.com/solutions/technique/gc-ms/wiley-registry-of-mass-spectral-data/">visit this website</a>.</blockquote><h4>About Wiley</h4>Wiley (NYSE: WLY) is a global leader in authoritative content and research intelligence for the advancement of scientific discovery, innovation, and learning. With more than 200 years at the center of the scholarly ecosystem, Wiley combines trusted publishing heritage with AI-powered platforms to transform how knowledge is discovered, accessed, and applied. From individual researchers and students to Fortune 500 R&amp;D teams, Wiley enables the transformation of scientific breakthroughs into real-world impact. 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Wiley releases the 2026 edition of the Wiley Registry of Mass Spectral Data to expand GC-MS identification intelligence

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