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Foundational uncertainties in terminal Ediacaran chronostratigraphy revealed by high-precision zircon U-Pb geochronology of the Nama Group, Namibia

The Nama Group of southern Namibia and northwestern South Africa hosts the best-dated mixed carbonate-siliciclastic foreland basin succession of the terminal Ediacaran [ca. 551 million years (Ma) ago to <538 Ma] and is key for resolving the chronology of early metazoan evolution. Numerous silicified volcanic tuff interbeds are present, but differing interpretations regarding the fidelity of their ages lead to different regional stratigraphic correlations, especially for the Urusis Formation of the Schwarzrand Subgroup. An expanded record of the Urusis Formation is found in the Swartpunt area of southern Namibia, which has yielded an important metazoan biota. But the succession in this area is preserved as a series of thrusts at the leading edge of the Gariep orogenic belt and zircon U-Pb data show systematic age repetition. We use regional stratigraphic and structural mapping, integrated with carbonate carbon isotope (δ 13 C carb ) chemostratigraphy and high-precision radioisotope U-Pb zircon geochronology from outcrop and recently acquired drill core to develop a temporally calibrated basin-wide depositional model. This integrated dataset either reflects complex zircon reworking, inheritance, or potential analytical biases (Scenario 1) or the presence of a Gariep-related cryptic décollement within the Spitskop Member that has resulted in stratigraphic repetition (Scenario 2). We investigate the evidence for and against both scenarios and consider their implications for stratigraphic and δ 13 C carb correlations between the Swartpunt area and coeval exposures along the Orange River border with South Africa. Given that these issues are in an area that hosts numerous silicified ash beds and extensive exposure, an inability to confidently discount either scenario highlights a level of compounding uncertainty in zircon U-Pb geochronology that must be considered when attempting to build global chronostratigraphic frameworks. Scenario 1 implies that some of the weighted mean ages and Bayesian eruption ages from the Swartpunt area may be >1 Myr older than the depositional age of their respective ash beds when assuming existing stratigraphic correlations. If this scenario is preferred, then a cautious approach would be to consider all weighted mean zircon U-Pb ages from ash beds to reflect maximum depositional ages. Both scenarios support deposition of the Huns Member >540 Ma in the Swartpunt area if the oldest weighted mean age reported here represents a near-depositional age, which has significant implications for the temporal calibration of important terminal Ediacaran ichnofossil assemblages and future cyclostratigraphic studies. Stratigraphic correlations common to both scenarios allow us to temporally calibrate a basin evolution model for the Nama Group. Temporal trends in initial hafnium isotope (εHf) compositions of zircon grains from ash beds throughout the succession may support progressive crustal thickening associated with underplating of the Damara orogenic belt along the northern periphery of the Kalahari craton from ca. 547 Ma to ca. 538 Ma. The compilation of new and published zircon U-Pb ages may also imply that the locus of carbonate platform development migrated from north to south (present co-ordinates), tracking the migration of foredeep subsidence.

Earth-Science Reviews↗

Occurrence of cyanazine compounds in groundwater: Degradates more prevalent than the parent compound

A recently developed analytical method using liquid chromatography/mass spectrometry was used to investigate the occurrence of cyanazine and its degradates cyanazine acid (CAC), cyanazine amide (CAM), deethylcyanazine (DEC), and deethylcyanazine acid (DCAC) in groundwater. This research represents some of the earliest data on the occurrence of cyanazine degradates in groundwater. Although cyanazine was infrequently detected in the 64 wells across Iowa sampled in 1999, cyanazine degradates were commonly found during this study. The most frequently detected cyanazine compound was DCAC (32.8%) followed by CAC (29.7%), CAM (17.2%), DEC (3.1%), and cyanazine (3.1%). The frequency of detection for cyanazine or one or more of its degradates (CYTOT) was more than 12-fold over that of cyanazine alone (39.1% for CYTOT versus 3.1% for cyanazine). Of the total measured concentration of cyanazine, only 0.2% was derived from its parent compound - with DCAC (74.1%) and CAC (18.4%) comprising 92.5% of this total. Thus, although DCAC and CAC had similar frequencies of detection, DCAC was generally present in higher concentrations. No concentrations of cyanazine compounds for this study exceeded water-quality criteria for the protection of human health. Only cyanazine, however, has such a criteria established. Nevertheless, because these cyanazine degradates are still chlorinated, they may have similar toxicity as their parent compound - similar to what has been found with the chlorinated degradates of atrazine. Thus, the results of this study documented that data on the degradates for cyanazine are critical for understanding its fate and transport in the hydrologic system. Furthermore, the prevalence of the chlorinated degradates of cyanazine found in groundwater suggests that to accurately determine the overall effect on human health and the environment from cyanazine its degradates should also be considered. In addition, because CYTOT was found in 57.6% of the samples collected from alluvial aquifers, about 2-5 times more frequently than the other major aquifer types (glacial drift, bedrock/karst, bedrock/nonkarst) under investigation, this finding has long-term implications for the occurrence of CYTOT in streams. It is anticipated that low-level concentrations of CYTOT will continue to be detected in streams for years after the use of cyanazine has terminated (scheduled for the year 2000 in the United States), primarily through its movement from groundwater into streams during base-flow conditions.

Iowa↗

Insights and strategic opportunities from the USGS 2024 Per- and Polyfluoroalkyl Substances (PFAS) Interagency Workshop

Introduction In 2021, the U.S. Geological Survey (USGS) published Circular 1490 titled, “Integrated Science for the Study of Perfluoroalkyl and Polyfluoroalkyl Substances (PFAS) in the Environment: A Strategic Science Vision for the U.S. Geological Survey” (Tokranov and others, 2021). Circular 1490 was created to be a resource for USGS scientists prioritizing and planning research related to per- and polyfluoroalkyl substances (PFAS) and to be a guide for developing partnerships with other scientists, State and Federal agencies, and stakeholders engaged in PFAS research and management and mitigation of the environmental and human-health effects of PFAS. This USGS PFAS Strategic Science Vision document was intended to be the foundation for a “living strategic vision,” periodically providing updates on the state of USGS PFAS research, emerging PFAS data gaps and needs, and progress on interagency and stakeholder PFAS partnerships and priorities. To meet this objective, the USGS planned to host an Interagency and Stakeholder PFAS Workshop every 2–3 years. During September 10–12, 2024, the USGS hosted the first Interagency and Stakeholder PFAS Workshop in Reston, Virginia. The Workshop brought together experts from other Federal agencies (U.S. Environmental Protection Agency, National Institute of Environmental Health Sciences, Food and Drug Administration, Department of Defense [Air Force, Army]), State agencies (Washington Fish and Wildlife, Virginia Department of Transportation), and academia (Harvard University, University of Maryland) to address key challenges relating to the measurement and modeling of PFAS and the implications for environmental health. Participants engaged in in-depth discussions centered around six pivotal topics related to PFAS: (1) sampling protocols, methods and interpretation; (2) environmental sources, source apportionment, and occurrence; (3) environmental fate and transport; (4) human and wildlife exposure routes and risk; (5) bioconcentration, bioaccumulation, and biomagnification; and (6) ecotoxicology and effects. Each topic had three breakout sessions. A recurrent theme of workshop discussions was how data on a nationwide scale for PFAS occurrence in various environmental matrices, including air, water, food crops, biota, soil, and streambed sediment could help to advance scientific understanding. Participants noted significant geospatial data gaps, particularly in the midwestern and southern United States and the Pacific Northwest. PFAS data collection tends to be more robust along the eastern seaboard and in California. Participants stressed how enhancing the integration of large and small datasets across various agencies could help to support national scale understanding of PFAS. To address these gaps, attendees suggested leveraging datasets from Federal entities like the USGS and the U.S. Department of Defense, State agencies, and municipal utility services to develop predictive contaminant detection and transport models. Improved coordination between water quality programs and USGS research could help to facilitate access to valuable data, leading to comprehensive databases that inform PFAS point (wastewater treatment plants and landfills) and nonpoint (runoff from land, atmospheric deposition, food packaging) sources, environmental transport mechanisms, environmental detection and concentrations, potential exposure routes, and health effects on different biota, including humans. A specific request was made to develop a map demarking the depth of modern (1953 or later) groundwater, which is susceptible to surface-derived anthropogenic (that is, human-made) contamination, based on tritium-age dating. Emphasis was placed on incorporation of hydrology, groundwater flow paths, groundwater–surface water interactions, and landscape factors in predictive statistical models as a step to improve contaminant source identification and tracking. Molecular fingerprinting approaches garnered attention as techniques to link specific PFAS mixtures detected in a sample to environmental sources and levels in biota (Dávila-Santiago and others, 2022). Integrating data from abiotic (that is, water, soil, and air) and biotic (that is, living organisms) systems identified as a research opportunity. For example, understanding the composition of soils and sediments, which include a mixture of mineral, plant, and animal components, could advance understanding of exposure pathways. The discussions highlighted opportunities to explore and understand the potential redistribution and biotic exposures of PFAS from biosolid and wastewater treatment plant effluent land application practices, in addition to atmospheric releases and discharges from landfill and wastewater treatment plants. Participants identified research gaps surrounding how these sources may contribute to contamination and may affect surrounding ecosystems, including a better definition of anthropogenic background concentrations. Moving forward, the collection of co-occurrence data was noted as a means to improve understanding of complex mixtures and to leverage companion modeling efforts focused on areas with high and low contamination levels to identify areas of concern and unaffected resources. Participants emphasized how centralized USGS databases and the establishment of sample-metadata archives can help to ensure that samples are preserved and accessible for future research. In conclusion, the workshop participants identified opportunities to bridge data gaps and improve measurement techniques, modeling frameworks, databases, and communication, to enhance the understanding of PFAS and their effects on environmental and human health. Upon completion of the workshop, participants indicated an interest in developing strategic data collection, modeling, and analytical approaches to address these challenges.

Open-File Report↗

ChemCam activities and discoveries during the nominal mission of the Mars Science Laboratory in Gale crater, Mars

At Gale crater, Mars, ChemCam acquired its first laser-induced breakdown spectroscopy (LIBS) target on Sol 13 of the landed portion of the mission (a Sol is a Mars day). Up to Sol 800, more than 188 000 LIBS spectra were acquired on more than 5800 points distributed over about 650 individual targets. We present a comprehensive review of ChemCam scientific accomplishments during that period, together with a focus on the lessons learned from the first use of LIBS in space. For data processing, we describe new tools that had to be developed to account for the uniqueness of Mars data. With regard to chemistry, we present a summary of the composition range measured on Mars for major-element oxides (SiO 2 , TiO 2 , Al 2 O 3 , FeO T , MgO, CaO, Na 2 O, K 2 O) based on various multivariate models, with associated precisions. ChemCam also observed H, and the non-metallic elements C, O, P, and S, which are usually difficult to quantify with LIBS. F and Cl are observed through their molecular lines. We discuss the most relevant LIBS lines for detection of minor and trace elements (Li, Rb, Sr, Ba, Cr, Mn, Ni, and Zn). These results were obtained thanks to comprehensive ground reference datasets, which are set to mimic the expected mineralogy and chemistry on Mars. With regard to the first use of LIBS in space, we analyze and quantify, often for the first time, each of the advantages of using stand-off LIBS in space: no sample preparation, analysis within its petrological context, dust removal, sub-millimeter scale investigation, multi-point analysis, the ability to carry out statistical surveys and whole-rock analyses, and rapid data acquisition. We conclude with a discussion of ChemCam performance to survey the geochemistry of Mars, and its valuable support of decisions about selecting where and whether to make observations with more time and resource-intensive tools in the rover's instrument suite. In the end, we present a bird's-eye view of the many scientific results: discovery of felsic Noachian crust, first observation of hydrated soil, discovery of manganese-rich coatings and fracture fills indicating strong oxidation potential in Mars' early atmosphere, characterization of soils by grain size, and wide scale mapping of sedimentary strata, conglomerates, and diagenetic materials.

Journal of Analytical Atomic Spectrometry↗

Pharmaceutical pollution of the world’s rivers

Environmental exposure to active pharmaceutical ingredients (APIs) can have negative effects on the health of ecosystems and humans. While numerous studies have monitored APIs in rivers, these employ different analytical methods, measure different APIs, and have ignored many of the countries of the world. This makes it difficult to quantify the scale of the problem from a global perspective. Furthermore, comparison of the existing data, generated for different studies/regions/continents, is challenging due to the vast differences between the analytical methodologies employed. Here, we present a global-scale study of API pollution in 258 of the world’s rivers, representing the environmental influence of 471.4 million people across 137 geographic regions. Samples were obtained from 1,052 locations in 104 countries (representing all continents and 36 countries not previously studied for API contamination) and analyzed for 61 APIs. Highest cumulative API concentrations were observed in sub-Saharan Africa, south Asia, and South America. The most contaminated sites were in low- to middle-income countries and were associated with areas with poor wastewater and waste management infrastructure and pharmaceutical manufacturing. The most frequently detected APIs were carbamazepine, metformin, and caffeine (a compound also arising from lifestyle use), which were detected at over half of the sites monitored. Concentrations of at least one API at 25.7% of the sampling sites were greater than concentrations considered safe for aquatic organisms, or which are of concern in terms of selection for antimicrobial resistance. Therefore, pharmaceutical pollution poses a global threat to environmental and human health, as well as to delivery of the United Nations Sustainable Development Goals.

Proceedings of the National Academy of Sciences↗