Abiotic synthesis of graphitic carbons in the Eoarchean Saglek-Hebron metasedimentary rocks.

Graphite in metasedimentary rocks of the Eoarchean Saglek-Hebron Gneiss Complex (Canada) is depleted in 13C and has been interpreted as one of the oldest traces of life on Earth. The variation in crystallinity of this oldest graphitic carbon could possibly confirm the effect of metamorphism on original biomass, but this is still unexplored. Here, we report specific mineral associations with graphitic carbons that also have a range of crystallinity in the Saglek-Hebron metasedimentary rocks. Petrographic, geochemical and spectroscopic analyses in the Saglek-Hebron banded iron formations suggest that poorly crystalline graphite is likely deposited from C-H-O fluids derived from thermal decomposition of syngenetic organic matter, which is preserved as crystalline graphite during prograde metamorphism. In comparison, in the Saglek-Hebron marble, disseminations of graphite co-occur with carbonate and magnetite disseminations, pointing to abiotic synthesis of graphitic carbons via decarbonation. Our results thus highlight that variably crystalline graphitic carbons in the Saglek-Hebron metasedimentary rocks are potential abiotic products on early Earth, which lay the groundwork for identifying the preservation of prebiotic organic matter through metamorphism on Earth and beyond.

Atmospheric deposition is an important pathway for inputting microplastics: Insight into the spatiotemporal distribution and deposition flux in a mega city.

Microplastics (MPs) refer to plastic particles with a size less than 5 mm, which attracted widespread attention as an emerging pollutant. The monitoring of atmospheric microplastics (AMPs) in a megacity was carried out to study the characteristics and spatiotemporal distribution of AMPs, explore the sources and estimate the deposition flux. The results showed that the annual average abundance of AMPs in Wuhan was 82.85 ± 57.66 n·m-2·day-1. The spatiotemporal distribution characteristics of AMPs show that spring was the highest season, followed by autumn, winter, and summer; the city center was higher than the suburbs. Fiber was the main type of AMPs in Wuhan, followed by fragment, film and pellet. The proportion of AMPs were mainly small (<0.5 mm) and medium (0.5-1.0 mm). Transparent and white were the main colors of AMPs, followed by red, brown. A total of 10 types polymers were detected, polyethylene terephthalate (PET) was dominant. There are positive correlations between AMPs and SO2, NO2 in the atmosphere, indicating that they might be influenced by intense human activity. The polycyclic aromatic hydrocarbons (PAHs) and AMPs in spring showed an extremely significant positive correlation (p < 0.05). AMPs might mainly originate from the wear and tear shedding of textiles, the aging of agricultural films and plastic waste based on their polymer types and main uses. The potential geographical sources of AMPs were mainly the surrounding cities. The annual deposition flux of AMPs was about 308 tons if there were no remove processes, which highlighted the importance of atmospheric transport and deposition of MPs. The analysis of the abundance, morphological characteristics and sources of AMPs can provide data support and reference for mega-cities with high global population activities, or cities in global mid-latitude regions.

Occurrence, distribution and risk assessment of microplastics and polycyclic aromatic hydrocarbons in East lake, Hubei, China.

The pollution of microplastics (MPs) and polycyclic aromatic hydrocarbons (PAHs) in the environment is a global problem, which has attracted extensive attention of many researchers. In present study, MPs and PAHs are investigated to study the impact of human activities and their possible relationship in China's second largest urban lake, East Lake. The abundance of MPs are 3329.19 ± 2059.26 particles/m3 and 2207.56 ± 1194.04 particles/kg in water and sediment, respectively. MPs are predominantly characterized by fibers, polypropylene (PP) and polyethylene (PE), colorlessness in water and sediment. The abundance of MPs in water with frequent human activities is higher, which is reversed in sediments, indicating that disturbance is not conducive to the enrichment of MPs in sediments. The concentration of 16 PAHs are 36.95 ± 13.76 ng/L and 897.08 ± 232.34 ng/g in water and sediment, respectively. PAHs in water are mainly 2-3-ring, while there are 4-ring PAHs in sediments. The good corresponding relationship between MPs and PAHs indicates that human activities have an important impact on the distribution of pollutants compared to the interaction of pollutants. In addition, the significant positive correlation between lakeshore length and water MPs abundance indicates that surface runoff may be an important source of water MPs. The pollution load index shows that MPs in sediment has reached moderate to severe pollution level, while the water is slightly polluted level. The potential ecological risk assessment results show that more than half of the sediment sites are at dangerous to very dangerous ecological risk level.

Metabolically diverse primordial microbial communities in Earth's oldest seafloor-hydrothermal jasper.

The oldest putative fossils occur as hematite filaments and tubes in jasper-carbonate banded iron formations from the 4280- to 3750-Ma Nuvvuagittuq Supracrustal Belt, Québec. If biological in origin, these filaments might have affinities with modern descendants; however, if abiotic, they could indicate complex prebiotic forms on early Earth. Here, we report images of centimeter-size, autochthonous hematite filaments that are pectinate-branching, parallel-aligned, undulated, and containing Fe2+-oxides. These microstructures are considered microfossils because of their mineral associations and resemblance to younger microfossils, modern Fe-bacteria from hydrothermal environments, and the experimental products of heated Fe-oxidizing bacteria. Additional clusters of irregular hematite ellipsoids could reflect abiotic processes of silicification, producing similar structures and thus yielding an uncertain origin. Millimeter-sized chalcopyrite grains within the jasper-carbonate rocks have 34S- and 33S-enrichments consistent with microbial S-disproportionation and an O2-poor atmosphere. Collectively, the observations suggest a diverse microbial ecosystem on the primordial Earth that may be common on other planetary bodies, including Mars.

Automated analysis of microplastics based on vibrational spectroscopy: are we measuring the same metrics?

The traditional manual analysis of microplastics has been criticized for its labor-intensive, inaccurate identification of small microplastics, and the lack of uniformity. There are already three automated analysis strategies for microplastics based on vibrational spectroscopy: laser direct infrared (LDIR)-based particle analysis, Raman-based particle analysis, and focal plane array-Fourier transform infrared (FPA-FTIR) imaging. We compared their performances in terms of quantification, detection limit, size measurement, and material identification accuracy and speed by analyzing the same standard and environmental samples. LDIR-based particle analysis provides the fastest analysis speed, but potentially questionable material identification and quantification results. The number of particles smaller than 60 µm recognized by LDIR-based particle analysis is much less than that recognized by Raman-based particle analysis. Misidentification could occur due to the narrow tuning range from 1800 to 975 cm-1 and dispersive artifact distortion of infrared spectra collected in reflection mode. Raman-based particle analysis has a submicrometer detection limit but should be cautiously used in the automated analysis of microplastics in environmental samples because of the strong fluorescence interference. FPA-FTIR imaging provides relatively reliable quantification and material identification for microplastics in environmental samples greater than 20 µm but might provide an imprecise description of the particle shapes. Optical photothermal infrared (O-PTIR) spectroscopy can detect submicron-sized environmental microplastics (0.5-5 µm) intermingled with a substantial amount of biological matrix; the resulting spectra are searchable in infrared databases without the influence of fluorescence interference, but the process would need to be fully automated.

Massive formation of early diagenetic dolomite in the Ediacaran ocean: Constraints on the "dolomite problem".

Paleozoic and Precambrian sedimentary successions frequently contain massive dolomicrite [CaMg(CO3)2] units despite kinetic inhibitions to nucleation and precipitation of dolomite at Earth surface temperatures (<60 °C). This paradoxical observation is known as the "dolomite problem." Accordingly, the genesis of these dolostones is usually attributed to burial-hydrothermal dolomitization of primary limestones (CaCO3) at temperatures of >100 °C, thus raising doubt about the validity of these deposits as archives of Earth surface environments. We present a high-resolution, >63-My-long clumped-isotope temperature (TΔ47) record of shallow-marine dolomicrites from two drillcores of the Ediacaran (635 to 541 Ma) Doushantuo Formation in South China. Our T∆47 record indicates that a majority (87%) of these dolostones formed at temperatures of <100 °C. When considering the regional thermal history, modeling of the influence of solid-state reordering on our TΔ47 record further suggests that most of the studied dolostones formed at temperatures of <60 °C, providing direct evidence of a low-temperature origin of these dolostones. Furthermore, calculated δ18O values of diagenetic fluids, rare earth element plus yttrium compositions, and petrographic observations of these dolostones are consistent with an early diagenetic origin in a rock-buffered environment. We thus propose that a precursor precipitate from seawater was subsequently dolomitized during early diagenesis in a near-surface setting to produce the large volume of dolostones in the Doushantuo Formation. Our findings suggest that the preponderance of dolomite in Paleozoic and Precambrian deposits likely reflects oceanic conditions specific to those eras and that dolostones can be faithful recorders of environmental conditions in the early oceans.

Raman spectra and surface changes of microplastics weathered under natural environments.

Raman spectroscopy can be used to effectively analyze submicron- to microsized microplastics, but Raman spectra of weathered microplastics commonly show deviations from those of unweathered microplastics and are often affected by fluorescence. However, studies of weathering-induced surface changes in microplastics have been limited to laboratory simulations. To systematically study Raman spectra and surface changes of microplastics weathered under natural environments, we collected microplastics from sediments around waste plastics processing and recycling industries in Laizhou City, Shandong Province, East China. Raman spectra of weathered microplastics differ greatly from standard spectra of unweathered plastic material. Peaks in the Raman spectra of weathered microplastics are weakened and even invisible. A preliminary Raman database of weathered microplastics (RDWP) including 124 Raman spectra of weathered microplastics was built to accurately identify microplastics in natural environments, and it is open to all users. FTIR spectroscopy revealed the presence of oxygen-containing functional groups and CC bonds related to oxidation and chain scission. SEM showed that weathered microplastics had rough surfaces and that PP was more easily fractured than PE. Complementary C and O elemental maps suggested that the O/C ratio is a potential indicator of oxidation degree. EDS revealed titanium on PET and PVC surfaces, which is related to titanium dioxide typically used as a light-blocking aid. Our data document that Raman spectroscopy has great potential in the identification of naturally weathered microplastics and that combined spectral and elemental analyses can be useful in deciphering the degradation processes of microplastics under natural conditions. CAPSULE: Raman spectra of weathered microplastics differ greatly from standard spectra. A Raman database of weathered microplastics is established. Surface changes of weathered microplastics were systematically studied.

The onset of widespread marine red beds and the evolution of ferruginous oceans.

Banded iron formations were a prevalent feature of marine sedimentation ~3.8-1.8 billion years ago and they provide key evidence for ferruginous oceans. The disappearance of banded iron formations at ~1.8 billion years ago was traditionally taken as evidence for the demise of ferruginous oceans, but recent geochemical studies show that ferruginous conditions persisted throughout the later Precambrian, and were even a feature of Phanerozoic ocean anoxic events. Here, to reconcile these observations, we track the evolution of oceanic Fe-concentrations by considering the temporal record of banded iron formations and marine red beds. We find that marine red beds are a prominent feature of the sedimentary record since the middle Ediacaran (~580 million years ago). Geochemical analyses and thermodynamic modelling reveal that marine red beds formed when deep-ocean Fe-concentrations were > 4 nM. By contrast, banded iron formations formed when Fe-concentrations were much higher (> 50 µM). Thus, the first widespread development of marine red beds constrains the timing of deep-ocean oxygenation.The evolution of oceanic redox state in the past is poorly known. Here, the authors present a temporal record of banded iron formations and marine red beds, which indicate deep-ocean oxygenation occurred in the middle Ediacaran, coinciding with the onset of widespread marine red beds.