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Researchers from the New Jersey Institute of Technology demonstrated different methods for predicting thermodynamic and transport parameters of Cd and Zn in soils and sediments sorbing to aluminum, iron, and manganese oxides.

Rare basal Pridoli plant fossils, which resemble the rhyniophytoid Hollandophyton colliculum and have exceptional three-dimensional cellular anatomy, are preserved as charcoal. As such, these fossils from Ludford Lane in the Welsh Borders are evidence of the earliest recorded wildfire and are the first documented from before the Devonian. The fossils represent the charred remains of a low-growing, low-diversity, in situ rhyniophytoid or cryptospore-bearing plant vegetation charred during a low-temperature fire. Keywords: Silurian, fires, charcoal, preservation, taphonomy.

With widespread occurrence and increasing concern of emerging contaminants (CECs) in source water, biologically active filters (BAF) have been gaining acceptance in water treatment. Both BAFs and graphene oxide (GO) have been shown to be effective in treating CECs. However, studies to date have not addressed interactions between GO and microbial communities in water treatment processes such as BAFs. Therefore, in the present study, we investigated the effect of GO on the properties and microbial growth rate in a BAF system. Synthesized GO was characterized with a number of tools, including scanning electron microscopy (SEM), energy dispersive x-ray spectroscopy (EDX), X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR), and Raman spectrometry. GO exhibited the characteristic surface functional groups (i.e., C-OH, C=O, C-O-C, and COOH), crystalline structure, and sheet-like morphology. To address the potential toxicity of GO on the microbial community, reactive oxygen species (ROS) generation was measured using nitro blue tetrazolium (NBT) assay. Results revealed that during the exponential growth phase, ROS generation was not observed in the presence of GO compared to the control batch. In fact, the adenosine triphosphate (ATP) concentrations increased in the presence of GO (25 μg/L - 1000 μg/L) compared to the control without GO. The growth rate in systems with GO exceeded the control by 20 % to 46 %. SEM images showed that GO sheets can form an effective scaffold to promote bacterial adhesion, proliferation, and biofilm formation, demonstrating its biocompatibility. Next-generation sequencing (Illumina MiSeq) was used to characterize the BAF microbial community, and high-throughput sequencing analysis confirmed the greater richness and more diverse microbial communities compared to systems without GO. This study is the first to report the effect of GO on the microbial community of BAF from a water treatment plant, which provides new insights into the potential of utilizing a bio-optimized BAF for advanced and sustainable water treatment or reuse strategies., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier Ltd. All rights reserved.)

Reactive iron (Fe) mineral coatings found in subsurface reduction-oxidation transition zones (RTZs) contribute to the attenuation of contaminants. An 18.3-m anoxic core was collected from the site, where constituents of concern (COCs) in groundwater included chlorinated solvents. Reactive Fe mineral coatings were found to be abundant in the RTZs. This research focused on evaluating reaction kinetics with anoxic sediments bearing ferrous mineral nano-coatings spiked with either tetrachloroethylene (PCE), trichloroethylene (TCE), or 1,4-dichlorobenzene (1,4-DCB). Reaction kinetics with RTZ sediments followed pseudo-first-order reactions for the three contaminants with 90% degradation achieved in less than 39 days. The second-order rate constants for the three COCs ranged from 6.20 × 10 -4 to 1.73 × 10 -3 Lg -1 h -1 with pyrite (FeS 2 ), 4.97 × 10 -5 to 1.24 × 10 -3 Lg -1 h -1 with mackinawite (FeS), 1.25 × 10 -4 to 1.89 × 10 -4 Lg -1 h -1 with siderite (FeCO 3 ), and 1.79 × 10 -4 to 1.10 × 10 -3 Lg -1 h -1 with magnetite (Fe 3 O 4 ). For these three chlorinated solvents, the trend for the rate constants followed: Fe(II) sulfide minerals > magnetite > siderite. The high reactivity of Fe mineral coatings is hypothesized to be due to the large surface areas of the nano-mineral coatings. As a result, these surfaces are expected to play an important role in the attenuation of chlorinated solvents in contaminated subsurface environments., Competing Interests: Declaration of Competing Interest The authors declare the following financial interests/personal relationships which may be considered as potential competing interests: Lisa Axe reports financial support was provided by The Chemours Company., (Copyright © 2022 Elsevier B.V. All rights reserved.)

The earliest evidence for land plants comes from dispersed cryptospores from the Ordovician, which dominated assemblages for 60 million years. Direct evidence of their parent plants comes from minute fossils in Welsh Borderland Upper Silurian to Lower Devonian rocks. We recognize a group that had forking, striated axes with rare stomata terminating in valvate sporangia containing permanent cryptospores, but their anatomy was unknown especially regarding conducting tissues. Charcoalified fossils extracted from the rock using HF were selected from macerates and observed using scanning electron microscopy. Promising examples were split for further examination and compared with electron micrographs of the anatomy of extant bryophytes. Fertile fossil axes possess central elongate cells with thick walls bearing globules, occasional strands and plasmodesmata-sized pores. The anatomy of these cells best matches desiccation-tolerant food-conducting cells (leptoids) of bryophytes. Together with thick-walled epidermal cells and extremely small size, these features suggest that these plants were poikilohydric. Our new data on conducting cells confirms a combination of characters that distinguish the permanent cryptospore-producers from bryophytes and tracheophytes. We therefore propose the erection of a new group, here named the Eophytidae (eophytes)., (© 2021 The Authors. New Phytologist © 2021 New Phytologist Foundation.)

Key sources of information on the nature of early terrestrial ecosystems are the fossilized remains of plants and associated organic encrustations, which are interpreted as either biofilms, biological soil crusts or lichens. The hypothesis that some of these encrustations might be the remains of the thalloid gametophytes of embryophytes provided the stimulus for this investigation. Fossils preserved in charcoal were extracted from Devonian Period (Lochkovian Stage, c. 410-419 Myr old) sediments at a geological site in Shropshire (UK). Scanning electron micrographs (SEMs) of the fossils were compared with new and published SEMs of extant bryophytes and tracheophytes, respectively. One specimen was further prepared and imaged by transmission electron microscopy. Fossils of thalloid morphology were composed almost entirely of cells with labyrinthine ingrowths; these also were present in fossils of axial morphology where they were associated with putative food-conducting cells. Comparison with modern embryophytes demonstrates that these distinctive cells are transfer cells (TCs). Our fossils provide by far the earliest geological evidence of TCs. They also show that some organic encrustations are the remains of thalloid land plants and that these are possibly part of the life cycle of a newly recognized group of plants called the eophytes., (© 2021 The Authors. New Phytologist © 2021 New Phytologist Foundation.)

In this study, a protocol was developed to identify reduction-oxidation (redox) transition zones in an effort to exploit natural source zone depletion processes. A sediment core with a total length of 18-m was collected from a site with historical contamination that includes chlorinated benzenes where the redox condition was preserved. In the four redox transition zones investigated, reactive iron coatings are characterized with a suite of analyses under anaerobic conditions. To distinguish surface coating mineralogy, X-ray diffraction, X-ray fluorescence, and field-emission scanning electron microscopy with an energy dispersive X-ray analyzer were applied along with a six-step sequential extraction process. The cycling of Fe and S, as an important contribution and indicator of ongoing natural attenuation processes for constituents of concern (COC), was delineated by using data from multiple and complementary analyses for isolating and identifying iron phases. Along with groundwater chemistry, contaminant concentrations, and microbial genera, attenuation of COCs is expected to be active and sustainable in redox transition zones, where there is an abundance of reactive iron mineral coatings cycling through biogeochemical reactions. Reactions in other redox transition zones may be limited where iron mineral coatings are not dominant., (Copyright © 2021 Elsevier B.V. All rights reserved.)

This study focused on comparing iron mineral coatings found in contaminated sediments from a cryogenic (Cryo Core) core versus an Anaerobic Core (collected under oxygen-free and ambient conditions). After thawing the Cryo Core in an oxygen-free glovebox, a suite of analyses was applied on sediments from both cores: pH, redox potential, X-ray fluorescence (XRF), X-ray diffraction (XRD), and field-emission scanning electron microscopy (FESEM) with energy dispersive X-ray analyzer (EDX). Among the iron minerals identified, crystalline pyrite was found throughout the Cyro Core sediment samples, which is in contrast to that observed for the Anaerobic Core. Moreover, mackinawite and greigite that were ubiquitous in the Anaerobic Core were not observed in Cryo Core samples. To better understand why the metastable minerals were not present, a freeze/thaw process was simulated on Anaerobic Core samples using a liquid‑nitrogen quench with surface coatings characterized by FESEM/EDX. In these quenched samples, mackinawite was no longer observed, and in its place was pyrite. In addition, both greigite and pyrite were found to be unique morphologically after quenching. Dissolution and re-precipitation of iron sulfide coatings during the freeze/thaw process appears to affect the geochemistry of the pore water through two main mechanisms of freeze-concentration and freezing potential., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2020 Elsevier B.V. All rights reserved.)

Reactive iron mineral coatings found throughout reduction-oxidation (redox) transition zones play an important role in contaminant transformation processes. This research focuses on demonstrating a process for effectively delineating redox transition zones at a site with historical contamination. An 18.3 meter core was collected, subsampled, and preserved under anoxic conditions to maintain its original redox status. To ensure a high vertical resolution, sampling increments of 5.08 cm in length were analyzed for elemental concentrations with X-ray fluorescence (XRF), sediment pH, sediment oxidation-reduction potential (ORP), total volatile organic carbon (TVOC) concentration in the sample headspace, and abundant bacteria (16S rRNA sequencing). Over the core's length, gradients observed ranged from 3.74 to 8.03 for sediment pH, -141.4 mV to +651.0 mV for sediment ORP, and from below detection to a maximum of 9.6 ppm TVOC concentration (as chlorobenzene) in the headspace. The Fe and S gradients correlated with the presence of Fe and S reducing bacteria. S concentrations peaked in the Upper Zone and Zone 1 where Desulfosporosinus was abundant, suggesting precipitation of iron sulfide minerals. In Zone 2, Fe concentrations decreased where Geobacter was abundant, potentially resulting in Fe reduction, dissolution, and precipitation of minerals with increased solubility compared to the Fe(III) minerals. Using complementary geochemical and microbial data, five redox transition zones were delineated in the core collected. This research demonstrates a systematic approach to characterizing redox transition zones in a contaminated environment., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2020 Elsevier B.V. All rights reserved.)

The presence of contaminants of emerging concern (CECs) in the aquatic environment has recently become a global issue. The very large number of CECs reported in the literature makes it difficult to interpret potential risks as well as the removal efficiencies, especially for the more recalcitrant compounds. As such, there is a need for indicator compounds that are representative of CECs detected in systems worldwide. In an effort to develop such a list, five criteria were used to address the potential for applying indicator compounds; these criteria include usage, occurrence, resistance to treatment, persistence, and physicochemical properties that shed light on the potential degradability of a class of compounds. Additional constraints applied included the feasibility of procuring and analyzing compounds. In total, 22 CECs belonging to 13 groups were selected as indicator compounds. These compounds include acetaminophen and ibuprofen (analgesic); erythromycin, sulfamethoxazole, and trimethoprim (antibiotics); diazepam and fluoxetine (antidepressants); carbamazepine (antiepileptic); atenolol and propranolol (β-blockers); gemfibrozil (blood lipid regulator); tris(2-chloroethyl)phosphate (TCEP) (fire retardant); cotinine (nicotine metabolite); atrazine, metolachlor, and N,N-diethyl-meta-toluamide (DEET) (pesticides); 17β-estradiol and cholesterol (steroids); caffeine (psychomotor stimulant); perfluorooctane sulfonate (PFOS) and perfluorooctanoic acid (PFOA) (surfactants); and iopromide (X-ray contrast agent). These thirteen groups of compounds represent CECs with the greatest resistance to treatment processes, most persistent in surface waters, and detected with significant frequency throughout the water cycle. Among the important implications of using indicator compounds are the ability to better understand the efficacy of treatment processes as well as the transport and fate of these compounds in the environment.

In biologically active filters (BAFs), microorganisms acclimated on the media surface are the key players responsible for removing organic water contaminants. In this study, next generation sequencing by Illumina MiSeq was used to characterize the microbial community structures in the influent, effluent, and media of a set of bench-scale BAFs that have been demonstrated with high removal efficiency (>75%) of 16 contaminants of emerging concern (CECs), which include a variety of pharmaceuticals (e.g., sulfamethoxazole and ibuprofen), X-ray contrast agent (i.e., iopromide), and pesticides (e.g., atrazine) that are prevalently found in municipal waste streams. Proteobacteria and Planctomycetes were the most abundant phyla in filter media, while the influent and effluent samples were dominated by Proteobacteria, Actinobacteria, and Chlamydiae. Factorial and principal component analysis revealed microbial structures in the media were significantly affected by the operation conditions, including media type (GAC versus dual media anthracite sand), EBCT (10 versus 18 min), and pre-ozonation. Detrended correspondence analysis demonstrated media materials predominantly governed the structures of the acclimated biofilm in BAFs as they provide direct attachment surface. This is in line with the higher microbial activity and better treatment performance exhibited by GAC BAFs compared to the dual media BAFs, corroborating the importance of filter media selection to promote the acclimation of active and robust biofilm for efficient CEC removal. Principal component analysis revealed the significant influence from ozonation, which does not only break down CECs, but also stimulates microbes that grow on the ozonation products. Partial canonical correlation analysis further proved the shaping of biofilm communities on the BAF media is more associated with media type and ozonation compared to EBCT. Putative CEC degraders are predicted based on their dominance in the media and degradation capabilities reported in previous literature. This is the first study to examine the relationship between the microbial community structure and the BAF operating parameters, which are both aligned with the treatment performance exhibited by the BAFs., (Copyright © 2018 Elsevier B.V. All rights reserved.)

The affinities of Prototaxites have been debated ever since its fossils, some attaining tree-trunk proportions, were discovered in Canadian Lower Devonian rocks in 1859. Putative assignations include conifers, red and brown algae, liverworts and fungi (some lichenised). Detailed anatomical investigation led to the reconstruction of the type species, P. logani , as a giant sporophore (basidioma) of an agaricomycete (= holobasidiomycete), but evidence for its reproduction remained elusive. Tissues associated with P. taiti in the Rhynie chert plus charcoalified fragments from southern Britain are investigated here to describe the reproductive characters and hence affinities of Prototaxites Thin sections and peels (Pragian Rhynie chert, Aberdeenshire) were examined using light and confocal microscopy; Přídolí and Lochkovian charcoalified samples (Welsh Borderland) were liberated from the rock and examined with scanning electron microscopy. Prototaxites taiti possessed a superficial hymenium comprising an epihymenial layer, delicate septate paraphyses, inoperculate polysporic asci lacking croziers and a subhymenial layer composed predominantly of thin-walled hyphae and occasional larger hyphae. Prototaxites taiti combines features of extant Taphrinomycotina (Neolectomycetes lacking croziers) and Pezizomycotina (epihymenial layer secreted by paraphyses) but is not an ancestor of the latter. Brief consideration is given to its nutrition and potential position in the phylogeny of the Ascomycota.This article is part of a discussion meeting issue 'The Rhynie cherts: our earliest terrestrial ecosystem revisited'., (© 2017 The Author(s).)

With the increasing concern of contaminants of emerging concern (CECs) in source water, this study examines the hypothesis that existing filters in water treatment plants can be converted to biologically active filters (BAFs) to treat these compounds. Removals through bench-scale BAFs were evaluated as a function of media, granular activated carbon (GAC) and dual media, empty bed contact time (EBCT), and pre-ozonation. For GAC BAFs, greater oxygen consumption, increased pH drop, and greater dissolved organic carbon removal normalized to adenosine triphosphate (ATP) were observed indicating increased microbial activity as compared to anthracite/sand dual media BAFs. ATP concentrations in the upper portion of the BAFs were as much as four times greater than the middle and lower portions of the dual media and 1.5 times greater in GAC. Sixteen CECs were spiked in the source water. At an EBCT of 18 min (min), GAC BAFs were highly effective with overall removals greater than 80% without pre-ozonation; exceptions included tri(2-chloroethyl) phosphate and iopromide. With a 10 min EBCT, the degree of CECs removal was reduced with less than half of the compounds removed at greater than 80%. The dual media BAFs showed limited CECs removal with only four compounds removed at greater than 80%, and 10 compounds were reduced by less than 50% with either EBCT. This study demonstrated that GAC BAFs with and without pre-ozonation are an effective and advanced technology for treating emerging contaminants. On the other hand, pre-ozonation is needed for dual media BAFs to remove CECs. The most cost effective operating conditions for dual media BAFs were a 10 min EBCT with the application of pre-ozonation., (Copyright © 2017 Elsevier Ltd. All rights reserved.)

With widespread occurrence of pharmaceuticals and personal care products (PPCPs) in the water cycle, their presence in source water has led to the need to better understand their treatability and removal efficiency in treatment processes. Fifteen indicator compounds were identified to represent the large number of PPCPs reported worldwide. Criteria applied to determine the indicator compounds included PPCPs widely used, observed at great frequency in aqueous systems, resistant to treatment, persistent in the environment, and representative of classes of organics. Through a pilot plant investigation to understand the optimal combination of unit process for treating PPCPs, 12 treatment trains with their additive and synergistic contributions were investigated; processes included dissolved air flotation (DAF), pre- and intermediate-ozonation with and without H 2 O 2 , intermediate chlorination, dual media filtration, granular activated carbon (GAC), and UV/H 2 O 2 . Treatment trains that achieved the greatest removals involved 1. DAF followed by intermediate ozonation, dual media filtration, and virgin GAC; 2. pre-ozonation followed by DAF, dual media filtration, and virgin GAC; and, 3. DAF (with either pre- or intermediate oxidation) followed by dual media filtration and UV/H 2 O 2 . Results revealed significant removal efficiencies for virgin GAC (preceded by DAF and intermediate ozonation) and UV/H 2 O 2 with an intensity of 700 mJ/cm 2 , where more than 12 of the compounds were removed by greater than 90%. Reduced PPCP removals were observed with virgin GAC preceded by pre-ozonation and DAF. Intermediate ozonation was more effective than using pre-ozonation, demonstrating the importance of this process targeting PPCPs after treatment of natural organic matter. Removal efficiencies of indicator compounds through ozonation were found to be a function of the O 3 rate constants (k O3 ). For compounds with low O 3 rate constants (k O3  < 10 M -1 s -1 ), H 2 O 2 addition in the O 3 reactor was required. Of the 15 indicator compounds, tri(2-chloroethyl) phosphate (TCEP) and cotinine were observed to be the most recalcitrant. Although UV/H 2 O 2 with elevated intensity (700 mJ/cm 2 ) was effective for PPCP removals, energy requirements far exceed intensities applied for disinfection., (Copyright © 2016 Elsevier Ltd. All rights reserved.)