Molecular-Scale Investigation on the Formation of Brown Carbon Aerosol via Iron-Phenolic Compound Reactions in the Dark.

Brown carbon (BrC) is one of the most mysterious aerosol components responsible for global warming and air pollution. Iron (Fe)-induced catalytic oxidation of ubiquitous phenolic compounds has been considered as a potential pathway for BrC formation in the dark. However, the reaction mechanism and product composition are still poorly understood. Herein, 13 phenolic precursors were employed to react with Fe under environmentally relevant conditions. Using Fourier transform ion cyclotron resonance mass spectrometry, a total of 764 unique molecular formulas were identified, and over 85% of them can be found in atmospheric aerosols. In particular, products derived from precursors with catechol-, guaiacol-, and syringol-like-based structures can be distinguished by their optical and molecular characteristics, indicating the structure-dependent formation of BrC from phenolic precursors. Multiple pieces of evidence indicate that under acidic conditions, the contribution of either autoxidation or oxygen-induced free radical oxidation to BrC formation is extremely limited. Ligand-to-Fe charge transfer and subsequent phenoxy radical coupling reactions were the main mechanism for the formation of polymerization products with high molecular diversity, and the efficiency of BrC generation was linearly correlated with the ionization potential of phenolic precursors. The present study uncovered how chemically diverse BrC products were formed by the Fe-phenolic compound reactions at the molecular level and also provide a new paradigm for the study of the atmospheric aerosol formation mechanism.

Main chemical and mineralogical components of the Rio Doce sediments and the iron ore tailing from the Fundão Dam disaster, Southeastern Brazil.

Since the Fundão Dam rupture in Southeastern Brazil caused an enormous amount of iron ore tailing (IOT) to be discharged into the Doce River Catchment, various works have been published on the soil, water, and biota contamination by potentially hazardous trace metals. However, the objective of this study is to investigate changes in the main chemical composition and the mineral phases, which has not been studied yet. We present an analysis of sediment samples collected in the Doce River alluvial plain, before and after the disaster, as well as the tailing deposited. Granulometry, main chemical composition by X-ray fluorescence spectrometry, mineralogy by X-ray diffractometry, quantification of mineral phases using the Rietveld method, and scanning electron microscope imaging are shown. We conclude that the Fundão Dam rupture introduced fine particles into the Doce River alluvial plain, increasing the Fe and Al content in the sediments. The high Fe, Al, and Mn contents in the finer iron ore tailing fractions represent environmental risks for soil, water, and biotic chains. The IOT mineralogical components, mainly the muscovite, kaolinite, and hematite present in the finer particles can increase the sorption and desorption capacity of harmful trace metals depending on the natural or induced redox conditions, which are not always predictable and avoidable in the environment.

Induction of spontaneous phenotype conversion in Ralstonia solanacearum by addition of iron compounds in liquid medium.

Ralstonia solanacearum is a soil-borne pathogen that causes bacterial wilt in plants. The wild-type strain of R. solanacearum undergoes spontaneous phenotype conversion (PC), from a fluidal to non-fluidal colony morphology. PC mutants are non-pathogenic due to reduced virulence factors, and can control wilt diseases as biological control agents. The induction factors of PC in R. solanacearum are currently unclear. Here, we investigated the effect of iron treatment on bacterial growth of wild-type strain and PC mutant, and PC of the wild-type strain in liquid medium. Interestingly, PC was frequently induced in the single cultured wild-type strain by iron treatment; however, PC was not induced in the co-culture. In a co-culture of both strains, the PC mutant showed increased growth compared to the wild-type strain by iron treatment. Furthermore, we investigated the effects of iron treatment on the bacterial growth and PC of the wild-type strain under different culture conditions of medium type (MM broth, BG broth, and water medium), iron compounds, and pH. In BG broth, PC occurred frequently regardless of iron treatment. In MM broth, the optimal conditions for high frequency induction of PC by iron treatments were treatment of iron (III) EDTA, and under pH 7-8. Conversely, PC was not induced by iron treatment in water medium and in MM broth under pH 5 conditions. Common to the culture conditions wherein PC was not induced by iron treatment, the bacterial density of the wild-type strain was as low as 106 CFU mL-1 or less. Finally, we investigated the effects on bacterial growth and PC of the wild-type strain by the iron treatment and addition of culture filtrate after cultivation of the wild-type strain at high concentration. In medium containing only the culture filtrate, PC did not occur. However, in medium containing the culture filtrate and iron, PC occurred frequently. Our results thus suggest that high-density growth of the wild-type strain as well as the presence of iron are involved in inducing PC in R. solanacearum.

Simulating Mars Drilling Mission for Searching for Life: Ground-Truthing Lipids and Other Complex Microbial Biomarkers in the Iron-Sulfur Rich Río Tinto Analog.

Sulfate and iron oxide deposits in Río Tinto (Southwestern Spain) are a terrestrial analog of early martian hematite-rich regions. Understanding the distribution and drivers of microbial life in iron-rich environments can give critical clues on how to search for biosignatures on Mars. We simulated a robotic drilling mission searching for signs of life in the martian subsurface, by using a 1m-class planetary prototype drill mounted on a full-scale mockup of NASA's Phoenix and InSight lander platforms. We demonstrated fully automated and aseptic drilling on iron and sulfur rich sediments at the Río Tinto riverbanks, and sample transfer and delivery to sterile containers and analytical instruments. As a ground-truth study, samples were analyzed in the field with the life detector chip immunoassay for searching microbial markers, and then in the laboratory with X-ray diffraction to determine mineralogy, gas chromatography/mass spectrometry for lipid composition, isotope-ratio mass spectrometry for isotopic ratios, and 16S/18S rRNA genes sequencing for biodiversity. A ubiquitous presence of microbial biomarkers distributed along the 1m-depth subsurface was influenced by the local mineralogy and geochemistry. The spatial heterogeneity of abiotic variables at local scale highlights the importance of considering drill replicates in future martian drilling missions. The multi-analytical approach provided proof of concept that molecular biomarkers varying in compositional nature, preservation potential, and taxonomic specificity can be recovered from shallow drilling on iron-rich Mars analogues by using an automated life-detection lander prototype, such as the one proposed for NASA's IceBreaker mission proposal.

Common and rare iron, sulfur, and zinc minerals in technogenically contaminated hydromorphic soil from Southern Russia.

Soils formed after the desiccation of Lake Atamanskoe, which has served as a reservoir for liquid industrial waste from the city of Kamensk-Shakhtinsky during a long time, were studied. These soils differ from zonal soils by a strong contamination with zinc and sulfur. Preliminary studies showed that Fe compounds fix a significant part of zinc. This requires to study S, Zn, and Fe minerals. In this work, Mössbauer spectroscopy was used for the identification of iron compounds and scanning electron microscopy was used for the microanalysis of these and other minerals. To facilitate the identification of Fe minerals, brown iron ocher was removed from a contaminated soil sample and analyzed. From electron microscopy and Mössbauer spectroscopy data, ocher contained hydrogoethite with a high content of sorption water and schwertmannite (a rare mineral, probably found in Russia for the first time). The chemical composition of this schwertmannite better corresponds to the Cashion-Murad model than to the Bigham model. Particles of partially oxidized magnetite and wustite enriched with zinc were revealed under electron microscope. Siderite with partial substitution of Fe2+ by Zn2+ was detected. Thus, contaminated hydromorphic soil contains both common minerals (illite, goethite, hematite, gypsum) and rare minerals (schwertmannite, Zn siderite, partially oxidized magnetite and wustite enriched with zinc).

A systematic evaluation of Flow Field Flow Fractionation and single-particle ICP-MS to obtain the size distribution of organo-mineral iron oxyhydroxide colloids.

Colloidal iron(III) oxyhydroxides (FeOx) are important reactive adsorbents in nature. This study was set up to determine the size of environmentally relevant FeOx colloids with new methods, i.e. Flow Field Flow Fractionation (FlFFF-UV-ICP-MS) and single-particle ICP-MS/MS (sp-ICP-MS) and to compare these with standard approaches, i.e. dynamic light scattering (DLS), nanoparticle tracking analysis (NTA), microscopy (TEM), membrane filtration, centrifugation and dialysis. Seven synthetic nano- and submicron FeOx with different mineralogy and coating were prepared and two soil solutions were included. The FlFFF was optimized for Fe recovery, yielding 70-90%. The FlFFF determines particle size with high resolution in a 1 mM NH4HCO3 (pH 8.3) background and can detect Fe-NOM complexes <5 nm and organo-mineral FeOx particles ranging 5-300 nm. The sp-ICP-MS method had a size detection limit for FeOx of about 32-47 nm. The distribution of hydrodynamic diameters of goethite particles detected with FlFFF, NTA and DLS were similar but the values were twice as large as the Fe cores of particles detected with sp-ICP-MS and TEM. Conventional fractionation by centrifugation and dialysis generally yielded similar fractions as FlFFF but membrane filtration overestimated the large size fractions. Particles formed from Fe(II) oxidation in the presence of NOM showed strikingly smaller organo-mineral Fe-Ox colloids as the NOM/Fe ratio increased. The soil solution obtained with centrifugation of an acid peat was dominated by small (<30 nm) Fe-OM complexes and organo-mineral FeOx colloids whereas that of a mineral pH neutral soil mainly contains larger (30-200 nm) Fe-rich particles. The FlFFF-UV-ICP-MS is recommended for environmental studies of colloidal FeOx since it has a wide size detection range, it fractionates in an environmentally relevant background (1 mM NH4HCO3) and it has acceptable element recoveries.

The bacterial community significantly promotes cast iron corrosion in reclaimed wastewater distribution systems.

BACKGROUND: Currently, the effect of the bacterial community on cast iron corrosion process does not reach consensus. Moreover, some studies have produced contrasting results, suggesting that bacteria can either accelerate or inhibit corrosion. RESULTS: The long-term effects of the bacterial community on cast iron corrosion in reclaimed wastewater distribution systems were investigated from both spatial (yellow layer vs. black layer) and temporal (1-year dynamic process) dimensions of the iron coupon-reclaimed wastewater microcosm using high-throughput sequencing and flow cytometry approaches. Cast iron coupons in the NONdisinfection and UVdisinfection reactors suffered more severe corrosion than did those in the NaClOdisinfection reactor. The bacterial community significantly promoted cast iron corrosion, which was quantified for the first time in the practical reclaimed wastewater and found to account for at least 30.5% ± 9.7% of the total weight loss. The partition of yellow and black layers of cast iron corrosion provided more accurate information on morphology and crystal structures for corrosion scales. The black layer was dense, and the particles looked fusiform, while the yellow layer was loose, and the particles were ellipse or spherical. Goethite was the predominant crystalline phase in black layers, while corrosion products mainly existed as an amorphous phase in yellow layers. The bacterial community compositions of black layers were distinctly separated from yellow layers regardless of disinfection methods. The NONdisinfection and UVdisinfection reactors had a more similar microbial composition and variation tendency for the same layer type than did the NaClOdisinfection reactor. Biofilm development can be divided into the initial start-up stage, mid-term development stage, and terminal stable stage. In total, 12 potential functional genera were selected to establish a cycle model for Fe, N, and S metabolism. Desulfovibrio was considered to accelerate the transfer of Fe0 to Fe2+ and speed up weight loss. CONCLUSION: The long-term effect of disinfection processes on corrosion behaviors of cast iron in reclaimed wastewater distribution systems and the hidden mechanisms were deciphered for the first time. This study established a cycle model for Fe, N, and S metabolism that involved 12 functional genera and discovered the significant contribution of Desulfovibrio in promoting corrosion.

Mössbauer spectroscopic study of transformations of iron species by the cyanobacterium Arthrospira platensis (formerly Spirulina platensis).

In the present paper, Mössbauer spectroscopic studies of dry biomass samples of the cyanobacterium Arthrospira platensis (formerly known as Spirulina platensis) were performed with regard to metabolic iron accumulation. 57Fe Mössbauer parameters of iron in the biomass correspond to ferrihydrite. Spectra of iron hydroxides in A. platensis biomass differ from those of iron complexes with ethylenediaminetetraacetic acid injected to Zarrouk culture medium. The limit of saturation of A. platensis trichomes with iron in the form of ferrihydrite was found to be 5 µg/ml (0.09 µmol/ml) Fe in the culture medium. Conglomerates precipitated in the medium at higher iron concentrations also contain ferrihydrite but the ratio of the crystal lattice forms is different from that in the biomass.

Detection of the iron complexes with hydrolysis products of cephalexin and cefradine upon high-performance liquid chromatography/electrospray ionization mass spectrometry analysis.

RATIONALE: Cephalosporins (e.g. cephalexin, cefradine) are a major group of widely used ß-lactam antibiotics. Hydrolysis of the ß-lactam ring is an important reaction (often undesired) which leads to deactivation of ß-lactams. To the best of our knowledge there is no electrospray ionization mass spectrometry (ESI-MS) data reported concerning the products of hydrolysis of cephalosporins. METHODS: The hydrolysis of cephalexin and cefradine was performed in aqueous NaOH solutions. After the process the solutions were analyzed by high-performance liquid chromatography (HPLC)/ESI-MS. The elemental compositions of the ions discussed were confirmed by the accurate mass measurements on a quadrupole time-of-flight (QTOF) mass spectrometer. RESULTS: Unexpectedly, complexes between the hydrolysis products of cephalexin and cefradine (CFLh and CFRh ) and iron cation were detected upon HPLC/ESI-MS analysis, namely the ions [(CFLh -H)2 +Fe]+ and [(CFRh -H)2 +Fe]+ , although iron was not added to the analyzed solutions or to the mobile phase. These ions were found to be very stable in the gas phase. CONCLUSIONS: The detection of the complexes between the hydrolysis products of cephalosporins and iron may have a positive impact on the sensitivity and specificity of HPLC/ESI-MS analyses of the hydrolysis products of some cephalosporins.

Mobility of multiple heavy metalloids in contaminated soil under various redox conditions: Effects of iron sulfide presence and phosphate competition.

The mobility of heavy metalloids including As, Sb, Mo, W, and Cr in soil was investigated under both reducing and oxidizing conditions. The effects of soil mineralogy and the presence of competitive anions were studied as important factors affecting the mobility of these contaminants. Batch experiments conducted with the addition of oxidized and fresh FeS exhibited enhanced sorption rates for As and W under oxidizing conditions, and for Mo under reducing conditions. The inhibitory effect of phosphate on the sorption rates was most apparent for As and Mo under both oxidizing and reducing conditions, while only a small phosphate effect was observed for Sb and W. For Sb and W mobility, pH was determined to be the most important controlling factor. The results of long-term batch experiments revealed that differences in the mobility of metalloids, particularly As, were also influenced by microbial activity in the oxidizing and reducing conditions.

The Search for Hesperian Organic Matter on Mars: Pyrolysis Studies of Sediments Rich in Sulfur and Iron.

Jarosite on Mars is of significant geological and astrobiological interest, as it forms in acidic aqueous conditions that are potentially habitable for acidophilic organisms. Jarosite can provide environmental context and may host organic matter. The most common extraction technique used to search for organic compounds on the surface of Mars is pyrolysis. However, thermal decomposition of jarosite releases oxygen into pyrolysis ovens, which degrades organic signals. Jarosite has a close association with the iron oxyhydroxide goethite in many depositional/diagenetic environments. Hematite can form by dehydration of goethite or directly from jarosite under certain aqueous conditions. Goethite and hematite are significantly more amenable than jarosite for pyrolysis experiments employed to search for organic matter. Analysis of the mineralogy and organic chemistry of samples from a natural acidic stream revealed a diverse response for organic compounds during pyrolysis of goethite-rich layers but a poor response for jarosite-rich or mixed jarosite-goethite samples. Goethite units that are associated with jarosite, but do not contain jarosite themselves, should be targeted for organic detection pyrolysis experiments on Mars. These findings are extremely timely, as exploration targets for Mars Science Laboratory include Vera Rubin Ridge (formerly known as "Hematite Ridge"), which may have formed from goethite precursors. Key Words: Mars-Pyrolysis-Jarosite-Goethite-Hematite-Biosignatures. Astrobiology 18, 454-464.

Impacts of water quality on the corrosion of cast iron pipes for water distribution and proposed source water switch strategy.

Switch of source water may induce "red water" episodes. This study investigated the impacts of water quality on iron release, dissolved oxygen consumption (ΔDO), corrosion scale evolution and bacterial community succession in cast iron pipes used for drinking water distribution at pilot scale, and proposed a source water switch strategy accordingly. Three sets of old cast iron pipe section (named BP, SP and GP) were excavated on site and assembled in a test base, which had historically transported blended water, surface water and groundwater, respectively. Results indicate that an increasing Cl- or SO42- concentration accelerated iron release, but alkalinity and calcium hardness exhibited an opposite tendency. Disinfectant shift from free chlorine to monochloramine slightly inhibited iron release, while the impact of peroxymonosulfate depended on the source water historically transported in the test pipes. The ΔDO was highly consistent with iron release in all three pipe systems. The mass ratio of magnetite to goethite in the corrosion scales of SP was higher than those of BP and GP and kept almost unchanged over the whole operation period. Siderite and calcite formation confirmed that an increasing alkalinity and hardness inhibited iron release. Iron-reducing bacteria decreased in the BP but increased in the SP and GP; meanwhile, sulfur-oxidizing, sulfate-reducing and iron oxidizing bacteria increased in all three pipe systems. To avoid the occurrence of "red water", a source water switch strategy was proposed based on the difference between local and foreign water qualities.

Synthesis of whey peptide-iron complexes: Influence of using different iron precursor compounds.

Iron-binding peptides are an alternative for increasing the bioavailability of iron and to decreasing its pro-oxidant effect. This study aimed to synthesize and characterize peptide-iron complexes using FeCl2 or FeSO4 as the iron precursor compounds. Whey protein isolate (WPI), WPI hydrolyzed with pancreatin, and its fractions obtained via ultrafiltration (cut-off 5kDa) were used as ligands. The fluorescence intensity of the ligands significantly decreased as the iron concentration increased as a result of metal coordination with the iron-binding sites, which may have led to changes in the microenvironment of tryptophan. For both iron precursor compounds, the primary iron-binding site was carboxylate groups, and the linkage occurred via a bidentate coordination mode with two vibrational modes assigned to the COOFe linkage. However, infrared spectroscopy and thermal analysis results showed that the dynamics of the interaction is different for the iron precursor. The iron source may be of great importance because it may impact iron absorption and the pro-oxidant effect of the mineral.

Simultaneous determination and speciation analysis of arsenic and chromium in iron supplements used for iron-deficiency anemia treatment by HPLC-ICP-MS.

This work proposes the use of high performance liquid chromatography coupled to inductively coupled plasma mass spectrometry (HPLC-ICP-MS) for simultaneous speciation of arsenic and chromium in iron supplements used for the treatment of anemia. The sample preparation procedure recommended for the total determination of arsenic and chromium was established using acid digestion in a microwave assisted oven. For speciation analysis, however, the microwave-assisted extraction procedure involved the use of water as extraction solvent at 90°C for 30min. The chromatographic separation was performed using a mobile phase containing 1.0mM tetrabutylammonium hydroxide (TBAH), 0.7mM ethylenediaminetetraacetic acid (EDTA) and 5% methanol at pH 7.2. Helium was used in the collision cell for elimination of the interferences. Under optimized conditions, the separation and detection of the As(III), As(V), Cr(III) and Cr(VI) species can be performed in 5min, permitting their quantification with the external calibration technique with standards prepared in the mobile phase. The limits of quantification obtained were 0.008, 0.010, 0.5 and 0.14µgg-1, for As(III), As(V), Cr(III) and Cr(VI), respectively. The accuracy of the method was evaluated and confirmed by addition/recovery tests. The recoveries obtained varied from 81% to 110%. The proposed method was applied to the speciation analysis of arsenic and chromium in commercially available iron supplements acquired in several cities in Brazil and Spain. The content of the species ranged from 0.01 to 1.3µgg-1 for arsenic, and from 0.4 to 61.2µgg-1 for chromium.

Equilibrium and kinetic modeling of iron adsorption and the effect by chloride, sulfate, and hydroxyl: evaluation of PVC-U drinking pipes.

The update of pipeline was quick over the last few years and the plastic pipes were widely used in the drinking water distribution systems (DWDSs), especially in the small-diameter pipes. In this study, the iron adsorptive characteristics and the affecting factors in unplasticized poly(vinyl chloride) (PVC-U) pipe were investigated. Results showed that the average amount of iron in the 10-year-old PVC-U pipe's interior surface was 2.80 wt% which was almost 187 times larger than that in a new one. Goethite (α-FeOOH) and magnetite (Fe3O4) were the major iron compounds in the scales which covered on the old pipes' interior surface and showed loose and porous images under a scanning electron microscope. Moreover, the influence of the iron concentration on the adsorption amount and rate was discussed. The adsorption amount was significantly influenced by iron concentration, but similar adsorption rate was discovered. Notably, iron was quantitatively adsorbed by PVC-U pipe during the experimental period in accordance with the pseudo second order kinetic model. Meanwhile, regression model and response surface methodology were used to analyze the regular of iron adsorption in different concentrations of chloride (Cl-), sulfate (SO42-), and hydroxyl (OH-). It can be concluded that Cl- and OH- showed the strong ability of iron adsorption which were larger than SO42-.

Discovery and Characterization of Iron Sulfide and Polyphosphate Bodies Coexisting in Archaeoglobus fulgidus Cells.

Inorganic storage granules have long been recognized in bacterial and eukaryotic cells but were only recently identified in archaeal cells. Here, we report the cellular organization and chemical compositions of storage granules in the Euryarchaeon, Archaeoglobus fulgidus strain VC16, a hyperthermophilic, anaerobic, and sulfate-reducing microorganism. Dense granules were apparent in A. fulgidus cells imaged by cryo electron microscopy (cryoEM) but not so by negative stain electron microscopy. Cryo electron tomography (cryoET) revealed that each cell contains one to several dense granules located near the cell membrane. Energy dispersive X-ray (EDX) spectroscopy and scanning transmission electron microscopy (STEM) show that, surprisingly, each cell contains not just one but often two types of granules with different elemental compositions. One type, named iron sulfide body (ISB), is composed mainly of the elements iron and sulfur plus copper; and the other one, called polyphosphate body (PPB), is composed of phosphorus and oxygen plus magnesium, calcium, and aluminum. PPBs are likely used for energy storage and/or metal sequestration/detoxification. ISBs could result from the reduction of sulfate to sulfide via anaerobic energy harvesting pathways and may be associated with energy and/or metal storage or detoxification. The exceptional ability of these archaeal cells to sequester different elements may have novel bioengineering applications.

Biosynthesis of bifunctional iron oxyhydrosulfate by Acidithiobacillus ferroxidans and their application to coagulation and adsorption.

Coagulation and adsorption are important environmental technologies, which were widely applied in water treatment. In this study, a type of villous iron oxyhydrosulfate with low crystallinity, high content iron, sulfate and hydroxyl was synthesized by Acidithiobacillus ferrooxidans, which possessed coagulation and heavy metal adsorption ability simultaneously. The results showed that the Cu(II) adsorption capacity increased within a small range over the pH range of 3.0-5.0 but increased evidently over the range of 6.0-8.0. The maximal Cu(II) adsorption capacity of sample Af and Gf reached 50.97 and 46.08mg/g respectively. The optimum pH for Cr(VI) adsorption was 6.0, and the maximal adsorption capacity reached 51.32 and 59.57mg/g. The Langmuir isotherm can better describe the adsorption behavior of Cr(VI). Coagulation performance of the iron oxyhydrosulfate (Sh) has been significantly enhanced by polysilicic acid (PSA), which was mainly determined by PSA/Sh ratio, pH and coagulant dosage. Coagulation efficiency maintained approximately at 98% when the PSA/Sh ratio ranged from 0.4/0.1 to 1.0/0.1. Polysilicic acid worked efficiently in wide pH range extending, from 2 to 3.5. Coagulation performance improved significantly with the increasing of the coagulant dosage at lower dosage range, while, at higher dosage range, the improvement was not evident even with more coagulant addition.

Tissue Iron Distribution Assessed by MRI in Patients with Iron Loading Anemias.

Bone marrow, spleen, liver and kidney proton transverse relaxation rates (R2), together with cardiac R2* from patients with sickle cell disease (SCD), paroxysmal nocturnal hemoglobinuria (PNH) and non-transfusion dependent thalassemia (NTDT) have been compared with a control group. Increased liver and bone marrow R2 values for the three groups of patients in comparison with the controls have been found. SCD and PNH patients also present an increased spleen R2 in comparison with the controls. The simultaneous measurement of R2 values for several tissue types by magnetic resonance imaging (MRI) has allowed the identification of iron distribution patterns in diseases associated with iron imbalance. Preferential liver iron loading is found in the highly transfused SCD patients, while the low transfused ones present a preferential iron loading of the spleen. Similar to the highly transfused SCD group, PNH patients preferentially accumulate iron in the liver. A reduced spleen iron accumulation in comparison with the liver and bone marrow loading has been found in NTDT patients, presumably related to the differential increased intestinal iron absorption. The correlation between serum ferritin and tissue R2 is moderate to good for the liver, spleen and bone marrow in SCD and PNH patients. However, serum ferritin does not correlate with NTDT liver R2, spleen R2 or heart R2*. As opposed to serum ferritin measurements, tissue R2 values are a more direct measurement of each tissue's iron loading. This kind of determination will allow a better understanding of the different patterns of tissue iron biodistribution in diseases predisposed to tissue iron accumulation.

Preserved Filamentous Microbial Biosignatures in the Brick Flat Gossan, Iron Mountain, California.

A variety of actively precipitating mineral environments preserve morphological evidence of microbial biosignatures. One such environment with preserved microbial biosignatures is the oxidized portion of a massive sulfide deposit, or gossan, such as that at Iron Mountain, California. This gossan may serve as a mineralogical analogue to some ancient martian environments due to the presence of oxidized iron and sulfate species, and minerals that only form in acidic aqueous conditions, in both environments. Evaluating the potential biogenicity of cryptic textures in such martian gossans requires an understanding of how microbial textures form biosignatures on Earth. The iron-oxide-dominated composition and morphology of terrestrial, nonbranching filamentous microbial biosignatures may be distinctive of the underlying formation and preservation processes. The Iron Mountain gossan consists primarily of ferric oxide (hematite), hydrous ferric oxide (HFO, predominantly goethite), and jarosite group minerals, categorized into in situ gossan, and remobilized iron deposits. We interpret HFO filaments, found in both gossan types, as HFO-mineralized microbial filaments based in part on (1) the presence of preserved central filament lumina in smooth HFO mineral filaments that are likely molds of microbial filaments, (2) mineral filament formation in actively precipitating iron-oxide environments, (3) high degrees of mineral filament bending consistent with a flexible microbial filament template, and (4) the presence of bare microbial filaments on gossan rocks. Individual HFO filaments are below the resolution of the Mars Curiosity and Mars 2020 rover cameras, but sinuous filaments forming macroscopic matlike textures are resolvable. If present on Mars, available cameras may resolve these features identified as similar to terrestrial HFO filaments and allow subsequent evaluation for their biogenicity by synthesizing geochemical, mineralogical, and morphological analyses. Sinuous biogenic filaments could be preserved on Mars in an iron-rich environment analogous to Iron Mountain, with the Pahrump Hills region and Hematite Ridge in Gale Crater as tentative possibilities.

Biogenic Iron-Rich Filaments in the Quartz Veins in the Uppermost Ediacaran Qigebulake Formation, Aksu Area, Northwestern Tarim Basin, China: Implications for Iron Oxidizers in Subseafloor Hydrothermal Systems.

Fe-(oxyhydr)oxide-encrusted filamentous microstructures produced by microorganisms have been widely reported in various modern and ancient extreme environments; however, the iron-dependent microorganisms preserved in hydrothermal quartz veins have not been explored in detail because of limited materials available. In this study, abundant well-preserved filamentous microstructures were observed in the hydrothermal quartz veins of the uppermost dolostones of the terminal-Ediacaran Qigebulake Formation in the Aksu area, northwestern Tarim Basin, China. These filamentous microstructures were permineralized by goethite and hematite as revealed by Raman spectroscopy and completely entombed in chalcedony and quartz cements. Microscopically, they are characterized by biogenic filamentous morphologies (commonly 20-200 µm in length and 1-5 µm in diameter) and structures (curved, tubular sheath-like, segmented, and mat-like filaments), similar to the Fe-oxidizing bacteria (FeOB) living in modern and ancient hydrothermal vent fields. A previous study revealed that quartz-barite vein swarms were subseafloor channels of low-temperature, silica-rich, diffusive hydrothermal vents in the earliest Cambrian, which contributed silica to the deposition of the overlying bedded chert of the Yurtus Formation. In this context, this study suggests that the putative filamentous FeOB preserved in the quartz veins might have thrived in the low-temperature, silica- and Fe(II)-rich hydrothermal vent channels in subseafloor mixing zones and were rapidly fossilized by subsequent higher-temperature, silica-rich hydrothermal fluids in response to waning and waxing fluctuations of diffuse hydrothermal venting. In view of the occurrence in a relatively stable passive continental margin shelf environment in Tarim Block, the silica-rich submarine hydrothermal vent system may represent a new and important geological niche favorable for FeOB colonization, which is different from their traditional habitats reported in hydrothermal vent systems at oceanic spreading centers or volcanic seamounts. Thus, these newly recognized microfossils offer a new clue to explore the biological signatures and habitat diversity of microorganisms on Earth and beyond.