Sequential Extraction Protocol Research Articles

Adapted Sequential Extraction Protocol to Study Mercury Speciation in Gold Mining Tailings: Implications for Environmental Contamination in the Amazon.

Artisanal small-scale gold mining (ASGM), an increasingly prevalent activity in South America, generates mercury-contaminated tailings that are often disposed of in the environment, leading to the introduction of mercury into ecosystems and the food web, where it bioaccumulates. Therefore, studying the geochemical processes involved in the desorption and dissolution of mercury in these tailings is essential for critical risk evaluations in the short and long term. For this purpose, sequential extraction procedures (SEPs) can be useful because they help to identify the phases to which Hg is associated, although they also have limitations such as a lack of selectivity and specificity. In this work, we propose a modified four-step SEP: exchangeable mercury (F1), oxidizable mercury (F2), mercury bound to Fe oxides (F3), and strongly bound mercury (F4). To test this adapted sequential extraction method, we evaluated the Hg contamination in mercury-contaminated tailings of the Amazon basin. The results revealed a total mercury concentration of 103 ± 16 mg·kg-1 in the tailings, with a significant portion in F1 (28% of the total), where Hg was bioavailable. The large Hg concentration in F3 (36%) suggested that Fe oxides likely contribute to mercury retention. Together, the SEP results emphasize the urgent need for improved surveillance of gold mining activities and responsible tailings management practices to mitigate environmental contamination and safeguard the health of the Amazon ecosystem.

Sediment-redox dynamics in an oligotrophic deep-water lake in Tierra del Fuego: insights from Fe isotopes

AbstractFor long time in the history of Earth, ferruginous conditions governed the oceans. With the rise of oxygen during the Proterozoic era and the subsequent evolution of living organisms, worldwide deposition of iron formations occurred. These sedimentary units reveal the transition into oxic oceans, passing by local and transitory euxinic conditions, especially in coastal shelves. Constraining the iron cycle and the biogeochemical processes occurring in present and past ferruginous basins helps answering some of the question regarding global oxygenation, the evolution of life and past climate changes. Therefore, Fe speciation and Fe isotopes in both Proterozoic and recent sedimentary records have been widely used to reconstruct past basin dynamics and redox conditions in the sediment–water interface. However, sedimentation and early diagenesis can alter paleoredox proxies and their primary climate signals. In this work, we disentangled alteration processes occurring at the redox front below the sediment–water interface of a ventilated deep-water lake (Lago Fagnano, Argentina/Chile). A sequential extraction protocol was applied to characterize two reactive Fe pools: Fe oxyhydroxides and reduced iron. Subsequently, Fe isotopes were constrained to determine the main processes mobilizing Fe. At the redox front, ferric minerals reach a δ56Fe value of − 1.3‰ resulting from oxidation of dissolved Fe likely following a Rayleigh distillation effect. Dissolved Fe is produced right below via Fe reduction, as shown by the low ferric Fe content. Our observations delineate a redox cycle and a redox horizon undergoing constant upward migration, initiated by regular sedimentation. However, during events of increased rapid sedimentation (e.g., seismites) this dynamic cycle is interrupted inducing full or partial preservation of the Fe-rich redox front. In such case, oxidation of dissolved Fe is interrupted and can be recycled in ferrous minerals, such as Fe monosulfides and amorphous phases with δ56Fe values down to − 1.7 ‰. These findings have significant implications for the recording of biogeochemical cycles in the geological past, the use of Fe isotopes in freshwater-lake sediments for paleoclimate studies, and the progress of our knowledge regarding the geochemistry of past oceans.

Exchangeable versus residual metals in naturally aged plastic litter.

Metals may be associated with plastics as additives arising from manufacture or through acquisition from the environment, but these associations are often poorly defined or referred to synonymously when considering metal availability. In this study, samples of plastic litter (n = 22) have been collected from various environmental and industrial compartments of Lublin Province, Poland, and fractionated according to polymer type (polyethylene, polyethylene terephthalate, nylon, expanded polystyrene, polypropylene, and "mixed") before being micronised to < 2mm. Composites (n = 89) were subjected to two phases of a standardised and widely employed sequential extraction protocol (Bureau Communautaire de Reference; BCR) in order to define available (acid-soluble and exchangeable) and residual (soluble in boiling aqua regia) concentrations of Cd, Co, Cr, Cu, Fe, Mn, Ni, Pb, and Zn. For a given metal, total content, calculated by summing available and residual components, was highly variable, both between locations and amongst polymer categories, reflecting the heterogeneous distribution of a multitude of different additives. Overall, however, concentrations were greatest for Fe, with medians of several hundred to several thousand mg kg-1 amongst the different polymers, and lowest for Cd, Co, and Ni, where nearly all concentrations were below 10mgkg-1. Median percentage metal availabilities were greatest for expanded polystyrene and were above 25% for Mn and Zn and below 10% for Cr and Fe in all polymer types. These observations are largely, but not entirely, attributed to the relative contributions of metals acquired from the environment and metals present as additives and residues. Significantly, the approach employed allows direct comparisons of metal availability in plastics with metal availability in environmental solids in order to evaluate the overall impacts of plastics in metal risk assessments.

Cellulose fibers and ellagitannin-rich extractives from rambutan (Nephelium Lappaceum L.) peel by an eco-friendly approach

This study assesses the viability of an accelerated solvent extraction technique employing environmentally friendly solvents to extract ellagitannins while producing cellulose-rich fibers from rambutan peel. Two sequential extraction protocols were investigated: 1) water followed by acetone/water (4:1, v:v), and 2) acetone followed by acetone/water (4:1, v:v), both performed at 50 °C. The first protocol had a higher extraction yield of 51 %, and the obtained extractives featured a higher total phenolic (531.4 ± 22.0 mg-GAE/g) and flavonoid (487.3 ± 16.9 mg-QE/g) than the second protocol (495.4 ± 32.8 mg-GAE/g and 310.6 ± 31.4 mg-QE/g, respectively). The remaining extractive-free fibers were processed by bleaching using either 2 wt% sodium hydroxide with 3 wt% hydrogen peroxide or 4–5 wt% peracetic acid. Considering bleaching efficiency, yield, and process sustainability, the single bleaching treatment with 5 wt% of peracetic acid was selected as the most promising approach to yield cellulose-rich fibers. The samples were analyzed by methanolysis to determine the amount and type of poly- and oligosaccharides and studied by 13C solid-state nuclear magnetic resonance spectroscopy and thermal gravimetric analysis. The products obtained from the peels demonstrate significant potential for use in various sectors, including food, nutraceuticals, cosmetics, and paper production.

Sequential separation of critical metals from lithium-ion batteries based on deep eutectic solvent and electrodeposition

The rise and development of electric vehicles have brought much attention to the recycling of lithium-ion batteries (LIBs). However, the recovery of critical metals from LiNixCoyMn1−x−yO2 (NCM) is a challenge, especially for the nickel and cobalt, which have similar chemical properties. Here, a novel ternary deep eutectic solvent (DES) composed of choline chloride, ethylene glycol, and tartaric acid was proposed. Our protocol of DES synthesis, nickel separation, and leaching of cobalt and manganese were integrated into one step, which significantly simplified the recovery process. The crystallization occurring during DES leaching was subjected to detailed investigation. The lithium, nickel, and cobalt were sequentially separated as Li2CO3, NiO, and Co(OH)2 by anterior formic acid leaching and posterior electrodeposition. After electrodeposition, DES was reused. This work provides new ideas for the sequential separation of critical metals from NCM and has great application prospects.

Fractionation and characterisation of pectin-rich extracts from garlic biomass

Polysaccharides from garlic waste leaf and skin biomass have been isolated using a sequential extraction protocol and characterised using constituent sugar composition and linkage analysis, spectroscopy, chromatography and dilute solution viscometry. The results revealed that the isolated polysaccharides were predominantly pectins. The predominant monosaccharide in all samples was galacturonic acid (>61 %), followed by galactose and rhamnose. The pectins extracted from skin biomass were mainly homogalacturonan (83–91 %), whereas those extracted from leaf biomass comprised both homogalacturonan (62–65 %) and rhamnogalacturonan-I (35–38 %). The degree of methyl esterification of uronic acids in all samples was 44–56 %. The peak molecular weight of the main polysaccharide population in each sample was ∼ 350 x103 g/mol, with leaf extracts and the skin acidic extract containing a second, lower molecular weight peak. Overall, waste garlic biomass is a potential resource for commercial pectin extraction for use in food or pharmaceutical industries.

Proteomic Atlas of Atherosclerosis: The Contribution of Proteoglycans to Sex Differences, Plaque Phenotypes, and Outcomes.

Using proteomics, we aimed to reveal molecular types of human atherosclerotic lesions and study their associations with histology, imaging, and cardiovascular outcomes. Two hundred nineteen carotid endarterectomy samples were procured from 120 patients. A sequential protein extraction protocol was employed in conjunction with multiplexed, discovery proteomics. To focus on extracellular proteins, parallel reaction monitoring was employed for targeted proteomics. Proteomic signatures were integrated with bulk, single-cell, and spatial RNA-sequencing data, and validated in 200 patients from the Athero-Express Biobank study. This extensive proteomics analysis identified plaque inflammation and calcification signatures, which were inversely correlated and validated using targeted proteomics. The inflammation signature was characterized by the presence of neutrophil-derived proteins, such as S100A8/9 (calprotectin) and myeloperoxidase, whereas the calcification signature included fetuin-A, osteopontin, and gamma-carboxylated proteins. The proteomics data also revealed sex differences in atherosclerosis, with large-aggregating proteoglycans versican and aggrecan being more abundant in females and exhibiting an inverse correlation with estradiol levels. The integration of RNA-sequencing data attributed the inflammation signature predominantly to neutrophils and macrophages, and the calcification and sex signatures to smooth muscle cells, except for certain plasma proteins that were not expressed but retained in plaques, such as fetuin-A. Dimensionality reduction and machine learning techniques were applied to identify 4 distinct plaque phenotypes based on proteomics data. A protein signature of 4 key proteins (calponin, protein C, serpin H1, and versican) predicted future cardiovascular mortality with an area under the curve of 75% and 67.5% in the discovery and validation cohort, respectively, surpassing the prognostic performance of imaging and histology. Plaque proteomics redefined clinically relevant patient groups with distinct outcomes, identifying subgroups of male and female patients with elevated risk of future cardiovascular events.

Impaired Soil Health in Agricultural Areas Close to Fe-Ni Mines on Euboea Island, Greece, Caused by Increased Concentrations of Potentially Toxic Elements, and the Associated Impacts on Human Health

Agricultural soils close to mining establishments may suffer from airborne pollution, due to excavation and transportation activities. To assess the impact of soil pollution from potentially toxic elements (PTEs) on soil and human health in agricultural areas close to Fe-Ni mines, 36 composite topsoil samples were collected from central Euboea Island, Greece. The soils were analyzed for their physicochemical properties and for total and bioavailable Ni, Cr, Co, Mn, Fe, Pb, Cu, and Zn concentrations; the BCR sequential extraction protocol was additionally applied to all samples. Soil enrichment caused by the metals and the implications of soil degradation on the ecosystem were evaluated using the calculation of single pollution indices (PI) and the potential ecological risk index (RI), respectively. The hazard index (HI) for non-carcinogenic metals and life cancer risk (LCR) for carcinogenic metals were used to appraise the human health risks. Extremely high, very high, and considerably high total concentrations of Ni, Cr, and Mn, respectively, were determined. Though most of the total amounts of metals in soil samples were found to be related to the residual fraction, the considerable portion extracted in the first two steps of the BCR process can be regarded as able to introduce toxicity issues in the local biota. High PI values of Cr, Co, and especially Ni point to severely polluted soils, and the mean RI values indicate a considerable risk for biota. HI values &gt; 1 show increased possibilities for non-carcinogenic health issues in children, whereas the LCR values of Ni were above the critical limit, 1 × 10−4, for both children and adults.

Environmental bioavailability of arsenic, nickel and chromium in soils impacted by high geogenic and anthropogenic background contents

High arsenic, chromium and nickel in soils can pose a hazard to the ecosystem and/or human health. Large areas can be affected by elevated potentially toxic elements (PTE) background contents, entailing a significant effort for managing the potential risk. Assessing the environmental hazard associated to PTE-contaminated soils requires the determination of soil PTE environmental bioavailability, which reflects the capacity of these elements to be transferred to living organisms. Here we assess the environmental bioavailability of As, Cr and Ni in topsoils from the Liège basin and Belgian Lorraine, two areas in Wallonia, Belgium, affected by elevated As, Cr and Ni background contents. The source of soil As, Cr and Ni differs in Liège and Lorraine: anthropogenic in the former location and geogenic in the latter. The environmental bioavailability of PTE was determined using two complementary approaches: (1) by chemical fractionation with the Community Bureau of Reference (BCR) three-step sequential extraction protocol and (2) by estimating the phytoavailability using a plant-based biotest (Lolium multiflorum as plant model). The results show that total As (6–130 mg·kg−1), Cr (15–268 mg·kg−1), and Ni (8–140 mg·kg−1) contents in the Liège and Lorraine soils frequently exceed the soil clean-up standards. However, no positive correlation was found between the total contents and BCR extraction results or rye-grass contents, except for As in Liège soils. Total As, Cr or Ni contents surpassing soil standards do not necessarily result in elevated mobile, potentially mobilizable and phytoavailable contents. In general, environmental bioavailability of As, Cr and Ni is higher in soils from Liège basin compared to those sampled in Belgian Lorraine. The mobile and potentially mobilizable fractions of As, Cr and Ni account for <30 % of their total contents following the BCR extractions. Our study provides valuable information for sustainable management at the regional scale of soils containing high PTE contents.

Removal and environmentally safe disposal of As(III) and As(V)-loaded ferrihydrite/biosilica composites

Pure ferrihydrite and ferrihydrite-biosilica composite were synthesized and studied for the removal of As(III) and As(V). The synthesized materials have an adsorption capacity higher than some reported materials in the literature - 140 and 90 mg g−1 for As(III) and As(V), respectively. The pH of the solution was shown to impact greatly on As(V) adsorption, but not on As (III), which is stable as a protonated, uncharged oxyanion, at pH < 9.2. The adsorption products were subjected to thermal treatment (500 °C for 2 h), promoting ferric arsenate formation. The adsorbed As on ferrihydrite (Fh) was shown to inhibit the phase transformation of Fh to hematite. More so, thermal treatment was shown to oxidize As(III) to As (V). The changes in the adsorption residues after thermal treatment also had an impact on As mobility. The As (III) associated with the Fh phase increased from 42 to 95%, according to a sequential extraction protocol. Therefore, this work presents a process for As removal, followed by thermal treatment of arsenic-loaded ferrihydrites which enables environmentally safe disposal of As residues.

Tannin Extraction from Chestnut Wood Waste: From Lab Scale to Semi-Industrial Plant

The chestnut tree (Castanea sativa, Mill.) is a widespread plant in Europe whose fruits and wood has a relevant economic impact. Chestnut wood (CW) is rich in high-value compounds that exhibit various biological activities, such as antioxidant as well as anticarcinogenic and antimicrobial properties. These metabolites can be mainly divided into monomeric polyphenols and tannins. In this piece of work, we investigated a sustainable protocol to isolate enriched fractions of the above-mentioned compounds from CW residues. Specifically, a sequential extraction protocol, using subcritical water, was used as a pre-fractionation step, recovering approximately 88% of tannins and 40% of monomeric polyphenols in the first and second steps, respectively. The optimized protocol was also tested at pre-industrial levels, treating up to 13.5 kg CW and 160 L of solution with encouraging results. Ultra- and nanofiltrations were used to further enrich the recovered fractions, achieving more than 98% of the tannin content in the heavy fraction, whilst the removed permeate achieved up to 752.71 mg GAE/gext after the concentration (75.3%). Samples were characterized by means of total phenolic content (TPC), antioxidant activity (DPPH· and ABTS·), and tannin composition (hydrolysable and condensed). In addition, LC-MS-DAD was used for semiqualitative purposes to detect vescalagin/castalagin and vescalin/castalin, as well as gallic acid and ellagic acid. The developed valorization protocol allows the efficient fractionation and recovery of the major polyphenolic components of CW with a sustainable approach that also evaluates pre-industrial scaling-up.

Geochemical Characteristics of Iron in a Sediment Core at 63°40′ E, Eastern Southwest Indian Ridge: Implications on Regional Hydrothermal Activities and Source Origin

Iron is a limiting nutrient in the marine biogeochemical cycle, and hydrothermal processes at mid-ocean ridges are well-known as one of its sources to the water column. However, a major portion of the hydrothermal iron is precipitated near the source and plays an essential role in oceanic elemental cycling. Here, we carried out a detailed study on the geochemical characteristics of Fe, using a sequential chemical extraction protocol, in a short sediment core collected from the eastern Southwest Indian Ridge (SWIR) to understand the iron association in individual mineral phases. Major and trace and rare-earth element concentrations, positive europium anomaly, and rare-earth fractionation show that the source components in the sediment core are composed of biogenic, local mafic, ultramafic, and hydrothermal origin. Solid-phase Fe speciation results indicate that &gt;60% of Fe is associated with the Fe-oxides phase and indicate the hydrothermal plume particulates settled from the water column. A relatively low concentration of Fe associated with the pyrite and silicate (FeRes) phase suggests an erosion of sulphide and silicate minerals from the nearby vent field. The down-core variation reflects the transformation of primary ferrihydrite to more stable oxide mineral goethite/hematite and, to some extent, the formation of silicate minerals.

Compositional differences of β-glucan-rich extracts from three relevant mushrooms obtained through a sequential extraction protocol

In this work, a sequential fractionation protocol (cold and hot aqueous and alkaline extractions) and detailed compositional analysis (gross composition, monosaccharide analysis, FTIR, TGA) was applied to three relevant mushrooms in terms of global production (Grifola frondosa, Lentinula edodes and Pleurotus ostreatus) aiming to understand what is preferentially extracted during fractionation and how β-glucan extraction is affected by mushroom source. Room temperature aqueous extracts showed highest overall yields (56.3–82%) consisting of proteins, sugars and polyphenols. β-glucan content was highest in P. ostreatus and was concentrated in the more soluble fractions. On the contrary, a recalcitrant β-glucan in G. frondosa was mainly present in the residue (7.38%). L. edodes showed β-glucan populations distributed along aqueous and alkaline extracts, higher abundance of non-glucan polysaccharides and higher chitin purity (47.78%) in the residue. This work sets the basis for the rational design of extraction processes aiming to valorise mushroom biomass.

Investigating Biochar-Derived Dissolved Organic Carbon (DOC) Components Extracted Using a Sequential Extraction Protocol

Biochar-derived dissolved organic carbon (DOC), as the most important component of biochar, can be released on farmland, improving fertility and playing a role in soil amendment and remediation. The complexity of molecular structures and diversity of DOC compounds have influenced these functions to some extent. A sequential extract protocol consisting of water (25 °C), hot water (80 °C), and NaOH solution (0.05 M) was used to fully extract DOC compounds and gain a thorough understanding of the possible DOC components released from biochar. Rape straw (RS), apple tree branches (ATB), and pine sawdust (PS) were pyrolyzed at 300, 500, and 700 °C, respectively, to make nine distinct biochars. A TOC analyser, ultraviolet-visible spectroscopy (UV–vis), and excitation–emission fluorescence (EEM) spectrophotometer were used in conjunction with parallel factor analysis (PARAFAC) to determine the distribution of DOC content, the diversity of aromaticity, molecular weight characteristics and components of biochar-derived DOC. The results show that the relative distribution of water-extractable fractions ranged from 3.21 to 35.57%, with a low-aromaticity and extremely hydrophilic fulvic-acid-like compounds being found in the highest amounts (C2 and C3). The smallest amount of hot water-extractable components was produced from the release of small-molecule aliphatic compounds adsorbed on biochar and susceptible to migration loss once in a soil solution. More than half of the biochar-derived DOC was released in a NaOH solution, which primarily consisted of humic-acid-like compounds (C1), with higher molecular weights, more aromaticity, and lower bioavailability, according to the distribution of DOC in various extractants. In addition, the pyrolysis temperature and biomass type had a significant impact on the DOC properties released by biochar. As a result, the findings of this study showed that using a sequential extract protocol of water, hot water, and NaOH solution in combination with spectroscopic methods could successfully reveal the diversity of biochar-derived components, which could lead to new insights for the accurate assessment of potential environmental impacts and new directions for biochar applications.

Critical role of solvent extraction sequence in the fractional separation of alkaline lignin

Solvent-based method, especially solvent sequential extraction, is capable of tuning the molecular weight and structural characteristics of lignin for the fractional utilization of lignin. Three organic solvents, methanol, isopropanol and dichloromethane, were selected for sequential fractionation of AL following two sequences of gradually increasing and decreasing the HSP of these three solvents was reported in this work, to interrogate the role of extraction sequence in the fractional separation. GPC results revealed that the molecular weight of insoluble fractions obtained by gradually increasing the HSP value of the selected solvent was lower than that obtained from reverse extraction sequence. In addition, a decrease was found in PD of the separated fractions compared with AL no matter which extraction sequence was performed, especially the molecular weight and PD of the soluble fractions were dramatically reduced. In contrast, the PD value of the insoluble fractions was slightly smaller than that of AL, indicating that the solvent sequential extraction protocol was difficult to enrich the large molecular weight components in lignin. On the other hand, 2D HSQC NMR and thermal stability results showed that the content of β-O-4 linkages and the amount of residual carbon at 800 °C increased and decreased with the increase of molecular weight of insoluble fractions respectively, attributable to the polarity of the solvent selected and its ability to combine with lignin fragments to form hydrogen bonding. In view of these findings, the solvent extraction sequence is closely related to the molecular weight and structural properties of insoluble fractions and plays a critical role in the fractional separation.

Seasonal variation and mobility of trace metals in the beach sediments of NW Borneo

Miri city has a dynamic coastal environment, mainly influenced by intensive sedimentation from the Baram River and excessive trace metal loading by the Miri River, which are significant environmental concerns. As the mobility, bioavailability, and toxicity of the trace metals in the sediments are largely controlled by their particulate speciation, the modified BCR sequential extraction protocol was applied to determine the particulate speciation of trace metals in the coastal sediments of Miri, to unravel the seasonal geochemical processes responsible for known observations, and to identify possible sources of these trace metals. The granulometric analysis results showed that littoral currents aided by the monsoonal winds have influenced the grain size distribution of the sediments, enabling us to divide the study area into north-east and south-west segments where the geochemical composition are distinct. The Cu (>84%) and Zn (82%) concentrations are predominantly associated with the exchangeable fraction, which is readily bioavailable. Pb and Cd are dominant in non-residual fractions and other metals viz., Fe, Mn, Co, Ni, and Cr are dominant in the residual fraction. Using Pearson's correlation and factor analysis, the major mechanisms controlling the chemistry of the sediments are identified as association of Cu and Zn with fine fraction sediments, sulphide oxidation in the SW segment of the study area, atmospheric fallout of Pb and Cd in the river basins, precipitation of dissolved Fe and Mn supplied from the rivers and remobilization of Mn from the coastal sediments. Based on various pollution indices, it is inferred that the coastal sediments of NW Borneo are contaminated with Cu and Zn, and are largely bioavailable, which can be a threat to the local aquatic organisms, coral reefs, and coastal mangroves.

Optimization and assessment of a sequential extraction procedure for calcium carbonate rocks

Sequential extraction analyses are widely used for the determination of element speciation in sediments and soils. Typical sequential extraction protocols were developed to extract from low-carbonate samples and therefore are not necessarily suitable for high-carbonate samples. In this study, we tested increased reagent to sample ratios to adjust an existing sequential extraction procedure to analyze high-CaCO3 samples with concentrations ranging from 70 to above 90 %. Complete dissolution of the CaCO3 phase, and a higher extraction efficiency of manganese associated with the carbonate phase, was achieved when using four times the original reagent to sample ratio in the 2nd extraction step. This increase of reagent did not compromise the extraction of subsequent phases as shown by unaffected Fe concentrations in a low-carbonate sample. Hence, an essential outcome was that increasing the solution to sample ratio did not lead to the dissolution of other sedimentary phases, such as hydrous and crystalline iron oxides or sulfides. Thus, compared to other extraction protocols that use a lower reagent to sample ratio in the carbonate dissolution step, the new protocol allowed the complete extraction of oxide and sulfide phases in the following extraction steps. Furthermore, the study demonstrated the benefit of replacing Na-acetate with NH4-acetate to extract exchangeable ions and carbonates. We observed increased intensities for several analytes, i.e., trace metals such as Mo and As, due to less suppression of the analyte signal by NH4-acetate than by Na-acetate during analysis by inductively coupled plasma optical emission spectrometry (ICP-OES).

Iron isotope signature of magnetofossils and oceanic biogeochemical changes through the Middle Eocene Climatic Optimum

Magnetotactic bacteria (MTB) intracellularly precipitate magnetite (Fe3O4) crystals that can be preserved in the geological record. When MTB die, the so-called magnetofossils constitute valuable proxies for paleoenvironmental reconstructions and are suspected to represent some of the oldest traces of biomineralization on Earth. Yet, the biogenicity of putative magnetofossils found in ancient terrestrial and extra-terrestrial samples is still largely debated and their significance for past climate still holds uncertainties. Here we studied a sedimentary sequence from the Indian Ocean (ODP Hole 711A) recording the Middle Eocene Climatic Optimum (MECO) through which a magnetofossil-rich interval was deposited. We investigated for the first time the potential of Fe isotopes as a biosignature in magnetofossils and thoroughly describe MECO related paleoenvironmental disruptions based on major and trace element concentrations. Bulk sediment Fe isotopes showed limited variations, with δ56Fe around −0.13 ± 0.04‰ (n = 24), linked to detrital iron rather than MTB activity. Hence, a sequential chemical extraction protocol was applied to determine the specific composition of magnetite. We discuss analytical biases related to this protocol (i.e. partial phyllosilicate and Mn-oxide leaching) and apply corrections to the data. Outside the magnetofossil-rich interval, Fe isotope compositions of oxides (mainly biotic and/or abiotic magnetites and possibly Fe coprecipitated with Mn-oxides) display a small range averaging −0.54 ± 0.05‰, and are interpreted as reflecting dominantly hydrothermal contribution, a conclusion also supported by prominent Eu anomaly. In contrast, the magnetofossil-rich interval shows larger δ56Fe variability in oxides, from −0.12 to −0.94‰, decreasing upwards in the stratigraphic section. This interval likely records enhanced Fe supply from atmospheric fallout, increase in biological productivity (illustrated by increased Ba accumulation rate) and subsequent development of ferruginous conditions in the sediment porewater. Covariations of Fe isotope compositions and Mn/Fe ratios can be explained by a vertical migration of a redox front and associated diagenetic modifications. Precipitation of barite (BaSO4) in the sediments after organic matter decay probably favored the preservation of magnetofossils by decreasing SO42- concentration in porewaters and subsequent H2S production, which usually dissolve magnetite in the sulfidic zone. Finally, we model the evolution of porewater fluid and estimate Fe isotope fractionation between magnetofossils and fluid to Δ56Femag-Fe(II)aq = 0.1–0.3‰, a value significantly different from abiotic magnetite fractionation (~1.5‰). Contrasting with recent results on MTB laboratory culture, no mass independent fractionation of Fe isotopes was observed in the present study. Nevertheless, the diverse geochemical proxies presented here provide important constraints on paleoclimate and magnetofossil biogenicity evaluation.

Arsenic removal from industrial effluent: In-situ ferric sulfate production and arsenic partitioning in the residues

Ferric sulfate solution was producedin situby sulfating arsenic-bearing, hematite-rich calcines (56–62% Fe2O3) with sulfuric acid, both produced by roasting refractory gold ore. The solution was then used for arsenic precipitation in the treatment of effluents from the cyanidation plant. The conversion of hematite to ferric sulfate increased as the acid/calcine ratio increased and reached 60.7%, with 0.87 of the stoichiometric acid amounts. An iron sulfate solution (13.4 g.L−1 Fe and 2.32 g.L−1 As) was produced at the end of the calcine sulfation/dissolution. Arsenic removal varied between 99.4 and 99.8%. Arsenic concentration dropped from 1583.4 mg.L−1 to 5.31 mg.L−1 As, which is far less than the industrial circuit's typical concentration (15 mg.L−1). Hydrated calcium sulfates were the principal constituents in the arsenical residues (i.e., 42–50%). Its removal allowed the identification of ferric arsenate/arsenite coprecipitates, arsenical ferrihydrite, and hydrated calcium-iron hydroxy-arsenate and hydrated calcium using X-ray diffraction analyses and Raman spectroscopy. The sequential extraction protocol and microscope automatic system confirmed the arsenic carriers. These are ferric (aluminum) or calcium arsenate/arsenites, accounting for 71.2 and 72.8% total As, and minor arsenic adsorbed on iron oxyhydroxides. Arsenic was primarily found (63.3%) in the Fe,Al-AsOx coprecipitates in the industrial residue. A 17% As-richer sludge, as achieved here (4.18% As), would result in a lower sludge volume for disposal. Transportation and disposal costs would then drop. These benefits were confirmed along one year of industrial operation. The projected reduction in effluent treatment costs reaches 60%.

Impact of the Climate Change and the Recent Development of an Artificial Tropical Estuary on the Mobility and Distribution of Phosphorus: Case of Vridi Channel (Côte d'Ivoire)

This study focused on the effects of the climate change and the recent modification of Vridi channel on the mobility and distribution of phosphorus (P) in its superficial sediments. To best estimate this fact, the annual mobility and distribution of P were followed and compared before and after this development during two different annual periods, marked differently by the climate change effects. The first annual period has covered the period from April 2014 to March 2015 and this channel presented its former hydromorphology, with hydroclimatic conditions very close to that normal of Abidjan district. The second period annual has covered the period from October 2018 to September 2019 and this channel presented its current hydromorphology and, characterized by a rainfall drop and high ambient air temperatures compared to that normal of Abidjan district.&#x0D; A monthly sampling has been done at 5 cm below the surface sediment in this channel during each annual period. The mobility and distribution of P was assessed in the superficial sediments of this channel according two sequential extraction protocols: the modified Van Eck method and the modified Olsen method. Total phosphorus was assessed according AFNOR NF X31-147.&#x0D; The total phosphorus contents and all P fractions contents of these superficial sediments assessed by these two sequential methods and obtained over the period from April 2014 to March 2015 are higher than those determined over the period from October 2018 to September 2019. Thus, the recent development of this estuary, with as a corollary the modification of the physical and chemical characteristics of its superficial sediments, would have had the effect of clearing P towards the Atlantic Ocean and/or accelerating its sedimentation; hence the reduction of eutrophication risk of this aquatic ecosystem.