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Birnessite mineral

Birnessite is a layered manganese oxide mineral, listed as grandfathered in the September 2026 IMA-CNMNC list with formula (Na,Ca,K)0.6(Mn4+,Mn3+)2O4(H2O)1.5. Its composition and polytype vary. It is distinct from elemental manganese, mixed manganese ore and nodules, the buserite precursor used to prepare some synthetic analogues, and manganese oxalate products. The mechanisms below concern separately prepared synthetic sodium and cobalt-bearing forms, and a source-assigned poorly crystalline biogenic Mn-oxide/fungal composite. They do not establish behavior for natural ore or every birnessite polytype. No criticality designation is inherited from manganese.

Microbial & Biochemical Mechanisms (4)

Fungal culture-associated clearing and transformation of synthetic sodium birnessite

bioleaching Microbial

Associated Organisms: Aspergillus niger (NCBITaxon:5061), Serpula himantioides (NCBITaxon:80602)

In separate laboratory cultures, growing Aspergillus niger and Serpula himantioides cleared synthetic sodium-birnessite-amended agar and produced new crystals. The observations support dissolution-associated transformation, with manganese oxalate phases assigned in the Serpula arm by powder diffraction. Organic-acid-mediated mobilization and reprecipitation are the authors' mechanistic interpretation; metabolite concentrations and manganese oxidation-state changes were not measured. Neither a dissolved-manganese mass balance, isolated-product yield nor industrial recovery is established.

Experimental Context & Analytical Limits:
Wei2012 used A. niger ATCC 201373 and S. himantioides supplied by N. White, University of Abertay, without a strain accession or sequence for the latter. These were separate cultures, not a consortium. Sodium birnessite was supplied by S. Hillier and prepared by freeze-drying synthetic Na-buserite. The paper does not provide a specimen-specific initial composition, quantified phase purity or polytype refinement; its introductory mixed-cation formula is not a measured batch formula. Each 90 mm dish contained 20 cm3 malt extract agar with 0.5% (w/v) oxide and an 84 mm sterile cellophane membrane. A 5 mm leading-edge mycelial disc from cultures maintained for at least 7 days for A. niger or 14 days for S. himantioides was inoculated and grown at 25 degrees C in darkness, with at least three replicate plates. This evidence does not establish equivalent behavior for natural, substituted or otherwise prepared birnessites.
Curated Evidence Points:
Support Source: wei2012
Results on printed pages 1745-1746, Table 1 and Figure 1D report birnessite clearing during fungal growth. Figure 2I compares the abiotic feed morphology with crystals after 15 days of A. niger growth (J) and 5 or 23 days of S. himantioides growth (K-L). Table 3 reports initial surface pH 7.26, falling to 3.08 after 15 days for A. niger and 2.93 after 25 days for S. himantioides (six surface measurements). The 23-day growth/microscopy sampling and 25-day pH/clearing statements are retained as distinct times.
Partial Source: wei2012
Figure 4 assigns the recovered 5-day S. himantioides material to manganese oxalate trihydrate plus dihydrate (lindbergite), and the 23-day material to the dihydrate. These are source assignments from reference-pattern matching, not quantitative phase fractions. Crystals were extracted using 80 degrees C water and vacuum-dried overnight before analysis; no wet-culture or paired drying series excludes preparation-related hydration changes. The trihydrate is not assigned retrospectively to falottaite, and the Serpula diffraction result is not transferred to the A. niger arm. This is the same Wei2012 experiment also represented under lindbergite, not independent evidence.
Partial Source: wei2012
Table 1 reports growth and clearing-zone extension ratios and Table 2 biomass tolerance indices against no-oxide growth controls. None is an extraction fraction. The narrative's complete solubilization after 15 or 25 days rests on clearing rather than a dissolved-Mn balance; newly precipitated solids preclude interpreting it as complete aqueous recovery. Figure 2I supplies an abiotic morphology comparison, but no time-matched sterile diffraction, killed-biomass or pH-matched fungal series establishes microbial necessity or an exclusive cause.
Partial Source: wei2012
Figure 5 and the abiotic-test methods compare 50 microlitre additions of 0.5 M citric acid, oxalic acid or HCl to 5 mm wells in amended agar. The organic acids cleared birnessite, whereas HCl produced no significant halo in that test. These separate chemical assays support a possible organic-metabolite contribution without measuring fungal oxalate production or identifying their products by diffraction. Figure 3 EDX concerns a separate biogenic-MnOx feed; Figure 6 is a conceptual model, including speculative metal sorption, rather than direct evidence for every pathway or recovery application drawn.
Context_only Source: ncbi_niger
TaxID 5061 resolves the reported species name; it does not authenticate ATCC 201373 or establish a species-wide phenotype. That strain differs from the ATCC 1015 cultures used in other curated manganese studies.
TaxID 80602 resolves the reported species name, not the unaccessioned experimental isolate or a lineage within that species complex.

Fungal transformation of synthetic cobalt-bearing birnessite to oxalate-bearing solids

biomineralization Microbial

Associated Organisms: Aspergillus niger (NCBITaxon:5061)

Growing A. niger ATCC 1015 transformed a separately prepared synthetic cobalt-bearing birnessite into rosette-like solids assigned by the authors to manganese oxalate dihydrate (lindbergite), with cobalt detected by EDXA in examined transformed material. Matched uninoculated material retained birnessite-like diffraction. This supports culture-associated mineral transformation and cobalt association with the recovered solids, not a measured cobalt recovery fraction or demonstrated cobalt lattice substitution. Oxalate-mediated dissolution and precipitation are the authors' interpretation; cobalt reduction was proposed without a direct oxidation-state assay. No industrial deployment was demonstrated.

Experimental Context & Analytical Limits:
Ferrier2022 used living A. niger ATCC 1015 on 90 mm malt extract agar plates, approximately 25 cm3 medium containing 0.2% (w/v) powder below 90 micrometres, inoculated with a 5 mm leading-edge colony plug and incubated for 14 days at 25 degrees C in darkness. Synthetic feed was prepared from CoCl2 and KMnO4 with HCl at elevated temperature, washed, desiccated, acid-treated to exchange interlayer potassium, then recovered and dried. The printed nitric-acid recipe says 200 ml 0.1 HNO3 without a concentration unit; it is not silently completed here. Feed was heated at 105 degrees C for at least 24 hours before experiments. Table 1 reports partial XRF composition as 73.41% MnO, 7.74% Co and 4.48% K2O, using the source's mixed oxide/element basis; this is neither a refined mineral formula nor complete phase purity. Elements not present in synthesis solutions were excluded from that table. This arm is separate from the same paper's natural Nkamouna laterite and from Wei2012's sodium birnessite and A. niger ATCC 201373.
Curated Evidence Points:
Figures 6-7 (page 673) compare fine uninoculated feed particles with rosette-like recovered solids, and EDXA detects Mn, O and Co in both, with C in the transformed material and K no longer detected there. These qualitative spectra do not quantify cobalt incorporation or establish its oxidation state, binding site or chemical phase. Microscopy examples are reported as representative of several examinations, not a quantified transformed-particle fraction.
Figure 8 (page 674) matches the uninoculated control to birnessite and inoculated recovered solids to lindbergite. The caption heading incorrectly names Nkamouna laterite; its detailed caption, Results, traces and synthetic-arm methods identify Co-birnessite. Replicates were pooled for a subsample. The methods specify Cu-Kalpha XRD of ground powder on PVC slides over 3-60 degrees 2-theta, unlike the Co-radiation, acetone-smear XRPD used for the natural laterite. Reference-pattern agreement supports a source-assigned product, not quantitative phase purity or a detection limit for residual feed.
Table 2 reports day-14 surface pH 2.17 +/- 0.03 (n=6) for inoculated Co-birnessite agar, 2.26 +/- 0.02 (n=3) for mineral-free fungal agar, 6.43 +/- 0.04 (n=2) for uninoculated mineral agar and 5.32 +/- 0.02 (n=3) for uninoculated mineral-free agar; uncertainties are reported SD. The discussion's general increased-pH explanation does not match the lower fungal Co-birnessite mean relative to its fungal control. The 94.1% tolerance index is a dry-biomass ratio and 1.47 is a colony-extension-rate ratio, not metal extraction or recovery.
Procedures on page 675 recover debris by approximately 70 degrees C water washing followed by at least 48 hours desiccation. Preparation can affect hydration; in-culture phase identity is not independently established. The authors' total-transformation/solubilization wording rests on morphology and recovered diffraction, without dissolved-metal or total product mass balance. No measured oxalate time course, pH-matched acid-only, killed-biomass or cell-free metabolite controls isolate the proposed route. Direct Mn/Co oxidation-state or cobalt-site measurements are absent from the reported analyses; inferred reduction and a mixed oxalate lattice remain mechanistic interpretations.
Context_only Source: atcc1015
The collection resolves ATCC 1015 as A. niger with strain designation A1144 3528.7 and CBS 113.46. This supports catalogue identity, not authentication of the paper's experimental stock.
Context_only Source: ncbi_niger
TaxID 5061 resolves the species name, not strain-specific performance.

Cobalt sorption and surface oxidation by a freeze-dried fungal birnessite-bearing composite

biosorption Microbial

Associated Organisms: Paraconiothyrium sp. WL-2 (NCBITaxon:443224)

A laboratory-grown Paraconiothyrium sp. WL-2 culture produced a poorly crystalline Mn-oxide and fungal-tissue composite assigned by the authors primarily to birnessite. After recovery and freeze-drying, this material removed aqueous Co from nitrate solution; surface XPS was interpreted as sorbed Co(III). The microbial designation refers to the origin and retained biomass of the sorbent, not demonstrated active metabolism during cobalt treatment. The downstream experiment used prepared powder, not a growing culture. Neither a pure birnessite phase, intrinsic advantage of biological origin, isolated cobalt product, regeneration yield nor industrial recovery was established.

Experimental Context & Analytical Limits:
Sasaki2008 grew the wetland isolate in 150-200 ml PY medium in 500 ml flasks with 150 mg/L initial Mn(II), initial pH 6.6 buffered with PIPES, and 0.5 mg wet fungal inoculum as printed. Cultures were shaken at 100 rpm and 25 +/- 2 degrees C, shielded from light, for up to two weeks. Precipitates were collected on a 5 micrometre filter and rinsed; the next preparation sentence calls the material freeze-dried for 24 hours the filtrate, an unresolved wording ambiguity. The recovered powder was stored at 4 degrees C. Sorption used 0.020 g biogenic or 0.015 g chemically prepared oxide in 0.150 L solution, nominally 1 mmol/L solid Mn, 100 mmol/L KNO3, PIPES-buffered initial pH 6.5, 25 degrees C and 100 rpm shaking. Residual dissolved Co and Mn were measured after 0.2 micrometre filtration; time courses were duplicated. Methods give initial Co up to 175 micromol/L and 100-300 hours, whereas Figure 7 begins near 0.21 mmol/L and extends beyond 300 hours. These are source discrepancies, not a reconciled loading or endpoint.
Curated Evidence Points:
Section 3.1 and Figure 1 (pages 606-607) assign the noisy, poorly crystalline biogenic diffraction pattern primarily to birnessite while explicitly calling the assignments potentially indefinite. The reference-pattern formula is not a measured batch formula or a quantified phase fraction. The chemical comparator is assigned to ramsdellite, not abiotic birnessite. Figures 2-5 document retained fungal organics, morphology and porosity differences; reported specific areas are 81.4 versus 11.3 m2/g. Phase, surface area and biomass therefore confound attributing differences solely to microbial origin. No sterile formation time course or enzyme intervention establishes the culture's exclusive precipitation route.
Figure 7 and section 3.2 (page 609) show declining aqueous Co with both oxide preparations, with slower uptake and a lower final aqueous concentration for the biogenic composite in the displayed experiment. A matched amount of lyophilized fungal tissue alone showed no observed Co uptake. This supports an oxide-associated sorption contribution under these conditions, not a species-wide phenotype or proof that viable cells were needed during sorption.
The prose reports 160 versus 28.7 mmol Co per mol solid Mn and a 5.6-fold biogenic advantage. Those normalized values are not readily reproduced from the Figure 7 concentration changes and nominal 1 mmol/L solid Mn, and its initial Co differs from the methods limit. The text also mentions an unshown 0.55 mmol/L initial-Co experiment. No capacity, fold advantage or complete cobalt mass balance is adopted here; the directly displayed qualitative aqueous trend is retained. Methods also print 500 dm3 sorption flasks, unlike the 500 cm3 preparation vessels; the apparent unit error is not silently corrected into a measured vessel volume.
Figure 10 (pages 610-611) assigns the sorbed-Co XPS signal to Co(III), using Co 2p1/2 because the Co 2p3/2 region overlaps Mn 2s. Peak positions and absence of the expected Co(II) satellite support the authors' surface oxidation interpretation, not a bulk CoOOH mineral assignment, complete oxidation of all removed Co or product purity. Recovered sorption solids were air-dried for one week at 4 degrees C before XPS; no in situ redox time course is provided.
Figures 8 and 11 show Mn release even without Co and additional release with Co in the biogenic arm. Figure 11 subtracts the no-Co background; it does not plot total Mn dissolution. The abstract states that Mn(IV) reacts preferentially over Mn(III), whereas the Results and discussion on pages 610-611 infer preferential Mn(III) reaction over Mn(IV). This unresolved source conflict precludes adopting a preferred Mn oxidant or a unique stoichiometric redox pathway. Figure 9 is a surface Mn XPS comparison, not a closed redox or dissolved-metal balance.
Context_only Source: ncbi_wl2
TaxID 443224 resolves the exact strain-labelled Paraconiothyrium sp. WL-2 node. Although NCBI assigns species rank, it is not a resolved named species or evidence authenticating the experimental stock; no other Paraconiothyrium species is substituted.
Context_only Source: genbank_wl2
AB303550.1 records strain WL-2, the same taxon cross-reference and Japanese wetland provenance with ribosomal/ITS sequence information. It corroborates the isolate label, not a functional gene assignment, enzyme mechanism or verification of the exact 2008 culture stock.

Competitive cobalt and nickel sorption on a freeze-dried fungal oxide

biosorption Microbial

Associated Organisms: Paraconiothyrium sp. WL-2 (NCBITaxon:443224)

A separately reported 2009 laboratory experiment found preferential cobalt sorption over nickel from defined binary solutions using freeze-dried Mn oxide produced by Paraconiothyrium sp. WL-2 and described by the source as poorly crystalline birnessite. Nickel nevertheless inhibited cobalt uptake. Microbial involvement denotes the material's fungal origin; metabolism or viability during the sorption stage was not demonstrated. This adds mixed-solute evidence to the earlier 2008 cobalt-only study, not an independent replication of material production or a purified cobalt recovery process.

Experimental Context & Analytical Limits:
Section 2 (page 2643) used 0.020 g freeze-dried biogenic oxide or 0.015 g freeze-dried chemical oxide in 0.150 L solution, both nominally 1 mmol/L solid Mn, with 100 mmol/L KNO3, PIPES-buffered initial pH 6.5, 25 degrees C and 100 rpm shaking for 300 hours in duplicate. Binary assays nominally fixed Co at 0.3 mmol/L and varied Ni from 0.1 to 1.0 mmol/L; Figures 7-8 and Table 2 give actual initial pairs (Co,Ni) of (0.31,0.10), (0.35,0.35) and (0.34,1.00) mmol/L, plus a Co-only comparator. Filtrates passed a 0.2 micrometre membrane before ICP-MS. The fungal preparation was not demonstrated to be phase-pure, and no new diffraction pattern or culture-production time course is provided in this paper. Its nominal birnessite identity does not identify natural ore or every birnessite polytype.
Curated Evidence Points:
Figures 7-8 and Table 2 (pages 2646-2647) show greater fractional cobalt than nickel depletion in the binary biogenic assays and less cobalt uptake at higher nickel loading. Equation 3 defines the dimensionless selectivity coefficient as alpha_Co=(X_Co/C_Co)/(X_Ni/C_Ni), where X and C are mole fractions in sorbed and aqueous phases. For the three listed initial pairs, Table 2 reports alpha_Co 7.92, 7.47 and 17.7 for the biogenic preparation and 5.65, 2.23 and 2.65 for the chemical comparator. These are reported phase-distribution ratios, not removal percentages, isolated-product purities or recovery yields. No replicate-level raw dataset is supplied to independently reproduce the coefficients; the displayed time courses support the narrower preferential-sorption observation.
Section 2 identifies the chemical comparator as ramsdellite, with specific area 11.5 m2/g versus 81.4 m2/g for the fungal oxide. Phase, area, composition and retained biomass are not matched. Section 3 (page 2644) reports preliminary cellular-tissue controls with no Co or Ni sorption, but provides no displayed control dataset. No no-sorbent time course or sterile formation series is displayed. Comparative uptake therefore does not isolate a uniquely biological binding mechanism or require living cells. The earlier 2008 characterization remains a related material study, not a newly replicated 2009 mineral-purity measurement.
Figures 1-4 and 7-8 display Mn release from the fungal preparation, followed by decreases in dissolved Mn, including release without added Co or Ni. Figures 9-11 show ex situ XPS interpreted as predominantly Co(III) and Ni(II) at the recovered solid surfaces. Binary-assay solids were collected on 0.45 micrometre filters and lyophilized overnight before XPS. These observations support sorption-associated surface redox differences, not complete bulk cobalt oxidation, a measured CoOOH mineral yield or a closed dissolved-plus-solid metal balance.
Table 1 (page 2644) gives average Mn oxidation states 3.09 and 3.68 for biogenic and synthetic material, whereas the adjoining prose gives 3.17 and 3.70. The prose also invokes a lack of Mn(III) in synthetic oxide although Table 1 reports a Mn(III) mole fraction of 0.296. No single reconciled oxidation-state inventory or uniquely preferred Mn oxidant is adopted. Figure 12 is a proposed binding-site scheme, not direct site occupancy imaging; specific vacancy/edge routes and CoOOH coprecipitation remain interpretations rather than quantified products.
Single-solute Figures 1-4 are distinct from the binary assays. Section 2 lists Co up to 1.7 mmol/L and Ni up to 2.11 mmol/L, while Figure 2 includes 2.19 mmol/L Co and Figure 3 includes 2.31 mmol/L Ni. Figures 5-6 are fitted isotherms rather than independent measurements; Figure 5 normalizes sorbed quantities to mass of Mn(III,IV), excluding Mn(II), not total composite mass. No fitted capacity is transferred to a natural feed, and no source-wide mass-normalization advantage is asserted. Different reported post-sorption preparation from the 2008 study also precludes pooling both papers as identical assay replicates.
Context_only Source: ncbi_wl2
The freshly checked NCBI taxon 443224 retains the exact Paraconiothyrium sp. WL-2 label. Its species rank does not resolve a formally named species or authenticate the 2009 culture stock; no taxonomic reassignment or enzyme-level causality is inferred.

Sources & References

  1. ima_2026_09: IMA-CNMNC. The New IMA List of Minerals, September 2026. Birnessite row, PDF page 26; introductory definitions and distribution terms.
    https://cnmnc.units.it/files/editor/IMA_Master_List_(2026-09).pdf (accessed 2026-10-12)
  2. birnessite_handbook: Mineralogical Society of America, Handbook of Mineralogy. Birnessite, one-page entry revised 6/2/2021; formula, polytypes, synthetic cell data and original mineral-description references.
    https://www.handbookofmineralogy.org/pdfs/Birnessite.pdf (accessed 2026-10-12)
  3. wei2012: Wei, Hillier and Gadd (2012). Biotransformation of manganese oxides by fungi: solubilization and production of manganese oxalate biominerals. Environmental Microbiology 14(7). Complete nine-page primary PDF, printed pages 1744-1752; Figures 1-6, Tables 1-3 and Experimental procedures. Publisher and bibliographic metadata instead end at 1753.
    https://doi.org/10.1111/j.1462-2920.2012.02776.x (accessed 2026-10-12)
  4. ncbi_niger: NCBI Taxonomy 5061. Aspergillus niger, current species node.
    https://api.ncbi.nlm.nih.gov/datasets/v2/taxonomy/taxon/5061/dataset_report (accessed 2026-10-12)
  5. ncbi_himantioides: NCBI Taxonomy 80602. Serpula himantioides, current species node.
    https://api.ncbi.nlm.nih.gov/datasets/v2/taxonomy/taxon/80602/dataset_report (accessed 2026-10-12)
  6. ferrier2022: Ferrier, Csetenyi and Gadd (2022; first online 2021). Fungal transformation of natural and synthetic cobalt-bearing manganese oxides and implications for cobalt biogeochemistry. Environmental Microbiology 24(2):667-677. Synthetic Co-birnessite arm: Figures 6-8, Tables 1-2 and procedures on pages 674-675; complete publisher PDF deposited at Dundee.
    https://doi.org/10.1111/1462-2920.15526 (accessed 2026-10-12)
  7. atcc1015: ATCC 1015. Aspergillus niger culture collection entry and strain designation.
    https://www.atcc.org/products/1015 (accessed 2026-10-12)
  8. sasaki2008: Sasaki, Matsuda, Urata, Hirajima and Konno (2008). Sorption of Co2+ Ions on the Biogenic Mn Oxide Produced by a Mn-Oxidizing Fungus, Paraconiothyrium sp. WL-2. Materials Transactions 49(3):605-611. Complete publisher PDF, Figures 1-11 and all methods; J-STAGE lists zero separate supplementary files.
    https://doi.org/10.2320/matertrans.M-MRA2007888 (accessed 2026-10-12)
  9. ncbi_wl2: NCBI Taxonomy 443224. Paraconiothyrium sp. WL-2, strain-labelled unclassified taxon; current NCBI Datasets taxonomy response.
    https://api.ncbi.nlm.nih.gov/datasets/v2/taxonomy/taxon/443224/dataset_report (accessed 2026-10-12)
  10. genbank_wl2: GenBank AB303550.1. Paraconiothyrium sp. WL-2 ribosomal DNA and ITS sequence; strain WL-2 and taxon 443224 cross-reference.
    https://www.ncbi.nlm.nih.gov/nuccore/AB303550.1 (accessed 2026-10-12)
  11. sasaki2009: Sasaki, Kaseyama and Hirajima (2009). Selective Sorption of Co2+ over Ni2+ Using Biogenic Manganese Oxides. Materials Transactions 50(11):2643-2648, final paginated publisher PDF; Figures 1-12, Tables 1-2 and section 2. Advance publication 7 October 2009; November 2009 issue. Publisher lists zero supplementary files.
    https://doi.org/10.2320/matertrans.M-M2009821 (accessed 2026-10-12)

Curation History

Timestamp Curator Action Summary
2026-10-12T00:48:58Z codex (GPT-6; codex) CREATE Added birnessite identity and the Wei2012 synthetic sodium-form feed experiment, retaining separate fungi, phase and preparation uncertainty, control limits and the distinction between clearing and metal recovery.
2026-10-12T01:23:37Z codex (GPT-6; codex; root and packaging agent) EDIT Added separate Ferrier2022 synthetic cobalt-bearing transformation and Sasaki2008 prepared fungal composite sorption experiments, preserving prior Wei2012 science, source discrepancies, uncertain phase and redox attribution, and the distinction from isolated cobalt recovery.
2026-10-12T01:54:56Z codex (GPT-6; codex) EDIT Added the separate Sasaki2009 binary Co/Ni sorption assay on freeze-dried fungal oxide, retaining defined selectivity ratios, comparator and phase limitations, source conflicts and no isolated-product recovery claim. Preserved all previous science and immutable history sessions.

Record source: data/records/birnessite.yaml