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Birnessite

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Formula:
(Na,Ca,K)0.6(Mn4+,Mn3+)2O4 · 1.5H2O
System:
Monoclinic
Colour:
Black; dark brown in ...
Lustre:
Sub-Vitreous, Resinous, Waxy, Sub-Metallic, Dull, Earthy
Hardness:
Name:
Named in 1956 by Lloyd Hugh Parker Jones and Angela Alice Milne for the type locality at Birness, Scotland, UK. Earlier called "manganous manganite" by McMurdie (1944).
Isostructural with:
Generally massive, either earthy or as a resinous to dull fine-grained deposit. Sometime is a replacing material of manganese minerals, including silicates. Occurs in some manganese oxide dendrites. Rarely as dark brown needle crystals. Birnessite Group.
See also vernadite.

Many manganese oxides are better identified using infra-red spectroscopy than by x-ray diffraction because of issues of crystal size, disorder, etc. (Potter and Rossman, 1979).

Compare 'UM1979-06-O:CaHMn' (reported as the Ca analogue, but structurally different).

May mineralize fungal (Alternaria spp., Cladosporium spp.) hyphae, as known from a siderite boulder and from a soil (vide Burford et al., 2003).


Classification of Birnessite

Approved, 'Grandfathered' (first described prior to 1959)
4.FL.45

4 : OXIDES (Hydroxides, V[5,6] vanadates, arsenites, antimonites, bismuthites, sulfites, selenites, tellurites, iodates)
F : Hydroxides (without V or U)
L : Hydroxides with H2O +- (OH); sheets of edge-sharing octahedra
7.5.3.1

7 : MULTIPLE OXIDES
5 : (AB)2X3
7.18.11

7 : Oxides and Hydroxides
18 : Oxides of Mn

Physical Properties of Birnessite

Sub-Vitreous, Resinous, Waxy, Sub-Metallic, Dull, Earthy
Diaphaneity (Transparency):
Opaque
Comment:
Usually fine-grained massive
Colour:
Black; dark brown in transmitted light
Streak:
Dark brown to brown
Hardness (Mohs):
Tenacity:
Brittle
Density:
3 g/cm3 (Measured)    3.4 g/cm3 (Calculated)
Comment:
Usually earthy

Optical Data of Birnessite

Type:
Uniaxial (-)
RI values:
nω = 1.730 nε = 1.690
Birefringence:
0.040
Max Birefringence:
δ = 0.040
Image shows birefringence interference colour range (at 30µm thickness) and does not take into account mineral colouration.
Surface Relief:
High
Dispersion:
weak to moderate
Optical Extinction:
Parallel. Refractive indices not far from pyrochroite.
Comments:
The mineral is pseudo-uniaxial (-); an identification by optical properties is impossible.

Chemical Properties of Birnessite

IMA Formula:
(Na,Ca,K)0.6(Mn4+,Mn3+)2O4 · 1.5H2O
Elements listed in formula:
Analytical Data:
Electron microprobe analysis of a marine nodule from the Caribbean Sea; total Mn calculated as MnO2, H2O content calculated from the mass balance
SiO2   (0.9)
MnO2  (75.8)
FeO    (0.55)
CoO    (0.14)
NiO    (0.80)
CuO    (0.33)
MgO    (6.2)
CaO    (0.39)
Na2O   (1.9)
K2O    (1.8)
Cl     (0.1)
H2O   (10.89)
S      (0.2)

sum   100.00 wt.-%
Common Impurities:
Cl,Co,Cu,Fe,K,Ni,Mg,S,Si

Crystallography of Birnessite

Crystal System:
Monoclinic
Class (H-M):
2/m - Prismatic
Space Group:
B2/m
Cell Parameters:
a = 5.175 Å, b = 2.850 Å, c = 7.337 Å
β = 103.18°
Ratio:
a:b:c = 1.816 : 1 : 2.574
Unit Cell Volume:
V 105.36 ų (Calculated from Unit Cell)
Z:
1
Morphology:
Rarely in platelets, to 50 µm; commonly extremely finely crystalline, spherulitic, cellular. Rarely as divergent sprays of acicular crystals.
Comment:
Z also given as 0.5
X-Ray Powder Diffraction Data:
d-spacingIntensity
7.08 (100)
3.547 (28)
2.468 (17)
2.333 (43)
2.031 (24)
1.711 (29)
1.426 (17)
Comments:
Birnessite frequently yields only 2-4 x-ray diffraction peaks. Data above recorded on a marine nodule from the Caribbean Sea; all reflections are typically very broad. See extensive d-value set ICDD 23-1046 (synthetic): 7.09 (100), 5.60 (10), 3.56 (80), 2.74 (10), 2.58 (10), 2.56 (10), 2.51 (70), 2.47 (10), 2.42 (60), 2.31 (10), 2.26 (10), 2.25 (10), 2.21 (40) 2.15 (40), 2.14 (40), 2.09 (10), 1.97 (10), 1.94 (10), 1.86 (40), 1.82 (40), 1.81 (40), 1.77 (20), 1.75 (10), 1.66 (20), 1.63 (20), 1.55 (10), 1.53 (10), 1.52 (10), 1.47 (60), 1.43 (50), 1.41 (40) 1.37 (20). Data from ICDD 13-105 and 18-802 have been superceded.

Occurrences of Birnessite

Type Occurrence of Birnessite

General Appearance of Type Material:
Black coating or cement on pebbles
Geological Setting of Type Material:
Concretion in an unconsolidated glacial sedimentary deposit
Associated Minerals at Type Locality:

Relationship of Birnessite to other Species

Structurally related to group(s):
Common Associates:
4.FL.TrébeurdeniteFe22+Fe43+O2(OH)10(CO3) · 3H2O
4.FL.05WoodalliteMg6Cr2(OH)16Cl2 · 4H2O
4.FL.05IowaiteMg6Fe23+(OH)16Cl2 · 4H2O
4.FL.05JamboriteNi2+1-xCox3+(OH)2-x(SO4)x · nH2O where [x≤1/3; n≤(1-x)]
4.FL.05MeixneriteMg6Al2(OH)18 · 4H2O
4.FL.05MuskoxiteMg7Fe43+(OH)26 · H2O
4.FL.05FougèriteFe42+Fe23+(OH)12(CO3) · 3H2O
4.FL.10HydrocalumiteCa4Al2(OH)12(Cl,CO3,OH)2 · 4H2O
4.FL.15KuzeliteCa4Al2(OH)12(SO4) · 6H2O
4.FL.20Aurorite(Mn2+,Ag,Ca)Mn34+O7 · 3H2O
4.FL.20ChalcophaniteZnMn34+O7 · 3H2O
4.FL.20ErnienickeliteNiMn34+O7 · 3H2O
4.FL.20JianshuiiteMgMn34+O7 · 3H2O
4.FL.25WoodruffiteZn2Mn54+O12 · 4H2O
4.FL.30AsbolaneMn4+(O,OH)2 · (Co,Ni,Mg,Ca)x(OH)2x · nH2O
4.FL.35BuseriteNa4Mn14O27 · 21H2O
4.FL.40Ranciéite(Ca,Mn2+)0.2(Mn4+,Mn3+)O2 · 0.6H2O
4.FL.40Takanelite(Mn2+,Ca)2xMn4+1-xO2 · 0.7H2O
4.FL.55CianciulliiteMg2Mn2+Zn2(OH)10 · 2-4H2O
4.FL.60JenseniteCu32+Te6+O6 · 2H2O
4.FL.65LeisingiteCuMg2Te6+O6 · 6H2O
4.FL.70Akdalaite(Al2O3)5 · H2O
4.FL.75CafetiteCaTi2O5 · H2O
4.FL.80MouriteUO2Mo56+O16 · 5H2O
4.FL.85DeloryiteCu4(UO2)Mo2O8(OH)6
7.18.1ManganositeMn2+O
7.18.2HausmanniteMn2+Mn23+O4
7.18.3PyrolusiteMnO2
7.18.4RamsdelliteMn4+O2
7.18.5AkhtenskiteMnO2
7.18.6FeitknechtiteMn3+O(OH)
7.18.7ManganiteMn3+O(OH)
7.18.8GroutiteMn3+O(OH)
7.18.9NsutiteMnx2+Mn4+1-xO2-2x(OH)2x
7.18.10PyrochroiteMn2+(OH)2
7.18.12Aurorite(Mn2+,Ag,Ca)Mn34+O7 · 3H2O
7.18.13CianciulliiteMg2Mn2+Zn2(OH)10 · 2-4H2O

Other Names for Birnessite

Name in Other Languages:
German:Birnessit
Simplified Chinese:水钠锰矿
钠水锰矿
Spanish:Birnessita

Other Information

Not fluorescent in UV
Health Risks:
No information on health risks for this material has been entered into the database. You should always treat mineral specimens with care.

References for Birnessite

Reference List:
McMurdie, H.F. (1944) Microscopic and diffraction studies on dry cells and their raw materials. Transactions of the Electrochemical Society: 86: 313. [M.A. 9-227.]

McMurdie, H.F., Golovato, E. (1948) Study of the modifications of manganese dioxide. Journal of research of the National Bureau of Standards: 41: 589-600.

Feitknecht, W., Marti, W. (1945) Uber die oxydation von Mn(OH)2 mit molekularem sauerstoff. Helvetica Chimica Acta: 28: 129-148. (in German)

Jones, L.H.P., Milne, A.A. (1956) Birnessite, a new manganese oxide mineral from Aberdeenshire, Scotland. Mineralogical Magazine: 31: 283-288.

Fleischer, M. (1957) New mineral names. American Mineralogist: 42: 440-444.

Brown, F.H., Pabst, A., Sawyer, D.L. (1971) Birnessite on colemanite at Boron, California. American Mineralogist: 56: 1057-1064.

Glover, E.D. (1977) Characterization of a marine birnessite. American Mineralogist: 62: 278-285.

Potter, R.M., Rossman, G.R. (1979) The tetravalent manganese oxides: identification, hydration, and structural relationships by infrared spectroscopy. American Mineralogist: 64: 1199-1218.

Chukhrov, F.V., Gorshkov, A.I., Rudnitskaya, E.S., Beresovskaya, V.V., Sivtsov, A.V. (1980) Manganese minerals in clay: a review. Clays and Clay Minerals: 28: 346-453.

Kim, S.J. (1980) Birnessite and rancieite problem: their crystal chemistry and new classification. Journal of the Geological Society of Korea: 16: 105-113.

Burns, R.G., Burns, V.M., Stockman, H. (1983) A review of the todorokite-buserite problem: Implications to the mineralogy of marine manganese nodules: American Mineralogist: 68: 972-980.

Dunn, P.J., Fleischer, M., Francis, C.A., Langley, R.H., Kissin, S.A., Shigley, J.E., Vanko, D.A., Zilczer, J.A. (1984) New mineral names. American Mineralogist: 69: 810-815.

Golden, D.C., Dixon, J.B., Chen, C.C. (1986) Ion exchange, thermal transformations, and oxidizing properties of birnessite. Clays and Clay Minerals: 34: 511-520.

Golden, D.C., Chen, C.C., Dixon, J.B. (1987) Transformation of birnessite to buserite, todorokite, and manganite under mild hydrothermal treatment. Clays and Clay Minerals: 35: 271-280.

Post, J.E., Veblen, D.R. (1990) Crystal structure determinations of synthetic sodium, magnesium and potassium birnessite using TEM and the Rietveld method. American Mineralogist: 75: 477-489.

American Mineralogist (1990): 75: 477-489 (abstract).

Manceau, A., Gorshkov, A.I., Drits, V.A. (1992) Structural chemistry of Mn, Fe, Co, and Ni in manganese hydrous oxides: Part II. Information from EXAFS spectroscopy and electron and X-ray diffraction. American Mineralogist: 77: 1144-1157.

Lanson, B., Drits, V.A., Silvester, E., Manceau, A. (2000) Structure of H-exchanged hexagonal birnessite and its mechanism of formation from Na-rich monoclinic buserite at low pH. American Mineralogist: 85: 826-838.

Lanson, B., Drits, V.A., Gaillot, A., Silvester, E., Plançon, A., Manceau, A. (2002) Structure of the heavy-metal sorbed birnessite: Part I. Results from X-ray diffraction. American Mineralogist: 87: 1631-1645.

Yang, D.S., Wang, M.K. (2002) Syntheses and characterization of birnessite by oxidizing pyrochroite in alkaline conditions. Clays and Clay Minerals: 50: 63-69.

Burford, E.P., Kierans, M., Gadd, G.M. (2003) Geomycology: fungi in mineral substrata. Mycologist: 17(3): 98-107.

Villalobos, M., Lanson, B., Manceau, A., Toner, B., Sposito, G. (2006) Structural model for the biogenic Mn oxide produced by Psuedomonas putida. American Mineralogist: 91: 489-502.

Johnson, E.A., Post, J.E. (2006) Water in the interlayer region of birnessite: Importance in cation exchange and structural stability. American Mineralogist: 91: 609-618.

Drits, V.A., Lanson, B., Gaillot, A. (2007) Birnessite polytype systematics and identification by powder X-ray differaction. American Mineralogist: 92: 771-788.

Aldi, K.A., Cabana, J., Sideris, P.J., Grey, C.P. (2012) Investigation of cation ordering in triclinic sodium birnessite via 23Na MAS NMR spectroscopy. American Mineralogist: 97: 883-889.

Cygan, R.T., Post, J.E., Heaney, P.J., Kubicki, J.D. (2012) Molecular models of birnessite and related hydrated layered minerals. American Mineralogist: 97: 1505-1514.

Internet Links for Birnessite

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Localities for Birnessite

map shows a selection of localities that have latitude and longitude coordinates recorded. Click on the symbol to view information about a locality. The symbol next to localities in the list can be used to jump to that position on the map.
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