Reichenbachite from Cornwall and Portugal
R. S. W. BRAITHWAITE
Chemistry Department, University of Manchester Institute of Science and Technology,Manchester, M60 1QD, UKAND

G. RYBACK
42, Bell Road, Sittingbourne, Kent, ME10 4EB, UK

Abstract
Infrared spectroscopy is a rapid method of distinguishing between pseudomalachite and its polymorphs
reichenbachite and ludjibaite. This technique, backed by X-ray diffraction has shown that a number ofspecimens labelled 'pseudomalachite' from Cornwall, in particular from Old Gunnislake mine, are ofreichenbachite, thus identified for the first time from the British Isles. Reichenbachite has also been
identified with pseudomalachite from Miguel Vacas mine, Vila Vigosa, Evora, Portugal. Identification ofpseudomalachite from a number of other localities world-wide has been confirmed, and some specimens
have been shown to be arsenatian.
KEYWOROS:reichenbachite, pseudomalachite, ludjibaite, infrared spectroscopy, Cornwall, Portugal.

Introduction
PSEUDOMALACHITE (Hausmann, 1813) is theaccepted name for the copper phosphate mineraldescribed under a variety of names, including
ehlite (Breithaupt, 1832), lunnite (Bernhardi,.
1839), and prasine (Breithaupt, 1841), andassigned various compositions, but now formulated Cus(PO4)z(OH)4. It has been reported fromnumerous worldwide localities. British pseudomalachite ('lunnite'), from an unspecified locality in
Cornwall, was first analysed by Heddle (1855).
Maskelyne and Flight (1872) gave an analysis of'prasine' which was supplied by the dealer Richard
Talling and was associated with white olivenite,
and was therefore probably also Cornish,
although no locality is given. Church (1873)
analysed three Cornish, but not further localized
specimens of 'ehlite' and concluded that they were
the phosphate analogue of cornwallite andidentical with the 'pseudomalachite' 'of Dana'(actually of Hausmann) and the 'ehlite' ofBreithaupt. According to Rudler (1905), specimens of 'lunnite or pseudomalachite' from
Botallack, Cornwall, were analysed by Professor
Church, but the reference given (J. Chem. Soc.,1865, p. 2) is incorrect. No relevant paper by
Church other than that mentioned above has been
traced, and Botallack as a locality has not been
mentioned in the literature again until recently(Bowell, 1992). Kingsbury (1952) specifies five
localities for 'pseudomalachite' in Cornwall.

Description
Old Gunnislake mine, Calstock, Cornwall, is oneof the best known British localities for'pseudomalachite' (K_ingsbury, 1952), but in 1982
we observed that specimens from here gave
infrared spectra similar to but distinctly different
from that of authentic pseudomalachite.
Moreover, three out of six early 19th century
specimens of typical 'pseudomalachite' in the Lady
Elizabeth Cornwallis collection in Maidstone
Museum, labelled 'compact malachite' or'malachite' from Cornwall, also gave theabnormal infrared pattern. In 1987 a sample ofreichenbachite, the newly described polymorph ofpseudomalachite (Sieber et al., 1987), became
available to the authors and its infrared spectrum

Mineralogical Magazine, September 1994, Vol. 58, pp. 449-454
9 Copyright the Mineralogical Society

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R. S. W. BRAITHWAITE AND G. RYBACK

mentioned above. In addition, a batch of specimens said to have come from Williams' shaft
dumps of the same mine (SX 430 7185) in 1986
also proved to be reichenbachite, but anotherspecimen from this dump was of normalpseudomalachite, as was a specimen consisting of
9a green crust underlying arsenatian libethenite
crystals from East Gunnislake mine (SX 433 718).
Normal pseudomalachite was also confirmed on
three specimens labelled 'Gunnislake mine' or 'Old
Gunnislake mine', so it appears that bothpolymorphs occur at Gunnislake, reichenbachite
perhaps being more common, particularly onmaterial known to have come from Michael's
shaft (e.g. that collected by the authors).
Fro. 1. Scanning electron photomicrograph of reich- Unfortunately, the two polymorphs appear to beenbachite crystals from Cornwall. Off Maidstone indistinguishable except by X-ray diffraction orMuseum specimen 179. Lady E. Cornwallis infrared spectroscopy.
Collection.
Reichenbachite has hitherto been reported only
from the type locality, Reichenbach, Germany(Sieber et aL, 1987) and from Lubietova ( =was found to be identical with those of the Libethen), Slovakia (Hyrsl, 1991). The discovery
abnormal 'pseudomalachite' specimens from Old of the Gunnislake occurrence prompted us toG u n n i s l a k e mine. The identification was study 'pseudomalachite' samples from a wide
confirmed by X-ray powder diffraction at the range of localities, though concentrating particuNatural History Museum, London, and is the first larly on SW England, using infrared spectroscopy
as a rapid and easy method of distinguishingof reichenbachite from the British Isles.
Reichenbachite from Old Gunnislake mine was between the polymorphs. This led to theparticularly common on Michael's shaft dump identification of reichenbachite from Miguel(National Grid Reference SX 430 719), formerly a Vacas mine, Vila Vi~osa, Evora, Portugal. This
well-known collecting site marked by an ivy- mine is a known locality for pseudomalachite
covered chimney, but now built over. It is a (Magalh~es et al., 1988), but specimens collectedsupergene mineral, of late generation, typically by one of us (RSWB) from the dumps in 1969 were
forming dark green crusts to mammillary coatings, shown to carry reichenbachite. This forms darksometimes several mm thick, with compact, green, matt-surfaced mammillary coatings andindistinctly fibrous radiating structure, and with small spherules, closely associated with libethenminutely drusy outer surfaces. Scanning electron ite crystals and usually underlying the latter. Onephotomicrographs (Fig. 1) show the crystal specimen displays small globules of reichenbachite
terminations displayed on such drusy surfaces, dispersed on libethenite crystals and on a someand may be compared with the SEM photograph what darker green coating of compact fibrousof the type material figured in Sieber et al (1987). radiating pseudomalachite, on which the libethenThe coatings are usually found as crack fillings ite is sprinkled. The matrix of these specimens is ofand cavity linings on a matrix of milky, somewhat white vein quartz and 'limonite' in a grey slate.Theiron-stained, vein quartz with some decomposed localities at which normal pseudomalachite has
feldspar; occasionally they are associated with been confirmed by our survey are listed in Table 1;chrysocolla, fibrous malachite or rectangular note that some are arsenatian, easily distinguishedplates of metatorbernite. A fine specimen in the by infrared spectroscopy by the enhanced
Natural History Museum, London (BM 1973,72, absorption in the 840 c m - ' r e g i o n (cf. pyromorfrom R. W. Barstow) exhibits well-formed emerald phite group; see Braithwaite, 1990).
green 0.02 mm platy crystals of reichenbachite on
the dark green surface of a bluish-green
Polymorphs
translucent massive crust of reichenbachite 1 - 2
Studies of synthetic phases formed by hydromm thick.
Seven specimens from Old Gunnislake mine thermal techniques in the C u O - P 2 O s - H 2 0
have now been confirmed as reichenbachite by system revealed the formation of three polyinfrared spectroscopy, together with the three morphs of Cus(PO4)2(OH)4 , which were labelled
Maidstone Museum specimens from Cornwall PM ( p s e u d o m a l a c h i t e ) , P P M and Q P M

REICHENBACHITE FROM CORNWALL AND PORTUGAL

451

TABLE 1. List o f localities at which pseudomalachite h a s been confirmed b y infrared spectroscopy (thiswork)

Locality
England: Cornwall:
Wheal Carpenter, Gwinear
Penberthy Croft mine, St Hilary
South Wheal Frances, Illogan
Tolcarne mine, Camborne
United mines, St Day
Wheal Unity, St Day
Wheal Phoenix, Linkinhorne
West Wheal Phoenix, Linkinhorne
Gunnislake mine, Calstock
Old Gurmislake mine, Calstock
East Gunnislake mine, Calstock

Remarks

Specimens
examined

Arsenatian, underlying malachite
Bright-green minute spherules Cb)
With libethenite crystals and malachite
Arsenatian, with libethenite crystals
Nev 1985,3530.
BM 31243.
incl. BM 1929,216.
BM 44671, 44672, 44673.
MI 1985,12199; BM 61333.

One specimen was arsenatianSpecimen BM 61333COis arsenafian
One specimen was from Williams
shaft dump
Underlying libethenite crystals

England: Devon:
Bampfylde mine, North Molton

3England." Cumbria:
Potts Gill mine, Caldbeck Fells
Low Pike trial, Caldbeck Fells
Short Grain, Caldbeck Fells

Arsenatian
Arsenatian, with bayldonite
Arsenatian123

Scotland." Kirkcudbrightshire:
Auchencairn baryte mine, Rerrick

Translucent drusy crusts on quartz(d)2Portugal: Evora:
Miguel Vacas mine, Vila Vigosa
Germany: Rheinland-Pfalz:
Ehl
Rheinbreitbach
St Josephsberg mine, Virneberg

Museumspecimen numbers C~incl. BM 1968,134 &1968,135.

3121BM 42476.
incl. M/C Mus. N3799.
M/C Mus. N3807.

Slovakia:
Lubietova (= Libethen)1

M/C Mus. N3816.

Zaire:
Kambove, Katanga
M'sesa mine, Kalanga

22incl. BM 1968,316.

Zambia:N'changa mine, Chingola
Chambishi, between Chingola & Kitwe
Bwana M'kubwa, Ndola

41
1BM 1929,1633.

Arsenatian, sheafy pseudomorphs?

USA: New Jersey:
Old Schyler mine, North Arlington'Dihydrite', thin green crust

1

M/C Univ. Geol. Dept. 2847.

Chile(?):
Tambillos'Tagilite', with massive libethenite

1

M/C Mus. N3806.

Australia:
Tottenham, N.S.W.

1(a) M/C = Manchester. BM, Nev and MI = Natural History Museum, London. All other specimens from theauthors' collections, or submitted to the authors by various collectors.
(b) Infrared result inconclusive; XRD indicates pseudomalachite with broadened bands (J. G. Francis, pers. comm.).
(c) This is the 'erinite' specimen identified as pseudomalachite by Berry (1951).
(d) Confirmed by XRD on one specimen: Livingstone (1993).

452

R . S . W . BRAITHWAITE AND G. RYBACK99))

9I!

YuU!

3800

9IIi!

3100

1200

1000
800
Wavcnumbcr, cm-16~)0i

400

FIo. 2. Fourier Transform intYared spectra of pseudomalachite, reichenbachite and ludjibaite, measured innujol mulls. No absorption between 3100 and 1200 cm-1. PM = pseudomalachite, N'Changa mine, Zambia; R= reichenbachite, Old Gunnislake mine, Cornwall; L = ludjibaite, Lubietova, Slovakia.
(Shoemaker and Kostiner, 1981). Their crystal
structures were determined, indicating spaceg r o u p s P21/c, P21/a a n d P1 r e s p e c t i v e l y(Shoemaker et al., 1977; Anderson et al., 1977;
Shoemaker et al., 1981). Subsequently PPM wasidentified in nature as reichenbachite (Sieber et aL,1987), and QPM was found at Ludjiba, Zaire, anddescribed as ludjibaite (Piret and Deliens, 1988).
More recent work suggests that other polymorphs
might exist in nature and, indeed, the existence ofa fourth, triclinic polymorph, 'XPM', has been
predicted by Shoemaker and Kostiner (1981).

cm -1 range, using a variety of spectrometers ofboth grating and Fourier Transform types.
Examples of the spectra obtained of reichenbachite, pseudomalachite and ludjibaite areshown in Fig. 2, and wavenumbers and assignments of absorption maxima are listed in Table 2.
Although intergrowths of these species arecommon, and successive layers of nodules may
be composed of different polymorphs, the spectra
tend to show one or other of the species rather
than mixtures, p r o b a b l y because of carefulsampling under the microscope.
Conclusion

Infrared spectroscopy

The infrared spectra of a considerable number ofsamples (Table 1) were measured mostly in nujolmulls between KBr plates, over the 4000-400

Infrared spectroscopy is a rapid method of
distinguishing between the polymorphs pseudomalachite, reichenbachite and ludjibaite. Most
'pseudomalachite' specimens studied from Old

REICHENBACHITE FROM CORNWALL AND PORTUGAL

453

TABLE 2. W a v e n u m b e r s (era -t) and probable assignments o f infrared absorption m a x i m a o f
pseudomalachite, reichenbachite and ludjibaite
PMR

3436 fs
3387 fs

3409 s

N3180 vvw,br1098 vs(1020) vs999 vs953 s
889 m812 fs
756 fs
610 s
550 m,sp
530 m
510 fw
480 fw
446 m
417 m
360 m
338 m
285 w
250 w

(~3370)3180 vw,br1098 vs1042 vs992 vs(~955)(~920) m
839 m
770 m
( ~ 620)
606 s
546 m
505 m
475
455 fw
410 fw
390 w,br
330 w
258 fw(250)

L3625 vw
3419 s3413 s(~3370)3180 vw,br
1107 s1040 vs997 vs970 s(~925)(~890) vw
827 m
769 fs
627 m
601 s
546 m
530 fw
504 m
474 fw
459 fw
419 fw
n.d.
n.d.
n.d.
n.d.

Assignments

O - H stretch
v3 of PO 4
possibly withCuO-H
PO4 v~ or v31)
C u O - H deformation 2/)

C u O - H deformationor P04 v473
P04 v4)PO4 v2
Cu-O stretch

br = broad, f = fairly, m = medium, n.d. = not determined, s = strong, sp = sharp, v = very, w = weak.
Values in brackets are for shoulders:
PM = pseudomalachite, N'Changa mine, Zambia; R = reichenbachite, Old Gunnislake mine, Cornwall; L =ludjibaite, Lubietova, Slovakia.
Notes (Reference: Braithwaite, 1983)
1 Compare band at 950 cm-t in libethenite, unaffected by deuteration.
2 Compare band at 810 cm-l in libethenite, shifted by deuteration.
3 Similar in libethenite, but not in the arsenate olivenite.
Gunnislake mine, Cornwall, consist o f the Plx/ap o l y m o r p h reichenbachite, identified for the firstt i m e f r o m the British Isles. M o s t o f the'pseudomalachites' studied from other localities
consist of the normal P21/c polymorph, and someare arsenatian. Specimens from Miguel Vacas
mine, Vila Vi~osa, Evora, Portugal have proved
to contain both reichenbachite and pseudomalachite.

Acknowledgments
W e thank A. D. H a r t of the Natural History
M u s e u m , L o n d o n , for selecting and m a k i n gavailable samples from the N H M collections,and J. D. Francis, also of the N H M , for X-ray

diffraction work. Staff of the Maidstone andManchester Museums, and R. Tayler are also to
be thanked for supplying specimens for study. W e
are also grateful to I. Brough, of the Manchester
M a t e r i a l s Science C e n t r e , U . M . I . S . T . a n d
University of Manchester, for SEM photography.

References
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der Mineralogie, 2nd. edn., 578.

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R . S . W . BRAITHWAITE AND G. RYBACKBerry, L. G. (1951) On pseudomalachite andcornetite. Amer. Mineral., 36, 484-503.
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[Manuscript received 9 November 1993:
accepted 5 January 1994]