With the intention of doing a study of the CrO:-/Cr,O:-equilibrium in aqueous solution, we have carefully re-examined the Raman spectra of CrO:-, Cr,O:-and CICrO;. Diluting stepwise an aqueous solution of 00:-ion we have showed the non-existence of the HCrO; species which was previously considered to exist in such systems. By studying the effect of pH on the Raman spectra we calculated the constant for the equilibrium: 2 Cr0:-+ 2H'S Cr20:-+H20 to be log (jZ2 = 13.77 k 0.02 (20 "C and KNO, 0.8 M). Using this value of the constant, we were able to establish the distribution diagram of the Cr0:-and Cr20:-species versus pH.

In addition to C r 0 2 -and Cr,O?-, species such as H2Cr04, HCr04-and HCr,O?-have been considered to exist in Cr(V1) equilibria in aqueous solution. The Raman spectra of dilute solutions of Cr(V1) at different pH have confirmed the non-existence of the last three species in a Cr(V1) concentration range between 0.1 M and the lower detection limit of concentration (CQ 0.003 M). The proposed equilibrium, 2Cr0:-+ 2H+eCr20$-+ H@, seems to be the only one existing between pH 1 and 11. A quantitative Raman study of the influence of ionic strength on the corresponding apparent formation constant pk2 led us to the determination of the equilibrium constant at zero ionic strength, namely log Pz2= 14.85f0.04 at 25 'C. In more acidic aqueous Cr(V1) solutions, up to 12 M in HN03, preliminary investigations corroborated the presence of the trichromate and tetrachromate species.

Systematic mineralogical investigations, carried out on panned stream concentrates from the northwestern part of the Cambro-Ordovician Stavelot massif (Belgium), led to the discovery of nodular gray monazites. These were later identified in situ in black slates associated with conglomeratic levels containing phosphatic material. Microscopic investigation shows that gray monazites are authigenic and predate cleavage. To test the hypothesis of a sedimentary origin for rare earth elements, samples of shales, phosphatic conglomerates, and monazite concentrates were submitted to sequential inductively coupled plasma analysis. Results show that the rare earth element pattern in gray monazites is a reflection of the abundance of these elements in the host rock. This suggests a model invoking desorption of the rare earth elements from their clayey support and differential precipitation of rare earth phosphates in the sediment initiated by P mobility during diagenesis. The genetic model for gray monazite mineralization assumes three essential and complementary phenomena: (1) sedimentation of clays in a reducing marine environment, (2) a phosphate anomaly in the same lithological sequence, and (3) evolution to low-grade epizonal metamorphic conditions. These nonrestrictive genetic conditions clearly suggest that gray monazites have been generally overlooked and must be much more widespread than believed. The economic interest of gray monazite lies in potential stream or beach placers. Their low Th content and comparatively high Eu content are interesting features in the scope of ore beneficiation. (Figs. 1 and 2). Discovery of Gray Monazite in the Stavelot Massif NODULAR gray monazite has been identified in numerous panned stream sediment concentrates collected in an area located south of Spa where a 15-km ridge (Vecqu•e) composed of Middle and Upper Cambrian sedimentary rocks extends northeastward from the Ambl•ve valleyOther Belgian occurrences of gray monazites were recently reported by Nonnon (1984) in the Cambrian of the Rocroi massif and by Limbourg (1986) in Lower Devonian rocks of the NeufchSteau synclinorium (Fig. 1). Elsewhere in Europe, gray monazite has been recorded in the Ordovician and Dinantian of Brittany (Donnot et al., 1973), in the Ordovician of northwest Spain (Vaquero, 1979), and in lower Paleozoic rocks of Wales and southwest England (Read et al., 1987). Other occurrences of nodular gray monazites were reported by Rosenblum and Mosier (1983) notably from Taiwan, USSR, Zaire, Gabon, Alaska, and Montana.

Experimental data for eleven rare‐earth elements (REE) obtained by inductively coupled plasma spectrometry (ICP) in five French geochemical reference standards (BE‐N, BR, DR‐N, GS‐N and FK‐N)are presented. The method is based on acid digestion of the sample and cation‐exchange separation from matrix elements. Together with these new determinations an updated compilation of these reference materials are presented. Good agreement between the present results and previously preferred and published values obtained by various analytical techniques is observed. The values obtained in the present work corroborate the validity of the outlined method.

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