Mineralogical Magazine, August 2007, Vol. 71(4), pp. 461–476 Metamorphic effects on agate found near the Shap granite, Cumbria, England: as demonstrated by petrography, X-ray diffraction and spectroscopic methods 1, 2 2 T. MOXON *, S. J. B. REED AND M. ZHANG 1 55 Common Lane, Auckley, Doncaster DN9 3HX, UK 2 Department of Earth Sciences, University of Cambridge, Downing Street, Cambridge CB2 3EQ, UK [Received 18 June 2007; Accepted 18 December 2007] ABSTRACT Agates from a 430 Ma host at Stockdale Beck, Cumbria, England have been characterized. The crystallite size of the Stockdale Beck agates was found to be ~60% greater than any other agates from five regions aged 400À1100 Ma. Raman spectroscopy identified moganite in all agates tested except those from Stockdale Beck. Infrared spectroscopy showed that the silanol content of the Stockdale Beck agates was near zero. The properties of agates from Stockdale Beck and the 1.84À3.48 Ga metamorphosed hosts found in Western Australia were similar but different from agates found in other hosts aged 400À1100 Ma. Cathodoluminescence demonstrates further differences between agates from hosts aged 13À1100 Ma and those from Stockdale Beck and Western Australia. Agates from the latter areas have a lower proportion of defects causing a red emission band (~660 nm) but an increased proportion of defects causing blue (~470 nm) and orange (~640 nm) emission bands. Agates found in hosts aged 13À1100 Ma are also differentiated from the Stockdale Beck and Western Australian agates in a ternary plot of the relative intensities of violet to blue to orange emission bands. Single scans producing this combination of colours are only found in the Stockdale Beck and Western Australian agates. The properties shown by the Stockdale Beck and Western Australian agates demonstrate that an agate or chalcedony infill can be used to identify post-deposition palaeoheating within a host rock. KEYWORDS: agate, chalcedony, moganite, IR, Raman, XRD, cathodoluminescence. Introduction light. The rhythmic deposition of Fe oxide spots CHALCEDONY is a variety of microcrystalline produced red and yellow banding. Thin sections a-quartz that generally displays a fibrous texture of agates can show continuous breaks at right under the polarizing microscope. Agate is banded angles to the fibrous growth thus creating fine chalcedony that is sometimes formed as a cavity banding. Horizontally formed bands, implying infill within an igneous environment. The most gravity control, are only found in a limited frequently seen banding in agates is a repetitive number of agate regions. Agates are deposited wall-lining of gas vesicles that creates a series of world-wide within a variety of volcanic rocks but onion-like layers. Moxon (1991) attributed the sedimentary and metamorphic agate hosts are banding to various causes. Opticaland electron much rarer. microscopy showed that the white bands were Agate has very high silica purity with non- composed of a plate-edge-like texture that volatile impurities being <1% (Flo¨rke et al., reflected incident light but scattered transmitted 1982). The major impurity in agate is the total water (free H2O and defect-site silanol SiÀOH) with a concentration of up to 2% (Graetsch et al., * E-mail: [email protected] 1985). However, most agate is a mixture of two DOI: 10.1180/minmag.2007.071.4.461 silica polymorphs: moganite and a-quartz. The # 2007 The Mineralogical Society T. MOXON ET AL. crystalstructure of moganite has been described as England. The agate-parent rocks were formed in the alternate stacking of layers of left- and right- the last major volcanism after the formation of the handed quartz on the unit-cell scale (Miehe and Borrowdale Volcanic Group. However, both the Graetsch, 1992). The moganite content in igneous- nature and age of the hosts have proven to be hosted agate and chalcedony varies from zero problematic. (Moxon et al., 2006) to ~70% (Parthasarathy et Early accounts of the host rock considered a al., 2001; Pop et al., 2004). It has been rhyolite lava flow as the most likely origin (Gale demonstrated that the moganite content and et al., 1979). However, after a detailed re- defect-site water in agates decreases over the assessment of the agate hosts by Millward and first 400 Ma while the crystallite size of a-quartz Lawrence (1985), they concluded that the increases (Moxon and Rı´os, 2004). A good observed textures are more indicative of welded correlation was shown between agate crystallite tuff and ought to be regarded as a rheomorphic size and the age of host rocks <400 Ma. Brazilian ignimbrite. and Northumbrian agates were exceptions and it Two fist-sized samples of host rock were was proposed that they were formed during known collected at Stockdale Beck and sliced. Both later periods of volcanic activity (Moxon and Rı´os, contained a mixture of host (h), hematite banding 2004). In general, the formation of wall-lining in agate (ag) and chalcedony (ch) (Fig. 1b); one agates can be regarded as occurring within a few sample also contained milky macrocrystalline million years of the host. The crystallite size and quartz. These two rock sections show that agate the defect-site water content were shown to be or brown chalcedony has filled all available approximately constant in agates from hosts aged spaces within the host rock, giving the impres- 400À1100 Ma. It was argued that the cessation of sion of a simultaneous deposition of host and crystallite growth is due to the completion of a agate. This silica infill of the Stockdale Beck moganite ? chalcedony transformation. host is unusualand contrasts with the typical Stockdale Beck, Cumbria, England is ~5 km igneous amygdales illustrated by samples found from the Shap granite and the Stockdale Beck in weathered basalt from the Isle of Mull agates were examined in order to determine (Fig. 1d). whether the later granite intrusion had affected Gale et al. (1979), using the Rb-Sr method, the physicalproperties. These Cumbrian agates determined the agate-host age at 421Ô 3 Ma. A re- were compared with agates from other locations examination of the same data by Compston et al. around the world with emphasis given to (1982) suggested that the Stockdale Beck host is similarly-aged hosts. In addition to the changes at least 430Ô7 Ma; this date will be used in the produced by low-temperature ageing, agates can later discussion. The nearby Shap granite has been also be affected by thermal events. A study of dated at 394Ô3 Ma (Wadge et al., 1978). agates from the metamorphosed hosts of the Pilbara Craton, Western Australia showed an advanced crystallization, zero moganite and in Agate samples some cases a partialbreakdown in the fibrous Stockdale Beck agates chalcedony (Moxon et al., 2006). The agates in The Stockdale Beck agates used in the study are this study have been characterized using a variety separate fragments, whole nodules and agate of techniques: X-ray diffraction (XRD) to assess removed from the two samples of host rock. crystallinity, optical and scanning electron micro- The agates have poor banding and can be scopy (SEM) to assess microstructure, cathodo- classified primarily into two types. One group luminescence (CL) to assess structural defects, has a grey translucency and is mainly band-free Raman spectroscopy to assess the moganite chalcedony (Fig. 1a); a second type has faint content and infrared (IR) spectroscopy to assess hematite bands. All the Stockdale Beck agates the water content. Throughout the paper, the examined lack the more intense regular rhythmic numbers in parentheses are Ô one standard wall-lining bands typified by a Mexican agate deviation. shown in Fig. 1c. Stockdale Beck agate host rocks Reference agates These agates occur in a small area in the Agates from hosts aged 400À1100 Ma have an Stockdale Beck, Longsleddale, Cumbria, approximately constant density, crystallite size 462 METAMORPHOSED AGATE, SHAP, ENGLAND FIG.1.(a) A sliced Stockdale Beck nodule revealing grey chalcedony. (b) Sectioned host rock from Stockdale Beck showing: agate (ag), host rock (h) and brown chalcedony (ch). (c) Wall-lining agate from Chihuahua, Mexico. (d) Typical small amygdales found in a basalt host, Isle of Mull, Scotland: agate (ag) and celadonite (ce) are shown. The Isle of Mull sample shows celadonite as both an outer covering of agate and an infill of empty gas vesicles. Scale bars: 1 cm. and defect-site water and a small moganite Basin and from the 2.72 Ga and 3.48 Ga hosts in content (Moxon and Rı´os, 2004; Moxon et al., the Pilbara Craton, Western Australia, provided 2006). Agates from five different regions aged samples that had been subjected to low-grade 400À1100 Ma provided comparative materialfor metamorphism. A list of the agates used in the the 430 Ma Stockdale Beck samples. A further study is given in Table 1. suite of agates from hosts aged 13À391 Ma were added to the older samples for a CL investigation. Samples from Woolshed Creek Hut, Canterbury, Experimental methods New Zealand, were from a similar host rock: an Petrography 89 Ma ignimbrite (Barley et al., 1988). A previous Around 30 thin sections of whole agates cut study has shown that post-deposition heating can approximately parallel to the fibrous growth were alter the character of agates (Moxon et al., 2006). used for generalpetrographic comparisons with Agates from the 1.84 Ga hosts in the Yerrida the agates of Stockdale Beck. 463 T. MOXON ET AL. a b c d TABLE 1. Agate samples used for XRD , Raman, IR and CL. Region Age of host Site and sample number (Ma) (Collectors named in acknowledgements) 1. Yucca Mt., USA** 13*3 Yucca Mt., HD 2257d (LN) 2. Mt Warning, Queensland, Australia 23*3 Oxley River, 2d,3a,4d,5a,7d,9d (JRi) 3.