Regional lithogeochemical data from the Southern Uplands have been used to characterize a distinctive stratigraphy across this region. A suite of 840 point-counted and petrographically classified greywacke samples were used to establish chemical fingerprints for a series of greywacke-dominated lithostratigraphical units. These fingerprints were then used to evaluate a further 1455 greywacke samples collected throughout the Southern Uplands and Longford Down and enabled a series of strike-parallel geochemical tracts to be defined.

Four principal geochemical groups are recognized, relating to cratonic- and volcanic-derived greywacke provenances and both carbonate-rich and hydrothermally altered greywackes. Volcanic-derived units display higher Ti, Fe, Mg, Ca, Na, Mn, Cr, Ga, Ni, Sr, V and Zn values than their cratonic counterparts, which, with the exception of the carbonate-rich Hawick Group, display higher Si, K, La, Nb, Rb, Th and Zr. Volcaniclastic greywackes display REE patterns dissimilar to typical post-Archean upper crust, but similar to their andesitic components, whereas cratonic groups have REE patterns close to that of upper crust. Systematic strike-parallel geochemical variation in the Southern Uplands is controlled by petrographical differences which directly reflect provenance, with individual lithostratigraphical units derived from variable mixtures of ophiolitic, calc-alkaline, acid-igneous, low-grade metamorphic and carbonate-rich detritus.

The Southern Uplands greywacke succession (Scotland) accumulated at the Laurentian margin of the Iapetus Ocean. It was sequentially incorporated into an imbricate, accretionary thrust complex until closure of the ocean. Thereafter the thrust belt propagated across the suture zone as a foreland thrust belt directed towards the hinterland of Avalonia. A foreland basin migrating ahead of the thrust belt was the depositional site for the southernmost Southern Uplands units and the Windermere Supergroup (English Lake District). A Nd-isotope study has shown that juvenile ophiolitic detritus was introduced into the oldest, mid-Ordovician, Southern Uplands greywackes before two distinct provenance areas evolved: one supplying juvenile andesitic detritus in addition to a quartzo-feldspathic component, the other Proterozoic and exclusively quartzo-feldspathic. Bimodal composition continued into the early Silurian but was overlapped from late in the Ordovician by greywackes with intermediate Nd-isotope composition. This was not a simple mixing effect since the andesitic component is not represented and the necessary juvenile component comes from granodioritic and felsitic lithologies. Intermediate eNd values are then a consistent feature through the Silurian both in the younger strata of the Southern Uplands and in the earliest foreland basin turbidites of the Windermere Supergroup. The transition suggests cessation of volcanicity and erosion of deeper levels of the provenance terrane(s), possibly linked to the evolution of the basin system from active margin, accretion-related, to a foreland setting. To the north of the Southern Uplands terrane, beyond the Southern Upland Fault, a Caradoc to Wenlock turbidite sequence occupies inliers within the Midland Valley. The older greywackes contain abundant juvenile ophiolite and plutonic detritus in addition to a quartzofeldspathic metamorphic component; there are similarities with the most northerly part of the Southern Uplands. From the late Ordovician, εNd values systematically decline so that early Llandovery Midland Valley greywackes are exclusively quartzo-feldspathic, derived from an ancient source indistinguishable in isotopic terms from that periodically supplying the Southern Uplands. In general the Llandovery Midland Valley provenance was significantly more mature than that contemporaneously supplying the Southern Uplands. Thereafter, the Midland Valley latest Llandovery and early Wenlock greywackes contain a higher proportion of a juvenile component, and by the early Wenlock, greywackes from the Midland Valley, Southern Uplands and Lake District terranes are similar in terms of εNd. A common provenance seems likely and suggests that by the mid-Silurian all three terrenes were in close proximity.

In the Irish Caledonides, volcanism has been significant in terrane identification and in reconstructions of the Appalachian/Caledonian orogen. Crucial to these reconstructions is the recognition of ocean margins using obducted ocean floor relics (ophiolites) and supra-subduction zone volcanic assemblages. The volcanic rocks provide much evidence for the affinity of a terrane, however, by analogy with present day examples, the ocean floor sediments may provide the best way of tracing both ocean-floor magmatic activity, and continental source areas. This investigation shows that the Irish Lower Palaeozoic volcanogenic terranes can be discriminated in terms of their shale geochemistry, which also gives information on their provenance and environment of deposition. South Mayo shales are dominated by volcaniclastic material derived both from both an arc and from an ophiolitic source. The Northern and Central belts of the Central Terrane show very similar lithogeochemistries, apparently derived in part from intermediate to silicic volcanic complexes. The Ordovician-Silurian inliers that straddle the Suture Zone, here termed the Southern Domain, show a chemistry close to that of the Leinster Terrane, which, coupled with a greater degree of sea-floor weathering, suggests a terrane with sediment of both volcanic and continental provenance being deposited in deeper water further from land. Across the suture the Leinster Terrane shows a mature chemistry which clearly suggests a continental provenance, together with a volcanogenic input from supra-subduction volcanism. This maturity is probably due to slower rates of sedimentation with longer residence times for volcanic detritus, plus the existence of a deeply weathered continental basement.