Lithium with your tonic, Sir?

In Cornwall, significant efforts are underway to drill, pump and extract lithium from geothermal waters circulating through faults in the region’s underlying granite. The lithium will be used to create zero-carbon, battery quality lithium chemicals that will help power the UK’s green revolution.

This drive to exploit lithium-bearing waters in Cornwall can be traced back to the discovery of lithium-rich geothermal waters found in mine workings at Unite Mines in 1864 (Miller, 1864). Lithium-rich brines were subsequently found in other Cornish metal mines, and in coal mines in the north of England. In mid-Victorian times, chemical analysis of water was routine, and lithium could be accurately measured. The measurements were extended to spa waters, which were very widespread, and were commonly reported in grains per gallon, to four decimal places. One grain per gallon is 17.14 ppm, so the purported resolution was exceptional.

Medicinal waters

The use of spa waters extends back many centuries to a time when holy wells were as prevalent in England, Wales and Scotland as they still are on Irish maps. Wells were found in all bedrock from granites to chalk. Then, they were special places to take water, with a spiritual bonus and a reputation for healing powers. All that changed following the Protestant Reformation in the 1500s, when any suggestion of adherence to the old religious customs became potentially dangerous. But those wells which had been attributed healing properties were transformed into recreational centres with medicinal benefits – spas as we understand them now were taking shape. To underpin their claim to heal people, the waters had to be analysed.

To underpin their claim to heal people, the waters had to be analysed

At first, analyses were limited to major anions (chloride, sulphate, carbonate) and cations. But in the wake of the industrial revolution, when analyses became reliable records of scientific data, differences in composition became clearer and were linked, rightly or wrongly, to the treatment of specific medical conditions. For example, the waters at Woodhall Spa, Lincolnshire, were found to be anomalously rich in iodine and bromine, and were recommended for nervous complaints and arthritis. The wells at Epsom provided the original magnesium-rich Epsom salts used as a relaxant. Many waters were found to be highly sulphurous, derived from pyritic shales or evaporites, and when drunk in several pints at one go were good for cleaning out the digestive system (to be polite). When lithium was found in spa waters, in about 1860, it became recommended as a treatment for gout, and as a general tonic. Its reputation was such that ‘lithia waters’ were highly prized, and became the foci of successful spa centres, particularly on the European continent and in North America.

Spas in Britain and Ireland had their share of lithium, with the element found in the waters of Bath (Roscoe, 1864), in over 30 wells at the spa town of Harrogate, and in several springs at Llandrindod Wells, including the ‘lithia saline spring’, which was measured to have about three times as much lithium as the French spa at Royat, itself a lithium hot spot (British Medical Journal, 1909). Some advertisements described the Llandrindod spring as ‘the finest in Europe’, although the waters were also radioactive and contain traces of the hard-to-detect poison thallium (Ray, 1930). At nearby Llangammarch Wells, case studies reported in the British Medical Journal were interpreted to indicate health benefits from lithium (Jones, 1903).

The demand for lithium to drink was high not just at the spas, but also at the dinner table. To meet demand, spas despatched bottles of their water across Britain’s rapidly expanding railway network. Victorian diners didn’t mind where the lithium came from as long as it was in a labelled bottle (sound familiar?), and so developed a big trade in mineral waters to which lithium had been added. In London at least, there was a clearing house for distributing bottled spa waters. Among the many advertisers of the period, the most prominent included Ellis & Son in North Wales who marketed Ruthin Waters, and Blake, Sandford and Blake of Piccadilly, both of whom sold aerated lithia water for gout, with lithium citrate added. Lithia water from Pitkeathly Wells in Scotland was also widely recommended for treating gout (Anon, 1895), as well as a range of conditions from rheumatism to morning sickness, advertised in journals from Sporting Life to The Gentlewoman. Advertisements commonly included endorsements by medical practitioners. In the US in the late 1900s, Lithia Coke combined lithium-bearing water with the base syrup used for Coca-Cola, while in 1929 the drink 7-Up started as a tonic water containing lithium, before it was eventually removed for safety reasons in 1948. Also in the US, lithium-bearing groundwater was used to brew Lithia Beer from the nineteenth century and has seen a recent resurgence. Back in Europe, at least one Spanish winemaker is making a virtue of using grapes from lithium-rich soil, and claiming health benefits transferred to the wines!

Advertisement for spa waters at Llangammarch Wells, including barium water and lithia water with analytical data. (Credit: The Medical Annual, 1906, public domain)

Advertisement for powders which dissolve to provide lithia water for travellers. (Credit: Illustrated London News, 28 May 1898, public domain)

Advertisement for Lithia Water and Leeches, by Appointment to The Queen. (Credit: Dublin Medical Press, 7 March 1860, Public domain)

A fresh look

Interest in the health benefits of lithium in spa waters remained high throughout the 20^th century and continue today. For example, in the Irish Parliament in Dublin in 1973, politician William Loughnane [1915 – 1982] said of the spa town Lisdoonvarna, “I advised the Minister for Health recently, when we were discussing rheumatism, that he should make a full investigation of the fact that the drug lithium was discovered in the waters of Lisdoonvarna. Lithium is a drug which lifts you. You do not have to go on “reefers”. If you go to Lisdoonvarna and take the waters in sufficient quantity you get this old lift.” (Dáil Éireann, 1973). Similarly, renowned medical writer William A.R. Thomson [1905 – 1983] suggested that while the Pitkeathly Wells in Scotland closed in the 1940s, their high lithium content merited a fresh look (Thomson, 1982).

Pitkeathly Wells in Scotland was famed for its lithium-bearing mineral water. (Credit: Graham Ellis, Cross Tower, CC BY-SA 2.0, via Wikimedia Commons.)

More recently, attention has focused on lithium as a mood stabiliser, with claims of potential links between naturally occurring, lithium-enriched drinking water and reduced dementia and suicide rates prompting NHS-supported investigations in both England and Scotland (e.g., Duthie et al., 2023; Kabacs et al., 2011; Memon et al., 2020).

Geological correlation

The natural lithium content has been measured and published for about 30 spa waters in Britain (Fig. 1, 2). While potentially biased towards analyses that included the measurement of lithium, there is enough correlation with geology to suggest that the map of lithium-bearing spas has value.

Figure 1 | Lithium contents in parts per million for spa waters in Britain. Definitions of the codes used for the map locations, as well as chlorine and temperature data are available in Supplementary Table 1 (below).

Figure 2 | Lithium contents in a range of waters, including British spa waters (shown bold). Pitkeathly water has five orders of magnitude more lithium than typical drinking water in Scotland. Data sources are available in Supplementary Table 2 (below).

For example, the spas of central Wales, and a group of spas in southern Scotland, are all close to Lower Palaeozoic black shales. Carbonaceous shales tend to be richer in lithium, but these older shales also experienced greater thermal alteration, which would have allowed greater liberation of the lithium (Lee, 2022). The spas of Harrogate, Buxton and Matlock have all been linked to water circulation through mid-Carboniferous shales and limestones, and this link could be extended to Lucan (Dublin) and Lisdoonvarna in Ireland. In contrast, the spas of southeast England (e.g. Tunbridge Wells, Sydenham Wells, Epsom) have never yielded lithium. The two spas with the highest lithium levels at Bridge of Allan (37 ppm; Ray, 1931) and Pitkeathly (reported equivalent to ~129 ppm lithium; Tibbles, 1907) are both in the Lower Devonian Ochil Volcanic Formation in central Scotland. Water-rock interaction involving similar plate margin andesites and rhyolites is a major source of recoverable lithium in the surface environment (Chen et al., 2020). The volcanic rocks in Scotland were coeval and comagmatic with some of the most lithium-rich granites in the British Isles, the late Caledonian suite in Grampian, southern Scotland, northern England and Leinster (Parnell & Armstrong, 2023).

The current demand for lithium – whether for medicinal purposes or the green revolution – suggests there are lessons to be learned from the descendants of those holy wells.

Authors

Prof John Parnell, School of Geosciences, University of Aberdeen, UK

Dr Joe Armstrong, School of Geosciences, University of Aberdeen, UK

Acknowledgements

We thank Jamie Bowie for help with figures.

Further reading

• Anon (1895) The New Treatment of Gout by Pitkeathly Cum Lithia. Reid & Donald, Chemists, George Street, Perth. 31pp.
• British Medical Journal (1909) Llandrindod Wells. British Medical Journal, May 22 1909, 1245-1246.
• Chen, C. et al. (2020) Lithium systematics in global arc magmas and the importance of crustal thickening for lithium enrichment. Nature Communications 11:5313. https://doi.org/10.1038/s41467-020-19106-z.
• Dáil Éireann (1973) Debate, Thursday, 15 Nov 1973, Volume 268 No. 14. Electoral (Amendment) (No. 2) Bill, 1973: Second Stage (Resumed). Dáil Éireann, Dublin; https://www.oireachtas.ie/en/debates/debate/dail/1973-11-15/40/
• Duthie, A.C. et al. (2023) Low-level lithium in drinking water and subsequent risk of dementia: Cohort study. International Journal of Geriatric Psychiatry 38(3):e5890.
• Johnson, F.N. (1984) The History of Lithium Therapy. Palgrave Macmillan, London.
• Jones, W.B. (1903) The mineral waters of Llangammarch Wells. British Medical Journal 2, 1055-1057.
• Kabacs, N. et al (2011) Lithium in drinking water and suicide rates across the East of England. The British Journal of Psychiatry 198, 406-407.
• Lee, K.J. (2022) Potential of petroleum source rock brines as a new source of lithium: Insights from basin-scale modeling and local sensitivity analysis. Energy Reports 8, 56-68.
• London and North Western Railway (1912) The Spas of Central Wales. London and North Western Railway, London. 59pp.
• Memon, A. et al. (2020) Association between naturally occurring lithium in drinking water and suicide rates: A systematic review and meta-analysis of ecological studies. The British Journal of Psychiatry 217(6), 667 – 678; https://doi.org/10.1192/bjp.2020.128
• Miller, W.A. (1864) Chemical examination of a hot spring containing caesium and lithium, in Wheal Clifford, Cornwall. Chemical News 10, 181-182.
• Parnell, J. & Armstrong, J.G.T. (2023) Surface expression of Late Caledonian magmatic lithium concentration, in the Rhynie Chert, UK. Geochemistry: Exploration, Environment, Analysis, 23. https://doi.org/10.1144/geochem2023-028.
• Ray, M.B. (1930) Br. J. Actinother. Physiother. 5, 32-33.
• Ray, M.B. (1931) A medical review of the British spas. Part XII. Bridge of Allan Spa. British Journal of Physical Medicine 6, 35-36.
• Roscoe, H.E. (1864) Note on the existence of lithium, strontium and copper in the Bath water. Chemical News 10, 158.
• Thomson, W.A.R. (1982) The over-all value of spas and spa treatment. Royal Society of Health Journal 102, 185-189.
• Tibbles, W. (1907) Food and Hygiene. London, Rebman Ltd.

SUPPLEMENTARY INFORMATION

Supplementary Table 1 | The chemistry (lithium, Li; chlorine, Cl) and temperature of spas in Great Britain

The map codes identify the sites shown in figure 1.

Supplementary Table 2 | Published mean lithium contents for a range of waters (values in mg/l)

For the compositions plotted in figure 2.

Supplementary references

• Albu, M., Banks, D. & Nash, H. (1997) Mineral and Thermal Groundwater Resources. Springer-Science, Berlin.
• Andrews, J.N., Burgess, W.G., Edmunds, W.M., Kay, R.L.F. & Dee, D.J. (1982) The thermal springs of Bath. Nature, 298, 339-343.
• Bothamley, C.H. (1893) The mineral waters of Askern, in Yorkshire. Journal of the Chemical Society, 63, 685-696.
• Burrell, B.A. (1914) The analysis of Ilkley spa water. Proceedings of the Yorkshire Geological Society, 19, 14-17.
• Duthie, A.C., Hannah, J., Batty, G.D., Dreary, I.J., Starr, J.M., Smith, D.J. & Russ, T.C. (2023) Low-level lithium in drinking water and subsequent risk of dementia: Cohort study. International Journal of Geriatric Psychiatry, 38; https://doi.org/10.1002/gps.5890
• Edmunds, W.M. & Robins, N.S. (1998) The saline waters of Llandrindod and Builth, Central Wales. Journal of the Geological Society, 155, 627-637.
• Embrey, G. (1918) Mineral waters in and near Gloucester, with some suggestions as to how the important constituents have been formed. Proceedings of the Cotteswold Naturalists’ Field Club, 20, 29-43.
• Embury, G. (1904) Analysis of radium sulphur spring. In: https://www.llandrindod-wells.com/analysis.html
• Harrison, W. (1892) Ripon Millenary, A Record of the Festival; Also a History of the City, Arranged under its Wakemen and Mayors from the Year 1400. W. Harrison, Ripon.
• Johnstone, W. (1879) Analysis of the water of St. Dunstan’s Well, Melrose. Chemical News, 39, 259-260.
• Johnstone, W. (1881) Analysis of Kingstead chalybeate spring. Chemical News, 43, 140-141.
• Kavanagh, L., Keohane, J., Cleary, J., Garcia Cabellos, G. & Lloyd, A. (2017) Lithium in the natural waters of the South East of Ireland. International Journal of Environmental Research and Public Health, 14, 561; doi: 10.3390/ijerph14060561.
• Lewis, S.J. (1921) Recent applications of the spectroscope and spectrophotometer to science and industry. Journal of the Royal Society of Arts, 69, 785-791.
• MacDonald, A.M., Ó Dochartaigh, B.E., Kinniburgh, D.G. & Darlinte g, W.G. (2008) Baseline Scotland: Groundwater Chemistry of Southern Scotland. British Geological Survey Open Report, OR/08/62. British Geological Survey, Keyworth.
• Manley, C.H. (1916) The densities and refractive indices of the Leamington Spa water. The Analyst, 41, 267-269.
• Manning, D.A.C. & Strutt, D.W. (1990) Metallogenetic significance of a North Pennine springwater. Mineralogical Magazine, 54, 629-636.
• Ord, W.M. & Garrod, A.E. (1895) The Climates and Baths of Great Britain volume 1. Royal Medical and Chirurgical Society of London, Macmillan.
• Peile, H. (1888) An analysis of Shotley Bridge spa water. The Journal of the Society of Chemical Industry, 7, 14-15.
• Ray, M.B. (1931) A medical review of the British spas. Part XII. Bridge of Allan Spa. British Journal of Physical Medicine, 6, 35-36.
• Seidel, U., Jans, K., Hommen, N., Ipharraguerre, I., Lüersen, K., Birringer, M. & Rimbach, G. (2020) Lithium content of 160 beverages and its impact on lithium status in Drosophila melanogaster. Food, 9; doi:10.3390/foods9060795
• Smedley, P.L. (2010) A survey of the inorganic chemistry of bottled mineral waters from the British Isles. Applied Geochemistry, 25, 1872-1888.
• Thorpe, T.E. (1868) Analysis of the water of the holy well, a medicinal spring at Humphrey Head, North Lancashire. Journal of the Chemical Society, 21, 19-25.
• Thorpe, T.E. (1894) The mineral waters of Cheltenham. Journal of the Chemical Society, 65, 772.
• Tibbles, W. (1907) Food and Hygiene. London, Rebman Ltd.
• Tichborne, C.R.C. & James, P. (1883) Mineral Waters of Europe Including a Short Description of Artificial Mineral Waters. London, Baillière, Tindall & Cox.
• Watson, W.B. (1905) British health resorts. The Practitioner, 74, 845-854.

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