1. Natural and anthropogenic signatures in Irish soil: A view from the local to the continental scale Ray Scanlon 1, Katherine Knights 1, Mairead Glennon 1 and Patrick O’Connor 2 1 Geological Survey of Ireland 2 Presently Consultant Geochemist

2. Introduction Anthropogenic vs natural signatures –Anthropogenic: Diffuse and point sources –Natural: Geology – Mineralised areas and “Natural Background” Look at Lead (Pb) at a variety of scales –One example of potentially harmful element. –What can we see and why?

3. GEMAS At the continental scale, the occurrence of ore deposits, geology (certain rock types enriched in specific elements) and climate play the key role in determining the observed element distribution patterns. Surprisingly, neither agriculture nor diffuse contamination play a key role in determining the chemical composition of European agricultural soil. Why? –Is scale of GEMAS data a limiter to determining soil quality at EU scale?

4. Scale? Ireland offers an opportunity to consider this question:- A variety of soil surveys have been conducted at various scales: Continental – National – Regional - Local A number of approaches have been undertaken, or are underway, to examine the input of anthropogenic versus natural inputs into soil quality based on these data. Look at Pb at a variety of scales, and by various techniques.

5. Lead (Pb) in Soil in Ireland Economic: Globally significant Zn and Pb province; Mineral exploration worth nearly €1 Billion to Irish economy annually. Health: Pb as a heavy metal – potentially harmful element; Diffuse – traffic, fossil fuel, other? “Point Source” – Urban signature and industry.

6. Soil Contamination: Impacts on Human Health : http://ec.europa.eu/science-environment-policy Science Communication Unit, University of the West of England, Bristol (2013). Science for Environment Policy In- Depth Report: Soil Contamination: Impacts on Human Health. Report produced for the European Commission DG Environment, September 2013. Available at: http://ec.europa.eu/science-environment-policy

7. Continental - National – Regional - Local (From Reimann et al., 2012, Fig. 2, p.534) (From Scheib et al., 2014)

8. GEMAS Pb UK/IRL The spatial distribution of arable and grazing land soil is similar, too. Maps indicate both anthropogenic and geological controls (mainly mineralisation) on the distribution of high Pb concentrations (>60 mg/kg). Elevated levels in areas of Cornwall-Devon, Snowdonia, southern Pennines and the west of the Southern Uplands can be attributed to mineralisation and subsequent mining activities. Elevated levels across most of northern England, The Midland Valley (Edinburgh) and southern Wales can be attributed to heavy industry. Scale of data – Max – min extent – limits interpretation of basic maps and statistics here. –Signal swamped by large neighbour?

9. Continental - National – Regional - Local EPA/Teagasc soil geochemical atlas of Ireland 1100 samples (From Fay et al., 2007, p.9) (From Fay et al., 2007, p.79)

10. Fay et al. 2007 Levels of Pb in Eastern Ireland are attributed to a combination of urbanisation and historical mining activity. Similar levels in the North-East can be partly attributed to mineralisation. In Limerick, levels above 40 mg/kg Pb are attributed to mineralisation. Extreme Pb concentrations, measured in Irish soil with values above 500 mg/kg, are coincident with local pollution sources, e.g., Tipperary near Silvermines.

11. Tellus (Northern Ireland, UK) and Tellus Border Surveys Urban Mineralisation Continental - national – regional - local

12. Continental - National – Regional - Local Urban Geochemistry - SURGE Dublin Pb www.gsi.ie/surge Pb (Glennon et al., 2012, Fig. 9, p.21) (Glennon et al., 2012, Fig. 30, p.79)

13. Techniques used to investigate components Local Exploratory Data Analysis (Glennon et al., 2012, 2014) Univariate & multivariate analysis (Harris et al., in prep.) Factor Analysis (Healy, 2013) Regional Exploratory Data Analysis (Knights & Scanlon, 2013) Principal Component Analysis (Dempster et al., 2013) Self Modelling Mixture Resolution (Ander et al., in prep) Natural Background Concentrations (McIlwaine et al., 2014)

14. Techniques used to investigate components National Exploratory Data Analysis (Fay et al., and Zhang et al.) Multivariate analysis (Zhang et al.,) Continental Exploratory Data Analysis (Reimann et al., 2014) Factor Analysis (Lado et al., 2008; Saaltink et al., 2013)

15. Local Lead boxplots by land zone (Glennon et al., 2012, Fig. 29, p.77) (Glennon et al., 2012, Fig. 30, p.79) (Cave et al., 2013)

16. Factor Analysis – Dublin Soil Pb associated with P, Ti and Hg - Strong Urban “Bullseye” (From Healy, 2013, Fig. 11, p.30)

17. Regional Natural Background Concentrations Spatially defined domains “UK method” (Ander et al., 2013) “Finnish Method” ( Tarvainen & Jarva, 2011 ) (From McIlwaine et al., 2014, Fig. 3)

18. Regional Self-modelling mixture resolution (From Cave & Ander, Fig 15, p.16) (From Cave & Ander, 2013, Fig. 17, p.19) From Cave & Ander, 2013, Fig. 9, p.13)

19. Conclusions GEMAS atlas does not show strong evidence of Pb diffuse pollution affecting the quality of European soil: Issue of scale of signal rather than scale of survey? Experience from Ireland and elsewhere shows that GEMAS data have the potential to demonstrate scale of diffuse pollution on the European scale Need to apply sophisticated geostatistical and data mining tools. References

20. SLIDE 6: Science Communication Unit, University of the West of England, Bristol, 2013. Science for Environment Policy In-Depth Report: Soil Contamination: Impacts on Human Health. Report produced for the European Commission DG Environment, September 2013. Available at: http://ec.europa.eu/science-environment-policy SLIDE 7: Reimann, C., Flem, B., Fabian, K., Birke, M., Ladenberger, A., Négrel, P., Demetriades, A., Hoogewerff, J., The GEMAS Project Team, 2012. Lead and lead isotopes in agricultural soils of Europe - The continental perspective. Applied Geochemistry, 27, 532- 542, http://www.sciencedirect.com/science/article/pii/S088329271100494X http://www.sciencedirect.com/science/article/pii/S088329271100494X Scheib, A.J., Flight, D., Breward, N., O’Connor, P. and Scanlon, R., 2014, The soil geochemistry of agricultural land in Britain and Ireland, Joint publication of the British Geological Survey and the Geological Survey of Ireland, in preparation SLIDE 9: Fay, D., Kramers, G., Zhang, C, McGrath, D. and Grennan, E., 2007. Soil Geochemical Atlas of Ireland, Teagasc and the Environmental Protection Agency, 120 pp., http://erc.epa.ie/safer/iso19115/display?isoID=105 http://erc.epa.ie/safer/iso19115/display?isoID=105 SLIDE 12: Glennon, M., Scanlon, R.P., O’Connor, P.J., Finne, T.E., Andersson, M., Eggen, O., Jensen, H.K.B. & Ottesen, R.T., 2012. Dublin SURGE Project: Geochemical baseline for heavy metals and organic pollutants in topsoils in the greater Dublin area. Technical Report, Geological Survey of Ireland, Dublin, 198 pp. http://www.gsi.ie/NR/rdonlyres/1F23753A-D662-44D3-AE78- 5029700472AE/41993/DublinSoilUrbanGeochemistry.pdf http://www.gsi.ie/NR/rdonlyres/1F23753A-D662-44D3-AE78- 5029700472AE/41993/DublinSoilUrbanGeochemistry.pdf SLIDE 13: Glennon, M., Scanlon, R.P., O’Connor, P.J., Finne, T.E., Andersson, M., Eggen, O., Jensen, H.K.B. & Ottesen, R.T., 2012. Dublin SURGE Project: Geochemical baseline for heavy metals and organic pollutants in topsoils in the greater Dublin area. Technical Report, Geological Survey of Ireland, Dublin, 198 pp. http://www.gsi.ie/NR/rdonlyres/1F23753A-D662-44D3-AE78- 5029700472AE/41993/DublinSoilUrbanGeochemistry.pdf http://www.gsi.ie/NR/rdonlyres/1F23753A-D662-44D3-AE78- 5029700472AE/41993/DublinSoilUrbanGeochemistry.pdf Glennon, M., Harris, P., Ottesen, R.T., Scanlon, R.P. and O’Connor, P., 2014. The Dublin SURGE Project: Geochemical baseline for heavy metals in topsoils and spatial correlation with historic industry in Dublin, Ireland. Journal of Environmental Geochemistry and Health, 36(2), 235-254. Special Issue on the 9th International Symposium on Environmental Geochemistry, http://link.springer.com/article/10.1007%2Fs10653-013-9561-8 http://link.springer.com/article/10.1007%2Fs10653-013-9561-8 Harris, P., Glennon, M, Scanlon, R. and Rigby, J., Visualising the risk of heavy metal soil contamination for Greater Dublin using multivariate empirical maximum likelihood kriging. Draft paper in preparation

21. References SLIDE 13 (continued from previous page): Glennon, M., Scanlon, R.P., O’Connor, P.J., Finne, T.E., Andersson, M., Eggen, O., Jensen, H.K.B. & Ottesen, R.T., 2012. Dublin SURGE Project: Geochemical baseline for heavy metals and organic pollutants in topsoils in the greater Dublin area. Technical Report, Geological Survey of Ireland, Dublin, 198 pp. http://www.gsi.ie/NR/rdonlyres/1F23753A-D662-44D3-AE78- 5029700472AE/41993/DublinSoilUrbanGeochemistry.pdf http://www.gsi.ie/NR/rdonlyres/1F23753A-D662-44D3-AE78- 5029700472AE/41993/DublinSoilUrbanGeochemistry.pdf Glennon, M., Harris, P., Ottesen, R.T., Scanlon, R.P. and O’Connor, P., 2014. The Dublin SURGE Project: Geochemical baseline for heavy metals in topsoils and spatial correlation with historic industry in Dublin, Ireland. Journal of Environmental Geochemistry and Health, 36(2), 235-254. Special Issue on the 9th International Symposium on Environmental Geochemistry, http://link.springer.com/article/10.1007%2Fs10653-013-9561-8 http://link.springer.com/article/10.1007%2Fs10653-013-9561-8 Harris, P., Glennon, M, Scanlon, R. and Rigby, J., Visualising the risk of heavy metal soil contamination for Greater Dublin using multivariate empirical maximum likelihood kriging. Draft paper in preparation Healy, R., 2013. Efficacy of Integrating Factor Scores and GIS in the Spatial Modelling of Geochemical Data, Unpublished thesis, National University of Ireland, Galway, Specialist Diploma in Environmental Sustainability, 71 pp. (For info a revised version of this thesis is available online from the author at http://www.academia.edu/5765378/Integration_of_Factor_Analysis_and_GIS_in_Spatial_Modelling_of_the_Dublin_Surge_Geoc hemical_Data_Set). http://www.academia.edu/5765378/Integration_of_Factor_Analysis_and_GIS_in_Spatial_Modelling_of_the_Dublin_Surge_Geoc hemical_Data_Set Knights, K.V. and Scanlon, R.P., 2013. Tellus: regional-scale baseline geochemical mapping of soil, stream sediment and stream water for the island of Ireland, Mineralogical Magazine, 77(5) 1482, http://goldschmidt.info/2013/abstracts/finalPDFs/1482.pdf http://goldschmidt.info/2013/abstracts/finalPDFs/1482.pdf Dempster, M., Dunlop, P. Scheib, A. and Cooper, M., 2013. Principal component analysis of the geochemistry of soil developed on till in Northern Ireland. Journal of Maps, DOI:10.1080/17445647.2013.789414 Ander, El., Johnson, C.C, and Cave, M.R., 2013. End-Project Report: Application of the Tellus Border soil chemistry data to the Agricultural Sector in Ireland. Report by the British Geological Survey, Keyworth, Nottingham, 27 pp. (This will be published online shortly) McIlwaine, R., Cox, S., Doherty, R., Palmer, S., Ofterdinger, U and McKinley, J., 2014, Comparison of methods used to calculate typical threshold values for potentially toxic elements in soil, Environmental Geochemistry and Health, http://link.springer.com/article/10.1007/s10653-014-9611-x#http://link.springer.com/article/10.1007/s10653-014-9611-x# SLIDE 14: Fay, D., Kramers, G., Zhang, C, McGrath, D. and Grennan, E., 2007. Soil Geochemical Atlas of Ireland, Teagasc and the Environmental Protection Agency, 120 pp. http://erc.epa.ie/safer/iso19115/display?isoID=105 http://erc.epa.ie/safer/iso19115/display?isoID=105 Chaosheng Zhang, Deirdre Fay, David McGrath, Eamonn Grennan, Owen T. Carton, 2008. Statistical analyses of geochemical variables in soils of Ireland. Geoderma, 146, 378–390 http://dx.doi.org/10.1016/j.geoderma.2008.06.013http://dx.doi.org/10.1016/j.geoderma.2008.06.013

22. References SLIDE 14 (continued from previous page): Filzmoser, P., Reimann, C. & Birke, M., 2014. Univariate data analysis and mapping. Chapter 8 In: C. Reimann, M. Birke, A. Demetriades, P. Filzmoser & P. O’Connor (Editors), Chemistry of Europe's agricultural soils – Part A : Methodology and interpretation of the GEMAS data set. Geologisches Jahrbuch (Reihe B - 102), Schweizerbarth, 67-81. Ladoa, L, R., Henglb, T. & Reutera, H., I., 2008. Heavy metals in European soils: A geostatistical analysis of the FOREGS Geochemical database. Geoderma, 148, 189–199, http://dx.doi.org/10.1016/j.geoderma.2008.09.020 http://dx.doi.org/10.1016/j.geoderma.2008.09.020 Saaltink, R., Griffioen, J., Mol, G., Birke, M. & The GEMAS Project Team, 2013. Geogenic and agricultural controls on the geochemical composition of European agricultural soils. Journal of Soils and Sediments, 14, 121- 137, http://link.springer.com/article/10.1007%2Fs11368-013-0779-y http://link.springer.com/article/10.1007%2Fs11368-013-0779-y SLIDE 15: Cave, M.R. & Ander, El., 2013. End of Project Report: Application of the Tellus Border soil chemistry data to the identification of sources of diffuse pollution in Ireland. Report by the British Geological Survey, Keyworth, Nottingham, 52 pp. (Available online shortly) Glennon, M., Scanlon, R.P., O’Connor, P.J., Finne, T.E., Andersson, M., Eggen, O., Jensen, H.K.B. & Ottesen, R.T., 2012. Dublin SURGE Project: Geochemical baseline for heavy metals and organic pollutants in topsoils in the greater Dublin area. Technical Report, Geological Survey of Ireland, Dublin, 198 pp. http://www.gsi.ie/NR/rdonlyres/1F23753A-D662-44D3-AE78- 5029700472AE/41993/DublinSoilUrbanGeochemistry.pdf http://www.gsi.ie/NR/rdonlyres/1F23753A-D662-44D3-AE78- 5029700472AE/41993/DublinSoilUrbanGeochemistry.pdf SLIDE 16: Healy, R., 2013. Efficacy of Integrating Factor Scores and GIS in the Spatial Modelling of Geochemical Data. Unpublished thesis, National University of Ireland, Galway, Specialist Diploma in Environmental Sustainability, 71 pp. SLIDE 17: McIlwaine, R., Cox, S., Doherty, R., Palmer, S., Ofterdinger, U. & McKinley, J., 2014. Comparison of methods used to calculate typical threshold values for potentially toxic elements in soil. Environmental Geochemistry and Health, doi:10. ​ 1007/ ​ s10653-014- 9611-x; http://link.springer.com/article/10.1007/s10653-014-9611-x#http://link.springer.com/article/10.1007/s10653-014-9611-x# Ander, E.L, Johnson C.C., Cave, M.R., Palumbo-Roe, B., Nathanail, P. & Lark, R.M., 2013. Methodology for the determination of normal background concentrations of contaminants in English soil. Science of The Total Environment, 454–455, 604- 618, http://www.sciencedirect.com/science/article/pii/S0048969713002878 http://www.sciencedirect.com/science/article/pii/S0048969713002878 Tarvainen, T. & Jarva, J., 2011. Using geochemical baselines in the assessment of soil contamination in Finland. Chapter 15 In: C.C. Johnson, A. Demetriades, J. Locutura & R.T. Ottesen (Editors), Mapping the Chemical Environment of Urban Areas. Wiley- Blackwell, Chichester, 223-231, doi: 10.1002/9780470670071.ch15

23. References SLIDE 18: Cave, M.R. & Ander, E.L., 2013. End of Project Report: Application of the Tellus Border soil chemistry data to the identification of sources of diffuse pollution in Ireland. Report by the British Geological Survey, Keyworth, Nottingham, 52 pp. (Available online shortly).