GEMAS – soil, geology and health implications “All substances are poisons; there is none which is not a poison. The right dose differentiates a poison and a remedy” Paracelsus ( ) Anna Ladenberger (Source:

Rocks and minerals → food, water, air → human body; Soil is a direct source of nutrients, micro-elements and macro-elements – so called mineral elements; Geochemical mapping: detection of geochemical anomalies and establishing natural background level, at continental and regional scale; GEMAS results can be used to elaborate the relationship between natural geological factors and health in humans and animals; GEMAS results improve the understanding of the influence of ordinary environmental factors on the geographical distribution of health problems; GEMAS results can be used in environmental medicine, environmental geochemistry, medical geology, etc. Soil composition and health implications:

Macronutrients e.g., Ca, Fe, K, Mg, P, S (required in large amounts in diet) Micronutrients e.g., B, Cu, Co, Cr, F, I, Li, Mn, Mo, Ni, Se, V, Zn Examples of toxic elements: As, Be, Cr, Cd, Hg, Pb, Tl (Source:

bone and membrane structure (Ca) water and electrolyte balance (Na, K, Cl) metabolic catalysis (Zn, Cu, Se, Mg, Mo) oxygen binding and transport (Fe) hormone effects (I, Cr) Sixteen trace elements are established as being essential for good health

MICRONUTRIENTS ( B, Cu, Co, Cr, F, I, Li, Mn, Mo, Ni, Se, V, Zn ) NON-ESSENTIAL (As, Be, Cd, Pb, Sb, Sn, Ti) PATTERNS OF INFLUENCE OF THE ELEMENTS assimilation increase MACRONUTRIENTS ( Ca, Fe, K, Mg, P, S ) deficit good no difference deficit good toxic lethal tolerable toxic lethal (From Siegel, 2002)

Element (bio)availability Soil varies widely in concentrations of macro- and micro- (trace) elements, even without human induced environmental contamination and agriculture. Soil (or sediment) horizons can have high concentrations of: Ions released from weathering; Ions introduced as fertilisers (P, K, S); Environmental pollutants (heavy metals, etc.). High concentrations do not mean that the element is ’available’!

250 mg/kg 60 mg/kg 10 mg/kg (From Reimann et al., 2014, Fig , p.463) (From Reimann et al., 2014, Fig , p.462) Zinc (Zn) is an essential micronutrient Zinc deficiency is widespread in soil Nearly 50% of the soil on which cereals are grown have levels of available Zn low enough to cause Zn deficiency The median in Ap soil is 45 mg/kg with a typical range from 10 to 200 mg/kg. (Alloway, 2008) Zinc (Map of Zinc deficiency in World crops From Alloway, 2008, Fig. 6.5, p.109)

Zinc essential for over 300 enzymes antioxidant Symptoms of Zn deficiency include: poor plant growth loss of appetite (anorexia) decreased immune function Zinc (From Reimann et al., 2014, Fig , p.465)(From Mann et al., 2014, Fig , p.219)

Once identified, zinc-deficient soil can be easily treated with fertilisers containing zinc to provide an adequate supply of zinc to crops! Zinc (Source: )

Arsenic 10 mg/kg toxicity: arsine gas > inorganic (As 3+ ) > organic (As 3+ ) > inorganic (As 5+ ) > organic (As 5+ ) > As 0 up to 60% of arsenic in soil can be bioavailable! keratosis, skin lesions cancerogenic (skin, lungs, bladder, kidney, liver) (From Reimann et al., 2014, Fig , p.149) (From Reimann et al., 2014, Fig , p.150)(From: Centeno & Finkelman, 2007, Photo 2b, p.64)

Cornwall, UK, up to 2% As in soil Lazio region, high As in groundwater (25-80 µg per l), used for crop irrigation Massif Central, high As in soil (young volcanism, Au, Pb-Zn deposits) Arsenic (From Reimann et al., 2014, Fig , p.152) (From Reimann et al., 2014, Fig , p.153) (From Reimann et al., 2014, map on DVD)

Environmental and health problems? Black shale - Natural source of As ( black shale is often enriched in trace elements, such as arsenic, cadmium; some are essential, others are not) Skellefte mining district - High As in soil and groundwater On the local scale (From Ladenberger et al., 2013, p.18)

To summarise….. GEMAS data can be applied to soil quality assessment GEMAS data show the geographical distribution of potential hazard areas at the continental scale GEMAS data highlight the potential links between soil chemistry and health issues GEMAS data can be used for risk characterisation and identification of areas prone to element deficiency

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Geological impacts on nutrition Geological sources of nutrients: silicates (Mn, Se), sulphides (Zn, Se, Cu, Mo), native (Fe), carbonates (Ca, Mg) Mineral elements cannot be derived from the biosynthesis of food plants or animals – they must be obtained from soils and pass through food systems to humans in food forms Anthropogenic sources of metals in soil: Mineral extraction and processing, smelting and refining of mineral ores Power generation – fossil fuel (coal combustion & coal waste), nuclear, geothermal Metallurgical and chemical industries, brick, pipe, cement manufactures, ceramics, glass industry, plastics, paint, fertiliser manufacture Waste disposal (municipal refuse, leachate from landfill sites, fly ash, sewage sludge, nuclear waste) Agriculture (fertilisers, nitrates in ground water, DDT, pesticides, irrigation practices, crop burning) Transportation (auto emissions, atmosphere contamination, mostly by CO 2, pollution by Pb, Mn, Ni, V, Cd, Cu, PGE) Supplementary material

Dietary sources of essential elements Soil as a source of mineral elements; Mineral elements are metabolized and stored by plants and animals, e.g., seafood is the best source of I, Cl, meat is the best source of Fe, protein-rich foods are the best source of Zn, Cu, Se; The best diet – optimal mineral nutrition – mixed diet based on diverse selection of foods; Fortified foods and nutritional supplements is a common practice. Essential elements in plants are crucial for: optimal crop development healthy crop strong crop high nutritional properties Essential elements crucial for humans and animals healthy life!!! (Source: files/15403/fccb090b21b8e f3470a.jpg)

(Source: Mercury - elemental (Hg 0 ) - inorganic (mercurous, Hg 1+ or mercuric, Hg 2+ ) - organic (methyl-, ethyl-, or phenylmercury) Allowed limit according to Natural Protection Agency Background (From Ottesen et al., 2014, Fig. 4, p.4) Residential SGV

Hg: in food (fish); exposure from dental amalgam fillings; disinfectant, antibacterial, antiparasitic; crop fungicide (methyl mercury); vaccine preservative, nasal spray. Health effects: neurobehavioral disorders; severe mental retardation; coma; pneumonitis, respiratory failure; kidney failure; acrodynia (painful extremities, apathy, pink colour, photofobia). Mercury (Source:

(From Reimann et al., 2014, Fig , p.264) (From Ottesen et al., 2013, Fig. 6, p.8) (From Reimann et al., 2014, Fig , p.267) (From Ottesen et al., 2013, Fig. 8, p.10, based on data from Wheeler & Ummel, 2008) (Source:

mobile under oxidising alkaline conditions (pH>7.5) binds to organic matter immobile under reducing conditions immobile under low pH – forms complexes with Fe oxides dietary source of Se: mushroom, garlic, sea food, liver and kidneys, fish, flour, whole-grain products Essential element (enzymes, antioxidant) Anticancer activity Narrow range between dietary deficiency (<40 µg per day) and toxicity (>400 µg per day) Selenium 0.4 mg/kg 0.6 mg/kg (From Reimann et al., 2014, Fig , p.389)

High in Se: black shale, phosphatic rocks, sulphides, coal, humus rich soil in coastal regions, volcanic ashes (tuffs), fine-grained sediments Anthropogenic Se: burning fossil fuels, smelting, sewage sludge, manure, pesticide, phosphate fertilisers, photocopier, anti-fungal pharmaceuticals, lubricating oils, ink Se toxicity in drinking water (Reggio) Selenosis in Limerick (cattle, horses) Selenium (From Reimann et al., 2014, Fig , p.391)(From Reimann et al., 2014, map on DVD)

Se deficiency: common in Sweden, Finland, Denmark heart disease (Keshan disease) bone and joint disease, rheumatics poor growth and development weak immune respond Se toxicity: Se excess causes hair loss, nerve and liver damage, caries, garlic smell of breath, blue staining of nails; Population can adapt to high selenium intake without showing major clinical symptoms. Selenium (Photo courtesy: Gerald F. Combs, USDA)

Element (bio)availability Low availability of elements to plants can be the result of: Primary deficiency in soil; High degree of sorption; Antagonistic effects between two or more elements (e.g., Mo and Cu). Adsorption (retention) of anions and cations is enhanced by the presence of: Certain clay minerals (e.g., soil with parent material of sandstone often has low concentrations of essential trace elements due to inherent chemical composition and low adsorptive capacity because of low clay content); Hydrous oxides of iron, manganese and aluminum. pH exerts a major control over bioavailability!

 Natural occurrence is common in water and soil  Primary uses in agriculture, forestry, animal husbandry, wood preservation, pigments, semiconductor industry (arsine gas)  Inorganic arsenical compounds are of greatest concern Risk areas: arid areas – evaporative concentrations; zones of mineralisation – oxidation of sulphide minerals may lead to the release of substantial quantities of arsenic and other heavy metals; large alluvial and delta plains (e.g., Danube Basin), inland basins, geologically young aquifers. Arsenic References

SLIDE 5 Siegel, F.R., Environmental geochemistriy of potentially toxic metals. Springer-Verlag, Berlin, 218 pp. SLIDES 7, 8, 10, 11, 19, 20, 21 Reimann, C., Demetriades, A., Birke, M., Filzmoser P., O ’ Connor, P., Halamic, J., Ladenberger, A. & the GEMAS Project Team, Distribution of elements/parameters in agricultural and grazing land soil of Europe. Chapter 11 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 103), Schweizerbarth, Alloway, B.J., Zinc in soils and crop nutrition. IZA Publication, International Zinc Association, Brussels, 139 pp. SLIDE 8 Mann, A., Reimann, C., Caritat, P. de & Turner, N., Mobile metal ion analysis of European agricultural soil. Chapter 13 In: C. Reimann, M. Birke, A. Demetriades, P. Filzmoser & P. O ’ Connor (Editors), Chemistry of Europe's agricultural soils – Part B: General background information and further analysis of the GEMAS data set. Geologisches Jahrbuch (Reihe B 103), Schweizerbarth, SLIDE 10 Centeno, J.A. & Finkelman, R.B., Global impacts of geogenic arsenic – A medical geology perspective. BRGM, G é osciences No. 5, , SLIDE 12 Ladenberger, A., Andersson, M., Reimann, C., Tarvainen, T., Filzmoser, P., Uhlb ä ck, J., Morris, G. & Sadeghi, M., Geochemical mapping of agricultural soils and grazing land (GEMAS) in Norway, Finland and Sweden – regional report. Geological Survey of Sweden, SGU-rapport 2012:17, 160 pp., SLIDES 17, 19 Ottesen, R.T., Birke, M., Finne, T.E., Gosar, M., Locutura, J., Reimann, C., Tarvainen, T., The GEMAS Project Team, Mercury in European agricultural and grazing land soils. Applied Geochemistry, 33, 1 – SLIDE 19 Wheeler, D. & Ummel, K., Calculating CARMA: Global estimations of CO 2 emissions from the power sector. Centre for Global Development Working Paper Number 145, 37 pp. References