Anthropogenic influence on trace element geochemistry of healing mud (peloid) from Makirina Cove (Croatia)

Abstract

Due to their balneotherapeutic features, the organic-rich sediments in Makirina Cove are an important source of healing mud. An environmental geochemistry approach using normalization techniques was applied to evaluate the anthropogenic contribution of trace metals to sediments used as healing mud. Sediment geochemistry was found to be associated with land-use change and storm events, as well as with proximity of a road with heavy traffic in the summer months. Local valley topography preferentially channels lithogenic and pollutant transport to the cove. Concentrations and distribution of trace metals indicate lithogenic (Ni, Cr, Co) and anthropogenic (Pb, Cu, Zn and Se) contributions to the sediments. The calculation of enrichment factors indicates a moderate (EFs between 2–3.5) input of anthropogenic Cu and Pb in surficial sediments to a depth of 10 cm. Patients using the Makirina Cove sediments as healing mud could be to some extent exposed to enhanced uptake of metals from anthropogenic sources via dermal contact.

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References

  1. Aloupi M, Angelidis MO (2001) Geochemistry of natural and anthropogenic metals in the coastal sediments of the island of Lesvos, Aegean Sea. Environ Pollut 113(2):211–219

    Article  Google Scholar 

  2. Appelo CAJ, Postma D (1994) Geochemistry, groundwater and pollution. A.A. Balkema, Rotterdam, The Netherlands, p 536

  3. ASTM (1982) Standard test methods for plastic limit and plasticity index of soils (D424–459). Annual book of ASTM standards 19:123–126

    Google Scholar 

  4. Baudouin C, Charveron M, Tarroux R, Gall Y (2002) Environmental contaminants and skin cancer. Cell Biol Toxicol 18:41–48

    Article  Google Scholar 

  5. Beer AM, Fey S, Walch S, Luthgens K, Ostermann T, Lukanov J (2001) The effect of peat components on endocrine and immunological parameters and on trace elements: results of two pilot studies. Clin Lab 47(3–4):161–167

    Google Scholar 

  6. Beer AM, Junginger HE, Lukanov J, Sagorchev P (2003) Evaluation of the permeation of peat substances through human skin in vitro. Int J Pharm 253(1–2):169–175

    Article  Google Scholar 

  7. Belzile N, Chen Y-W, Xu R (2000) Early diagenetic behaviour of selenium in lake sediments. Appl Geochem 15:1439–1454

    Article  Google Scholar 

  8. Brun LA, Maillet J, Richarte J, Herrmann P, Remy JC (1998) Relationships between extractable copper, soil properties and copper uptake by wild plants in vineyard soils. Environ Pollut 102:151–161

    Article  Google Scholar 

  9. Carra S, Carcangiu G, Padalino G, Palomba M, Tamanini M (2000) The bentonites in pelotherapy: chemical, mineralogical and technological properties of materials from Sardinia deposits (Italy). Appl Clay Sci 16(1–2):117–124

    Article  Google Scholar 

  10. Carretero I.M (2002) Clay minerals and their beneficial effects upon human health. Appl Clay Sci 21(3–4):155–163

    Article  Google Scholar 

  11. Cattaneo A, Correggiari A, Langone L, Trincardi F (2003) The late-Holocene Gargano subaqueous delta, Adriatic shelf: sediment pathways and supply fluctuations. Mar Geol 193:61–91

    Article  Google Scholar 

  12. Combs GF, Gray WP (1998) Chemopreventive agents: selenium. Pharmacol ther 79:179–192

    Article  Google Scholar 

  13. Constant F, Guillemin F, Collin JF, Boulange M (1998) Use of spa therapy to improve the quality of life clearance low back pain patients. Med Care 36:1309–1314

    Article  Google Scholar 

  14. Cremaschi M (1990) Stratigraphy and paleoenvironmental significance of the loess deposits on Susak Island (Dalmatian Archipelago). Quat Int 5:97–106

    Article  Google Scholar 

  15. Crusius J, Thomson J (2003) Mobility of authigenic rhenium, silver and selenium during post-depositional oxidation in marine sediments. Geochimica et Cosmochimica Acta 67:265–273

    Article  Google Scholar 

  16. Cutter GA, Bruland KW, (1984) The marine biogeochemistry of selenium: a re-evaluation. Limnol Oceanogr 29:1179–92

    Article  Google Scholar 

  17. da Conceição Freitas M, Andrade C, Rocha F, (2003) Lateglacial and Holocene environmental changes in Portuguese coastal lagoons. 1: The sedimentological and geochemical records of the Santo André coastal area. The Holocene 13(3):433–446

    Article  Google Scholar 

  18. Davies CJ, Long M, Donald M, Ashbolt N, (1995) Survival of fecal microorganisms in marine and freshwater sediments. Appl Environ Microbiol 61:1888–1896

    Google Scholar 

  19. De Lazzari A, Rampazzo G, Pavoni B, (2004) Geochemistry of sediments in the northern and central Adiatic Sea. Estuar Coast Shelf Sci 59(3):429–440

    Article  Google Scholar 

  20. Desmarais TR, Solo-Gabriele HM, Palmer CJ (2002) Influence of soil on fecal indicator organisms in a tidally influenced subtropical environment. Appl Environ Microbiol 68:1165–1172

    Article  Google Scholar 

  21. Dolenec T, Faganeli J, Pirc S (1998) Major, minor and trace elements in surficial sediments from the open Adriatic Sea: a regional geochemical study. Geologia Croatica 51(1):59–73

    Google Scholar 

  22. Dolenec M, Lojen S, Ogrinc N, Lambaša Ž (2002) Environmentally controlled variations of δ18O and δ13C in mollusc shells from Makirina Bay, the Murter Sea and Pirovac Bay (Central Adriatic)”. RMZ-Mater Geoenviron 49(1):85–99

    Google Scholar 

  23. Dumestre A, Sauve S, McBride M, Baveye P, Berthelin J (1999) Copper speciation and microbial activity in long-term contaminated soils. Arch Environ Contam Toxicol 36:124–131

    Article  Google Scholar 

  24. Durn G, Ottner F, Slovenec D (1999) Mineralogical and geochemical indicators of the polygenetic nature of terra rossa in Istria, Croatia. Geoderma 91:125–150

    Article  Google Scholar 

  25. Elkayam O, Ophir J, Brener S, Paran D, Wigler I (2000) Immediate and delayed effects of treatment at the Dead Sea in patients with psoriatic arthritis. Rheumatol Int 19:77–82

    Article  Google Scholar 

  26. Ferguson JE (1990) The heavy metals: chemistry, environmental impact and health effects. Pergamon, New York, p 412

  27. Förstner U, Wittmann GTW (1981) Metal pollution in the aquatic environment. Springer, Heidelberg, p 486

  28. Frankenberger WT, Enberg RA (1998) Environmental chemistry of selenium. Marcel Dekker, New York, p 713

  29. Fritz F (1978) Hydrogeology of Ravni Kotari and Bukovica, Croatia. Carsus Iugoslaviae 10(1):1–43

    Google Scholar 

  30. Gallagher DL, Johnston KM, Dietrich AM (2001) Fate and transport of copper-based crop protectants in plasticulture runoff and the impact of sedimentation as a best management practice. Water Res 35:2984–2994

    Article  Google Scholar 

  31. Gladney ES, Burns CE (1984) Compilation of elemental concentration data for the USGS geochemical exploration reference samples GSR-1 to GSR-6. Geostand Newsl 8(2):119–154

    Article  Google Scholar 

  32. Golchert B, Landsberger S, Hopke PK (1991) Determination of heavy metals in the Rock River (Illinois) through the analysis of sediments. J Radioanal Nucl Chem Artic 148(2):319–337

    Article  Google Scholar 

  33. Halevy S, Giryes H, Friger M, Grossman N, Karpas Z, Sarov B (2001) The role of trace elements in psoriatic patients undergoing balneotherapy with Dead Sea bath salt. Isr Med Assoc J 11:828–832

    Google Scholar 

  34. Jonathan MP, Ram-Mohan V, Srinivasalu S (2004) Geochemical variations of major and trace elements in recent sediments, off the Gulf of Mannar, the southeast coast of India. Environ Geol 45(4):466–480

    Article  Google Scholar 

  35. Klenner MF, Weber G (1981) Hygienic problems at the winning of peloids (peats and sludges of lakes) for balneological therapy. Zentralblatt fur Bakteriologie Mikrobiologie und Hygiene [B] 173(5):327–337

    Google Scholar 

  36. Kneckt P (2000) Serum selenium, serum alpha-tocopherol, and the risk of rheumatoid arthritis. Epidemiology 11(4):402–405

    Article  Google Scholar 

  37. Konrad K, Tatrai T, Hunka A, Vereckei E, Korondi I (1992) Controlled trial of balneotherapy in treatment of low back pain. Ann Rheum Dis 51(6):820–822

    Google Scholar 

  38. Kuldvere A (1989) Extraction of geological material with mineral acids for the determination of arsenic, antimony, bismuth, and selenium by hydride generation atomic absorption spectrometry. Analyst 114(2):125–131

    Article  Google Scholar 

  39. Lewan MD (1986) Stable carbon isotopes of amorphous kerogens from Phanerozoic sedimentary rocks. Geochimica et Cosmochimica Acta 50:1583–1591

    Article  Google Scholar 

  40. Li YH (1981) Geochemical cycles of elements and human perturbation, Geochimica et Cosmochimica Acta 45:2073–2084

    Article  Google Scholar 

  41. Lojen S, Ogrinc N, Vreča P, Samarđija Z, Dolenec T, Mišić, M. (1997) Remineralization of sedimentary organic matter and fluxes of dissolved nutrients in Makirina bay (Croatia). Technical report, University of Ljubljana , Slovenia—«Rudjer Bošković Institute, Center of Marine Research, Zagreb, Croatia, p 24

  42. Mandić V, Novak R, Dürigl T, Čepelak R, (1969) Peloid sites in the Nin Lagoon: results of exploration and medical significance. JAZU, Radovi Instituta u Zadru 16–17:753–786 (in Croatian)

  43. Mandić V and Čepelak R(1989) Balneological expertise of peloids from Pirovac. Technical report, Department of Physical Medical Rehabilitation, Medical Faculty, University of Zagreb, p 22 (in Croatian)

  44. Matthai C, Birch GF, Bickford GP (2002) Anthropogenic trace metals in sediment and settling particulate matter on a high-energy continental shelf (Sydney, Australia). Mar Environ Res 54(2):99–127

    Article  Google Scholar 

  45. Matz H, Orion E, Wolf R (2003) Balneotherapy in dermatology. Dermatol Ther 16(2):132–140

    Article  Google Scholar 

  46. Mercone D, Thomson J, Croudace IW, Troelstra SR (1999) A coupled natural immobilisation mechanism for mercury and selenium in deep-sea sediments. Geochimica et Cosmochimica Acta (63):1481–1488

  47. Mihelčić G, Lojen S, Dolenec T, Kniewald G (2006) Trace metals conservation in Morinje Bay sediment: historical record of anthropogenic imissions into a shallow Adriatic bay. Croatica Chemica Acta 79(1):161–167

    Google Scholar 

  48. Miko S, Halamić J, Peh Z, Galović L (2001) Geochemical baseline mapping of soils developed on diverse bedrock from two regions in Croatia. Geol Croatica 54(1):53–118

    Google Scholar 

  49. Morgenstern H, Machtey I (1983) Serum zinc and copper levels in rheumatoid arthritis. Arthritis Rheum 26:933–934

    Article  Google Scholar 

  50. Nguyen M, Revel M, Dougados M (1997) Prolonged effects of 3-week therapy in a spa resort on lumbar spine, knee and hip osteoarthritis: follow-up after 6 months. A randomized controlled trial. Br J Rheumatol 36:77–81

    Article  Google Scholar 

  51. Nissenbaum A, Rullkötter J, Yechieli Y (2002) Are the curative properties of “Black mud” from the Dead sea due to the presence of bitumen (asphalt) or other types of organic matter? Environ Geochem Health 24:327–335

    Article  Google Scholar 

  52. Novak R (1981) Physical characteristics of peloids with special retrospection on mud of Adriatic shore and islands. Zdravstvo 11(2):66–74 (in Croatian)

    Google Scholar 

  53. Oldfield F, Asioli A, Accorsi CA, Mercuri AM, Juggins S, Langone L (2003) A high resolution late-Holocene palaeo environmental record from the central Adriatic Sea. Quater Sci Rev 22:319–342

    Article  Google Scholar 

  54. Oluić M, Bodrožić D, Mandić V, Novak R, Čepelak R (1984) Peloids of the Karin sea and its application in health protection. Pomorski zbornik 22:437–465 (in Croatian)

    Google Scholar 

  55. Poensin D, Carpentier PH, Fechoz C, Gasparini S, (2003) Effects of mud pack treatment on skin microcirculation. Joint Bone Spine 70:367–370

    Article  Google Scholar 

  56. Ridgway J, Shimmeild G (2002) Estuaries as repositories of historical contamination and their impact on shelf seas. Estuar Coast Shelf Sci 55:903–928

    Article  Google Scholar 

  57. Rowell DL (1995) Soil science: methods and applications. Longman Scientific and Technical, Singapore, p 350

  58. Shani J, Barak S, Levi D, Ram M, Schachner ER, Schlesinger T, (1985) Skin penetration of minerals in psoriatics and guinea pigs bathing in hypertonic salt solutions. Pharmacol Res Commun 17:501–512

    Article  Google Scholar 

  59. Shotyk W, Weiss D, Kramers JD (2001) Geochemistry of the peat bog at Etang de la Gruère, Jura Mountains, Switzerland, and its record of atmospheric Pb and lithogenic trace elements (Sc, Ti, Y, Zr, Hf and REE) since 12,370 14C yr BP. Geochimica et Cosmochimica Acta 65(14):2337–2360

    Article  Google Scholar 

  60. Shultz LG (1964) Quantitative interpretation of mineralogical composition from X-ray and chemical data for the Pierre Shale. US Geological Survey, professional papers, 391-C, p 31

  61. Sukenik S, Buskila D, Neumann L, Kleiner-Baumgarten A, (1992) Mud pack therapy in rheumatoid arthritis. Clin Rheumatol 11:243–247

    Article  Google Scholar 

  62. Sukenik S, Giryes H, Halevy S, Neumann L, Flusser D, Buskila D (1994) Treatment of psoriatic arthritis at the Dead Sea. J Rheumatol 21:1305–1309

    Google Scholar 

  63. Sukenik S (1996) Balneotherapy for rheumatic diseases at the Dead Sea area. Isr J Med Sci 32:16–19

    Google Scholar 

  64. Sukenik S, Baradin R, Codish S, Neumann L, Flusser D, Abu-Shakra D (2001) Balneotherapy at the Dead Sea area for patients with psoriatic arthritis and concomitant fibromyalgia. Isr Med Assoc J 3:147–150

    Google Scholar 

  65. Summa V, Tateo F (1999) Geochemistry of two peats suitable for medical uses and their behaviour during leaching. Appl Clay Sci 15:477–489

    Article  Google Scholar 

  66. Šparica M, Koch G, Belak M, Miko S, Šparica Miko M, Viličić D, Dolenec T, Bergant S, Lojen S, Vreča P, Dolenec M, Ogrinc N, Ibrahimpašić H (2005) Recent sediments of Makirina Bay (northern Dalmatia, Croatia): their origin viewed through a multidisciplinary approach. Geologia Croatica 58(1):21–71

    Google Scholar 

  67. Surić M, Juračić M, Horvatinčić H, Krajcar Bronić I (2005) Late Pleistocene–Holocene sea-level rise and the pattern of coastal karst inundation: records from submerged speleothems along the Eastern Adriatic Coast (Croatia). Mar Geol 214(1–3):163–175

    Google Scholar 

  68. Tarp U, Stengaard-Pedersen K, Hansen JC, Thorling EB (1992) Glutathione redox cycle enzymes and selenium in severe rheumatoid arthritis: lack of antioxidative response to selenium supplementation in polymorphonuclear leucocytes. Ann Rheum Dis 51:1044–1049

    Article  Google Scholar 

  69. Tishler M, Brotovski Y, Yaron M (1995) Effect of spa therapy in Tiberias on patients with ankylosing spondylitis. Clin Rheumatol 14:21–25

    Article  Google Scholar 

  70. Tyson RV (1995) Sedimentary organic matter. Organic facies and palynofacies. Chapman and Hall, p 615

  71. Van der Weijden CH (2002) Pitfalls of normalization of marine geochemical data using a common divisor. Mar Geol 184(3–4):167–187

    Article  Google Scholar 

  72. Vreča P, Dolenec T (2005) Geochemical estimation of copper contamination in the healing mud from Makirina Bay, central Adriatic. Environ Int 31(1):53–61

    Article  Google Scholar 

  73. Wang W, Fisher NS, Luoma SN (1996) Kinetic determinations of trace element bioaccumulation in the mussel Mytilus edulis. Mar Ecol Prog Ser 140:91–113

    Article  Google Scholar 

  74. Wigler I, Elkayam O, Paran D, Yaron M (1995) Spa therapy for gonarthrosis: a prospective study. Rheumatol Int 15:65–68

    Article  Google Scholar 

  75. Zehr JP, Oremland RS (1987) Reduction of selenate to selenide by sulphate-respiring bacteria: Experiments with cell suspensions and estuarine sediments. Appl Environ Microbiol 53:1365–1369

    Google Scholar 

  76. Zhang Y, Zahir ZA, Frankenberger WT Jr (2004) Fate of colloidal-particulate elemental selenium in aquatic systems. J Environ Qual 33(2):559–564

    Article  Google Scholar 

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Miko, S., Koch, G., Mesić, S. et al. Anthropogenic influence on trace element geochemistry of healing mud (peloid) from Makirina Cove (Croatia). Environ Geol 55, 517–537 (2008). https://doi.org/10.1007/s00254-007-0997-y

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Keywords

  • Healing mud
  • Balneotherapy
  • Geochemistry
  • Trace metals
  • Normalization
  • Enrichment factors
  • Pollution