Abstract
The volatile monoterpene α-pinene has been measured in sediments of a selected area at “Carlos Anwandter” Nature Sanctuary, a Ramsar protected wetland located at the northwest of Valdivia City, south-central Chile. The ecosystem was seriously damaged by an uncontrolled liquid emission of a pulp mill (CELCO-Arauco) located about 15 km upstream of Rio Cruces during 2004. Exploratory data analysis was applied to analytical data collected from sediment samples, having found α-pinene as a reiterative chemical at relatively high concentrations in some specific areas of the wetland. The decrease of the total concentration of α-pinene in the area under study is coincident with a point contamination that occurred during 2004 (12,240 ng g−1) showing a decay in 2005 (7,890 ng g−1) and middle of 2006 (4,060 ng g−1). The following years, last 2006, 2008, and 2009, show a relatively constant concentration with a clear tendency toward baseline levels (2,460–2,640 ng g−1). Since the decrease of concentrations of α-pinene in sediments in the period 2004–2009 shows an opposite trend as compared to the surface area increase of pine and eucalyptus plantation in Region de Los Rios, and not having found potential sources of α-pinene by anthropogenic activities other than the pulp mill in the area under study, it may be finally concluded that this compound did not enter the bodies of water from a gradual and natural process; instead there is a base to sustain anthropogenic input. α-Pinene in sediments may be a plausible chemical tracer capable of detecting pollution events over time and its impacts in aquatic ecosystems as well as changes in aquatic ecosystems produced by improperly treated pulp mill liquid emissions that use pine and eucalyptus species.
Similar content being viewed by others
References
Abrahim, D., Braguini, W. L., Kelmer-Bracht, A. M., & Ishii-Iwamoto, E. L. (2000). Effects of four monoterpenes on germination, primary root growth and mitochondrial respiration of maize. Journal of Chemical Ecology, 26, 611–624.
Abrahim, D., Francischini, A. C., Pergo, E. M., Kelmer-Bracht, A. M., & Ishii-Iwamoto, E. L. (2003). Effects of α-pinene on the mitochondrial respiration of maize seedlings. Plant Physiology and Biochemistry, 41, 985–991.
Bero, B. N., Reiboldt, A., Davis, W., Bedard, N., & Russel, E. (2011). Low temperature fluidized wood chip drying with monoterpene analysis. European Journal of Wood and Wood Products, 69, 545–552.
Button, D. K., & Jüttner, F. (1989). Terpenes in Alaskan waters: concentrations, sources, and the microbial kinetics used in their prediction. Marine Chemistry, 26, 57–66.
CONAF (2008). Catastro del Uso de Suelo y Vegetación. Monitoreo y actualización Región de los Ríos. Corporación Nacional Forestal (CONAF), Recursos Forestales, Plantaciones, Chile. Available at www.Conaf.cl. (Accessed on Sept. 9, 2012).
CONAMA-UACH (2005) Estudio sobre origen de mortalidades y disminucion poblacional de aves acuáticas en el Santuario de la Naturaleza Carlos Anwandter, en la Provincia de Valdivia. Convenio Complementario Específico N° 1210-1203/2004-12-14. Final Report. Direccion Regional Conama Xª Region de los Lagos - Universidad Austral de Chile (2005 a), 146 pp. Available at: http://www.ceachile.cl. (Accessed on Aug. 29, 2013).
Copolovici, L. O., & Niinemets, Ü. (2005). Temperature dependencies of Henry’s law constants and octanol/water partition coefficients for key plant volatile monoterpenoids. Chemosphere, 61, 1390–1400.
Copolovici, L. O., & Niinemets, Ü. (2007). Salting-in and salting-out effects of ionic and neutral osmótica on limonene and linalool Henry’s law constants and octanol/water partition coefficients. Chemosphere, 69, 621–629.
Di Marzio, W. & McInnes (2005). Ramsar Advisory Mission: Chile . Mission report. Carlos Anwandter Sanctuary (Rio Cruces), Chile, March 29–April 4, 2005. Available at: http://otros.conaf.cl/modules/contents/files/unit0/file/e553addb784f7ea672ef86b3d39a4191.pdf. (Accessed on Sept. 25, 2012).
Environment Canada (2003). National assessment of pulp and paper environmental effects monitoring data: a report synopsis. National Water Research Institute, Burlington. NWRI Scientific Asssessment Series No. 2. 28 pp.
Gershenzon, J., & Dudareva, N. (2007). The function of terpene natural products in the natural world. Natural Chemistry and Biology, 3(7), 408–414.
Harding, L., Pretorius, J., & McGurk, M. (2007). Recent changes in the Rio Cruces: comment on Mulsow and Grandjean (2006). Ethics in Science and Environmental Politics, 2007, 1–3.
Hewitt, L. M., Pryce, A. C., Parrott, J. L., Marlatt, V., Wood, C., Oakes, K., & Van der Kraak, G. J. (2003). Accumulation of ligands for aryl hydrocarbon and sex steroid receptors in fish exposed to treated effluent from a bleached sulfite/groundwood pulp and paper mill. Environental Toxicology and Chemistry, 22(12), 2890–2897.
Hynynen, J., Palomäki, A., Merläinen, J., Witick, A., & Mántykoski, K. (2004). Pollution history and recovery of a boreal lake exposed to a heavy bleached pulping effluent load. Journal of Paleolimnology, 32, 351–374.
INFOR (2010). Superficie de Bosques Plantados por Especie y Región. Web site: http://www.infor.cl/archivos/series_estadisticas/Recurso_Forestal/recurso_forestal3.pdf. (Accessed on Sept. 9, 2012).
Johnson, G. (2002). State of the art report on multivariate chemometric methods in environmental forensics. Environmental Forensics, 3, 59–79.
Juuti, S., Arey, J., & Atkinson, R. (1990). Monoterpene emission rate measurements from a Monterey pine. Journal of Geophysical Research-Atmospheres, 95, 7515–7519.
Kukkola, J., Knuutinen, J., Paasivirta, J., Herve, S., Pessala, P., & Schultz, E. (2011). Size-exclusion chromatographic study of ECF and TCF softwood kraft pulp bleaching liquors. Environmental Science and Pollution Research, 18, 1049–1056.
Lacorte, S., Latorre, A., Barceló, D., Rigol, A., Malmqvist, A., & Welander, T. (2003). Organic compounds in paper-mill process waters and effluents. Trends in Analytical Chemistry, 22(10), 725–737.
López, D., Chamorro, S., Silva, J., Bay-Smith, E., & Vidal, G. (2011). Chronic effects of Pinus radiate and Eucaliptus globules Kraft mill effluents and phytosterols on Daphnia magna. Bulletin of Environmental Contamination and Toxicology, 87, 633–637.
McDonald, A. G., Dare, P. H., Gifford, J. S., Steward, D., & Riley, S. (2002). Assessment of air emissions from industrial kiln drying of Pinus radiata wood. Holzals Roh-Und Werkstoff, 60, 181–190.
McMaster, M. E., Parrott, J. L. & Hewitt, L.M. (2003). A decade of research on the environmental impacts of pulp and paper mill effluent in Canada (1992–2002). National Water Research Institute, Burlington. NWRI Scientific Assessment Report Series, 4, 84.
Mercier, B., Prost, J., & Prost, M. (2009). The essential oil of turpentine and its major volatile fraction (α- and β-pinenes): a review. International Journal of Occupational Medicine and Environmental Health, 22(4), 331–342.
Morrison, R. D. (2000). Critical review of environmental forensic techniques: part I. Environental Forensics, 1, 157–173.
Mulsow, S., & Grandjean, M. (2006). Incompatibility of sulphate compounds and soluble bicarbonate salts in the Rio Cruces waters: an answer to the disappearance of Egeria densa and black-necked swans in a RAMSAR sanctuary. Ethics in Science and Environmental Politics, 2006, 5–11.
Munkittrick, K. R., McMaster, M. E., Portt, C. B., Vanderkraak, G. J., Smith, I. R., & Dixon, D. G. (1992). Changes in maturity, plasma sex steroids levels, hepatic mixed-function oxygenase activity, and the presence of external lesions in lake whitefish (Coregonus clupeaformis) exposed to bleached kraft mill effluent. Canadian Journal of Fisheries and Aquatic Sciences, 49, 1560–1569.
Nishida, N., Tamotsu, S., Nagata, N., Saito, C., & Sakai, A. (2005). Allelopathic effects of volatile monoterpenoids produced by Salvia leucophylla: inhibition of cell proliferation and DNA synthesis in the root apical meristem of Brassica campestris seedlings. Journal of Chemical Ecology, 31, 1187–1203.
Oakes, K. D., McMaster, M. E., Pryce, A. C., Munkittrick, K. R., Portt, C. B., Hewitt, L. M., MacLean, D. D., & Van Der Kraak, G. J. (2003). Oxidative stress and bioindicators of reproductive function in pulp and paper mill effluent exposed white sucker. Toxicological Science, 74, 51–65.
Orrego, R., Guchardi, J., Hernandez, V., Krause, R., Roti, L., Armour, J., Ganeshakumar, M., & Holdway, D. (2009). Pulp and paper mill effluents treatments have differential endocrine-disrupting effects on rainbow trout. Environmental Toxicology and Chemistry, 28, 181–188.
Ramirez, C., Carrasco, E., Mariani, S. & Palacios N. (2006). Decay of Egeria densa (Luchecillo) on the nature sanctuary of the Cruces River (Valdivia, Chile): A Plausible Hypothesis. Ciencia & Trabajo, (Año 8), 20, 79–86.
Reinhardt, E. G., Nairn, R. B., & Lopez, G. (2010). Recovery estimates for the Río Cruces after the May 1960 Chilean earthquake. Marine Geology, 18, 18–33.
Rolon, A. S., & Rocha, O. (2011). Does pine occurrence influence the macrophyte assemblage in Southern Brazil ponds? Hydrobiologia, 675, 157–165.
Sacchetti, G., Maietti, S., Muzzoli, M., Scaglianti, M., Manfredini, S., Radice, M., & Bruni, R. (2005). Comparative evaluation of 11 essential oils of different origin as functional antioxidants, antiradicals and antimicrobials in foods. Food Chemistry, 91, 621–632.
Sibley, P. K., Legler, J., Dixon, D. G., & Barton, D. R. (1997). Environmental health assessment of the benthic habitat adjacent to a pulp mill discharge. I. Acute and chronic toxicity of sediments. Archives of Environmental Contamination and Toxicology, 32, 274–284.
Sibley, P. K., Dixon, D. G., & Barton, D. R. (1998). Environmental assessment of benthic impacts associated with pulp mill discharges. II. Distribution of sediment EOX in relation to environmental factors. Archives of Environmental Contamination and Toxicology, 34(2), 158–166.
Singh, H. P., Batish, D. R., Kaur, S., Arora, K., & Kohli, R. (2006). α-Pinene inhibits growth and induces oxidative stress in roots. Annals of Botany, 98, 1261–1269.
Soto-Gamboa, M., Lagos, N., Quiroz, E., Jaramillo, E., Nespolo, R., & Casanova-Katny, A. (2007). Causes of the disappearance of Egeria densa and black-necked swans in a RAMSAR sanctuary: comment on Mulsow and Grandjean (2006). Ethics in Science and Environmental Politics, 2007, 7–10.
Strömvall, A. M., & Petersson, G. (1993). Photooxidant-forming monoterpenes in air plumes from kraft pulp industries. Environental Pollution, 79, 219–223.
Taherpour, A., Maroofi, H., Changizi, M., Shoushtari, R. V., Larijani, K., & Kazempour, A. (2011). Chemical compositions of the essential oil and calculation the biophysicochemical coefficients of the components of Hymenocrater longiflorus Benth. of Iran. Natural Science, 3, 104–108.
Tambosi, J. L., Di Domenico, M., Schirmer, W. N., Jose, H., & Moreira, R. D. P. M. (2006). Treatment of paper and pulp wastewater and removal of odorous compounds by a Fenton-like process at the pilot scale. Journal of Chemical Technology and Biotechnology, 81, 1426–1432.
Thiel, L., & Hendricks, F. (2004). Study into the establishment of an aroma and fragrance fine chemicals value chain in South Africa (Tender Number T79/07/03). Final report. Part two/four. Report: aroma chemicals derived from effluent from the paper and pulp industry. Melrose Arch: Triumph Venture Capital. Available at: http://www.thedti.gov.za/industrial_development/docs/fridge/Aroma_Part2.pdf. (Accessed on Aug. 29, 2013).
U.S. EPA. (2001). Methods for collection, storage and manipulation of sediments for chemical and toxicological analyses: technical manual. EPA 823-B-01-002. Washington, D.C: U.S. Environmental Protection Agency, Office of Water.
U.S. EPA. (2002). Method 3570 (SW-846): microscale solvent extraction (MSE). Washington, D.C: U.S. Environmental Protection Agency. Available at: http://www.epa.gov/sam/pdfs/EPA-3570.pdf.
World Wide Fund for Nature (WWF) (2005). Findings and recommendations report. WWF international assessment mission for the Carlos Anwandter Nature Sanctuary and CELCO pulp mill controversy in Valdivia, Chile. November 2005, 24 pp. Available at: http://awsassets.panda.org/downloads/final_wwf_rio_cruces_report_english.pdf.
Zunino, M. P., & Zygadlo, J. A. (2004). Effect of monoterpenes on lipid oxidation in maize. Planta, 219, 303–309.
Acknowledgments
This work was supported by the Universidad Austral de Chile, project DID-2008-07. The financial support for this study is gratefully acknowledged. The authors of this study want to thank to Dr. Daisaku Ikeda, President of SGI, for his valuable support on the protection of the environment and human life.
Author information
Authors and Affiliations
Corresponding author
Rights and permissions
About this article
Cite this article
Palma-Fleming, H., Foitzick, M., Palma-Larrea, X. et al. The Fate of α-Pinene in Sediments of a Wetland Polluted by Bleached Pulp Mill Effluent: Is It a New Clue on the “Carlos Anwandter” Nature Sanctuary Wetland Case, Valdivia, South of Chile?. Water Air Soil Pollut 224, 1729 (2013). https://doi.org/10.1007/s11270-013-1729-4
Received:
Accepted:
Published:
DOI: https://doi.org/10.1007/s11270-013-1729-4