Atmospheric Chemistry and Physics www.atmos-chem-phys.net 1680-7316 1680-7324 9 17 2009 10.5194/acp-9-6479-2009 http://www.atmos-chem-phys.net/9/6479/2009/ http://www.atmos-chem-phys.net/9/6479/2009/acp-9-6479-2009.html http://www.atmos-chem-phys.net/9/6479/2009/acp-9-6479-2009.pdf 6479 6494 2009-09-08 Distribution and sources of bioaccumulative air pollutants at Mezquital Valley, Mexico, as reflected by the atmospheric plant Tillandsia recurvata L. A. Zambrano García C. Medina Coyotzin A. Rojas Amaro D. López Veneroni L. Chang Martínez G. Sosa Iglesias Dirección Ejecutiva de Investigación y Posgrado, Instituto Mexicano del Petróleo, México D.F., Mexico Universidad Michoacana de San Nicolás de los Hidalgo, Morelia, Mexico Mezquital Valley (MV), a Mexican wastewater-based agricultural and industrial region, is a "hot spot" of regulated air pollutants emissions, but the concurrent unregulated ones, like hazardous metals and polycyclic aromatic hydrocarbons (PAH), remain undocumented. A biomonitoring survey with the epiphytic Tillandsia recurvata was conducted there to detect spatial patterns and potential sources of 20 airborne elements and 15 PAH. The natural δ13C and δ15N ratios of this plant helped in source identification. The regional mean concentration of most elements was two (Cr) to over 40 times (Ni, Pb, V) higher than reported for Tillandsia in other countries. Eleven elements, pyrene and chrysene had 18–214% higher mean concentration at the industrial south than at the agricultural north of MV. The total quantified PAH (mean, 572 ng g−1; range, 143–2568) were composed by medium (65%, phenanthrene to chrysene), low (28%, naphthalene to fluorene) and high molecular weight compounds (7%, Benzo(b)fluoranthene to indeno(1,2,3-cd)pyrene). The δ13C (mean, −14.6&permil;; range, −15.7&permil; to −13.7&permil;) was consistently lower than −15&permil; near the major petroleum combustion sources. The δ15N (mean, −3.0&permil;; range, −9.9&permil; to 3.3&permil;) varied from positive at agriculture/industrial areas to negative at rural sites. Factor analysis provided a five-factor solution for 74% of the data variance: 1) crustal rocks, 39.5% (Al, Ba, Cu, Fe, Sr, Ti); 2) soils, 11.3%, contrasting contributions from natural (Mg, Mn, Zn) and saline agriculture soils (Na); 3) cement production and fossil fuel combustion, 9.8% (Ca, Ni, V, chrysene, pyrene); 4) probable agricultural biomass burning, 8.1% (K and benzo(g,h,i)perylene), and 5) agriculture with wastewater, 5.2% (δ15N and P). These results indicated high deposition of bioaccumulative air pollutants at MV, especially at the industrial area. Since T. recurvata reflected the regional differences in exposition, it is recommended as a biomonitor for comparisons within and among countries where it is distributed: southern USA to Argentina. Aboal, J. R., Real, C., Fernández, J. A., and Carballeira, A.: Mapping the results of extensive surveys: the case of atmospheric biomonitoring and terrestrial mosses, Sci. Total Environ., 356, 256–274, 2006. Bairwise, A. J. G.: Role of nickel and vanadium in petroleum classification, Energ. Fuel., 4, 647–652, 1990. Benzig, D. H., Arditti, J., Nyman, L. P., Temple, P. J., and Adams, J. P.: Effects of ozone and sulfur dioxide on four bromeliads, Environ. Exp. Bot., 32(1), 25–29, 1992. Boutton, T. W.: Stable carbon isotope ratios of natural materials: II, Atmospheric, terrestrial, marine and freshwater environments, in: Carbon Isotope Techniques, edited by: Coleman, D. C. and Fry, B., 173–185, 1991. Branquinho, C., Gaio-Oliveira, G., Augusto, S., Pinho, P., Máguas, C., and Correia, O.: Biomonitoring spatial and temporal impact of atmospheric dust from a cement industry, Environ. Pollut., 151(2), 292–299, 2008. Brenninkmeijer, C. A. M., Janssen, C., Kaiser, J., Röckmann, T., Rhee, T. S., and Assonov, S. S.: Isotope effects in the chemistry of atmospheric trace compounds, Chem. Rev., 103, 5125–5161, 2003. Brighina, L., Papini, A., Mosti, S., Cornia, A., Bocchini, P., and Galleti, G.: The use of tropical bromeliads (\it Tillandsia spp.) for monitoring atmospheric pollution in the town of Florence, Italy, Rev. Biol. Trop., 50(2), 577–584, 2002. Bukata, A. R. and Kyser, T. K.: Carbon and nitrogen isotope variations in tree-rings as records of perturbations in regional carbon and nitrogen cycles, Environ. Sci. Technol., 41, 1331–1338, 2007. Cabrera Ruíz, R. B. E., Gordillo Martínez, A. J., and Cerón Beltrán, A.: Inventario de contaminación emitida a suelo, agua y aire en 14 municipios del Estado de Hidalgo, México, Rev. Int. Contam. Ambie., 19(4), 171–171, 2003. Castro, L. V. and Vazquez, F.: Fractionation and characterization of Mexican crude oils, Energ. Fuel., 23(3), 1603–1609, 2009. CEPAL-SEMARNAT: Evaluación de las externalidades ambientales de la generación termoeléctrica en México, http://www.semarnat.gob.mx/informacionambiental/Publicacion/ext.pdf, 2004. Cervantes-Medel, A. and Armienta, M. A.: Influence of faulting on groundwater quality in Valle del Mezquital, Mexico, Geofísica Internacional, 43(3), 477–493, 2004. Cifuentes, E., Blumenthal, U., Ruíz Palacios, G., Bennett, S., and Peasey, A.: Epidemiological panorama for the agricultural use of wastewater: The Mezquital Valley, Mexico, Salud P\'ublica México, 36, 3–9, 1994. Cole, M. L., Valiela, I., Kroeger, K. D., Tomansky, G. L., Cebrian, J., Wigand, C., McKinney, R. A., Grady, S. P., and Carvalho da Silva, M. H.: Assessment of a $\delta^15$N isotopic method to indicate anthropogenic eutrophication in aquatic ecosystems, J. Environ. Qual., 33, 124–132, 2004. Conti, M. E. and Cecchetti, G.: Biological monitoring: lichens as bioindicators of air pollution assessment – a review, Environ. Pollut., 114, 471–492, 2001. Coplen, T. B.: Discontinuance of SMOW and PDB, Nature, 375, 285~pp., 1995. Crayn, D. M., Winter, K., and Smith, J. A. C.: Multiple origins of crassulacean acid metabolism and the epiphytic habit in the Neotropical family Bromeliacea, PNAS, 101(10), 3703–3708, 2004. De Sousa Pereira, M., Heitmann, D., Reifenhäuser, W., Ornellas Meire, R., Silva Santos, L., Torres, J. P. M., Malm, O., and Körner, W.: Persistent organic pollutants in atmospheric deposition and biomonitoring with \textitTillandsia usneoides (L.) in an industrialized area in Rio de Janeiro state, southeast Brazil – Part II: PCB and PAH, Chemosphere, 67, 1736–1745, 2007. Downs, T. J., Cifuentes-García, E., and Buffet, I. M.: Risk screening for exposure to groundwater pollution in a wastewater irrigation district of the Mexico City region, Environ. Health Persp., 107(7), 553–561, 1999. EPA: Method 6010C. Inductively Coupled Plasma-Atomic Emission Spectrometry, Revision 3, 30~pp., 2000. Espinosa Pena, M., Manjarrez, A., and Campero, A.: Distribution of vanadyl porphyrins in a Mexican offshore heavy crude oil, Fuel Process. Technol., 46, 171–182, 1996. Figuereido, A. M., Nogueira, C. A., Saiki, M., Milian, F. M., and Domingos, N.: Assessment of atmospheric metallic pollution in the metropolitan region of São Paulo, Brazil, employing \textitTillandsia usneoides L. as biomonitor, Environ. Pollut., 145(1), 279–292, 2007. Friedel, J. K., Langer, T., Siebe, C, and Stahr, K.: Effects of long-term waste water irrigation on soil organic matter, soil microbial biomass and its activities in central Mexico, Biol. Fert. Soils, 31(5), 441–421, 2000. Flores-Delgadillo, L., Hernández-Silva, G., Alcalá-Martínez, R., and Maples-Vermeersch, M.: Total contents of cadmium, copper, manganese and zinc in agricultural soils irrigated with wastewater from Hidalgo, Mexico, Rev. Int. Contam. Ambie., 8(1), 37–46, 1992. Ganor, E., Altshuller, S., Foner, H. A., Brenner, S., and Gabay, J.: Vanadium and nickel in dustfall as indicators of power plant pollution, Water Air Soil Pollut., 42, 241–252, 1988. Gerdol, R., Bragazza, L., Marchesini, R., Medici, A., Pedrini, P., Benedetti, S., Bovolenta, A., and Coppi, S.: Use of moss (\textitTortula muralis Hedw.) for monitoring organic and inorganic air pollution in urban and rural sites in Northern Italy, Atmos. Environ., 36, 4069–4075, 2002. González-Méndez, B., Siebe, C., Fiedel, S., Hernández, J. M., and Ruíz-Suárez, L. G.: N2O emissions from soil irrigated with untreated wastewater in central Mexico, J. Soil Sci. Plant Nutr., 8(3), 185, 2008. Hernández-Silva, G., Flores-Delgadillo, L., Maples-Vermeersch, M., Solorio-Munguía, J. G., and Alcalá-Martínez, J. R.: Riesgo de acumulación de Cd, Pb, Cr y Co en tres series de suelos del DR03, Estado de Hidalgo, México, Revista Mexicana de Ciencias Geológicas, II(1), 53–61, 1994. Hietz, P. and Wanek, W.: Size-dependent variation of carbon and nitrogen isotope abundances in epiphytic bromeliads, Plant Biol., 5, 137–142, 2003. Hietz, P., Wanek, W., and Popp, M.: Stable isotopic composition of carbon and nitrogen and nitrogen content in vascular epiphytes along an altitudinal transect, Plant Cell Environ., 22, 1435–1443, 1999. Huerta, L., Contreras-Valadez, R., Palacios-Mayorga, S., Miranda, J., and Calva-Vasquez, G.: Total element composition of soils contaminated with wastewater irrigation by combining IBA techniques, Nucl. Instrum. Meth B, 189, 158–162, 2002. Husk, G. J., Weishampel, J. F., and Schlesinger.: Mineral dynamics in Spanish moss, \textitTillandsia usneoides L. (Bromeliacea), from Central Florida, USA, Sci. Total Environ., 321, 165–172, 2004. Hwang, H. M., Wade, T. L., and Sericano, J. L.: Concentrations and source characterization of polycyclic aromatic hydrocarbons in pine needles from Korea, Mexico, and United States, Atmos. Environ., 37, 2259–2267, 2003. Jimenez, B. and Chávez, A.: Quality assessment of an aquifer recharged with wastewater for its potential use as drinking source: "El Mezquital Valley" case, Water Sci. Technol., 50(2), 269–276, 2004. Jung, K., Gebauer, G., Gehre, M., Hoffmann, D., Weißflog, L., and Schüürmann, G.: Anthropogenic impacts on natural nitrogen isotope variations in \textitPinus sylvestris stands in an industrially polluted area, Environ. Pollut., 97(1-2), 175-181, 1997. Kelly, S. D., Stein, C., and Jickells, T. D.: Carbon and nitrogen isotopic analysis of atmospheric organic matter, Atmos. Environ., 39, 6007–6011, 2005. Krupa, S.: Effects of atmospheric ammonia (NH3) on terrestrial vegetation: a review, Environ. Pollut., 124, 179–221, 2003. Liu, X. Y., Xiao, H. Y., Liu, C. Q., Li, Y. Y., and Xiao, H. W.: Stable carbon and nitrogen isotopes of the moss \textitHaplocladium microphyllum in an urban and a background area (SW China): the role of environmental conditions and atmospheric nitrogen deposition, Atmos. Environ., 42, 5413-5423, 2008. Lozano, R. and Bernal, J. P.: Characterization of a new set of eight geochemical reference materials for XRF major and trace element analysis, Revista Mexicana de Ciencias Geológicas, 22(3), 329–344, 2005. Lucho-Constantino, C. A., Álvarez-Suárez, M., Beltrán-Hernández, R. I., Prieto-García, F., and Poggi-Varaldo, H. M.: A multivariate analysis of the accumulation and fractionation of major and trace elements in agricultural soils in Hidalgo State, Mexico irrigated with raw wastewater, Environ. Int., 31(3), 313–323, 2005. Macko, S. A. and Parker, P. L.: Stable nitrogen and carbon isotope ratios of beach tars on South Texas Barrier Islands, Mar. Environm. Res., 10, 93–103, 1983. Malm, O., de Freitas Fonseca, M., Hissnauer Miguel, P., Rodríguez Bastos, W., and Neves Pinto, F.: Use of epiphyte plants as biomonitors to map atmospheric mercury in a gold trade center city. Amazon, Brazil, Sci. Total Environ., 213(1–3), 57–64, 1998. Mariotti, A.: Natural N-15 abundance measurements and atmospheric nitrogen Standard calibration, Nature, 311, 685–687, 1974. Martin, C. E.: Physiological ecology of the Bromeliaceae, Bot. Rev., 60(1), 1–82, 1994. Norra, S., Handley, L. L., Berner, Z., and Stüben, D.: $^13$C and $^15$N natural abundances of urban soils and herbaceous vegetation in Karlsruhe, Germany, Eur. J. Soil Sci., 56(5), 607–620, 2005. Ortega-Larrocea, M. P., Siebe, C., Bécard, G., Méndez, I., and Webster, R.: Impact of a century of wastewater irrigation on the abundance of arbuscular mycorrhizal spores in the soil of the Mezquital Valley of Mexico, Appl. Soil Ecol., 16(2), 149–157, 2001. Pardo, L. H., McNulty, S. G., Bogs, J. L., and Duke, S.: Regional patterns in foliar $^15$N across a gradient of nitrogen deposition in the northeastern US, Environ. Pollut., 149, 293–302, 2007. Pearson, J., Wells, D. M., Seller, K. J., Bennett, A., Soares, A., Woodall, J., and Ingrouille, M. J.: Traffic exposure increases natural $^15$N and heavy metal concentrations in mosses, New Phytol., 147(2), 317–326, 2002. Pichlmayer, F., Schöner, W., Seibert, P., Stichler, W., and Wagenbach, D.: Stable isotope analysis for characterization of pollutants at high elevation alpine sites, Atmos. Environ., 32(23), 4075–4085, 1998. Pierce, S., Winter, K., and Griffiths, H.: Carbon isotope ratio and the extent of daily CAM use by Bromeliaceae, New Phytol., 156, 75-83, 2002. Pignata, M. L., Gudiño, G. L., Wannaz, E. D., Plá, R. R., González, C. M., Carreras, H. A., and Orellana, L.: Atmospheric quality and distribution of heavy metals in Argentina employing \textitTillandsia capillaris as a biomonitor, Environ. Pollut., 129, 59–68, 2002. Pirintsos, S. A. and Loppi, S.: Biomonitoring atmospheric pollution: the challenge of times in environmental policy on air quality, Environ. Pollut. 151(2), 269–271, 2008. Prinzhofer, A., Vega, M. A. G., Battani, A., and Escudero, M.: Gas geochemistry of the Macuspana Basin (Mexico): thermogenic accumulations in sediments impregnated by bacterial gas, Mar. Petrol. Geol., 17, 1029–1040, 2000. Puente, M. E. and Bashan, Y.: The desert epiphyte \textitTillandsia recurvata harbours the nitrogen-fixing bacterium \textitPseudomonas stutzeri, Can. J. Bot., 72, 406–408, 1994. Pyatt, F. B., Grattan, J. P., Lacy, D., Pyatt, A. J., and Seward, M. R. D.: Comparative effectiveness of \textitTillandsia usneoides L. and \textitParmotrema praesorediosum (Nyl.) Hale as bio-indicators of atmospheric pollution in Louisiana (U.S.A.), Wate Air Soil Poll., 111, 317–326, 1999. Rossini Oliva, S. and Raitio, H.: Review of cleaning techniques and their effects on the chemical composition of foliar samples, Boreal Environ. Res., 8, 263–272, 2003. Schmitt, A. K., Martin, C. E., and Lüttge, U. E.: Gas exchange and water vapor uptake in the atmospheric bromeliad \textitTillandsia recurvata L, Bot. Acta, 102, 80–84, 1989. Schrimpff, E.: Air pollution patters in two cities of Colombia according to trace substances contents of an epiphyte \textitTillandsia recurvata, Water Air Soil Poll., 21(1–4), 279–316, 1984. Segala, E. A., Baêsso, B. M., and Domingos, M.: Structural analysis of \it Tillandsia \it usneoides L. exposed to air pollutants in São Paulo city-Brazil, Water Air Soil Poll., 189, 61–68, 2008. SEMARNAT-INE.: Inventario Nacional de Emisiones de México, 1999, Secretaría del Medio Ambiente y Recursos Naturales/Instituto Nacional de Ecología, México, D F., 409~pp., 2006. Siebe, C.: Acumulación y disponibilidad de metales pesados en suelos regados con aguas residuales en el distrito de riego 03, Tula, Hidalgo, México, Revista Internacional de Contaminación Ambiental, 10(1), 15–21, 1994. Siebe, C.: Nutrient inputs to soils and their uptake by alfalfa through long-term irrigation with untreated sewage effluent in Mexico, Soil Use Manage., 14, 119–122, 1998. Siebe, C., and Cifuentes, E.: Environmental impact of wastewater irrigation in central Mexico: an overview, Int. J. Environ. Heal. R., 5, 161–173, 1995. Silva-Mora, L.: Geología volcánica y carácter químico preliminar de las rocas de la regón Tula-Polotitlán, Estados de Hidalgo, México y Querétaro, México, Revista Mexicana de Ciencias Geológicas, 14(1), 50–77, 1997. Skinner, R. A., Ineson, P., Jones, H., Sleep, D., Leith, I. D., and Sheppard, L. J.: Heathland vegetation as a bio-monitor for nitrogen deposition and source attribution using $\delta ^15$N values, Atmos. Environ., 40, 498–507, 2006. Sloof, J. E.: Lichens as quantitative biomonitors for atmospheric trace element deposition, using transplants, Atmos. Environ., 29(1), 11–20, 1995. SMA.: Gestión Ambiental del Aire en el Distrito Federal: Avances y Propuestas, 2000–2006, Secretaría del Medio Ambiente, Gobierno del Distrito Federal, México, 2006. Smodiš, B., Pignata, M. L., Saiki, M., Cortés, E., Bangfa, N., Markert, B., Nyarko, B., Arunachalam, J., Garty, J., Vutchkov, N., Wolterbeek, H. Th., Steinnes, E., Freitas, M. C., Lucaciu, A., and Frontasyeva, M.: Validation and application of plants as biomonitors of trace atmospheric pollution- a co-ordinated effort in 14 countries, J. Atmos. Chem., 49, 3–13, 2004. Solga, A., Burkhardt, J., Zechmeister, H. G., and Frahm, J. P.: Nitrogen content, $^15$N abundance and biomass of the two pleurocarpous mosses \textitPleurozium schreberi (Brid.) Mitt. and \textitScleropodium purum (Hedw.) Limpr. in relation to atmospheric nitrogen deposition, Environ. Pollut., 134, 465–473, 2005. Solga, A., Eichert, T., and Frahm, J. P.: Historical alteration in the nitrogen concentration and $^15$N natural abundance of mosses in Germany: indication for regionally varying changes in atmospheric nitrogen deposition within the last 140 years, Atmos. Environ., 40, 8044–8055, 2006. St Clair, S. B., St. Clair, L. L., Mangelson, N. F., and Weber, D. J.: Influence of growth form on the accumulation of airborne copper by lichens, Atmos. Environ., 36, 5637–5644, 2002. Surendra, P. V.: Geochemical and Sr-Nd-Pb isotopic evidence for a combined assimilation and fraccional crystallisation process for volcanic rocks from the Huichapan caldera, Hidalgo, Mexico, Lithos, 56(2–3), 141–164, 2001. Vázquez-Alarcón, A., Justin-Cajuste, L., Siebe-Grabach, C., Alcántar-González, G., and de la Isla de Bauer, M. L.: Cadmio, niquel y plomo en agua residual, suelo y cultivos en el Valle del Mezquital, Hidalgo, México, Agrociencia, 35, 267–274, 2001. Wannaz, E. D. and Pignata, M. L.: Calibration of four species of \it Tillandsia as biomonitors, J. Atmos. Chem., 53(3), 185–209, 2006a. Wannaz, D. E., Carreras, H. A., Pérez, C. A., and Pignata, M. L.: Assessment of metal accumulation in two species of \it Tillandsia in relation to atmospheric sources in Argentina, Sci. Total Environ., 361, 267–278, 2006b. Wigand, C., McKinney, R. A., Cole, M. L., Thursby, G. B., and Cummings, J.: Varying stable nitrogen isotope ratios of different coastal marsh plants and their relationships with wastewater nitrogen and land use in New England, USA, Environ. Monit. Assess., 131, 71–81, 2007. Wolterbeek, H. Th.: Biomonitoring of trace element air pollution: principles, possibilities and perspectives, Environ. Pollut., 120, 11–21, 2002. Wolterbeek, H. Th., Bode, P., and Verburg, T. G.: Assessing the quality of biomonitoring via signal-to-noise ratio analysis, Sci. Total Environ., 180, 107–116, 1996.