Free Standard AU & NZ Shipping For All Book Orders Over $80!
Register      Login
Environmental Chemistry Environmental Chemistry Society
Environmental problems - Chemical approaches
Shopping Cart: ( empty )
You are here: Home > Journals > EN > EN14208
RESEARCH ARTICLE
Contents Vol 12(4)

Seasonal changes in chlorine and methoxyl content of leaves of deciduous trees and their impact on release of chloromethane and methanol at elevated temperatures

W. Colin McRoberts A D , Frank Keppler B , David B. Harper C and John T. G. Hamilton C
+ Author Affiliations
- Author Affiliations

A Food Science Branch, Sustainable Agri-Food Sciences Division, Agri-Food and Biosciences Institute, Newforge Lane, Belfast BT9 5PX, UK.

B Institute of Earth Sciences, Im Neuenheimer Feld 234-236, D-69120 Heidelberg, Germany.

C School of Biological Sciences, Queen’s University Belfast, 97 Lisburn Road, Belfast BT9 7BL, UK.

D Corresponding author. Email: colin.mcroberts@afbini.gov.uk

Environmental Chemistry 12(4) 426-437 https://doi.org/10.1071/EN14208
Submitted: 1 October 2014  Accepted: 3 April 2015   Published: 1 July 2015

Environmental context. Chloromethane is the most abundant naturally produced chlorine-containing organic compound, responsible for ~16 % of chlorine-catalysed stratospheric ozone destruction. A significant source of this gas is emission from biomass by reaction between chloride ion and methoxyl groups of the biopolymers pectin and lignin. The seasonal changes in the chlorine and methoxyl pools observed in leaves of several deciduous tree species have implications for understanding chlorine volatilisation during biomass burning and estimation of the global chloromethane budget.

Abstract. Atmospheric chloromethane (CH3Cl) plays a role in the destruction of stratospheric ozone. Previous studies suggest an important source of this gas is emission from leaves and leaf litter at ambient and elevated (150–350 °C) temperatures. In this study, the total chlorine and OCH3 content of leaves of the deciduous temperate tree species ash, beech, Norway maple and oak were measured throughout the 2004 and 2005 growing seasons. The total chlorine content increased with leaf age. The overall seasonal accumulation varied between five- and twenty-one fold, dependent on both year and species. Throughout the 2004 growing season, the OCH3 pool and the release of CH3Cl and methanol (CH3OH) from leaves of ash and Norway maple were monitored on heating to 350 °C. The amounts of CH3Cl released increased linearly as leaf chlorine accumulated whereas emissions of CH3OH did not substantially change. Conversion of chlorine to CH3Cl was lower in the spring than during the summer and autumnal senescence period, ranging from 22 to 58 %. No correlation was found between leaf OCH3 content and either CH3Cl or CH3OH release. The percentage conversion of OCH3 to the summed concentrations of CH3OH and CH3Cl ranged from 41 to 66 %. The plant components pectin and lignin were identified as two major sources of the CH3 group in CH3Cl and CH3OH and emissions ceased when the OCH3 pool contributing the methyl moiety was exhausted (>350 °C). These findings have implications for estimation of CH3Cl release during biomass burning and for our understanding of chlorine volatilisation during energy production from biomass.


References

[1]  S. A. Montzka, S. Reimann, Scientific assessment of ozone depletion: 2010, in Global Ozone Research and Monitoring Project – Report 52 2011, Ch. 1 (World Meteorological Organization: Geneva).

[2]  R. C. Rhew, B. R. Miller, R. F. Weiss, Natural methyl bromide and methyl chloride emissions from coastal salt marshes. Nature 2000, 403, 292.
| Natural methyl bromide and methyl chloride emissions from coastal salt marshes.Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DC%2BD3cXns1Chsg%3D%3D&md5=71a507101c661b0ddf5b379fb1d47bf0CAS | 10659844PubMed |

[3]  Y. Yokouchi, M. Ikeda, Y. Inuzuka, T. Yukawa, Strong emission of methyl chloride from tropical plants. Nature 2002, 416, 163.
| Strong emission of methyl chloride from tropical plants.Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DC%2BD38XisFShtLk%3D&md5=5abe234f0664972972b0fbeb9801bb54CAS | 11894090PubMed |

[4]  Y. Yoshida, Y. H. Wang, T. Zeng, R. Yantosca, A three-dimensional global model study of atmospheric methyl chloride budget and distributions. J. Geophys. Res. Atmos. 2004, 109, D24309.
| A three-dimensional global model study of atmospheric methyl chloride budget and distributions.Crossref | GoogleScholarGoogle Scholar |

[5]  S. Gebhardt, A. Colomb, R. Hofmann, J. Williams, J. Lelieveld, Halogenated organic species over the tropical South American rainforest. Atmos. Chem. Phys. 2008, 8, 3185.
| Halogenated organic species over the tropical South American rainforest.Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DC%2BD1cXhtVakurrO&md5=21e8b1d46952f9333ded6fee30e28a2bCAS |

[6]  E. Blei, C. J. Hardacre, G. P. Mills, K. V. Heal, M. R. Heal, Identification and quantification of methyl halide sources in a lowland tropical rainforest. Atmos. Environ. 2010, 44, 1005.
| Identification and quantification of methyl halide sources in a lowland tropical rainforest.Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DC%2BC3cXhs1Sku7c%3D&md5=9caa52c62e5139375461b838dab7e9b2CAS |

[7]  J. T. G. Hamilton, W. C. McRoberts, F. Keppler, R. M. Kalin, D. B. Harper, Chloride methylation by plant pectin: an efficient environmentally significant process. Science 2003, 301, 206.
| Chloride methylation by plant pectin: an efficient environmentally significant process.Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DC%2BD3sXlsF2gu7o%3D&md5=4a6b499255506015754ba9d67131a150CAS |

[8]  F. Keppler, D. B. Harper, T. Rockmann, R. M. Moore, J. T. G. Hamilton, New insight into the atmospheric chloromethane budget gained using stable carbon isotope ratios. Atmos. Chem. Phys. 2005, 5, 2403.
| New insight into the atmospheric chloromethane budget gained using stable carbon isotope ratios.Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DC%2BD2MXht1Kgs7rM&md5=69b9b7a8984e8a5964cd3a15e1365070CAS |

[9]  E. Blei, M. R. Heal, Methyl bromide and methyl chloride fluxes from temperate forest litter. Atmos. Environ. 2011, 45, 1543.
| Methyl bromide and methyl chloride fluxes from temperate forest litter.Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DC%2BC3MXhvVahsr8%3D&md5=ca7d4dddb831e7b0781db1ff87db0502CAS |

[10]  L. Derendorp, A. Wishkerman, F. Keppler, C. McRoberts, R. Holzinger, T. Rockmann, Methyl chloride emissions from halophyte leaf litter: dependence on temperature and chloride content. Chemosphere 2012, 87, 483.
| Methyl chloride emissions from halophyte leaf litter: dependence on temperature and chloride content.Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DC%2BC38XjsFGjtLo%3D&md5=b4773f721c82416bf5d76e6f23f06d26CAS | 22225707PubMed |

[11]  F. Keppler, R. M. Kalin, D. B. Harper, W. C. McRoberts, J. T. G. Hamilton, Carbon isotope anomaly in the major plant C-1 pool and its global biogeochemical implications. Biogeosciences 2004, 1, 123.
| Carbon isotope anomaly in the major plant C-1 pool and its global biogeochemical implications.Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DC%2BD2MXpsFWgu7s%3D&md5=03e7c9a79caea587950477d284914d56CAS |

[12]  A. Wishkerman, S. Gebhardt, C. W. McRoberts, J. T. G. Hamilton, J. Williams, F. Keppler, Abiotic methyl bromide formation from vegetation, and its strong dependence on temperature. Environ. Sci. Technol. 2008, 42, 6837.
| Abiotic methyl bromide formation from vegetation, and its strong dependence on temperature.Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DC%2BD1cXpslOhtLk%3D&md5=1b0a8e7cbb72141fa84c79ba374e5f3cCAS | 18853797PubMed |

[13]  L. Derendorp, R. Holzinger, A. Wishkerman, F. Keppler, T. Rockmann, Methyl chloride and C2–C5 hydrocarbon emissions from dry leaf litter and their dependence on temperature. Atmos. Environ. 2011, 45, 3112.
| Methyl chloride and C2–C5 hydrocarbon emissions from dry leaf litter and their dependence on temperature.Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DC%2BC3MXltVKqtL4%3D&md5=0c0c8d64e28a3618aa0ee33b8d211124CAS |

[14]  N. Yassaa, A. Wishkerman, F. Keppler, J. Williams, Fast determination of methyl chloride and methyl bromide emissions from dried plant matter and soil samples using HS-SPME and GC-MS: method and first results. Environ. Chem. 2009, 6, 311.
| Fast determination of methyl chloride and methyl bromide emissions from dried plant matter and soil samples using HS-SPME and GC-MS: method and first results.Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DC%2BD1MXhsVSlu77N&md5=0d8a6fe2197e80f29b84df382f119413CAS |

[15]  Y. Sailaukhanuly, Z. Sarossy, L. Carlsen, H. Egsgaard, Mechanistic aspects of the nucleophilic substitution of pectin on the formation of chloromethane. Chemosphere 2014, 111, 575.
| Mechanistic aspects of the nucleophilic substitution of pectin on the formation of chloromethane.Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DC%2BC2cXhtFWgtb7E&md5=22cf8e209b5f7ba2e90610ddf98b446dCAS | 24997968PubMed |

[16]  C. R. Curtis, T. L. Lauver, B. A. Francis, Foliar sodium and chloride in trees – seasonal variations. Environ. Pollut. 1977, 14, 69.
| Foliar sodium and chloride in trees – seasonal variations.Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DyaE1cXjtFai&md5=7c8fe815a0cc8602a086b292ac9700c9CAS |

[17]  I. K. Edwards, Y. P. Kalra, F. G. Radford, Chloride determination and levels in the soil – plant environment. Environ. Pollut. B 1981, 2, 109.
| Chloride determination and levels in the soil – plant environment.Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DyaL3MXhtlygtrw%3D&md5=307c869c802572e155892e856a87a29fCAS |

[18]  W. Ernst, Variation in mineral contents of leaves of trees in Miombo woodland in south central Africa. J. Ecol. 1975, 63, 801.
| Variation in mineral contents of leaves of trees in Miombo woodland in south central Africa.Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DyaE28Xhtlals74%3D&md5=f44d7c9188dda89ee4e63ba13b422047CAS |

[19]  J. M. Lobert, W. C. Keene, J. A. Logan, R. Yevich, Global chlorine emissions from biomass burning: reactive chlorine emissions inventory. J. Geophys. Res. Atmos. 1999, 104, 8373.
| Global chlorine emissions from biomass burning: reactive chlorine emissions inventory.Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DyaK1MXjtFylur4%3D&md5=987b2ee380c349f087813ce5920bea96CAS |

[20]  R. Watling, D. B. Harper, Chloromethane production by wood-rotting fungi and an estimate of the global flux to the atmosphere. Mycol. Res. 1998, 102, 769.
| Chloromethane production by wood-rotting fungi and an estimate of the global flux to the atmosphere.Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DyaK1cXlsFCjtrw%3D&md5=c5457aa4b15e03ae375bc4c07b2a5255CAS |

[21]  T. Watanabe, M. R. Broadley, S. Jansen, P. J. White, J. Takada, K. Satake, T. Takamatsu, S. J. Tuah, M. Osaki, Evolutionary control of leaf element composition in plants. New Phytol. 2007, 174, 516.
| Evolutionary control of leaf element composition in plants.Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DC%2BD2sXmsFOktLs%3D&md5=afc9abbf28b82b21b8c5e4e66e86b886CAS | 17447908PubMed |

[22]  A. Monti, N. Di Virgilio, G. Venturi, Mineral composition and ash content of six major energy crops. Biomass Bioenergy 2008, 32, 216.
| Mineral composition and ash content of six major energy crops.Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DC%2BD1cXitFarsbg%3D&md5=45905aad1ecea8a5709c0f775d141226CAS |

[23]  J. Pelloux, C. Rusterucci, E. J. Mellerowicz, New insights into pectin methylesterase structure and function. Trends Plant Sci. 2007, 12, 267.
| New insights into pectin methylesterase structure and function.Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DC%2BD2sXmtlWgs7k%3D&md5=eb395b59198e1357fd0e5b57fabaeca7CAS | 17499007PubMed |

[24]  K. H. Caffall, D. Mohnen, The structure, function, and biosynthesis of plant cell wall pectic polysaccharides. Carbohydr. Res. 2009, 344, 1879.
| The structure, function, and biosynthesis of plant cell wall pectic polysaccharides.Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DC%2BD1MXhtFarsrbF&md5=2662fc820e7be078895f3a3f45bbaaa1CAS | 19616198PubMed |

[25]  D. Mohnen, Pectin structure and biosynthesis. Curr. Opin. Plant Biol. 2008, 11, 266.
| Pectin structure and biosynthesis.Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DC%2BD1cXmsVGmu78%3D&md5=9bd4ca1268327e9e6f184e353106544bCAS | 18486536PubMed |

[26]  J. P. Knox, Pectins and Their Manipulation (Eds G. B. Seymour, J. P. Knox) 2002, pp. 131–149 (Blackwell Publishing: Oxford, UK).

[27]  B. L. Ridley, M. A. O’Neill, D. A. Mohnen, Pectins: structure, biosynthesis, and oligogalacturonide-related signaling. Phytochemistry 2001, 57, 929.
| Pectins: structure, biosynthesis, and oligogalacturonide-related signaling.Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DC%2BD3MXksVygsb8%3D&md5=61a4f597b85c9bdcb707d0467f205124CAS | 11423142PubMed |

[28]  W. Boerjan, J. Ralph, M. Baucher, Lignin biosynthesis. Annu. Rev. Plant Biol. 2003, 54, 519.
| Lignin biosynthesis.Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DC%2BD3sXntFSnsrg%3D&md5=4a6f28d4f8ea969d83cb60f2c6da443aCAS | 14503002PubMed |

[29]  Suhas, P. J. M. Carrott, M. M. L. Ribeiro Carrott, Lignin – from natural adsorbent to activated carbon: a review. Bioresour. Technol. 2007, 98, 2301.
| Lignin – from natural adsorbent to activated carbon: a review.Crossref | GoogleScholarGoogle Scholar |

[30]  E. Adler, Lignin chemistry – past, present and future. Wood Sci. Technol. 1977, 11, 169.
| Lignin chemistry – past, present and future.Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DyaE1cXisVeruw%3D%3D&md5=f8021c75b197441bb645ae65daecb805CAS |

[31]  D. B. Harper, J. T. Kennedy, Effect of growth-conditions on halomethane production by Phellinus species – biological and environmental implications. J. Gen. Microbiol. 1986, 132, 1231.
| 1:CAS:528:DyaL28Xkt1Wnt78%3D&md5=9a57d77db687e5a47b84e5adb8f273ccCAS |

[32]  P. J. White, M. R. Broadley, Chloride in soils and its uptake and movement within the plant: a review. Ann. Bot. 2001, 88, 967.
| Chloride in soils and its uptake and movement within the plant: a review.Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DC%2BD38Xpt1WisQ%3D%3D&md5=096bc45957e7eaaaf09f7dc987fe031dCAS |

[33]  R. Albert, G. Pescoller-Tiefenthaler, Nutrient content and ionic pattern in beech (Fagus sylvatica L.) from natural stands in eastern Austria and ecological implications. Vegetatio 1992, 101, 81.
| Nutrient content and ionic pattern in beech (Fagus sylvatica L.) from natural stands in eastern Austria and ecological implications.Crossref | GoogleScholarGoogle Scholar |

[34]  E. Jakab, O. Faix, F. Till, Thermal decomposition of milled wood lignins studied by thermogravimetry mass spectrometry. J. Anal. Appl. Pyrolysis 1997, 40–41, 171.
| Thermal decomposition of milled wood lignins studied by thermogravimetry mass spectrometry.Crossref | GoogleScholarGoogle Scholar |

[35]  E. Jakab, O. Faix, F. Till, T. Szekely, The effect of cations on the thermal decomposition of lignins. J. Anal. Appl. Pyrolysis 1993, 25, 185.
| The effect of cations on the thermal decomposition of lignins.Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DyaK3sXlvVeis7w%3D&md5=a62402d635e4271491f1b026270a6e5bCAS |

[36]  J. A. Conesa, A. Marcilla, J. A. Caballero, Evolution of gases from the pyrolysis of modified almond shells: effect of impregnation with CoCl2. J. Anal. Appl. Pyrolysis 1997, 43, 59.
| Evolution of gases from the pyrolysis of modified almond shells: effect of impregnation with CoCl2.Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DyaK2sXmsV2rt7k%3D&md5=655389af0fc56ebfe647c9bdc1e58d5dCAS |

[37]  T. Sariyildiz, J. M. Anderson, Variation in the chemical composition of green leaves and leaf litters from three deciduous tree species growing on different soil types. For. Ecol. Manage. 2005, 210, 303.
| Variation in the chemical composition of green leaves and leaf litters from three deciduous tree species growing on different soil types.Crossref | GoogleScholarGoogle Scholar |

[38]  S. Jacquemoud, J. Verdebout, G. Schmuck, G. Andreoli, B. Hosgood, Investigation of leaf biochemistry by statistics. Remote Sens. Environ. 1995, 54, 180.
| Investigation of leaf biochemistry by statistics.Crossref | GoogleScholarGoogle Scholar |