The degradation of chlorophyll — a biological enigma

Some 10⁹tonnes of chlorophyll are destroyed each year on land and in the oceans. The fate of these chlorophylls is, however, largely unknown. This review describes the developmental stages at which chlorophyll breakdown occurs in aquatic and terrestrial biological systems, and the destruction arising from herbivory, disease, pollution and other physical hazards. At the cellular level, an attempt is made to separate the breakdown of chlorophyll during senescence from the many other events associated with cell destruction and death. A consideration of the more important chemical and biophysical properties of chlorophylls and their derivatives is provided, together with data on their spectral properties. The biosynthetic and biodegradative pathways of chlorophyll metabolism are, so far as is possible, described with some predictions as to the likely fate of the missing tonnes. Two types of degradation are recognized; the first involves up to five defined enzymes concerned with the early stages, the second covers the less well defined enzymic and non‐enzymic destruction of the macrocyclic structure. These degradative reactions are compared with the reactions implicated in the breakdown of other porphyrins including haems in plants and animals. A brief description is given of the occurrence of breakdown products of chlorophyll in past biomass, including those of geological significance and those in a more recent archaeological context. Finally, the economic significance of chlorophyll breakdown is considered in the context of agriculture and horticulture, veterinary and medical sciences, food colouring and cosmetic industries, and the multi‐million‐dollar attraction of autumn leaf fall to tourism. Contents Summary 256 I. Introduction 256 II. Chlorophylls: global production and destruction 259 III. Chlorophylls: nomenclature and chemical characteristics 260 IV. Chlorophyll metabolism 268 V. Chlorophyll degradation during senescence 274 VI. Other degradative conditions 278 VII. Breakdown products in past biomass 287 VIII. Pathways of degradation 289 IX. Economic importance 291 Acknowledgements 294 References 294