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Printed in Great Britain. All rights reserved Copyright @ 1991 Pergamon Press plc
Abstract-Within the ideal assumptions: (1) two Photosystems for photosynthetic fixation of COz, (2)
all solar photons with A 700 nm are absorbed, (3) the photon requirement is 8 for each CO, molecule
fixed and O2 molecule evolved and (4) the principal stable product of photosynthesis is d-glucose. the
theoretical maximum efficiency of conversion of light to stored chemical energy in green-plant type
(oxygen-evolving)photosynthesis in bright sunlight is calculated to be 13.0%. Thermodynamic argu-
ments are presented which indicate that a photosynthetic system with one Photosystem would be
highly unlikely to be able to drive each electron from water to evolve 0, and reduce CO,. The
practical maximum efficiency of photosynthesis under optimum conditions is estimated to be 8-9%.
545
546 and DAVID
JAMESR. BOLTON 0. HALL
complexes associated with each of the two photo- energy of Chl* is internal energy and not Gibbs
systems, the Emerson "red-drop" effect, and wave- energy. The chemical potential of Chl* (or the avail-
length dependent oxidation and reduction of the able energy for chemical energy storage) is obtained
cytochrome b-f complex (Emerson, 1958; Duysens, from the expression
1962; Barber, 1987; Andreasson and Vanngard, pchi* = u
g -k (kT/e)en (XChI.) (2)
1988). Furthermore Bolton (1978a, 1979) has pre-
sented arguments which indicate that if photo- = 1.80 + 0.0259 en (2.4 x = 1.35 eV
synthesis were to operate with only one photo- [Eq. (2) is the same as Eq. (6) of Parson (1978);
system, it would have to function almost at the see also Ross et al. (1976)].
thermodynamic limit. Since the reported efficiences Reaction (l), under the photosynthesis operating
of 17-18% are not compatible with the assumption conditions, requires a Gibbs energy output of at least
of two photosystems in photosynthesis, we expand 1.29 eV. Thus if photosynthesis were to operate with
on Bolton's arguments here. one photosystem, it would have to do so with very
Under the conditions in which reaction (1) occurs, small losses other than the unavoidable theoretical
the following are the values of the important ther- losses. This is equivalent to attempting to design an
modynamic functions for reaction (1) (Bolton, almost frictionless Carnot heat engine. The result of
1978a): this thermodynamic analysis is that we can reject the
AH = 467 kJ mol-' hypothesis of one photosystem, which, although not
AG = 496 kJ mol-' impossible, is highly implausible.
E = 1.29eV In our subsequent analysis we shall assume a
two-photosystem mechanism, a scheme which was
As Parson (1978) and Bolton (1978a, 1979) have evolved more than 3 billion years ago by cyanobac-
pointed out, it is very important to use thermody- teria and has remained virtually unchanged since
namic functions calculated for the actual conditions then (Rao et al., 1985).
under which photosynthetic C 0 2 fixation is occur-
ring. However, for comparison, we also give the
values of these functions calculated under standard All solar photons incident on the system with wave-
conditions (gases at 1 atm pressure) lengths A less than the threshold wavelength
A, = 700 nm are absorbed
AHv = 467 kJ mol-'
This is clearly an overstatement, as in a leaf some
AGO = 479 kJ mol-'
incident photons are reflected and others trans-
E" = 1.24eV
mitted; however, this assumption is necessary for
The difference between AG and AGO arises from purposes of calculating the maximum efficiency.
the work necessary to compress the gases to the The characteristic wavelengths for Photosystems I
standard state. and I1 are 700 and 680 nm, respectively. However,
Light absorbed by a chloroplast eventually in broadband sunlight photons up to 700 nm are
appears as excited-state energy (I, of reaction center utilized effectively, so we shall use 700 nm as the
chlorophyll entities. As there are two photosystems, threshold wavelength A,.
one operating at 690 nm (Photosystem 11) and the We use the analysis procedure of Bolton et al.
other operating at 700 nm (Photosystem I), four (1985) and the standard global Air Mass 1.5 sunlight
photons are observed by each photosystem for every spectral irradiance distribution Ei (W m-2 nm-I)
oxygen molecule evolved. Thus for every C 0 2 mole- tabulated by Hulstrom et al. (1985) vs wavelength
cule fixed and O2 evolved, there are four photons (A) in approx. 10 nm intervals. We require the inte-
absorbed at 680 nm and four at 700 nm. The aver- grated photon flux j, (photons m-* s-') up to the
age photon energy is thus 1.80 eV corresponding to long wavelength threshold A, = 700 nm
the average wavelength of 690 nm.
If we assume that the only route of decay for the
(3)
chlorophyll excited states (Chl*) is radiative decay
(fluorescence), the excited state lifetime of chloro- from which we obtain jg = 1.223 x lo2' photons
phyll a would be 19.0 ns (Connolly et al., 1982). m-2 s-I
Under these conditions and the photon flux incident
from a standard solar irradiance (vide infra), a
steady-state kinetic analysis (Archer and Bolton, The photon requirement per C 0 2 fixed and 0 2
However, an extra photon may be required to prod- determining the efficiencies to be expected under
uce the additional (third) AT for the complete C02 operating conditions:
fixation cycle in order to produce the phosphorylated
sugars necessary for starch and sucrose synthesis Incomplete absorption
(Halliwell, 1984; Lawler, 1987). Although the quan-
tum requirement of photosynthesis is known to vary Bjorkman and Demmig (1987) measured the frac-
somewhat with wavelength (Baleigh and Biddulph, tion q,,of light absorbed by leaves of 37 species of
1957; Evans, 1987), we assume that the quantum C3-type vascular plants. They found that q. varied
requirement for the fixation of one C 0 2 and evolution from 0.75 for a thin shade leaf of cotton to 0.90
of one O2molecule is the minimum possible value of for a thick Eucalyptus leaf. We shall assume their
8 for all absorbed wavelengths. average value of 0.84.