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8 Change in Gibbs Free Energy Under Environmentally Realistic Conditions

8 Change in Gibbs Free Energy Under Environmentally Realistic Conditions

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3  Energetic Considerations in Organohalide Respiration



39



Under environmentally more realistic conditions, ΔG values are slightly lower

(see Box 1 for calculation details). At H2 partial pressures of 10 Pa (10−4 atm)

and Cl− concentrations of 1 mM, ΔG for hydrogenolysis will be −5.7 kJ/mol less

favorable than under standard conditions. Relative to the aforementioned values of

120–170 kJ/reaction this effect is negligible. Taking physiological concentrations

of organohalogens of 1–100 µM also into consideration would make hydrogenolysis −28.5 to −39.9 kJ/mol less favorable; however, the concentrations of the

organic hydrogenolysis products are likely in the same range (1–100 µM), which

would make hydrogenolysis −22.8 to −34.2 kJ/mol more favorable. At equimolar

concentrations these effects cancel each other out.



3.9 Comparison with Other Electron Acceptors

Change in Gibbs free energy (ΔGo′) values for hydrogenolysis of −120 to

−170 kJ/mol translate into redox potentials of 210–470 mV, i.e., they are com−

parable to the redox couple NO−

3 NO2 (Eo′ = 433 mV). This is substantially

lower than the redox potential for O2 (Eo′ = 818 mV), but much higher than the

redox potentials for sulfate reducing (SO2−

HS−; Eo′ = −217 mV) and metha4

nogenic (CO2/CH4; Eo′ = −244 mV) environments. Hydrogenolysis is thus rare

under aerobic conditions, where O2 is an energetically much more favorable electron acceptor. Under sulfate reducing and methanogenic conditions, on the other

hand, hydrogenolysis is the more energetically favorable process. This implies

that growth of organohalide-respiring organisms can be sustained at low hydrogen concentrations where H2-based sulfate reduction and methanogenesis would

be exergonic. Observations by Löffler et al. (1999) are in line with this paradigm

(Fig. 3.4). These authors showed that dehalogenating organisms can remove

hydrogen to very low levels (<0.04 Pa, which at equilibrium for hydrogen between



Fig. 3.4  Measured hydrogen thresholds under various electron acceptor conditions. Filled circles,

sulfate reduction and methanogenesis; open squares, fumarate reduction, nitrate reduction, ammonification and iron reduction; filled triangles, organohalide respiration (Data Löffler et al. 1999)



40



J. Dolfing



Fig. 3.5  Thermodynamic prediction of the H2 thresholds below which methanogenesis, sulfate

reduction and organohalide respiration become endergonic under otherwise standard conditions



gas phase and aqueous phase translates into a concentrations <0.3 nM) where it

is out of reach for sulfate reducers and methanogens: measured H2 thresholds

for sulfate reducing and methanogenic organisms are in the range of 0.1–2 Pa

(1–15 nM), and 0.6–12 Pa (5–95 nM), respectively. Interestingly, the H2 levels

where organohalide respiration would become endergonic are many orders of

magnitude lower than the levels hydrogen thresholds for organohalide respiration

measured experimentally (Fig. 3.5). This indicates that organohalide respiration is

under kinetic rather than thermodynamic control.



3.10 Co-metabolic Reductive Dehalogenation

Given that reductive dehalogenation is a highly exergonic reaction, there is considerable energy available to the organisms that catalyze this reaction. However,

not all those organisms are able to harness this energy. Methanogens are a case in

point. Their metabolism involves highly reducing corrinoids and other cofactors

that fortuitously dechlorinate a wide variety of halogenated compounds (Schrauzer

and Katz 1978; Smith and Woods 1994; Dolfing 1995; van Eekert 1999; van

Eekert et al. 1999). Not harnessing the energy liberated by the dehalogenation

reaction is for the organisms involved not only a missed opportunity, it is actually a cost, as the reducing equivalents used in the process could have been used

more productively elsewhere in their metabolism, in case to produce methane.

Typical growth yields of hydrogenotrophic methanogens are in the range of 1 to

8 g dry weight per mole of methane produced (Vogels et al. 1988). Per mole of

hydrogen used for reductive dechlorination methanogens thus forfeit 0.25–2 g new

biomass. From an environmental engineering point of view, co-metabolic conversion of halogenated compounds can potentially lead to new technologies, especially for xenobiotic compounds. Chlordecone, a highly chlorinated pesticide, is a

case in point. Currently no organisms are known that can grow with chlordecone



3  Energetic Considerations in Organohalide Respiration



41



as electron acceptor, even though its dechlorination is highly exergonic (Dolfing

et al. 2012). Methanogens, however can dechlorinate this compound (Schrauzer

and Katz 1978; Jablonski et al. 1996), which suggests that methanogenic biomass

can be used to remove this persistent organic compound from waste streams and

the environment.

Löffler et al. (1999) have pointed out an energetic/thermodynamic approach

that allows distinction between metabolic and co-metabolic degradation of halogenated organics based on the premise that conservation of the considerable

amount of energy available from organohalide respiration results in distinct biomass formation in and by organohalide-respiring organisms. The energy gain per

electron for organohalogens as electron acceptor is higher than for sulfate or bicarbonate (methanogenesis) as electron acceptor, but lower than for nitrate or oxygen as electron acceptor. This is reflected in the fraction of electrons (fe) that is

used for biomass formation (0.30–0.37), which is higher than the fe for methanogenesis (0.05) and sulfate reduction (0.06–0.16) but lower than the fe for nitrate

and oxygen respiration (0.43 and 0.46, respectively). The point here, as made by

Löffler et al. (1999) though is that the fractions of electrons flowing to biomass

formation and to reduction of the catabolic electron acceptor can be fairly easily

determined, which makes for an elegant tool to distinguish between metabolic and

co-metabolic organohalide respiration in pure cultures. In mixed cultures, however

a substantial portion of the electrons can flow to other electron acceptors, making

it difficult to accurately assess the extent of electron flow to the presumed organohalide respirers.



3.11 Anaerobic Oxidation and Fermentation

of Organohalogens

The presence of a halogen substituent renders a compound more oxidized than its

nonhalogenated analog, and the thermochemical characteristics of halogens are

such that their presence decreases the amount of energy available when organohalogens are mineralized under aerobic conditions, i.e., with oxygen as electron

acceptor (Dolfing 2003). Whether or not the presence of a halogen substituent

decreases the amount of energy available when an organohalogen is mineralized

under anaerobic conditions depends on the electron acceptor used. Under deni746 mV), this amount decreases with

trifying conditions (Eo′ NO−

3 NO2 = 

increasing degree of chlorination (Fig. 3.6). Coupled to sulfate reduction or

methanogenesis, on the other hand, the presence of chloro-substituents increases

the amount of energy available from mineralization. For most practical applications, though the main message of this evaluation is that mineralization of organohalogens is in principle always an exergonic process, irrespective of the electron

acceptor used: The poor biodegradability of many of these compounds is caused

by ecophysiological and evolutionary intricacies, not by a lack of potential energy.



J. Dolfing



42



−∆G(kJ/mol)



3000



nitrate



nitrate



sulfate



CO2



4



5



2000



1000



0



1



2



3



# of chlorines



−∆G(kJ/mol)



1500



nitrate



nitrate



CO2



sulfate



1000



500



0

1



2



3



4



5



6



# of chlorines



Fig. 3.6  Change in Gibbs free energy for the complete mineralization of pentachlorophenol

(upper panel) and hexachloroethane (lower panel) with nitrate, sulfate or carbon dioxide as

electron acceptor. Mineralisation of organics results in the generation of reducing equivalents.

The thermodynamic value of these reducing equivalents depends on the electron acceptor used.

Per mole of reducing equivalents (H2) this is 224 kJ for denitrification, 150 kJ for ammonification, 38 kJ for sulfate reduction, 33 kJ for methanogenesis respectively. Each chloro-substituent

reduces the potential amount of H2 produced (cf. Table 3.4), while yielding upon mineralization

about 150 kJ. Hence the above pattern: under denitrifying conditions the presence of chloro-substituents reduces the amount of energy liberated upon mineralization (224 > 150), under ammonification conditions the effect is neutral (150 = 150) and so on



One of the consequences of being good electron acceptors is that many organohalogens are fermentable, at least in theory (Dolfing 2000). Fermentations are disproportionation reactions in which a portion of the substrate is oxidized while the

remainder is reduced (Madsen 2008); no external electron acceptor is involved.

An example of an organohalogen that in theory can be fermented is trichloroethane. At least two pathways can be envisaged: fermentation of trichloroethane to

acetate: C2H3Cl3 + 2H2O → CH3COO− + 4 H+ + 3Cl− (ΔGo′ = −371 kJ/

mol), and fermentation of trichloroethane to ethane: 7C2H3Cl3 + 12H2O → 4

C2H6 + 6CO2 + 21H+ + 21Cl− (ΔGo′ = −377 kJ/mol). Ethane itself is not



3  Energetic Considerations in Organohalide Respiration



43



Table 3.4  Change in Gibbs free energy (ΔGo′) values for the mineralization and fermentation of

chlorinated phenolsa

Reactants

Mineralization

C6HOCl5 + 11H2O

C6H2OCl4 + 11H2O

C6H3OCl3 + 11H2O

C6H4OCl2 + 11H2O

C6H5OCl + 11H2O

C6H6O + 11H2O

Fermentation to acetate

4C6HOCl5 + 26H2O

4C6H2OCl4 + 24H2O

4C6H3OCl3 + 22H2O

4C6H4OCl2 + 20H2O

4C6H5OCl + 18H2O + 2CO2

4C6H6O + 16H2O + 4CO2

aGibbs



Products



ΔGo′ (kJ)

















6CO2 + 9H2 + 5H+ + 5Cl−

6CO2 + 10H2 + 4H+ + 4Cl−

6CO2 + 11H2 + 3H+ + 3Cl−

6CO2 + 12H2 + 2H+ + 2Cl−

6CO2 + 13H2 + H+ + Cl−

6CO2 + 14H2



−456.5

−293.2

−135.4

17.9

169.5

315.6

















9CH3COO− + 29H+ + 20Cl− + 6CO2

10CH3COO− + 26H+ + 16Cl− + 4CO2

11CH3COO− + 23H+ + 12Cl− + 2CO2

12CH3COO− + 20H+ + 8Cl−

13CH3COO− + 17H+ + 4Cl−

14CH3COO− + 14H+



−670.0

−530.5

−396.4

−266.8

−138.9

−16.5



free energy data for halophenols are taken from Dolfing and Novak (2015)



fermentable to acetate as ethane-based acetogenesis would require reduction of

CO2: 4C2H6 + 2H2O + 6CO2 → 7 CH3COO− + 7H+ (ΔGo′ = 11 kJ/mol).

Similar games can be played with halogenated aromatics. For example, in theory

fermentation of dichlorophenol could encompass formation of phenol according

to 7C6H4OCl2 + 11H2O → 6C6H6O + 14HCl + 6CO2 (ΔGo′ = −253 kJ/mol) or

alternatively dichlorophenol can be fermented to acetate C6H4OCl2 + 5H2O → 

3CH3COOH + 2HCl (ΔGo′ = −116.7 kJ/mol). Table 3.4 lists the stoichiometry

and energetics of the complete mineralization of chlorinated phenols. Combining

these data with the stoichiometry and energetics of acetate formation from H2/

CO2 (2CO2 + 4H2 → CH3COO− + H+ + 2H2O; ΔGo′ = −94.9 kJ/mol) yields

an overview of the energetics of chlorophenol fermentation to acetate and HCl

(Table 3.4). These calculations are purely theoretical though. The fermentation

reactions presented in Table 3.4 are thermodynamically possible but have not been

seen in the environment.

There are actual examples of organohalide fermentation though. In 1996,

Dehalobacterium formicoaceticum was isolated and characterized as a strictly

anaerobic bacterium utilizing dichloromethane (DCM) as source of carbon and

energy, metabolizing dichloromethane according to 3CH2Cl2 + CO2 → 2HCO

O− + CH3COO− + 6Cl− + 9H+ (Mägli et al. 1996, 1998). The organism was

isolated from a mixed culture in which dichloromethane was fermented according to 2CH2Cl2 + 2H2O → CH3COO− + 4Cl− + 5H+ (Mägli et 

al. 1995).

More recently, Justicia-Leon et al. (2012) observed that dichloromethane can

support fermentative growth of Dehalobacter sp.: in a mixed culture the organisms thrived on DCM, DCM was not reductively dechlorinated, and acetate was

produced. Interestingly, this implies that Dehalobacter growth is not limited to



44



J. Dolfing



organohalide respiration and these organisms can also shift metabolism to fermentation. Whether this is a propensity of Dehalobacter as a genus, or that individual

species can make this shift remains to be seen. Similarly, it remains to be seen

whether organisms can be found that ferment dichloromethane according to 2C

H2Cl2 + 2H2O → CH3COO− + 4Cl− + 5H+ (ΔGo′ = −243.7 kJ/mol DCM)

rather than 3CH2Cl2 + CO2 + 4H2O → 2HCOO− + CH3COO− + 6Cl− + 9H+

(ΔGo′ = −225.6 kJ/mol DCM). It should be noted that these observations support

dichloromethane fermentation as a process, but not necessarily as a metabolism.

There is still no proof that one organism can ferment dichloromethane without

an external electron acceptor: D. formicoaceticum uses CO2 as addition electron acceptor, and there still are no pure cultures of dichloromethane fermenting

Dehalobacter species.



3.12 Defluorination

All organohalogens are characterized by strong carbon–halogen bonds, but

among these, the carbon–fluorine bond is the strongest. Indeed, the C–F bond is

the strongest single bond formed by carbon. This is reflected in the short bond

length, the high bond dissociation energy, and due to fluorine’s high electronegativity, the high polarity of the C–F bond (Reineke 1984). These characteristics may

well be the reasons why microbial growth based on organofluoride respiration has

not yet been observed. Thermodynamics, or better, a lack of available energy, is

not the explanation. The scarce Gibbs free energy values available for organofluorides—such values are less readily available than the corresponding values for

organochlorides or—bromides—indicate that the amount of energy available from

defluorination is similar to (or slightly lower than) the amount of energy available

from dechlorination. Thus, the reason why organofluoride respiration has never

been observed is kinetic rather than thermodynamic. Though unfortunate, from an

environmental point of view this conclusion is encouraging. Given that energy is

available from defluorination organisms may eventually come to the fore (evolve)

that are able to harness and exploit this energy, even for the notoriously persistent

perfluorinated compounds (Parsons et al. 2008).

Goldman (1965) has described the first hydrolytic fluoroacetate dehalogenase

already back in 1965, and similar enzymes have been described since (Murphy

2010) in aerobic bacteria. Under anaerobic conditions, defluorination has long

been elusive. Vargas et al. (2000), when testing for anaerobic degradation of fluorinated aromatics, observed that these compounds were recalcitrant under sulfate

reducing and methanogenic conditions; these authors isolated denitrifying organisms that could mineralize 2- and 4-fluorobenzoate, but the first step in the degradation pathway was not a reductive defluorination. Recently however Davis

et al. (2012), using a novel, elegant fluoroacetate assay, isolated the first anaerobe

in possession of a reductive defluorinase and presented evidence in support of the

hypothesis that the organism can harness energy from defluorination. Significantly,



3  Energetic Considerations in Organohalide Respiration



45



Davis et al. obtained their isolate from an anaerobic environment, a bovine rumen

in Australia, that had been under long term exposure to fluorinated organics as

the animals from which the bacteria were isolated had been eating plants that are

known to produce fluoroacetate. Gribble (2002) has cataloged a wide variety of

naturally occurring organofluorine compounds. Taken together, these observations

suggest that it is opportune to continue screening for and studying the potential

degradation of (per)fluorinated compounds under anaerobic conditions.



3.13 Organohalide Respiration and ATP Generation

It has been reiterated now several times in the preceding paragraphs that reductive

dechlorination is a (very) exergonic process, also under environmentally realistic

conditions and that microorganisms can potentially harness considerable energy

from this reaction. Just how much energy the organisms actually harness from

organohalogen respiration and how much biomass is generated based on organohalogens respiration is beyond the scope of this chapter. These aspects will be

discussed in detail in a later chapter of this book (Mayer-Blackwell et al. 2015).

Nevertheless, it seems prudent to point out here that organohalogen respiration

yields in theory, enough energy for ATP generation via substrate level phosphorylation. Biomass yields are highly variable and—depending on the organism and

the substrate used—in the range of about 0.3–5.6 g dry weight per mole of chloride produced (Ding et al. 2014). As mentioned above, Vogels et al. (1988) have

summarized that biomass production by hydrogenotrophic methanogens is in the

same range [1–8 g dry weight per mole of product (methane)]. But as production

of one mole of methane requires four moles of H2, versus a consumption of one

mole of H2 per mole of chloride produced, organohalogen respirers produce about

four times more biomass per mole of hydrogen consumed. These trends scale with

the amounts of Gibbs free energy available from these two reactions. This implies

that organohalogen respiring organisms have developed efficient mechanisms to

harness the energy available from this process: they are good at what they do, just

as good as methanogens in what they are doing.



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Part II



Diversity of Organohalide-Respiring

Bacteria



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8 Change in Gibbs Free Energy Under Environmentally Realistic Conditions

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