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suggests that organic compounds containing co- organohalogens has increased dramatically since 1968,
valently bound halogens are found only infre- and the current number of identified compounds
quently in living organisms ( I ) . Although this stands at about 2000 (5). Consequently, this review pro-
observation was undeniable 25 years ago, it is vides a very limited glimpse of this fascinating field of
nothing but a myth today. natural products.
chlorinated Occurrence
and other halo- Simple alkanes and
genated chemi- related compounds.
cals are dis- The simplest natural
charged into organohalogen com-
our biosphere by pounds-halogenated
plants, marine organ- alkanes-are abundant
isms, insects, bacte- on our planet (Table 2 ) .
ria, fungi, and mam- Chloromethane is pro-
mals, and by other duced by marine algae
natural processes. En- (101, giant kelp ( I f ) ,
zymatic, thermal, and wood-rotting fungus
other natural pro- (12). the ice plant ( l o ) ,
cesses are constantly cultivated mushrooms
occurring in t h e (131, the pencil cedar
oceans, in the atmos- 1141, the evergreen cy-
phere, and in the soil press ( 1 4 ) , several
that lead to the forma- Fomes fungi (15), and
tion of chlorinated phytoplankton (16).
phenols and myriad Chloride ion is nor-
other chlorinated mally present in plants,
chemicals, including wood, soil, and miner-
dioxins a n d CFCs, als (12, 141, and their
that previously were combustion inevitably
thought to result only leads to the formation
from the actions of of organochlorine com-
humans. It is clear pounds. Consequently,
that these natural pro- forest fires ( 1 7);brush
cesses have been pro- and vegetation burning
ducing chlorinated ( I 8);and volcanoes ( 14,
compounds and have 19, 201, including the
been a vital compo- eruptions of Mt. St.
nent of our ecosystem Helens ( 2 2 ) and
for eons. Kilauea (221, all pro-
Chlorine is in the
political and environ- -
duce sienificant and. in
some cases, massive
mental spotlight (21, quantities of chloro-
a n d a n aggressive methane. This global
campaign by the envi- emission rate of chloro-
ronmental organiza-
tion Greenpeace to
ban summarily a l l
production and uses
- methane from the ma-
rine and terrestrial bio-
mass is 5 million tons
per year (23),whereas
of chlorine (and bro- anthropogenic chloro-
methane emissions are
only 26,000 tons per
year (12). Several other
s i m p l e haloalkanes
and the first Interna- also have natural
tional Conference on sources (Table 2).
Naturally Produced GCD?ON W. GRIBBLE In addition to the
Organohalogens was Iartn b College, Hanovel; N H 037 simple one- and two-
held last year in The carbon halogens (Table
Netherlands (3). Not I 21, numerous haloge-
only are naturally oc- nated alcohols, ketones,
curring organohalogen compounds ubiquitous in our carboxylic acids and amides, aldehydes, epoxides, and
environment, but concentrations of some of these alkenes have also been isolated and characterized from
chemicals exceed their anthropogenic levels. Although marine algae (24-26).Indeed, nearly 100 different chlo-
myriad examples of chlorine-, bromine-, iodine-, and rinated, brominated, and iodinated compounds have
even several fluorine-containing natural products exist been found in Asparagopsis taxiformis, the favorite ed-
(41, the present review focuses principally on organo- ible seaweed of most Hawaiians (24).The following are
chlorine compounds. samples of those chlorinated compounds (p. 312A):
310 A Envimn. Sci. Technol.. VoI. 28. No. 7. 1994 0013-936X/94/0927-31OA$04.50/00 1994 American Chemical Society
0 CI tons per year) (14, 28). It has been CH,Cl, CH,CCI,
proposed that HCI and HF can react
cgc K CCI3 Br
Br+Br with organic compounds to pro-
duce organohalogens ( 2 8 ) . Al-
F,C=CF, FClCkCF,
CCl,FCClF, (Freon 113)
though the quantities may be small
compared with anthropogenic lev- Cl,C=CCl, CI,C=CHCl
els, several chlorofluorocarbons
(CFCs) have been detected in volca- The concentrations of these chemi-
nic gases from the Santiaguito vol- cals as measured in and around the
cano in Guatemala ( 1 9 )and the Kam- solfataric vents of the Kamchatka
The simple marine haloalkanes, chatka volcanoes in Siberia ( 1 4 ) . It volcanoes range from 0.4 ppb to
such as chloroform and bromoform, is estimated that 75% of the worlds 160 ppb of CFCs. Deep drill wells
could arise from in vivo haloform 500-700 active volcanoes are capa- (one mile or deeper) are also a
reactions, a mechanism that may ble of producing CFCs ( 1 4 ) . The source of several organochlorine
enable algae, for example, to secrete CFCs and compounds below show compounds and CFCs ( 1 4 ) .
continuously these antipredator the organochlorines produced by Terpenes a n d related com-
chemicals (24,271. these volcanoes. pounds. Terpenes are ubiquitous in
Volcanoes produce large quanti- terrestrial organisms and are essen-
ties of both hydrogen chloride (up CFC1, (Freon 11) CF,C1, (Freon 12) tial for life, but marine terpenes
to 3 million tons per year) and hy- were not discovered until 1955,and
drogen fluoride (up to 11 million CHF,Cl CHFCl, halogenated marine terpenes were
eel OH
ci%r
lac
0
i 0 2 3 -Cl CI )i+$cl
4 cI 5:(telfairine)
Br
p -
OH chloride, bromide, or iodide, and cesses such as reactions between
hydrogen peroxide, rapidly forms humic acid and soil microbes (chlo-
HRP
H202
active halogen, resulting in the ride and chloroperoxidase). Humic
death of bacteria and fungi by halo- acids are present not only in soil,
CI 17h,2OoC genation reactions ( 2 3 2 , 2 3 3 ) . It but also in rivers, lakes, and the
CI would appear that biohalogenation oceans ( 2 4 6 ) . The yearly net pro-
is an integral component of our im- duction of environmental humic
mune system! acid from the decomposition of or-
ganic material has been estimated at
Metabolism and biodegradation 63 billion tons ( 2 4 6 ) . This can be
Contrary to common perception, added to the estimated existing glo-
organohalogen compounds, both bal 1.0-1.5 trillion tons of soil hu-
PCDDs mic acids and one trillion tons of
natural and unnatural, are readily
metabolized and biodegraded to ha- ocean humic acid ( 2 4 6 ) .Numerous
lide ion by assorted microorgan- studies have demonstrated the ease
isms. The simple organochlorines with which humic acid model com-
CH,Cl,, CHCl,, CCl,, Cl,C=CC1,, pounds (phenolics)react with chlo-
and others can be degraded to CO, rine to produce chloroform and
(or other simple organics) and chlo- other simple organochlorines via
PCDFs ride by soil bacteria ( 2 3 4 ) .The soil chlorophenols ( 2 46-2 4 8 ) . As we
bacterium Pseudomonas putida ox- have seen, chloride is ubiquitous in
idizes chloro- and other haloben- soil, plants (200-10,000 ppm) (221,
(38 compounds identified; (214, CIS,Cl6 zenes to the cis-diol ( 2 3 5 ) .This is a rivers (average 8 ppm) ( 2 4 9 ) ,lakes
isomers dominate; ppm range) remarkably general reaction and ( 2 4 9 ) , and, of course, oceans (146,
succeeds even with fluorobenzene. 249). These ingredients, in combi-
The biodegradation of chlorophe- nation with natural chloroperoxi-
nols has been thoroughly studied. dase and other enzymes, provide a
Mechanisms of biogenic For example, 2,4-dichlorophenol is plausible rationale for the natural
chlorination rapidly metabolized in soils ( 2 3 6 ) , formation of chlorinated phenols.
Marine organisms, terrestrial and an exhaustive mechanistic Several studies have demonstrated
plants, fungi, microorganisms, and study of the degradation of this that the natural production of chlo-
mammals all contain haloperoxi- compound to chloride and CO, by rinated phenols and anisoles out-
dase enzymes that can chlorinate, the white-rot fungus Phanerochaete weighs their anthropogenic sources
brominate, and iodinate organic chrysosporium has been reported (244, 245).
compounds i n the presence of ( 2 37).This versatile and remarkable Although a vast number of halo-
chloride, bromide, or iodide ions, fungus is capable of degrading other genated compounds have been iso-
respectively ( 2 2 2 - 2 2 4 ) . Of 33 spe- chlorinated phenols ( 2 3 8 ) , DDT lated from natural sources ( 3 ) ,rela-
cies of Phaeophyceae algae from ( ~ 3 9 pentachlorophenol
), ( 2 4 0 ) ,and tively few marine organisms have
the Atlantic Coast, 2 2 displayed PCBs (142). been examined for their chemical
1
ing back to the 13th century (159). the Enrth'r A t m o s p h w r ; Springer-
i
1. i. Verlag: Berlin. 1990.
~
;2&
4 1 1 SOC.1973. 60. 347.
identical to the blue-green alga Nos- (16) Gschwend. 1'. M.: MacFarland. 1. K.:
toc, and other microfossils are mor- . .~ T , ' , ~
Newman. K. A. Science 1985. 227.
phologically indistinguishable from Gordon W. (;ribbk! is n professor and 1033.
Oscillotoria. two present-day spe- former choir mu^^ 0 1 the llepnrtn~entof (17)Palmer. T Y. Notirrr! 1976.263. 44.
cies rich in organohalogen com- C1tentistl:t~111 l~urtntouthCollege. He re- (18) Lovelock. J. E. Nolortr 1975. 256. 193.
(19) Staiber, R. E. PI nl. Geol. SOC. A,,).
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Function of natural from the University of Oregon. After o 215, 665.
organohalogens year at UCLA os n National Cancer lnsti- (21) Inn. E.C.Y. et al. Science 1981. 211,
tule Posfdocforal Fello~,,he joined the
Why does nature create organo- faculty of Dartmouth College in 1968.
821.
chlorine compounds? Many marine (22) Gerlach, T. M. 1. l/olcanol. Geofherm.
His research interests include the syn- Res. 1980, 7. 295.
and terrestrial organisms use or- thesis and isolation of biologically ac- (23)Rasmussen, R. A. et at. I. Geophys.
ganochlorine and other organohalo- tive natural products, heterocyclic Res. 1980. 85. 7350.
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fense-feeding deterrents, irritants, chemistry. 10. 40.
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A t m o s p h e r e a n d O c e a n s ; Wiley-
and analytical procedures t o assure
Interscience: New York, 1978. the quality of your chemicals. ACS specified
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514. organizations such as APHA, ASTM, FCC, SEMI,
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52. of this authoritative reference now comes in
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(154) Christophersen, C. In The Alkaloids; sary information on
Brossi, A. Ed.; Academic Press: New
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(155) Chevolot, L. et al. J. A m . Chem. SOC. 0 chromatography
1985, 207,4542. 0 colorimetry and turbidimetry
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1982,54, 1907. 0 gravimetric methods
(157) Corriero, G. et al. Tetrahedron 1989,
45, 277. 0 measurement of physical properties
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Abrams: New York, 1989. 0 solid reagent mixtures
(159) Paasivirta, J. et al. Chemosphere, 0 solvents for special purposes
1988, 27, 137.
(160) Fox, S. W.; Dose, K. Molecular Evo- 0 specifications and tests
lution and the Origin of Life; Marcel 0 standard volumetric solutions
Dekker: New York, 1977. 0 titrimetry
(161) Scheuer, P. J. Science 1990, 248,
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(162) Fenical, W. Science 1982, 215, 923. general elimination of boiling point and density specifications, the use of
(163) Schulte, G. R.; Scheuer, P. J. Tetra- LC in assay determinations, and a section on preparation of volumetric
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