Identification and Quantitation of Carbonate Compounds in Coal Fly Ash

Christopher F. Bauert and David F. S. Natusch'

Department of Chemistry, Colorado State University, Fort Collins, Colorado 80523

rn Alkali, alkaline earth, and ferrous carbonates have been

identified and quantitatively determined in several coal fly
ashes a t total carbonate concentrations of 0.058-0.86%.
Thermal evolved gas analysis for Con, a selective acid-leaching
procedure for carbonates, and metal analyses of the leachates
provide data for a mass balance between metals and carbonate. In some cases the leachable metal comes predominantly
from a carbonate species. High relative humidity promoted
COz absorption by fly ash regardless of the COz partial pressure. Although this study used ash removed by electrostatic
precipitators, flue-gas characteristics are likely to promote
carbonate formation on the ash in the plume.
The projected continued use of coal for power generation
reaffirms the need to study particulate emissions from coal
combustion, to assess and, if possible, to minimize adverse
environmental impacts. Most studies ,have focused on the
behavior of potentially toxic metals (1-41, organic compounds
( 5 , 6 ) and
, sulfur gases (7) with little information being generated on the inorganic compounds present. Techniques
giving compound-specific information have been hampered
by inadequate detection limits. Only major species have been
unequivocally identified, primarily by X-ray powder diffraction (8-10): quartz, mullite (3A1~03.2Si02),hematite,
magnetite, h e , and anhydrite (CaS0.d. X-ray photoelectron
spectrometry (XPS) has shown that binding energies for elements in fly ash are consistent with oxides for Al, Si, and Fe
and with Cas04 for Ca and S, but other compounds may have
the same binding energies (11,12). Evidence for sulfates of
Al, Ca, and Fe has been provided by Fourier transform infrared spectroscopy (13). Differential thermal analysis has
been applied widely to the minerals in coal (14) and to fly ash
(9), but to our knowledge in only one instance were mixed
carbonates of Ca, Mg, and Fe found (15).
Knowledge of the chemical forms of metals in fly ash is
highly desirable in order to predict the mobility of the metal.
Mobility has implications for inhalation toxicology and fly-ash
disposal because both require information on solubility. In
addition, utilization of ash as a raw material may benefit from
more complete information on ash chemistry.
The present study demonstrates that, in fact, carbonate
compounds occur in fly ashes, that the concentrations of individual compounds are trace level, and that the metals bound
as carbonates can be a significant fraction of the total mobile
metal.
t Present address: Water Chemistry Laboratory, University of
Wisconsin, Madison, WI 53706.

Experimental Section
Thermal Evolved Gas Analysis. Because carbonate
minerals decompose with the release of C02 at characteristic
temperatures (16),
evolved gas analysis (EGA) with carbonspecific detection was applied. The instrument is illustrated
in Figure 1.The furnace (Leco induction furnace, Model 521)
was temperature-programmed from room temperature to 1200
OC a t -190 OC/min by means of a motor-driven variable
transformer (I 7). Calibration of the temperature scale was
performed by using the melting points of several pure solids
a t the stated programming rate. Ca. 100 mg of fly ash was
spread in a thin layer (<1mm) on the bottom of a 2-cm diameter, quartz-enclosed, graphite crucible (Leco), which was
supported within the furnace coils by a quartz pedestal. Helium gas flowing a t 420 mL/min carried gases released from
the sample through a Pyrex transfer line into a microwave
cavity, The line was heated to 150 "C to prevent condensation
of water vapor.
Inside the cavity a He discharge was maintained continuously. Neutral atomic carbon emission at 1931.0 A was
monitored with a GCA-McPherson monochromator (Model
Eu700-56) modified to provide simultaneous correction for
background emission (18). Details of the cavity design and
operation are described elsewhere (19,20).The stated temperature program, He flow rate, and plasma operational parameters were adequate for detection of evolved C02.
Acid Evolved Gas Analysis. Verification of the thermal
EGA method was desired. A system was set up (Figure 2) to
take advantage of the reaction
2H+

+ MCOs(s)

M2+ Hz0

+ C0&)

Fly ash was placed into the flask, which was then purged
with He to eliminate atmospheric COz. After bypassing the
flask, aqueous HCl was added from the dropping funnel and
mixed with the ash by means of a magnetic stirrer, causing
dissolution of carbonate compounds and release of COZ.Then
switching the cell on-line swept the COZ into the plasma,
where C was monitored as before. Mixing for 10 min with 25
mL of 1M HCl was found below to provide a complete reaction.
The traps, the first of which contained indicating Drierite
and the second anhydrous CuSO4, performed a dual function.
First, water and HC1 vapors disturb the plasma and cause a
false C signal. Their quantities are reduced by absorption in
the respective traps. Although anhydrous CuSO4 is reported
as an HCl absorbent (21),the first trap alone was found to be
sufficient. Secondly, the traps delayed and elongated the COP
pulse such that a measurable signal resulted.

0013-936X/81/0915-0783$01.25/0 @ 1981 American Chemical Society

Volume 15, Number 7, July 1981

783

TMOlO
CAVITY

IHEI

Flgure 1. Thermal evolved gas analysis instrument.

Qh

DROPPING

FUNNEL

19

CAVlTY

H.

U
Figure 2. Acid evolved gas analysis system.

Leaching Procedure. By controlling the carbonate equilibrium with the amount of acid added, it is possible to dissolve
selectively the carbonate compounds as a group. For a given
amount of fly ash, we needed to determine the stoichiometric
number of moles of acid to add and the duration of mixing
required to assure complete dissolution. This was done easily
with the acid EGA apparatus (Figure 2).
For 100 mg of fly ash (Corrette) the total amount of C02
released by 25 mL of acid was determined for several concentrations of acid at a constant mixing time of 10 min. If the
acid strength is sufficient, the carbonate equilibrium will shift
completely to gaseous COz. The COz-release peak shape will
reflect only mass-transfer effects and will be independent of
acid concentration. If, however, acid strength is too small, only
part of the total carbonate will be present as COz, the rest
existing as bicarbonate or carbonate ions. Eventually, as COz
is purged, the solution equilibrium will shift, releasing more
COz, until equilibrium with the COz level in helium is reached.
The net effect is peak broadening and delay. One molar acid
was chosen to assure complete dissolution.
Duration of mixing was addressed by mixing 25 mL of 1M
HC1 with 100 mg of fly ash (Corrette) for variable lengths of
time before sweeping the C02 out of the reaction cell. If dissolution is complete, the peak width and the time at peak
maximum will be independent of mixing duration; for incomplete dissolutiofi the time at peak maximum and peak
784

Environmental Science & Technology

width will increase with shorter mixing times because the COB
generation is incomplete. Kinetic effects were absent after 10
min of mixing.
Metal Determinations. Iron was determined by atomic
absorption spectrometry with background correction (Varian,
Model 1250), Li and Rb were determined by flame emission
(Varian, Type AA-5), and the rest of the metals were determined by argon dc plasma emission using the Spectraspan I11
Echelle spectrometer (SpectraMetrics, Inc.). The first three
elements were assayed by the method of standard additions.
Since the Spectraspan gives direct concentration readout, the
results from it were verified by standard additions. All analyte
solutions contained 1000 ppm Cs as an ionization suppressant.
All thermal EGAs, acid EGAs, and leaching procedures
were performed on duplicate samples of four fly ashes:
Crawford and IGS from Illinois, Niagara from New York, and
Corrette from Montana. In addition, IGS was separated into
magnetic and nonmagnetic fractions by using a magnet.
The ashes were obtained from hoppers beneath the electrostatic precipitators and were sieved manually (Buckbee-Mears
Co. sieves) to obtain the <20-pm particles. In this way sample
homogeneity would be increased and sampling error reduced.
Quantitation of the EGA peak areas was achieved by using
CaC03 as a standard. A linear relationship between amount
of carbonate and peak area was assumed. Significant deviations from this assumption were minimized by using standards
close to the fly ashes in carbonate content.

Results
Thermal EGAs for the fly ashes are shown in Figure 3. Each
peak is characteristic of the decomposition of certain carbonate compounds. The large background for Niagara ash is
similar to the thermal EGA of graphite and of carbon black.
Optical microscopic examination showed that this ash contained significantly larger numbers of unburned or partially
burned coal particles than the other ashes. These particles are
easily distinguished because they are opaque and black and
have a Swiss cheese or striatedmorpho1ogy (22,23).
The total concentrations of carbonates in each ash are listed
in Table I for both EGA methods. It must be pointed out that
neither method has been subjected to rigorous evaluation, that

C ORR E T T E

I GS

>

N ON
MAGNETIC

CRAWFORD

--2
25

600

1200

25

600

1200

TEMPERATURE (C)

Figure 3. Thermal evolved gas analyses for carbon in fly ashes.

Table 1. Comparison of Total Carbonate by Thermal

and Acid Evolved Gas Analysis
c%*-,'

ppm

fly a&

thermal

acld

Crawford
Niagara
Corrette

2300 (26)
1700 (32)
2900 (22)
5200 (27)

4100 (49)
580 (39)
2400 (40)
8600 (52)

IGS
a

dgnlflcant
difference?

no
no

no

no

Percent relative average deviations are given in parentheses.

calibration of the sensitivity of response has been minimal,

that only duplicate samples of each ash were analyzed, and
that there may be considerable variability between the ash
aliquots. For these reasons, the numerical results must be
considered only semiquantitative. This interpretation is reflected by the large relative deviations associated with the
measured values. Consequently, the differences between the
two EGA methods are not significant. This indicates that both
yield reasonable estimates of carbonate content.
Identification of the compounds contributing to each of the
peaks in Figure 3 was obtained by running thermal EGAs of
the carbonates of Fe, Li, Na, K, Rb, Mg, Ca, Sr, and Ba, some
of which are shown in Figure 4. The decomposition temperatures of the pure compounds were consistent with literature
values allowing for use of a faster heating rate (16,24)herein,
which shifts obseqved peak temperatures upward. All of the
major and minor elements present in fly ash that form stable
carbonates are included in this set of standards. The identifications are in Table 11. Bicarbonates of Na and K were also
considered; however, since these compounds were found to
release COz by decomposition to the carbonates below -350
"C, their contribution to the fly-ash EGA profiles was considered negligible, except perhaps for Crawford. This possi-

bility is acknowledged in Table I1 but is not included in the

mass balance.
For most bases several compounds may be contributors to
each peak in the EGA profile of the fly ashes. Also listed are
the amounts of carbonate represented by each peak. Some
carbonates may, in fact, exist as mixed-metal mineral entities
or alkaline earth hydroxycarbonates. For most of these minerals, the COSrelease temperatures are the same as those for
the single-metal species within the temperature resolution of
this instrument (see dolomite in Figure 4). As a result, although specific mineral forms cannot be identified from the
COz evolution profiles, a given metal may be associated with
a specific COz peak, allowing a mass balance to be performed.
For example, a COZ peak around 800 OC could indicate calcite,
dolomite, or ankerite, but in any case it does indicate an association between Ca and CO32-. Henceforth, reference to a
particular metal carbonate refers to an association and not
necessarily to a particular crystalline form. The only major
mineral for which this approach may fail is ankerite because
its Fe component decomposes -150 OC higher than in pure
FeC03.
The leachate analyses are presented in Table 111. For each
element, the stoichiometric amount of carbonate that it could
bind was calculated and compared with the C032- present
(Table 11)in the appropriate EGA peak. If leaching removed
carbonates only, the sum of the contributions to each peak
calculated from the metal determinations would equal the
carbonate determined by EGA in that peak. In some cases,
however, species in addition to carbonates are dissolved. Although the mass balance is imperfect, limits can be placed on

Tab6 II. Concentrations of Carbonate on Fly Ashes

and Possible Counterions
fly ash

Crawford

reglon

cq2-, a ppm

total

2300 (26)
18 (26)
1400 (26)
620 (26)
250 (25)
1700 (32)
420 (26)
290 (35)
1000 (34)
2900 (22)
240 (23)
1300 (22)
540 (23)
810 (24)
5200 (27)
230 (25)
2300 (26)
720 (29)
1900 (27)
5300 (22)
290 (22)
2600 (22)
860 (22)
1500 (24)
3600 (22)
210 (23)
1900 (22)
550 (23)
890 (24)

1
2
3
4

Niagara

total
1
2

Cbrrette

total
1
2

3
4

IGS

total
1
2

3
4

IGS, Mag

total
1
2

3
4

IGS, Nonmag

25

100

400
800
TEMPERATURE r c )

ates.

1
2
3
4

1200

Figure 4. Thermal evolved gas analyses of alkaline earth carbon-

total

podble
counlerIon8

NaH, KH
Mg, Ca, Fe
Li, Na, Rb, Sr
K, Ba

Fe, Mg
Ca
Li, Na, K, Rb, Sr, Ba
Fe
Mg, Ca, Li
Na, K, Rb, Sr
Ba

Fe
Mg, Ca, Sr, Li
Na, K, Rb, Ba
7

Fe
Mg, Ca, Sr, Li

Na, K. Rb, Ba
7

Fe
Mg, Ca, Li
Sr, Ba, Na, K, Rb
7

Percent relative average deviations are given in parentheses.

Volume 15, Number 7, July

1981

785

the possible contributions from each metal (Table IV). An

example of the calculation is instructive.
Consider peak 3 of Corrette fly ash (Table 11), which contains contributions from Na, K, Rb, and Sr. Calculated from
the leachable metals in Table 111, the stoichiometric amounts
of carbonate that could be bound are 73,140, <3.5, and 1400
ppm, respectively, but only 541 ppm Cos2- is actually present
(Table 11).Obviously, Na, K, and Rb separately or together
cannot account for this, but Sr can. Therefore, Na, K, and Rb
contribute at most 73, 140, and <3.5 ppm, respectively; Sr
thus accounts at least for the remainder, namely, 320 ppm,
and might contribute all 540 ppm, with some Sr left over if the
other metals are not involved a t all. In Table IV then, Na, K,
and Rb are labeled less than and Sr is given limits from 320
to 540 ppm carbonate. Other overlapping contributions were
handled similarly.
The relative importance of carbonates as mobile species can
be assessed by dividing the amounts of metal in carbonates
(from Table IV) by the total leachable metal (Table 111).This
comparison is shown in Table V.
Several comments are in order. Comparison of IGS with
Corrette (Figure 3) shows that the former appears broader and
shifted to higher temperature. This may be due to a lower
thermal conductivity for IGS, which will delay thermal events
relative to the temperature scale. Recognition of this suggests

that peak 4 arises from Ba alone, as in Corrette, but recalculation of the mass balance indicates that Ba alone cannot account for all of the carbonate. Another possible explanation
is that unburned carbon particles are reducing oxides to form
CO, a reaction that is thermodynamically feasible for FezO3,
for instance (25),and known to occur in thermal analysis of
geochemical samples (26). However, few unburned carbon
particles were observed microscopically. The feature remains
unexplained.
Distinct differences between the magnetic and nonmagnetic
fractions of IGS fly ash (Figure 3) are apparent. The potential
for quantifying these differences in terms of discrete compounds, based on the EGA profiles, is limited by the inability
to resolve the individual features. In general, in the magnetic
fraction the carbonates represent a consistently greater
fraction of the total leachable metal (Table 111).The reason
for this difference may be that the magnetic particles are iron
rich and catalyze carbonate formation or that the carbonate
formation mechanism is a surface phenomenon and magnetic
particles have a greater surface area. These proposals are
purely speculative a t this point; additional experimental investigations would be required to determine why the magnetic
and nonmagnetic fractions differ.
Roughly half of the values in Tables IV and V are unqualified. All of the individual carbonate compounds are present

Table 111. Concentrationsa of Elements Leached from Fly Ashes

lly ash

Crawford
Niagara
Corrette
IGS
IGS, mag
IGS, nonmag

LI

No

Rb

Mg

Ca, %

Sr

Ba

Fe

41.5
38.0
16.1

5.88%
190
55.8
198
251
446

0.412%
950
188
268
242
380

19.2
<6.2
<10.0
<10.2
(7.9

1.82%
188
2.98%
494
230
534

12.0
0.485
12.0
4.05
1.56
4.58

0.678%

1.02%
376
0.433%
98.5
58.7
131

2.59 %
985
0.511%
0.292%
0.195%
0.341 %

8.5

5.2
8.4

<8.0

88.8

0.204%
10.5
7.8
12.4

ppm, unless noted otherwise, with respect to fly ash.

Table IV. Concentrationsa of Carbonate Compounds on Fly Ash

fly ash

LIzCO3

NazCO3

Crawford 1 2 2 0 ( 2 6 )

KzCO3

760-1100d(26)

570d(25)

RkCO3

FeCO3

wco3

CaC03

SrCO3

BaCO3

10.32(26) 0.26%d 0.19%d(26) 0.23%d(26) 0.11-0.15%d 820d(25)

(26)
(26)
c
820d(26) 600d(26)
490 (35)
1 1 5 0 (34)
1 6 8 0 (34)

Niagara

1 2 0 0 (34)

1 4 4 0 (34)

Corrette

1 8 6 (22)

1 1 3 0 (23)

IGS

1 3 4 (26)

460 (29)

470 (29)

IQS, M

5 2 8 (22)

580 (22)

430(22)

IGS, NM

1 4 5 (22)

340-970 (23)

1 6 7 0 (23) c

10.17%
(34)
1330(23) c

520 (23) 0.17-0.18% d0.20-0.21 % d800-1300

(22)
(22)
(23)
440 (25) 10.17%
0.18-0.39% C
(26)
(26)
560 (22) 1 8 0 0 (22) 0.34-0.43% 1 1 3 (22)
(22)
400 (22) 10.18%
O.O98-0.32% 1 2 1 (23)
(22)
(22)

0.33% (24)

180 (29)
110 (22)
1 2 4 0 (23)

a ppm, unless noted otherwise, with respect to fly ash. Percent deviations are given in parentheses. Negligible. For the following sets of elements, each
element contributesto the same E a peak and alone accwnts for all the carbonate presentthere. Value represents amount assuming none of the other contributing
elements is present: Ca and Mg in Corrette; Fe and Mg in Niagara; Fe, Mg, and Ca in Crawford: Sr and Na in Crawford; K and @ain Crawford.

Table V. Percent of Leachable Element a Attributable to Carbonate Form

fly aeh

No

LI

Crawford 0-100
Niagara 0-100
Corrette 0-100
IGS
IGS,M
IGS, NM
a

0-100
0-100
0-100

0.6-0.8d(27)
0-100
0-100
100 (30)
lOO(23)
33-94 (30)

Footnotes b-dare the same as those for Table IV.

~~~~

786

Rb

7.ad(26) 0-100
0-100
c
0-100
c
c
100 (45)
lOO(25)
c
0-100
c

Environmental Science & Technology

Fa

4.gd(37)
40d (32)
4.3 (28)
7.2 (29)
14(31)
5.7 (23)

Mg

3.0d(28)
91 (50)
1.6-1.7d(22)
0-100
0-100
0-100

Ca

0.ad(27)
4.0 (35)
0.7d(22)
1.7-3.8 (26)
8.7-11 (22)
0.8-2.8 (22)

Sr

9.3-13d(29)
0-100
23-39 (24)
c
0-100
0-100

8a

5.6d(25)
0-100
58 (26)
100 (36)
100 (22)
0-100

a t less than 1%.In most cases, the carbonate is a significant

fraction of the total leachable metal and for Na, K, and Ba
may even represent all of the leachable metal.
To determine the conditions under which fly ash would
adsorb COz, we decomposed all of the carbonates in a batch
of IGS ash by heating. The ash, which had partly fused, was
ground to a fine powder in a boron carbide mortar and pestle,
and portions were stored under various conditions. Afterward,
thermal EGAs were run to determine how much C02 had been
readsorbed. Table VI lists the exposure conditions and carbonate found. The capped bottle, representing dry exposure
conditions, showed relatively little C02 uptake, even over a
long period of time. Humid air, regardless of C 0 2 content,
promoted significant absorption of C02 after just 1 week.
Apparently, humid atmospheres promote C02 adsorption.
A further experiment supports this observation. IGS fly ash
was leached with 1M HCl, which has been shown to remove
all carbonates, in air and inside a glovebox containing argon.
A titrimetric method involving aqueous Ba(0H)z absorption
(27) demonstrated that the COz concentration was -0.5-1
ppm on a volume basis. Air contains -350 ppm. The ash was
recovered by filtration and dried, and a thermal EGA was run.
Carrying out the leaching procedure in air yielded 0.73%
Cos2-; performed under low-CO2 conditions, 0.5%C032- was
found.
It is apparent that moisture facilitates the absorption of C02
by fly ash despite low partial pressures of COB.This observation is consistent with studies of CaO and MgO, which indicate that limited chemisorption of COa occurs under dry
conditions below 400 OC (28,29).
Moisture, however, catalyzes
the absorption even a t relative humidities as low as 15%
(28).
Discussion

The occurrence of carbonates in fly ash is not surprising;

however, it is important to consider the significance of this
observation. Since the ashes studied were obtained from
electrostatic precipitator hoppers, two questions arise: (1)Are
the carbonates formed in the flue gas or in the hopper? (2) Can
the analytical results for hopper ash be extrapolated to the ash
which reaches the atmospheric environment as part of the
plume? To answer these, the conditions within the power
plant need to be considered.
If one assumes the boiler to be fired with -20% excess air
(30),the volume percent of C02 in the flue gas will be 16%,and
that of water vapor 7-10% (for air of 0-90% relative humidity).
Ratios of H to C in coal were used to calculate the lower value
(31).The fly ash leaving the boiler will be devoid of carbonates
since the temperature and the particle size opmineral carbonates in coal allow very rapid decomposition (10,32).We
will use CaO as a model compound. Above -400 C and below
the decomposition temperature of CaC03, COz can be adsorbed rapidly and extensively by CaO (28)even though the
relative humidity is much less than 1%.Much of the fly ash
is removed in the electrostatic precipitator where temperatures are -200 OC (33) and the relative humidity is <1%.
When the ash is allowed to cool in the hopper, it is likely to
Table VI. Exposure Study of COz-Free Fly Ash
condlllons

immediately after heating and grinding

capped bottle, no precautions, 3 months
desiccator with KOH as C o n absorber, dish of
water for moisture, 1 week
partly enclosed box, dish of water for moisture,
1 week
original ash

CQ2found, %

0
0.06
0.14

0.17
0.52

absorb more COa, readily aided by ambient moisture. Thus,

the carbonates determined in the ashes studied in this paper
may form in the flue gas or in the hopper.
Addressing the second question, we note that the matrix
composition of the emitted particles is not appreciably different from that of the hopper ash ( 3 , 3 4 ) .As the temperature
of the flue gas decreases along the stack and in the plume, the
relative humidity increases and saturation occurs around 35
OC. Thus, conditions are thermodynamically favorable for
formation of Ca(OH)2 and CaC03.
In addition, the kinetics of absorption are rapid; COz absorption by Ca(OH)2 is extensive only 5 min after exposure
(35).This indicates that the absorption can occur in the plume
before it disperses significantly.

Conclusions
No other analytical method has been shown to have the
potential for such detailed quantitation of carbonates at trace
levels. Admittedly, the instrumentation and analytical figures
of merit require considerable improvement. A moderate
amount of effort should provide significant gains.
Despite unrefined analytical procedures, the experimental
data and the consideration of flue-gas reactions prove that
carbonate compounds occur in fly ash removed by electrostatic precipitators and that these species are likely to be
present in ash released in the plume. Although the concentrations of specific compounds are below 1%by weight of ash,
under acidic leaching conditions some can contribute a significant fraction of the leachable metals.
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(12) Hulett, L. D.; Dunn, H. W.; Dale, J. M.; Emery, J. F.; Lyon, W.
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Received for review April 3,1979. Accepted March 2,1981,

Determination of the Biodegradability of Organic Compounds

Dickson Liu,* William M. J. Strachan, Karen Thomson, and Kazimiera Kwasniewska
Environmental Contaminants Division, National Water Research Institute, Canada Centre for Inland Waters, Burlington, Ontario,
Canada L7R 4A6

radability of organic compounds, many of which may be expected to enter the aquatic environments in the course of their
the relative biodegradability of both water-soluble and -inuse or ultimate disposal. Such an examination is required as
soluble organic compounds under various laboratory envian integral part of the hazard evaluation of new chemicals and
ronmental conditions has been developed. The degradation
in one form or another is proposed in the toxic substances
test system is based on the measurement of the primary biolegislation testing schemes of many of the worlds industrial
degradation rates of such substances in cyclone fermentors
nations.
under aerobic and anaerobic conditions, with and without
Because of the many variables involved, it is impractical to
cometabolites. The degradation is accomplished with a mixstudy the persistence of such compounds in all natural enviture of microorganisms from activated sludge, soil, and sedironments, and consequently several standard laboratory
ments, and abiotic processes are corrected for by the use of
procedures have been developed for the assessment of a
controls. Fenitrothion (O,O-dimethyl-O-(3-methyl-4compounds persistence (1-4). The shaker flask system of the
nitrophenyl) phosphorothioate) and 2,4-D ((2,4-dichloroOECD test used a chemically defined mineral medium with
phenoxy)acetic acid) were tested in the system. The former
the test substance as the carbon and energy source for the
was found to be more readily degraded under anaerobic
microorganisms ( I ). In a different system, Gledhill employed
cometabolism conditions (Tl/2= 1.0 day) than when the same
a continuous-flow activated sludge system representative of
system was aerobic (T1/2= 5.5 days); when fenitrothion was
a treatment plant operation for the evaluation of a substances
the sole carbon source (metabolism), its stability was greater
persistence (2). Sturm developed a screening test for the asstill, especially under aerobic conditions. The herbicide 2,4-D
sessment of the biodegradability of nonionic surfactants by
was easily degraded under aerobic conditions (T1/2= 1.8 and
following the C 0 2 evolution ( 3 ) . The model ecosystem of
3.1 days for cometabolism and metabolism, respectively);
Metcalf et al. was basically an aquarium with terrestrialhowever, under anaerobic conditions, its degradation rate was
aquatic interface and a seven-element food chain ( 4 ) .Unforgreatly decreased (Tl/z = 69 and 135 days, respectively) to the
tunately, examination of all of these tests reveals that there
point where the rates were comparable to those of abiotic
are basic differences in the degradation environments under
processes. The precision of the test system was checked with
which the test substances are idvestigated. As a result, comaniline and found to be f32% relative standard deviation on
parison between different studies in the literature is extremely
T1/2= 0.21 day for aerobic cometabolism.
difficult, and much of the data have only limited value with
regard to assessing the relative stability of chemicals. For
example, the persistence of 2,4-D in soils has been reported
to be between 4 weeks and 3 yr ( 5 ) ,reflecting the impact of
anoxic conditions on the chemicals persistence. This particIntroduction
ular problem is further compounded by the fact that certain
compounds, such as DDT, do not provide a suitable sole source
The fate of synthetic organic compounds in the environment is an area of international concern since the contamiof carbon and energy to support microbial growth (metabonation of natural waters with these man-made substances has
lism) and consequently other organic nutrients are needed to
constituted a major impact on aquatic ecosystems and hence
support the biodegradation microorganisms (cometabolism),
a fact which is frequently ignored in test systems. Another
represents a serious problem to the management of water
common drawback in interpreting most persistence studies
quality. Therefore, it is appropriate to examine for biodeg-

w A standard procedure and a new apparatus for determining

788

Environmental Science & Technology

0013-936X/81/0915-0788$01.25/0

@ 1981 American Chemical Society