Arch. Environm. Contam. Toxicol.
11, 69-72 (1982)
Occurrence of Polycyclic Aromatic Hydrocarbons in Municipal Sewage
Sludge Ashes
P a t r i c i a C., W s z o l e k I a n d T i m o t h y W a c h s
Toxic Chemicals Laboratory, New York State College of Agriculture and Life Sciences, Cornell University,
Ithaca, New York 14853 and Department of Chemistry, Cornell University, Ithaca, New York 14853
Abstract. S l u d g e a s h r e s i d u e s f r o m four cities that
i n c i n e r a t e m u n i c i p a l s e w a g e sludge w e r e a n a l y z e d
for isolated p o l y c y c l i c a r o m a t i c h y d r o c a r b o n s .
T o t a l a m o u n t s o f P A H s in the a s h e s w e r e in the
r a n g e o f 0.1 - 1/xg/g. T h e a s h c o n t a i n i n g the h i g h e s t
a m o u n t also e x h i b i t e d the g r e a t e s t v a r i e t y o f P A H s .
Polycyclic aromatic hydrocarbons (PAHs) have
b e e n l o n g r e c o g n i z e d as c o m b u s t i o n p r o d u c t s
w i d e l y d i s t r i b u t e d i n the e n v i r o n m e n t . O n e s o u r c e
of these compounds, some of which are car-
c i n o g e n i c a n d m u t a g e n i c , is refuse b u r n i n g ( N a t i o n a l
A c a d e m y o f S c i e n c e s 1972). R e c e n t s t u d i e s h a v e
p r o v i d e d a n a l y t i c a l d a t a for P A H s in fly ash (Eice-
m a n et al. 1979) a n d ash r e s i d u e s ( D a v i e s et al.
1976) f r o m i n c i n e r a t o r s c o m b u s t i n g r a w m u n i c i p a l
refuse. I n f o r m a t i o n is s c a r c e o n the p r e s e n c e of
P A H s a n d o t h e r t r a c e o r g a n i c c o m p o u n d s in a s h
r e s u l t i n g f r o m i n c i n e r a t i o n o f s e w a g e sludge, m u n i -
cipal w a s t e w h i c h has b e e n t r e a t e d a n d p a r t i a l l y
d i g e s t e d p r i o r to c o m b u s t i o n . It is i m p o r t a n t to
k n o w the b u r d e n of t o x i c a n t s in this ash, b e c a u s e
it is o f t e n d i s p o s e d of in landfills w h e r e l e a c h i n g
into g r o u n d w a t e r s m a y o c c u r , a n d it m a y also b e
u s e d as a n a m e n d m e n t to a g r i c u l t u r a l soils.
T e n cities supplied r e p r e s e n t a t i v e samples of
sludge a s h e s for a n a l y s i s . M u l t i e l e m e n t a n a l y s i s a n d
P C B a n a l y s i s h a v e b e e n r e p o r t e d for t h e s e a s h e s as
well as i n f o r m a t i o n c o n c e r n i n g the i n c i n e r a t i o n pro-
c e s s e s ( F u r r et al. 1979). D u r i n g a n a l y s i s for P C B s ,
the p r e s e n c e o f s i g n i f i c a n t a m o u n t s o f P A H s w a s
o b s e r v e d in a n e x t r a c t f r o m o n e of the s a m p l e s .
S u b s e q u e n t l y , f o u r o f the sludge a s h e s w e r e c h o s e n
for a s t u d y o f t h e i r P A H c o n t e n t . T h e a s h e s s e l e c t e d
are f r o m s e w a g e t r e a t m e n t p l a n t s in the s u r v e y t h a t
r e c e i v e d the largest i n d u s t r i a l c o n t r i b u t i o n (Saginaw,
M I a n d I n d i a n a p o l i s , I N ) a n d t h o s e r e c e i v i n g the
1Address correspondence to Patricia C. Wszolek
Archives of Environmental
Contamination
and Toxicology
largest p r o p o r t i o n o f d o m e s t i c s e w a g e ( H i l t o n , N Y
a n d L o r t o n , VA).
Experimental
The sludge ashes were air-dried, pulverized in a hammermill
containing a 3-ram sieve, mixed by tumbling, subsampled for
analysis, and stored at room temperature. Samples (40 g) from
each of the four cities were extracted in a Soxhlet apparatus for
six hr with 200 ml of 1:1 benzene:methanol. The method of Giger
and Schaffner (1978) was employed for subsequent isolation of
PAHs in the filtered and concentrated extracts using Sephadex
LH-20 (Pharmacia Fine Chemicals, Inc., Piscataway, NJ) and
silica gel (Fisher Scientific, 28-200 mesh) which had been washed
with methylene chloride and activated at 260~ C. Samples and
solutions were protected from light during extraction and isola-
tion. Benzene, toluene, methylene chloride, and hexane were
distilled-in-glass solvents supplied by Burdick and Jackson
(Muskegon, MI). Methanol was A.C.S. certified (Fisher Scien-
tific, Fairlawn, NJ). PAH compounds were isolated in the
methylene chloride fraction eluted in the final silica gel chro-
matography step for each extract. These fractions were carefully
evaporated by dryness at 30~ C; one rnl of toluene was added im-
mediately. Analysiswas by electron capture gas chromatographyand
combined gas chromatography-mass spectrometry. A Tracor 220
gas chromatograph equipped with a 6aNi detector and a glass
column (180 cm • 2 mm i.d.) packed with 3% OV-101 on 100/120
mesh Gas Chrom Q was used to obtain quantitative data for
major PAH components. Flow rate through the column was 30
cma/min nitrogen. Detector and injector temperatures were 310~
C and 250~ C, respectively. Various isothermal column oven
temperatures (150~ C, 170~ C and 225~ C) were used for each
isolated sample to resolve individual PAHs from other sample
components and possible isomers over a relatively wide range of
molecular weights (-150-300). Detector response was calibrated
with solutions of authentic standards (PAH Standards Kit plus
triphenylene) obtained from Analabs, Inc. (North Haven, CT).
A Finnigan Model 3300 gas chromatograph mass spactrometer
with a System Industries 150 data system, was used to obtain
electron impact (EI) spectra and negative ion electron capture
chemical ionization (NCI) spectra. The column was glass, 2 mm
x 150 cm, packed with 3% OV-101 on 100/120 mesh Gas Chrom
Q, and was programmed from 140~ to 300~C at 8~ C/min. Helium
(20 cm3/min)was the carrier gas for EI and methane, adjusted to
give a pressure of 1 Torr in the ion source, was the carrier gas for
NCI. Negative ions were formed by electron capture in a chemi-
0090-4341/82/0011-0069 $01.00
9 1982 Springer-Verlag New York Inc.
70 P.C. Wszolek and T. Wachs

Table 1. Data pertaining to municipal sewage sludge incinerator ashes

Ratio (%)
industrial:
Sewage domestic Combustion Combustion Feed rate
City treatment plant contribution unit temp, ~ tons/ha Additives

Hilton, NY Northwest Quadrant 2:98 multiple 775-870 4 aluminum sulfate

Treatment Plant (6) hearth
Indianapolis, IN Dept. Public Works 70:30 multiple 800-1000 5 dry sludge ash
(8) hearth
Lorton, VA Lower Potomac 10:90 multiple 775-870 5 ferric chloride, lime
Treatment Plant (6) hearth
Saginaw, MI Saginaw Wastewater heavily multiple 870-925 5 ferric chloride, lime
Treatment Plant industrial (6) hearth

a Moist sludge cake

ment. The residual ash was ultimately disposed in

Table 2. Anthracene in sludge ashes
landfills.
City Concentration (ng/g) Various PAH standards were carried through the
isolation procedure to assess recoveries: anthracene
Saginaw, MI 240
(5.6/zg); fluoranthene (12.5/zg); pyrene (26.4/zg);
Hilton, NY 230
Lorton, VA 180
1,2-benzanthracene (5.6 /zg); and benzo[ghi]-pery-
Indianapolis, IN 65 lene (4.0/zg). Recoveries were 4.3 /zg (77%); 10.3
/zg (82%); 21.2/~g (80%); and 3.6/zg (90%), respec-
tively. No correction for recoveries was applied
to quantitation of ash extract components. A pro-
Table 3. Major PAHs in Saginaw, Michigan sludge ash a cedure blank including extraction and isolation
Concentration steps exhibited no peaks interfering with the deter-
Mol. wt. ng/g mination o f compounds of interest. The limit of
178 anthracene 240
detection for the PAHs studied was approximately
192 methylanthracenes/-phenanthrenes 50/zg/g of ash (electron capture GC) and 25 /zg/g
202 fluoranthene 385 ash (GCMS in the EI mode).
202 pyrene 120 Because of the stability of their aromatic ring
206 ethylanthracenes/-phenanthrenes or
dimethylanthracenes/-phenanthrenes systems, the individual PAHs have simple mass
226 benzo[ghi]fluoranthene spectra which exhibit little fragmentation and the
228 1,2-benzanthracene 120 molecular ion is the base peak in every case. While
a Other less abundant PAH species tentatively identified in the electron
this feature is a good, sensitive indicator of the
impact GCMS data for Saginaw sludge ash are: Mol. wt. 184 dibenzo- compound class, it does not allow for a distinction
thiophene; 198 methyldibenzothiophenes; 204 methyl-4,5-methylenephen- between PAH isomers. Therefore, a combination of
anthrene; 212 ethyldibenzothiophenes; 216 methylfluoranthenes or meth-
ylpyrenes; 252 benzopyrenes, benzofluoranthenes or perylene
gas chromatographic retention time of resolved
species together with the individual mass spectrum
is required for identification. Quantitative data for
cal ion source with methane serving as the reagent gas (Stafford resolved PAH isomers were obtained by isothermal
et al. 1978).These negative ions were detected by a modification electron capture gas chromatography (Tables 2
of a conversion dynode system previously described (Hunt et al. and 3).
1976). The GC traces of final fractions isolated from the
four sewage sludge ashes showed that more PAHs
Results and Discussion were present in the Saginaw, MI ash then in the
other three ashes where only anthracene was found
Table 1 lists the estimated industrial contribution to in measurable amounts (Table 2). The GCMS data
the incoming sewage for each of four treatment were searched for the molecular ions of commonly
plants and summarizes some of the data pertinent to occurring PAHs and their alkylated homologs. The
the operation of their incinerators. Operating con- Saginaw ash contained a variety of PAH species
ditions appear to be similar among the plants except (Table 3). Electron impact mass chromatograms for
for the Indianapolis facility which re-incinerates its the most abundant of these species are shown in
ash and uses eight hearths versus six. All plants Figure 1. By contrast, only anthracene (m/e 178)
carried out primary and secondary sewage treat- and methylanthracene or methylphenanthrene (m/e
Polycyclic Hydrocarbons in Sewage Sludge Ash 71

I SUH
E - ~ 1,1 i i , l , I i ~ i 9 i 9 r - ~ , i 9 i i i *

i 9 , . L 9 ~ 9 i 9 ~ ' i 9 ~ i 1 , 1 . 1 i - i i - i i , i , 9

f - i 9 i , ~ i i i , l - [ , i 1 - 1 - [ , [ , 1 i .-
k_..._ -'/8
I , I , ~ i q~-i '1" i i ~

252
i 9 t ~ , i 9 i i i , l - i ~ i 9 , 9 i 9 i - , - ~ ' ~ h - ~ 9

/~.__.
__•L.• 202
, i i i . i 9i ~. i i -i i ; 9! i"~,--l~-i~-~'-i':~, i 9 i ~ ; j , , i ,~i= r i i i i i i ~ - j , )

-- ' t92

--~ 1q8
-- I ' ' ' ' ' ' ' ' ' 1 '
SOJN10 O
M IN. 5
14 0 200
I0
1 ~ 514 o . . . . . .
15
s .,idb
MIN. 5 lO 15
gdo 20

Fig. 1. Electron impact mass chromatograms for the most abun- Fig. 2. Negative ion electron capture chemical ionization mass
dant PAHs in Saginaw, M1 sewage sludge ash. The number in the chromatograms of selected PAH components in Saginaw, MI
upper right hand corner of each chromatogram is the mass of the sewage sludge ash. The number in the upper right hand corner of
molecular ion plotted. The top plot labeled " S u m " is a compos- each chromatogram is the mass of the molecular ion plotted. The
ite of all these molecular ions normalized in intensity to the most top plot labeled " S u m " is a composite plot of all these molecular
intense ion, rrde 202 ions normalized in intensity to the most intense ion, m/e 2%

192) were detected in electron impact GCMS data combustion temperature used at the Saginaw facil-
for the other ashes studied. ity was reported as 870~ to 925 ~ C (Table 1 ). The
The final fraction isolated from the Saginaw PAH content of the Saginaw sewage sludge prior to
sludge ash was further examined by GCMS under combustion is not known, but it is possible that
electron capture negative chemical ionization con- PAHs were present. The data show that the level of
ditions and PAHs of molecular weight 276, 278, and PAHs in sewage sludge ash residues can vary
300 were detected (Figure 2). The NCI technique widely. No clear correlation was found between the
allows greater sensitivity than the electron impact amount of PAHs and the industrial input into the
mode for compounds which capture electrons. In sewage of the cities studied.
addition, there was a mass or ionization discrimina-
tion favoring or enhancing the intensity of species at
higher mass relative to electron impact data for the Acknowledgment We are grateful for the use of the mass spec-
same mixture. This is particularly evident for the trometry facilities in the Department of Chemistry, Cornell Uni-
PAH species at m/e 252, 276, 278, and 300. There versity, and thank Dr. Donald J. Lisk for helpful discussions and
encouragement.
are several possible isomers at m/e 276 including
benzofluoranthenes and benzo[ghi]perylene; m/e
278 may be a dibenzanthracene; m/e 300 is probably
coronene. References

The distribution of P A H s o b s e r v e d in the

Saginaw sewage sludge ash is consistent with their Blumer, M.: Polycyclic aromatic compounds in nature. Scientific
American 234, 34 (1976).
formation at a temperature of about 800 ~ C or Committee on the Biological Effects of Atmospheric Pollutants:
somewhat higher. PAHs that bear no alkyl side Particulate polycyclic organic matter. National Academy of
chain or only one alkyl carbon (methyl-) predomi- Sciences, Washington, DC (1972).
nate in this temperature range (Blumer 1976). The Davies, I. W., R. M. Harrison, R. Perry, D. Ratnayaka, and
72
R. A. Wellings: Municipal incinerator as source of polynu-
clear aromatic hydrocarbons in environment. Environ. Sci.
Technol. 10, 451 (1976).
Eiceman, G. A., R. E. Clement, and F. W. Karsek: Analysis of
fly ash from municipal incinerators for trace organic com-
pounds. Anal. Chem. 51, 2343 (1979).
Furr, A. K., T. F. Parkinson, T. Wachs, C.A. Bache, W. H.
Gutemann, P. C. Wszolek, I. S. Pakkala, and D. J. Lisk:
Multielement analysis of municipal sewage sludge ashes.
Environ. Sci. Technol. 13, 1503 (1979).
Giger, W., and C. Schaffner: Determination of polycyclic aro-
matic hydrocarbons in the environment by glass capillary
gas chromatography. Anal. Chem. 50, 243 (1978).
P . C . Wszolek and T. Wachs
Hunt, D. F., F. C. Stafford, F. W. Crow, and J . W . Russell:
Pulsed positive negative ion chemical ionization mass spec-
trometry. Anal. Chem. 48, 2098 (1976).
Stafford, G. C., J. R. Ruher, and M. S. Story: A novel negative
ion detection system for a quadrupote mass spectrometer.
Proc. Annu. Conf. Mass Spectrom. Allied Top., 26th, 459
(1978).
Manuscript received December 8, 1980; accepted February 3,
1981.