EPA-600/D-81-066
A REVIEW OF OCCURRENCES AND TREATMENT OF POLYNUCLEAR
AROMATIC HYDROCARBONS
R. Kent Sorrell
Herbert J. Brass
Richard Reding
U.S. ENVIRONMENTAL PROTECTION AGENCY
Office of Drinking Water
Technical Support Division
5555 Ridge Road
Cincinnati, Ohio 45268
Published in
Environment International
Volume IV, 1980
February, 1981
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ABSTRACT
A literature review has been conducted into the scope of PAH contamination
of raw, finished, and distributed waters. The concentrations of PAHs in
drinking water sources range from nanogram to microgram-per-liter quantities.
Conventional treatment (flocculation, sedimentation, chlorination, and
filtration) appears to substantially reduce total PAH concentrations
present at higher concentrations in source waters. A major factor in
this reduction is the removal of PAHs adsorbed onto particulate matter.
The role of chlorination is not clear and reactions of PAHs with chlorine
may in fact produce products which themselves are deleterious. Activated
carbon can further assist in PAH removal. However, it may be inappropriate
for treatment of PAHs present at low concentrations. Water entering the
distribution system can become recontaminated via contact with reservoirs
and pipes coated with coal-tar or asphalt based products.
-------
Introduction
Polynuclear aromatic hydrocarbons (PAHs) are compounds of two or
more aromatic rings, where adjacent rings share two carbon atoms. The
molecular weights and relative carcinogenic potential of some PAHs that
have been detected in water are given in Table I. The high molecular
weight and nonpolar nature of PAHs afford compounds of low solubility in
water. The solubility ranges from 1.6 mg/1 for phenanthrene (Ph) to
0.01 - 4 yg/1 for benzo(a)pyrene (B(a)P) (Davis et al, 1942; Andelman
and Snodgrass, 1974). The concentrations of PAHs in surface waters,
however, are in part dependent on the organic loading of the aqueous
system, which affects PAH solubilities, and on the amount of suspended
particulate matter to which PAHs can adsorb. This is exemplified by the
occurrence of up to 1000 jjg/1 of B(a)P in coke or oil-gas plant effluents
(Wedgewood and Cooper, 1956). For raw water sources, the concentrations
are typically much lower.
Scope of PAH Contamination
Among the first studies performed to determine the magnitude of PAH
concentrations in water were those of Borneff. These investigations
dealt primarily with surface and ground waters located in Germany. The
data from one such study (Borneff and Kunte, 1964) are listed in Table
II. (Data given in these and subsequent tables and in the text are as
reported in the cited references. No attempt was made to evaluate
sampling and analytical procedures used or the significant figures
reported.) Surface waters in the Soviet Union have been shown to be
vulnerable to PAH contamination as well (Table III) (Andelman and
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Table I
PAHs Found in Water0
Structure
Name
Molecular
Weight
Relative
Carcinogenic
Activity
Anthracene An
178
Benzo(a)anthracene B(a)A 228
Benzo(b)fluoranthene B(b)F 252
Benzo(j)fluoranthene B(j)F 252
Benzo(k)fluoranthene B(k)F 252
Benzo(a)pyrene B(a)P
Benzo(e)pyrene B(e)P
252
252
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Table I
PAHs Found in Watera
Structure
Name
Molecular
Weight
Relative
Carcinogenic
Activity0
Benzo(ghi)perylene B(ghi)P
Chrysene Ch
Fluoranthene Fl
276
228
202
Indeno(l,2,3-cd)pyrene IP
276
Phenanthrene Ph
178
Perylene Per
Pyrene Pyr
252
202
a Sorrel 1, et.al., 1977.
b +++, ++, strongly carcinogenic; +, carcinogenic; +, uncertain or weakly
carcinogenic; -, not carcinogenic (NAS, 1972).
c Discussed 1n NAS Report (1977).
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Table II
Concentrations (ng/1) of PAHs in Surface and Ground Waters in Germany3
Location
Groundwater I
May, 1963
Groundwater II
August, 1963
Groundwater III
January, 1964
Danube R. at Ulm
April, 1964
Bodensee
May, 1964
Danube R. at Ulm
May, 1964
Main R. at Seligenstradt
July, 1963
Main R. at Seligenstradt
April, 1964
Rhine R. at Mainz
May, 1964
Rhine R. at Mainz
March, 1964
Fl
42.0
26.2
169.0
94.0
21.4
61.0
128.3
192.0
146.0
258.0
Pyr
b
b
104.0
74.5
b
0.3
109.8
92.8
b
2.0
B(a)A
b
1.0
23.2
11.0
5.0
14.0
14.4
16.2
53,5
185.0
B(J)F
b
1.0
10.0
10.1
13.0
23.4
35.7
75.5
21.3
150.0
B(b)F
0.8
1.0
11.5
24.2
7.7
23.9
32.1
67.0
77.8
156.0
Ch
b
b
b
b
b
b
38.2
b
b
b
B(a)P
0.1
0.6
23.4
0.6
1.3
b
2.4
6.5
49.2
114.0
B(ghi)P
0.8
0.5
17.5
9.5
3.2
9.5
21.2
25.9
43.2
134.0
B(k)F
0.8
0.5
10.0
7.7
2.7
14.1
10.6
21.6
27.4
117.0
IP
0.4
0.5
12.6
9.5
2.6
16.4
32.0
23.7
35.8
123.0
a Borneff and Kunte, 1964.
b Not reported.
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Table III
Occurrences of Benzo(a)pyrene in Surface Waters in the Soviet Union3
Source Concentration, ng/T
Moscow Reservoirs 4,000 - 13,000
Volga River 0.1
(below refinery)
Pskov Region <0.1
Sunzha River 50 - 3,500
(3-4 km below refinery)
Sunzha River 70 - 1,060
(25 km below refinery)
a Andelman and Snodgrass, 1974.
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Snodgrass, 1974). Their ubiquity is further illustrated by the data in
Tables IV (Acheson et al, 1976) and V (Lewis, 1975) where both the
Thames and Severn Rivers in England were investigated. These data
indicated that individual PAHs can occur in concentrations ranging from
the low ng/1 to pg/1 levels. The studies of waters in Europe are
currently being complemented by analyses of waters within the United
States. The U.S. EPA has been responsible for the bulk of data collected,
which to date have indicated that U.S. waters also contain PAHs.
The first attempt to gain comprehensive data on PAH levels in U.S.
waters was the National Organic Monitoring Survey, Phase I and II,
(NOMS, 1978), where mostly finished waters were sampled and analyzed.
These data indicated the presence of fluoranthene in several supplies
with an observed maximum value of 80 ng/1. The analyses of raw and/or
finished waters of 11 supplies in the U.S. are reported in another study
recently completed (Saxena et al, 1977; Basu et al, 1978) (Table VI). A
varying amount of PAH contamination in raw waters, 4.7 - 1600 ng/1 for 6
PAHs was found. This variation is believed to be a function of industrial
contamination. In general, the finished water data show reduced concentration
of PAHs. Note that some of the supplies use activated carbon in the
treatment process. The PAH reduction in raw water through conventional
treatment is apparent from data gathered by the Technical Support Division,
ODW, US EPA, (Table VII). However, reduction by treatment is not demonstrated
in every case. For example, while data from Cincinnati, OH, Cape Girardeau, MO,
Wheeling, WV, and Jefferson Parish, LA show excellent removal of 7 PAHs
(chrysene through indeno(l,2,3-cd)pyrene) using conventional treatment,
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Table IV
PAH Concentrations (ng/1) in the Thames River0
Compound
Fluoranthene
Pyrene
Benzo(a)anthracene and
Chrysene
Benzo ( b ) fl uoranthene
Benzo( j )f 1 uoranthene
Benzo(k)fl uoranthene
Benzo(a)pyrene
Benzo(e)pyrene
Perylene
Indeno(l ,2,3-cd)pyrene
Benzo(ghi)perylene
a Acheson, et.al., 1976.
b Summation of isomers.
c Not reported.
Kew Bridge
180
260
140
240
210
40
100
40
Location
Albert Bridge
20
50
270
150
c
c
70
40
Tower Bridge
180
230
530
430
130
120
110
30
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Table V
PAH Concentrations (ng/1) in the Severn Riverc
Compound
Fl uoranthene
Benzo(a)pyrene
Indeno(l ,2,3-cd)pyrene
Benzo ( k )f 1 uoranthene
Benzo(ghi)perylene
Atcham
15
1.5
6.1
0.8
2.0
Bewdly
28.5
6.5
3.9
4.0
6.3
Location
Holt
Fleet
21.5
9.2
7.8
3.1
10.5
Haw
Bridge
25.2
13.5
10.0
7.7
11.3
Maisemore
128.4
12.5
7.9
3.4
7.6
a Lewis, 1975.
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Table VI
Concentrations (ng/1) of PAHs in Raw and Finished Waters in the United States3
City F] uoranthene Benzo(j)fl uoranthene Benzo(k)fluoranthene Benzo(a)pyrene
Syracuse, NY
Finished
Buffalo, NY
Raw
Finished
Pittsburgh, PAC
Raw
Finished
Huntington, WVAd
Raw
Finished
Philadelphia, PA
Raw
Finished
Endicott, NY
Finished
Hamnondsport , NY
Finished
New York City, NY
Finished
Lake George, NY
Finished
New Orleans, LA
Finished
Wheeling, MVAe
Raw
Finished
b
b
b
408.3
b
23.5
2.4
114.3
8.9
4.3
b
b
b
b
756.5
94.5
b
b
b
35.7
0.3
5.0
0.3
42.6
b
0.2
0.3
1.2
0.3
b
180.7
1.4
a Saxena, et.al., 1977.
b Indicates not detected, with a detection limit ranging from 0.1 - 4.
c Two stage activated carbon treatment; powdered A.C., then granulatec
d Granulated A.C. filtration.
e Addition of powdered A.C.
0.4
0.6
b
19.1
0.2
3.6
0.2
33.0
b
b
0.1
0.7
0.1
0.6
115.5
b
6 ng/1.
A.C. filtration.
0.3
0.3
0.2
42.1
0.4
5.6
0.5
41.1
0.3
0.2
0.3
0.5
0.3
1.6
206.4
2.1
Indeno(l ,2,3-cd)pyrene
b
b
b
60.4
1.2
9.5
1.2
72.4
1.7
0.7
0.9
2.2
0.9
b
180.0
7.8
Benzo(ghi)perylene
0.4
3.8
0.7
34.4
0.7
10.7
2.5
48.4
4.0
2.9
1.9
1.8
2.6
2.2
147.0
32.7
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Table VII
PAHs in Raw and Finished Waters in the United States3 (ng/1]
Compound
Ph
Fl
Pyr
1-MP
An
Ch
B(a)A
Per
B(e)P
8(a)P
B(ghi)P
B(b)F
B(k)F
DiB(ah)A
IP
Total
Cincinnati
OH
Raw Fin
14
<7
<14
<6
b
4
4
b
b
9
<1
5
3
<1
<4
39
a Sorrel 1 , et.al. ,
b Not analyzed.
10
<3
<4
<4
b
<1
<1
<1
<1
<1
<1
<1
<1
<1
°
10
1979.
New Orleans Miami Seattle Portland
LA FL WA OR
Distributed Raw Fin Raw Fin Raw
14 6 14 10 12 8
<5 <4 <4 <4 <8 4
<3 <4 <6 <4 <6 6
b <2 <1 <1 <1 <1
b b b b b b
<1 <1 2 <1 2 <1
<1 <1 <1 <1 <1 <1
<1 <1 <1 <1 <1 <1
<1 <1 <1 <1 <1 <1
<1 <1 <1 <1 <1 <1
<1 <1 <1 <1 <1 <1
<1 <1 <1 <1 <1 <1
<1 <1 <1 <1 <1 <1
<1 <1 <1 <1 <1 <1
<1 <1 <1 <1 <1 <1
14 6 16 10 14 18
Columbus Cape Girardeau
OH MO
Fin Raw Fin
3 14 5
1 11 1
<1 9 <1
<1 <1 <1
b 1 <1
<1 5 <1
<1 4 <1
<1 b <1
<1 b <1
<1 4 <1
<1 4 <1
<1 4 <1
<1 2 <1
<1 <1 <1
<1 <3 <1
4 58 6
Wheeling
wv
Raw Fin
9 4
15 4
15 2
5 <1
b <1
8 <1
9 <1
<4 <1
b <1
13 <1
9 <1
16 <1
7 <1
1 <1
<12 <1
107 10
Jefferson
LA
Raw
20
25
18
5
2
8
9
7
<14
12
7
9
3
<2
<9
125
Parish
Fin
14
7
3
<2
<2
<2
<2
b
<2
<2
b
<2
<2
<2
<2
24
Tucson
AZ
Raw
10
<2
<2
<2
<2
<2
<2
b
<2
<2
b
<2
<2
<2
<2
10
-------
data from Miami and Seattle indicated no removal for the lower molecular
weight (PAHs) phenanthrene, fluoranthene, and pyrene.
Removal of PAHs From Contaminated Waters
Effective removal of PAHs from raw water appears to be closely
related to particulate removal and thus, conventional water treatment
practices are generally quite effective. Data in Table VIII (Lewis,
1975) indicates consistently higher quantities of PAHs associated with
the suspended solids, than with the aqueous portion. In their study of
the treatment process, Crane et al. (1978) found clarification, i.e.
removal of particulates, reduced the PAH level from 50 ng/1 to less
than 10 ng/1 (Figure 1). It also can be seen that chlorination and the
use of activated carbon (most probably powdered) can affect PAH reduc-
tion. Samples from the point of prechlorination and addition of activated
carbon reveal a PAH reduction of 35 ng/1. What portion of this reduction
is due to activiated carbon is not clear, as the chlorination process
itself can contribute to PAH reduction.
Chlorination
The effects of chlorination on PAHs have been investigated by
several researchers. Il'nitskii et al (1971) found a PAH reduction
after 30 min contact time with 0.5 mg/1 chlorine residual. A summary
of some of the investigations concerning the reactions of PAHs in the
presence of chlorine, is given in Table IX (Oyler and Carlson, 1978).
The removal of PAHs that might be attributable to chlorination during
normal treatment is given in Table X (Harrison et al., 1976). These
data were obtained after an initial chlorine dose of 5 mg/1 at a pH of
7.5; the free chlorine residual at 3 hours contact time was 0.5 mg/1.
11
-------
Total PAHs (ng/1)
50. . . .100
River
Active carbon and
prechlorination
Alum and
Polyelectrolyte
After Clarification
After Filtration
Finished Water
FIGURE 1
12
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Table VIII
Concentrations (ng/1) of PAHs in the River Trent and its Tributaries6
PAHs in Suspended Solids
R.
R.
R.
R.
R.
R.
R.
R.
Location
Trent - Hanford
Dove - Mapleton
Dove - Above Rocester
Trent - Yoxall
Trent - Walton
Amber - Ambergate
Trent - Willington
Derwent - Little Eaton
Reservoir Water - Derwent
Fl
165.0
18.0
12.0
121.1
150.0
20.0
77.0
22.0
1.2
Final Treated Water - Derwent
R.
R.
a
b
c
Soar - Kegworth
Trent - Keadby
Lewis, 1975.
The participate matter filterec
Filtrate of water sample.
14.0
928.0
from
B(a)P
57.0
8.8
7.8
51.0
95.0
15.0
54.0
9.4
0.8
No
14.0
504.0
IP
39.0
5.8
4.5
46.0
66.0
24.0
42.0
6.1
0.6
Suspended
11.0
195.0
B(k)F
33.0
6.8
4.7
33.0
76.0
11.0
36.0
8.4
0.5
Matter
13.0
265.0
b
B(ghi)P
72.0
12.5
10.5
65.0
138.0
57.0
71.0
13.6
1.7
26.0
688.0
PAHs in Solution0
Fl
15.0
4.0
4.8
4.8
6.6
16.0
6.0
3.7
1.3
0.8
1.1
15.0
B(a)P
0.5
0.2
0.2
0.4
0.9
1.8
0.4
0.2
0.1
0.1
0.1
0.2
IP
1.2
0.8
0.4
0.6
0.7
8.0
0.4
0.0
0.7
0.0
0.2
0.2
B(k)F
0.5
0.2
0.2
0.3
0.9
1.0
0.5
0.2
0.1
0.1
0.3
0.1
B(ghi)P
1.6
0.9
0.7
1.0
1.9
11.0
1.1
0.8
0.4-
0.4
0.7
0.5
water sample.
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Table IX
Aqueous Chlorination Reactions of Polynuclear Aromatic
Hydrocarbons: Selected Results From Literature Reports
Compound
benzo(a)pyrene
Compound
ug/1
1
1
Chlorine
mg/1 pH
0.5
0.3
Time (Hr)
0.5
0.5
2
Products/Comments
81% reduction
94% reduction
82% reduction
92% reduction
Reference
Tralsttman and
Manita, 1966
benzo(a)pyrene
benzo(a)pyrene
benzo(a)pyrene
0.3
0.5
0.4-
0.6
3
3
22
2
13
0.5
2.0
24
2.0
24
Products identified:
5-chloro-3,4-benzo-
pyrene and 3,4-benzo-
pyrene quinone
50% reduction
50% reduction
83% reduction
50% reduction
100% reduction
Products identified:
5-chloro-3,4-benzo-
pyrene and 3,4-benzo-
pyrene-5,8-quinone
68-75% reduction
80-83% reduction
88-90% reduction
90% reduction
95% reduction
Products identified:
5-chloro-and 5, 8, 10
trichloro-derivatives
Graef and
Nothhafft,
1963
Gabovich,
et.al., 1969
Mueller and
Reichert, 1969
-------
Table IX (Cont'd)
Aqueous Chlorination Reactions of Polynuclear Aromatic.
Hydrocarbons: Selected Results From Literature Reports0
Compound
benzo(a)pyrene
aromatic fraction
fraction of
diesel fuel
Compound
ug/1
10.5
4.3
11.25
13.62
12.70
13.50
Chlorine
rng/1
6
6
6
6
6
6
100
pH Time (Hr)
1.5
3.0
6.0
1.5
3.0
6.0
7.2 1
30
Products/Comments
anionic detergent present
86% reduction
anionic detergent present
82% reduction
anionic detergent present
92% reduction ^
Tween 80 present
85% reduction
Tween 80 present
88% reduction
Tween 80 present
92% reduction
chloro-C2 3naphthalene
identified
100% reduction of naph-
thalene, phenathrenes,
anthracenes
Reference
Sforzol ini ,
et.al., 1971
Reinhard,
et.al., 1976
naphthalene 10000
1-methyl-naphtha- 0.53
lene
fluorene 0.33
anthracene 0.97
30
24
1.2
12.4
6.0
4.1
7.0
6.5
16
0.5
3.75
66% naphthalene, 3-2%
1-chloronaphthalene,
and 1% 1,4-dichloro-
naphthalene
1-chloro-4-methyl-
napthalene (73% yield)
fluorene (73% yield)
anthraquinone (78% yield)
Smith, et.al.,
1977
Oyler, et.al.,
1978
-------
Table IX (Cont'd)
Aqueous Chlorination Reactions of Polynuclear Aromatic.
Hydrocarbons: Selected Results From Literature Reports'
Compound
Compound ug/1
phenanthrene
1 -methyl phenan-
threne
fluoranthene
benz ( a ) anthracene
benz(e)acepherianthry-
lene
benz(k)f 1 uoranthene
pyrene
pyrene
benz(a)anthracene
0.24
0.23
0.24
0.18
0.24
0.24
30.62
43.09
14.3
3.2
3.2
3.05
Chlor.ine
mg/1 pH
3.7 6.8
26.3 6.0
19.5 4.2
25.6 4.0
22.0 5.9
23.9 4.0
6
6
6
6
2+0.25
2+0.25
Time (Hr)
0.5
3
3
3
3
3
6.0
6.0
6.0
6.0
0.5
0.5
Products/Comments
phenanthrene (77% yield)
phenanthrene (86% yield)
9-chl orophenanthrene
(4% yield)
phenanthrene (9% yield)
9-chl orophenanthrene
(38% yield)
monochl oro-1 -methyl
phenanthrene (8% yield)
fluoranthene (63% yield)
fluoranthene (42% yield)
fluoranthene chlorohydrin
(32% yield)
Tween 80 present
31% reduction
Tween 80 present
11% reduction
Tween 80 present
27% reduction
Tween 80 present
22% reduction
37% reduction
distilled water
83% reduction
Reference
ibid
Sforzolini ,
et.al., 1977
Sforzolini,
et.al., 1973
and 1974
distilled water
-------
Table IX (Cont'd)
Aqueous Chi ori nation Reactions of Polynuclear Aromatic
Hydrocarbons: Selected Results From Literature Reports
Compound Chlorine
Compound ug/1 mg/1 pH Time (Hr)
benz(a)pyrene
benzo(k)f 1 uoranthene
benz(e)acephenanthry-
lene
fluorene
naphthalene
acenaphthalene
pyrene
a Oyler and Carlson,
3.06 2+0.25 0.5
3.08 2+0.25 0.5
3.04 2+0.25 0.5
200 9.8 7.0 24
100 10 7.0 24
200 10 7.0 24
50 10 7.0 24
1978.
Products/Comments Reference
100% reduction
distilled water
23% reduction
distilled water
15% reduction
distilled water
65% reduction Spath, 1972
no chloro products
identified
82% reduction
no chloro products
identified
100% reduction
menochloro product
identified
100% reduction
no chloro products
identified
b Tween 80 is a general -purpose emulsifier and surface active agent.
-------
Table X
a
Concentrations (ng/1) of PAHs at Various Stages of Water Treatment Works
Compound
Fluoranthene
Pyrene
Benzo(a)anthracene and
Chrysene
Benzo(b)f 1 uoranthene
Benzo(j)fl uoranthene
Benzo(k)fl uoranthene
Benzo(a)pyrene
Benzo(e)pyrene
Perylene
Indeno(l ,2,3-cd)pyrene
Benzo(ghi)perylene
a Harrison, et.al., 1976
b Summation of isomers.
c Not reported.
River
Intake
150
100
90
147
c
c
69
72
•
After
Reservoir
140
75
72
132
51
39
66
63
After
Filtration
81
45
33
39
30
24
27
33
After
Chi ori nation
45
18
12
21
9
c
9
9
18
-------
The loss of PAHs from the filtered water averaged approximately 60%.
Factors such as pH, temperature, contact time, and concentration of the
chlorinating agent can have a profound effect on removal rates (Harrison
et al, 1976). Removal through chlorination should not be viewed neces-
sarily as a desirable effect. Chlorination does not necessarily remove
the PAH moiety. Rather, chlorine can react with PAHs synthesizing new
compounds which most likely remain in solution. Presently, little is
known about these new compounds or their character; however, some data
on the reaction products are listed in Table IX.
Activated Carbon
The effective removal of organic compounds, including PAHs, by
activated carbon is dependent on the type of carbon used and its physical
properties as well on specific compounds being adsorbed. In addition,
removal is dependent on both kinetic and equilibrium considerations.
The contact time as well as the concentrations of specific PAHs are of
prime importance (Hansen, 1979). The traditional perception has been
that only activated carbon can significantly reduce PAH concentrations
in water. Borneff's work is among the most widely quoted in support of
this contention. In a paper by Borneff and Fischer (1962), activated
carbon filtration is credited with 99% removal of PAHs from water filtered
by prior seepage through river bank soil. Again, in laboratory testing,
99% removal of PAHs (300 ug/1) was demonstrated for 10 types of activated
carbon (Borneff, 1978).
Other authors have attributed efficient removal of PAHs during
treatment to the use of activated carbon. This is evident in a paper by
Lewis (1975). Comparing from Table XI the PAH concentrations in the
19
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"Colwick F3" sample (raw water after biological pretreatment, copper
coagulant, sedimentation and rapid sand filtration) to the Colwick Gl
sample (F3 water after activated carbon filtration), Lewis viewed the
reduction from 11 ng/1 to 1.2 ng/1 for 5 PAHs as confirmation that
activated carbon is the only effective agent in reducing levels of PAHs.
While the relative reduction of F3 to Gl is 90%, the absolute reduction
(9.8 ng/1) of the PAHs, when compared to the original amount of PAHs in
the raw water "Colwick B" (480 ng/1), is only 2%. Colwick F3, conventional
treatment, apparently affords a 98% reduction, due to the removal of the
PAH enriched particulates. From a recent paper, (Saxena et al, 1978),
it has been inferred that the most effective removal process involves
the use of a two stage activated carbon treatment. The data in Table
XII does not convincingly support this contention, but in fact, is
consistent with removal by conventional treatment. A comparison of
Pittsburgh (2 stage treatment PAC addition, then GAC filter bed) with
Philadelphia (conventional treatment) shows that for 3 of the 6 PAHs,
the conventional treatment alone was more effective. In reality, there
is probably little difference in effectiveness between the two treatment
processes for PAH reduction, if initial concentrations and analytical
precision are considered.
Use of activated carbon for the removal of PAHs present at very low
nanogram-per-1Her concentrations appears to have limited applicability.
As an example, one can compare the raw and finished water data for
Appleton, WI (GAC filtration) and Champaign, IL (no activated carbon
added) (Table XIII). For all but one of the 6 PAHs, the percent removal
of the noncarbon treatment was equal or greater than that of the carbon
treated water.
20
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Table XI
PAHs in Treatment Plant Water (ng/1)'
Source
PAHs in Suspended Solids
F1 B(a)P IP B(k)F B(ghi)P
PAHs in Solution
F1 B(a)P IP B(k)F B(ghi)P
K)
River Trent
Colwick-B
(Raw Water)
Colwick-F3
(Finished Water)
Colwick-Gl
(Granular Activated
Carbon Filtered Water)
133.0 96.0 75.0 47.0
No Suspended Matter
No Suspended Matter
111.0 16.0 0.5 0.5 0.5 0.8
9.3 0.3 0.6 0.4 0.6
0.8 0.2 d d 0.2
a Lewis, 1975.
b The particulate matter filtered from water sample.
c Filtrate of water sample.
d Present at less than quantitation limits.
-------
Table XII
Comparison of Conventional and Two Stage Activated Carbon Treatment'
Concentration, ng/1
Compound
Pittsburgh, PAD
Raw Finished
Philadelphia, PAL
Raw Finished
Fluoranthene 408.3 d
Benzo(j)fluoranthene 35.7 0.3
Benzo(k)fluoranthene 19.1 0.2
Benzo(a)pyrene 42.1 0.4
Indeno(l,2,3-cd)pyrene 60.4 1.2
Benzo(ghi)perylene 34.4 0.7
114.3
42.6
33.0
41.1
72.4
48.4
8.9
d
d
0.3
1.7
4.0
a Saxena, et.al., 1977.
b Two stage activated carbon treatment; powdered A.C. - then
granulated A.C. filtration (~* 30-40 min empty bed contact time)
c Conventional treatment.
d Not detected, limits ranging from 0.1 - 4.6 ng/1.
22
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Table XIII
Comparison of Carbon Treated Versus Non-Carbon Treated Water3
Concentration, ng/1
Compound
Fl uoranthene
Benzo( j )f 1 uoranthene
Benzo{k)fl uoranthene
Benzo(a)pyrene
Indeno(l ,2,3-cd)pyrene
Benzo ( gh i ) pery 1 ene
Appleton,
Raw Fi
c
0.7
0.5
0.6
0.9
4.3
WIb
nished
c
0.4
0.2
0.4
1.4
3.7
Champaign
Raw Fi
c
0.6
0.7
c
1.9
3.7
, 11.
nished
c
0.3
0.3
c
0.9
1.3
a Basu, et.al., 1978.
b 6AC Filtration - Filtersorb 400 (-10 min empty bed contact time)
c Not detected.
23
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In another series of experiments, under more controlled circumstances,
finished waters were passed through a sand replacement filter or pilot
column of granulated activated carbon, Table XIV (Sorrell et al, 1979).
The resulting effluents showed a maximum reduction in PAHs of only 6
ng/1, where the influent was less than 23 ng/1. However, when the
influent was at 80 ng/1, the PAH concentration was lowered to 16 ng/1, a
reduction of 64 ng/1 (80%). These results seem to support the contention
that activated carbon is "uneconomical" for the removal of PAHs at
concentrations of less than 30 ng/1 (Borneff, 1977).
In an additional study, Borneff (1978) presented the results for
PAH removal at two water treatment plants. At the Wiesbaden-Schierstein
plant, water which was pretreated by sedimentation and flocculation was
passed through a granular activated carbon column of Norit PKH (1-3 mm).
The water at the head of the column was found to contain 70 ng/1 of PAHs
(probably the total for 8 PAHs). Upon exiting the column, the concentration
was only 8 ng/1, or 90% reduction. A plant on the Danube river using
pretreated water (35 ng/1 PAHs) afforded only a 12% reduction of PAHs
after passage over activated carbon at a flow rate of 12.7 m/h. From
these studies it would appear that activated carbon is not always appropriate
for the removal of PAHs at low concentrations in finished waters. These
same studies, however, demonstrate that GAC can provide an effective
barrier against unexpectedly high levels of PAHs.
Distribution System
Regardless of the effectiveness of the treatment techniques used in
removing PAHs, the finished water can become recontaminated during
containment in storage tanks or in transit through pipes with a coal tar
24
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Table XIV
Concentrations (ng/1) of PAHs in Carbon Column Influents (Inf) and Effluents (Eff)
Miami, FL Seattle, WA
Compound Inf Effc Inf Effc
Phenanthrene 11 6 6 8
Fl uoranthene <3 <2 <5 <2
Pyrene <4 <2 <4 <3
1 -Methyl Pyrene <1 <1 <1 <1
Anthracene b b b b
Chrysene <1 <1 <1 <1
Benzo(a)anthracene 1 <1 1 <1
Perylene <1 <1 <1 <1
Benzo(e)pyrene <1 <1 <1 <1
Benzo(a)pyrene <1 <1 <1 <1
Benzo(ghi)perylene <1 <1 <1 <1
Benzo(b)fl uoranthene <1 <1 <1 <1
Benzo(k)fl uoranthene <1 <1 <1 <1
Dibenzo(a,h)anthracene <1 <1 <1 <1
Indeno(l ,2,3-cd)pyrene <1 <1 <1 <1
Total 12 6 78
a Sorrel 1, et.al., 1979.
b Not analyzed.
c Virgin carbon (Filtersorb 400) used in a pilot column with
bed contact time.
d Exhausted carbon (Westvaco WVG) used in a sand replacement
average empty bed contact time of 18 minutes.
e Fresh carbon (Filtersorb 400).
Inf
14
4
4
<2
<2
<2
<2
<2
<2
<2
<2
<2
<2
<2
<2
22
Jefferson
Effd
10
6
3
<2
<2
<2
<2
<2
<2
<2
<2
<2
<2
<2
<2
19
Parish,
Inf
52
11
17
<2
<2
<2
<2
b
<2
<2
b
<2
<2
<2
<2
80
TA
Effe
14
<2
2
<2
<2
<2
<2
<2
<2
<2
<2
<2
<2
<2
<2
16
19 minute empty
filter
with an
25
-------
base lining (Goldfarb et al., 1979, Borneff and Kunte, 1965). To some
extent, this is also true of pipes lined with asphaltic base materials.
A laboratory study (Sorrell, et al., 1977) has demonstrated leaching of
PAHs (70 ng/1, mostly phenanthrene) from pipe with an asphalt base
coating.
For coal tar based coatings, a recent study (DWRD, 1980) has found
nanogram to microgram per liter concentrations in contacted water. In
this study, 4 glass plates, coated with coal tar enamel, were placed in
a TLC chamber affording a high surface area to volume ratio. Tap water
was allowed to flow through the system at a measured rate. Prior to
sampling the tap water was stopped for 3 days, then continued after
sampling. The results in Table XV at 25 and 165 days show significant
leaching of the target compounds in both samples, indicating that under
the test conditions leaching was likely to continue for a long period of
time. It should be noted that these laboratory studies cannot be used
to predict concentration of PAHs under real distribution system conditions,
even when the same type of coating is in use.
The magnitude of contamination in distribution systems will be
determined in part by the age of the coating, contact time of the water,
surface area to water volume, the type of coating used, appropriate
application, deposition of carbonate, etc. The data base for PAHs
leaching from distributed water systems located in the United States
is, to date, limited. The supplies listed in Table XVI do not demonstrate
a consistent trend with regard to contamination and the type of lining
used. Similar results have been reported by other researchers (Crane et
al., 1978, Basu and Saxena, 1977).
26
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Table XV
Plate Test Concentrations
a,b
(Tig/1)
Compound
25 days1
165 daysc
Phenanthrene
Fluoranthene
Pyrene
1 -Methyl pyrene
Anthracene
Chrysene
Benzo(a)anthracene
Perylene
Benzo(e)pyrene
Benzo(a)pyrene
Benzo(ghi)perylene
Benzo(b)fluoranthene
Benzo(k)fluoranthene
Di benzo( a, h) anthracene
Indeno (1,2,3-cd) pyrene
230,000
34,000
20,000
< 1 ,600
23,000
1,000
1,100
Present
Present
78
< 30
170
100
< 10
< 58
290,000
46,000
27,000
< 290
14,000
1,300
1,300
Present
Present
110
< 40
140
89
3
< 50
a DWRD (1980) 2
b Plate contact area/volume water was '-838 cfn /I
c Temperature of water at 25 day ^ 18°C; at 165 days
20°C.
27
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Table XVI
Concentration (ng/1) of PAH., in Finished and Distributed Waters3
Compound
Ph
Fl
Pyr
1-MP
An
Ch
B(a)A
Per
B(e)P
B(a)P
B(ghi)P
B(b)F
B(k)F
DiB(ah)A
IP
Total
Standish, MEb Ludlow, MAb Columbus, OHC
Fin Dista Fin Dista Fin Dista'T
5 57 23 3 17
2 10 11 1 13
15 11 <1 8
<1 <1 <1 <1 <1 <1
<1 <1 <1 <1
<1 <1 <1 <1 <1 4
<1 <1 <1 <1 <1 3
<1 <1 <1 <1 <1 <1
<1 <1 <1 <1 <1 <1
<1 <1 <1 <1 <1
<1 <1 <1 <1 <1 2
<1 <1 <1 <1 <1 4
<1 <1 <1 <1 <1 3
<1 <1 <1 <1 <1 <1
<1 <1 11 <1 <4
8 72 56 4 54
Portland, ORb'c Seattle, WAb Colorado Springs, C0b
Raw Distc>9 Fin Diste Fin Diste
8 3300 2 32 3 29
4 640 38 26
6 340 22 <1 <1
<1 <1 <1 <1 <1 <1
<1 <1 <1 <1
<1 /.6 <1 <1 <1 <1
<1 2 <1 <1 <1 <1
<1 <1 <1 <1 <1 <1
<1 <1 <1 <1 <1 <1
<1 <1 <1 <1 <1 <1
<1 <1 <1 <1 <1 <1
<1 3 <1 <1 <1 <1
<1 <1 <1 <1 <1 <1
<1 <1 <1 <1 <1 <1
<1 <1 <1 <1 <1 <1
18 4300 7 42 5 35
00
a < Indicates that the compound may or may not have been present at less than this concentration
b Zoldak, 1978
c Sorrel 1, et al., 1979
d Asphalt lining
e Coal tar lining
f Sediment present in water sample
g Taken at the end of a low demand 24" transmission line
-------
Toxicology and Present Standards
From a human toxicological (carcinogenic) viewpoint, there appears
to be scant data upon which to base a maximum contaminant level (MCL)
for drinking water. The U.S. National Academy of Sciences (1977) has
only attempted to evaluate one PAH, benzo(a)pyrene indicating the available
data were insufficient for establishing risk estimates.
Presently, the most widely quoted standard for PAHs is that of the
World Health Organization which set a 200 ng/1 maximum permissible
concentration for the sum of six PAHs (fluoranthene, benzo(a)pyrene,
benzo(b)fluoranthene, benzo(k)fluoranthene, benzo(ghi)perylene and
indeno(l,2,3-cd)pyrene) in drinking water (WHO, 1971). The six PAHs
were chosen because they could be easily analyzed and not necessarily
because of their toxicological properties, as only three of the six PAHs
are thought to possess carcinogenic characteristics.
The philosophy of this standard is that tap water derived from
surface water should contain no more PAHs than the tap water derived
from ground water (Crathorne and Fielding, 1978). Using the data of
Borneff and Kunte, the average figure for total (6) PAHs in tap water
derived from ground water was 100 ng/1. A factor of 2 was added to
account for natural variation, hence 200 ng/1.
Andelman and Suess (1970) discussed the concept that carcinogen
consumption from water should not exceed 1/10 that from urban air.
This relates to about 17 ng/1 of carcinogenic material from water. But
again it is based on a "natural" background concept and without benefit
of toxicological data.
29
-------
Conclusions
In addition to the requirement for more toxicological data, further
investigation to establish the scope of PAH contamination in U.S. waters
(raw, finished, and distributed) seems appropriate. While present data
would indicate conventional treatment is capable of reducing PAH concen-
trations well below the WHO limits, little information is available as
to the products resulting from chlorination or their toxicology. Even
if research proved these by-products to be of no concern, deterioration
of the finished water quality can occur within the distribution system.
The primary sources of such contamination would be from coal-tar or
asphaltic materials used to line pipes and storage tanks.
30
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it US GOVERNMENT PRINTING OFFICE 1981 -757-064/OZ86
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