t “699

LIBRARIES
MICHIGAN STATE UNIVERSITY
EAST LANSING, MlCH. 48824

This is to certify that the

thesis entitled

"Residue analysis of municipal sludges
for organochlorine pesticides and
polychlorinated biphenyls"

presented by

Kraidi Adjobi Nicolas

has been accepted towards fulfillment
of the requirements for

Masters _ Entomology
degree in

 

 

7

Major pr or

9%%
Date Oj/hf/93

0-7639 MS U is an Affirmative Action/Equal Opportunity Institution

 

gluRNIr‘ MATERIA'§:
‘?., .\O' "t

RESIDUE ANALYSIS OF MUNICIPAL SLUDGES
FOR ORGANOCHLORINE PESTICIDES

AND POLYCHLORINATED BIPHENYLS

By

Kraidi Adjobi Nicolas

A THESIS

Submitted to
Michigan State University
in partial fulfillment of the requirements
for the degree of

MASTER OF SCIENCE

Department of Entomology
Pesticide Research Center

1983

191' 9751/

ABSTRACT

RESIDUE ANALYSIS OF MUNICIPAL SLUDGES
FOR ORGANOCHLORINE PESTICIDES

AND POLYCHLORINATED BIPHENYLS

BY

Kraidi Adjobi Nicolas

Municipal sewage sludges from Several Michigan communities were
analyzed for the presence of DDT analogs, lindane, aldrin, dieldrin,
endrin and PCBs.

The samples were extracted with methylene chloride via liquid/

liquid extraction. The cleanup was achieved through acid/base

'partitioning and activated florisil columns. Following separation

using activated silica gel, samples were injected into a gas
liquid chromatography equipped with N163 electron capture detector.
Residue concentrations of PCBs present in sludge varied from
traces to 1960 ug/kg. Pesticides concentrations were lower. DDT
showed the highest concentration among the pesticides at 17.50

ug/kg. Endrin and methoxychlor were not detected.

ACKNOWIEDGEMEN‘I‘S

I would like to express my sincere gratitude to my major
professor, Dr. Matthew Zabik for his encouragement, understanding and
guidance throughout the course of this investigation and my overall
study at Michigan State University. I extend my appreciation to
Dr. Richard Leavitt for his helpful discussions and suggestions.

I deeply thank the Ministry of Agriculture and the Government
of the Ivory Coast for their financial support. Grateful acknowledge-
ment is extended to Dr. A. Assa to have made everything possible to

extend my scholarship until completion of my study.

ii

TABLE OF CONTENTS

Ammms O C O O O O O O O O O O O O O O O O O O O O O O 0

LIST OF TABIE S O O O O O O O O O O O O O O O O O O O O O O O O .

LIST OF FIG-Ins O O O O O O O O O O O O O O O O O O O O O O O O O

INTRODUCT ION O O I O O O O O O O O O O O O O O O O O O O C O O O O

I.

II.

LITERATUM REVIEW 0 O O O O O O O O O O 0 O O O O O O O O O O

A.
B.
C.
D.
E.
F.
G.

Sludge Analysis . . . . . . . . . . . . . . . . . . .
volatiles . . . . . . . . . . . . . . . . . . . . . .
Phenols . . . . . . . . . . . . . . . . . . . . . . .
Aromatic Hydrocarbon . . . . . . . . . . . . . . . .
Phthalates . . . . . . . . . . . . . . . . . . . . . .
Aryl Phosphates . . . . . . . . . . . . . . . . . . .
Aromatic Amines . . . . . . . . . . . . . . . . . . .

WHICH mmons . O O O _ O O O O O O O O O O O O O O O O O O

A.

B.

mter 1318 I O O O O I O O O O O O O O O O O C O O O O

l. Glassware preparation . . . . . . . . . . . . . . .
2. Sample Collection . . . . . . . . . . . . . . . . .
3 O Reagants O O O O O O O O O O O O O O O O O O O O 0

M9 thOd s O O O O O O O O O O O O O O O O O O O O O 0 O
l. Extraction of organochlorine pesticides and PCBs. .

a. Solid samples . . . . . . . . . . . . . . . . .
b. LiWid smples O C O I O O O O O O O I O O O O O

2. Cleanup procedure and early separation of polar
Pesticj-des O I O O O O O O O O O I O O O 0 I O O I

a. Florisil chromatographic column preparation
and cleanup procedure . . . . . . . . . . . . .
b. Note on the variability in the activity of
florisil . . . . . . . . . . . . . . . . . . . .

3. Separation of the pesticides from PCBs by silica
gel 60 O O O O O O O O O O O O O I O O O I O O O O 0

iii

17
23
27
29
30
3O
32
32
32
32
33
34
34
34
35
36

39

4O

40

TABLE OF CONTENTS (Continued . . .)
Page
4. ‘ thitation O O O O O O O O O O O C O O O O O I O O 45

a. Organochlorine pesticides . . . . . . . . . . . . 45
J b. PCBs O I O O O O O O O O O O O I O O O O O O O O 45

III 0 “SULTS AND DISCIISS ION O O O I O O O O O O O O O O 0 O O O O 51
A. Results 0 O O O I O O O O O O I O O O O O O O O O O O 51
B. Comparison of the results with those available in
the literature . . . . . . . . . . . . . . . . . . . . 51
c O Pumeters tested 0 O O O I O O O O O O O O O O O O O 5 7

IV. CONCLUSIW O O O O O O O O O O O O O O O O O O O O O O O O C O 69

v. BIBLIOGRAPI‘Y O O O O O O O O O O O O O O O O O O O O O O O O 0 70

iv

LIST OF TABLES

Selected Organochlorine and PCBs . . . . . . . . .
Recovery of the pesticides and PCBs . . . . . . .
Composition of the different fractions collected .

Summary of data for the 103 sites analyzed . . . .

Pesticides concentrations in sewage sludges analyzed

PCBs concentrations in sewage sludges analyzed .‘.

38

42

52

53

55

FIGURE

10.

11.

12.

13.

14.

15.

LIST OF FIGURES

sup 1e 8 s ites I I I I I I I I I I I I I I I I I I I I I I 7
Scheme of the Extraction Procedure . . . . . . . . . . . 37

Cleanup and Separation Procedures of PCBs and
Pestic ides I I I I I I I I I I I I I I I I I I I I I I I 4 3

Gas chromatogram of PCB 1254 standard . . . . . . . . . . 47
Gas chromatogram of PCB 1260 standard . . . . . . . . . . 48

Gas chromatogram.of the mixture PCB 1254 and PCB 1260
Standard I I I I I I I I I I I I I I I I I I I I I I I I 49

Gas chromatogram.of a sample analyzed . . . .u. . . . . 50

Lindane mean and median concentration vs. size of
mmlation I I I I I I I I I I I I I I I I I I I I I I I 5 9

Lindane mean and.median concentration vs. population
in mans was I I I I I I I I I I I I I I I I I I I I I I 5 9

DDD mean and median concentration vs. population in
thous ands I I I I I I I I I I I I I I I I I I I I I I I I 6 o

DDD mean and median concentration vs. population in
mounds I I I I I I I I I I I I I I I I I I I I I I I I 60

DDE mean and median concentration vs. size of
Population I I I I I I I I I I I I I I I I I I I I I I I I 6 1

DDE mean and median concentration vs. size of
”Pulation I I I I I I I I I I I I I I I I I I I I I I I 6 l

DDT mean and median concentration vs. size of
mmlation I I I I I I I I I I I I I I I I I I I I I I I 6 2

DDT mean and median concentration vs. size of
mpuation I I I I I I I I I I I I I I I I I I I I I I I 6 2

vi

LIST OF FIGURES (Continued . . .)

F IGU RE
16. PCB-1254 mean and median concentration vs. size of
”Pal ation I I I I I I I I I I I I I I I I I I I I
17. PCB~1254 mean and median concentration vs. size of
”Pal ado n I I I I I I I I I I I I I I I I I I I I
18. PCB»1260 mean and median concentration vs. size of
Popul ation I I I I I I I I I I I I I I I I I I I I
19. PCBPlZSO mean and median concentration vs. size of
Popul at 10 n I I I I I I I I I I I I I I I I I I I I
20. DDD mean and median concentration vs. % industrial
input I I I I I I I I I I I I I I I I I I I I I I I
21. DDD mean and median concentration vs. % industrial
inmt I I I I I I I I I I I I I I I I I I I I I I I
22. DDT mean and median conc entration vs. % industrial
input I I I I I I I I I I I I I I I I I I I I I I I
23. DDT mean and median concentration vs. 8 industrial
input I I I I I I I I I I I I I I I I I I I I I I I
24. PCB-1260 mean and median concentration vs. %
industrial input I I I I I I I I I I I I I I I I I
25. PCB-1260 mean and median concentration vs. %

indus tr ial input I I I I I I I I I I I I I I I I I

vii

INTRODUCTION

Sewage sludge is obtained from the processing of waste waters
from domestic and/or industrial areas. It may be liquid, semi-
liquid or solid, according to the extent of water removal. Con-
sidering its sources, sewage may contain any kinds of contaminants,
and a significant number of bacteria, fungi and microbes as well.

The value of sludge-as fertilizer is as old as agricultural
practices. Application of human wastes to the soil is an integral
part of the traditional agriculture. In the Orient, human wastes
had been collected and used for crap fertilization for centuries.
The most extensive and successful operations were begun around 1850,
but the most sophisticated system seemed to be the one at wass-
mannsforf, Germany (1930) where sewage was treated in anaerobic
digester before both the liquid effluent and the sludge were dis-
tributed to farms (Allen, Jonathan, 1973).

In the United States, the use of sewage effluent for crop
irrigation on a large scale started in the early twentieth century.
The most successful experiment seems to be that of the Waste Water
Renovation and Conservation Project of Pennsylvania State University
which monitors the effects of secondary sewage effluents on forests
and croplands.' Throughout the country, several other interesting
projects were undertaken. They include: the Metropolitan Sanitary
District of Greater Chicago; Muskegon, Michigan; Santee, California;
East San Francisco Bay; University of Michigan. A number of facts
have led to the beneficial management of sewage products (Hays,

(Barbara D., 1977):

2
1. The discharging and dumping of raw and/or treated

.sewage into our surface waters and the incineration
of dried sludges has led to unacceptable levels of
pollution.

2. Critical water shortages have encouraged consider-
ation of the use of sewage effluent as a source of
irrigation water

3. Increasing costs of maintaining soil nutrients and
soil structure suggest that a valuable fertilizer
and soil amendement are being wasted by disposing
sewage effluent and sludge into the ocean, burying
it, or incinerating it.

4. The increasing cost of energy has led some planners
to consider sewage as a source of energy, as methane
gas produced during the anaerobic digestion of
sewage sludge can be captured and used for heating
purposes

5. The high cost of alternative technologies make sewage
land application attractive

6. .Sludges have been recognized for centuries as soil
conditioner and fertilizer.

On the other hand, a number of environmental and health
questions have been raised as to whether or not land application
of sewage plant products can cause unreasonable risks. Some of
the problems associated with the disposal of sludge to agricultural
land may be the following (Hays, 1977):

1. Public acceptance of the beneficial use of sewage

3

sludge or effluent on land

2. Diseases, bacterial, viral and parasitic may be
transmitted through the man - sewage - soil crop -
man cycle

3. Toxic ions (particularly nitrates), and toxic heavy
metals, such as cadmium, mercury, lead, copper,
nickel, zinc, arsenic, etc., as well as persistent
organic chemicals may accumulate in the ground water,
soil or crops, making the water unsafe for drinking,
the soil unable to support future plant growth, or
crop products too risky to eat.

Due to mismanagement or lack of proper management monitoring of
some sludge disposal systems, there has been a history of soil,
plant and ground water contamination from heavy metals, toxic‘
organics and pathogenic bacteria. With the increased input of
household chemicals and industrial effluents into municipal sewage
systems, the problem of waste disposal has come into the forefront
for federal, state and local agencies. Passage of the Federal
Water Pollution Control Act in 1972 has caused a huge increase
in the amount of sewage sludge requiring disposal. Under
Michigan's Act 64, the "Hazardous waste Management Act", sludges
which contain hazardous organic materials present at concentrations
from 1-to 1,000 ppm are designated "notification waste" and may
subsequently be designated "hazardous waste". This designation
tags the sludge as a potential environmental pollutant and must

be disposed of properly and continually monitored by the waste-

4
water treatment facility affected. Ultimately, the Michigan

Department of Natural Resources must enforce and regulate the
management of such wastes.

In order to manage wastes prOperly it is important to know
if they contain hazardous materials and if so, in what levels,
in order that they may be used safely, detoxified or disposed of
via incineration or an approved landfill. For this reason the
Michigan Department of Natural Resources and the United States
Environmental Protection Agency contracted researchers from
Michigan State University to characterize 250 sewage treatment
plant sludge (Figure 1). These sludges came from throughout
the state and were analyzed for the following toxic substances

or potential xenobiotics.

 

2,3,4,5-Tetrachlorophenol
2,3,4,6-Tetrachlorophenol

PHENOLS PURGEABLES
o-Chlorophenol Acrylonitrile
meChlorophenol Chlorobenzene
p-Chlorophenol p-Chlorotoluene
o—Cresol o-Dichlorobenzene
meCresol m-Dichlorobenzene
p-Cresol p-Dichlorobenzene
2,3-Dichlor0phenol 1,2-Dichloropr0pane
2,4-Dichlorophenol 1,3-Dichloropropane
2,5—Dichlorophenol 1,3-Dichloropropene
2,6-Dichlorophenol Ethylbenzene
3,4—Dichlorophenol Hexachloro-1,3-butadiene
3,5-Dichlorophenol Hexachloroethane
2,3-Dimethylphenol Pentachloroethane
2,4-Dimethylphenol Styrene
2,5-Dimethylphenol Tetrachloroethylene
2,6-Dimethylphenol 1,2,3-Trichlorobenzene
3,4-Dimethylphenol 1,2,4-Trichlorobenzene
3,5-Dimethylphenol 1,3,S-Trichlorobenzene
4,6—Dinitro—o-cresol 1,2,3-Trichlor0propane
2,4—Dinitrophenol 1,2,3—Trichlor0propene
Hydroquinone

Pentachlorophenol

Phenol -

PHENOLS (continued)

2,3,5,6aTetrachlorophenol
2,3,4-Trichlorophenol
2,3,5-Trichlorophenol
2,3,6-Trichlorophenol
2,4,5-Trichlorophenol
2,4,6—Trichlor0phenol
3,4,5—Trichlor0phenol

AROMATIC HYDROCARBONS

 

Biphenyl

Hexachlorobenzene
Mercaptobenzothiazole
Naphthalene
Polychlorinated biphenyls
1,2,3,4-Tetrachlorobenzene
1,2,3,5—Tetrachlorobenzene
1,2,4,5-Tetrachlorobenzene

BASES

Benzidine
3,4—Dichloroaniline
3,3-Dichlorobenzidine
p-Nitroaniline

PHTHALATES

 

Butylbenzylphthalate
Diethylphthalate
Dimethylphthalate
Di-N-Butylphthalate
Di-N-Octylphthalate
Dioctylphthalate

NITROBENZENES

 

1Chloro-2,4-dinitrobenzene'
1Chloro-2,6-dinitrobenzene
1Chloro-3,A-dinitrobenzene
1Chloro-2—nitrobenzene
1Chloro-4—nitrobenzene
2,4-Dinitrotoluene
2,6-Dinitrotoluene
Nitrobenzene
Pentachloronitrobenzene

TRIARYL PHOSPHATE ESTERS
Cresyldiphenyl Phosphate

Tricresyl Phosphate
Trixylene Phosphate

In this study, interest was given to several chlorinated
pesticides and polychlorinated biphenyls.(Table 1).

Two hundred-thirty-seven sewage treatment plants throughout
Michigan were sampled by the Michigan Department of Natural
Resources (Jacobs & Zabik, 1980). These sludges were sampled
From various stages of the treatment process which varied from
city to city incuding raw sludge, primary aerobic digested,
secondary aerobic digested, anaerobic digested, Purifax sludge,
filtered, lagooned, and drying bed sludge. The Purifax sludge
is specially treated via a patented super chlorination process
in order to decrease its active biological activity and subsequent

odor. The sewage treatment plants sampled have inputs varying

Table l - Selected Organochlorine pesticides and PCBs

ORGANOCHLORINE PESTICIDES
Lindane p,p'-DDD
Aldrin p,p'-DDE
Dieldrin p,p'—DDT

Endrin ~ Methoxychlor
POLYCHLORINATED BIPHENYLS (PCBs)

Aroclor 1254

Aroclor 1260

unicipel flute Truman: Pleat: Sampled

Figure 1

 

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8

from totally residential to a large percentage in industrial sources.
Community population may also vary from a few hundred to several I
million individuals, therefore each community usually treats its
waste in a fairly unique manner which leads to a great diversity
in treatment processes.
My purpose in this study is to determine if:
1. The selected organochlorine components are present
in the sewage sludges at a measurable level
2. There is any correlation between concentration level
of the pesticides and the PC35 and the size of the
population
3. There is any correlation between concentration level
of the pesticides and the PC88 and the percentage of

waste inputs

I. LITERATURE REVIEW

A. Sludge Analysis

Thanks to the Federation of Sewage, Sewage Works and Industrial
wastes Association, two fairly complete volumes on sewage treatment
and utilization were compiled in the late forties. At this early
date the Subcommittee of Utilization of Sludge as Fertilizer published
a 120 page report on the soil requirements, sludge characteristics,
treatment processes and economics of sludge application to
agricultural lands (Pearse, 1945). Then in 1950, the Subcommittee
on Chlorination of Sewage and Industrial waste Practices released
another report taking an indepth look at several waste chlorination
practices and chemical effects of chlorination (Gilcreas, 1950).
Even though modern analytical techniques for the day were employed
in both reports, the trace analytical capability which we have
today had not yet been developed. The only reference in either
paper to the potential hazards of organic toxicants in sludges
concerned was the treatment of phenolics in effluents by Dow
Chemical Company in Midland, Michigan. Actual analyses for
organics were limited to the various forms of nitrogen present
as nutrients. From this date forward, no analytical methods
were published on the analysis of sludge for organic compounds
until the late 19703. As a matter of fact, the literature is
quite void of any noteworthy strides in sewage or wastewater

analysis prior to the early 19703. Before 1970, less than 100

different organic compounds had been identified in water let

10
alone municipal sewage sludges. In the early 19703, a split
developedinthe area of wastewater analysis. One group become
primarily concerned with chlorination of wastewaters and the other
with characterization of organics in wastewaters. The developments
of both of these groups helped to pave the way for sludge analysis.
Some of the key workers in the effects of chlorination include:
Jolley, (1973, 1975); Glaze et al. (1973); and Kopperman (1975).
In a search for a better understanding of the effect of chlorin-
ation onorganic components, new techniques were developed and
utilized for trace component determinations.

Various techniques also began to emerge once an effort was
exerted toward the characterization of organics in wastewater. -
Workers in this field included: Katz et al. (1972); Kleopfer'
and Fairless (1972); the Environmental Protection Agency (1973);
Baird et al. (1974); Keith (1974, 1976); Manka (1974); Telliard
(1977); Lichtenberg (1978); Jungclaus (1978); Cooper (1978);

Mousa and Whitlock (1979); walton and Eicemen (1978); Heller
(1978); Narkis (1978); Lamparski (1978); Carter (1978); waite
(1978); Jenkins et a1. (1978); Argamon (1978); and Hall (1978).
Although a review of all these works would be too extensive
and far reaching for the specifics of this paper, please note
how the analysis of organic compounds in wastewaters bloomed
about 1978. ‘Much of the work during this time period involved
either the analysis of phenols or chlorinated pesticides in
municipal and industrial wastewaters.

The largest amount of work completed to date involving sludge

ll
analysis has been concerned with heavy metal contamination (Keith,
1974). Several studies have shown the detrimental effects of high
heavy metal concentration to both crops and mammals (Jalinek and
Broude, 1978).

The first modern techniques used in a comprehensive character-
ization of organics in sewage effluents was by Garrison, Pope and
Allen of the United States Environmental Protection Agency from
1971 to 1976 (Garrison, et al., 1976). In this work, 80 specific
volatile organic compounds were identified in raw and treated
domestic wastewaters primarily by G.C./M.S. This indeed was the
first step toward the characterization of organics in sludge.

In 1977 two publications discussed the management and effect
of sludge used on land. The first was a National Science Foundation
risk assessment of land application of municipal sludge (Jones and
Fred, 1977). The National Science Foundation concluded that
chemical contaminants "suspected" to be present in municipal sludge
could have adverse effects on the environment as a result of land
application practices. The second publication was from the Bureau
of Foods, the Food and Drug Administration (Jelinek and Braude,
1977). In the FDA's study, levels of selected chlorinated
pesticides, lead and cadmium were considered with the following
recommendations made:

a. Sludges should not contain more than 20 ppm cadmium,

100 ppm lead or 10 ppm PCBs on the dry basis.
b. In support of the limits proposed by the W 124/NC118
Committees of Land Grant Colleges, the maximum total

which should ever be added to an average soil (cation

12
exchange capacity of 5—15) is 9 lbs. of cadmium/acre and

900 pounds of lead/acre.

c. Crops which are customarily eaten raw should not be planted
within 3 years after the last sludge application.

d. Crops such as green beans, beets, etc., which may contam-
inate other foods in the kitchen before cooking should not
be grown on sludge-treated land unless the sludge gives a
negative test for pathogens.

e. Because sewage can be regarded as filth, food physically
contaminated with sludge can be considered adulterated even
though there is no direct health hazard; hence, sludge
should not be applied directly to growing or mature crops
where sludge particles may remain in or on the food.

f. Commercial compost and bagged fertilizer products derived
from sludges should be labeled proPerly to minimize any
contamination of crops in human food chain which may result
from their use.

Richard Doyle (1978) from the University of Maryland completed a
brief study under laboratory conditions on the effect of dairy manure
sludge on pesticide degradation. This study was carried out with
0-14 labeled pesticides. Doyle concluded that sludge application
to soils can alter the rate of pesticide degradation, either accel-
erating or hindering biological activity depending upon conditions.
Since this work was carried out totally in the laboratory instead
of the field, more work is necessary before any applications can
be made to environmental conditions. In 1979, a review was

completed on the value and effects of sludges for agricultural

13

use when contaminated with toxic elements (Sterritt, 1979).

In 1979, interim methods for measurement of organic priority
pollutants in sludges were produced by the U.S. Environmental
Protection Agency Environmental Menitoring and Support Laboratory in
Cincinnati, Ohio (E.P.A., 1979). This was the first serious
attempt to extract, cleanup and quantitate a group of organic
pollutants from sludge. Many extractions and cleanup techniqueS'
were attempted, yet all met serious reproducibility problems,
due to the sludge matrix. No data on percent recoveries of organics
from sludge was presented in this paper. These methods were the
basis for the E.P.A.'s officially proposed guidelines for the
analysis of priority pollutants in sludge (E.P.A., 1980). Once
again, no recoveries were given; the data base was small and inter-
laboratory testing was absent.

The environmental Protection Agency began monitoring 50 publicly
owned treatment works for the occurrence of organic priority pollu—
tants in sewage influent, effluent and sludge in 1979. In October
of 1979, a pilot study for this program was published which indi-
cated large inconsistencies and extremely poor reproducibility in
analysis techniques. Fortunately; since 1979, several other groups
have initiated sludge analysis programs, each with their own
methods of analysis. Hopefully, results from these undertakings
will give us a better idea of the problems we face and the
potentials for various sludge analysis techniques.

To date, none of the previously mentioned studies have been
completed. However, several have released interim reports on

their progress (EPA, 1980; Jacobs & Zabik, 1980). Here are

14

ongoing studies in sludge analysis for organics:

1.

Richard Rediske, Muskegon wastewater Treatment Plant,
Muskegon County Wastewater Management System, Michigan.

An ongoing monitoring program for 30 organic pollutants in
sewage influents, effluents and sludges. Sponsored by the
Environmental Protection Agency.

Dr. Tom Clovengor, University of Missouri. Seventy-four

municipal wastewater treatment facilities in Missouri.

'Study of the chemical compositions of municipal sewage

sludges in Missouri. Sponsored by Missouri-Department of
Natural Resources.

Dr. William Glaze, Southern California. Analysis Of
reclaimed wastewater for priority pollutants. Department

of Chemistry, North Texas University, Denton, Texas.

Vernon L. Stunp, Mid-Missouri Engineers Incorporated“
Evaluation of Purifax Process in field operation. A
comprehensive look at chlorinated organic compounds produced
by a "super chlorination" sludge treatment method. Spon-
sored by Basics in Flow Division of General Signal.

Howard Feiler, Burns and Roe Industrial Services Corporation.
Fate of Priority pollutants in publicly owned treatment
works. A comprehensive study of 50 POTWs for priority
pollutants. .

Linn Duling and Jillann Kobbee, Michigan Department of
Natural Resources. _The develOpment of methods for the
identification of potential toxic substances from

various wastewater discharges in the state of Michigan.

10.

11.

15

Michigan Department of Natural Resources through a

Toxic Substances Control Act Cooperative Agreement with

the U.S. Environmental Protection Agency.

Dan Schelton, CrOp and Soil Sciences, Michigan State
University. 'Biodegradation of phthalates, cresols,
monochlorophenols, methylbenzoic acids, and chlorobenzoic
acids in anaerobic sewage sludge. Sponsored by Office

of Toxic Substances, The Environmental Protection Agency.
Dr. Matthew Zabik, Pesticide Research Center, Michigan State
University. Analysis of 80 organic pollutants in 250
municipal sewage sludges throughout Michigan. Sponsored by
the Michigan Department of Natural Resources and the
Environmental Protection Agency.

Dr. Matthew Zabik, Pesticide Research Center, Michigan State
University. Field evaluation of the fate of hazardous
organic chemicals present in sewage sludge. Fate of
organic priority pollutants in sludges under field appli-
cation. Sponsored by the Michigan Department of Natural
Resources.

Jackson Elington and Dr. Edo Pellizzari, United States
Environmental Protection.Agency, Environmental Research
Laboratory, Athens, Georgia. "A comprehensive method for
the analysis of organics on solids, sediments and sludge".
EPA Contract No. 68-03-2994.

Dr. Zweidinger, U.S. EnvirOnmental Protection Agency,
Environmental Research Laboratory, Athens, Georgia.

"Analytical procedures for proposed toxics in wastewaters

16
and sludges." EPA Contract No. 68—03—2845.

Very much in line with the type of work now being completed was
a recent publication dealing with sludge stabilization and what
effects this biological and chemical inner play has on the resulting
organic composition (Hautenstein, 1981). Just as the 19703 were
the era of blooming organic analysis in wastewaters, the 19803 are
becoming the decade for development of sludge analysis techniques.
Analysis techniques are an essential tool. Much work has yet to be
done in order to characterize and determine the fate of potential

xenobiotics in municipal sludges.

17

B. volatiles-

The only published work to date dealing with the determination
of volatile organics in municipal sewage sludge is the Environmental
Protection Agency's proposed methods for sludge analysis of organic
priority pollutants released in March of 1980. This method suggests
analysis via Bellar and Lichtenberg's ”purge and trap" method.

Samples are to be diluted when the percent solids is too great for
accurate quantitation by this method. Since previous work in sludge
analysis of volatile and semi-volatile organics is limited, I will
highlight the advances made in the area of water analysis for these
components.

The most direct means of determining levels of a volatile organic
compound in an aqueous medium is by "direct injection" onto a gas/liquid
or high pressure liquid chromatographic column (Sugar, and Conway, 1968;
ASTM, 1973). This method is only possible when working with extremely
clean samples at high levels with column packing and detectors that
are inert to water vapor.

Liquid/liquid solvent extraction using either high or low boil-
ing solvents overcomes many of the problems faced with direct aqueous
injection techniques (E.P.A., 1971, Duenbostel, 1973). Some of the
problems which may plague the solvent extraction technique include
erratic or low extraction efficiencies and in some instances solvent
impurities. With the advent of capillary chromatography, solvent
interference problems have been greatly reduced due to improved separa-

tion and resolution of peaks.

18

Another widely used method for volatile analysis, especially
in an industrial setting such as analysis of flavors, is the direct
absorption of organics from water onto charcoal followed by solvent
extraction, and concentration (Grob, 1973; Polak, 1974). This method,
however, can suffer the same solvent contaminant disadvantages as
liquid/liquid extraction. Of course, some compounds are preferentially
absorbed into the charcoal, while others are not.

The "head-space" or ”head-gas” method of volatile analysis has
been used for many years. For this technique a sample is sealed in a
partially filled container and the volatiles allowed to partition into
the gas phase which is directly injected via a gas tight syringe into
a gas liquid chromatography (Dow Chemical, 1972). Recovery in this
instance is dependent upon the partition coefficient of each compound,
which must be known in order to calculate the concentration in the
aqueous phase. This equilibrium can be forced in the favor of the
gaseous phase by raising sample temperature, replacing the head-space
with inert gas of a lower density, or purging.

In 1974, Bellar and Lichtenberg developed a very useful technique
for volatile analysis which later was coined as the "purge and trap"
method due to two of the phases in the analysis (Bellar and Lichtenberg,
1974). This technique used the principle of head-space analysis but
improved the extraction efficiencies by purging with an inert gas. In
this way the partitioning continually proceeds in the direction of the
less saturated gaseous phase. A porous glass frit is used to bubble
nitrogen through the sample solution. The gas is then passed through a

series of absorbents at ambient temperature to trap the organic

19

constituents. After a sufficient volume of gas has swept through the
sample and the specific organic compound(s) of interest has been con-
centrated on the absorbent, it is then quickly described. The key to
the desorption process is removal of the organic components of interest
in a single concentrated slug onto a chromatographic column by raising
the traping column temperature at a rapid rate.

In 1976, Steichen of the Good Year Tire and Rubber Company
developed a head-space analysis technique for acrylonitrile and styrene
sensitive down to the 0.5 and 1.0 ppm level respectively (Steichen, 1976).
One year later workers at Dow Chemical devised a more sensitive coloro-
metric method that had been used in the past for acrylonitrile determina-
tion in aqueous media (Hall and Stevens, 1978). This technique was based
on the formation of a yellow colored acrylonitrile pyridine complex read
by a spectrophotometer at 535 nm.

Determination of volatile organic acids in municipal wastewater
was performed via steam distillation onto a silicic acid column in 1977
(Narkis and Henfeld-Furie, 1978). Vblatiles were recovered from the
silicic acid column by elution with n-butanol in chloroform and directly
injected into a gas chromatographic column. This was the first attempt
at characterizing the short chain organic acid content in sewage.

In 1978 two methods surfaced for analysis of acrylonitrile by
G.L.C. that were more sensitive, selective and reproducible than ever
before (Marano, et al., 1978; Pasquale, 1978). Both authors used

Carbowax 20 M,on Chromsorb W 60-80 mesh which allowed better recovery

20

of acrylonitrile through the column and nitrogen phosphorous specific
flame ionization detectors which achieved a 10 ppb level of
detection.

The Adolph Coors Company in conjunction with the University
of Colorado, developed a modified "purge and trap” method for trace
analysis of volatile organics in aqueous mediums (Peterson and
Eicemen, 1978). In this method small compact cartridges of porous
polymer sorption traps are used to collect the volatiles while sparging
the sample with an inert gas. These cartridges were then directly in-
serted into a gas chromatograph inlet system and heated for desorption.
This method is currently used in industrial hygiene for analysis of
volatiles in the work place.

In 1978 a team.of scientists from the Institute of Chemical
Technology in Czechoslovakia looked at the efficiency of the purge
and trap method previously described by Bellar and Lichtenberg
(vozhakova, et al., 1978). In this study several variables were con-
sidered including the stripping vessel design, volatility and the
effectiveness of various polymers in the concentration of organic
compounds. A porous glass fritted system was found to give the greatest
stripping efficiency and linearity over a wide concentration range in
the case of less volatile components. Each volatile compound tested
was shown to have unique recovery curves depending on purge time,

concentration, temperature and rate of desorption from the porous

polymer trap.

21

Much work was completed on the analysis of halogenated vola-
tile organics in drinking and waste water in 1979. Bellar and
Lichtenberg described in detail a semi-automated purge and trap
system for volatile analysis in drinking water. In this report
purge efficiencies for various compounds were discussed in relation
to purge volume and flow rate (Bellar and Lichtenberg, 1979).

Comparisons were also made on levels of halogenated volatiles
from various preservation techniques in aqueous matrices containing
free chlorine over an 8 day time period (Kopfler, et al., 1976). The
results showed a rapid increase in some halogenated compounds over
time when unpreserved, a gradual but linear increase when samples were
stored at 4°C and only a slight increase in samples preserved with
ferrocyanide. Both ferrocyanide and sodium thiosulfate proved effective
in reducing continued chlorination when compared to non-preserved
samples.

An article published in American Water werks Association dis-
cussed in detail a precise analysis technique of trihalomethanes by
liquid/liquid extraction with pentane (Trussell, et al., 1979). The
results demonstrated that the technique was accurate, sensitive, reproduc-
ible, and workable for large numbers of routine samples. In another study
a comparison of recoveries of trihalomethanes in drinking water was made
between purge and trap and liquid/liquid extraction with Methylcyclo-
hexane. Both methods showed comparable results with compensating
advantages to both procedures. Overall, the liquid/liquid extraction

technique maintained higher recoveries (Reding, et al., 1979).

22

Perkin Elmer Corporation described a newly designed head-space
analysis mechanism for adaption to gas chromatography (Widomski, 1979).
This technique solved the common problem of inadequate temperature
control and non-reproducibility of many poorly designed systems.

Purge and trap in conjunction with G.C./M.S. was applied to the
E.P.A.'s list of 19 volatile priority pollutants for analysis in
various types of waters. The method was tested successfully at the
5-50ug/L level and provided qualitative and semi-qualitative analysis
(Pereira and Hughes, 1980). The purge and trap G.C./M.S. priority
pollutant scan has become the most popular method of analysis for
environmental monitoring. Present E.P.A. recommended methods include
purge and trap in conjunction with G.C./M.S. The E.P.A.'s Methods 1624
and 1625 combine a radio isotope labeled dilution with purge and trap
G.C./M.S. for volatile and semivolatile organic compounds (E.P.A., 1980,
1980).

James Mieure from Monsanto undertook a survey of six techniques
for low-level multi-component volatile organic techniques in water
(Mieure, 1980). Included in the general overview were: static head-
space analysis, purge and trap, solid sorbents, liquid/liquid extraction,
steam.distillation, and semipermeable membranes. Increased demand
for purge and trap analysis techniques have resulted from governmental
recommendations. Researchers from the Tekmar Company recently presented
two papers taking an extensive look at the optimization of purge and
trap parameters and design considerations for automatic sampling

(westendorf, 1981; westendorf et al., 1981).

23
C. Phenols

Until 1980 no analysis of phenols from sludge had been reported.
However, several important developments in the area of phenol analysis
have been published. The past developments which have potential
importance in sludge analysis include: sorption resins, derivitiza-
tion techniques, organic acid G.L.C. columns, high pressure liquid
chromatography coupled with ultraviolet, fluorescence and electro-
chemical detection, preservation of phenols and gas chromatography
mass spectrometry.

A dimethylbenzene polystyrene copolymer resin produced by the
Rohm.and Haas Company was shown to be effective in the sorption of
substituted phenols (Paleos, 1969). Both the XAD-Z and XAD-7 resins
were tested for adsorption from water of phenol, m-chlorophenol, o-
nitrophenol, p-nitrophenol, 2,4-dichlorophenol and 2,4,6-trichlorophenol
at concentrations up to 2.4 moi/liter. A more extensive study of the
separation of nitrophenols on Amberlite XAD-Z resin was completed in
1972 (Grieser, 1972). Application of the XAD resin to chromatographic
techniques for determination of phenols in water originated at Iowa
State University (Chriswell, 1975). Later the XAD-Z resin was shown
to be effective in separating a large group of chloro-, nitro-, and
alkyl phenols via elution with buffers adjusted to various pHs. Sorption
of phenol, o-cresol, mecresol and 2.6-xylenol from water on a macroporous
polymer and subsequent thermal desorption onto a G.L.C. column was demon-
strated in 1979 by a group of Czechoslovakian scientists (Voznakova and

Pope, 1979). XAD resins have been used for concentrating organics from

24

wastewaters before and after treatment (Jolly, 1973; Glaze, 1981).
Recovery efficiencies from XAD polymers are good for some compounds
and poor for others. The reason for poor recoveries may be either
poor absorption (polar organics, such as natural organics after oxi-
dation with ozone or chlorine, low molecular weight acids and alcohols)
or poor desorption (some long chain aliphatics and polynuclear
aromatics).

Throughout the years many procedures have been used for the
derivitization and analysis of phenolic compounds by gas chromatography
(Seiber et al., 1972). Markedly improved resolution of derivatized
methyl phenols was provided with the introduction to open tubular
columns and eventually capillary columns (Hvivnak, 1971). In 1979
an extensive reference of phenolic trimethylsilyl derivatives was
compiled according to their retention time on methyl and phenyl sili-
cone G.L.C. columns (Mattsson and Peterson, 1977). This study attempted
to draw a relationship between structure and retention of various
phenolic derivatives. Two groups showed the use of derivatization in
order to magnify sensitivity of certain phenols on a electron-capture
detector (Lamparski and Nestrik, 1978; McCallum and Armstrong, 1973).
Heptafluorobutyrylimidazole, pentafluorobenzoate and dimethyldichloro—
silane were used as derivatizing agents for this extremely sensitive
technique able to detect phenols in the part per billion range. The
effectiveness of these two techniques was proven when both capillary
chromatography and derivatization were combined in the analysis of a

complex environmental matrix of coaltar waste (Buryan et al., 1978).

25

In an attempt to improve separation of phenolics by gas
liquid chromatography without derivatization, several "organic acid"
columns were developed (Supelco, 1978). A special high pressure
liquid chromatographic column has also been introduced for better
resolution of more complex organic acid mixtures Bio-Rad, 1980).

High performance liquid chromatography is well suited for the
analysis of phenolic components. A comparison between several normal-
phase and reverse-phase systems demonstrated the specificity of each
column. For example, alkyl phenols were shown to have superior
separation on a reverse phase C-18 column (Schabron, 1978). Good
separation of E.P.A. priority pollutant phenols has also been demon-
strated with a newly developed micropak Su C-18 column (Realin, 1981).
Various detection systems have been coupled with H.P.L.C. in the past.
Trace level detection of phenols including the priority pollutants
has been shown to be achievable by direct ultraviolet detection
(Bhatia, 1973; Realini, 1979). Fluorescence has been applied to
phenol and alkylphenols demonstrating superior relative detectability
over ultraviolet detection systems (Ogan and Katz, 1979 & 1981).

A highly sensitive technique down to 0.4 ppb has been reported by
using fluorescence spectroscopy and detecting Cerium III after phenols
react with Cerium IV (Wblkoff and Lavose, 1974).

Since 1952 the use of electrochemistry to monitor liquid
chromatographic column effluent has been realized. The advent of
amperometric detectors especially designed for liquid chromatography
in lieu of colorometric detectors has revolutionized this area
(Kissinger, 1974, 1977, 1978). Electrochemical analysis is the most

sensitive and selective method of detection for most easily oxidizable

26

or reducable components. Amperometric detection has been shown to

be 100 to 1,000 times more sensitive than ultraviolet detection for
various aromatic phenols and amines (Sternson and DeWitte, 1977).
Application of amperometric electrochemical detection to the

analysis of phenols in environmental samples has been widespread.
Several recent papers have dealt extensively with the exact parameters
for the determination of various phenolics in water and wastewater
(Armentrout, at al., 1979; King, 1980; Mayer, 1981; Shroup, 1981;
McCrory, 1981).

Quantitation and characterization of phenols from complex
environmental samples via gas chromatography mass spectrometry has been
reported by several authors (Schmidt, 1974 et al., Shackelford and
webb, 1979).

An indepth study on preservation techniques for phenolic come
pounds in wastewaters by an Environmental Protection Agency team.indi-
cated the necessity of chemical preservation as well as storage at 4 C
immediately upon sample collection (Carter and Huston, 1978). An
exhaustive report on the environmental effects of and accepted detec-
tion methods for all of the chlorophenol isomers was conducted by a
group from the University of Wisconsin (Kozak, et al., 1979).

Kozak's report may very well be considered "out of date" in respect
to the analytical techniques suggested due to the great stride in

analysis over the past few years.

27

D. Aromatic Hydrocarbons

Polychlorinated hydrocarbons have been the object of much
attention in recent years due to their inertness in the environment.
Of particular interest are the chlorinated pesticides and PCBs.
Following heavy usage as agricultural pesticides and in industry
respectively, these groups of chemicals had been widely distributed
throughout the environment (Brown et al., 1970-72; Veith, 1971; Ahmed,
1976: Edwards, 1971; Peakall, 1970). They found their way to sewage
plant systems via domestic and industrial wastes. Sharing similar
physical and chemical properties, they were found to interfere with
each other's analysis (Jensen, 1966; Reynolds, 1969; Risebrough et al.,
1971). Therefore, the proper determination of each group had relied
greatly on adequate methodology to separate them before gas-liquid
chromatography analysis is performed.

The first attempt was to destroy or alter the pesticides
through a nitration treatment in order to determine the PC83, or to
convert PCBs in decachlorobiphenyl whose EC signal was compared to a
known amount of Aroclor 1254 converted to decachlorophenyl. Neither
method had proven effective and was quickly abandoned. The nitration
treatment affected the less polychlorinated biphenyls, but not all
pesticides (Reynolds, 1969; Risebrough, 1969). Furthermore, the
nitrated compounds had longer retention times and interfered with sub-
sequent injection. The conversion method required an additional
analytical step.

The second group of analytical techniques was aimed to allow the

28

special separation of many chlorinated hydrocarbon pesticides from
PCBs. Authors involved in finding a device for the separation
included Reynolds (1969, 1970), Armour and Burke (1970), Koeman et al.
(1969), Mulhern (1968), and EPA (1971, 1979, 1980, 1982). Reynolds
reported on an activated florisil column technique which separated
heptachlor, aldrin, BBB, and PCB with the first elution (60 ml n-
hexane) from lindane; heptachlor epoxide, DDD, and DDT with the second
elution (40 m1 508 ethyl ether in hexane). Armour and Burke developed
a method utilizing a silicic acid-celite column which elute aldrin and
PCBs with the first fraction (250 m1 petroleum ether), and lindane,
heptachlor, dieldrin, endrin, p,p' - DUE, o,p' - DDT, p,p' - DDT, and
p,p' - DDD with the second fraction (200 ml acetonitrile-hexane-methylene
chloride 1:19:80). Koeman et al., used an activated florisil column,
eluted the apolar compounds including DOE and PCB with hexane, and
then dieldrin and endrin with 10% diethyl ether in hexane (Peakall and
Lincer, 1970). Muelhern reported on a method which utilized silica gel-
coated thin layer plates and a hexane/ethyl ether solvent system (Ibid).
The EPA also has followed the same trend in developing better
methodology for the analysis and water and wastewater. The first
report to be published was in 1971 and gathered the "current best avail-
able procedure for the analysis of water and wastewater". Other EPA
reports appeared in 1979, 1980 and 1982 devoted specifically to chlor-
inated hydrocarbons and PCBs and aimed, among other goals, to provide

'a reliable means of separating the chlorinated compounds from the sample

29

matrix, isolating them from interferences and separating and
detecting the individual compounds. Also, extensive data were
presented on extraction efficiencies of single component pesticides
and multicomponent formulations, comparison of florisil and gel
permeation chromatography procedures.

The problem with most of these methods was that they
were not totally reproducible, or if they were, there did not exist
a clearcut separation between the compounds to separate. An
interesting paper was published by McIntyre et al. (1980) who
evaluated individual steps in the analytical procedure for the
determination of PCBs and organochlorine pesticides in sewage
sludge. The influence of solids concentrations upon extraction
efficiency were also statistically analyzed. Another problem resides
in the quantitation of PCBs. As a matter of fact, there does not
exist a single uniform method to quantify PCBs chromatograms, al-
though some attempts were made by Chan and Sampson (1975) and by

webb and McCall (1973).

E. Phthalates

The potential of phthalate ester plasticizers leaching into
various contents stored in plastic containers is real (Jaeger
and Rubin, 1970, 1972). Phthalates may also enter the environment

through production of wastes both during the industrial process

30

and due to the disposal of plastics. Several authors have assessed
the environmental safety of phthalate ester exposure (Gledhill

et al., 1980: Lawrence and Tuell, 1980).

F. Aryl Phosphates

Aryl phosphates are routinely used as flame retardent
plasticizers and in hydraulic fluids, both of which offer an avenue
to environmental exposure. One publication has been released which
discusses an analytical technique for analysis of triaryl phosphate
esters in fish (Lombardo and Egvy, 1979). Several reports have
been published concerning the environmental impact of aryl phosphate

esters (E.P.A., 1978; Howard and Deo, 1979).

G. Aromatic Amines

Benzidine and 3,3-dichlorobenzidine are used in dyes and pig-
ments; both have received much attention due to their potential
carcinogenicity to humans (E.P.A., 1978, 1979). 3,3-dichlorobenzidine
has also been shown to photodegrade to benzidine (Banerjee et al.,
1978). A gas liquid chromatographic detection technique has been
described for benzidine and other aromatic amines in the aquatic
environment (Jenkins, et al., 1978). Aromatic amines which can be
easily oxidized are well suited for high pressure liquid chromatography

and electrochemical detection. Several publications have addressed

31
the question of aromatic amine determinations by liquid chromato-
graphic electrochemical detection (Rice and Kissinger, 1979;

Riggin and Howard, 1979; Shoup, 1980).

32

II . ANALYTICAL METHODS

A. Materials
1. Glassware preparation

All glassware (separatory funnels, flasks, teflon seals, and
chromatographic columns) were thoroughly washed with detergent in
hot water as soon as possible, rinsed several times with tap water,
then distilled water and finally with acetone. The glassware was
then heated overnight at 450 C. Teflons were dried in an oven at
less than 100 C to prevent degradation of the silicone layers.

Glassware which had contained PCBs extracts was treated
differently. Being thermally stable, PCBs were not eliminated by
heating in the furnace alone. Also, the glassware which had previously
contained PCBs was first rinsed several times with acetone and
"pesticide-quality” hexane before heating in the furnace.

2. Sample collection

Sewage sludge samples were collected from 203 municipal waste-
water treatment plants and 10 industrial and non-municipal facilities
statewide (Figure 1) by the Michigan Department of Natural Resources,
Water Quality Division, over a sixdmonth period (from June 1980 to
December, 1980). Two types of samples were collected at each site!
one for volatile and semi-volatile organics, and another for non-
volatile organics and inorganics. The volatiles and semi-volatiles
were collected in 200 m1 widemouth screw cap bottles with zero head-

space and salad with teflon-lined caps. The non—volatiles were

33

collected in 2-1iter wide-mouth, amber screw cap jars with aluminum

foil lined caps. Every sample was properly labelled (number, date

and time) with an indelible ink and kept at 4 C. In our work we were

interested only in the non-volatile samples.

For data handling, manipulation and storage, a program was

written for a Digital PUP-11 computer. This program had the follow—

ing purposes:

1. To

f.
g.
2. To
on
3. To

store information on:

all sample sites

all cities, counties or townships

the population served by each treatment facility

the percent industrial input into each treatment system
all municipal sewage plant treatment parameters

all solids parameters

all organic compound levels

perform various mathematical and statistical functions
the data.

list specific information requested from all sites in

a variety of formats.

3. Reagents

- Solvents: Hexane (H), Acetonitrile (ACN), Dichloromethane (DCM)-

all of pesticide quality.

- Solvent mixtures:

1. Mixture A: 50% DCM-0.35% ACN - 49.65% H

2. Mixture B: 80% DCM - 1% ACN - 19% H

3. Mixture C: 10% DCM in hexane

34

- Chemicals
1. Sodium hydroxide NaOH - 0.1N and 6 N
2. Sulfuric acid H2504 - 0.1 N
3. Sodium sulfate - Na SO (ACS) granular, anhydrous

2 4

4. Florisil - PR grade, 60-100 mesh, activated in oven at
135°C for 48 hr. After cooling in dessicator at room
temperature, the activated florisil was stored in dark
in glass containers with foil-lined screw cap. Enough
florisil from the same batch has been submitted to the
same treatment to be used during the entire work.

5. Silica gel 60, particle size 0.063-0.200mm (70-230 mesh
ASTM), activated at 130°C for 48 hr., cooled in a

dessicator at room temperature and kept in glass containers

with foil-lined screw cap.

B. Methods
1. Extraction of organochlorine pesticides and PCBs
The chlorinated pesticides and PCBs may be classified as
neutral compounds. Their extraction is not straight forward. In most
cases, they are co-extracted with base compounds. Neutrals are
ultimately obtained by separating bases, usually by liquid-liquid.
a. Solid samples
Solid samples were completely dried at 50 C and then
soxhlet extracted with 200 ml DCM for 24 hours. Usually, 50 g samples

were weighed for the extraction. The extract then passed through a

'35

series of liquid-liquid extraction to ultimately.yield the neutral

fraction which contained the pesticides and PCBs. The extraction

procedure was as follows:

the soxhelet extract was transferred quantitatively to 250 m1
centrifuge bottle, 100 m1 0.1N NaOH was added and shaken for
1 minute, and then centrifuged at 2500 rpm for 10 minutes.
The aqueous layer was kept aside and the sample was extracted
two more times as before using 100 ml 0.1N NaOH.
The aqueous fractions were combined for acid components extraction.
The solvent fraction was the base/neutral fraction. It was
extracted three times with 100 ml 0.1N H280 . The aqueous
fractions were kept for base compounds extraction.
The remaining solvent fraction contained the pesticides and
the PCBs (neutrals).

b. Liquid samples

Liquid samples were extracted as follows:
a determined volume of sample (usually 250 ml) was quantitatively
transferred to aVS00 ma separatory funnel and made basic
(tested with pH paper) with 6N NaOH and then extracted three
times with 50, 25 and 25 ml DCM. The aqueous fractions contained
the acid compounds, the solvent fraction was the base/neutral
fraction.

Bases and neutrals were separated through acid/base partitioning

with 0.1 N 82804. Bases were extracted three times with 100 m1

36

0.1 N H2804.

PCBs and organochlorine pesticides which were kept for the

The DCM fraction contained the neutrals, i.e.

next step.
Figure 2 summarizes the overall scheme of the extraction procedure.

2. Cleanup procedure and early seperation of polar pesticides

All environmental samples required one or more cleanup
steps before analysis. This was especially true for sewage sludges
containing up to 100% organic materials. They may be constituted
by fatty acids; fats, proteins, phthalates, triglycerides, asphalts,
detergents, and petroleum fuels. An appreciable amount (lo-15%)
of these organic materials was co-extracted with the compounds of
interest. It was therefore necessary to remove those organic sub-
stances through cleanup procedure.

Several cleanup methods have been used, alone or in combina-
tion; they include: separation based on the size of the components
with gel permeation chromatography (GPC), separation by polarity
using alumna, florisil or silica gel columns and acid-base
partitioning. The GPC method has been frequently used for the
ranoval of fats and fatty acids (Stalling, 1... Tindle,. R.C., and
John, J.L., 1972; Mauser, J.M. and Cooke, W. M., 1981: Hopper, M.L.,
1981). Silica gel, florisil and alumna chromatographic columns
are even more popular (Mills, F.A., 1959 and 1970; Wessel, J.R.,
1969; Pesticide Analytical Manual, Vol. 1, 1971; Mills, P.A. et al.,

1972; Ambrus, A. et al., 1981; Longbottom, J.E., 1982). In this

37

Figure 2. Scheme of the Extraction

Procedure

24 h Soxhlet Extraction with DCM

1

Add 100 ml 0.1 N NaOH
to 250 m1 Centrifuge bottle

Centrifuge

 

l

DCM

v
Extract w/ 100 m1 0.1N NaOH-—1

 

w
DCM

 

Extract w/100 m1 0.1N NaOH __,

—: Aqueous Fraction-—. Acid Extrn.

 

Base-Neutral fraction

Extract w/100 ml 0.1 N HZSO4—1

l

DCM

Extract w/lOO ml 0.1N H 50 --

1 2 4

DCM

 

Extract w/100 ml 0.1N H SO

: Aqueous Fraction

 

1 2 4

DCM

Pestitices & PCBs

Base Extraction

38

TABLE 2. Recovery of pesticides and PCBs studied

 

Compound Average percent recovery
%
Lindane 79.2
Aldrin -
Dioldrin 73.1
Endrin 85
Methoxychlor 91
DDD 83.1
DUE 79.6
DDT 82.5
PCB-1254 82.2

PCB-1260 81.3

39

study acid/base partitioning followed by a florisil column separation
were the cleanup steps. The acid/base partitioning was carried out
throughout the extraction procedure.

a. Florisil chromatographic column preparation and cleanup procedure

The chromatographic column separation by florisil was performed
using glass columns with 10 mm internal diameter and 51 cm long. The
columns were dry-packed with 10 gms of fully activated florisil over
20 cm. This was done by taping gently the chromatographic tube. These
conditions facilitated greater resolution of polar from nonepolar
pesticides from.mixtures of pesticides of PCBs. Each column was topped
with 2 cm anhydrous Na SO

24'
Two solvent systems were used for the elution. The procedure

and prewetted with 50 ml hexane.

was as follows:

a) The extract was transferred to the column, letting it pass
through: then the container was rinsed two times with 5 ml hexane and
rinse washes were transferred to column: finally, the column walls
were rinsed. The column was not allowed to dry during this procedure
until the cleanup was completed.

b) The nonpolar pesticides (Lindane, Aldrin, DDE, DDD and DDT)
and the PCBs were eluted with 150 m1 eluant C, consisting of 10% DCM
in hexane (Fraction S).

c) The polar pesticides (endrin, dieldrin, methoxychlor) were
eluted with 250 m1 eluant A (50% DCM - 0.35% ACN - 49.65% H). The
fraction collected was named fraction A. This fraction was concentrated

and put into 0.1 m1 vial for injection on GC-EC column.

40

This procedure was adapted from Mills, P.A. et al., procedure
(1972) which was an alternative to the old method using mixtures of
ethyl ether-petroleum ether in the florisil column chromatographic
cleanup for pesticide residue analysis.

b. Note on the variability in the activity of florisil

Florisil is a polar adsorbent reported to have a large surface
area, which is the basis for its adsorptive properties. It has been
shown that the adsorptive capacity of florisil varies from lot to
lot, due to varying sodium sulfate content (Mills, Paul A., 1968).
Several methods had been attempted to compensate or adjust for the
variability of adsorbancy of different batches of florisil. Among
them, lauric acid method is largely used. In our experiment, we did
not feel it necessary to go through that step. Rather, the chromato-
graphic column was standardized using a mixture of pesticides and PCBs.
Great care has been taken to keep florisil activity constant by avoid-
ing long exposure of the treated florisil to humidity.

3. Separation of the pesticides from PCBs by silica gel 60

For the quantitative determination of the DDT group of
pesticides and PCBs, it was necessary to separate one group from
the other as it is now well established that they interfere with deter-

mination of the other. Several column chromatographic separation

41

procedures, more or less successful, have been published. The pro-
cedure we used was based on that of Amour and Burke (1970), which
was refined by Griffin, D.A. et al. (1980), and by Nowicki, 3.0.
(1981). It was as follows:

a) The chromatographic column was dry-packed with 10 g of
fully activated silica gel 60 over 22 cm, and topped with 2'cm Nazso4
anhydrous.

b) The column was prewashed with 30 ml hexane. An approximate
column flow of l cm/min was maintained. The column was not allowed to
go dry from this point.

c) The cleaned up extract containing PCBs and pesticides in
3 ml solvent or less was transferred quantitatively to the column, and
eluted in this order:

- first, aldrin and PCBs with 65 m1 hexane (Fraction C)

- then, lindane, DDE, DDD and DDT with 250 m1 eluant B

(Fraction B). Both fraction B and C were concentrated
to 0.05 ml for injection.

Figure 3 summarized the cleanup and separation procedures and
Table 3 the composition of the different fractions collected.

The Armour and Burke method utilized a silicic-celite-545 (4 to
1 ratio) column for the separation which required air pressure to
deliver an elution rate of 5ml/min. This was inconvenient in our case
because we did not have the available material to devise a system

applicable to several columns at the same time. Further, it has been

42

 

 

20o om

eon .moo .ooo .oaeesao 0 scene amaszua «a Hoe museum
coaumummom

om

mmom .cquoaa m cacao: Hum mowadm

mmUm . Boo
.moa .oaa .cfiuoao .osmocaq m 200 aoa meauoam ms ocean
memo.m¢
uoaboaxocuar .s«uo~m«o.:auecm a .264 amm.onzuo oom sameness
acoucoo ouosam coauoeuh acumam aco>aom aconuomoc

oeuooadoo mcoauoewm acoMOMMfiu on» mo coeuwmomsoo .m names

43

Figure 3. Cleanup and Separation Procedures of PCBs and
Pesticides

 

L Extractj

Florisil Column

 

 

 

 

 

 

 

 

 

Eluant C
I Fraction S is Silica Gel Column
.___.Hexane
Eluant Ba_____Jn
[_Fraction A Fraction B [Fraction Cw]

 

 

 

 

 

 

Cleanup Step Separation PCBs-Pesticides

"u--------~--“_‘-’~----—

44

reported (Masumoto, H.T., 1972; Huckins, J.N., et al., 1976) that silicic
acid-celite mixture is not always homogeneous, causing the elution pattern
to vary from.column to column. Another problem of the separation resided
in the coelution of aldrin with PCBs and the lack of clear cut separation
between p,p'-DDE and PCBs. Improvement of the method has been attempted
using an internal standard such as azulene, acting as a visual aid to monitor
column chromatographic fractionation (Nowicki, G., 1981), or eliminating
celite in the procedure and adding azulene as monitor (Griffin, D.A. et al.,
1980). While Armour and Burke and Nowicki methods utilized 3% water de-
activated silicic—celite, Griffin used fully activated silicic acid and
reported the best separation with less than 8% p,p'-DDE in the PCBs fraction.
Our own separation using fully activated silica gel 60 has provided accept-
, able fractionation, except that aldrin eluted in the PCBs fraction as in the
case of Armour and Burke method. This did not pose a serious problem since
aldrin was eluted before or at the same time as the very first eluting
peaks of the less chlorinated PCBs. In addition, aldrin was more sensitive
than the PCBs to the GC-EC detector at the same concentration. The problem
arose, however, during the course of analysis when we realized that a huge
interference masked the first eluting peaks, including aldrin. Aldrin
could thus not be quantitated.

The silicic acid-celite 545 chromatographic column of Armour and
Burke, and similar methods developed by other researchers (Berg, o.w., et al.,
1972; Wells, D.E. et al., 1977) for the quantitative separation of DDT
and analogs from PCBs, suffered many variations, as reported in the
literature. Although some attempts were made to improve the method, none
had given to date a complete separation of the two classes of compounds.

This denoted the difficulty of reproducing this separation.

45
4. Quantitation
a. Organochlorine pesticides
A standard curve was constructed for each.pesticide from.different
concentrations of standard solutions. A 2 ul-volume of standard solution
was injected into a gas liquid chromatograph equipped with Ni63 electron
capture detector at the following parameters:

- detector: 300 C

column: 6 ft x 1/8 in. i.d., packed with 11% ov-l7+QF1 on 80-100
gas chrom. Q, 190 C
- nitrogen flow: 30 m1/min

- Chart speed: 0.2 inch/min

Attenuation 10x8

E C voltage: 30V
The concentration for each compound was determined by the computer from its

standard and the following equation: (A) (Vt)
ug/l - (Vi (Vs)

where: A - amount of material injected (in nanograms)
Vi - volume of extract injection in ul (here 2u1)
Vt I volume of total extract (ul)
Vs - volume of liquid sludge (ml) or weight of solid sludge (gm)
b. PCBs
No unified way exists to quantitate PCBs in environmental samples.
It is generally recognized that the prime area of uncertainty in PCBs
methodology lies in the interpretation of the gas chromatogram (Burke,
J.A., 1972; Sawyer, L.D., 1973) although some laboratories (Chau, A.S.Y.
and Sampson, R.C.J’., 1975; Webb, ms. and McCall, A.C., 1973) attempted

to present a uniform approach. But generally, quantitation was based on

46
the direct comparison of an unknown electron capture chromatogrmm with
those of PCBs standards. Our method of quantitation was based on the
following observations:
1. The gas chromatogram.profiles of the sludge samples closely
approximated those obtained from.a mixture of PCBs-1254 and 1260.
2. The PCBs-1260 standard peak with retention time RT-174mm
(peak 13) did not get any contribution from PCB-1254 in the mixture,
while peak 9 of PCB-1260 and peak 11 of PCB-1254 showed up at the same
retention time RT-95mm
Therefore:
1. The peak 13 of PCB-1260 was used to quantitate PCB-1260 in
sludge samples.
2. The peak 11 of PCB-1254 in the mixture (PCBs 1260 and 1254)
was used to quantitate PCB-1254 in the sample, the contribution of PC8-
1260 peak being deducted.
Standard curves of peak 13 and peak 9 of PCB-1260 and peak 11
of PCB-1254 were constructed and used to quantitate levels of the compounds
in the samples. The gas chromatograph employed was a Tractor 560
equipped with a 63Ni EC detector. Chromatograph conditions were as
follows :
Column - 6 ft x 1/8 in i.d. glass coil packed with 3% SE-30 on
Chromosorb WBHP

Temperature - oven 200 C

Carrier - N2 at 50 psi with flow maintained at 30 mlflmin at column
temperature 200 C

Injection - 2 ul, on column

Attenuation - 8 x 10

-- -......... u .u .\.. .3 ~ :..~.~ L.u 2:..L “w.,..~u...:..-~.,d 7......» ~\ .;.--~n\\..~

47

 

 

 

 

 

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as .xa
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.:HE\HE om .Nz I umfiuumo

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amIz .soaao oos\om ac momImm acouauam Nm "season
"moowufiocou cacomquumEouru

oumocmum quH mom mo Bmumoumsooco new q muswam

.‘ .—-- _—

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.
n-ooou-no- .0..- .0.
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6 com .om HZme I souomumo
o cog I cm>o

mmIz .Eouco ooH\om co NomImm mcooaaam Nm I oasaoo
“chfiufipcoo aficomuwoumeouco moo

fiumccmum OONH mum mo EmeOumEOHSU mac m wHSth

49

 

 

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I amNzImoa
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nu ma

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azIz .Eosbo ooa\om so chmm acouosom em I aaafioo
acofiueecoo cecamumoumeoucu

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50

 

 

 

 

 

 

 

 

 

 

 

 

 

carr'

 

 

 

»
so .xa
amNzImua
+
a .xa
oeNzIaoa

me .xa
oeNzImoa

ca x m I aofiumscmuu<
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o«a\H8 om .Nz I umfiuumu

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o O¢~ I cm>o

mar: .Eouco co~\ow co NOMImm mcooaaam Nm I casaoo
msoauaocoo somquumEouco

omuzamcm mHoEmm m mo EmumOumEosno mac n muswfim

51
III RESULTS AND DISCUSSION

A. Results.

Residue concentrations of PCBs present in sludge varied from
traces to 1.9 ppm. Pesticides concentrations were lower. DDT
showed th highest concentration among the pesticides at 17.50
ppb (Tables 5 and 6). Endrin and methoxychlor were not detected.

A clean separation was not obtained for aldrin. A summary of the
results is given in table 4.

The concentrations found were scattered, especially for PCB—1254
ranging from nearly 2 ppm down to 1.13 ppb, and for PCB—1260 from
433 ppb to 0.51 ppb, DDT from 17.5 ppb to 0.08 ppb, and DDD from
12.4 ppb to 0.02 ppb. This wide dispersion of the results may
represent the variable nature and composition of sewage effluents.

Among the pesticides, DDT was found in the highest concentrations
with levels as high as 17.5 ppb and an average level of 1.75 ppb.
DDD was next highest with an average level of 0.58 ppb and with the
highest concentration being greater than 12 ppb. The higher
concentrations of DDD were recorded on the sites where DDT levels
were high. DDE and lindane were present apparently in similar
concentrations with 0.24 ppb and 0.26 ppb respectively.

Higher concentrations of PCBs than the pesticides were present.
PCB-1254 was determined to have the highest level (1.9 ppm) in the

sludges analyzed.with an average above 0.6 ppm.

B. Comparison of the results with those available in the literature
An analytical survey of several municipal sewage sludges of

American cities by Fur, et al. (1976) showed PCB concentrations

52

 

 

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Hm.0 N~.0 «0.0 em.~ 0N.0 ocmocaq
~0.N m0.~ 00.0 0m.n~ m~.~ Han
0~.0 NN.0 No.0 m0.0 q~.0 man
00.~ 0H.0 No.0 00.~H 00.0 000
0m.0 «0.0 m~.0 0~.N 05.0 cwuoamwo
I I. I1 laaav ..3 are wa\wsv I I I
coaumw>oo oumocmum msHm> sowed: m=Hm> sod msam> swam venom uosoam owmum>< ocsooaoo

oouhamcm moufim m0“ ecu you mono mo unmeasm I a canoe

Table 5 Pesticides concentrations (ng/kg dry wt.) in sewage sludges analyzed

LINDONL(h) HEINOX‘CHLUR(L

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53

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(

Table 5 continued

54

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Table 6 continued

56

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SUIOOF'TION (0 FOR LIST)?

)

57
ranging from about 23 ppm (Denver) to 0.01 ppm (San Francisco).

Erikson and Pellizzari (1979), using GC/MS/computer detected
individual isomer, with total PCBs of about 11 ppm. In 1974,
Dube, et al. reported concentrations of 0.05 - 2.8 ppb PCBs in
sewage effluents collected at numerous Wisconsin cities. The
concentrations in those studies were all expressed on a wet weight
basis. They would be even higher if they were reported on a dry
weight basis, as in this study. Consequently, the concentrations
of PCBs found in sludges in this study were equal to or relatively
lower than those reported in the literature.

Likewise, DDT analogs and other pesticides reported in this
study were equal or lower than those published in the literature
(Harper and Gotte, 1977; Frank, et al., 1977).

C. Parameters tested

An attempt has been made to find if any trend exists between
the level concentration detected and the number of population and
the percentage of industrial input (Figures 8-25). The percent
industrial input is defined as the ratio of the total industrial
input over the flow of the treatment facility.

For most of the chemicals studies, there seems to exist a
decreasing trend in the concentration as the population increases
(Figures 8, 9, 11-15). This is in accordance with previous
similar comparisons with total phenols analyzed in sewage (Phillips,
1981). ,However, this trend was not observed when different group-
ings of population were made (Figures 18 and l9). A study by 0
Harper, et a1. (l977) showed a linear regression between total BHC

concentration in a river water and urban population density.

59

 

500

400
300
200
100

.us hut mx\m:
coauouuaouaoo swarms w:u.:ooa ocoocaq

Population in thousands

.us haw wx\wc
refiyouucoocco cmfiooe psm.cooa aroused

 

Population in thousands

60

1000

Figure 10

 
 

600

      

m m

.us %uv wx\w:
cowuouucooaoo cmfiooa was now: can

‘00

*0

Population in thousands

 

800

Figure 11

Av
w

400

m o

.u3 xup wx\mc
cofiuouuaooooo rowers was new: man

Population in thousands

61

Figure 12

 

m m .

300

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SOfiHfiHUGOU—uou 000.005 000 0003 ”DD

Population in thousands

 

150

m m o
1

.u3 xuo wx\wo
coaumuufimoaoo amfiooi was some men

Population in thousands

62

Figure 14

2400

2000

 

1600
1100

.u3 xuv mxxwa
conouuamosoo amigo... can some .80

w m o

8

   

Population in thousands

5
1
m.
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F

 

.uz mun mx\m:
coauouucoocoo noises on... some .50

Population in thousands

63

Figure 16

40'
5O

.uB who coed x wx\w:
coauouunoucoo swarms was some enmu mom

 

nu .
«4 MW .u

Population in thousands

Figure 17

 

.u3 zoo coca x wx\w:

coaumuusmucoo swarms can some «mud mom

Population in thousands

64

Figure 18

4O .
3O

 

o
z

.u3 moo coon x mx\m=
coaumuucmucou nuance was some coma mom

0 0

Population in thousands

 

a m. m. w

J: are 82 x 9:?
cowuouuamocoo swarms was some coma mom

Population in thousands

65

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

alias
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.uz %no mx\w:
soauouuamucou “5255 was some an:

Percent industrial input (2)

 

 

 

 

 

 

 

 

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coauouuooocoo amends poo dogs can

(7.)

Percent industrial input

66

 

 

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w

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Figure 22

 

 

 

 

 

 

 

 

 

 

 

 

 

 

T u
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3

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.u3 hum cog x mx\mc
aofiuouuamucoo nuance was some 900

(7.)

Percent industrial input

PCB 1260 mean and median concentration

ng/kg x 1000 dry wt.

PCB 1260 mean and median concentration

ng/kg x 1000 dry wt.

67

Figure 24
29 *1

l8 #-

15%3

 

 

 

 

 

 

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Percent industrial input (2)

2.1 «-——1'

13.. Figure 25

V

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Percent industrial input (2)

0
I00
2

«at

68
In the case of level concentration vs. percent industry, no trend

was observed (Figures 20-25).

69
IV. CONCLUSION

Thus far, studies concerning organic environmental pollutants in
sewage effluents and sludges have been limited. No doubt, interest will
increase in an era where energy conservation and safe disposal of hazardous
wastes are primary concerns.

Many problems in sewage analysis remain. The areas which require
the greatest amount of work at this time include:

1. Uniform and representative sampling

2. sample preservation and stabilization

3. Improved cleanup and separation techniques for solvent

extractable materials

4. Development of a quality control program to evaluate analysis

techniques.

Most of the compounds analyzed were detected at the ppb level or
below. This low concentration level may be in part due to the very nature
of the samples and the possible biological decomposition of the components
studied. According to the Michigan Department of Natural Resources, sludge
management division, no written law regulates the concentration of chlorin-
ated pesticides in sludges to be applied to farmland. Each case is treated
individually. However, sewage sludges containing below 50 ppm could be applied
to crop land. Thus, the sewage sludges analyzed for the selected PCBs and
organochlorine pesticides could be used in the sludge management program.
It should be noted that the uses of the chemicals considered in this study
were severely restricted more than a decade ago. Therefore, a slow decrease
was expected (due to their nature) of their concentrations in environmental
samples. Naturally, sludge management program is a coherent program which

takes into account other toxic organic chemicals and heavy metals as well.

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