EPA 660/2-74-077
September 1974
Environmental Protection Technology Series
Organic Compounds Entering
Ground Water From A Landfill
*< Pfff&
Office of Research and Development
U.S. Environmental Protection Agency
Washington, D.C. 20460
-------
RESEARCH REPORTING SERIES
Research reports of the Office of Research and
Monitoring, Environmental Protection Agency, have
been grouped into five series. These five broad
categories were established to facilitate further
development and application of environmental
technology. Elimination of traditional grouping
was consciously planned to foster technology
transfer and a maximum interface in related
fields. The five series are:
1. Environmental Health Effects Research
2. Environmental Protection Technology
3. Ecological Research
4. Environmental Monitoring
5. Socioeconomic Environmental Studies
This report has been assigned to the ENVIRONMENTAL
PROTECTION TECHNOLOGY series. This series
describes research performed to develop and
demonstrate instrumentation, equipment and
methodology to repair or prevent environmental
degradation from point and .non-point sources of
pollution. This work provides the new or improved
technology required for the control and treatment
of pollution sources to meet environmental quality
standards.
EPA REVIEW NOTICE
This report has been revieved by the Office of Research and
Development, EPA, and approved for publication. Approval
does not signify that the contents necessarily reflect the
vievs and policies of the Environmental Protection Agency,
nor does mention of trade names or commercial products
constitute endorsement or recommendation for use.
For nte by tbe Superintendent of Document*, U.S. Government Printing Office, Washington, D.C. 20402 - Price $1.15
-------
EPA-660/2-74-077
September
ORGANIC COMPOUNDS ENTERING
GROUND WATER FROM A LANDFILL
by
James M. Robertson
Craig R. Toussaint
Monica A. Jerque
School of Civil Engineering and Environmental Science
University of Oklahoma
Norman, Oklahoma 73069
Grant No. R801417
Project No. 21 AKQ-13
Program Element 1BA024
Project Officer
Dr. William J. Dunlap
Robert S. Kerr Environmental Research Laboratory
Subsurface Environmental Branch
P. 0. Box 1198
Ada, Oklahoma 74820
Prepared for
OFFICE OF RESEARCH AND DEVELOPMENT
U. S. ENVIRONMENTAL PROTECTION AGENCY
WASHINGTON, D. C. 20460
-------
ABSTRACT
Organic compounds leached into ground water from a landfill containing
refuse deposited below or near the water table were investigated. Ground
water from wells within or near the landfill and a control well was sampled
by modified low-flow carbon adsorption procedures incorporating all glass-
teflon systems to preclude introduction of extraneous organics. Column
chromatography, solubility separation, and gas chromatography-mass spectrometry
were employed for separation, identification, and quantitation of individual
compounds in organic extracts. The ground water was shown to contain low
levels of many undesirable organic chemicals leached from the landfill.
Of those compounds identified (over 40), most were chemicals commonly
employed in industry for manufacturing many domestic and commerical
products. The source of these compounds was apparently manufactured
products discarded in the landfill, since it had not received appreciable
wastes from industrial operations. Because the age of the refuse in the
area studied was at least three years, the compounds identified were
believed to be substances leached very slowly from the refuse and/or
transported away from the landfill very slowly because of adsorption on
aquifer solids. Potential long-term pollution of ground water by
industrial organic chemicals from landfills may be indicated by this
work.
This report was submitted in fulfillment of Project Number 21 AKQ-13,
Grant Number R801417, by the School of Civil Engineering and Environmental
Science, University of Oklahoma, under the sponsorship of the U. S.
Environmental Protection Agency. Work was completed as of May 1974.
ii
-------
CONTENTS
Page
Abstract ii
List of Figures iv
List of Tables v
Acknowledgements vi
Sections
I Conclusions 1
II Recommendations 3
III Introduction 4
IV Experimental 7
Description of the site 7
Experimental wells 8
Investigative procedures 8
V Results and Discussion 21
Total organic carbon analysis 21
Initial phase of study 23
Final phase of study 24
VI References 45
iii
-------
FIGURES
No. Page
1 Well Locations at Norman Landfill 9
2 Carbon Adsorption Column for Sampling Ground Water 11
3 Solubility Separation of CAE3II 20
4 Gas Chromatogram of CCE3II, Landfill Well 26
5 Gas Chromatogram of CCEC, Control Well 27
6 Gas Chromatogram of CAE3II, Landfill Well 28
7 Gas Chromatogram of CAEC, Control Well 29
•Iv
-------
TABLES
No. Page
1 Maximum BOD and COD Values Obtained from Landfill 5
Leachates
2 Fractions Prepared from CCE3II by Silica Gel Column 17
Chromatography
3 Fractions Prepared from CCE3II-SG7 by Silica Gel 18
Column Chromatography
4 Total Organic Carbon in Ground Water in the Vicinity 22
of the Landfill
5 Weights of Carbon Chloroform and Carbon Alcohol Extracts 25
6 Compounds Identified in CCE3II and CAE3II 31
-------
ACKNOWLEDGEMENTS
The Authors wish to express sincere appreciation to William J. Dunlap,
whose expert guidance and countless hours of assistance made possible
the successful completion of this project.
Special appreciation is due to D. Craig Shew, whose assistance in mass
spectrometry was invaluable, and to Marion R. Scalf for advice and
assistance in site preparation and drilling of wells.
The patience and assistance of Jack W. Keeley and his willingness to
address difficult environmental problems are appreciated in making this
project possible.
vi
-------
SECTION I
CONCLUSIONS
1. The landfill investigated in this study was contributing low levels of
many undesirable organic chemicals to the ground water with which it
was in contact. Principal among the compounds identified were chem-
icals commonly employed in industry for the manufacture of a wide
array of products.
2. Since the refuse in the test area of the landfill had apparently been
in place for several years and undergone initial stabilization, the
compounds identified in this study were probably those which were
leached very slowly from the more intractable refuse and/or which
were transported away from the region of refuse deposition very
slowly because of significant adsorption on aquifer solids.
3. The introduction of many industrial organic chemicals into ground
water by the landfill studied indicates that even those landfills
which do not receive appreciable quantities of solid wastes from in-
dustrial operations may pollute ground waters with industrial organic
compounds, probably by leaching of such substances from finished
products manufactured for domestic and commercial use which ulti-
mately are deposited in landfills.
4. The potential for long-term pollution of ground water by industrial
organic chemicals from landfills in contact with the water table may
be indicated by this study. Such pollution could persist for many
years after closing of landfills because of: slow leaching of organic
compounds from discarded manufactured products which serve as reser-
voirs of these compounds; and/or slow "chromatographic" movement of
adsorbed, intractable compounds away from the landfill site.
5. If long-term pollution of ground water by landfills does occur it is
likely often to be insidious, involving quantities of pollutants too
low to noticeably alter the physical properties of the water being
degraded. Such pollution is of concern because the effects of long-
term ingestion of water containing low levels of organic compounds
such as those identified in this study are largely unknown.
6. The compounds identified in this study comprised only a small portion
of the total organic matter in the sampled ground water because the
carbon chloroform and carbon alcohol extracts prepared by low-flow
carbon adsorption apparently contained less than ten percent of the
total organic carbon in the water and many of the compounds present
in these extracts were not readily amenable to the chromatographic
procedures employed in this work.
-------
Realistic evaluation of the problem of ground water pollution by
organic compounds leached from landfills will require the develop-
ment of additional information concerning the generation and/or
release of organic compounds from refuse, the persistence of such
compounds in subsurface environments, and the mobility of recalci-
trant organic compounds in ground water aquifers.
-------
SECTION II
RECOMMENDATIONS
1. Comprehensive investigations should be conducted to further elucidate
the nature and extent of ground-water pollution by organic compounds
leached from landfills. The potential for long-term pollution of
aquifers by industrial organic chemicals leached from discarded manu-
factured products should receive special attention.
2. Methods providing better recovery of organic compounds from ground
water than low-flow carbon adsorption should be developed and utiliz-
ed to obtain improved qualitative and quantitative information in
future investigations. The use of macroreticular resins as adsorb-
ents should be explored for this purpose. Also, analytical methods
should be expanded to permit study of compounds of higher molecular
weight and polarity than those identified in the investigation re-
ported herein.
3. The temporal release of organic compounds from landfill refuse into
ground water should be investigated. Variables such as type and com-
paction of refuse, degree of saturation, oxidation-reduction condi-
tions, and age of the landfill should be correlated with rates of
generation and release of organic compounds and identities of these
pollutants.
A. The movement and Icogevit}' of organic compounds leached from land-
fills in aquifers of varying geological types should be examined.
Consideration should be given to possible slow, "chromatographic"
migration through aquifers of zones of pollutants originally concen-
trated near landfill sites because of significant adsorption on
aquifer solids. Information should be developed concerning the per-
sistence in saturated subsurface environments of various classes of
organic compounds contributed to ground water" by landfills.
5. Information concerning the health effects of long-term ingestion of
water containing low levels of organic compounds'such as those iden-
tified in the study reported herein should be developed as quickly as
possible by qualified environmental health science groups. Such
information would greatly aid evaluation of the seriousness of the
problem of ground water pollution by organic chemicals from landfills,
and would also be helpful in assessing other ground-water as well as
surface-water pollution problems.
-------
SECTION III
INTRODUCTION
The 1968 National Survey of Community Solid Waste practices in the
United States indicated that well over ninety percent of the 800
million pounds of municipal solid waste produced daily was deposited
at land disposal sites.1 A majority of these disposal sites failed
to meet the federal and state regulations for sanitary landfills. Open
burning was practiced at many of them and placement of solid waste into
or near the water table was a common occurrence. In spite of a national
effort to improve solid waste disposal methods, over 13,804 open dumps
were reported last year (1973).2 In addition to the obvious pollution
caused by open dumps, many of the disposal sites presently designated
as sanitary landfills are polluting the nation's precious ground water
supplies through direct contact or by the process of leaching. Leaching
is the process of dissolving or otherwise placing solids, liquids or
gases in solution by the action of water moving through the parent
material. Leaching of chemicals from a land disposal site can occur due
to direct horizontal flow of ground water or as a result of vertical
leaching by percolating water from rainfall or runoff. No accurate fig-
ures are available for the amount and severity of ground water pollution
by improperly disposed solid waste; however, the few reports on this sub-
ject which have been published would suggest that the problem is very
serious.
Some recent well-documented cases of ground water pollution from solid
waste disposal in California3, South Dakota1*, and Illinois5 have
indicated that very high concentrations of organic materials may be
initially released from landfills located in or near the water table.
Landfills receiving substantial amounts of percolation of runoff waters
also produced leachates high in organics. The peak production of
organics (measured as biochemical oxygen demand, BOD, or chemical oxygen
demand, COD) usually occurred within a few months although some land-
fills required periods of approximately six months to one year for peak
production to occur. Examples of BOD and COD values obtained from some
of the landfill leachates are shown in Table 1.
-------
Table 1: MAXIMUM BOD AND COD VALUES OBTAINED FROM LANDFILL LEACHATES
Landfill leachate
source
Riverside, Cal.
Puente, Cal.
Scholl Canyon, Cal.
Blackwell, 111.
Du Page, 111.
BOD mg/liter
59
9,200
1,200
54,610
14,080
COD mg/liter
-
9,280
5,750
39,680
8,000
Reference
State of Califor-
nia 19693
State of Califor-
nia 19693
State of Califor-
nia 19693
Hughes, et.al.
19715
Hughes , et . al .
19715
Variables which were considered to be important factors in the relatively
wide range of BOD and COD values obtained include the following:
hydrology, geology, topography, type of refuse, and the age of the
refuse cell. The hydrological conditions of the areas included widely
varying quantities of precipitation and ground water with corresponding
effects on rates of leaching. Geological aspects of the areas included
such factors as different soil types above and below the cells as well
as different types of underground formations present. These character-
istics have been shown to greatly influence the ability of water to
move through the cells and thus affect leaching rates of organics. In
addition, the type of soil would also exert an influence on the amount
of adsorption of organic materials. Topographical features of the
areas influenced water runoff and percolation rates and consequently
affected leaching rates. The types of refuse deposited in the cells
exerted a considerable effect on BOD's and COD's produced in leachates
since the deposited refuse represented the raw material for this pro-
duction. For example, a waste high in garbage content would produce
high BOD and COD values in leachates rapidly while a waste containing
a large percentage of more durable materials such as plastics, paper,
and wood would be expected to decompose much more slowly with much
lower amounts of BOD and COD being produced. The ages of the refuse
cells appeared to be important factors in the quantities of organics
present in leachates. An initially high release of organics was
usually followed by a much lower release over the next several years.
Experiments involving leaching of refuse in columns, lysimeters and
bins have resulted in very high BOD values ranging from 3000 mg/1 to
> 30,000 mg/1.6'7 Most of these studies used relatively large volumes
of leach water in order to maximize leaching rates. An interesting
study was conducted in Britain in which refuse was placed into inter-
mittent and continuous contact with water. In one experiment, deposited
-------
refuse was completely submerged in bins. Horizontal flow of water
through the refuse resulted in an accelerated rate of leaching. High
initial values of BOD, organic carbon, and organic nitrogen occurred
shortly after each new addition of refuse. These wet cells also pro-
duced high concentrations of chloride, sulfate, and ammonia.
The studies cited above clearly show that pollution of ground water
by organic material leached from land disposal sites can and does
occur extensively and is likely to pose a serious threat to ground
water quality. Practically no information has previously been
developed, however, concerning the nature of the organic pollutants
entering ground water as a result of leaching of solid waste, leaving
a major gap in the knowledge needed to evaluate the actual extent of
the hazard entailed in such pollution. Public land disposal sites
have been used extensively until recently for deposition of virtually
all of the nation's solid waste including hazardous industrial, hospi-
tal, and agricultural waste such as pesticides, plasticizers, solvents,
phenolic compounds, and many others. Currently, the bulk of waste from
great quantities of products manufactured for domestic and commercial
use continues to be placed in land disposal sites, and these products
contain or have been produced from a vast array of potentially hazard-
ous organic chemicals. It is obviously important to know if pollution
of ground water by leaching of such materials from disposal sites is
occurring.
The investigation described in this report consisted of an effort to
identify specific organic pollutants contributed to ground water by a
landfill near Norman, Oklahoma. The investigation consisted of two
principal phases of study. During the initial phase sampling procedures
and analytical methods were developed, and organic constituents of
ground water obtained from wells in and near the landfill were examined
for the presence of polychlorinated biphenyls (PCB's) and subjected to
some further study directed towards identification of individual organic
compounds present. The PCB's were given special attention because of
concern for their hazardous properties and the high probability that
most of these compounds and products in which they are used have been
deposited in land disposal sites when their useful lives have ended.
The data obtained in the identification work in this phase were limited,
because of difficulties encountered in sampling the ground water for
recovery of organics and the unavailability of analogous organic frac-
tions from a suitable control well for comparison purposes. The second
phase, undertaken to correct these deficiencies, was essentially a better
controlled, more thorough effort to identify major organic compounds
contributed to ground water by the landfill.
-------
SECTION IV
EXPERIMENTAL
DESCRIPTION OF THE SITE
The Norman landfill is located approximately one mile south of the city
of Norman, Oklahoma, on the north bank of the South Canadian River
in McClain County, Oklahoma. At this point the river's direction is
essentially from northwest to southeast and the flow in the river is
normally very low except during high rainfall periods.
The water table at the landfill site is quite high, averaging from
2 to 5 ft below the surface in the lower half, adjacent to the South
Canadian River. The soil consists of quatenary recent alluvium composed
of silt, sand, clay, gravel, and dune sand. All of the soil is
moderately or highly permeable. The depth of the alluvial sand layer
varies from 35 ft to 40 ft and overlays a 300 ft impervious layer of
dense clay and chert gravel, referred to locally as the "red bed".
The landfill was originally operated by the city of Norman for a
period of 38 years as a dump in which there was no restriction con-
cerning the type of material disposed of and in which open burning
was practiced. During flood periods, the landfill was partially
inundated by flood waters. The river bank in at least one place was
eroded by flood waters so that old debris is now visible on the bank.
No flooding has occurred in recent years because of upstream flood
control dams.
Beginning in 1960, large quantities of refuse were placed in trenches
approximately 10 ft deep which had been dug by a dragline to obtain
sand for a sand and gravel company. These trenches intercepted the
water table in many places since the ground water is within a few feet
of the surface in a large portion of the landfill area. In this
operation, garbage trucks dumped their loads near the working end of
each trench. A bulldozer then pushed a layer of refuse approximately
12 ft thick over and into the trench which contained as much as 5 to
8 ft of water. The deposited material was later covered with approxi-
mately 6 in of cover material. Cover material used was that available
at the site, and was essentially a fine, permeable sand as described
earlier in this section.
The trench type of operation was carried out from approximately 1960
to the spring of 1972 when new state solid waste legislation required
the operators to change the method of operation to a modified area fill
in order to help prevent further ground water contamination. In this
-------
method, solid wastes were deposited in layers at least 2 ft above
the water table and covered at least weekly.
Within the past year, the deposited wastes have been covered almost
daily and, at the present time, the site is classified as a sanitary
landfill. The newer portion of the landfill has been in operation
approximately 15 years.
The direction of ground water flow at the newer landfill was determined
in the spring of 1972.8 The direction of flow of ground water was
considered to be normal to the contours and approximately 7 west of
south.
EXPERIMENTAL WELLS
Four wells were used in this study. Three of these were test wells
in or adjacent to the new landfill site. The fourth well was a control
well located approximately one mile northwest of the landfill site.
The locations of test wells No. 2, 3, and 4 are shown in Figure 1.
Well No. 4 was drilled in April of 1972, and cased with galvanized
iron pipe to a depth of 15 ft. It was perforated from 9 to 15 ft
and held 12 ft of standing water. Well No. 2 was drilled in November,
1971, and cased to a depth of 40 ft with 38.5 ft of water. The lower
10 ft were perforated. Well No. 3 was drilled in November, 1972, in
the southeastern portion of the new landfill where the age of the
refuse was approximately three years. This well was drilled through
a refuse layer 20 to 22 ft thick. The total depth of well No. 3 was
32 ft and the lower 12 ft were perforated. It contained 17 ft of
standing water. The control well was drilled in October, 1973 , and
was cased to 42 ft. It was perforated in the bottom 12 ft and held
37 ft of standing water. Well No. 2 and the control well were drilled
to the "red bed". Wells No. 3 and 4 were not drilled to the "red bed"
but did have solid iron plates at the bottom to prevent sand intrusion.
All of the wells were gravel packed with fine gravel and coarse sand
to help prevent the surrounding sand from filling them. The packing
also allowed surrounding ground water to flow into the wells at faster
rates. Each of the wells was thoroughly bailed and pumped initially
after drilling and was also pumped prior to sampling.
INVESTIGATIVE PROCEDURES
General Procedures
Stringent precautions were exercised throughout the investigation to
prevent contamination of samples with extraneous organic matter. Only
pesticide grade solvents or analytical reagent grade solvents which were
redistilled in glass were used. All glassware was subjected to a
8
-------
CONTROL
WELL
0.7 MILES
I
LANDFILL
LEGEND
DIRT ROAD
SAMPLING WELLS X
BLACKTOP ROAD
1 in = 533 ft
WATER TABLE
CONTOUR LINE
FIGURE 1, WELL LOCATIONS AT NORMAN LANDFILL
-------
rigorous cleaning procedure which entailed: thorough washing with
detergent solution; rinsing with tap water; soaking in dichromate
cleaning solution; thorough tap water rinsing; multiple rinsing with
distilled water; rinsing with glass-distilled acetone; and oven drying.
Sample materials were allowed to contact only clean glass and Teflon.
Ground water samples were analyzed at various times during both
phases of the investigation for total dissolved organic carbon, employ-
ing a Dow-Beckman Carbonaceous Analyzer (single channel).9
Gas chrotnatographic analysis of organic fractions obtained in the
investigation was achieved by means of Varian Model 204B and Varian
Model 2100 gas chromatographs. A Finnigan Model 1015C gas chroma-
tograph-mass spectrometer with both electron impact and chemical
ionization sources and Systems Industries System 150 data system was
employed for collecting and processing mass spectral data for various
organic fractions isolated during the studies. Computerized mass
spectra matching programs based on libraries of mass spectra at the
National Institutes of Health, Bethesda, Maryland, and Battelle Memorial
Institute, Columbus, Ohio, were utilized in evaluating mass spectral
data for identification of individual organic compounds.1°
Procedures Employed in the Initial Phase of Study
Sampling Procedures - Organic components in ground water from well
No. 3, within the new landfill, and well No. 2, downstream from the
landfill near its edge, were sampled for analysis in this phase of
study. The sampling procedures employed during most of this work
incorporated a modified version of the low-flow carbon adsorption
method11'12, with the ground water being pumped from the saturated
zone directly through columns containing activated carbon to adsorb
and recover the organic compounds.. Glass columns 3 in X 18 in were
employed (Figure 2). They were constructed from 3 in diameter Pyrex
drain line and could be disassembled for packing and unloading, with
the two sections being held together by a Pyrex drain pipe coupler
with a Teflon gasket. Columns were plugged at both ends with solvent-
extracted glass wool and were packed with 30 mesh activated carbon
(Nuchar C-190, Plus 30, Herbert Chemical Co., St. Bernard, Oh}.
For sampling, a packed column was placed in a vertical position at the
top of the casing of the well to be sampled. A suitable length of
Teflon tubing was attached to the bottom inlet of the column and ex-
tended down the well shaft into the saturated zone. The ground water
was then pumped up the tubing and through the carbon column by an
impeller type (centrifugal) pump attached by Teflon tubing to the out-
let (downstream) end of the column. Flow rates and quantities of water
sampled were determined by collecting the discharge water from the pump
in suitable containers and measuring the volume.
10
-------
TO punp
•.i • .
Wy-.:'.'-.'
V -1 :
• , -.- .
J_
T
GLASS WOOL
3" PYREX DRAIN LINE
•ACTIVATED CARBON
PYREX DRAIN LINE
"COUPLER-TEFLON SEAL
-GLASS WOOL
TEFLON TUBING
FROtf WELL
FIGURE 2, CARBON ADSORPTION COLUMN FOR
SAMPLING GROUND WATER
11
-------
The use of an all glass and Teflon system from the saturated zone to
the outlet of the carbon adsorption column and placement of the pump
on the downstream side of the column virtually precluded introduction
of any organic contaminants during sampling of the ground water.
However, considerable difficulty was encountered during this phase
of the study in attempting to attain desired low rates of flow
(approximately 100 ml/min) of water through the carbon columns when
using impeller (centrifugal) type pumps. Although several pumps of
this type were tried, including those operating on both A.C. and
B.C. current, none was found capable of sustained operation at the
low flow rate needed. Consequently, the flow rates achieved in carbon
adsorption sampling of the ground water analyzed in this phase of
study were non-uniform and higher than optimum. These flow rates and
the volumes of water sampled were: well No. 2, 400 ml/min, 100 gal
(379 1); well No. 3, 175 ml/min, 42 gal (159 1).
Organic compounds in ground water from well No. 3, within the landfill,
were also sampled during this phase of study by sorption on Amberlite
XAD-2, an insoluble cross-linked polystyrene polymer supplied as 20-50
mesh beads (Rohm and Haas Co., Philadelphia, Pa.). This method was
reported by Harvey to be very effective in recovering PCB's from aqueous
samples.13 A 3 X 21 cm column of XAD-2 containing 150 cm3 of the resin
was employed. Before the column was packed, the resin was washed with
several volumes of distilled water, extracted twice for 18 hr each time
in a Soxhlet extractor with acetonitrile, and finally washed thoroughly
with additional distilled water to remove the acetonitrile. A glass
wool plug was placed at the inlet end of the column to serve as a pre-
fliter.
Because of clogging problems, ground water could not be pumped directly
from the saturated zone through the amberlite column. Instead, ground
water was drawn from the water table through a Teflon tube into a
closed carboy at the well head by maintaining a vacuum in the carboy.
Five gallons of water were then filtered through a prewashed glass
fiber filter and passed through the resin column at full gravity flow.
The flow rate through the column was 100 ml/min, initially, but had
decreased to 60 ml/min when passage of the water sample neared comple-
tion.
Desorption of Sampled Organic Material - When sampling was completed
the carbon adsorption columns were drained to remove excess water. The
carbon containing the organic material adsorbed from the sampled water
was then dried carefully by passing nitrogen through the columns for
approximately 24 hr while heating gently at temperatures not exceeding
65 C. The dried carbon from each column was transferred to modified,
large-size (220 ml) Soxhlet extractors and extracted with chloroform
for 36 hr. The carbon chloroform extracts (CCE's) obtained were
filtered through solvent-extracted glass fiber filters to remove any
carbon fines present, and were concentrated at low temperature under
12
-------
vacuum in rotary evaporators. The CCE's from ground water from wells
No. 2 and No. 3 were designated CCE2 and CCE3, respectively.
Upon completion of the sampling procedure using Amberlite XAD-2, the
column was drained of excess water and the glass wool pre-filter was
removed. Organic compounds adsorbed on the resin were eluted by
successively passing 200 ml of hot ethanol and 500 ml of distilled
water through the column at full gravity flow. The combined ethanol-
water eluate was extracted three times with 50 ml portions of hexane.
The hexane extracts were combined, dried with anhydrous sodium sulfate,
and carefully concentrated to a volume of 5 ml in a rotary evaporator.
Analysis of Organic Extracts - Both CCE2 and CCE3 were subjected to
liquid-solid chromatography on columns of silica gel to obtain fractions
of less complexity for further study. These CCE's were chromatographed
on 12 X 15 cm columns dry-packed with 100-200 mesh Silicar CC-7
(Mallinckrodt Chemical Works, St. Louis, Mo.) which were eluted succes-
sively with 200 ml each of hexane, benzene, chloroform, and a mixture
of chloroform-methanol (1:1, v/v). Eight 100 ml fractions were col-
lected, with each of the four eluting solvents producing two fractions.
The CCE silica gel fractions and the hexane extract prepared from
the Amberlite XAD-2 eluate were subjected to gas chromatography on the
following columns: 5.3% DC-200 on 80/100 mesh Gas Chrom Q (Applied
Science Laboratories, State College, Pa.); 3% OV-1 on 100/120 mesh
Gas Chrom Q; and, 10% QF-1 on 80/100 mesh Gas Chrom Q. The chromato-
grams obtained were compared with chromatograms produced under the
same conditions by a series of standard PCB's (Arochlor 1232, 1242,
1248, 1254, 1260, and 1262). Those fractions which appeared, on the
basis of the retention times of their constituent compounds, possibly
to contain PCB's were further investigated by combined gas chromato-
graphy-electron impact mass spectrometry (GC-MS) with computerized
data acquisition and processing. Spectra of the compounds indicated
by their gas chromatography retention times as possible PCB's were
individually examined. The acquired data were further examined by the
limited mass search technique in order to detect any spectra contain-
ing ion fragments characteristic of PCB's. Spectra found to contain
such fragments were then examined in their entirety. Finally, the
combined benzene fractions from both CCE2 and CCE3 were subjected to
a GC-MS procedure involving selected ion monitoring during the data
acquisition step in order to attain enhanced sensitivity for the detec-
tion of PCB's.15
Further investigation of the hexane and benzene fractions obtained by
silica gel column chromatography of CCE's 2 and 3 was then undertaken
in an effort to characterize compounds comprising a significant portion
of these fractions. Mass spectra obtained by GC-MS of the various
fractions were examined by standard interpretive procedures based on
mass'spectral fragmentation theory and by computerized spectral matching
programs which permitted comparison of the unknown spectra with the
13
-------
contents of the mass spectral libraries at Battelle Columbus and
National Institutes of Health. Identifications of compounds in the
CCE fractions achieved by mass spectral interpretation or matching
were further substantiated, when standards were available, by directly
comparing the behavior during gas chromatography and GC-MS of the CCE
compounds with that of standard compounds under identical conditions.
Procedures Employed in the_ Final Phase of Study
Sampling Procedures - Ground waters from well No. 3, within the land-
fill, and a newly drilled control well located approximately one mile
from the upstream edge of the landfill and 1.5 miles from well No. 3,
were sampled for organic components during this phase of the study.
The wells were sampled simultaneously and by identical procedures in
order that comparison of organic matter from the control and landfill
wells would clearly reveal the extent and nature of organic contamina-
tion of ground water by the landfill and provide a guide for selection
of compounds which should receive priority attention in identification
studies.
The sampling procedures employed were essentially those developed
in the initial phase of study which were based on the low-flow carbon
adsorption method. However, the carbon columns differed from those
used in the first phase of study in that they incorporated no joints,
but were single piece units fabricated from single lengths of 3 in
diameter Pyrex glass tubing. This one-piece design was used to elimi-
nate the possibility of any leakage of air into the columns through
joints, since occasional small leaks were observed around the Teflon
gaskets of the couplers for the two-piece columns used in the initial
work. Also, the centrifugal pumps employed in the initial studies were
replaced by variable speed peristaltic type pumps ("Masterflex" 7545
Variable Speed Drive with 7014 pump head, Cole-Farmer Instrument Co.,
Chicago,111.) which permitted sustained pumping of ground water from the
water table tnrough carbon adsorption columns at accurately controlled,
constant, low flow rates. Power was provided to the pumps at the field
sites by portable gasoline-operated 1500 watt AC generators.
Sampling was accomplished by pumping ground water from each of the two
wells through essentially identical carbon columns for 126 hr at a rate
of 100 ml/min. In this manner 200 gal (757 1) of water was sampled
at each location.
Desorption of Sampled Organic Material - Upon completion of sampling
the carbon columns containing the adsorbed organics from the water from
well No. 3 and the control well were drained to remove-excess water,
sealed with solvent washed aluminum foil, and transported immediately
to the laboratory for processing. A third carbon column which had been
-------
prepared identically and at the same time as the columns used for
sampling, but which had not had any water passed through it, was
processed with the sampling columns to serve as a blank.
The glass columns were scored with a glass saw, and then were carefully
broken open to permit removal of the carbon in a special carbon-
handling room designed to minimize the potential for contamination
of the carbon during processing. The carbon was carefully transferred
to Pyrex glass dishes and dried at approximately 40°C for 48 hr under
a gentle flow of clean air in a Precision-Freas mechanical convection
oven (Model 845, Precision Scientific Company, Chicago, 111.). The
air inlet of the oven was equipped with a carbon filter to prevent
contamination from the atmosphere.
The dried carbon was transferred to 2200 ml modified Soxhlet extractors
and extracted for 48 hr with chloroform. The CCE's obtained from the
blank carbon and the carbon employed in sampling well No. 3 and the
control well were designated CCEB, CCE3II, and CCEC, respectively.
These extracts were filtered through solvent-extracted glass fiber
filters to remove carbon fines and then vacuum concentrated at tempera-
tures not exceeding 27 C in rotary evaporators to a final volume of
3 ml each.
The chloroform-extracted carbon samples were dried in the Soxhlet
extractors by passing a gentle stream of warm, dry air through the
extraction chambers via the siphon tubes for 20 hr. The carbon was
then extracted for 32 hr with pure ethanol, and the carbon alcohol
extracts (CAE's) were filtered and concentrated in the same manner as
the CCE's. However, it was necessary to filter the CAE's through
extracted glass fiber filters when volumes of about 10 ml had been
attained in order to remove precipitated material. These precipitates,
together with solid material which had precipitated on the flask walls
during evaporation, were dried and weighed. The filtered CAE's were
then further evaporated to the following final volumes: 4.0 ml for
CAE3II, from well No. 3; 2.0 ml for CAEC, from the control well; and,
1.0 ml for CAEB, from the blank.
Analysis of Organic Extracts - Aliquots of each of the concentrated
CCE's and CAE's were carefully evaporated to dryness in tared foil
cups in order to determine the weights of soluble material dissolved
in the concentrates. The total weights of the CCE's and CAE's were
calculated from these weights and the weights of material which had
precipitated during preparation of the concentrated extracts.
CCE3II and CAE3II, prepared from water from the landfill well, were
compared by gas-liquid chromatography on an OV-1 column under identical
operating conditions with corresponding CCE's and CAE's from the control
well water and carbon blank. This comparison indicated those organic
substances readily amenable to gas chromatography in CCE3II and CAE3II
that had been contributed to ground water by the landfill and provided
15
-------
a basis for selection of subsequent analytical steps employed in
analysis of these extracts.
CCE3II was subjected to liquid-solid chromatography on micro silica
gel columns to obtain fractions of less complexity for further study.
Initially, a 7 X 76 mm column of 100/200 mesh Silicar CC-7 was pre-
pared by dry packing and subsequent washing with hexane to wet the
column and determine the void volume. A 1.5 ml aliquot of CCE3II
was charged to the column by carefully adsorbing it on a small portion
of Silicar CC-7, suspending the Silicar containing the adsorbed CCE
in a small quantity of hexane, and carefully placing this suspension
on top of the column. The column was eluted successively with 8 ml
each of hexane, benzene, and chloroform-methanol (1:1), followed by
5 ml of methanol. The fractions of 2 or 3 ml each were collected
after a volume of hexane equivalent to the void volume had been eluted.
These fractions were designated CCE3II-SG1 through 10 as shown in
Table 2.
The 10 fractions from the silica gel column were each carefully con-
centrated to a volume of 1 ml in a rotary evaporator. The concentrated
fractions, together with the hexane representing the void volume of
the column, were then examined by gas chromatography on OV-1. Fractions
CCE3II-SG4, 5, 6, and 7 were found to contain sufficient quantities of
organic compounds to warrant further study, with fractions SG4, 5,and 6
appearing amenable to conclusive investigation by GC-MS without addi-
tional purification. Fraction CCE3II-SG7, which contained a very signif-
icant portion of the organic compounds of the parent CCE, was quite
complex and hence was rechromatographed on a fresh 7 X 76 mm column
of Silicar CC-7. Elution was accomplished with a total volume of 370
ml of solvent ranging in polarity from hexane to methanol, with 26
fractions being collected as shown in Table 3. Collection of fractions
and the sequence of eluting solvents were based partially on the move-
ment from the column of fluorescent zones which were detected under
366 nm U.V. light. The fractions were examined by gas chromatography
on an OV-1 column, and several groups of fractions which appeared to
contain very little organic matter or low levels of essentially the
same components were recombined, as indicated in Table 3. All fractions
were concentrated to approximately 1 ml each by rotary evaporator and
then examined by gas chromatography on columns packed with 3% OV-1
and 3% Carbowax 20M to develop experimental conditions for use in GC-MS
studies.
The various fractions obtained by silica gel column chromatography of
CCE3II were analyzed by GC-MS to achieve identification of individual
compounds therein. Essentially the same procedures were employed as
in the previously described initial phase of this study, except that
fractions were subjected to chemical ionization as well as electron
impact mass spectrometry in order to gain additional information of
• considerable value in structural characterization. Standard mass
16
-------
Table 2: FRACTIONS PREPARED FROM CCE3II BY
SILICA GEL COLUMN CHROMATOGRAPHY
Fraction
CCE3II-SG1
CCE3II-SG2
CCE3II-SG3
CCE3II-SG4
CCE3II-SG5
CCE3II-SG6
CCE3II-SG7
CCE3II-SG8
CCE3II-SG9
CCE3II-SG10
Total volume
2 ml
3 ml
3 ml
2 ml
3 ml
3 ml
2 ml
3 ml
3 ml
5 ml
Eluting solvents
Hexane
Hexane
Hexane
Benzene
Benzene
Benzene
Chlorofonn-Methanol (1:1)
Chlorof orm-Methanol (1 : 1)
Chlorofonn-Methanol (1:1)
Methanol
17
-------
Table 3: FRACTIONS PREPARED FROM CCE3II-SG7
BY SILICA GEL COLUMN CHROMATOGRAPHY
Fraction
CCE3II-SG7-SGla
SG2a
a
" SG4v
SG5b
b
SG6D
11 SG7
11 SG8
SG9°
11 SG10C
SG11C
11 SG12
" SG13
SG146.
c Recombined as CCE3II-SG7-SG9-KL1.
d Recombined as CCE3II-SG7-SG14-*20.
e Recombined as CCE3II-SG7-SG23+26.
18
-------
spectral interpretative procedures and computerized spectral matching
programs were utilized for examination of spectra, and additional
corroborative evidence for the structures of compounds identified on
the basis of their spectra was obtained by direct comparison with
standard compounds whenever such standards were available. When
possible, the quantities of the identified compounds in the original
CCE and various fractions obtained from it were estimated by com-
paring their peak heights on gas chromatograms with the peak heights
produced by known quantities of standard compounds chromatographed
under identical conditions. These data were then used to calculate
estimated concentrations of the identified organic compounds in the
sampled ground water.
CAE3II, the carbon alcohol extract from well No. 3, was separated
into fractions of less complexity by classical solubility separation
procedures.16'17 A 1.5 ml aliquot of the concentrated CAE (total
volume 4 ml) was dissolved in 30 ml of diethyl ether, filtered, and
extracted successively with water, dilute hydrochloric acid, and dilute
sodium hydroxide, as shown in Figure 3. Five fractions, namely ether
insolubles, water solubles, bases, acids, and neutrals were obtained.
The ether insolubles fraction contained an appreciable quantity of
material (0.3 g), while the water solubles fraction was of lesser, but
still significant, weight (0.05 g). However, because of the polarity
and probable complexity of these fractions and time limitations on
this investigation, no further studies of the ether insolubles and
water solubles were conducted.
The bases, acids, and neutrals fractions were dried on anhydrous
sodium sulfate columns and concentrated to 1-2 ml each in rotary evap-
orators. Examination of these fractions by gas chromatography on an
OV-1 column indicated that the acids fraction, designated CAE3II Acids,
contained a total quantity of organic compounds several orders of mag-
nitude greater than that present in the other fractions. Hence, the
acids fraction was selected for further study.
The CAE3II Acids fraction was subjected to gas chromatography and GC-MS,
employing columns packed with 10% SP1200/l-% H3POif on 80/100 mesh
Chromasorb W AW (Supelco, Inc., Bellefonte, Pa.). Both electron impact
and chemical ionization mass spectrometry were utilized, and procedures
for identification and quantitation of individual compounds were essen-
tially identical with those employed for the CCE3II compounds as pre-
viously described.
A small aliquot of the CAE3II Acids fraction was allowed to react with
14% boron trifluoride in methanol18 to esterify carboxylic acids and
hence, permit detection and quantitation of any acids of higher molecular
weight which might be present. However, time limitations permitted only
a cursory examination by gas chromatography of this methylated fraction.
19
-------
1.5 ml CAE3II
Dissolve in
30 ml Diethyl
Ether, Filter
Ether Solution
Extract 3X
w/ 10 ml H20
Residue
Ether Insolubles
Ether Layer
Extract 3X
w/ 10 ml 5%
HC1
H?0Layer
Water Solubles
Ether
Layer
H?0
Extract 3X
w/ 10 ml 5% NaOH
IX w/ 10 ml H20
Layer
Make basic
(PH>10)
Extract 3X
w/ 10 ml Ether
Ether Layer
Neutrals
HpO
Layer
Acidify (pH
-------
SECTION V
RESULTS AND DISCUSSION
TOTAL ORGANIC CARBON ANALYSIS
Table A presents data for total dissolved, non-volatile carbon analyses
of water from: well No. 3, within the landfill; well No. 2, at the edge
of the landfill approximately 230 ft southwest of well No. 3; well No. 4,
at the edge of the new landfill approximately 865 ft west northwest of
well No. 3; and the control well, approximately one mile from the north-
west edge of the landfill. The data for wells No. 2 and 4 for May, 1972,
were obtained by other investigators before the beginning of this study.
These data indicate relatively low levels of organic carbon in ground
water in and near the landfill. Water from well No. 3, within the
landfill, showed a maximum TOC of only 34.2 mg/1 and a minimum of 11.1
mg/1. Analogous data for wells No. 2 and 4, on the periphery of the
landfill, were respectively: 23.0 and 5.5 mg/1; and, 28.0 and 8.0
mg/1. Loss of volatile organic compounds during removal of carbonate
from the samples prior to TOC determination may have reduced the values
obtained to some extent. Most likely, however, the relatively low TOC
values reflect the age of the landfill in the vicinity of the wells
where sampling of ground water was accomplished. Newspapers recovered
from well No. 3 during drilling indicated the solid waste in this
region of the fill had been in place for at least three years. Hence,
the major portion of readily leachable organic matter would almost un-
doubtedly have long since been removed from the waste, and only those
organic compounds which leached very slowly from the solids in the
landfill or which persisted for considerable periods of time in the
immediate vicinity of the landfill after being released from the solid
refuse would have been present by the time this study was undertaken.
The considerable temporal fluctuations of TOC's in ground water from
the various wells probably resulted from climatic factors. During the
first five months of 1973 unusually high rainfall occurred in the
Norman area. Hence, the higher TOC in water from well No. 3, within
the landfill, may have resulted from both a Higher water table, which
brought more waste within the zone of saturation, and increased
vertical leaching from unsaturated refuse. Similarly, the reduced
TOC's in water from wells No. 2 and 4, outside of the fill, may have
reflected dilution by high levels of fresh recharge water. The in-
creased levels of organic carbon in wells 2 and 4 in August may simply
reflect decreased fresh water recharge accompanying dry weather condi-
tions, coupled with the arrival at these wells of water containing
higher quantities of organic matter leached from the landfill during
the earlier very wet period. Similarly, by August a decreasing water
21
-------
Table 4: TOTAL ORGANIC CARBON IN GROUND WATER
IN THE VICINITY OF THE LANDFILL
(mg/D
Well No.
2
3
4
Control
Location
Edge of the landfill,
230 ft southwest of
well No. 3
In the landfill
Edge of landfill,
approximately 865
ft west northwest
of well No. 3, in
old dump area
Approximately one
mile northwest of
landfill edge
TOC (Filtered)
5/6/72
9.0
a
13.0
~
c
6/6/73
5.5
34.2
8.0
c
8/10/73
23.0
13.0
28.0
c
9/28/73
13.2
16.3
-
c
5/24/74
b
11.1
-
4.6
a Well drilled 11/15/72.
b Well inadvertantly destroyed by landfill operator in January, 1974.
c Well drilled 10/15/73.
22
-------
table and less vertical leaching likely combined to result in a lower
level or organic carbon in well No. 3.
INITIAL PHASE OF STUDY
Analysis for PCB's
The hexane and benzene fractions obtained by silica gel column chroma-
tography of the CCE's from wells No. 2 and 3 and the hexane fraction
prepared by sampling well No. 3 with Amberlite XAD-2 all contained sub-
stances which, on the basis of their GC retention times, could have
been PCB's. Mass spectra of "these compounds clearly showed, however,
that none of them were PCB's. Evaluation of GC-MS data from the various
fractions by limited mass search techniques and utilization of GC-MS
procedures involving selected ion monitoring for further examination of
the silica gel column fractions likewise failed to produce any evidence
to indicate the presence of PCB's in ground water in or near the land-
fill. The minimum concentration of PCB's which the methods employed in
this study could have detected in the sampled ground water is conserva-
tively, estimated to be 50 ng/1.
The failure to detect PCB's in the ground water in and near the Norman
landfill is not surprising. These compounds are very insoluble in
water and tend to be adsorbed very strongly to soil. It is probable,
then, that PCB's introduced into the landfill would be largely adsorbed
on soil particles within a short distance of the point of deposition.
The quantities of PCB's in the adjacent water would then be functions
of the distribution coefficients for the various isomers in a soil-water
system, and these coefficients are undoubtedly very highly weighted
toward the soil phase. Some slow diffusion of PCB's outward from the
landfill could occur over a period of years, but the proportion present
in the ground water would probably remain so minute as to be undetect-
able and probably not environmentally significant.
Characterization of Other Organic Compounds
Data obtained by GC-MS of the hexane fractions -prepared by silica gel
column chromatography of CCE3 indicated that these fractions probably
contained a mixture of aliphatic hydrocarbons as well as some elemental
sulfur. Gas chromatographic analysis of analogous fractions from CCE2
indicated them to be essentially identical in composition to the CCE3
hexane fractions. Identification of individual compounds from these
rather complex fractions would have required extensive additional prep-
arative work, and was not attempted during this investigation.
Mass spectra of several of the more predominant compounds in the silica
gel benzene fractions from both CCE2 and 3 indicated these substances
23
-------
to be esters of dicarboxylic acids, particularly phthalic acid. Four of
these were identified with reasonable certainty on the basis both of
their mass spectra and GC retention times as diethyl phthalate,
diisobutyl phthalate, dioctyl phthalate, and dioctyl adipate. Two
others were tentatively identified as di-n-butyl phthalate and butyl-
carbobutoxymethyl phthalate. All of these diesters were present in
the benzene fractions from both CCE2 and 3. Concentrations appeared to
be generally higher in CCE3, however.
Some evidence was also obtained for the presence of two cresols in
the CCE3 benzene fractions.
FINAL PHASE OF STUDY
Comparison of CCE's and CAE's from Well No. 3, Control Well,
And Carbon Blank
Visual comparison of the various CCE's and CAE's showed CCE3II, prepared
from ground water from well No. 3, to be deep yellow in color, while
CCEC, from the control well water, was light yellow, and CCEB, from the
carbon blank, was practically colorless. Similarly, CAE3II was deep
yellow-orange, CAEC was yellow, and CAEB was pale yellow. Both CCE3II
and CAE3II were very odorous, while the control and blank CCE's and
CAE's were essentially odorless.
Table 5 presents the weights, in terms both of total weight and weight
per liter of sampled water, of the various CCE's and CAE's. As these data
show, CCE3II contained approximately 25 times as much material as CCEC
and more than 100 times the weight of material in CCEB, while CAE3II
contained in the neighborhood of four times the quantity of material
contained by -CAEC and CAEB, the control and blank.
The observations and data presented above clearly indicated the pres-
ence of much greater quantities of organic constituents in the ground
water in the locale of the Norman landfill than in ground water from
the same aquifer approximately one mile upstream from the landfill
perimeter. This situation was further illustrated by comparison of
the various CCE's and CAE's by gas chromatography, as shown in Figures
4 through 7. These chromatograms were obtained by chromatographing,
under identical conditions, aliquots of CCE3II and CCEC representing
190 ml of ground water from well No. 3 and the control well, respec-
tively, and aliquots of CAE3II and CAEC representing 380 ml of ground
water from these wells. Analogous chromatography of suitable aliquots
of CCEB and CAEB, from the carbon blank, produced chromatograms which
are not shown here but which were very similar to those obtained for
CCEC and CAEB. These chromatographic comparisons revealed in the
ground water from the landfill the presence of a complex array of
organic compounds which were readily amenable to gas chromatography
and which were either not present, or were present in very much less
quantity, in ground water not subject to the influence of the landfill.
24
-------
Table 5: WEIGHTS OF CARBON CHLOROFORM AND CARBON ALCOHOL EXTRACTS
*
Source
Well No. 9
Control Well
Carbon Blank
Weight of CCE
Total.mg
304.5
11.9
2.6
mg/1
0.402
0.016
0.0033
Weight of CAE
Total, mg
1219.1
314.2
262.5
mg/1
1.610
0.415
0.3473
Weight of CCE+CAE
Total.mg
1523.6
326.1
264.8
mg/1
2.013
0.431
0.3503
Weight of
activated
carbon in
column, g
274
255
213
S3
a Calculated as if this carbon had actually been employed for sampling of 757 1 of water
-------
OV-1 ON 1DO/120 MES
LUMN TEMf3,: 80-260° a 8°/KIN
FIGURE /j. GAS CHROMATOGRAM OF
CCE3II, LANDFILL WELL
26
-------
FIGURES, GAS CHROMATOGRAM OF
CCEC, CONTROL WELL
27
-------
FIGURE 6. GAS CHROMATOGRAM OF
CAE3II, LANDFILL HELL
28
-------
' I I"
FIGURE?, GAS CHROMATOGRAM OF
CAEC, CONTROL WELL
29
-------
It was obvious that practically all of the major organic components
of CCE3II and CAE3II which were of sufficient volatility for gas
chromatography had been contributed to the ground water by the landfill,
and identification of any of these compounds would, therefore, be
helpful in elucidating the effect of the landfill on ground water.
Identification of Compounds in CCE3II and CAE3II
Table 6 presents a tabulation of those compounds which were identified
in the carbon chloroform and carbon alcohol extracts prepared from
ground water from well No. 3. The CCE and/or CAE fraction(s) in which
the compound was identified, information concerning the method of
identification, and additional pertinent data such as industrial uses
and toxicity information are presented for each compound. Also,
estimates of the quantities present in the sampled water are given for
those compounds for which quantitative evaluations were achieved.
The general structures of all of the compounds listed in Table 6 were
established beyond reasonable doubt. However, it should be noted
that exact positions of substituent attachment and chain branching were
not achieved for a few compounds, such as the two 63 alkylbenzenes
in CCE3II-SG7-SG9-*!! and some of the Cy, C&, and Cg isomeric acids,
because of unavailability of required standards or failure of GC
columns to separate closely related compounds.
There was strong evidence for the presence in the various fractions
of several compounds in addition to those listed in Table 6, but their
structures were not considered sufficiently confirmed for inclusion in
this Table. These "possible" compounds and the fractions in which
they were found were: a CB ketone, CCE3II-SG6; a glycol ether,
CCE3II-SG7-SG12; triethyleneglycol ether and a diester of adipic acid,
CCE3II-SG7-SG13;* and benzoic and nonanoic acids, CAE3II Acids. Also,
GC examination of the CAE3II Acids fraction after it had reacted with
boron trifluoride-methanol gave evidence for the probable presence
of relatively low quantities of C12, Cm, C16, and C18 fatty acids.
This was not confirmed by GC-MS studies, however, due to time limita-
tions.
Some of the major higher boiling compounds in CCE3II, as indicated
by number on the chromatogram pictured in Figure 4, were: 1, diethyl
phthalate (4 yg/1); 2, butylcarbobutoxymethyl phthalate; 3, dioctyl
phthalate (2.4 yg/1); and, 4 and 5, the compounds tentatively identi-
fied as a triethyleneglycol ether and a diester of adipic acid. Diace-
tone alcohol (10.9 yg/1), p-cresol (8.6 yg/1), cyclohexanol (1.0 Pg/1),
camphor (0.9 yg/1), and o- and p-xylene (0.6 and 0.9 yg/1, respectively)
were the major lower boiling compounds identified in this CCE, but no
attempt has been made to indicate these compounds in Figure 4 because
of the complexity of the early portion of the chromatogram.
30
-------
Table 6: COMPOUNDS IDENTIFIED IN CCE3II AND CAS3II
Compound
Estimated
concentration
in ground
water yg_/_l
Fraction !
Identi-
fication
code a
Remarks
Fenchone
Camphor
2,6-di-Tertiarybutyl
Benzoquinone
Diethyl Phthalate
0.2
CCE3II-SG4
0.9
CCE3II-SG4
4.1
CCE3II-SG4
CCE3II-SG4
SR
SR
CS(0.874)
SR
Used as a "generally regard-
ed as safe" (GRAS) flavor-
ing, present in paper
mill's raw waste.2^
Used as a plasticizer for
cellulose esters and
ethers; moth and mildew
preventive; flavoring.
Neoplastic effects pro-
duced experimentally in
19
rats.
21
Hydroquinone precursor is
used as an antioxidant;
polymerization catalyst.19
Used as a plasticizer; sol-
vent for cellulose acetate;
camphor substitute; per-
fume fixative; wetting
agent; insecticides; alco-
hol denaturant.19 Bitter
taste; moderately toxic
when ingested.21
-------
Table 6: COMPOUNDS IDENTIFIED IN CCE3II AND CAE3II (Continued)
Compound
Estimated
concentration
in ground
water yg/1
Fraction
Identi-
fication
codea
Remarks
N3
2,6-di-Tertiaryamyl
Benzoquinone
Diisobutyl Phthalate
Di-n-Butyl Phthalate
Butylcarbobutoxy-
methyl Phthalate
Butylbenzyl Phthalate
Dicyclohexyl Phthalate
0.1
0.2
CCE3II-SG4
CCE3II-SG4 and
CCE3II-SG7-SG4+6
CCE3II-SG4
CCE3II-SG4
CCE3II-SG4
CCE3II-SG4
CS(0.321)
SR
SR
SI
SI
SR
Hydroquinone precursor is
used as an antioxidant;
polymerization catalyst.
19
Used as a plasticizer.
19
Used as a plasticizer;
polymerization catalyst;
oxidant. Oral toxic
dose in man, 140 mg/kg
produces central nervous
system effects.2*
Used as a plasticizer.
19
Used as a plasticizer for
polyvinyl and cellulose
resins. 9
Used as a plasticizer for
rubber, polyvinyl chlorides>
and other polymers;
mildly aromatic odor.19
-------
Table 6: COMPOUNDS IDENTIFIED IN CCE3II AND CAE3II (Continued)
Compound
Dioctyl Phthalate0
p-Cresol
o-Xylene
p-Xylene
Cyclohexanol
Estimated
concentration
in ground
water yg/1
2.4
14.6
0.6
0.9
1.0
Fraction
CCE3II-SG4
CCE3II-SG5 and
CAE3II Acids
CCE3II-SG7-SG7
CCE3II-SG7-SG7
CCE3II-SG7-SG7
Identi-
fication
code
SR
SR
SR
SR
SR
Remarks
Used as a plasticizer for
polyvinyl chlorides and
other vinyls. Slight
odor.19
Used as an active constit-
uent of creosote.19
Used in manufacture of
phthalic anhydride;
insecticides; motor fuels;
dyes.19 Moderately
toxic.19
Used in synthesis of tere-
phthalic acid for polyes-
ter resin synthesis
(dacron, mylar, etc); in-
secticides. Moderately
toxic.19
Used in making phenolic
insecticides; lacquer
polishes; plastics; ger-
micides; source of adipic
acid for nylon manufac-
ture. 19
U)
-------
Table 6: COMPOUNDS IDENTIFIED IN CCE3II AND CAE3II (Continued)
Compound
Estimated
concentration
in ground
water yg/1
Fraction
Identi-
fication
code a
Remarks
N-Ethyl-p-Toluenesul-
fonamide
N-Ethyl-o-Toluenesul-
fonamide
c
Cs Alkylbenzenes
(2 compounds)
Diacetone Alcohol
Butoxyethanol
0.1
10.9
CCE3II-SG7-SG8
CCE3II-SG7-SG8
CCE3II-SG7-SG9-KL1
CCE3II-SG7-SG9+11
CCE3II-SG7-SG9-KL1
SI
SI
SI
SR
SR
Used as a plasticizer.
Moderately toxic.19
Used as a plasticizer.
Moderately toxic.19
C3 alkylbenzene isomers
, are found in American
petroleum.22
Used as a solvent for
cellulose acetate, vari-
ous oils, resins, dyes,
tars, and waxes; also used
in hydraulic compression
fluids; wood preservatives;
and metal cleaning."
Used as a solvent for nitro-
cellulose resins, sprays,
lacquers, and enamels.19
Oral LDcQ for rats is 470
mg/kg.2*
-------
Table 6: COMPOUNDS IDENTIFIED IN CCE3II AND CAE3II (Continued)
Compound
Ethyl Carbamate
Tri-n-Butyl Phosphate
p-Toluenesulfonamide
Estimated
concentration
in ground
water yg/1
.
1.7
_
Fraction
CCE3II-SG7-SG9-KL1
CCE3II-SG7-SG9->11
CCE3II-SG7-SG12
Identi-
fication
code a
CP
SR
CP
Remarks
Used as a solvent for
various organics; solu-
bilizer and cosolvent fo
pesticides, fumigants,
and cosmetics.22 Proved
experimentally to be
carcinogenic .
Used as a plasticizer;
antifoam agent; solvent
for nitrocellulose,
cellulose acetate, heat
exchange medium; di-
electric.19 Moderately
toxic by ingestion.19
Used as a plasticizer;
fungicide; mildewicide
in paints; also resin
synthesis. Oral LD^o i-n
birds is 75 mg/kg.
U)
Ui
-------
Table 6: COMPOUNDS IDENTIFIED IN CCE3II AND CAE3II (Continued)
Compound
Methyl Pyridine
N, N-Diethylf ormamide
Triethylphosphate
Bis-2-Hydroxypropyl-
ether
Estimated
concentration
in ground
water ug/1
-
-
0.3
-
Fraction
CCE3II-SG7-SG12
CCE3II-SG7-SG12
CCE3II-SG7-SG12
CCE3II-SG7-SG21
Identi-
fication
code
CS (0.504)
CP
SR
CP
Remarks
Comes from dry distillation
of coal and bones. Used
in insecticide manufacture;
dyes; rubber; used as
solvent; and in making
vinyl pyridine.19 Mod-
erately toxic, strong un-
pleasant odor.19
Used in rubber manufacture.2"
Used as a plasticizer for
resins, plastics, gums;
pesticide manufacture;
catalyst: solvent; lacquer
remover. Highly toxic,
i causes cholinesterase in-
hibition.22
A dimerization product of
propylene glycol which is
used as a non-toxic anti-
freeze in dairies and
breweries; a substitute
for ethylene glyxiol and
manufacture of synthetic
resins.22
OJ
-------
Table 6; COMPOUNDS IDENTIFIED IN CCE3II AND CAE3II (Continued)
LO
•-J
Compound
3-Methylcyclopentan-
1,2-Diol
Acetic Acid
Isobutyric Acid
,
Estimated
concentration
in ground
water u8/l
••
_
48.7
Fraction
CCE3II-SG7-SG21
CAE3II Acids
CAE3II Acids
Identi-
fication
, a
code
CS (0.755)
SR
SR
Remarks
Used in manufacturing plas-
tics, insecticides, vinyl
acetate, and photographic
chemicals; oil well acidi-
zing and food additive.
Pungent odor.22
Used in the manufacture
of esters for solvents,
flavors, and perfumes;
disinfection; tanning
agent ; deliming hides .
LD5o in rats is 280 mg/kg.19
Pungent odor like that of
butyric acid, but not so
unpleasant, mild irritant.22
Detection of odor in water
at 8.1 mg/1 and of taste
in water at 1.6 mg/1.23
-------
Table 6: COMPOUNDS IDENTIFIED IN CCE3II AND CAE3II (Continued)
Compound
Estimated
concentration
in ground
water g/1
Fraction
Identi-
fication
code
Remarks
Butyric Acid
1.5
CAE3II Acids
SR
Isovaleric Acid
0.7
CAE3II Acids
SR
U)
00
Valeric Acid
1.1
CAE3II Acids
SR
Used as an emulsifying agent;
disinfectant; gasoline
sweetener; perfume ester
preparation and deliming
agent.19 Neoplastic effects
have been produced in
rats.21 Obnoxious odor.
Used in flavors, perfumes,
and manufacture of seda-
tives.22 Occurs in tobac-
co and several other plants;
also, occurs in hop oil.
Acid taste, disagreeable
rancid-cheese odor. Detec-
tion of odor in water at
0.7 mg/1.23
Used as an intermediate in
perfumery. Unpleasant
odor.22
-------
Table 6: COMPOUNDS IDENTIFIED IN CCE3II AND CAE3II (Continued)
Compounds
2-Ethylhexanoic Acid
Isomeric Cg Acid
Isomeric Cg Acid
^
Isomeric Cy Acid
Estimated
concentration
in ground
water g/1
4.2
17. ld
0.2d
7.5e
Fraction
CAE3II Acids
•^
CAE3II Acids
CAE3II Acids
CAE3II Acids
Identi-
fication
code
SR
SI
SI
SI
Remarks
This acid is a typical low
to medium weight isoacid
Salts used for varnish
driers, heat stabilizers
for vinyl resins, grease
as thickening agents in
certain lacquers and
paints , inhibition of
sludge, and varnish depos
tion in mineral oils.
Compound itself used as
a plasticizer and in
alkyd resins.24
Refer to 2-ethylhexanoic
acid above, which has
similar characteristics.
Refer to 2-ethylhexanoic
acid above, which has
similar characteristics.
Refer to 2-ethylhexanoic
acid above, which has
similar characteristics.
U)
-------
Table 6: COMPOUNDS IDENTIFIED IN CCE3II AND CAE3II (Continued)
Compound
Isomeric Cg Ac±dc
Cyclohexanecarboxyllc
Acid
Caprylic Acid
Caproic Acid
Estimated
concentration
in ground
water Vfe/1
_
2.8
0.6
1.1
Fraction
CAE3II Acids
CAE3II Acids
CAE3II Acids
CAE3II Acids
Identi-
fication
code
SI
SR
SR
SR
Remarks
Refer to 2-ethylhexanoic
acid above, which has
similar characteristics.
Used in insecticide formu-
lation; as a stabilizer
for vulcanized rubber;
paints and varnishes;
lubricating oils; dry
cleaning soaps.19
i
An intermediate in the
manufacture of esters
used in perfumery; in
manufacture of dyes.
Slightly unpleasant ran-
cid taste.22
Used in the manufacture of
esters for artificial
flavors and of hexyl
derivatives, especially
hexylphenols , hexylre-
sorcinol, etc.22 Charac
teristic goat-like odor.
-------
Table 6: COMPOUND IDENTIFIED IN CCE3II AND CAE3II (Continued)
Compound
Heptanolc Acid
Estimated
concentration
in ground
water g/1
1.0
Fraction
CAE3II Acids
Identi-
fication
code
SR
Remarks
Found in the various fusel
oils in appreciable
amounts. Has been ob-
served in rancid oils.
Disagreeable, rancid odo
SR - Comparison with standard (MS and GC).
CP - Good comparison with standard spectrum plotted from NIH library of mass spectra.
CS - Matching with high similarity index from Batelle library of mass spectra.
SI •"- Interpretation of mass spectrum - consistent with spectra of known similar compounds.
b Determined as N, N-dimethyl-p-toluenesulfonamide.
c General sttucture confirmed beyond reasonable doubt, but position of substitution or chain
branching not determined because necessary standards were unavailable or compounds were not
separated by G.C. columns employed.
d Determined as 2-ethylbutyric acid, but probably is not this compound.
e Determined as n-heptanoic acid.
-------
CCE3II, like CCE3 in the initial phase of study, was found to contain
elemental sulfur. However, in marked contrast to the rather complex
mixture of aliphatic hydrocarbons noted in the hexane fractions ob-
tained by silica gel column chromatography of CCE's 2 and 3 in the
initial phase of study, essentially no organic compounds were found
in the silica gel hexane fractions from CCE3II, and no evidence for
the presence of significant levels of aliphatics was noted in any
other fractions prepared from this CCE. This may indicate major
differences in the organic components contributed to ground water
by the landfill at the different times of sampling for the two phases
of study, although other compounds identified in the first phase of
study such as the phthalic esters, were essentially the same as those
found in the later work. Sampling anomalies resulting from the ten-
dency of the very water-insoluble aliphatic hydrocarbons to agglomerate
and separate from water could possibly be involved, but this seems
unlikely. The loss of aliphatic hydrocarbons during sample preparation
in the second phase of study is virtually precluded as a possibility
because of the success achieved during this phase in recovering substan-
ces of higher volatility than the aliphatics found in the initial
study. The possibility that the aliphatic hydrocarbons found in the
initial phase of study were contaminants introduced in obtaining and
processing CCE's cannot be completely eliminated. However, the presence
of aliphatic hydrocarbons in most landfills would not be unexpected.
The major compounds readily amenable to gas chromatography in CAE311
were relatively low boiling, as shown by the chromatogram in Figure 4.
The principal compounds identified in this extract and their estimated
concentrations in the sampled ground water were: isobutyric acid
(48.7 yg/1); an isomeric Ce acid (17.1 yg/1); an isomeric Cy acid
(7.5 yg/1); 2-ethylhexanoic acid (4.2 yg/1), and p-cresol (6.0 yg/1).
A few of the compounds identified by this study as pollutants contri-
buted to ground water by the Norman landfill could be leachates of
natural products, including foods, or possibly end products of micro-
bial metabolism of organic compounds. For example, the short chain,
normal carboxylic acids are found in many foods and plants; acetic
and butyric acids are common^end products of anaerobic metabolism of
carbohydrates; and phenolic substances are ubiquitous phytochemicals.
As Table 6 indicates, however, practically all of the identified com-
pounds are employed industrially in the manufacture of a wide array
of products for domestic and commercial use which are likely to ulti-
mately find their way to landfills. The phthalic acid esters are a
case in point. These compounds are used very extensively as plasticiz-
ers for production of polymers employed in such diverse products as
food wrap film, garden hose, upholstery, electrical insulation, and
clothing. Such products are almost undoubtedly the source of the
phthalates contributed to ground water by the Norman landfill. Hence,
although the Norman landfill receives hardly any industrial wastes
directly, leaching of manufactured products deposited in this landfill
42
-------
is apparently responsible for introduction of pollutants commonly
associated with industrial wastes into ground water underlying and
within the landfill.
The compounds identified in this study, while appearing to comprise
a major portion of those substances which were readily amenable to
gas chromatography in CCE3II and CAE3II, were actually present in
ground water from well No. 3 only in very low concentrations. The
sum of the concentrations in the ground water of all the compounds
obtained from CCE3II and CAE3II was 125 yg/1. Even if the concentra-
tions of those compounds which were identified ,but for which no
quantitative data were obtained .could be added to this value it would
still be relatively low. However, in evaluating the significance of
the quantitative data obtained in this work it should be noted that
these data must be considered minimum values because of quantitative
inadequacies of the carbon adsorption method. These inadequacies re-
sult because: activated carbon may fail to quantitatively adsorb dis-
solved organic compounds from sampled water; complete recovery of
adsorbed compounds from the activated carbon may not be accomplished
during-extraction; and, volatile sample components may be lost during
drying of the activated carbon. This is illustrated by comparing the
total combined weight of CCE3II and CAE3II, 2.012 mg/1, with the
average TOG value for water from well No. 3 of 13.4 mg/1 during the
period August 1973 to May 1974. Obviously, less than 10 percent of
the organic matter present in the sampled ground water was recovered
in the CCE and CAE if the organic equivalent of 13.4 mg carbon/1 is
considered. Much of this loss may reflect the failure of macromolecu-
lar material to be adsorbed on the activated carbon column and/or the
irreversible adsorption of highly polar compounds on the carbon. A
considerable loss of compounds which should have appeared in the CCE
and CAE as components amenable to gas chromatography may well be
indicated, however, and the actual concentrations in the ground water
of the compounds identified in this study may be much higher than
indicated.
As previously noted, the low total organic carbon values for ground
water in the landfill and the history of the Norman landfill both in-
dicate that initial extensive leaching and subsequent stabilization of
refuse in the studied area of the landfill probably had occurred before
this investigation was begun. Hence, the compounds identified in this
study probably are substances which are leached very slowly from the
refuse in the landfill and/or substances which persist for considerable
periods of time in the aquifer in the vicinity of the refuse from which
they were leached because of sorption on the earth solids comprising
the aquifer. This observation implies the potential for long-term
insidious pollution of ground water by undesirable organic chemicals
from landfills. Slowly decaying domestic and commercial products in
landfills would appear likely to serve as reservoirs feeding low levels
of industrial organic pollutants into aquifers for many years after the
43
-------
landfills have been closed and forgotten. Even those substances which
are sorbed relatively strongly on aquifer solids could ultimately
pose a pollution threat if they were resistant to biochemical and
abiotic degradation in the ground water environment. Such compounds
could move as zones by slow, "chromatographic" migration to finally
reach wells providing water for consumption by humans or domestic
animals. Because of the low levels of pollutants likely to be involved,
physical properties of the polluted ground water would probably not
be altered sufficiently to indicate the presence of the offending
compounds. This presence could be a matter of considerable concern,
however, since the health effects of chronic ingestion through water
of even very low levels of compounds such as those identified in this
study are largely unknown. This, coupled with the great difficulty
involved in removing pollutants, particularly those which tend to
adsorb significantly on aquifer solids, from a polluted aquifer, dic-
tate the need for further investigation of this potential problem. In
particular, information concerning the mobility and longevity in the
ground water environment of compounds such as those in Table 6 are
needed. The observation in the initial phase of study that water in
well No. 2, outside the landfill, contained the same phthalic acid
esters as water from well No. 3, within the landfill, seems to indicate
movement of these substances in the aquifer, particularly since well
No. 2 sampled only water in the lower 10 ft of the aquifer. Information
of this type is, however, generally very scarce.
Although many of the major organic compounds of CCE3II and CAE3II that
were readily amenable to gas chromatography were identified during
this study, the major portions of these extracts were not charac-
terized. The weight of CCE3II was 402 yg/1, and that of CAE3II was 1610
yg/1, while the total weights of the compounds identified in these
extracts were only 32 yg/1 and 93 yg/1, respectively. Much of the
missing material may be accounted for in CCE3II-SG7-SG20^-26 fractions,
and in CAE3II-ether insolubles, water solubles, and acids fractions;
it was probably composed to a large extent of compounds that were too
polar and/or too high in molecular weight to yield readily to gas
chromatography. Had time permitted, study of these fractions by prep-
aration of suitable derivatives for analysis by gas chromatography and
utilization of liquid chromatography procedures would probably have
yielded much additional information concerning the organic pollutants
contributed to ground water by the landfill investigated.
44
-------
SECTION VI
REFERENCES
1. Muhlich, A. J., A. J. Klee, and P. W. Britton. Preliminary
Data Analysis, 1968 National Survey of Community Solid Waste
Practices. Public Health Service, Cincinnati, OH. Publi-
cation Number 1867. 1968. 483 p.
2. McElwee, W. C. Environmental Protection Agency, personal
communication, Washington, DC. May 1974.
3. Sanitary Landfill Studies, Appendix A: Summary of Selected
Previous Investigations. California State Department of Water
Resources, Sacramento, CA. Bulletin Number 147-5. July 1969.
4. Andersen, J. R. and J. N. Dornbush. Influence of Sanitary
Landfill on Ground Water Quality. J Amer Water Works Ass.
59:457-470, April 1967.
5. Hughes, G. M., R. A. Landon, and R. N. Farvolden. Hydrology
of Solid Waste Disposal Sites in Northeastern Illinois. Illinois
State Geological Survey, Environmental Geology Notes, Urbana, IL.
Publication Number 45. April 1971. 25 p.
6. Report on the Investigation of Leaching in a Sanitary Landfill.
California State Water Pollution Control Board, Sacramento, CA.
Publication Number 10. 1954. 92 p.
7. Ministry of Housing and Local Government. Pollution of Water
by Tipped Refuse. Report of the Technical Committee on the
Experimental Disposal of House Refuse in Wet and Dry Pits. Her
Majesty's Stationary Office, London, UK. 1961. 141 p.
8. Garbutt, G. H. Report of the Preliminary Study of a Landfill
in McClain County, Oklahoma. University of Oklahoma, (unpub-
lished special project report. Norman, OK. .June 1972.) 16 p.
9. Method for Chemical Analysis of Water and Wastes. Environmental
Protection Agency, Cincinnati, OH. July 1971. p. 221-229.
10. Webb, R. G., A. W. Garrison, L. H. Keith, and J. H. McGuire.
Current Practice in GC-MS Analysis of Organics in Water.
Environmental Protection Agency, Corvallis, OR. Report
Number EPA-R2-73-277. 1973. p. 37-41.
45
-------
11. Breidenbach, A. W., J. J. Lichtenberg, C. F. Henke, D. J.
Smith, J. W. Eichelberger, Jr., and H. Stierle. The Identi-
fication and Measurement of Chlorinated Hydrocarbon Pesticides
in Surface Waters. U. S. Department of the Interior, Federal
Water Pollution Control Administration, Washington, DC. 1966.
p. 44-50
12. Booth, R. L., J. N. English, and G. N. McDermott. Evaluation
of Sampling Conditions in the Carbon Adsorption Method.
J Amer Water Works Ass. 57:215-220, 1965.
13. Harvey, George R. Adsorption of Chlorinated Hydrocarbons from
Seawater by a Crosslinked Polymer. Woods Hole Oceanographic
Institute, Environmental Protection Agency, Washington, DC.
Report Number EPA-R2-73-177. March 1973. 26 p.
14. Hites, R. A. and K. Bieman. Computer Evaluation of Continuously
Scanned Mass Spectra of Gas Chromatographic Effluents. Anal
Chem. 42:855-860, 1970.
15. Eichelberger, J. W., L. E. Harris, and W. L. Budde. Application
of Gas Chromatography-Mass Spectrometry with Computer Controlled
Repetitive Data Acquisition from Selected Specific Ions. Anal
Chem. 46:227-232, 1974.
16. Shriner, R. L., R. C. Fuson, and D. Y. Curtin. The Systematic
Identification of Organic Compounds, Fifth Edition. New York,
NY. John Wiley and Sons, Inc., 1965. p. 67-107.
17. Breidenbach, A. W., J. J. Lichtenberg, C. F. Henke, D. J.
Smith, J. W. Eichelberger, Jr., and H. Stierle. The Identi-
fication and Measurement of Chlorinated Hydrocarbon Pesticides
in Surface Waters. U. S. Department of the Interior, Federal
Water Pollution Control Administration, Washington, DC. 1966.
p. 12-14.
18. Metcalfe, L. D. and A. A. Schmitz. The Rapid Preparation of
Fatty Acid Esters for Gas Chromatographic Analysis. Anal Chem.
33:363-364, 1961.
19. Hawley, G. G., Ed. The Condensed Chemical Dictionary, Eighth
Edition. New York, NY. Van Nostrand Reinhold Co., 1971. 971 p.
20. Webb, R. G., A. W. Garrison, L. H. Keith, and J. H. McGuire.
Current Practice in GC-MS Analysis of Organics in Water.
Environmental Protection Agency, Corvillis, OR. Report Number
EPA-R2-73-277. 1973. p. 37-41.
46
-------
21. Christensen, H. E., Ed. The Toxic Substances List. Department
of Health, Education, and Welfare. National Institute for
Occupational Safety and Health, Rockville, MD. Publication
Number HSM 72-10265. June 1972. 563 p.
22. Stecher, P. G. The Merck Index. Rahway, NJ. Merck and Co.
Inc., 1968. 1713 p.
23. Stahl, W. H., Ed. Compilation of Odor and Taste Threshold
Values Data. American Society for Testing and Materials,
Philadelphia, PA. 1973.
24. Mark, H. F., Ed. Encyclopedia of Chemical Technology. New
York, NY. John Wiley and Sons, Inc., 1970. Vol 8. p. 849-850.
47
-------
I SELECTED WATER
1 RESOURCES ABSTRACTS
TRANSACTION FORM
3. Accession No,
w
4. Title
ORGANIC COMPOUNDS ENTERING GROUND WATER FROM
A LANDFILL,
7. Autbor(s)
Robertson, J., Toussaint, C. R., and Jerque, M.
£.
f,
A PerformingQtgsut'zatfoA
Report No.
9. Organization
University of Oklahoma
School of Civil Engineering and Environmental Science
Norman, Oklahoma
10. Project No.
21 AKQ, Task 13
11. Contract/Grant No.
R801417
13. Type c' Rtpot. and
Period Covered
Sponsoring.Organization
75. Supplementary Notes
U. S. Environmental Protection Agency Report No. EPA-660/2-74-077, September
16. Abstract
Organic compounds leached into ground water from a landfill containing refuse
deposited below or near the water table were investigated. Ground water from wells
within or near the landfill and a control well was sampled by modified low-flow
carbon adsorption procedures incorporating all glass-teflon systems to preclude
Introduction of extraneous organics. Column chromatography, solubility separation,
and gas chromatography-mass spectrometry were employed for separation, identification,
and quantitation of individual compounds in organic extracts. The ground water was
shown to contain low levels of many undesirable organic chemicals leached from the
landfill. Of those compounds identified (over 40), most were chemicals commonly
employed in industry for manufacturing many domestic and commercial products. The
source of these compounds was apparently manufactured products discarded in the
landfill, since it had not received appreciable wastes from industrial operations.
Because the age of the refuse In the area studied was at least three years, the
compounds identified were believed to be substances leached very slowly from the
refuse and/or transported away from the landfill very slowly because of adsorption
on aquifer solids. Potential long-term pollution of ground water by Industrial
organic chemicals from landfills may be indicated by this work.
17a. Descriptors
*Ground water, *Landfills, *Water pollution, *0rganlc compounds, *Leachate,
Water pollution sources, Water pollution control, Organic wastes, Gas chromatograph,
Mass spectrometry, Path of pollutants, Activated carbon, Polychlorinated biphenyls,
Environmental effects, Aquifers, Sampling, Organic acids
776. Identifiers
*Carbon adsorption method, Organic Carbon, Refuse, Industrial organic chemicals
I7c. COWRR Field & Group 05B
IS. Availability
19.
20. Security Class.
22, JPrr'e*
Send To:
WATER RESOURCES SCIENTIFIC INFORMATION CENTER
U.S. DEPARTMENT OF THE INTERIOR
WASHINGTON, D. C. 2O24O
Abstractor J. Robertson
institution University of Oklahoma
WRSIC 1O2 vREV. JUNE 1971)
------- |