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Toxic chemicals in an abandoned phenolic waste site
Chemosphere,Vol.12,No.ll/12,pp Printed in Great Britain
1619-1632,1983
0045-6535/83 $ 3 . 0 0 + .OO ©1983 Pergamon P r e s s Ltd.
TOXIC CHEMICALS IN AN ABANDONED PHENOLIC WASTE SITE John J. McCreary, JoAnn G. Jackso~ John Zoltek, Jr~ Department of Env. Eng. Sciences University of Florida Galnesville, Florida 32611 Abstract The nature and extent of pollution was determined at the site of a former pinetar manufacturer. Compound distributions at various areas about the site revealed that, in addition to groundwater leaching of soluble phenolics, insoluble contaminants were spread by a dike-breach incident and subsequent construction activities. Differences in the patterns of chemicals in various wells suggested that more than one source of pollution occurred. The distribution of compounds about the site indicated that a general clean-up would not be cost-effective. Placement of an interceptor to collect groundwater seepage that contaminates surface water is being considered as an alternative. Introduction Recently there has been an increase in public awareness
concerning hazardous wastes
beginning with the publicity related to the Love Canal problem and growing with the discovery I of numerous hazardous waste sites throughout the country. The public's concern has led to the establishment
of a $1.6 billion superfund by the U.S. Congress
to clean up 418 of the
nation's most dangerous waste sites. Organic leachate from abandoned waste sites poses a threat to the contamination surface water and particularly especially
insidious
groundwater
supplies.
since many of the mechanisms
The potential
of
threat to groundwater
is
through which surface waters are cleansed
are diminished or completely absent in the ground. An appropriate
rationale
to the analysis of hazardous waste sites would be to
examine the nature of these sites on a generic basis. literature dealing with the characterization
There are numerous
reports in the
and clean-up of coal-tar and creosote wastes.
Compounds associated with these sites include soluble phenolics as well as insoluble polynuclear aromatic hydrocarbons. were migrating
Ehrllch et al. 2 found that phenol and naphthalene
from the site of a former coal-tar distillation
phenolics were anaerobically
plant.
The
degraded by methane producing bacteria 3 and naphthalene was
attenuated by adsorption onto the aquifer sediments.
Delfino 4 reported on the contamination
of groundwater after a phenol spill from a railroad car. phenol contaminated
and wood-treating
contaminant!
Approximately
adjacent wells over a period of over 2.5 years.
1619
35,000 liters of
1620
The clean-up of creosote wastes has also been described.
Ball 5 reported on ground-
water contamination that resulted from drain lines from an unconnected concrete sump at a former wood preserving plant site.
The water and preservatives were pumped out, separated
in an oil/water separator and the original pond site was backfilled with impermeable clay. The contamination of Lake Superior by surface runoff and groundwater infiltration of creosote preserving wastes was investlgated. 6
The creosote could be removed by pumping wells with
subsequent treatment of the wastewater by chemical or biological oxidation on activated carbon.
Investigators have demonstrated oxidative efficiencies for phenols in wood preserving
wastes of from 92 to 97 percent using activated sludge, trickling filters, or soil percolation 7 processes. The site involved in this research was located at a former plne-tar manufacturer in Gainesville,
Florida (pop. I00,000).
Phenolic waste products formerly stored on the
site have contaminated the shallow water table and are leaching into surface waters. surface drainage enters a major creek with considerable impact to aquatic life.
The
In addition,
there is concern that the pollutants in the shallow aquifer will contaminate deeper aquifers which serve as sources of drinking water in Florida. Previous History From the 1930's to 1967 the site was used for the production of charcoal and pinetar products by the destructive distillation of pine stumps.
In the 1950's the plant employed
I00 people and produced one-third of the world's pine-tar products.
Originally waste from
this process was discharged north, off the site into a swamp (Figure I).
In the mid 1940's
the production was significantly expanded and wastewater, which consisted of residual pine tars and phenolic compounds, was collected in three surface impoundments on the northwest corner of the property.
Wastewater was generated from water used to quench hot charcoal as
it was removed from retorters in the distillation process.
It is indicated from historical
data that the lagoons were allowed to drain by two methods, percolation into the soil and surface discharge (approximately 6000 gal/day) through small channels into the swamp north of the plant site. in the area.
Part of the discharge flowed into a drainage ditch which entered a major creek
At the time the plant was in operation, a study demonstrated that 367 species
of plants and animals upstream of the discharge were reduced to 163 species im=ediately down8 stream. In 1967 the facility was closed and the property was sold with the surface impoundments to a local investor.
In the fall of 1967, employees of the investor breached a dike
wall of the impoundment allowing approximately 1.4 million gallons of waste liquor to flow eastward, possibly by means of a ditch located on old
~lans
of the property.
This ditch
intercepted the creek and newspaper articles from this time indicated that people residing in the area complained of phenolic odors and a black, tar-llke substance flowin B down the creek.
Figure I.
SWAMP
*
Plan of Creosote Facility in Gainesv~lle, Florida, circa 1960 wlth Well Locations
.:,.,.DV ~ / /
IMPOUNDMENTS
.
Figure 2.
6
"
AR DEALERSHIP
N, .........
~
~rT
:
~"
/
Site of the Former Creosote Facility as it Exists Today with Well Locations
CAR DEAL ERSMm
3@
I ~-:r---; / ~,--
~
" [-I
2
SWAMe -; *
~J
1622
The owner was subsequently fined and forced to assist in clean-up and removal of the tar from the surface ditch. However, much of the clean-up procedure did not involve actual removal of the contaminants from the site, but involved mixing the contaminants until they blended with the existing soil. Approximately ten years later the property was re-sold and developed into an industrial park.
Two car dealerships and a shopping center now exist on a portion of the old
site (Figure 2). In 1979, the U.S. EPA (Region IV) conducted a hazardous waste site investigation and found phenol concentrations measured greater than I000 ~g/l immediately downstream of the waste input into the creek.
In addition, a variety of priority pollutants including
naphthalene, acenaphthene, phenol, 2,4-dimethylphenol, benzene and toluene were found at the I0
-
200 ~g/l level. 9 Presently the undeveloped portion of the original site has sparse vegetation,
phenolic odors and tar fragments in the sand. drainage ditch that empties into the creek.
Contaminants are continually leaching into the There is also concern that contaminants could
penetrate into the underlying Floridan aquifer from which the city of Gainesville obtains its drinking water.
The well fields for the city are located approximately 2.2 miles to the
northeast of the original lagoons. The objectives of the present study were to determine the nature and extent of the pollution at the old industrial site.
This was to be the first step in evaluating whether
possible clean-up or containment of the wastes could be effected. Materials and Methods Samples of water and soll were obtained by drilling 2 inch wells at various locations (Figures i and 2).
Well sites were located at the original site of contamination (Well i),
upgradient (Wells 3, 4 and 7) and downgradient (Wells 2, 5 and 6) of the expected pollutant plume.
The type, depth and water level in each well are listed in Table I.
feet the Hawthorne layer, a clay a q u i c l u d e w a s
reached.
Below 30 - 35
Drilling did not extend through this
layer in order to avoid contaminating the Floridan aquifer. Initially wells were drilled with a hollow-stem auger and split-spoon samples were taken below the auger.
After the shallow water table was reached (approximately 7 - I0 feet)
samples were not retained by the split-spoon and water backed up inside the hollow bit.
To
minimize exposure to contaminants and facilitate the procedure, alternate methods were employed Soil was collected from that displaced to the ground surface by rotation of the auger and from the bottom of the bit when it was removed from the hole. For the majority of the wells, PVC-pipe was inserted into the hollow auger and the auger was removed, leaving the well pipe.
Stainless steel point-driven wells were used as
casings for two well sites where high concentrations of the organic substances occurred. A PVC cased well was also drilled in a non-contaminated area (Well 7, Figure I) to provide water to be used as an organic blank.
Compounds common to this well and the other PVC-lined
wells were not attributed to the original pollutlon. I0 Two of the wells could be pumped continuously (Wells 4 and 5), and these were pumped
PVC
PVC
PVC
PVC
Stainless Steel
PVC
PVC
3
4
4A
4B
5
6
7
3
40.5
30
25
30
30
30
30
30
15
20
25
Depth (ft)
20
20
5
20
20
20
20
I0
5
5
5
Screen 3 Depth (ft)
Well Characteristics
All screens were at the bottom of the wells
PVC wells were hollow - augered
steel casings were point driven
PVC 2
2
Stainless
Stainless Steel
IB
2
Stainless Steel
IA
!
Stainless I Steel
Type Casing
1
Well #
Table i.
183.5
171.3
174.8
180.7
180.7
180.7
182.5
175.0
180.5
180.5
180.5
Surface Elev. ~MSL)
Very odorous - phenolics somewhat oil texture to soil. Pumped poorly. No odors. Mostly fill dirt. Pumped easily.
164.9
170.9
odors.
Only slight phenolic Pumped easily.
All wells in #4 series had an unusual odor - not phenolic. Fine mist from well 4A caused well drillers headaches and nausea. Pumped easily.
Only s]ight phenolic odor. Pumped poorly. No odors. Pumped poorly.
All wells in the #I series were very odorous. The soil between 5 and 12 feet had a gummy texture. The wells did not pump easily.
Description
171.4
173.1
173.1
173.1
174.6
172.1
173.0
173.0
173.0
Water Elev. (MSL)
LO
1624
until at least I0 bore volumes of water had passed before sampling.
The remaining wells were
pumped dry and the water that flowed back in was collected using a glass bailer.
All water
samples were collected in 250 ml brown glass bottles with screw-caps over teflon-lined seals (Pierce Scientific, Rockford, IL). Both soil and water samples were stored at 4°C until analysis in order to deter bacterial decomposition.
Grain size of the soil was determined using a hydrometer method II and
mechanical sieve analysls. 12
After removing the organic compounds with a concentrated solution
of sodium or calcium hypochlorite, the soil was dispersed with sodium hexametaphosphate and settled in a cylindrical column.
The sediment mixture at the bottom of the cylinder was fur-
ther fractionated by mechanical sieving, and the clay-slzed fraction was analyzed by X-ray diffraction. The soll samples were Soxhlet extracted with a methylene chloride - methanol mixture (Distilled-in-Glass, Burdick and Jackson, Muskegon, MI) for at least eight hours or until the solvent in the extraction thimble appeared clear in color.
The extracted soll was air-dried
under a hood for several days before a dry weight was obtained on an electronic top-loading balance (Mettler PR-1200, Princeton, NJ). Water samples were filtered, transferred to a two liter separatory funnel, acidified with approximately 0.5 ml of sulfuric acid and extracted with 20, I0 and I0 ml volumes of methylene chloride.
The combined extracts were filtered through anhydrous Na2SO 4 and rotary
evaporated to several microliters.
The sample was rediluted to slightly more than one ml
with methylene chloride and adjusted to exactly one ml with a slow stream of nitrogen gas. This volume was then transferred to a two ml crimp-seal vlal. Ten microliters of internal standard were added to all crlmp-seal vials containing extracts.
The internal standard solution was 205.3 mg DlO-anthracene (Aldrich Chemical Co.,
Milwaukee, WI) dissolved into 20 mls of benzene (Nanograde solvent, Mallinckrodt, St. Louis, MO). One to two mlcroliters of each extract were splitlessly injected into a 30 meter DB-5 fused silica capillary column (J & W Scientific, Rancho Verde, CA) and analyzed by gas chromatography -mass spectrometry (5985B GC/MS, Hewlett Packard, Avondale, PA). was held at 30°C for 5 minutes and then progran~ned at 10°C/min to 280°C.
The column
Periodically,
10%
formic acid in methanol was injected on the column in order to prevent tailing of the phenolic compounds.
Mass spectral identifications were made by comparison to tabulated spectra libra-
ties 13'14 and confirmed by obtaining pure standards wherever possible. extracts were quantltated using QUANTID and IDFILE data system.
Compounds in the
programs supplied with the Hewlett Packard
Two modifications were made to the QUANTID procedure; the integral match window
was changed from one to three and the retention time scan window was changed from a value of 50 to I0 due to the sharpness of the capillary peaks.
QUANTID was successful in calculating
approximate concentrations; major peak concentrations were confirmed manually using the QUANTID formulas and reconstructed ion areas.
Although standard curves of the area ratios
of various organics and Dl0-anthracene were linear over several orders of magnitude, the results were only semi-quantitative since no attempt was made to evaluate recovery efficiencles in the
1625
extraction procedure
and the internal standard was added after the extraction was completed.
The concentrations reported are useful primarily for comparison purposes. Results and Discussion Hydrogeological investigations revealed that shallow groundwater was migrating to the north and east of the industrial site (Table I).
Wells 2, 5 and 6 were expected to
receive contaminants from the old lagoon since they were situated in the direction of groundwater flow. 2.
Groundwater parameters were determined with a pump test and are listed in Table The permeability of 495 gal/day-ft 2 is approximately that of a silty to clean sand. 15
Well logs taken in the study area showed the sands to be a coarse to fine-grained quartz sand and clayey sand with an approximate thickness of 30 to 35 feet.
A clay fraction ranging from
3.34 to 37.77 percent of the soil sample consisted of the clay mineral kaolinite and a clay size fraction of quartz.
Slight amounts of montmorillonite were found in several well logs
at depths of 5 to 7 feet.
The presence of montmorillonite below kaolinite suggests that the
upper soil consisted of fill material.
A blueish-gray highly plastic clay (Hawthorne Formation)
underlies the sands in this area and is estimated to be approximately 90 to 150 feet thick. This formation is the confining layer for the Floridan aquifer.
Table 2.
Summary of Groundwater Parameters II,400 gallons/(da~-ft) 495 gallons/day-ft ~ 0.24 - 0.53 ft/day 0.3 0.79 - 1.8 ft/day O. 004 0.152
Transmissivity Hydraulic Conductivity Discharge velocity Estimated Porosity Average Linear Velocity Storage Capacity Specific Yield
A typical chromatogram of a site 1 soil extract is shown in Figure 3 and the numbered peaks are identified in Table 3. terpenes and polynuclear hydrocarbons.
The compounds represented three categories; phenols,
Major compounds adsorbed to the soil included the
terpenes; alpha pinene, camphene, O-cymene and limonene; as well as dihydroxy acetophenone an alkyl phenanthrene.
and
All of these compounds have been listed as products of the destructive
distillation of resinous pines; and organics associated with pyroligneous acid, tar oils and charcoal. 16 The soil concentrations of selected compounds are shown by site in Table 4.
It
is obvious that there were negligible concentrations of compounds in the soil of 3, 4 and 7. This was expected since these areas were upgradient of the original lagoons.
The maximum con-
centrations of compounds were greatest in the soil of site 1 followed by site 6 with considerably smaller quantities at sites 2 and 5.
It was expected that the concentrations should be
high at site 1 due to the fact that the site was situated immediately over the old lagoons.
1626
Most
of
extent much
the compounds
associated
in t h e g r o u n d w a t e r
lower
due
concentrations
Figure
3.
Total
of
with
to t h e i r
low water
the c o m p o u n d s
Ion Current
~4
the soil would
found
Chromatogram
not
leach
solubilities. at s i t e s
of a S o i l
or migrate 17
2 and
This
was
to a s i g n i f i c a n t borne
out b y
5.
Extract
from
Site
i.
10
tt,
,.~
>~__I I. Toluene
23.
2,5-Dimethylphenol *
2. 3.
Ethylbenzene p-Xylene
24. 25.
Camphor * 3,5-Dimechylphenol *
4.
Dimethylfuran
26.
Borneol *
5. 6.
Ethsnone l-(2-furanyl) Cumenol
27. 28.
a-Terplnol Dihydroxyacetophenone *
7.
~-Pinene *
29.
Ethoxybenzaldehyde
8.
Camphene *
30.
Dimethylnaphthalene *
9.
Menthane
31.
Isopropylnaphthalene
I0.
Phenol
32.
Phenylphenol (deriv,)
II.
m-Terpinene
33.
C3 Naphthalene
12. 13.
C~ne * Limonene *
34. 35,
C 3 Naphthalene DI0 Anthracene (internal standard)
14.
B-Phellandrene
36.
Methylphenanthrene
15.
o~Cresol *
37,
Methylpheuanthrene
16.
m-Cresol *
38.
4-Epidehydrosbietal
17.
p-Cresol *
39.
C 2 Benzanthraeene
18.
A11o-oclmene
40.
Dlmethylphen~nthrene
19.
o_MethoxTpheno I *
41.
C3 P h e n a n t h r e n e
20. 21.
Fenchone * Fenchyl alcohol •
42. 43.
C 4 phenanthrene Methyldehydroabletate
22.
2,4-Dimethylphenol * c onf ir me d by comparin~ the r e t e n t i o n
Table
3.
Compounds
Identified
time and t h e ma•s spectrum to s p u r e • t a n d a r d
in t h e S o i l
Extract
from
Site
1 (Figure
3).
the
1627
The high concentrations to groundwater movement. concentrate
of compounds in the soll at site 6 could not be attributed
Compounds would not be expected to leach from site 1 and selectively
at site 6 without also concentrating
at 5.
This might occur if the sorptive capa-
city of the soil at site 6 was much greater than that at site 5, however there appeared to be little difference content data.
in the soil character at the two areas based on size fractionation
Another explanation was that the contaminated
located from the region near the old lagoon. of suspended material breaching
incident)
the industrial
and clay
soil at site 6 had been trans-
This movement may have been a result of deposition
in a drainage ditch that led from the lagoon (possibly during the dike
or as a result of physical movement during the construction
operations
for
park now located at the area.
Table 4.
Highest Reported Concentrations
of Selected Compounds
in Soll Analyses
C~/~ram) Compquqds S Lee
t
S tee
S ice 2
Sice
S Lee
S ice
Sice
3
&
5
6
7
I.
~-Plnene
285
15
N.D.*
N.D.
<0.5
23
N,D,
2.
Camphene
275
3
N.D.
N.D.
<0.5
117
g.D.
3.
p-Cymene
210
16
N.D.
N.D.
8
300
N.D.
4.
Limonene
920
10
N.D.
N.D,
2
660
N.D.
5.
o-Cresol
.55
34
N.D.
N.D.
12
21
N.D.
6.
D-Camphor
78
17
N.D.
N.D.
32
|t5
N.D.
7.
D1hydroxyacetophen(,ne
260
7
N.D.
N.D.
<0.3
<0.3
N.D.
8.
C -phen~nthrene
215
55
N.D.
N.D.
<0.3
175
N.D,
9.
Mechyldehydro-
405
163
N.D.
<0.3
360
N.D.
abtecace
*N.D. - noC d e c e = c e d
A typical histogram of the concentration shown in Figure 4. 5 - I0 feet, centrations leaching,
For most compounds,
the approximate
of
the greatest
~ -pinene with soil depth at site I is concentrations
depth of the groundwater
occurred in the region of
level below the surface.
The lower con-
in the vadose zone may have been a result of losses by volatilization,
and mechanical mixing with less contaminated
Highest concentrations
rainwater
soil during construction operations.
may have occurred at the groundwater
interface since the immiscible tars
and oils may have floated on the top of the saturated zone.
Ramsey et al. 18 observed a similar
phenomenon
in groundwater
samples taken with depth at a wood-treatlng
The concentrations
facility.
of compounds at various depths in the soll at the original lagoon
site (site I) could not be correlated with the percent sand, silt or clay content, apparent correlation between the coarse silt content and concentration
however an
of several compounds was
1628
obtained. 5.
A plot of percent coarse silt yrs. 0-cymene concentration is illustrated in Figure
It would be expected that the clay-size fraction would have the highest concentration of 19 The quan-
adsorbed contaminants primarily due to the large ratio of surface area to mass.
tity of compound adsorbed on a soll fraction, however, is a function of its partition coefficient and the percent weight of the soil fraction.
An intermediate grain size might adsorb
the largest quantity of compound if the smallest-size fractions were only minor components. This did not occur in our study since the percent clay-size fraction was often greater than the coarse silt.
The correlation obtained may simply indicate that adsorptive processes were
not dominant in retaining the compounds in the soil.
Often water contained oil droplets and
floating tars, indicating that some of the organic compounds existed as a separate phase.
Figure 4.
Histogram of the Concentration of =-Pinene with Depth at Site 1
~ 2*e ~ a,e
u ,2e
e@
e D l P T . ~FT,
Figure 5.
Correlation of 0-Cymene Concentration with the Coarse Silt Content in the Soll of Site I
, :o,s*
*-¢,1|.*
.C|.TnaT,O
i~e/el
1629
A summary of the major compounds and concentrations found in the water analyses is presented in Table 5.
The chromatograms are shown for comparison in Figure 6.
It is obvious
from the figure that Wells I, 2, 5 and 6 had similar pollutants whereas Wells 3 and 4 had quite different contaminants.
Wells over the old impoundment site (I, IA and IB) and those
along the path of the groundwater (Wells 2, 5 and 6) had the highest concentrations of phenolic compounds.
The concentrations were generally highest in Wells I and 6 followed by Wells
5 and 2.
Table 5.
Concentrations of Major Compounds in Water Samples Analyses (ug/l)
C~Dounds
1,
Well 1A
G-cresol mop-Cresol 2,5 - and 3,4Dimethyl phenol Methoxyl-phenol A l l y l pheno]
1700 3300 ND
1100 2300 3100
130 380
120 60
TOTAL PHENOL CONCENTRATIONS
5510
6680
Well 1B
Well 2
Well 3
Well 4
Well 4A
Well 4B
Well 5
Well 6
5200 11100 3300
920 3100 1800
4 3 I
<0.3 <0.3 4
9 50 130
22 95 2
1700 3800 3900
2900 6200 9400
Well 7
Phenols A. B. C. D. E.
2.
Well 1
3300 4.0 22900
15 30
1 <.._44
5865
9
O.S <._~3 4.5
ND <.3
2 0.4 3
ND 10
80 <2
340 570
2 2
189
129
g480
19410
9
2
Aromatic Hydrocarbons A. B, C. D.
I-Methyl Naphthalene 2-Methyl Naphthalene Naphthalene Acenaphthene TOTAL AROMATIC HYDROCARBONS
II
8
2
2
130
75
110
50
.9
50
14
.9
<2
3
70
60
80
40
1
60
2
90 ND
110 ND
140 ND
40
NO
710
740
860
670
140
330
_~
40
~_
115
118
142
45
1080
102fi
1220
815
140
440
47
170
lS0
17~0
S__ES
N~
3.
D-Camphor
1600
1200
1400
530
18
7
30
30
1500
16C0
12
4.
Borneol
4700
1700
790
640
2
1.4
20
2
3300
7100
7
S.
Alpha-Terpineol
hiD
140
410
90
2
<,2
<.3
3
80
390
2
6.
Dihydroxyacetophenone
2400
290
3300
380
<.3
<.2
<.3
<.3
<2
33C0
14
25
9
7,
FenchyI Alcohol
47
92
37
.3
.4
2
4
1200
97
8.
Fenchone
79
.7
2
20
<.I
<.I
2
S
200
27
I
9.
Limonene
2B
9
39
48
1
1
2
3
38
130
2
p-cymene
79
.7
2
<20
<.1
<.1
2
5
210
27
1
10.
*ND - Not Detected
Well 2 m a y h a v e received contamination as a result of some northerly groundwater flow, as well as the previous history of surface drainage to the swamp north of the site. Wells 5 and 6 received pollutants from northwesterly groundwater flow and surface drainage related to the dlke breaching incident.
It is interesting to note that site 5 was contaminated
with water soluble compounds but had negligible levels of water insoluble materials associated with the soil (Table 4).
This suggested that water transport had been the dominant mechanism
for contamination at this site.
1630
Figure 6.
Total Ion Current Chromatograms of Well Waters at Sites 1 - 6 Note that vertical scales are different (see Table 4).
.....
1
~...~.~
-
~L~._._L~.
WELL
I
6
,I
__j
TIME
?
.i~,A._._
Wells 3 and 4, upgradlent of the original phenolic
contaminants
contaminated acenapthene. (Figure 6).
contaminated
present in Wells I, 2, 5 and 6.
with high concentrations
of naphthalene,
The patterns of contamination The old surface impoundments
wells did not receive groundwater
_
0 9 101 1 1 2 1314 t S l ~ 17 181~ 2 0 2 1 2 2 2 3 2 4 2 E 2~ 2 , " 2 0 2 9 3 0 3 1 3 2 3 3 3 4 3 ~ .
area, did not contain the
However Wells 3 and 4 were similarly l-methyl and 2-methyl naphthalene
of the two wells were virtually
were not the source of these contaminants
from that area and the concentrations
since the
of these compounds at
3 and 4 were much greater than in any other well.
The destructive
involves a process in which an immiscible
such as benzene or naphth~ is used to
remove water from wood chips by azeotropic the presence of the naphthalene
solvent,
distillation.
and related compounds
more likely that these compounds may have originated
distillation
of pine stumps
This solvent addition may explain
in the groundwater.
Howeve~ it appears
from leaching at a location off the site.
Well 3, at the extreme western border of the property, was contaminated. treating facility and railroad
and
identical
tracks existed west of the area (Figure 2).
A similar wood-
1631
The concentration
of phenolic
contaminants
in Wells I, IA and IB showed the same
correlation with depth found with the soil samples.
Well
i, drilled to 25 feet had less phenol
than IA at 20 feet, and Well IB had the highest phenol concentration A stormwater detention pond presently lagoons
(Figure 2).
contaminated
exists directly over a portion of the old
A water sample from this pond did not contain compounds
groundwater,
lutants underneath
at 15 feet (Table 5).
indicating
that a bentonite
found in the
clay layer effectively
sealed the pol-
the pond.
It was apparent that surface water contamination was the primary source of pollution from the site. approximately
The drainage ditch bordering 2 - 3% of the concentrations
the east of the property contained phenols at
in the water of Well 6.
These concentrations
mained relatively constant until the ditch joined Hogtown Creek approximately northwest.
There was no evidence of deep groundwater
reduced by the time that the aquiclude was reached compounds were migrating
contamination,
re-
I mile to the
soil concentrations
were
(Figure 4), and there was no evidence that
through the aquiclude and into the Floridan aquifer.
Conclusions i.
Three major classes of compounds were found on the old industrial
and condensed aromatics.
site; phenols,
terpenes
All compounds were expected byproducts of the destructive distilla-
tion of pine stumps which had occurred at the site from the 1930's to 1967. 2.
The compounds partitioned
between soll and water as a function of their water solubilities.
The highly soluble phenols were present were found associated with the soil.
in water and insoluble compounds
The depth profile of compound concentration
of the original lagoon site was correlated with the coarse silt content. were probably not dominant 3.
throughout
site 6 were attributed vities.
Groundwater
soluble compounds 4.
Additional
in the lagoons.
in the soil
Adsorptive
processes
in retention of the compounds.
In addition to groundwater
contaminants
such as the terpenes
transport,
the area.
other mechanisms were responsible
High concentrations
to the former dike-breachlng
transport appeared
for distributing
of insoluble compounds
incident and subsequent
in the soil at
construction
to also be important due to the concentrations
acti-
of water
in the water of Wells 2 and 5.
contaminants
found in Wells 3 and 4 were not attributed
Contamination
gested that pollutants
to the compounds stored
at Well 3, at the extreme western border of the property,
from a railroad
spillage or other industrial
sug-
activity were migrating
to this area. 5.
The distribution
of compounds around the site suggested
entire area would not be cost-effective.
Since the greatest
curring as a result of surface water contamination,
that a general clean-up of the impact of the pollution
placement of an interceptor
is oc-
in the drainage
ditch along the eastern border of the property is being considered as a treatment alternative.
1632
The authors wish to thank Dr. Donald Robinson of the Cabot Carbon Foundation; Ron Ferland, Gainesville City Engineer and Nancy Gourlie of the Alachua County Pollution Control Federation for invaluable advice and cooperation, and Carl Miles and Kurt Batsel for help during the GC/MS portion of the work. John J. McCreary is now deceased. References i. T.H. Maugh, Science, 204, 819, 1979. 2. G.G. Ehrllch, D.F. Goerlitz, E.M. Godsy, M.F. Hult, Groundwater,
20, 703, 1983.
3, E.M. Godsy, D.F. Goerlitz, G.G. Ehrllch, Bull. Environ. Contam. Toxicol., 30, 261, 1983. 4. J.J. Delfino, Chapter 17 in Drlnking Water Qu~llty Enhancement Through Source Protection, R.B. Pojasek, Ed., Ann Arbor Science Pub. Inc., Ann Arbor, MI, 275, 1977. 5. J. Ball, in Proc. Ind. Waste Conf., 36, 195, 1982. 6. G.E. Thompson, Proc. Ont. Ind. Waste Conf., 25, 250, 1978. 7. J.V. Dust and W.S. Thompson, Forest Products Journal, 23, 59, 1973. 8. B.B. Sundaresan, E.C. Bovee, D.E. Wilson, J.B. Lackey, J. Water Polln. Cntrl. Fed., 37, 1536, 1965. 9. United States Environmental Protection Agency Region IV. Hazardous Waste Site Investigation Phase I, Cabot Carbon Site, Gainesville, Florida, 1980. 10. Environmental Protection Agency Handbook for Sampling and Sample Preservation of Water and Wastewater. Environmental Monitoring and Support Laboratory, Cincinnati, OH, 1982. 11. G.J. Bouyocous, Agronomy Journal, 54, 464, 1962. 12. Krumbein and Pettljohn, Manual of Sedimentary Petrology, Appleton -Century -Crofts, Inc., New York, 77, 1938. 13. Eight Peak Index of Mass Spectra. 1974.
Mass Spectrometry Data Centre.
AWRE Reading, U.K.,
14. Registry of Mass Spectral Dataa, E. Strenhagen, S. Abrahamsson, F.W. McLafferty, Eds., Vol. i - 4, John Wiley & Sons, New York, N.Y. 15. R. A. Freeze and J.A. Cherry, Groundwater, Prentice-Hall Inc., Englewood Cliffs, N.J., 1979. 16. J.A. Kent, Riegel's Handbook of Industrial Chemistry, Litton Educational Publishing, Inc., 1974. 17. Seidell, Solubilities of Organic Compounds, Inc., New York, 1941.
Vol. 2, 3rd. edition, D. Van Nostrand Co.,
18. W.L. Ramsey, R.R. Steimle, J.T. Chaconas, in Management of Uncontrolled Hazardous Waste Sites, 212, 1981. 19. T. Mill, e__~tal., Laboratory Protocols for Evaluating the Fate of Organic Chemicals in Air and Water. EPA Contract #68-03-2227 submitted to EPA Environmental Research Laboratory, Athens, GA. (Received
in The
Netherlands
21 A u g u s t
1983)
1619-1632,1983
0045-6535/83 $ 3 . 0 0 + .OO ©1983 Pergamon P r e s s Ltd.
TOXIC CHEMICALS IN AN ABANDONED PHENOLIC WASTE SITE John J. McCreary, JoAnn G. Jackso~ John Zoltek, Jr~ Department of Env. Eng. Sciences University of Florida Galnesville, Florida 32611 Abstract The nature and extent of pollution was determined at the site of a former pinetar manufacturer. Compound distributions at various areas about the site revealed that, in addition to groundwater leaching of soluble phenolics, insoluble contaminants were spread by a dike-breach incident and subsequent construction activities. Differences in the patterns of chemicals in various wells suggested that more than one source of pollution occurred. The distribution of compounds about the site indicated that a general clean-up would not be cost-effective. Placement of an interceptor to collect groundwater seepage that contaminates surface water is being considered as an alternative. Introduction Recently there has been an increase in public awareness
concerning hazardous wastes
beginning with the publicity related to the Love Canal problem and growing with the discovery I of numerous hazardous waste sites throughout the country. The public's concern has led to the establishment
of a $1.6 billion superfund by the U.S. Congress
to clean up 418 of the
nation's most dangerous waste sites. Organic leachate from abandoned waste sites poses a threat to the contamination surface water and particularly especially
insidious
groundwater
supplies.
since many of the mechanisms
The potential
of
threat to groundwater
is
through which surface waters are cleansed
are diminished or completely absent in the ground. An appropriate
rationale
to the analysis of hazardous waste sites would be to
examine the nature of these sites on a generic basis. literature dealing with the characterization
There are numerous
reports in the
and clean-up of coal-tar and creosote wastes.
Compounds associated with these sites include soluble phenolics as well as insoluble polynuclear aromatic hydrocarbons. were migrating
Ehrllch et al. 2 found that phenol and naphthalene
from the site of a former coal-tar distillation
phenolics were anaerobically
plant.
The
degraded by methane producing bacteria 3 and naphthalene was
attenuated by adsorption onto the aquifer sediments.
Delfino 4 reported on the contamination
of groundwater after a phenol spill from a railroad car. phenol contaminated
and wood-treating
contaminant!
Approximately
adjacent wells over a period of over 2.5 years.
1619
35,000 liters of
1620
The clean-up of creosote wastes has also been described.
Ball 5 reported on ground-
water contamination that resulted from drain lines from an unconnected concrete sump at a former wood preserving plant site.
The water and preservatives were pumped out, separated
in an oil/water separator and the original pond site was backfilled with impermeable clay. The contamination of Lake Superior by surface runoff and groundwater infiltration of creosote preserving wastes was investlgated. 6
The creosote could be removed by pumping wells with
subsequent treatment of the wastewater by chemical or biological oxidation on activated carbon.
Investigators have demonstrated oxidative efficiencies for phenols in wood preserving
wastes of from 92 to 97 percent using activated sludge, trickling filters, or soil percolation 7 processes. The site involved in this research was located at a former plne-tar manufacturer in Gainesville,
Florida (pop. I00,000).
Phenolic waste products formerly stored on the
site have contaminated the shallow water table and are leaching into surface waters. surface drainage enters a major creek with considerable impact to aquatic life.
The
In addition,
there is concern that the pollutants in the shallow aquifer will contaminate deeper aquifers which serve as sources of drinking water in Florida. Previous History From the 1930's to 1967 the site was used for the production of charcoal and pinetar products by the destructive distillation of pine stumps.
In the 1950's the plant employed
I00 people and produced one-third of the world's pine-tar products.
Originally waste from
this process was discharged north, off the site into a swamp (Figure I).
In the mid 1940's
the production was significantly expanded and wastewater, which consisted of residual pine tars and phenolic compounds, was collected in three surface impoundments on the northwest corner of the property.
Wastewater was generated from water used to quench hot charcoal as
it was removed from retorters in the distillation process.
It is indicated from historical
data that the lagoons were allowed to drain by two methods, percolation into the soil and surface discharge (approximately 6000 gal/day) through small channels into the swamp north of the plant site. in the area.
Part of the discharge flowed into a drainage ditch which entered a major creek
At the time the plant was in operation, a study demonstrated that 367 species
of plants and animals upstream of the discharge were reduced to 163 species im=ediately down8 stream. In 1967 the facility was closed and the property was sold with the surface impoundments to a local investor.
In the fall of 1967, employees of the investor breached a dike
wall of the impoundment allowing approximately 1.4 million gallons of waste liquor to flow eastward, possibly by means of a ditch located on old
~lans
of the property.
This ditch
intercepted the creek and newspaper articles from this time indicated that people residing in the area complained of phenolic odors and a black, tar-llke substance flowin B down the creek.
Figure I.
SWAMP
*
Plan of Creosote Facility in Gainesv~lle, Florida, circa 1960 wlth Well Locations
.:,.,.DV ~ / /
IMPOUNDMENTS
.
Figure 2.
6
"
AR DEALERSHIP
N, .........
~
~rT
:
~"
/
Site of the Former Creosote Facility as it Exists Today with Well Locations
CAR DEAL ERSMm
3@
I ~-:r---; / ~,--
~
" [-I
2
SWAMe -; *
~J
1622
The owner was subsequently fined and forced to assist in clean-up and removal of the tar from the surface ditch. However, much of the clean-up procedure did not involve actual removal of the contaminants from the site, but involved mixing the contaminants until they blended with the existing soil. Approximately ten years later the property was re-sold and developed into an industrial park.
Two car dealerships and a shopping center now exist on a portion of the old
site (Figure 2). In 1979, the U.S. EPA (Region IV) conducted a hazardous waste site investigation and found phenol concentrations measured greater than I000 ~g/l immediately downstream of the waste input into the creek.
In addition, a variety of priority pollutants including
naphthalene, acenaphthene, phenol, 2,4-dimethylphenol, benzene and toluene were found at the I0
-
200 ~g/l level. 9 Presently the undeveloped portion of the original site has sparse vegetation,
phenolic odors and tar fragments in the sand. drainage ditch that empties into the creek.
Contaminants are continually leaching into the There is also concern that contaminants could
penetrate into the underlying Floridan aquifer from which the city of Gainesville obtains its drinking water.
The well fields for the city are located approximately 2.2 miles to the
northeast of the original lagoons. The objectives of the present study were to determine the nature and extent of the pollution at the old industrial site.
This was to be the first step in evaluating whether
possible clean-up or containment of the wastes could be effected. Materials and Methods Samples of water and soll were obtained by drilling 2 inch wells at various locations (Figures i and 2).
Well sites were located at the original site of contamination (Well i),
upgradient (Wells 3, 4 and 7) and downgradient (Wells 2, 5 and 6) of the expected pollutant plume.
The type, depth and water level in each well are listed in Table I.
feet the Hawthorne layer, a clay a q u i c l u d e w a s
reached.
Below 30 - 35
Drilling did not extend through this
layer in order to avoid contaminating the Floridan aquifer. Initially wells were drilled with a hollow-stem auger and split-spoon samples were taken below the auger.
After the shallow water table was reached (approximately 7 - I0 feet)
samples were not retained by the split-spoon and water backed up inside the hollow bit.
To
minimize exposure to contaminants and facilitate the procedure, alternate methods were employed Soil was collected from that displaced to the ground surface by rotation of the auger and from the bottom of the bit when it was removed from the hole. For the majority of the wells, PVC-pipe was inserted into the hollow auger and the auger was removed, leaving the well pipe.
Stainless steel point-driven wells were used as
casings for two well sites where high concentrations of the organic substances occurred. A PVC cased well was also drilled in a non-contaminated area (Well 7, Figure I) to provide water to be used as an organic blank.
Compounds common to this well and the other PVC-lined
wells were not attributed to the original pollutlon. I0 Two of the wells could be pumped continuously (Wells 4 and 5), and these were pumped
PVC
PVC
PVC
PVC
Stainless Steel
PVC
PVC
3
4
4A
4B
5
6
7
3
40.5
30
25
30
30
30
30
30
15
20
25
Depth (ft)
20
20
5
20
20
20
20
I0
5
5
5
Screen 3 Depth (ft)
Well Characteristics
All screens were at the bottom of the wells
PVC wells were hollow - augered
steel casings were point driven
PVC 2
2
Stainless
Stainless Steel
IB
2
Stainless Steel
IA
!
Stainless I Steel
Type Casing
1
Well #
Table i.
183.5
171.3
174.8
180.7
180.7
180.7
182.5
175.0
180.5
180.5
180.5
Surface Elev. ~MSL)
Very odorous - phenolics somewhat oil texture to soil. Pumped poorly. No odors. Mostly fill dirt. Pumped easily.
164.9
170.9
odors.
Only slight phenolic Pumped easily.
All wells in #4 series had an unusual odor - not phenolic. Fine mist from well 4A caused well drillers headaches and nausea. Pumped easily.
Only s]ight phenolic odor. Pumped poorly. No odors. Pumped poorly.
All wells in the #I series were very odorous. The soil between 5 and 12 feet had a gummy texture. The wells did not pump easily.
Description
171.4
173.1
173.1
173.1
174.6
172.1
173.0
173.0
173.0
Water Elev. (MSL)
LO
1624
until at least I0 bore volumes of water had passed before sampling.
The remaining wells were
pumped dry and the water that flowed back in was collected using a glass bailer.
All water
samples were collected in 250 ml brown glass bottles with screw-caps over teflon-lined seals (Pierce Scientific, Rockford, IL). Both soil and water samples were stored at 4°C until analysis in order to deter bacterial decomposition.
Grain size of the soil was determined using a hydrometer method II and
mechanical sieve analysls. 12
After removing the organic compounds with a concentrated solution
of sodium or calcium hypochlorite, the soil was dispersed with sodium hexametaphosphate and settled in a cylindrical column.
The sediment mixture at the bottom of the cylinder was fur-
ther fractionated by mechanical sieving, and the clay-slzed fraction was analyzed by X-ray diffraction. The soll samples were Soxhlet extracted with a methylene chloride - methanol mixture (Distilled-in-Glass, Burdick and Jackson, Muskegon, MI) for at least eight hours or until the solvent in the extraction thimble appeared clear in color.
The extracted soll was air-dried
under a hood for several days before a dry weight was obtained on an electronic top-loading balance (Mettler PR-1200, Princeton, NJ). Water samples were filtered, transferred to a two liter separatory funnel, acidified with approximately 0.5 ml of sulfuric acid and extracted with 20, I0 and I0 ml volumes of methylene chloride.
The combined extracts were filtered through anhydrous Na2SO 4 and rotary
evaporated to several microliters.
The sample was rediluted to slightly more than one ml
with methylene chloride and adjusted to exactly one ml with a slow stream of nitrogen gas. This volume was then transferred to a two ml crimp-seal vlal. Ten microliters of internal standard were added to all crlmp-seal vials containing extracts.
The internal standard solution was 205.3 mg DlO-anthracene (Aldrich Chemical Co.,
Milwaukee, WI) dissolved into 20 mls of benzene (Nanograde solvent, Mallinckrodt, St. Louis, MO). One to two mlcroliters of each extract were splitlessly injected into a 30 meter DB-5 fused silica capillary column (J & W Scientific, Rancho Verde, CA) and analyzed by gas chromatography -mass spectrometry (5985B GC/MS, Hewlett Packard, Avondale, PA). was held at 30°C for 5 minutes and then progran~ned at 10°C/min to 280°C.
The column
Periodically,
10%
formic acid in methanol was injected on the column in order to prevent tailing of the phenolic compounds.
Mass spectral identifications were made by comparison to tabulated spectra libra-
ties 13'14 and confirmed by obtaining pure standards wherever possible. extracts were quantltated using QUANTID and IDFILE data system.
Compounds in the
programs supplied with the Hewlett Packard
Two modifications were made to the QUANTID procedure; the integral match window
was changed from one to three and the retention time scan window was changed from a value of 50 to I0 due to the sharpness of the capillary peaks.
QUANTID was successful in calculating
approximate concentrations; major peak concentrations were confirmed manually using the QUANTID formulas and reconstructed ion areas.
Although standard curves of the area ratios
of various organics and Dl0-anthracene were linear over several orders of magnitude, the results were only semi-quantitative since no attempt was made to evaluate recovery efficiencles in the
1625
extraction procedure
and the internal standard was added after the extraction was completed.
The concentrations reported are useful primarily for comparison purposes. Results and Discussion Hydrogeological investigations revealed that shallow groundwater was migrating to the north and east of the industrial site (Table I).
Wells 2, 5 and 6 were expected to
receive contaminants from the old lagoon since they were situated in the direction of groundwater flow. 2.
Groundwater parameters were determined with a pump test and are listed in Table The permeability of 495 gal/day-ft 2 is approximately that of a silty to clean sand. 15
Well logs taken in the study area showed the sands to be a coarse to fine-grained quartz sand and clayey sand with an approximate thickness of 30 to 35 feet.
A clay fraction ranging from
3.34 to 37.77 percent of the soil sample consisted of the clay mineral kaolinite and a clay size fraction of quartz.
Slight amounts of montmorillonite were found in several well logs
at depths of 5 to 7 feet.
The presence of montmorillonite below kaolinite suggests that the
upper soil consisted of fill material.
A blueish-gray highly plastic clay (Hawthorne Formation)
underlies the sands in this area and is estimated to be approximately 90 to 150 feet thick. This formation is the confining layer for the Floridan aquifer.
Table 2.
Summary of Groundwater Parameters II,400 gallons/(da~-ft) 495 gallons/day-ft ~ 0.24 - 0.53 ft/day 0.3 0.79 - 1.8 ft/day O. 004 0.152
Transmissivity Hydraulic Conductivity Discharge velocity Estimated Porosity Average Linear Velocity Storage Capacity Specific Yield
A typical chromatogram of a site 1 soil extract is shown in Figure 3 and the numbered peaks are identified in Table 3. terpenes and polynuclear hydrocarbons.
The compounds represented three categories; phenols,
Major compounds adsorbed to the soil included the
terpenes; alpha pinene, camphene, O-cymene and limonene; as well as dihydroxy acetophenone an alkyl phenanthrene.
and
All of these compounds have been listed as products of the destructive
distillation of resinous pines; and organics associated with pyroligneous acid, tar oils and charcoal. 16 The soil concentrations of selected compounds are shown by site in Table 4.
It
is obvious that there were negligible concentrations of compounds in the soil of 3, 4 and 7. This was expected since these areas were upgradient of the original lagoons.
The maximum con-
centrations of compounds were greatest in the soil of site 1 followed by site 6 with considerably smaller quantities at sites 2 and 5.
It was expected that the concentrations should be
high at site 1 due to the fact that the site was situated immediately over the old lagoons.
1626
Most
of
extent much
the compounds
associated
in t h e g r o u n d w a t e r
lower
due
concentrations
Figure
3.
Total
of
with
to t h e i r
low water
the c o m p o u n d s
Ion Current
~4
the soil would
found
Chromatogram
not
leach
solubilities. at s i t e s
of a S o i l
or migrate 17
2 and
This
was
to a s i g n i f i c a n t borne
out b y
5.
Extract
from
Site
i.
10
tt,
,.~
>~__I I. Toluene
23.
2,5-Dimethylphenol *
2. 3.
Ethylbenzene p-Xylene
24. 25.
Camphor * 3,5-Dimechylphenol *
4.
Dimethylfuran
26.
Borneol *
5. 6.
Ethsnone l-(2-furanyl) Cumenol
27. 28.
a-Terplnol Dihydroxyacetophenone *
7.
~-Pinene *
29.
Ethoxybenzaldehyde
8.
Camphene *
30.
Dimethylnaphthalene *
9.
Menthane
31.
Isopropylnaphthalene
I0.
Phenol
32.
Phenylphenol (deriv,)
II.
m-Terpinene
33.
C3 Naphthalene
12. 13.
C~ne * Limonene *
34. 35,
C 3 Naphthalene DI0 Anthracene (internal standard)
14.
B-Phellandrene
36.
Methylphenanthrene
15.
o~Cresol *
37,
Methylpheuanthrene
16.
m-Cresol *
38.
4-Epidehydrosbietal
17.
p-Cresol *
39.
C 2 Benzanthraeene
18.
A11o-oclmene
40.
Dlmethylphen~nthrene
19.
o_MethoxTpheno I *
41.
C3 P h e n a n t h r e n e
20. 21.
Fenchone * Fenchyl alcohol •
42. 43.
C 4 phenanthrene Methyldehydroabletate
22.
2,4-Dimethylphenol * c onf ir me d by comparin~ the r e t e n t i o n
Table
3.
Compounds
Identified
time and t h e ma•s spectrum to s p u r e • t a n d a r d
in t h e S o i l
Extract
from
Site
1 (Figure
3).
the
1627
The high concentrations to groundwater movement. concentrate
of compounds in the soll at site 6 could not be attributed
Compounds would not be expected to leach from site 1 and selectively
at site 6 without also concentrating
at 5.
This might occur if the sorptive capa-
city of the soil at site 6 was much greater than that at site 5, however there appeared to be little difference content data.
in the soil character at the two areas based on size fractionation
Another explanation was that the contaminated
located from the region near the old lagoon. of suspended material breaching
incident)
the industrial
and clay
soil at site 6 had been trans-
This movement may have been a result of deposition
in a drainage ditch that led from the lagoon (possibly during the dike
or as a result of physical movement during the construction
operations
for
park now located at the area.
Table 4.
Highest Reported Concentrations
of Selected Compounds
in Soll Analyses
C~/~ram) Compquqds S Lee
t
S tee
S ice 2
Sice
S Lee
S ice
Sice
3
&
5
6
7
I.
~-Plnene
285
15
N.D.*
N.D.
<0.5
23
N,D,
2.
Camphene
275
3
N.D.
N.D.
<0.5
117
g.D.
3.
p-Cymene
210
16
N.D.
N.D.
8
300
N.D.
4.
Limonene
920
10
N.D.
N.D,
2
660
N.D.
5.
o-Cresol
.55
34
N.D.
N.D.
12
21
N.D.
6.
D-Camphor
78
17
N.D.
N.D.
32
|t5
N.D.
7.
D1hydroxyacetophen(,ne
260
7
N.D.
N.D.
<0.3
<0.3
N.D.
8.
C -phen~nthrene
215
55
N.D.
N.D.
<0.3
175
N.D,
9.
Mechyldehydro-
405
163
N.D.
<0.3
360
N.D.
abtecace
*N.D. - noC d e c e = c e d
A typical histogram of the concentration shown in Figure 4. 5 - I0 feet, centrations leaching,
For most compounds,
the approximate
of
the greatest
~ -pinene with soil depth at site I is concentrations
depth of the groundwater
occurred in the region of
level below the surface.
The lower con-
in the vadose zone may have been a result of losses by volatilization,
and mechanical mixing with less contaminated
Highest concentrations
rainwater
soil during construction operations.
may have occurred at the groundwater
interface since the immiscible tars
and oils may have floated on the top of the saturated zone.
Ramsey et al. 18 observed a similar
phenomenon
in groundwater
samples taken with depth at a wood-treatlng
The concentrations
facility.
of compounds at various depths in the soll at the original lagoon
site (site I) could not be correlated with the percent sand, silt or clay content, apparent correlation between the coarse silt content and concentration
however an
of several compounds was
1628
obtained. 5.
A plot of percent coarse silt yrs. 0-cymene concentration is illustrated in Figure
It would be expected that the clay-size fraction would have the highest concentration of 19 The quan-
adsorbed contaminants primarily due to the large ratio of surface area to mass.
tity of compound adsorbed on a soll fraction, however, is a function of its partition coefficient and the percent weight of the soil fraction.
An intermediate grain size might adsorb
the largest quantity of compound if the smallest-size fractions were only minor components. This did not occur in our study since the percent clay-size fraction was often greater than the coarse silt.
The correlation obtained may simply indicate that adsorptive processes were
not dominant in retaining the compounds in the soil.
Often water contained oil droplets and
floating tars, indicating that some of the organic compounds existed as a separate phase.
Figure 4.
Histogram of the Concentration of =-Pinene with Depth at Site 1
~ 2*e ~ a,e
u ,2e
e@
e D l P T . ~FT,
Figure 5.
Correlation of 0-Cymene Concentration with the Coarse Silt Content in the Soll of Site I
, :o,s*
*-¢,1|.*
.C|.TnaT,O
i~e/el
1629
A summary of the major compounds and concentrations found in the water analyses is presented in Table 5.
The chromatograms are shown for comparison in Figure 6.
It is obvious
from the figure that Wells I, 2, 5 and 6 had similar pollutants whereas Wells 3 and 4 had quite different contaminants.
Wells over the old impoundment site (I, IA and IB) and those
along the path of the groundwater (Wells 2, 5 and 6) had the highest concentrations of phenolic compounds.
The concentrations were generally highest in Wells I and 6 followed by Wells
5 and 2.
Table 5.
Concentrations of Major Compounds in Water Samples Analyses (ug/l)
C~Dounds
1,
Well 1A
G-cresol mop-Cresol 2,5 - and 3,4Dimethyl phenol Methoxyl-phenol A l l y l pheno]
1700 3300 ND
1100 2300 3100
130 380
120 60
TOTAL PHENOL CONCENTRATIONS
5510
6680
Well 1B
Well 2
Well 3
Well 4
Well 4A
Well 4B
Well 5
Well 6
5200 11100 3300
920 3100 1800
4 3 I
<0.3 <0.3 4
9 50 130
22 95 2
1700 3800 3900
2900 6200 9400
Well 7
Phenols A. B. C. D. E.
2.
Well 1
3300 4.0 22900
15 30
1 <.._44
5865
9
O.S <._~3 4.5
ND <.3
2 0.4 3
ND 10
80 <2
340 570
2 2
189
129
g480
19410
9
2
Aromatic Hydrocarbons A. B, C. D.
I-Methyl Naphthalene 2-Methyl Naphthalene Naphthalene Acenaphthene TOTAL AROMATIC HYDROCARBONS
II
8
2
2
130
75
110
50
.9
50
14
.9
<2
3
70
60
80
40
1
60
2
90 ND
110 ND
140 ND
40
NO
710
740
860
670
140
330
_~
40
~_
115
118
142
45
1080
102fi
1220
815
140
440
47
170
lS0
17~0
S__ES
N~
3.
D-Camphor
1600
1200
1400
530
18
7
30
30
1500
16C0
12
4.
Borneol
4700
1700
790
640
2
1.4
20
2
3300
7100
7
S.
Alpha-Terpineol
hiD
140
410
90
2
<,2
<.3
3
80
390
2
6.
Dihydroxyacetophenone
2400
290
3300
380
<.3
<.2
<.3
<.3
<2
33C0
14
25
9
7,
FenchyI Alcohol
47
92
37
.3
.4
2
4
1200
97
8.
Fenchone
79
.7
2
20
<.I
<.I
2
S
200
27
I
9.
Limonene
2B
9
39
48
1
1
2
3
38
130
2
p-cymene
79
.7
2
<20
<.1
<.1
2
5
210
27
1
10.
*ND - Not Detected
Well 2 m a y h a v e received contamination as a result of some northerly groundwater flow, as well as the previous history of surface drainage to the swamp north of the site. Wells 5 and 6 received pollutants from northwesterly groundwater flow and surface drainage related to the dlke breaching incident.
It is interesting to note that site 5 was contaminated
with water soluble compounds but had negligible levels of water insoluble materials associated with the soil (Table 4).
This suggested that water transport had been the dominant mechanism
for contamination at this site.
1630
Figure 6.
Total Ion Current Chromatograms of Well Waters at Sites 1 - 6 Note that vertical scales are different (see Table 4).
.....
1
~...~.~
-
~L~._._L~.
WELL
I
6
,I
__j
TIME
?
.i~,A._._
Wells 3 and 4, upgradlent of the original phenolic
contaminants
contaminated acenapthene. (Figure 6).
contaminated
present in Wells I, 2, 5 and 6.
with high concentrations
of naphthalene,
The patterns of contamination The old surface impoundments
wells did not receive groundwater
_
0 9 101 1 1 2 1314 t S l ~ 17 181~ 2 0 2 1 2 2 2 3 2 4 2 E 2~ 2 , " 2 0 2 9 3 0 3 1 3 2 3 3 3 4 3 ~ .
area, did not contain the
However Wells 3 and 4 were similarly l-methyl and 2-methyl naphthalene
of the two wells were virtually
were not the source of these contaminants
from that area and the concentrations
since the
of these compounds at
3 and 4 were much greater than in any other well.
The destructive
involves a process in which an immiscible
such as benzene or naphth~ is used to
remove water from wood chips by azeotropic the presence of the naphthalene
solvent,
distillation.
and related compounds
more likely that these compounds may have originated
distillation
of pine stumps
This solvent addition may explain
in the groundwater.
Howeve~ it appears
from leaching at a location off the site.
Well 3, at the extreme western border of the property, was contaminated. treating facility and railroad
and
identical
tracks existed west of the area (Figure 2).
A similar wood-
1631
The concentration
of phenolic
contaminants
in Wells I, IA and IB showed the same
correlation with depth found with the soil samples.
Well
i, drilled to 25 feet had less phenol
than IA at 20 feet, and Well IB had the highest phenol concentration A stormwater detention pond presently lagoons
(Figure 2).
contaminated
exists directly over a portion of the old
A water sample from this pond did not contain compounds
groundwater,
lutants underneath
at 15 feet (Table 5).
indicating
that a bentonite
found in the
clay layer effectively
sealed the pol-
the pond.
It was apparent that surface water contamination was the primary source of pollution from the site. approximately
The drainage ditch bordering 2 - 3% of the concentrations
the east of the property contained phenols at
in the water of Well 6.
These concentrations
mained relatively constant until the ditch joined Hogtown Creek approximately northwest.
There was no evidence of deep groundwater
reduced by the time that the aquiclude was reached compounds were migrating
contamination,
re-
I mile to the
soil concentrations
were
(Figure 4), and there was no evidence that
through the aquiclude and into the Floridan aquifer.
Conclusions i.
Three major classes of compounds were found on the old industrial
and condensed aromatics.
site; phenols,
terpenes
All compounds were expected byproducts of the destructive distilla-
tion of pine stumps which had occurred at the site from the 1930's to 1967. 2.
The compounds partitioned
between soll and water as a function of their water solubilities.
The highly soluble phenols were present were found associated with the soil.
in water and insoluble compounds
The depth profile of compound concentration
of the original lagoon site was correlated with the coarse silt content. were probably not dominant 3.
throughout
site 6 were attributed vities.
Groundwater
soluble compounds 4.
Additional
in the lagoons.
in the soil
Adsorptive
processes
in retention of the compounds.
In addition to groundwater
contaminants
such as the terpenes
transport,
the area.
other mechanisms were responsible
High concentrations
to the former dike-breachlng
transport appeared
for distributing
of insoluble compounds
incident and subsequent
in the soil at
construction
to also be important due to the concentrations
acti-
of water
in the water of Wells 2 and 5.
contaminants
found in Wells 3 and 4 were not attributed
Contamination
gested that pollutants
to the compounds stored
at Well 3, at the extreme western border of the property,
from a railroad
spillage or other industrial
sug-
activity were migrating
to this area. 5.
The distribution
of compounds around the site suggested
entire area would not be cost-effective.
Since the greatest
curring as a result of surface water contamination,
that a general clean-up of the impact of the pollution
placement of an interceptor
is oc-
in the drainage
ditch along the eastern border of the property is being considered as a treatment alternative.
1632
The authors wish to thank Dr. Donald Robinson of the Cabot Carbon Foundation; Ron Ferland, Gainesville City Engineer and Nancy Gourlie of the Alachua County Pollution Control Federation for invaluable advice and cooperation, and Carl Miles and Kurt Batsel for help during the GC/MS portion of the work. John J. McCreary is now deceased. References i. T.H. Maugh, Science, 204, 819, 1979. 2. G.G. Ehrllch, D.F. Goerlitz, E.M. Godsy, M.F. Hult, Groundwater,
20, 703, 1983.
3, E.M. Godsy, D.F. Goerlitz, G.G. Ehrllch, Bull. Environ. Contam. Toxicol., 30, 261, 1983. 4. J.J. Delfino, Chapter 17 in Drlnking Water Qu~llty Enhancement Through Source Protection, R.B. Pojasek, Ed., Ann Arbor Science Pub. Inc., Ann Arbor, MI, 275, 1977. 5. J. Ball, in Proc. Ind. Waste Conf., 36, 195, 1982. 6. G.E. Thompson, Proc. Ont. Ind. Waste Conf., 25, 250, 1978. 7. J.V. Dust and W.S. Thompson, Forest Products Journal, 23, 59, 1973. 8. B.B. Sundaresan, E.C. Bovee, D.E. Wilson, J.B. Lackey, J. Water Polln. Cntrl. Fed., 37, 1536, 1965. 9. United States Environmental Protection Agency Region IV. Hazardous Waste Site Investigation Phase I, Cabot Carbon Site, Gainesville, Florida, 1980. 10. Environmental Protection Agency Handbook for Sampling and Sample Preservation of Water and Wastewater. Environmental Monitoring and Support Laboratory, Cincinnati, OH, 1982. 11. G.J. Bouyocous, Agronomy Journal, 54, 464, 1962. 12. Krumbein and Pettljohn, Manual of Sedimentary Petrology, Appleton -Century -Crofts, Inc., New York, 77, 1938. 13. Eight Peak Index of Mass Spectra. 1974.
Mass Spectrometry Data Centre.
AWRE Reading, U.K.,
14. Registry of Mass Spectral Dataa, E. Strenhagen, S. Abrahamsson, F.W. McLafferty, Eds., Vol. i - 4, John Wiley & Sons, New York, N.Y. 15. R. A. Freeze and J.A. Cherry, Groundwater, Prentice-Hall Inc., Englewood Cliffs, N.J., 1979. 16. J.A. Kent, Riegel's Handbook of Industrial Chemistry, Litton Educational Publishing, Inc., 1974. 17. Seidell, Solubilities of Organic Compounds, Inc., New York, 1941.
Vol. 2, 3rd. edition, D. Van Nostrand Co.,
18. W.L. Ramsey, R.R. Steimle, J.T. Chaconas, in Management of Uncontrolled Hazardous Waste Sites, 212, 1981. 19. T. Mill, e__~tal., Laboratory Protocols for Evaluating the Fate of Organic Chemicals in Air and Water. EPA Contract #68-03-2227 submitted to EPA Environmental Research Laboratory, Athens, GA. (Received
in The
Netherlands
21 A u g u s t
1983)