ENVIRONMENTAL PROTECTION AGENCY
OFFICE OF ENFORCEMENT
EPA-330/2-77-028
Compliance Monito ring
Commonwealth Oil Refining Company, Inc.
Penuelas, Puerto Rico
(August 1977)
NATIONAL ENFORCEMENT INVESTIGATIONS CENTER
DENVER, COLORADO
AND /
REGION II. NEW YORK 1
DECEMBER 1977
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ENVIRONMENTAL PROTECTION AGENCY
Office of Enforcement
EPA-330/2-77-028
COMPLIANCE MONITORING
COMMONWEALTH OIL REFINING COMPANY, INC.
Penuelas, Puerto Rico
August 1977
December 1977
National Enforcement Investigations Center - Denver
and
Region II - New York
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CONTENTS
I INTRODUCTION 1
II SUMMARY AND CONCLUSIONS 3
III RECOMMENDATIONS 6
IV SURVEY METHODS AND RESULTS 7
Flow Measurement 7
Sampling and Analysis 11
REFERENCES 25
FIGURE
1 Schematic of Wastewater Discharges
Commonwealth Oil Refining Co 9
TABLES
1 Final Effluent Limitations 13
2 Summary of Oil and Grease and
Sulfide Data 14
3 Field Measurements and Analytical Data . 15
4 Comparison of Compliance Monitoring
Results with Permit Limitations. ... 16
5 Organic Data 18
6 Toxicity of Organic Compounds 20
APPENDICES
A Reconnaissance and NPDES Inspection
B Flow Measurement
C Chain-of-Custody Procedures
D Water Quality and Sediment Sampling, Tallaboa Bay,
Puerto Rico
E GC-MS Analyses of Industrial Wastewater
Outfalls, Penuelas, P.R., and Selected
Fish Collections from Guayanilla-
Tallaboa Bay, P.R.
F Organic Analyses Methodology
G Laboratory Evaluation
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I. INTRODUCTION
The Commonwealth Oil Refining Company, Inc. (CORCO) at Penuelas,
Puerto Rico operates a Class C oil refinery-petrochemical facility
consisting of a 100,000 barrels/day (bbl/d) crude oil refinery and
50,000 bbl/d crude naphtha petrochemical works. The refinery receives
crude oil from South America and the Middle East for production of
gasoline, kerosene, jet fuel, diesel oil, fuel oil, propane, butane,
LPG, and naphtha. The petrochemical works converts naphtha to aroma-
tics, such as BTX (benzene-toluene-xylene), orthoxylene, and raffinate.
These compounds are intermediates which are used to produce plastici-
zers, emulsions, latexes, lacquers, paints, polyester fibers, tire
cords, nylon fibers, carpets, plastics, etc.
The Environmental Protection Agency (EPA) Region II issued a
National Pollutant Discharge Elimination System (NPDES) Permit No.
PR0000345 on November 21, 1974. The final effluent net limitations
became effective July 1, 1977 and continue through December 31, 1979.
CORCO was issued an Administrative Order on July 25, 1975, by the
EPA. The order cited numerous and serious violations of the NPDES
permit effluent limitations, including failure to submit an Implementa-
tion Plan and failure to perform prescribed thermal and analytical
monitoring. The Order dictated an abatement schedule and stipulated
that "any failure to carry out the requirements of this Order or the
remaining requirements of the permit will..." result in enforcement
action.
The CORCO Discharge Monitoring Reports (DMR's) through March 1976
showed monthly violations of initial permit limitations, although the
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2
Company had stated that it would meet its limitations by June 30, 1976.
EPA notified CORCO by letter, March 22, 1976, that no enforcement action
would be taken provided that the Company installed necessary equipment
to eliminate permit violations after July 1, 1976. However, the DMR's
after June 30, 1976 continued to show numerous NPDES permit violations.
EPA, Region II, New York, requested the National Enforcement
Investigations Center (NEIC) to determine the compliance of six in-
dustries in the Tallaboa Bay area, Puerto Rico. This report discusses
compliance of CORCO with its NPDES permit limitations. A reconnaissance
inspection of the CORCO facility was made March 31 to April 1, 1977 to
evaluate process operations, waste treatment facilities monitoring
locations and the status of compliance with permit schedules [Appendix
A]. The compliance monitoring survey was conducted August 9 through 11,
1977 by NEIC and Puerto Rico Environmental Quality Board (EQB) personnel.
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II. SUMMARY AND CONCLUSIONS
1. A compliance monitoring survey was conducted August 9 through 11,
1977 by NEIC and EQB personnel. All parameters limited in the NPDES
permit were monitored. In addition, CORCO effluent and Tallaboa Bay
sediment samples were analyzed for organic compounds. Based on infor-
mation provided by company officials, the refinery and petrochemical
plant were operating at 66,000 and 30,000 bbl/d (66 and 60% of capacity)
respectively at the time of the survey.
2. The NPDES permit requires that the company continuously monitor
temperature in both the Guayanilla Bay water intake and refinery discharge
(outfall 001) and discharge flows (outfalls 001 and 002). Company
personnel only measure instantaneous flows and temperature twice per
week. The permit also specifies that once through cooling water and
storm water runoff flows are to be measured. The company has not
complied with these requirements.
The discharge from outfall 001 ranged from 365,000 to 368,000
m /day (96.5 to 97.3 mgd). If these data are typical of normal flow
conditions, an instantaneous flow measurement would be within 10% of
the actual flow. Company personnel currently do not measure all waste-
water being discharged through outfall 002. A flow meter (i.g., venturi
meter) should be included in the discharge line downstream of all waste-
water sources.
3. Survey results show that CORCO was in violation of both the
daily average and daily maximum NPDES limitations for BOD, T0C, oil and
grease, sulfide, phenol and ammonia. The maximum temperature limita-
tions were also exceeded. The waste loads and temperatures found
during the survey and those permitted are compared below:
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4
Permit Limitations Survey Data
Daily Avq. Daily Max. Daily Avq. Daily Max.
kg/day lb/day kg/day lb/day kg/day lb/day kg/day lg/day
BOD
282
620
523
1,150
2,210
4,870
2,780
6,140
TOC
620
1,379
1,150
2,530
675
1,490
1,400
3,080
Oil and
Grease
90
198
168
369
1,300
2,870
2,455
5,420
Phenol
1.83
4.03
3.78
8.33
260
570
593
1,295
Ammonia
(N)
188
260
354
780
715
1,570
819
1,800
Sulfide
1.5
3.31
3.36
7.38
130
290
220
490
Temperature-001
(Gross °
(Net °C)
c)
36.7
7.2
39
9
002 (Gross °
c)
30
44
4. The analytical results show that CORCO discharges petroleum hydro-
carbons, alkanes, substituted alkanes and aromatics to Tallaboa Bay.
(Three of the organic compounds found in the CORCO discharges (bi-
phenol, bromoform and naphthalene) appear on the Natural Resources
Defense Council - EPA list of Priority Pollutants. Several of the
compounds were also identified in Tallaboa Bay sediment samples which
show that the CORCO discharges are contributing to the buildup of
organic materials in the Bay.
Analytical data on fish flesh collected at the time of a fish kill
in February 1977, as well as subsequent to the kill, show that the fish
contained seven organic compounds.
Seven of the organic compounds identified in the CORCO wastewaters
have known aquatic toxicity. These data show that 5 compounds (cumene,
toluene, trimethylbenzene isomer, p-xylene and o-xylene) were only
slightly toxic and the other 2 (dicyclopentatrene and napthalene) are
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5
moderately toxic. Discharge concentrations of the two substances,
however, were only in the range of 1/20 to 1/100 of the 96 hour median
tolerance limits. In addition, toluene, m-xylene and p-xylene are known
to cause fish tainting.
5. The C0RC0 analytical laboratory performs NPDES self-monitoring
analyses. An evaluation of this laboratory showed that the Company was
not performing BOD and oil and grease analyses according to approved
methods. Specifically BOD blanks were not run to determine if the solu-
tion water exerts a BOD demand and from blanks contain residues as high
as 1/mg/l indicating possible freon contamination. Also, the laboratory
does not have an analytical quality control program.
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III. RECOMMENDATIONS
It is recommended that the Commonwealth Oil Refining Company,
Inc. be required to:
1. Install, maintain and calibrate monthly continuous flow measure-
ment devices on outfalls 001 and 002, and temperature recorders on
outfall 001 and the Guayanilla Bay water intake.
2. Install additional biological or similar treatment and/or modify
process operations as required to reduce BOD, oil and grease, phenol,
ammonia and sulfide waste loads by 6, 13, 140, 5 and 85 times, respectively.
3. Install additional cooling towers or cooling ponds to reduce the
temperature to a maximum of 27 and 30°C respectively for outfalls 001
and 002.
4. Initiate an analytical quality control program which includes a
regular program of replicate and spiked samples to determine precision
and accuracy of analyses performed.
In addition it is recommended that the company be required to
monitor its discharges for organic compounds and that limits be
established for specific organic compounds based on one year's self-
monitoring data.
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IV. STUDY METHODS AND RESULTS
The water supply for the CORCO facility includes two salt water
intakes (one from Guayanilla Bay and the other from Tallaboa Bay), a
desalinization plant and well water. The salt water is used for cooling
and desalnization plant feed. The desalinized and well water are used
ic
for boiler feed, process, cooling and domestic purposes.
The refinery wastewater treatment facility consists of a sour water
stripper, caustic waste neutralization, API separators and lagoon system
prior to the discharge channel. Wastewater treatment in the petro-
chemical works includes an API separator, storm surge pond, and air
stripping unit which removes light aromatic hydrocarbons. All treated
process wastewaters, noncontact cooling water, tank farm drainage, storm
waters, boiler blowdowns, and desalination plant blowdown are discharged
into Tallaboa Bay through two outfalls designated as 001 and 002.
Domestic wastes are disposed of in septic tanks.
FLOW MEASUREMENT
According to the CORCO NPDES permit, flow is to be measured con-
tinously for both outfalls 001 and 002. Continuous flow recorders were
to be installed by August 31, 1975. Once-through cooling water flows
are to be either directly measured or calculated weekly. Storm water
runoff which receives treatment is to be measured and recorded daily.
In addition, all storm water segregated from the wastewater treatment
system is to be either directly measured or calculated whenever such a
discharge exists. At the time of survey, the company had not complied
with these permit requirements.
* One cooling tower located in the petrochemical plant uses fresh water.
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8
Once-through cooling water, treated refinery process wastewater,
tank farm drainage, and storm waters are discharged into Tallaboa Bay
through a channel designated as outfall 001 [Figure 1]. Company person-
nel calculate instantaneous flows by measuring the water depth and
surface velocity as the wastewater passes through three 72-inch culverts
[Appendix B]. Surface velocity is determined by timing a floating
object as it passes through the center culvert. This velocity is then
multiplied by 0.8 to obtain average velocity. The company has developed
a graph which is used to convert water depth to cross sectional area;
assuming that equal volumes pass through each conduit, flow is then
calculated (i.e. Q = 3VA) [Attachment 1 of Appendix B].
NEIC and EQB personnel also measured outfall 001 flows at the
culverts. To assure equal flow through each culvert, the elevations on
each end of the. pipes were checked and flow through each pipe was measured.
Results verified that each culvert was installed at the same grade and
contained one third of the flow. NEIC flow values were compared to
those obtained using the company method (i.e. floating object). Results
show that the calculated flow was + 5% of the measured flow. [Appendix
B].
During the survey, the outfall 001 discharge flow was calculated
from hourly velocity measurements using a magnetic flow meter. Flows
ranged from 365,000 to 368,000 m^/day (96.5 to 97.3 mgd). If these flow
data are typical then the instantaneous flow data being submitted by
C0RC0 on DMR's are within 10% of actual flow.
The petrochemical works process wastes and noncontact cooling
water, desalination plant blowdown, and boiler blowdown are discharged
approximately 305 m (1,000 feet) into Tallaboa Bay through a submerged
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9
Samp 1ing
Station
CORCO
Petrochemical
Plant
CORCO
Refinery
Oxochem Discharge
Process wastes and
cool l ng-wate4
Caribe
Isoprene
Discharae
agoons
Puerto Rico
Olefi ns
Di scharae
y ^Sampling Station
Outfall 001
TALLABOA BAY
Outfall 002
Figure 1. Schematic of Wastewater Discharges
Commonwea 1 th Oil Refining Company
Penuelas, Puerto Rico
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10
pipe (outfall 002) [Figure 1]. Company personnel indicated that flow
was measured using a pitot tube [Appendix A]. Information obtained at
the time of the survey, however, show that flow in outfall 002 is determined
using meters which record desalination plant cooling water and blowdown
rates and by calculating cooling tower blowdown rate [Appendix B] . The
treatment plant effluent however is not measured. The company should
install a flow meter (e.g. orifice meter, magnetic flow meter, venturi
meter, etc.) downstream of all petrochemical wastewater sources to
continuously measure the total amount of wastewater being discharged, a
NPDES permit requirement.
During the survey, NEIC and EQB personnel obtained hourly flows in
outfall 002 by using the company installed meters and calculating cooling
tower blowdown. Results show that the discharge from desalination plant
and cooling tower remained essentially constant ranging from 44,000 to
45,000 m /day (11.6 to 11.9 mgd). Due to the configuration, it was not
possible to measure either the wastewater treatment or total petro-
chemical plant discharge. The obtained flow data therefore are less
than actual and loads calculated on these data are conservative.
Company personnel measured the incoming sea water flows using a
3
pitot tube. These flows were reported as 436,000 and 54,500 m /day
(115.2 and 14.4 mgd), respectively for the Guayanilla Bay and Tallaboa
Bay intakes. As the pumping rate remained constant, these data are
considered applicable for the entire survey.
* This outfall line also receives wastes from Oxochem Enterprise,
Caribe Isoprene Corporation and Puerto Rico Olefins.
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11
SAMPLING AND ANALYSIS
The NPDES permit requires CORCO to sample each discharge (outfalls
001 and 002) twice per week. With the exception of oil and grease, all
samples are to be flow-weighted 24-hour composites. Oil and grease
samples are specified as grab. Company personnel use automatic samplers
to collect equal volume time composites. At the time of the reconnais-
sance inspection all analyses, including oil and grease, were being
performed on these 24-hour composite samples [Appendix A]. Company
officials were advised that the permit specified oil and grease grab
samples and subsequently the Company corrected its procedures.
As previously noted the flows in outfall 001 remained fairly constant
(i.e. within + 10%) during the study. If these flows are typical, then
the results from both the time-weighted and flow-weighted composits
should be comparable.
The permit also requires that the company continuously monitor the
temperature of the Guayanilla Bay water intake and refinery discharge
(outfall 001). The Company currently measures temperatures based on
grab samples, twice per week.
During the reconnaissance inspection [Appendix A] potential prob-
lems with sampling locations were noted. Prior to the compliance monitoring
survey, however, EQB and NEIC personnel determined that outfall 002
sampling location provided representative samples (flow was turbulent)
and outfall 001 sampling station was not influenced by wind or tidal
actions (dye introduced into the outfall showed positive flow under
these conditions). Based on the above observations, samples were collected
at the same points used by the company.
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12
Compliance monitoring was conducted August 9 to 11, 1977 by NEIC
and EQB personnel. Monitoring was performed for all parameters speci-
fied in the NPDES permit [Table 1]. The seawater intakes were sampled
to ascertain net pollutant loads. Effluent (outfalls 001 and 002) and
intake samples were manually collected hourly and composited on a flow-
weighted basis. Grab samples were collected three times daily for oil
and grease and sulfide analyses. Grab samples were also collected twice
for organic analyses. All samples were preserved and/or stored at 4°C
until analyzed. Field measurements of pH and temperature were made
periodically. Analyses for BOD, TSS, oil and grease, phenol and sulfide
were performed by EQB and NEIC personnel in a field laboratory located
at Parguara. All other samples were air freighted to the NEIC laboratory,
Denver, Colorado. Established chain-of-custody procedures [Appendix C]
were followed in the collection of all samples and field data and for
all laboratory analyses.
Limited water quality monitoring [Appendix D], including sediment
sampling, was conducted August 14 in Tallaboa Bay. Fish collected from
the Bay by the U.S. Coast Guard and fishermen as a result of and subsequent
to a February 1977 fish kill were analyzed by NEIC for organic compounds
[Appendix E].
Results of the compliance monitoring are contained in Tables 2 and
3. A comparison of these results with the permit limitations [Table 4]
shows that the Company exceeded both daily maximum and daily average
BOD, TOC, oil and grease, sulfide, phenol and ammonia criteria. The
maximum temperature limitations for both outfalls 001 and 002 were also
exceeded daily. The daily average BOD, oil and grease, phenol, ammonia
and sulfide loads, for example, were 2,210, 1,300, 260, 715 and 130
kg/day respectively, which are more than 6, 13, 140, 5 and 85 times
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13
Table 1
FINAL EFFLUENT LIMITATIONS
(Effective July 1, 197?)
COMMONWEALTH OIL REFINING COMPANY3 INC.
PENUELAS3 PUERTO RICO
Discharge Serial No. Parameter
Discharge Limitation (Net)
Daily Avg.
Daily Max.
kg/day lb/day kg/day lb/day
Total for 001 & 002
(Dry weather flow)t
001
002
Flow
_
BOD,
282
620
523
1,150
T0C
620
1,379
1,150
2,530
TSS
184
405
314
691
Oi1/grease
90
198
168
369
Phenols
1.83
4.03
3.78
8.33
Ammonia as N
118
260
354
730
Sulfides
1.5
3.31
3.36
7.38
Total Chromium
4.59
10.1
7.91
17.4
Hexavalent Chromium
0.078
0.171
0.445
0.98
pH
range 6-9
Thermal limits
Thermal limits
a) Maximum discharge temperature
not to exceed 36.7°C (98.0°F)
b) The discharge intake temperature
difference shall not exceed
7.2°C (13.0°F)
c) The net amount of heat added
to the receiving water shall
not exceed 0.153 Billion K cal/hr
(0.607 Billion Btu/hr)
The maximum discharge temperature
shall not exceed 30.0°C (36.0°F)
t During storm water runoff, the following loads may be added to the above
limitations, providing the excess flow is properly measured (+ 15%):
3 "3
kg/m Ib/m gal kg/m lb/m gal
BOD
0.026
0.21
0.048
0.040
Tor
0.057
0.462
0.106
0.88
TSS
0.017
0.13
0.029
0.24
Oi 1/grease
0.008
0.067
0.015
0.126
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14
Table 2
SUil'ARY OF OIL AND GREASE AND SULFIDE DATAf
COl-O'.'xTALTH OIL REFI.IIIIG COMPANY, IilC.
PeruclGC, Puerto Rico
Station Description Date
(Aug )
Instantaneous Flow
Oil
and Grease+'
Sulfide
mVday
mgd
mg/1
kg/day
lb/day
mg/1
kg/day
lb/day
Guayanilla Bay 9
436,000
115 2
<2
<0 2
Water Intake
436,000
115 2
<2
<0 2
436,000
115 2
<2
<0 2
10
436,000
115 2
4
1,750
3,840
<0 2
436,000
115 2
5
2,180
4,800
0 2
85
190
436,000
115.2
3
1,310
2,880
0 2
85
190
4-
Daily load'
4-4.
1,750
3,840
55
125
11
436,000
115.2
2
870
1,920
<0 2
436,000
115 2
<1
<0 2
436,000
115 2
3
1,310
2,880
<0.2
Daily load
725
1,600
Tallaboa Bay 9
54,500
14 4
3
165
360
<0 2
Water Intake
54,500
14.4
6
330
720
<0 2
54,500
14 4
<2
<0.2
Daily load
165
360
10
54,500
14 4
7
380
840
<0 2
54,500
14.4
6
330
720
<0.2
54,500
14 4
5
270
600
<0 2
Daily load
330
720
11
54,500
14 4
<1
<0 2
54,500
14 4
2
no
240
<0 2
54,500
14 4
<1
-
Daily load
35
80
Refinery Wastewater 9
383,600
101 3
6
2,300
5,070
0 8
310
680
Discharge
383,600
101 3
8
3,070
6,760
<0.2
(outfall 001)
359,800
95 1
5
1,800
3,960
1.0
360
790
Daily load ^
2,390
5,260
220
490
Met Daily load' 1'
2,390
5,260
220
490
10
383,600
101.3
4
1,540
3,380
<0 2
341 ,100
90 1
17
5,800
12,800
0 5
170
380
325,500
86 0
4
1,300
2,870
0 5
160
360
Daily load
2,880
6,350
110
250
Net Daily load
1,130
2,510
55
125
11
373,000
98 6
2
750
1,640
<0 2
381,800
100 9
4
1,530
3,370
0.5
190
420
325,500
86.0
1
330
720
-
Daily load
870
1,910
60
140
Net Daily load
145
310
60
140
Petrochemical 9
43,900
11 C
4
170
390
<0.2
Wastewater
44,300
11 7
6
270
590
<0.2
Discharge
43,900
11 6
6
260
590
<0 2
<0utfa" 002> Daily load
230
523
Net Daily load
65
160
10
44,300
11.7
4
180
390
0 5
22
49
44,700
11.8
6
270
590
0 5
22
"9
43,900
11 6
4
130
390
2.8
123
270
Daily load
210
455
56
123
Net Daily load
0
0
56
123
11
44,300
11 7
_
<0 2
44,700
11 C
6
2/0
S°fi
<0 2
43,100
11.4
3
130
235
<0.2
Daily load
200
440
Net Daily load
165
360
~ Data based or grab canplcs, loads ~c.cea on irstanvareous flows.
*+ Hcxana CTtractaolc materials
+ J"{' Daily load io the avcra c of tie C i>ist^rtareou3 loads for any one day
Ttrt ,Jcc daily lo^z is dtscraracd locc *".* us intake load
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Table 3
FIELD MEASUREMENTS AND ANALYTICAL DATA*
COMMONWEALTH OIL REFINERY CO'lPANY, INC.
PemtelaSj Puerto Rico
Station
Description
0ate++
Aug.
Flow
pH
Range
Temp.
Range
°C
B00
TSS
Phenol
T0C
Ammonia
mJ/day
(mgd)
mg/'
1 kg/day
(lb/day)
mg/l
kg/day
(lb/day)
mg/l
kg/day
(lb/day)
mg/l
kg/day
(1b/day
mg/l
)
kg/day
(lb/day)
Guayamlla Bay
10
436,000
7.2-8.8
28-30
<2
14
6,100
<0.01
4
1 ,740
0.01
4.4
Water Intake
(115.2)
(13,450)
(3,840)
(9-6)
11
436,000
7.2-8.2
29-33
<2
8
3,490
<0.01
4
1,740
<0.01
(115.2)
(7,690)
(3,840)
12
436,000
7.1-8.2
29-31
<2
10
4,360
<0.01
4
870
<0.01
(115.2)
(9,600)
(1,920)
Tallaboa Bay
10
54,500
6.4-9.0
29-33
<2
8
435
0.08
4.4
5
270
<0.01
Water Intake
(14.4)
(960)
(9.6)
(600)
11
54,500
7.0-8.6
28-32
<2
8
435
<0.01
2
110
<0.01
(14.4)
(960)
(240)
12
54,500
6.9-8.3
28-32
<2
6
325
<0.01
2
110
<0.01
(14.4)
( 720)
(240)
Refinery Waste-
10
368,300
6.3-8.9
35-39
5
1,840
16
5,900
0.24
88
6
2,210
2.21
815
water Discharge
(97.3)
(4,060)
( 13,000)
(195)
(4,870)
(1 ,790)
(Outfall 001)
11
365,200
7.1-8.3
35-38
5
1,830
9
3,290
0.26
95
5
1,830
1.83
670
(96.5)
(4,030)
7,240
(210)
(4,020)
( 1 ,470)
12
366,300
6.6-8.8
35-39
7
2,560
10
3,660
1.6
590
6
2,200
1.77
650
( 96.8)
( 5,650)
8,070
( 1 ,290)
(4,840)
( 1,430)
Petrochemical
10
44,000
7.1-8.6
38-44
<3
10
440
0.06
2.6
5
220
0 09
4.0
Wastewa ter
(11 6)
(970)
(5.8)
(490)
(8.7)
Di scharge
(Outfall 002)
11
45,000
5.1-8.8
36-44
4
100
13
580
0.06
2.7
4
180
0.04
1.8
(11 9)
(400)
(1,290)
(6 0)
(400)
(4.0)
12
44,000
7.6-8.2
40-44
5
220
11
480
0.06
2 6
4
180
0.09
4.0
(11.6)
(490)
(1,070)
(5.8)
(400)
(8.7)
t Sarnples were also analyzed for total and hexavalent chronrtiun. All sanjiles were less than the detectable
hints (i.e. 0.02 and 0.01 mg/l).
tt Date is ending date of composite sample (i.e. composite from OGOO 8/9 to 0500 8/10 will be dated 8/10).
+ tt Lero than values were reported on samples which had insufficient depletion.
-------
16
Table 4
COMPARISON OF COMPLIANCE MONITORING RESULTS
WITH PERMIT LIMITATIONS
COMMONWEALTH OIL REFINERY COMPANY, INC.
Net Permit Limitations Net Survey data t
Dai1y Avq. Dai 1y Max. Daily Avq Daily Max.
Parameter kg/day lb/day kg/day lb/day kg/day lb/day kg/day lb/day
BOD
282
620
523
1,150
2,210
4,870
1,840-
2,780
4,060-
6,140
TOC
620
1,379
1,150
2,530
675
1,490
160-
1,400
340-
3,080
TSS
184
405
314
691
100
230
5-
155
10-
690
Oil and Grease
90
198
168
369
1,300
2,870
310-
2,455
670-
5,420
Phenol
1.83
4.03
3.78
8.33
260
570
88-
593
195-
1,295
Ammonia (N)
188
260
354
780
715
1,570
654-
819
1,440-
1,800
Sulfide
1.5
3.31
3.36
7.38
130
290
60-
220
140-
490
Total Chromium
4.59
10.1
7.91
17.4
0
0
0
0
Hexavalent
0.078
0.171
0.445
0.98
0
0
0
0
Temperature-001
Max.
Max.
(Gross)
(Net)
36.7°C
7.2°C
38-39
5-9
Heat added to receiving
water (Net) 0.507
bi11 ion
Btu/hr
0.309-0
560
002
Max.
(Gross)
30°C
36-44
t Net survey data are the suns
of the net loads from both
outfalls 001 and 002
-------
17
the permit limitations. At the time of the survey the refinery and
petrochemical plant were only operating at 66,000 and 30,000 barrel/ day
(66 and 60% capacity), respectively.
Samples were collected of both C0RC0 discharges for organic analyses
[Appendix F]. The results show that these discharges contained petroleum
hydrocarbons, alkanes, substituted alkanes, and many aromatics at levels
ranging in concentration from 5 to 540 ppb [Table 5]. Comparison of
these organic compounds with the Registry of Toxic Effects of Chemical
Substances1 (RTECS) show that 17 have known toxic effects. Three of the
compounds found in the C0RC0 discharges (biphenyl, bromoform and naphthalene)
appear on the Natural Resources Defense Council - EPA list of Priority
*
Pollutants.
Toxicity data on the 17 compounds listed in RTECS are presented in
Table 6. These data were correlated by Chemical Abstract Service number
and molecular formula to distinguish between compounds of the same name
that may have widely differing toxic effects. Aquatic toxicity data
were available for 7 compounds. Dicylopentadiene and naphthalene are
considered moderately toxic in the aquatic environment and the remaining
five compounds (cumene, toluene, trimethylbenzene isomers, p-xylene and
o-xylene) are slightly toxic;1 test organisms were usually fin fish.
The range of reported 96-hour median tolerance limits (TLrrigg) for each
compound is listed in the table.
As shown in Table 5, about 2 kg (4 lb)/day of dicyclopentadiene was
present in the discharge from outfall 002 on both August 9 and 11. The
discharge of naphthalene from outfall 001 was 9 kg (19 lb)/day on August
11 and 60 kg(131 lb)/day on August 9. Concentrations of the two substances
were in the range of 1/20 to 1/100 of the TLnigg. Discharges of the
slightly toxic xylenes were larger (29 to 108 kg/day), but concentrations
* Consent Decree: Natural Resources Defense Council v. Train,
June 8j 1976.
-------
Table f.
ORGANIC DATA
COMMONWEALTH OIL REFINING COMPANY, INC.
Penuelas, Puerto Rico
Parameter
Reten.+~1'
Time Date
(Mm ) (Aug.)
Guayamlla Water Intake
Cone. Load
ug/1 kn/day lb/day
Tallaboa Hater Intake
Load
Cone.
po/i kn/day 1b/day
Cone
vg/1
001 Discharge
Load
kg/day lb/day
002 Discharge
Load
Cone.
yg/1 kg/day 1b/day
.'-I + p - xylene
4.4
9
280
108
2 37
80
4
8
11
. 180
69
152
25
1
2
[iromoform
4.5
9
40 18 39
0-xylene
4 8
9
100
38
85
60
3
6
11
75
29
63
45
2
4
Cumene (isopropylbenzene)
5.4
9
5
2
4
M-ethyl toluene
6.2
9
75
29
63
11
35
13
30
1,3,5-Trimethylbenzene
6.3
9
55
21
47
11
30
12
25
0-Ethyltoluene
6.6
9
45
17
38
6
0.3
0.6
11
23
9
19
1,2,4-Trimethylbenzene
6.9
9
150
58
127
11
40
15
34
4,4-Dimethyl-2-Pentanone
rrimethylbenzene Isomer
Dicyclopentadiene
Bieye 1odihydrocyclopentadlene
Isomer
7.1
7 2
7.5
7.75
8.2
0.1
0.3
80
35
31
13
68
30
0 4
0.9
20
0.6
1 .4
45
2
4
47
1 .4
3.1
45
2
4
6+
0.2
0.4 .
Indan
8.3
9
11
30;
111
12
5
25
12
Sec Butyl Benzene
8.8
9
11
45I
14I
17
5
38
12
Methyl Isopropylbenzene
9.0
9
11
451
14
17
5
38
12
Dihydro-3a,4,7,7a-Tetrahydro-4,7-
4.
Methanoindene Isomer
9.2
11
U 0.03 0 1
II II
9.5
11
1 0.03 0.1
Undecane
9.5
9
50
19
42
7
0 3
0.7
11
6
2
5
9
0.4
0.8
Naphthalene
11.2
9
11
155
23.
60
9
131
19
Dimethyl Indan
11.6
9
45I
17
38
11
14
5
12
Dodecane
11.9
9
65
25
55
6
0.3
0.6
11
6.
2
5
9
0 4
0.9
6-Methyl Benzo(b)Thiophene
13.1
9
11
45}
17
17
7
38
14
2-Methyl naphthalene
13.7
9
330
127
279
17
0 8
1.7
11
240
92
203
40
1 8
3.9
-------
Table S (Cont, )
ORGANIC DATA
COMMONWEALTH OIL REFINING CCUPANY, INC.
Penuelas, Puerto Rico
Reten. Guayamlla Water Intake Tallaboa Hater Intake 001 Discharge 002 Discharge
Parameter Time Date Cone. Load Cone. Load Cone. Load Cone. Load
(Mm.) (Aug.) pg/1 kg/day lb/day ug/1 kq/day lb/day pg/1 ka/day lb/day yg/1 kg/day lb/day
Tridecane
14.2
9
25
10
21
Biphenyl
15.3
9
55
21
47
50
2
5
11
9
4
8
65
3
6
Ethyl naphthalene
15.9
9
70
27
59
50
2.3
5
11
125
48
106
30
1.3
3
Tetradecane
16.2
9
11
40
30
1.8
1.3
4
3
Dimethyl naphthalene Isomer
16.3
9
490
188
415
11
315
121
267
1,2-Dimethylnaphthalene
16.5
9
540
207
457
170
8
17
11
485
186
410
100
4
10
Dimethyl naphthalene Isomer
16.9
9
130
50
110
45
2
4 5
11
150
58
127
17
0.8
1 .7
II
1J 3
9
20
1
2
Pentadecane
18.4
9
80
31
67
40
1 8
4
11
30
12
25
30
1.3
3
Trimethylnaphthalene Isomer
18.8
9
60
23
51
100
5
10
11
100
38
85
60
3
6
II
19.5
9
45
17
38
75
3
8
11
75
29
63
45
2
4
II
19.7
9
30
15
20
75
3
8
11
45
17
38
50.
2
5
Methyl Acenaphthalene
19.9
9
11
6s;
45
3
2
6
4
llexadecane
20.4
9
60
23
51
40
1.8
4 0
11
35
13
30
35
1.6
3.4
Heptadecane
22 3
9
70
27
59
70
3
7
11
55
21
47
60
3
6
Pristane
22.4
9
40
1.8
4.0
11
.J.
40
1.8
4 0
Dibenzothiophene
23.2
9
1 5
6
13
Octadeeane
24.2
9
60
23
51
65
3
7
24.5"
11
40
15
34
50
2
5
Phytane
9
30
1.4
3.0
11
30*
23t
1.0
2.2
Methyl Phenanthrene
26.2
9
12
25
30j
1 4
3.0
11
14
5
12
1 5
0.7
1.5
Monadecane
26.7
9
60
23
51
70
3
7
11
23
9
19
50
2
5
Eicosane
29.9
9
30
12
25
55
2 5
5.5
11
14
5
12
30
1.3
2.9
Heneicosane
34.1
9
15
6
13
30
1.4
3 0
11
6
2
5
17
0.8
1.7
t Compound identified but not confirmed by mass spectrometry. Standards were not available at time of report.
tt Retention time is the actual time compounds remained in the column (after eanple injection) before the date peak was recorded.
-------
Table 6
TOXICITY Or ORG'NIC COMPOUND^
Compound Name
Hoiecular
Formula
Chemical
Abstracts
Service No
Aquatic Toxicity
TT
Other Toxicity Data
tt
Recommended Limits
Anthracene
C14 H10
Binhenyl *-i2H10
Bromo form
(Methane,
Trlbromo-)
Cumene
Dicyclopentadiene
CHBr,
C9H12
C10H12
120-12-7
92-52-4
75-25-2
98-82-8
77-73-6
NR
NR
NR
TLm96 100-10 ppm
Oral-rat, TDLo 18 gm/kg/78 WI,
carcinoqenic effects, subcutan-
eous-rat, TDLo 3,300 mg/kg/33 WI,
neoplastic effects
Inhalation-human, TDLo 4,400
pq/m , irritant effects, oral-rat,
LD50 3,280 mg/kg, subcutaneous-
mouse, TDLo 46 mg/kg, neoplastic
effects, oral-rabbit, LD50 2,400
ng/kg
Subcutaneous-mouse, LD50 1,820
mg/kg, subcutaneous-rabbit, LD50
410 mg/kg
Oral-rat, LD50 1,400 mg/kg. In-
halation-rat, LC50 8,000 ppm/4H,
inhalation-mouse, LCLo 2,000 ppm
TLm96 100-10 ppm Oral-rat, LD50 353 mg/kg, mhalation-
rat, LCLo 500 ppm/4H, lntraperi-
toneal-rat, LD50 200 mg/kg, mtra-
oeritoneal-mouse, LD50 200 mg/kg,
skin-rabbit, LD50 5,080 mg/kg
NR
OSHA Standard (a 1r)
TWA 0 2 ppm
OSHA Standard (air)
TWA 0 5 ppm (skin)
OSHA Standard (air)
TllA 50 ppm (skin)
ACGIH RL {air)
TLV CL 5 ppm
o-Ethyltoluene
Indan
Nanhthalene
C9H12
C9H10
C10H8
611-14-3 NR Oral-rat, LDLo 5,000 mg/kg
496-11-7 NR Oral-rat, LDLo 5,000 mg/kg
91-20-3 TLm96 10-1 npm Oral-child, LDLo 100 mg/kg,
oral-rat, LD50 1,780 mg/kg,
subcutaneous-rat, TD 3,500 mg/kg/
98 DI, neoplactic effects, mtra-
peritoneal-mouse, LDLo 150 mg/kg
NR
MR
OSHA Standard (air)
TWA 10 ppm
Phenanthrene
C14H10
85-01-8
NR
Oral-mouse, LD50 700 mg/kg, skin-
nouse. TDLo 71 mg/kg, neoplastic
effects
NR
1 ' ' ' '' '' ' "J 'h'Jic hlJacte oj Chemical Substance-, - Nlull!
' USfi Col}"mS are m - not reported, TUn«r, - nfi-ho., and Health Act of 1"70, '
1WA - t inj-ueifjhted average concentration, ACf.IH - American Conference of Government Industrial Hyqien
lets, TLX - threshold limit value, CL - cetltnn
no
o
-------
Table 6 (Continued)
TOXICITY OF ORGANIC COfPOUNDS1
Compound Name Molecular Chemical Aquatic Toxicity Other Toxicity Data Recommended Limits
Formula Abstracts
Service No.
Sec Butyl Benzene ^10^14
135-98-8
NR
Toluene
C7H8
Trimethylbenzene CqH,?
Isomers
1 ,2,4-Trimethylbenzene CgH-jj
1,3,5-Trimethylbenzene C0H,,,
(Mesitylene)
m-Xylene C8H10
p-Xylene CgH1Q
108-88-3 TLm96 100-10 ppm
95-63-6
108-67-8
NR
NR
108-38-3
106-42-3
Oral-rat, LD50 2,240 mg/kg
Inhalation-human, TCLo 200 ppm;
inhalation-man, TCLo 100 ppm,
oral-rat, LD50 5,000 mg/kg,
inhalation-rat, LCLo. 4,000 ppm/
4H, intraperitoneal-rat, LDLo.
800 mg/kg, subcutaneous-rat,
LDLo- 5,000 mg/kg, intraperi toneal -
rat, LD50 1,640 mg/kg; inhalation-
mouse, LC50: 5,300 ppm, skin-rabbit,
LD50- 14 gm/kg
25551-13-7 TLm96: 100-10 ppm NR
NR
TLm96. 100-10 ppm
Oral-rat, LDLo: 5,000 mg/kg;
intraperitoneal-rat, LDLo 2,000
mq/kq, lntraperitoneal-guinea pig,
LDLo 1 ,788 mg/kg
Inhalation-human, TCLo- 10 ppm,
inhalation-rat, LCLo 2,400 ppm/
24H, intraperitoneal-rat, LDLo'
1 ,500 mg/kg, intraperitoneal-
guinea pig, LDLo 1,303 mg/kg,
effects central nervous system
Oral-rat, LD50- 5,000 mg/kg,
inhalation-rat, LCLo 8,000 ppm/
4H, intraperitoneal-rat, LDLo
2,000 mg/kg, subcutaneous-rat,
LDLo 5,000 mg/kg
Oral-rat, LD50 5,000 mg/kg,
intraperitoneal-rat, LDLo 2,000
mg/kg, subcutaneous-rat, LDLo
5,000 mg/kg; inhalation-mouse,
LCLo 3,400 ppm
NR
0SHA Standard (air)
TWA 200 ppm
0SHA Standard (air)
TLV 25 ppm
0SHA Standard (air)
TLV 25 ppm
ACGIH RL (air)
TLV 25 ppm
OSHA standard (air)
TWA 100 ppm
OSHA Standard (air)
TWA 100 ppm
o-Xylene C8H10
95-47-6
TLm96: 100-10 ppm
Oral-rat, LDLo 5,000 mg/kg;
intraperitoneal-rat, LDLo-1,500
mg/kg, subcutaneous-rat, LDLo
2,500 mg/kg, inhalation-mouse, LCLo-
6,920 ppm
OSHA Standard (air)
TWA 100 ppm
-------
22
were well below the TLmgg range. Other compounds with reported aquatic
toxicities were at low levels. Although the compounds detected were
present in levels below those known to cause acute toxicity for single
compounds, data were inadequate to define if acute toxicity could occur
as a result of synergistic effects of the combined discharges. Also, no
data were available on long term chronic effects, although such effects
could occur.
As noted earlier, a fish kill occurred in Tallaboa Bay in February
1977. Analytical data on fish collected both at the time of and sub-
sequent to the kill [Appendix E] showed that the fish contained eleven
complex organics in concentrations ranging from <0.3 to 27 yg/gr. Seven
of these compounds (i.e. dicyclopentadiene, toluene, pentadecane, hexa-
decane, heptadecane, octadecane and nonadecane) were also identified in
samples collected from the C0RC0 discharges in April and/or August 1977.
With the exception of toluene and dicyclopentadiene, these organics were
not detected in any other industrial discharge. Toluene was also found
in the discharges from Puerto Rico Olefins, PPG and Union Carbide and
dicyclopentadiene in the Caribe Isoprene Corporation discharge [Appendix
E].
Dicyclopentadiene and toluene are moderately toxic to fish.1
Toluene was reported to be the major cause of tainting of fish in a
Japanese bay receiving wastewaters from petroleum and petrochemical
industries.2 Both m-xylene and p-xylene were also reported to cause
fish tainting. Although these latter two compounds were not identified
in the fish samples, they were present in the C0RC0 discharges. These
data show that substances known to be toxic to fish and/or cause fish
flesh tainting were discharged by C0RC0.
The results of water quality and sediment sampling in Tallaboa Bay
[Appendix D] show that the combined industrial waste discharges from the
6 industries cause water quality standard violations. Specifically,
water temperatures increased more than 2.2°C over ambient water temperatures,
-------
23
maximum temperatures exceeded 34°C and buildup of sludge deposits,
visible oil films and suspended solids were present in the Bay.
Sediment samples collected at selected Bay stations contained 32
different organic compounds, including normal paraffins, aromatic
hydrocarbons, cyclic hydrocarbons and alkanes [Table 2 of Appendix D].
The samples collected near the mouth of CORCO outfall 001, contained 21
of these compounds. A comparison of these 21 compounds to those iso-
lated in CORCO outfall 001 [Table 5] shows that the following compounds
were contained in both samples.
Compound Sediment Effluent
Concentration Concentration
Aug. 14 Aug 9 Aug 11
mg/gm mg/1
Undecane
70
50
6
Dodecane
75
65
6
Tridecane
90
25
Pentadecane
75
80
30
Hexadiecane
55
60
35
Heptadecane
50
70
55
Octadecane
45
60
40
Nonadecane
40
60
23
Dimethylnaphthalene
190
130
150
Trimethyl naphthalene
95
60
100
The presence of the same compounds in both the sediment and wastewater
discharge show that CORCO effluents contribute to the buildup of organic
materials in Tallaboa Bay.
-------
24
During the survey, NEIC analytical personnel conducted an evalua-
tion of the company laboratory which performs NPDES self-monitoring
analyses [Appendix G]. Deviations from Standard Methods and techniques
were observed in the BOD test (e.g. a dilution water blank was not run
to determine if the blank exerted a BOD demand on the sample). Results
of oil and grease analysis showed that blank samples contained residues
as high as 11 mg/1. These results indicate possible contamination of
the freon used in the tests. In addition, the laboratory did not have
an analytical quality control program to ensure that analyses are
correct.
-------
25
REFERENCES
1. Christensen, H. E. and Fairchild, E. J., Eds. June 1976. Public
Health Service - Center for Disease Control, National Institute for
Occupational Safety and Health, Rockville, Maryland.
2. Identification of Substances in Petroleum Causing Objectionable
Odour in Fish. Okayama Univ. (Japan). Dept. of Public Hygiene.
Water Research, Vol. 7, No. 10, p 1493-1504, Oct. 1973.
-------
APPENDICES
Reconnaissance and NPDES Inspection
Flow Measurement
Chain-of-Custody Procedures
Water Quality and Sediment Sampling
Tallaboa Bay, Puerto Rico
GC-MS Analyses of Industrial Wastewater Outfalls
Penuelas, Puerto Rico and Selected Fish
Collections from Guayanilla-Tallaboa Bays,
Puerto Rico
Organic Analyses Methodology
Laboratory Evaluation
-------
APPENDIX A
RECONNAISSANCE AND NPDES INSPECTION
-------
A-l
RECONNAISSANCE AND NPDES INSPECTION
COMMONWEALTH OIL REFINING COMPANY, INC. (CORCO)
Penuelas, Puerto Rico
March 31-April 1, 1977
Inspection by
Mr. E. Struzeski, Jr, NEIC-Denver, USEPA
Ms. Margarita Irizarry, San Juan office, USEPA
Dr. Cho-Ching, Region II, New York, USEPA
Company Representatives Contacted
Mr. Edert Ortiz, Environ. Protection Group, CORCO, Penuelas, P.R.
809/843-3030
Mr. Uriel Ojeda, Environ. Protection Group, CORCO, Penuelas, P.R.
Mr. Jose Ruiz, Environ. Protection Group, (responsible for conduct of
NPDES monitoring and chemical and physical analysis), CORCO,
Penuelas, P.R.
Mr. Jaime V. Biaggi, President, Laboratories de Analysis
Ambiental, P.O. Box 525, San German, P.R. 00753, 809/851-2105
and 832-4949 (CORCO's sub-contractor for carrying out one year
biological monitoring program and triaxial isotherms required
by NPDES Permit)
Mr. James F. (Bud) Morlock, Jr., Vice Pres. Operations, Labora-
torio de Analysis Ambiental., San German, P.R.
BACKGROUND
The CORCO complex at Tallaboa (Penuelas), P.R. comprises a crude
oil refinery with a nominal capacity of 161,000 barrels/day together
with a series of petrochemical plants either wholly owned or partly
owned by CORCO and more or less situated at the same site.
-------
A-2
These include the following:
The main CORCO Refinery receiving crudes from Venezuela, other
South American sources and the middle-East, producing gasoline,
kerosene, jet fuel, diesel oil, fuel oil, propane, butane,
LPG, and naphtha feedstocks for the on-site CORCO petrochemical
works.
The CORCO Petrochemical Works which receives naphtha from the
CORCO refinery plus outside naphtha and converts to the
aromatics BTX (benzene-toluene-xylene), orthoxylene, and
raffinate. Raffinate is a main feedstock for the adjacent
Puerto Rico Olefins plant and the Oxochem Enterprise Petro-
chemical plant. The CORCO Petrochemicals, Inc. Works is
divided into the CPI-1 and CPI-2 sectors.
The CORCO NPDES permit includes three other units which are
the wholly CORCO-owned Cyclohexane, Inc. on-site works; the
wholly CORCO-owned Styrochem Corporation on-site works; and
the Hercor Chemical Corporation on-site works (50% CORCO-owned
and 50% Hercules-owned, but managed by CORCO). The Styrochem
Corp. works receives xylenes from the CORCO Petrochemical
Works and produces ethylbenzene (Cap. 11 Mil. gals/yr).
According to CORCO personnel, the Styrochem Corp. works has
been shut down for the last 6 months. The Cyclohexene, Inc.
works receives benzene from the CORCO Petrochemical Works and
produces cyclohexane (Cap. 40 Mil. gal/yr). The Hercor
Chemical Corp. works basically receives xylenes and converts
to paraxylene (Cap. 525 Mil. lbs/yr). For purposes of the
NPDES Permit, the Styrochem, Cyclohexane and Hercor works are
combined with the CORCO Petrochemical Works. The Cyclohexane
-------
A-3
plant is physically located within the CORCO CPI-I (Aromatics)
Works, and the Hercor and Styrochem plants are physically
located within the CORCO CPI-2 (Aromatics) Works.
The NPDES Permit classifies the CORCO operations as a Subcategory
C Oil-Refinery-Petrochemical facility consisting of a 100,000
barrel/day crude oil refinery together with a 50,000 barrel/day
crude naphtha Petrochemical Works where 15% or more of refinery
production may be described as first generation petrochemical
and isomerization products.
The CORCO Petrochemical Works produces benzene, toluene,
xylenes and orthoxylenes which are employed as solvents but
also represent intermediates for a wide range of synthesized
chemical products. Orthoxylene is employed in eventual
production of plasticizers, emulsions, latexes, lacquers and
paints. Paraxylene from the Hercor works is used to produce
polyester fibers and films, apparel, tire cords and photographic
film. Cyclohexene from the Cyclohexene works is covnerted
into nylon fibers, apparel, carpets and hosiery. Ethylbenzene
from the Styrochem Corp. is employed for a wide range of
plastics, floor tile, home and building products.
Remaining petrochemical operations which are part of the CORCO
complex but which are not included in the CORCO NPDES Permit
include:
The Puerto Rico Olefins Petrochemical Works (50% CORCO owned
and 50% PPG owned), which receives raffinate, fuel gas, fuel
oils, gas, oil and naphtha and produces pentanes, and the
olefins-ethylene, propylene and butadiene as final products
(Cap. 2.1 Bil. lbs/yr). Pentanes are delivered to the adjacent
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A-4
Caribe Isoprene Corp. plant in the same complex. Propylene is
delivered to the adjacent Oxochem Enterprise plant in the same
complex.
The Oxochem Enterprise Petrochemical Works (50% CORCO owned
and 50% W. R. Grace owned), which receives raffinate, oxygen
and propylene and manufacturers oxo alcohols (Cap. 245 Mil.
lbs/yr). These materials are employed in production of
plasticizers and plastic products.
The Caribe Isoprene Corporation Works (10% CORCO owned and 90%
Nippon Zeon and Mitsubishi owned) which essentially receives
pentanes and manufactures isoprene monomer and dicyclopentadiene
(Cap. 30,000 Tons/yr). These materials are employed in
production of rubber and plastic additives, tires, resins and
sealents.
The complete CORCO complex, Companies represented, raw materials
and products, are illustrated in a diagram attached to this report. The
Puerto Rico Olefins, Caribe Isoprene and Oxochem Enterprise operations
have separate NPDES Permits. However, it is noted that waste discharges
from the latter three plants all empty into CORCO's 002 discharge
Outfall. This Outfall is maintained by CORCO and leased to the other
Companies for their respective usage. CORCO has never provided a plot
plan to the EPA. Attempts have been made to develop a rough layout for
CORCO and this is given in an attachment to this report.
CORCO apparently is in considerable economic difficulty. Under
pressure from holding banks, CORCO is expected to shortly divest itself
of numerous joint ventures thereby increasing cash flow of the present
Company. CORCO reports they currently have about 1,300 direct employees
plus hundreds of contract employees. Severe problems with the unions
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A-5
are indicated. The CORCO Refinery and Petrochemical Works are operating
considerably below capacity. Mr. Edert Ortiz upon checking the records
stated over the past 18 months that the refinery has been operating at
76% to 87% of capacity and as of April 1, 1977 was around 75% of capacity.
The CORCO Petrochemical Works over the past 18 months has been operating
around 50% or slightly higher, and at present is about 50% of capacity.
Outside suppliers of naphtha are said to be increasingly reluctant to
extend a credit line to CORCO. Production at CORCO may continue to
decrease before becoming better.
The Public Notice accompanying issuance of the NPDES Permit to
CORCO provides description of the 001 and 002 discharges from the
Penuelas Refinery and Petrochemical Works. Discharge 001 primarily
consists of once-through cooling water from Refinery Plant Units Nos. 1,
2 and 3, refinery process water, tank farm drainage, storm water, and a
small quantity of sanitary effluents. The average daily flow of Dis-
charge 001 to Tallaboa Bay is 98 MGD. Existing treatment facilities
relevant to Discharge 001 consist of an API oil-water separator and four
lagoons. Discharge 002 consists of process and non-contact cooling
water from petrochemical plants CPI-1, and CPI-2, as well as concentrated
salt blowdown from the CORCO desalinization plant. Boiler blowdown is
also found in the 002 waste stream. Existing waste treatment facilities
relevant to Discharge 002 include within the CPI-1 sector an API separator,
storm surge pond and an air stripping unit. Existing treatment for the
CPI-2 sector includes an API separator and the air stripping unit mentioned
above. The purpose of the stripper is to remove light aromatic hydrocarbons
from the 002 wastes prior to discharge. Average daily flow of Discharge
002 is 2.5 MGD entering into Tallaboa Bay.
Upon approaching the CORCO complex the AM of March 31, we were
greeted by dense, black smoke and an apparent fire in the middle of the
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A-6
area. It was soon learned a large compressor had failed on a major vent
system in the Refinery No. 2 sector at approximately 0800 hours on March
31. The failure resulted in a substantial vacuum over the entire system
in turn creating a tremendous burning flare. This source is normally
considered to be a "smokeless" flare by C0RC0. The dense black cloud
with resulting fire had an opacity of 100 percent and persisted to at
least 1320 hours on April 1 at which time the EPA team left the CORCO
premises. Mr. Ortiz received an estimate that $60,000 worth of products
were being consumed per hour in this mishap. CORCO did not have an
available standby compressor and was rebuilding the damaged unit responsible
for the extended burnout.
NPDES PERMIT CONDITIONS
Tho CORCO NPDES Permit has an effective period of Dec. 31, 1974
through Dec. 31, 1979. The Permit covers two Outfalls, i.e. 001 and 002
and is divided into Initial Limitations applicable through June 30, 1977
and Final Limitations thereafter. Schedule II requirements continue
until startup of treatment facilities designed to comply with July 1,
1977 Limitations; Schedule III requirements commence with startup of the
treatment facilities (July 1, 1977); and Schedule IV requirements
coincide with effluent values reaching steady-state conditions. Although
not specified, allowance for treatment plant shakedown apparently starts
July 1, 1977 and extends for an undesignated period of time thereafter.
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I. Initial effluent limitations include as follows:
Net lbs/day
Parameter Avg. Daily Max. Daily
For 001 BOD,-
600
TSS
1,700
Oil/Grease
300
Ammonia as N
260
Sulfides
3
Phenols
20
PH
6 to 9 at any time
For 002 BODc
245
TSSd
409
TOC
51
Sulfides
34
PH
6 to 9 at any time
Final effluent limitations effective July 1, 1977 include as follows
Net lbs/day
Parameter
Avg. Daily Max. Daily
Total for 001 and
002 (Dry Heather Flow)
BOD
620 1,150
TOC
1,379 2,530
TSS
405 691
Oil/Grease
198 369
Phenols
4.03 8.33
Ammonia as N
260 780
Sulfides
3.31 7.38
Total Chromium
10.1 17.4
Hex. Chromium
0.171 0.98
Total for 001 and 002 (Wet Weather Flow) - when rain runoff occurs
through treatment facility, the
following waste load allocations
shall be permitted in addition to those for Dry Weather Flow
providing that the excess flow is properly measured.
Allowable Ibs/MGD Excess Flow (Gross)
Parameter Avg. Daily Max. Daily
BODr 0.21 0.40
TOC 0.462 0.88
TSS 0.13 0.24
Oil/Grease 0.067 0.126
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C. Two Additional Provisions are incorporated in the NPDES Permit
pertaining to: 1) Additional Storm Water that has been segregated from
the main waste stream; 2) Once-through Cooling Water which for CORCO
more or less refers to spent sea water. The storm water provision is
given as: "Any additional storm water that has been segregated
from the main waste stream, shall not exceed a TOC concentration of 35
mg/1 or an Oil/Grease concentration of 15 mg/1 when discharged."
According to Region II, the allowable loads for once-through
cooling waters are to be incrementally added to Dry Weather Flows based
upon "a TOC concentration not to exceed 5 mg/1 (NET)."
III. Thermal Limitations are specified for the five year period of the
Permit as follows:
For 001 - Max. discharge temperature shall not exceed 98°F (36.7°C)
The difference between discharge and intake temperature
shall not exceed 13.0°F (7.2°C).
The NET amount of heat to be added to the receiving water
shall not exceed 0.607 Bil. BTU/hr (0.153 Bil Kcal/hr).
For 002 - Max. discharge temperature shall not exceed 86°F (30.0°C)
IV. Schedule II sampling and analytical requirements are specified as:
Parameter Frequency and Type of Sample
For 001 and
002 B0Dc
TOC5
TSS
Sulfides
Ammonia as N
Phenols
Oi 1/Grease
Total and Hex. Chromium
(if chromium compounds
are used)
PH
1/Mo. 24-hr Composite
1/Mo. 24-hr Composite
1/Mo. 24-hr Composite
1/Mo. 24-hr Composite
1/Mo. 24-hr Composite
1/Mo. 24-hr Composite
1/Mo. 24-hr Composite
1/Mo. 24-hr Composite
1/Mo. Grab
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A-9
And where Net loads are applicable, the surface water intake is to
be sampled with the same frequency and type of sample as specified above
for each parameter.
V. Schedule III and IV sampling and analytical requirements are
specified as follows:
Frequency
Frequency
Type of
Parameter
Sch .III
Sch. IV
Sample
001- BOD,
2/Wk
1/Wk
24-hr Composite
002 TSS5
2/Wk
1/Wk
24-hr Composite
T0C
2/Wk
1/Wk
24-hr Composite
Phenols
2/Wk
1/Wk
24-hr Composite
Ammonia as N
2/Wk
1/Wk
24-hr Composite
Sulfides
2/Wk
1/Wk
24-hr Composite
Oil/Grease
2/Wk
1/Wk
Grab
Total and Hex
. Chromium
24-hr Composite
(if Cr. cmpds. used)
PH
2/Wk
1/Wk
Grab
And where Net Loads are applicable, the surface water intake is to
be sampled with the same frequency and type of sample as specified above
for each parameter. It is also noted in the case of Net Loads the
Permit prescribes when the surface water source(s) is pretreated for the
removal of pollutants that the intake level of the pollutant to be used
in calculating the NET, is the pollutant level after the pretreatment
steps.
VI. Thermal sampling shall be conducted from March 31, 1975 to December
31 , 1979 as follows:
Parameter Min. Frequency, Sample Type
For 001 Discharge Temp. Continuous
Intake Temp.
Discharge Flow
For 002 Discharge Temp. 1/Wk, Grab
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VII. Flow measurement is specified as continuous for both Outfalls 001
and 002. Continuous flow recorders were to be completed by August 31,
1975 (see letter of 6/24/75 from Mr. Richard Flye, EPA Region II to Mr.
Wm. Hall, C0RC0, New York, N.Y.). Furthermore, flow of once-through
cooling water is to be determined by direct measurement or calculation,
and recorded on a weekly basis. Flow of storm water segregated from
the main waste system is to be determined by direct measurement or cal-
culated and recorded daily whenever such discharge occurs. The flow
of storm water runoff which passes through the main treatment system
shall be determined by direct measurement and recorded daily. It is
importantly noted up through April 1977, CORCO has complied with none
of the above flow measurement criteria, especially the installation of
continuous recorders for 001 and 002.
VIII. A Biological Monitoring program designed to determine the effects
of CORCO's discharges upon the biological community in Tallaboa Bay
lasting 12 or more months, together with triaxial isotherms was due to
start in 1975. However, it was mutually agreed between the Company and
EPA that this study would commence no later than April 1, 1977. The
Laboratorio de Analysis Ambiental of San Germdn, P.R. will be subcon-
tractor for CORCO on these studies. The subcontractor on March 31, 1977
indicated in his bioassay studies the sea urchin will be used. Although
this organism is quite prevalent in Puerto Rico, qualified EPA biologists
should determine if its sensitivity is sufficient for the planned studies.
IX. Additional requirements of the NPDES Permit include:
. An implementation schedule for eliminating bypass of the waste
treatment facilities which would allow entry of untreated or
partially treated wastes to receiving waters was to have been
submitted to the EPA for approval by March 28, 1975. C0R0 has
not yet submitted such plans to the EPA covering bypass conditions
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A-ll
which were still existing on April 1, 1977. The Permit
further indicates if such bypassing is not eliminated, the per-
mittee shall then by August 31, 1975 install flow measurement
units with continuous recorders on all waste treatment facility
bypass lines. Similarly, the Company has not complied with
the latter provisions.
. The permittee shall provide by July 31, 1975, an alternate
source of power to operate all waste treatment facilities, or
the Company shall indicate in writing to the EPA, that production
shall be controlled, or the discharge handled in such manner
that in the event the primary source of power to the waste
treatment facilities fails, the discharges \.o the receiving
waters will comply with the Permit limits. Up through April,
1977, CORCO has not provided an alternate source of power nor
has it provided equivalent guarantees to protect the receiving
wate^ body.
. The NPDES Permit per se, does not mention necessity for a Spill
Prevention Control and Countermeasure plan. However, communication
between the EPA and CORCO supports this requirement. Information
of March 31 - April 1 describes the availability of two SPCC
plans, one for the docks and another for the Production Works.
An SPCC evaluation visit was conducted by Mr. Joseph Marishak of
the EPA, Region II offices on May 27, 1976, but the outcome of
this visit and relative status of CORCO's SPCC plans are not
known.
The USEPA, Region II office on July 25, 1975 issued an Administra-
tive Order against CORCO for numerous and serious violations of the
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A-12
NPDES Permit. The Order dictated future compliance in accordance with
a prescribed schedule and stipulated that failure to carry out require-
ments of the Order or the remaining requirements of the Permit would
subject the Permittee to further enforcement provisions of the Federal
Water Pollution Control Act Amendments of 1972.
In March, 1976, the EPA noted that the DMR's submitted by CORCO
persuant to its permit had failed to indicate even one monthly period
since the permit became effective whereby the effluent limitations had
been achieved. It was therefore assumed that CORCO had been in continuous
violation of its permit. Despite this finding, the EPA withheld enforcement
action since CORCO had announced intentions to reach Initial Limitations
by June 30, 1976. In this regard, the EPA advised the Company if it
failed to install the necessary waste abatement equipment by June 30,
1976, or if CORCO continued thereafter to be in violation of Permit
limitations, the Company would then be subjected to immediate enforcement
action, including referral of the case to the U.S. Attorney for imposition
of civil penalties. The EPA further indicated such enforcement action
would address any and all violations that had occurred since the effective
date of the Permit. Discharge Monitoring Reports subsequent to June 30,
1976 continue to show CORCO having numerous and substantial violations
of the NPDES Permit.
WATER INTAKES SERVING CORCO REFINERY AND PETROCHEMICAL WORKS
Water supply for the CORCO complex includes two sea water intakes -
one from Guayanilla Bay and the other from Tallaboa Bay plus the de-
salinization plant and a series of groundwater wells. The Guayanilla
Bay sea water intake has a rated capacity of 110,000 gpm ^160 MGD, and
the Tallaboa Bay sea water intake is rated at 40,000 gpm ^ 58 MGD.
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Actual capacity of the sea water intakes is considerably less than rated
values. The desalinization plant with a rated capacity of 5 MGD is
capable of reducing salt content from 20,000 ppm to 5 ppm. The groundwater
wells previously rated around 3,000 gpm are now running a peak flow of
only about 1,000 gpm ^ 1.3 MGD. The Tallaboa sea water intake provides
for cooling water needs of the Oxochem Enterprise plant, and Puerto Rico
Olefins besides the CPI sector needs of CORCO itself.
The Guayanilla Bay water intake located directly south of the Water
Resources Power plant is protected by a wire screen and metal boom. The
intake station contains 4 electric pumps each rated at 12,500 gpm and 3
diesel pumps each rated at 20,000 gpm. There are normally 3 diesel and
two electric pumps in use with a rated capacity of 85,000 gpm % 123 MGD.
Both sea water intakes are equipped with Kenney filters for removal of
suspended matter and the two systems are further chlorinated. The
Tallaboa Bay ocean intake is situated east of CORO's 002 Outfall and is
protected by three fixed wire mesh screens in the intake channel plus a
stationary screen immediately in front of the intake pumps. Three pumps
are available at the Tallaboa Bay sea water intake each rated at 13,500
gpm. Two pumps are normally used ^ 27,000 gpm ^ 40 MGD. As cited
above, real volumes of sea water pumped for cooling are significantly
less than rated values.
The cooling towers at CORCO are all on sea water except for the
tower in the CPI-1 sector which operates on fresh water. As far as
known, no chromium compounds are presently used by CORCO in corrosion
control at the CORCO complex. The cooling towers do receive algae
control additives. Various Betz reagents are utilized for water system
conditioning as follows:
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A-14
Betz compounds 403 (a zinc salt combined with an amino phosphoric
acid derivative and caustic soda) - 1 gal/day for the CPI-1
sector and 5 gal/day in the CPI - 2 sector
Betz compound 65 (a zinc sulfate salt) - 5 gal/day in CPI-1 and
25 gal/day in CPI-2
Betz compound 407C (succinic acid derivative and isopropanol) -
1 gal/mo at both CPI-1 and CPI-2
Betz compound 38 (Bis(trichloromethyl) sulfone methylene
bisthiocyanate isopropanol) - 5 gal/week at each of CPI-1
and CPI-2
The Company does not employ the best possible locations for sampling
its sea water intakes. Guayanilla Bay Waters are sampled from the
shoreline a few hundred feet distant from the intake and the Tallaboa
Bay waters are taken on the other side of intake channel away from the
pump station. Neither is sampled within the intake system per se, and
sampling does not takexinto account the straining action of he Kenney
filters said to be present on both sea water withdrawal systems. The
Company analyses Tallaboa Bay sea water samples in calculating NET loads
on the 002 Discharge. Similarly, Guayanilla Bay sea waters are used for
calculating NET loads on the 001 Discharge.
Sanitary Sewage
Sanitary wastes are disposed of via a series of septic tanks or
cesspools throughout the C0RC0 complex. Soils are relatively impermeable
and the tanks require cleaning every 3 to 4 months. The Company reports
no runoff from the sanitary systems to surface watercourses.
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A-15
WASTE RECOVERY AND TREATMENT SYSTEMS AT CORCO COMPLEX
Waste treatment units are situated at dispersed locations throughout
the CORCO plant grounds. Unfortunately, the Company has not yet pro-
vided the EPA with a plot plan of the process facilities and its treat-
ment units which creates considerable difficulty in understanding the
CORCO systems. CORCO claims by July 1, 1977, they will have constructed
the equivalent of secondary treatment for process wastes. However,
based upon expected facilities as described below, it is not easy to
see how this can be the case.
1. Sour water stripper and caustic waste neutralization located
in the main refinery area.
2. Sour stripper effluent cited above is conveyed to two refinery
single-cell API separators, then a Wemco flotation unit (still
under construction) and through a series of earthen lagoons
before discharge to 001. Spent cooling waters are combined
with the partially treated process wastes in the lagoons and
are reflected in the 001 Discharge.
3. Single covered, double (parallel) cell API separator located
in the petrochemical CP I-1 sector. The effluent from this API
unit feeds to the API separator found in sector CPI-2.
4. Treatment in the petrochemical CPI-2 sector consists of a single,
double (parallel) cell API separator followed by a Wemco flotation
unit, then an air stripper before discharge to the 002 Oufall.
The refinery sour water stripper recently completed receives
various inflows including that from the caustic neutralization system.
Ammonia, H^S and phenols are stripped off and sent to the sulfur plant.
The stripped wastewater effluents are conveyed to the refinery API
separators at the bottom of the hill. It was learned that the caustic
neutralization sub-system has not yet been implemented. The sour water
stripper has a rated capacity of 200 gpm.
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A-16
The existing refinery API separators consist of two single-chamber
settlers operating in parallel, each approximately 17 ft wide by 74 ft
long. The existing API's are said to have a capacity of 2,800 gpm.
During our inspection, only one of the two units was functioning.
Besides the sour water stripper stream, other influents to the API
system include water from slop oil tank separation, various oily sewers
from Refinery Plant Nos. 1, 2 and 3, an oily stream from a 16,000 barrel
tank storing ballast from ships, and possible diversion from the storm
water ditch in the refinery area. A third API separator is being
installed which will increase the rated capacity at the refinery API
separator site from 2,800 to 4,200 gpm. According to Company plans,
flow meters are due to be installed on the effluent from the three API
separators but as far as known, no real progress is being made on these
items. Previous Company plans indicate provisions for bypassing of
refinery API separator effluent around all subsequent waste treatment
units direct to the 001 C0RC0 canal and the Bay. However, C0RC0
representatives on April 1 claimed there would be no such bypassing.
The refinery API separator effluent under the July 1, 1977 treatment
scheme will pass through a Wemco flotation unit (rated at 6,000 gpm vs.
current discharge of less than 2,000 gpm) and then enter into either the
No. 1 or the No. 2 unit of three 400 ft x 300 ft lagoons in parallel.
Nine floating aerators will be added to the No. 1 (or No. 2) Lagoon for
the purpose of aerating and providing some biological floe for specialized
treatment of process waste in this pond. There are no provisions for
recycling around the process lagoon.
Sea water previously used for cooling in the C0RC0 complex will
enter into Lagoons 1 and 3 in parallel. Currently, process wasters in
the refinery sector passing through the existing treatment works are
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A-17
estimated between 1,000 to 2,000 gpm, and the spent sea water cooling
flows are estimated between 70,000 and 100,000 gpm ^ 100 to 140 MGD. In
actuality, the Company does not measure the wastewater streams and has
no firm figures on these flows. A leaping concrete weir is available in
the spent sea water channel a few hundred yards upstream of the treatment
lagoons. However, even the Company personnel were unsure of the service-
ability of the weir.
As of April 1, 1977, the Wemco flotation unit was on site but not
yet fully installed. The No. 1 Lagoon requires appreciable work before
it is put into service. A schematic of the refinery API separators and
the terminal wastewater treatment works including the No. 4 shallow
oxidation lagoon is given in an attachment to this report. The diagram
shows both the existing flow pattern and the flow pattern predicted
after July 1, 1977. Waste removal efficiencies for the projected treat-
ment were largely prepared by the engineering staff of COfO itself and
have not been independently verified.
The Storm Water Ditch immediately upstream of the effluent from
Lagoon No. 4 entering this same ditch is equipped with a metal baffle
plate which may be used for trapping oils and/or debris. This section
of the channel was coated with previous deposits of oil and flotable
material was caught behind the baffle. CORCO personnel remarked that
this channel upstream of the effluent of the lagoons contains crude
clean waters plus drainage from an ESS0 service station on Route 127.
The crude clean waters represent the waters separated from the crudes at
the refinery, i.e. some 3% x 100,000 barrels/day = 140,000 gpd. No flow
measurement or sampling are conducted on this upstream section of the
storm drain.
Between the bottom end of Lagoon No. 4 and the mouth of the CORCO
effluent canal near the Bay, a total of eleven floating booms have been
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A-18
installed by CORCO. This channel has very rapid flow and a water depth
between 8 to 10 feet deep. The CORCO people mentioned the USCG inspects
this canal every day for the presence of oil sheen. However, there
seemed to be no difficulty in observing oil sheen at various points on
the canal even at the terminus of the canal entering the Bay. At the
site of Peerless Chemical, one small pipe was noted discharging a very
small amount of what appeared to be a hot condensate into the CORCO
canal a short distance from the mouth. At least one possible discharge
pipe was also visible on the Bay side of the Peerless Chemical property.
CORCO conducts NPDES monitoring on the effluent channel either
immediately upstream or immediately downstream of the triple barrel
conduit on the canal. From inspection of the water line on the CORCO
effluent canal, this waterway is tidal upstream and beyond the CORCO
waste treatment lagoons. The present Company sampling point would
therefore seem to be highly questionable. Sampling and flow measurement
for process and cooling waters, and for storm waters should very much be
conducted separately and not influenced by high tides. Considerably
more effort will need to be expanded to obtain reliable NPDES data vs
the present monitoring program. The current frequency of monitoring is
believed inadequate and should be sufficiently increased.
Remaining waste handling and treatment sub-systems at CORCO comprise
those used inside the petrochemical complexes CPI-1 and CP 1-2. The
Hercor and Styrochem plants are additionally served by the oil treatment
facilities at CP 1-2. Treatment at the CPI-1 sector consists of a double-
cell API separator. This API unit is covered; each cell measures
approximately 8.5 ft x 70 ft. The CPI-1 unit rated at 600 gpm is said
to currently handle about 400 gpm. During the EPA inspection, one cell
was functioning properly whereas the other was heavily clogged with
sludge and had little throughput. The effluent from the CPI-1 separators
is routed a considerable distance to the CPI-2 process sector located at
the bottom of the hill.
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A-19
CPI-2 treatment includes an API dual chamber (each approximately 10
ft wide x 80 ft long) separator to be followed by a Wemco flotation unit
(awaiting connection) followed by an air stripper for removal of hydro-
carbons. The air stripper receives wastewater at the top and forced air
at the bottom. The wastewater cascades downward over a series of plates
and aromatics are released into the overhead stream. During the EPA
inspection only one of the two cells in the API separator was functional.
The other cell was completely down for repairs and the skimmer arm had
been pulled. Bypassing of API effluent around the flotation unit and
air stripper is believed possible. Oils recovered from both the CPI-1
and CPI-2 separators are conveyed to slop oil tanks. The process
effluent is carried southward over a plant storm drain and then over the
Tallaboa River for connection to the 002 C0RC0 waste disposal pipeline.
Known waste sources to the 002 connection include desalinization plant
brine 1,275 gpm; CPI - 2 API effluent - 200 gpm; cooling tower blowdown
210 gpm; and boiler blowdown - 15 gpm = total of 1,700 gpm. Updated
information must be obtained from C0RC0 on the nature and amount of
wastes entering this outfall since present 002 flows from C0RC0 are
estimated around 6,000 gpm -v, 9 MGD. Treatment units and waste streams
in the CPI-2 C0RC0 sector are shown in an accompanying sketch to this
report.
Surface drainage containing significant traces of oil was observed
entering the Tallaboa River from the C0RC0 petrochemical complex CPI-2
via the above mentioned plant storm drain. Dry weather flow within this
plant storm drain was estimated on April 1, 1977 to be 1-2 cfs C0RC0
personnel state the black color of this stream entering the Tallaboa
River is caused by the presence of sulfolene. This waste stream is
believed to be principally made up of various condensate, washdown of
pads and other units, and unknown sources. Although a storm drain is
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A-20
involved, the observed flow is thought to contain only minimum amounts
of storm and ground waters. This stream is considered to be a strictly
unauthorized discharge under the prevailing NPDES Permit.
The 002 sampling point utilized by C0RC0 for the NPDES Permit
provides for neither representative sampling nor the possibility of
accurate flow measurement. C0RC0 personnel indicate they insert a pitot
tube down into a 3-inch diameter riser on the outfall. Good flow
measurement is highly improbable besides the fact that continuous flow
instrumentation was to have been installed by C0RC0 on or before August
1975 under conditions of the NPDES Permit. The lead end of flexible
tubing off a Sigma motor with automatic sample compositer is fed into
this riser one day a month for NPDES purposes. Past results for C0RC0
002 are highly suspect and this NPDES sampling location must be completely
revised.
Temperature measurements taken at the present 002 sampling point
has exceeded Permit limitations. However, the Company contends the few
thousand feet of pipeline before this outfall reaches the sea will
significantly cool this discharge and the permitted temperatures refer
only to the final point of release into Tallaboa Bay. When the Company
was questioned on this point, Mr. Biaggi of Laboratorio de Analysis
Ambiental explained he had taken temperature readings in the Bay after
did not provide for this type of condition. Mr. Edert Ortiz of CORCO
attempted to defend a mixing zone concept which seemed irrelevant to the
situation at hand. It was fairly evident the Company has no correlation
between temperatures at the end of the 002 discharge line vs the 002
sampling point discounting the fact that the latter will very likely not
give representative data. Another sample point is available on the
CORCO 002 combined outfall approximately 70 feet from the shoreline of
Tallaboa Bay but extremely limited access and the question of representa-
tive sampling also prevails for this downstream point.
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OTHER NPDES OBSERVATIONS AND MISCELLANEOUS
For NPDES analyses, CORCO reports that field samples are routinely
handled through their chemical and physical plant analytical laboratories.
Apparently no cross-checking of analytical results is carried out with
any outside labs. The Company states that they have performed no hydro-
carbon or similar specialized analyses on plant wastewaters. All analyses
are performed on 24-hour composite samples including oil and grease.
Glass collection bottles are said to be used in all sampling. The
laboratory representative indicated that samples when received are
preserved chemically or by icing. NPDES analyses generally require from
2 to 5 days for completion after samples are received. Both manual and
automatic means have been employed by CORCO for composite samples.
Sigmamotors with peristaltic intake are reported available for automatic
sampling.
Partial information received from CORCO indicate alternate power
supply had not been provided for the on-site waste treatment works.
With pov/er failure, possible overflow to the storm water system can
result. Company personnel stated that waste bypassing would not occur
except during power failure.
The Tallaboa River was observed below the entry of the (unauthorized)
storm water drain receiving CPI-2 petrochemical sector wastes. There
was ample evidence of oily water and oily sludges over an appreciable
stretch of the Tallaboa River deposited over a reasonably long period of
time.
On April 1, 1977, the EPA inspection team toured the western edges
of Guayanilla Bay by boat to view oil remaining in the mangroves near
-------
A-22
the shoreline from a previous CORCO crude oil spill of mid-March 1977.
This spill had been estimated at 320 to 1,000 barrels and through April
1 had required approximately $100,000 in cleanup costs by the U. S.
Coast Guard. The roots of the mangroves were determined to be signifi-
cantly coated with oil over extensive reaches of the western shoreline
of Guayanilla Bay. Because of very difficult access to the shoreline
and to affected portions of the trees, the usefulness of further oil
cleanup efforts was debatable.
On April 11, 1977 at 1415 hours, the EPA inspection team observed
the Muriatti Oil cleanup Company in action with two vacuum trucks and
appreciable manpower recovering oil from the Tallaboa River immediately
below the Route 127 road bridge. It was learned that the Muriatti crews
had been pumping oil for two nights and two days. The U. S. Coast Guard
arrived on scene April 11. CORCO personnel reported to us that a couple
hundred barrels of fuel oil No. 2 had escaped from the boiler operations
and entered the Tallaboa River upstream via the main storm drain serving
the CP I-2 process sector. The oil spill had been retained downstream at
Route 127 by a concrete retainer. About one-half mile of River had been
heavily coated with oil.
-------
COMMONWEALTH 1EFIMIUG COMPANY. INC
Petroleum and Petrochemical Complex
Benzene
Orthoxylene
;.ro»HR(7Trrrp'r-
Maleic and Phthallc Anhydride
End Pr
T Agricultural O-imicals
£ Food Ad
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Crude and
Unfin.sred Oils |
r -r-i
Benzene
Cumene/Phenol and Acetone
Propylene
KT" - TTT-
In ' it
¦ » » »r... ],
*• |. ' •
Adhesive*
N,lon F bers
Solvents
Gasoline
Jet Fuel
Propylene
i»•}, im !»• -.
i Kerosene
Ammonia
d
Auto Parts
j Fuel Otis
Appliances
Polyester F bp's and Fi'r*
^ Apparel
Xylenes
Paraxyleno
Naphtha
C £ TireCcrds
Photographic Fl'i
(Benzene, Toluene.
I Xylenes. Orthoxytene
Naphtha
Plastiozers
[~EmuIstons Ljte»f s and Lc ,
Paints
Orthoxylene
Toluene
Benzene
hemieal Intermedials
Sol.tnts
Benzene
Raflmate
Cyclohexane
Nylon Fibers
Apparel Carpets Hosier
Xylenes
3 r.i
Ethylbenzeno
li
FuetGas
Plastics
Floor Tiles
AppUarces
Budding P odicts
Bo* les Ccnla nos
Home Furnish ngs
Fooucor
Toys
Gas Oil Naphtha
Styrene
J
Fuel Oils
Styrene
Polymers
Copolymers
Benzene
»f-Ti 'T'
Acrylomtrile
'I'lt'h'tf . 1
Olefins and Diolelins Ethylene, Propylene Butadiene
Ethylene
J I Butadiene
* 'I I- t lOJ.Ia'l
»"•>, Mil.)
Pentanes
isoprene Monomer and Oicyclopentadiene
—'T7-.T 7-rr~T7\'r—~~r*ir; - ^TTTCTr^-
^ Rubber and Plastic Addit <
L.I 1.t»
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Sealant*
Ml'-jji Ml.n
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BLZZXXZC ,
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)-ii h
Oxo Alcohols
Plasticizors
Plastic Products
Rafunate
rz3 WhoOy o*n*d by Co'co
Joint ««nturva
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Q3 In pitnmng iUg«
LU End ptoducrt
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COZCO OOi
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A-26
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STo/?m x>i?An)S A WD
002 OUTFALL CctJtJ ECTioN
A-J//77_ v*_ ^
-------
APPENDIX B
FLOW MEASUREMENT
-------
B-l
APPENDIX B
FLOW VERIFICATION AND MEASUREMENT PROCEDURES
The Commonwealth Oil Refining Company (CORCO) is permitted to
discharge wastes through two discharge points (001 and 002). Provisions
of this permit specify measurement of flow on a continuous basis and
flow meters to meet this requirement were to have been installed no
later than August 31, 1975. Additionally, direct measurement of flow
from storm water runoff which passes through the main treatment system
is required. As of August 1977 continuous flow measurement devices had
not been installed.
During the compliance monitoring inspection flows were measured as
follows.
Outfall 001
Waste discharges into outfall 001 consist of the effluent from the
lagoon systems and once-through cooling water. These two discharges
enter a common ditch and discharge into the bay. The wastewater flows
under a service road in three 72-inch culverts. The velocity in the
center culvert was measured with an electromagnetic flow meter. The
flow was calculated from the equation Q = AV and then multiplied by
three to account for flow in the additional two culverts. To assure a
balance of equal flow through each of the culverts, the elevations on
each end of the pipes were measured and flow through each pipe measured
individually for comparison of equal flow. Results of these comparisons
verified that each pipe was installed at the same grade and elevations
and that the product of the flow through the center culvert times three
was a reasonable estimate of the sum of the flow of each pipe measured
individually.
-------
B-2
CORCO personnel also measure flow in this manner. However, instead
of measuring the velocity by means of a meter, a floatable object is
timed passing through the center culvert and velocity calculated
[Attachment 1]. Comparison between the two methods showed that the
calculated flow was +_ 5% of the measured flow.
During the survey, flow was measured hourly as described above.
The daily average flow was calculated based on the 24 instantaneous
measurements.
Outfall 002
Outfall 002 consists of waste streams which originate at the
following locations:
1. Cooling water from Desalting Plant Module 3.
2. Cooling water from Desalting Plant Module 4.
3. Blowdown from Desalting Plant Module 1.
4. Blowdown from Desalting Plant Module 2.
5. Blowdown from Desalting Plant Module 3.
6. Blowdown from Desalting Plant Module 4.
7. Blowdown from Cooling Tower at CPI-2.
The waste stream from the desalting plant (items 1-6 above) are
all measured by means of orifice plates with signals transmitted
to strip chart recorders located in the desalting plant central control
room. Plant calibration on these recording systems is performed on a
"demand basis" or when an operator notices a discrepancy. Calibration
includes checking the dP cell zero to 100% at increments of 25, 50 and
75% with a Wallace Tiernan calibrator. A tolerance of ^2% is considered
acceptable on the above checks. The calibration procedure does not
include any checks on the orifice plate (i.e. determining size, etc.),
-------
B-3
only on the recording and telemetering portion of the system. The last
date of calibration could not be determined, since records are not kept.
The cooling tower blowdown from CPI-2 (Item number 7), is calcu-
lated as follows:
1. Temperature difference between the cooling water return and
cooling tower supply is measured.
2. Pump recirculation rate is calculated from pump measures and
efficiency curves.
3. Hardness of make-up water and recirculation water is measured.
4. Blowdown is calculated as follows:
blowdown = Harness'concentration - 1
Where: Evaporation = 0.01 x Recirculation rate x AT
Hardness ratio = Hardness - recirculation rate
Hardness - makeup
Total wastewater discharged was determined by summing the above
individual flows, the same procedure used by C0RC0 personnel [Attachment
2]. During the survey, flows were determined once/hr for units 1-6.
Because the cooling tower blow down rate remained constant, this dis-
charge was measured once/day. Total daily flows were calculated from
the 24 individual values.
-------
B-4
METHOD FOR COMPUTING THE FLOW AT DISCHARGE 001 OF CORCO
This is a very simple, easy and cheap method, that can be used
by anyone with a little knowledge of mathematics. We measure the flow
by computing it from definition:
TOTAL FLOW = TOTAL FLOW AREA X AVERAGE FLOW VELOCITY
(PERPENDICULAR TO FLOW)
Ft.3/min. = Ft.^ X Ft./min. : N Gal/Min.
In this method we have only to know the flow area and the flow velocity.
To know the flow area we have to know how much empty are the three
culverts. I found the relation between flow area and inches of diameter
(perpendicular to the surface of water) empty inside the culverts. There
are three culverts of 72 inches i.d. and 86 feet long. So on graph #3
and #3a we have this relation between the total flow area (ft.2) and the
inches of inside diameter empty of flow.
To know the velocity we can use a float, or something similar,
that is thrown on the water at the entrance of the center culvert. We
measure how much time (sec.) is necessary to pass the culvert (more
specific 86 feet). Mow we compute the velocity by:
86 feet f T sec. X 60 sec./min. = Velocity Ft./Min.
VJe have to make a correction to this surface velocity. This is
done multiplying by 0.8 and now we have the average velocity.
The total flow can be computed from the known area and average
velocity. This is known in terns of cubic feet per minute and can be
changed to gallons per minute dividing by 0.1337.
* CORCO publication
-------
B-5
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-------
B-6
-------
B-7
ATTACHMENT 2
PROCEDURE TO DETEHMIHE FLO'V THROUGH DISCHAP.CE 002*
A. Streams going to D-002:
1. Cooling water from Desalting Plant Module 3
2. Cooling water from Desalting Plant Module U
3. Blo-^down from Desalting Plant Module 1
b. Slowdown from Desalting Plant Module 2
5. Slowdown from Desalting Plant Module 3
6. Blowdo'.n from Desalting Plant Module k
7. Slowdown from Cooling To^ver at CP I-2
B. Procedure to determine flow:
1. Cooling water from Desalting Plant Modules 3 £¦
Signal fron orifice meters in modules go to continuous flow
recorders on control board of respective modules. The reading
on the charts are changed to gpm using Table 1.
2. B1 oi/downs from Desalting Plant Modules 3 £. it.
Signals from orifice meters in plants go to continuous flow
recorders on control board of the respective modules. Reading
on charts are changed to gpm using Table 2.
3. Slowdown from Desalting Plant Modules 1 £. 2.
Signals from orifice meters for make-up and distillate production
go to continuous flow recorders on control board of respective modul
Readings on charts are changed to gpm using Tables 3 and b, Blojdo.M
value is obtained by subtracting the distillate production from the
make-up.
*», Cooling tO/jer blowdown.
a) Obtain temperature of cooling tower return water.
b) Obtain tenperature of cooling tov/er supply W3tcr.
c) Determine temperature difference.
d) Obtain recirculation rate (in gpm) by pumps discharge pressure
and obtain gom from performance curve of punps.
e) Determine evaporation which is 1% of recirculation water for
every 10° T.
f) Determine hardness in make-up water and recirculation water.
g) Determine ratio of recirculation water hardness and nake-up
hardness.
BIowdown = Evaporo ti on
hardness concentration ratio -I
* CORCO publication
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-------
APPENDIX C
CHAIN-OF-CUSTODY
-------
C-l
ENVIRONMENTAL PROTECTION AGENCY
NATIONAL ENFORCEMENT INVESTIGATIONS CENTER
CHAIN OF CUSTODY PROCEDURES
June 1, 1975
GENERAL
The evidence gathering portion of a survey should be characterized by the minimum
number of samples required to give a fair representation of the effluent or water body
from which taken. To the extent possible, the quantity of samples and sample loca-
tions will be determined prior to the survey.
Chain of Custody procedures must be followed to maintain the documentation necessary
to trace sample possession from the time taken until the evidence is introduced into
court. A sample is in your "custody" if:
1. It is in your actual physical possession, or
2. It is in your view, after being in your physical possession, or
3. It was in your physical possession and then you locked it up in a manner so
that no one could tamper with it.
All survey participants will receive a copy of the survey study plan and will be
knowledgeable of its contents prior to the survey. A pre-survey briefing will be held
to re-appraise all participants of the survey objectives, sample locations and Chain
of Custody procedures. After all Chain of Custody samples are collected, a de-briefing
will be held in the field to determine adherence to Chain of Custody procedures and
whether additional evidence type samples are required.
SAMPLE COLLECTION
1. To the maximum extent achievable, as few people as possible should handle
the sample.
2. Stream and effluent samples shall be obtained, using standard field sampling
techniques.
3. Sample-tags (Exhibit I) shall be securely attached to the sample container
at the time the complete sample is collected and shall contain, at a minimum,
the following information: station number, station location, data taken,
time taken, type of sample, sequence number (first sample of the day -
sequence No. 1, second sample - sequence No. 2, etc.), analyses required and
samplers. The tags must be legibly filled out in ballpoint (waterproof ink).
4. Blank samples shall also be taken with preservatives which will be analyzed
by the laboratory to exclude the possibility of container or preservative
contamination.
5. A pre-printed, bound Field Data Record logbook shall be maintained to re-
cord field measurements and other pertinent information necessary to refresh
the sampler's memory m the event he later takes the stand to testify re-
garding his actions during the evidence gathering activity. A separate
set of field notebooks shall be maintained for each survey and stored in a
safe place where they could be protected and accounted for at all times.
Standard formats (Exhibits II and III) have been established to minimize
field entries and include the date, time, survey, type of samples taken,
volume of each sample, type of analysis, sample numbers, preservatives,
sample location and field measurements such as temperature, conductivity,
-------
C-2
DO, pH, flow and any other pertinent information or observations. The
entries shall be signed by the field sampler. The preparation and conser-
vation of the field logbooks during the survey will be the responsibility
of the survey coordinator. Once the survey is complete, field logs will be
retained by the survey coordinator, or his designated representative, as a
part of the permanent record.
6. The field sampler is responsible for the care and custody of the samples
collected until properly dispatched to the receiving laboratory or turned
over to an assigned custodian. He must assure that each container is in his
physical possession or in his view at all times, or locked in such a place
and manner that no one can tamper with it.
7. Colored slides or photographs should be taken which would visually show the
outfall sample location and any water pollution to substantiate any con-
clusions of the investigation. Vlritten documentation on the back of the
photo should include the signature of the photographer, time, date and site
location. Photographs of this nature, which may be used as evidence, shall
be handled recognizing Chain of Custody procedures to prevent alteration.
TRANSFER OF CUSTODY AND SHIPMENT
1. Samples will be accompanied by a Chain of Custody Record which includes the
name of the survey, samplers' signatures, station number, station location,
date, time, type of sample, sequence number, number of containers and analy-
ses required (Fig. IV). When turning over the possession of samples, the
transferor and transferee will sign, date and time the sheet. This record
sheet allows transfer of custody of a group of samples in the field, to the
mobile laboratory or when samples are dispatched to the NEIC - Denver labora-
tory. When transferring a portion of the samples identified on the sheet to
the field mobile laboratory, the individual samples must be noted in the
column with the signature of the person relinquishing the samples. The field
laboratory person receiving the samples will acknowledge receipt by signing
in the appropriate column.
2. The field custodian or field sampler, if a custodian has not been assigned,
will have the responsibility of properly packaging and dispatching samples
to the proper laboratory for analysis. The "Dispatch" portion of the "Chain
of Custody Record shall be properly filled out, dated, and signed.
3. Samples will be properly packed in shipment containers such as ice chests, to
avoid breakage. The shipping containers will be padlocked for shipment to
the receiving laboratory.
4. All packages will be accompanied by the Chain of Custody Record showing iden-
tification of the contents. The original will accompany the shipment, and a
copy will be retained by the survey coordinator.
5. If sent by mail, register the package with return receipt requested. If sent
by common carrier, a Government Bill of Lading should be obtained. Receipts
from post offices, and bills of lading will be retained as part of the perma-
nent Chain of Custody documentation.
6. If samples are delivered to the laboratory when appropriate personnel are not
there to receive them,,the samples must be locked in a designated area within
the laboratory in a manner so that no one can tamper with them. The same per-
son must then return to the laboratory and unlock the samples and deliver
custody to the appropriate custodian.
-------
C-3
LABORATORY CUSTODY PROCEDURES
1. The laboratory shall designate a "sample custodian." An alternate will be
designated in his absence. In addition, the laboratory shall set aside a
"sample storage security area." This should be a clean, dry, isolated room
which can be securely locked from the outside.
2. All samples should be handled by the minimum possible number of persons.
3. All incoming samples shall be received only by the custodian, who will in-
dicate receipt by signing the Chain of Custody Sheet accompanying the samples
and retaining the sheet as permanent records. Couriers picking up samples at
the airport, post office, etc. shall sign jointly with the laboratory custodian.
4. Immediately upon receipt, the custodian will place the sample in the sample
room, which will be locked at all times except when samples are removed or
replaced by the custodian. To the maximum extent possible, only the custo-
dian should be permitted in the sample room.
5. The custodian shall ensure that heat-sensitive or light-sensitive samples,
or other sample materials having unusual physical characteristics, or re-
quiring special handling, are properly stored and maintained.
6. Only the custodian will distribute samples to personnel who are to perform
tests.
7. The analyst will record in his laboratory notebook or analytical worksheet,
identifying information describing the sample, the procedures performed
and the results of the testing. The notes shall be dated and indicate who
performed the tests. The notes shall be retained as a permanent record in
the laboratory and should note any abnormal ties which occurred during the
testing procedure. In the event that the person who performed the tests is
not available as a witness at time of trial, the government may be able to
introduce the notes in evidence under the Federal Business Records Act.
8. Standard methods of laboratory analyses shall be used as described in the
"Guidelines Establishing Test Procedures for Analysis of Pollutants,"
38 F.R. 28758, October 16, 1973. If laboratory personnel deviate from
standard procedures, they should be prepared to justify their decision dur-
ing cross-examination.
9. Laboratory personnel are responsible for the care and custody of the sample
once it is handed over to them and should be prepared to testify that the
sample was in their possession and view or secured in the laboratory at all
times from the moment it was received from the custodian until the tests
were run.
10. Once the sample testing is completed, the unused portion of the sample to-
gether with all identifying tags and laboratory records, should be returned
to the custodian. The returned tagged sample will be retained in the sample
room until it is required for trial. Strip charts and other documentation
of work will also be turned over to the custodian.
11. Samples, tags and laboratory records of tests may be destroyed only upon the
order of the laboratory director, who will first confer with the Chief,
Enforcement Specialist Office, to make certain that the information is no
longer required or the samples have deteriorated.
-------
C-4
EXHIBIT I
EPA, NATIONAL ENFORCEMENT INVESTIGATIONS CENTER
Station No.
Date
Time
Sequence No.
Station Location
fnmp
_BOD
_Solidj
.COD
.Nutrient!
.Metals
_Oil and Grease
_D.O.
.Bad.
.Othor
Samplers:
Remarks / Pr oiervative:
Front
ENVIRONMENTAL PROTECTION AGENCY
OFFICE OF ENFORCEMENT
NATIONAL ENFORCEMENT INVESTIGATIONS CENTER
BUILDING 53, BOX 25227, DENVER FEDERAL CENTER
DENVER, COLORADO 80225
Back
-------
EXHIBIT II
:0R
SURVEY, PHASE.
DATE
fYPE OF SAMPLE.
ANALYSES REQUIRED
STATION
NUMBER
STATION DESCRIPTION
0£
UJ
Z
<
z
o
u
UJ
a.
>-
PRESERVATIVE
a
Z
<
O
O
C3
a:
o
z
IEMARXS
n
i
cn
-------
EXHIBIT III
Samplers:
FIELD DATA RECORD
STATION
NUMBER
DATE
TIME
TEMPERATURE
°C
CONDUCTIVITY
jxmhoj/cm
pH
S.U.
D.O.
mg/l
Goge Hf.
or Flow
Fl. orCFS
a
cn
-------
EXHIBIT IV
ENVIRONMENTAL PROTECTION AGENCY
Office Of Enforcement
NATIONAL ENFORCEMENT INVESTIGATIONS CENTER
Building 53, Box 25227, Denver Federal Center
Denver, Colorado 80225
CHAIN OF CUSTODY RECORD
C-7
SURVEY
SAMPLERS: {Signature}
STATION
NUMBER
STATION LOCATION
date
TIME
SAMPLE type
SEQ
NO
NO OF
CONTAINERS
ANALYSIS
REQUIRED
Water
Air
Comp
Grab
-
Relinquished by: /StgnofureJ
Received by: /Signature)
Date/T i me
Relinquished by: (Signature)
Received by: (Signature)
Dole/Time
Relinquished by: (Signature)
Received by: fSignd ture)
Dale/Time
Relinquished by: (.Signofu'
Received by Mobile Laboratory for field
anoly sisi fStgnufu'tJ
Date/Time
Dispatched by: /SignofwreJ
Dale/Ti
ime
Received for Laboratory by:
Date/T
ime
Method of Shi pment.
Distribution Orig — Accompany Shipment
1 Copy—Survey Coordinator Field Fitei
cpo es* -
-------
APPENDIX D
WATER QUALITY AND SEDIMENT SAMPLING
TALLABOA BAY, PUERTO RICO
-------
ENVIRONMENTAL PROTECTION AGENCY D"1
OFFICE OF ENFORCEMENT
NATIONAL ENFORCEMENT INVESTIGATIONS CENTER
BUILDING 53, BOX 25227, DENVER FEDERAL CENTER
DENVER, COLORADO 80225
to Jim Hatheway, Coordinator DATE October 27, 1977
from John Ellison
subject Water Quality and Sediment Sampling, Tallaboa Bay, Puerto Rico
Water quality parameters in Tallaboa Bay were measured to deter-
mine the effects of the petrochemical industry discharges into western
Tallaboa Bay. Eight stations [Figure 1] were established including a
control station east of the discharges. Scuba divers working from a
boat collected sediment samples, measured SOD rates, and made visual
observations. Temperature, pH and phytoplankton samples were also
collected.
The waters of western Tallaboa Bay [Figure 1] were found to be
severely degraded. This water quality degradation was characterized by
the following conditions which are a violation of Puerto Rico Water
Quality Standards [Attachment 1]:
1. Water temperatures in excess of a 4°F (2.2°C) rise above
ambient water temperatures and/or in excess of 93°F (34°C).
2. Presence of sludge in Tallaboa Bay.
3. Visible oil films and suspended solids.
Another environmentally degrading condition, not a specific water
quality standards violation, was sediment oxygen demand rates approximately
twice (4.3 vs. 2.4 g02/m2/day) as high as eastern Tallaboa Bay.
Three overriding conditions influenced the water quality of Tallaboa
Bay:
-------
D-2
Corco
South Coast
Steam Plant -
Corco Treotment
Lagoons
Union Carbide \
Union Carbide Cooling
^"~*(\Water Intake Canal
Union Carbide
Effluent Canal
/^Corco Submerged Outfoll
TALLABOA
Corco Effluent
Canal
s>-New Union
¦Carbide WT P.
05
• 07
Punta
Guayanilla
Cayo Porguera
• 08
Cayo Rio
Cayo Palomas
Cayo Caribe
SCALE IN MILES
1/2
Cayo Maria Langa
ure / Wafer on
d Sediment Quality, T a 11 a b o a Bay, Puerto Rico
August 1977
-------
D-3
1. Wastes and cooling waters discharged by the petrochemical
industries into Tallaboa Bay.
2. Location of waste outfalls from these sources in western
Tallaboa Bay.
3. Tidal currents and winds which force the waste streams to
the far western shore of Tallaboa Bay along Punta Guayanilla.
Analytical results from Tallaboa Bay are presented in Table 1 and
discussed in detail in the following sections. Study methods are con-
tained in Attachment 2.
Temperature and pH
The temperature at Station 05 (mouth of Union Carbide canal) was
35°C which exceeds the 93°F (34°C) permitted by water quality standards.
Temperatures at the other stations ranged from 26.5 to 27.5°C. Vertical
stratification was greatest at Stations 05 and 08. At the mouth of the
Union Carbide Canal (Station 05), the temperature ranged from 35°C at
the 1/3 depth to 28°C at the 2/3 depth a difference of 7°C in a 6 m
water column. Near Punta Guayanilla the temperature difference was
2.5°C, 31.5 vs. 29°C at 1/3 and 2/3 depth, repectively. The 31.5°C at
Punta Guayanilla and 35°C at the mouth of Union Carbide Canal are 4.5°C
and 8°C respectively, above the average ambient temperature (27°C), a
water quality standards violation (i.e., maximum allowable temperature
increase of 2.2°C). These data show that the warm effluents from the
C0RC0 001 and Union Carbide discharges floated on top of cooler bay
water and moved along Punta Guayanilla. Additional cooling facilities,
different discharge points, or better mixing could alleviate or elimi-
nate these temperature standards violations in Tallaboa Bay.
The pH values ranged from 7.4 to 8.1 and no water quality standards
violations (<6.8 or >8.5) were noted.
-------
Table 1
WATER AND SEDIMENT QUALITY DATA
TALLABOA BAY, PUERTO RICO
August 1977
Time
0930
0900
0945
0950
1445
1450
1245
1525
Range
Water
Depth
4.5
7.2
6.3
6.0
6.0
1.0
10.5
4.5
1.0-
10.5
Trans- Soft
parency Sedi-
pH Secchi ment
T73 273 T]Z 273 Depth Depth
Depth Depth Depth Depth (m) (in)
(°C)
Temp.
Core-Characteristies
Grey SOD
Lt Brn B1 Org Clay-like Rate
Floe
Pep Mat.
(cm)
27.5 27.0
31.5 29.0
27.0-
35.0
Station 01
tt
27.0 26,5 7.9
27.0 27.5 7.4
8
27.0 7.8
27.0 27.0 7.9
30 m East of C0RC0 Submerged Discharge
7.9 1.8 0.5 15
Station 02
30 m South of C0RC0 Submerged Discharge
7.8 - 1.5 18 15
Station 03
30 m West of C0RC0 Submerged Discharge
7.9 2.4 1.6 19
Station 04
30 m North of C0RC0 Submerged Discharge
8.0 1.3 0.9
tt
tt
tt
10
Station 05
Mouth of Union Carbide Canal
35.0 28.0 7.4 7.5 0.2
1.6
Station 06
Mouth of C0RC0 001 Discharge
38
40
Station 07
Control (30 m East of Channel Buoy SE of C0RC0 Dock)
7.9 7.9 1.5 0.5 8 0
Station 08
West side of Tallaboa Bay near Punta Gayanilla
8.0 8.1 - 1.0 0
26.5-
29.0
7.4-
8.0
7.5-
8.1
0.2-
2.4
0.5-
1.6
0-19
40
0-40
15
13
16
38
0
0-38
gOg/m /day
4.3
2.4
2.4-
4.3
Predominate
Phytoplankton
Cladophora Enteromorpha
Rhizoclonium Cladophora
Diatoms
Cladophora Desmids
Filamentous Green Algae
Diatoms
t See Figure 1 for all Station Locations
tt CORCO submerged discharge contains wastewaters front CORCO Petrochemical plant,
Caribe Isoprene, Puerto Rico Olefins and Oxochem.
-------
D-5
Aesthetics
Suspended solids and oils were observed in Tallaboa Bay from the
CORCO 001 discharge, a violation of water quality standards. Algal
mats observed in the effluent from the CORCO treatment lagoons were
prevalent in the entire CORCO 001 discharge canal and at its mouth
(Station 06). Similar algal mats were observed at Station 08 settling
to the bottom of the bay. An oil spill on August 10 and 11, 1977 may
have contributed to the oil films observed August 14 from the CORCO
001 discharge. The oil spill involved an ESS0 tank farm and was in-
vestigated by the Coast Guard. No visible solids or oils were noted
from the CORCO 002 and Union Carbide discharges, but turbid conditions
were observed near these discharges.
Water transparency in Tallaboa Bay measured with a secchi disk
ranged from 0.2 to 2.4 m with the lowest reading recorded at the mouth of
the Union Carbide Canal. At the time of the water quality measurements,
strong east winds and seas limited water clarity in Tallaboa Bay.
However, the most turbid conditions were attributable to the CORCO 001
and Union Carbide waste discharges.
Sediment
A team of scuba divers examined the bottom sediments in Tallaboa
Bay. The bottom was covered with light brown floe over soft grey
clay-like material in the vicinity of Station 07, i.e., the reference
station. A middle layer of black organic deposits was observed near the
CORCO 002 discharge. The sediment depth increased west of this outfall.
Along Punta Guayanilla only black organic sediment deposits were ob-
served. Sand was visible at the end of the narrow spit of land separa-
ting the CORCO 001 and Union Carbide discharges. Algal mats similar to
those from the CORCO 001 discharge were observed along Punta Guayanilla.
Dense growths of filamentous algae were also observed along the shore-
line near the CORCO 002 discharge.
-------
D-6
Sediment core samples were collected at eight stations in Tallaboa
Bay. The depth of soft sediment ranged from 0.5 to 1.6 m with the
thickest accumulation associated with the waste outfalls. Organic
sediment deposits were observed at all stations except the control
southeast of the C0RC0 dock (Station 07). The organic sediment deposits
were thickest near C0RC0 001 and Union Carbide discharges and along
Punta Guayanilla. The original or natural Tallaboa Bay sand and clay
substrate along the eastern shore of Punta Guayanilla has been com-
pletely covered with black organic sediment deposits. Sediment cores
from Stations 05, 06 and 08 had strong petrochemical odors. In con-
trast, the core from Station 07 (control) contained light brown floe
over soft grey clay-like sediment and no hydrocarbon or black organic
sediment deposits were observed. The presence of these organic sediment
deposits, as a result of discharges from the petrochemical industries,
is a violation of water quality standards.
The sediment samples from Tallaboa Bay were analyzed by combined
gas chromatography/mass spectrometry (GC/MS). Results [Table 2] show
i
that 32 different compounds were identified in the samples. The com-
pounds (normal paraffins, aromatic hydrocarbons, cyclic hydrocarbons and
alkanes) are all hydrocarbons common to the petrochemical industry and
not found naturally. At least thirteen of these compounds were identi-
fied during the monitoring survey in the industrial effluents discharged
into Tallaboa Bay.
Twenty-one organic compounds were identified in the sediment
sample collected at the mouth of the C0RC0 001 discharge (Station 06).
The majority of these compounds were alkanes and aromatic hydrocarbons
ranging from 30 to 125 ppm concentration.
The sediment sample collected at the west end of Tallaboa Bay
(Station 08) showed the presence of numerous alkanes and substituted
alkanes. In total, about 50 compounds were present estimated at concen-
trations ranging from 10 to 20 ppm. The sediment samples collected at
-------
Table 2 D-7
' TALLABOA B/
August 14, 1977
SEDIMENT DATAf FROM TALLABOA BAY, PUERTO RICOff
Reten. Station+++
Comp0und j 02 03 04 05 06
1,1,3-Trimethylcyclohexane*
4.0
13
Nonane
5.0
20
Cumerie (isopropyl benzene)
5.4
2.3
Sec Butylcyclohexane
6.8
30
Decane
7.2
45
Dicyclopentadiene
7.75
6.0
Bicyclodihydropentadiene*
8.2
1.6
Undecane
9.5
70
Diisopropylbenzene Isomer*
10.5
6.0
Diisopropylbenzene Isomer*
11.0
5.2
Dodecane
11.9
75
Tridecane
14.2
90
Tetradecane
16.2
100
Dimethyl naphthalene
16.5
190
Biphenylene
17.0
2.0
Cyclohexan-1-01*
17.3
3.2
Acenaphthene
17.6
1.6
Isopropylnaphthalene Isomer*
18.0
50
Pen^adecane
18.4
75
Trimethylnaphthalene Isomer
18.8
95
Cyclopentene*
18.8
0.6
Isopropylnaphthalene Isomer*
19.2
50
Isopropylnaphthalene Isomer*
19.5
125
Tricyclopentadiene Isomer*
19.5
2.9
2.6
4.0
4.0
Hexadecane
20.4
55
Methyl Isopropylnaphthalene*
20.6
70
Heptadecane
22.3
50
Pristane
22.4
70
Octadecane
24.2
45
Phytane
24.5
50
Diisopropyl Phthalate*
25.0
2.3
Nonadecane
26.7
40
t All values are in \ig/gm (ppm). Detection limit was 0.5 ]ig/gm.
tt Sediments collected from 30 m. east of the CORCO submerged Outfall (Station
01) and the control station (Station 07) did not contain any detectable
amounts of organic compounds. The sediment collected from the west side of
Tallaboa Bay near Punta Guayanilla (Station 08) contained about SO Alkane
compounds at concentrations ranging from 10 to 20 ]xg/gm. Specific compounds>
howevery could not be identified.
ttt See Figure 1 for station location and Table 1 for station description.
* This compound was identified by GC/MS but not confirmed, as standards were
not available at the time of analyses. Quantitative results were estimated
by comparing the gas chromatography response of the sample compounds to
comparable standard compounds with similar gas chromatographic retention
times.
-------
D-8
Cable to
Sealed
Cable Port
Monitor
Septum
Dissolved
Oxygen Probe
(In Housing)
Agitator
Area
Clear
Plexiglas
Volume
Flange
Figure 2. In-Situ Sediment Oxygen Demand Chamber.
(Ellison, 1974)
-------
D-9
the control station (Station 07) did not contain any detectable amounts
of organic compounds.
Sediment Oxygen Demand
Sediment deposits in Tallaboa Bay exerted a substantial oxygen
demand on adjacent waters. The SOD rate was determined at a station
near the CORCO 002 discharge (Station 02) and a control site southeast
of the CORCO dock out of the zone of influence from known discharges
(Station 07). The rate at Station 02 was 4.3 vs. 2.4 g02/m2/day at the
control station [Table 1], Even higher SOD rates would be expected at
points where organic sediment deposits had completely covered the
bottom, such as near Punta Guayanilla. Time restraints prevented addi-
tional SOD work.
Phytoplankton
Surface grab samples from Stations 02, 05, 07 and 08 were examined
microscopically for phytoplankton. Filamentous green algae was ubiqui-
tous and the stations were similar except densities were extremely low
along Punta Guayanilla. The warm, oily surface waters apparently were
unsuitable for phytoplankton, but sedimented algae probably from the
CORCO treatment lagoons was observed in this area. Dense mats of
Cladophora3 Enteromorpha3 and Rhizoclonium were observed elsewhere
especially along the shores. Desmids and diatoms completed the observed
phytoplankton populations. Amphipods were observed in the phytoplankton
samples except at Station 08.
Comparison to 1971 Conditions
Western Tallaboa Bay appears to be more severely degraded now than
* Environmental effects of petrochemical waste discharges on Tallaboa
and Guayanilla Bay3 Puerto Rico3 EPA3 Athens3 Georgia3 Oct. ?13 pp.
-------
D-10
in 1974. Patterns and trends observed in 1971 have intensified.
Organic sediment deposits cover more of the bay and surface water
temperatures are higher. High SOD rates exert substantial oxygen
demand on adjacent waters. A chemical fish kill occurred in February
1977, and reports of fish tainting are numerous. The causes of the
degradation have expanded, i.e., additional petrochemical industries on
Tallaboa Bay. Tidal currents and winds as documented in 1971 apparently
move the increased amounts of polluting materials to the west and along
Punta Guayanilla.
-------
ATTACHMENT 1
WATER QUALITY STANDARDS
The waters of Tallaboa and Guayantlla Bay are classified for
industrial usage, Class SE. Puerto Rico Sanitary Regulation 131
contains the water quality standards adopted for Federal and Common-
wealth purposes. The applicable sections of this regulation are
reproduced below.
GENERAL CRITERIA
Article III - Pollution Discharges
A. It is hereby prohibited to any person, to directly or indirectly
throw, discharge, pour or dump and/or cause or allow to be thrown
discharged, poured, or dumped into the coastal waters of Puerto
any kind of domestic or industrial wastes with less than convent-
ional secondary treatment or control or its equivalent, or any
other substances capable of polluting or creating a potential
threat of pollution in such a way that coastal waters be rendered
below the minimum standards of purity established in these Rules
and Regulations.
B. Notwithstanding the foregoing prohibitions, the Secretary of
Health may upon application to that effect, grant permission for
drainage into the coastal waters when the discharged substances
have been previously submitted to a proper degree of treatment.
The degree of treatment will be as specified above in Part A,
Article III, unless it can be demonstrated to the Secretary of
Health, that a lesser degree of treatment or control with approved
ocean outfalls will not degradate the water quality. Since
these are also Federal standards, these waste treatment require-
ments will be developed in cooperation with the Federal Water
Pollution Control Administration.
C. Coastal waters whose existing quality is better than the estab-
lished standards as of the date on which such standards become
effective will be maintained at their existing high quality.
These and other coastal waters of Puerto Rico will not be lowered
in quality unless and until it has been affirmatively demonstrated
to water pollution control agency for Puerto Rico that such
change is justifiable as a result of necessary economic or social
development and will not interfere with or become injurious to
any assigned uses made of, or presently possible in, such waters.
This will require that any industrial, public, or private project
-------
D-12
or development which would constitute a new source of pollution
or an increased source of pollution to high quality waters will be
required, as part of the initial project design, to provide the
best practical degree of treatment available under existing
technology, and since these are also Federal standards, these
waste treatment requirements will be developed in cooperation
with the Environmental Protection Agency.
SPECIFIC CRITERIA
Article V - Classification and Standards of Quality for the Coastal
Waters of Puerto Rico
Class SE - Includes the coastal water which are destined for or may
be destined for industrial usages.
Quality Standards
The coastal waters included in Class SE shall not contain:
a. Floating solids, settleable solids, oils, and sludge deposits
which are readily visible and attributable to municipal, industrial
or other wastes or which increase the amounts of these constituents
in receiving waters or any other material or waste that would inter-
fere with the aesthetics of these waters.
b. Any type of garbage, cinder, ash, oil, sludge, or other refuse.
c. Dissolved oxygen in a concentration of less than four and a half
(4.5) milligrams per liter.
d. Toxic wastes, or deleterious substances alone or in combination
with other substance or wastes in sufficient amount as to prevent
the survival or propagation of fish life or impair the waters for
any other best usage as determined for the specific waters which
are assigned to this class.
e. A pH factor less than six and eight tenths (6.8) or more than
eight and five tenths (8.5).
f. A temperature more than A°F above ambient water temperature and
in no case in excess of 93°F.
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D-l 3
ATTACHMENT 2
STUDY METHODS
Core Sampling of Marine Sediments
Core of sediment were collected by NEIC scuba divers using 0.75 m
clear plastic tubes of 3 cm bore. The coring tube was manually inserted
through the soft surface sediments and approximately 1 m into the
underlying sediment. The top of the core tube was capped and the tube
withdrawn from the sediment. Before the tube was totally withdrawn
from the sediment the bottom end was also capped and the sample brought
to the surface. To remove the sample from the coring tube the top cap
was removed and the entrained liquid poured off. The bottom cap was
then removed and the sample extruded into a glass jar with a teflon-
1ined cap.
In-Situ Sediment Oxygen Demand Test
Sediment oxygen demand rates were measured from changes in the
dissolved oxygen concentration of water sealed in a clear plexiglass
chamber [Figure 2]. The cylindrical chamber was constructed to maximize
the ratio of bottom area to volume while allowing adequate circulation
of the water without disturbing the sediments. A metal flange seals
water within the chamber when pushed into soft bottom sediments.
Changes within the chamber were measured with a portable dissolved
oxygen meter. Each test was conducted for 30 minutes or longer. The
following calculation was used to determine SOD rates:
-------
D-14
SOD = ADLMU x LOi x HJjrs x 1 g
AT (hrs) A (m ) day 1,000 mg
where:
2
SOD = Sediment uptake rate in grams 02/m /day
ADO = Initial minus final dissolved oxygen in chamber in mg/1
AT = Test period in hours
V = Volume of confined water in 1 (17.06)
A = Bottom area within chamber in m (0.07)
Since V and A are constant the equation reduces to:
SOD = AD0 x 6.1 = g0?/m2/day
AT (hrs) L
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APPENDIX E
GC-MS ANALYSES OF INDUSTRIAL WASTEWATER OUTFALLS
PENUELAS, PUERTO RICO
AND
SELECTED FISH COLLECTIONS FROM GUAYANILLA-TALLABOA BAYS
PUERTO RICO
April 1977
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E-l
Director August 9, 1977
Edmund 0. Struzeski, Jr.
Industrial Waste Consultant
GC-MS Analysis of Industrial Wastewater Cutfalls, Penuelas, Puerto Rico,
and Selected Fish Collections from Guayanilla-Tallaboa Bays, Puerto
R1co, April 1977
Table I shows concentrations of eleven complex organics found in two
fish collected from the Guayanilla and Tallaboa Bay areas of Puerto
Rico during March-April 1977. Eight of these compounds were also
treasured in varying levels within the 5 industrial wastewater outfalls
1n the Penuelas area which were sampled during April 1977. The CORCQ
001 Outfall demonstrated the presence of six of the saca compounds
found present in the fish sacples. The Carlbe Isoprene Corp. outfall
showed the presence of two of the corapoonds found in the fish samples.
Toluene, which was verified in the fish sacples, was also confirnsd
in the C0RC0 001 and 002 Cutfalls, and 1n the PPG and the Union Carbide
outfalls. Unfortunately, industrial outfall samples were not secured
from Puerto Rico Olefins which discharges its waste into Tallaboa Eay.
Another firm In the Penuelas area, Oxochem Enterprises, does not dis-
charge to Guayanilla-Tallaboa Bays, and was not sacpled during April
1977. Tainting of cosrsrclal fish catches In Guayanilla Bay, if In
fact such tainting Incidents are occurring, have the highest probability
of occurrence of being associated with the C0RC0 outfalls and possibly
the CIC discharges. It 1s nevertheless noted that the HEIC GC/j'S data
1s still sketchy, the PRO effluent has not yet been sampled, and fish
tainting 1s likely Intensified by numerous product spills from the
industries in the area. C0RC0 has experienced the greatest nunfcer and
severity of product spillages, rlore HEIC sacjpllng and analysis should
be conducted for con^lex organics.
Table II shows that 42 different coasplex organic compounds were found
and identified in the five industrial wastewater outfalls. The C0RC0
001 outfall deranstrated a trass emission rate of 4,250 pgran/liter;
CCRC0 002 contained 262 vg/1; Caribe Isoprene has 1,615 yg/1; PPG showed
1,363 pg/1; and Union Carbide contained 280 ug/1. The C0RC0 001 outfall
had the greatest diversity of and highest level of organic compounds
which were largely hydrocarbons. The PPG effluent was characterized
by haloganated compounds. CIC was copprised of a nurcber of unsaturated
hydrocarbons. Considering the three additional compounds found 1n the
fish but not in the wastewater effluents, a total of 45 cocplex organics
was identified by the HEIC Laboratories for the Puerto Rico sarples.
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E-2
A few of these compounds were present in the 0.5 to 1.1 mg/1 (500 to 1,000
yg/1) range.
A limited search was made of the literature regarding the potential hazard
of some of the complex organics found in the Guayanilla, Puerto Rico sam-
ples. Kinkead, E.P., et.al, Toxicology and Applied Pharmacology, 20,
552-561, 1971 reports that Dic.yclepentadiene is slightly to moderately
toxic by the dermal route and highly toxic by the oral route in single-dose
studies. The Registry of Toxic Effects of Chemical Substances, 1975,
indicates low to moderate oral and dermal toxicity in animals studied.
Pi methylformami de, as found in the CIC effluent has moderate to low rela-
tive health hazard from concentrated short-term exposure, according to the
CRC Handbook of Analytical Toxicity, 1969. Sulfolane in the C0RC0 001
outfall appears to demonstrate relatively low oral toxicity in various
animal studies, according to the Registry of Toxic Effects of Chemical
Substances, 1975. Furfural present in the CIC discharge is an irritant
to various human body functions but its low volatility reduces the toxic
effects as reported by Sax in Dangerous Properties of Industrial Materials,
1968. The Toxic and Hazardous Industrial Chemical Safety Manual, ITII,
1975-1976, indicates furfural is relatively toxic and a relatively severe
irritant. The compound has moderate oral toxicity in rat studies. Tri-
chloroethane found in PPG effluents, is reported by Sax, 1968, as a fumi-
gant, has narcotic properties and acts as an irritant to the eyes, nose
and lungs. Trichloroethane may also be injurious to the liver and kidneys.
The Handbook of Analytical Toxicity, CRC, 1969, also reports that tri-
chloroethane has slight to marked relative health hazard from concentrated
short-term exposure.
Dibromochloromethane as evidenced in the PPG outfall is reported by Sax,
1968, in Dangerous Properties of Industrial Materials, to have unknown
toxicity but compounds of this type are generally irritant and narcotic
producing. Bromoform, also in the PPG outfall, has a moderate toxicity
rating via the air route according to Sax, 1968, in Dangerous Properties
of Industrial Materials. The Merck Index, 1976, reports that bromoform
overuse can lead to habituation or addiction. 1,4-Dioxane, as seen in
the Union Carbide Caribe effluent, has a moderatley high toxicity via
the air route as described by Sax, 1968, in Dangerous Properties of
Industrial Materials. The Merck Inde£ 1976, cites Dioxane as possibly
leading to CNS depression, necrosis of the liver and kidneys, and an
irritant to skin, lungs and mucous membranes. The Handbook of Analytical
Toxicology, CRC, 1969, describes Dioxane as showing moderate to low
relative health hazard from concentrated short-term exposure.
Furthermore, at least six of the 45 organic compounds found in the Penuelas
industrial wastewaters are included in the EPA listing of 129 potential
toxic compounds undergoing extensive study as per the stipulated NRDC-EPA
Consent Decree of June 7, 1976. These six substances comprise benzene,
toluene, 1,1,2-trichloroethane, tetrachloroethane, bromoform, toluene and
tetrachlorethylene.
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E-3
Expansion of complex organic sampling and analysis of industrial effluents
and fish in the Guayanilla Bay area of Puerto Rico is thought to be rela-
tively advantageous for enforcment purposes. The fish sampling program
should be carefully designed by the Biology Branch of NEIC to ensure the
best possible data return. NEIC should also be prepared to develop a
Relative Toxicity Index based upon a detailed literature search to access
various data bases available to NEIC and provide extensive in-house inter-
pretation. It is recommended that NEIC conduct a field study as described
above, preferrably during its on-site study of the Penuelas industries in
August-September 1977.
5 Enclosures
cc: Ass't. Director, Technical Prograns, NEIC wo/encl.
Chief, Enforcement Specialist Office, NEIC wo/encl. /
Chief, Field Operations Branch, NEIC wo/encl.
Chief, Chemistry Branch, NEIC wo/encl.
Mr. A1 Ossinger, Chemistry Branch, NEIC wo/encl.
Mr. Harvey Boyle, Chemistry Branch, NEIC wo/encl.
Dr. Doug Seba, Technical Liaison Off.,NEIC wo/encl.
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E-4
TABLE I
ORGANIC COMPOUNDS FOUND IN FISH SAMPLES CROSS-CORRELATED
WITH INDUSTRIAL OUTFALLS
Compound
Formula
ug/gram
Fish
Same Compound Found In
Industrial Outfalls As Shown
Toluene
C7 H8
27 (1)
8 (3)
CORCO
CORCO
PPG
UC
001
002
Pentadecane
C15
H32
0.9 (1)
0.6 (2)
5 (3
CORCO
001
Hexadecane
C16
H34
1.9 (1)
1.0 (2)
CORCO
001
Heptadecane
C17
H36
3.9 (1)
1.4 (2)
20 (3)
CORCO
001
Octadecane
C18
H38
1.2 (1)
<0.3 (2)
CORCO
001
Nonadecane
C19
H40
38 (1)
1.7 (2)
CORCO
001
Trlcyclopentadi ene
C15
H18
15 (3)
CIC
Methylcyclohexene
C7
H14
5 (1)
-
Dicyclopentadiene
C10
H12
18 (3)
CIC
Eicosane
C20
H42
<0.3 (2)
-
Heneicosane
C21
H44
1.8 (2)
-
(1) Large fresh fish collected on April 12, 1977 from Guayanilla Bay, viscera.
(2) Frozen fish obtained from U. S. Coast Guard, Ponce, P.R., viscera. Fish
was originally obtained by USCG on March 2, 1977 from local fishermen in
Guayanilla, P.R. area. The latter fish was thought to be associated with
a fish kill and fish tainting incident occurring around February 15, 1977
in Guayanilla and Tallaboa Bays.
(3) Same fish as (2) above, fish flesh analyzed.
-------
TAB^E II
ORGANIC COMPOUNDS FOUND IN PENUELAS, PUERTO RICO INDUSTRIAL WASTEWATER OUTFALLS
CROSS-CORRELATED WITH FISH SAMPLES
Compound
Formula
vq/i
CORCO
cSrco
yg/l
yq/1
vg/
001
002
CIC
PPG
uc
Toluene
C7 H8
68
200
-
310
30
Butyl acetate
C6 H12 °2
24
-
-
-
-
n-Octane
C8 H18
52
40
-
75
-
m-and p-Xylene
C8 H10
160
-
-
-
-
o-Xylene
C8 H10
10
-
-
-
-
n-Nonane
Cg H20
29
-
-
-
-
Cumene
Cg H12
94
-
-
-
-
Trimethylbenzene
Cg H12
140
-
-
-
-
n-Decane
C10 H12
75
-
-
-
Undecane
C11 H24
298
-
-
-
-
Sulfolane
C4H8°2S
770 (est)
-
-
m
-
Dodecane
C12 H26
470
-
-
-
-
1,3-Dicyclohexylbutane
C16 H30
45 (est)
-
-
-
-
Trldecane
C13 H28
450
-
-
-
-
Tetradecane
C14 H30
370
-
-
-
m
Dimethyl naphthalene
C12 H12
170
-
m
-
Pentadecane
C15 H32
340
m
-
Same Compound
Found In Fish
I
cn
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TABLE II
ORGANIC COMPOUNDS FOUND IN PENUELAS, PUERTO RICO INDUSTRIAL WASTEWATER OUTFALLS
CROSS-CORRELATED WITH FISH SAMPLES(Cont'd)
Compound
Formula
yg/1
CORCO
001
yg/1
coRcn
002
vg/i
cic
viq/l
PPG
vg/1
UC
Same Compound
Found in Fish
3-Methylbi cyclononadi ene
Tricyclopentadiene
1-Bromo-2-Chloroethane
1,1,2-Trichloroethane
Dlbromochloromethane
Tetrachloroethane
Bromoform
2-Hydroxyisobutyric
acid
Acetaldehyde diacetate
Bromocyclobutene
3-Bromocyclohexene
1,4-Dioxane
2-Methyl-l,3,6-
Trioxocane
C10 H14
C15 H18
C2H4BrCl
C2H3C13
CHBr2Cl
C2C14
CHBr-s
C4H8°3
C6H10°4
C4H5B**
CgHgBr
C4H8°2
C6H12°3
40 (est) -
12 (est) -
140 (est) -
250 (est) -
150 (est) -
140
150
12 (est) -
8 (est) -
100 (est) -
30 (est) -
30 (est)
¦ 220 (est)
TOTALS
262 1,615
yg/1 yg/1
1,365 280
yg/1 yg/1
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TABLE II
ORGANIC COMPOUNDS FOUND IN PENUELAS, PUERTO RICO INDUSTRIAL WASTEWATER OUTFALLS
CROSS-CORRELATED WITH FISH SAMPLES(Cont'd)
vq/l vg/l vg/l vg/l vg/l
Compound Formula CORCO CORCO Same Compound
001 002 CIC PPG UC Found In Fish
Hexadecane
C16 H34
480
-
-
X
Heptadecane
C17 H36
160
-
-
X
Octadecane
C18 H38
37
-
-
X
Nonadecane
C19 H40
18
-
-
X
Trimethylcyclopentane
C8 H18
-
13
-
-
Cycloheptane
C7 H14
-
5
-
-
Ethylidene diacetate
C6H10°4
-
<3
-
-
Tetrachloroethylene
C2H2CI4
—
<2
_ _
Benzene
C6 H6
-
-
8
-
N.N-Dimethylformamide
c3h7no
-
-
1,100
-
Furfural
C5H4°2
-
-
25
(est) -
2-Butylfuran
C8H12°
-
-
250
(est) -
B^cyclodihydro-r
dipentadiene
C10 H14
m
tm
20
(est) -
Dlcyclopentadiene
C10 H12
w
•
160
(est) - X
2
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APPENDIX F
ORGANIC ANALYSES METHODOLOGY
-------
F-l
ORGANIC ANALYSES METHODOLOGY
The effluent, fish flesh, and sediment samples from Puerto Rico were
analyzed by combined gas chromatography/mass spectrometry (GC/MS). Quantitative
results were obtained using flame ionization (FID) gas chromatography
and comparing the peak heights of the sample components to those of
standard compounds run concurrently. Where standards were not available,
quantitative results were obtained by comparing the gas chromatography
responses of the sample compounds to comparable standard compounds with
similar gas chromatographic retention times. The compounds were con-
firmed by GC/MS analysis of standards, and by coincidence of gas chroma-
tographic retention times with standards. Where standard compounds were
not available, identification was made by mass spectra only. Analytical
procedures follow.
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F*2
A. Water Samples: The pH "was measured on all samples and ranged from
5 to 6. A 3500 ml water sample was extracted in a 4 liter separatory funnel
with 150 ml methylene chloride followed by a second extraction with 100 ml
methylene chloride. The combined extract was added to a 2 x 10 cm column
of sodium sulfate prewetted with methylene chloride. The column was then
eluted with 100 ml of acetone. The combined extract was concentrated on a
hot water bath in a Kuderna-Danish evaporative concentrator to 10 ml.
B. Sediment Samples: Approximately 200 gms of wet sediment was spread
in a flat Pyrex dish and air dried for 24 hours. A 20 gm sample was extracted
in a Waring Blendor with 150 ml acetone for 2 minutes. The acetone was de-
canted off and the sediment was extracted again with 150 ml hexane and the
hexane decanted off. The combined extract was filtered through Whatman #3
paper, then added to a 2 x 10 cm column of sodium sulfate prewetted with
hexane. The dried extract was concentrated on a hot water bath in the
Kuderna-Danish concentrator to 10 ml.
A 5 gm sample of the air dried sediment was put in a convection oven
for 24 hours at 105°C for a dry weight calculation.
C. Gas Chromatography: The samples (1 ul) were screened and measured
quantitatively by FID gas chrom?tography. Quantitative estimates were made
by comparing peak heights of the sample components to those of standard
compounds run concurrently. The following conditions were used:
Instrument: Varian Model 1440
Detector: FID
Column: 2 mm ID x 10' - Glass 6% 0V-101 on 60/80 mesh GC-Q
Carrier Gas: Helium
Flow: 20 ml/min
Temperatures:
Injector: 230°C
Column: Temperature Program 80-220°C 05°C/min
Detector: 250bC
D. Gas Chromatography/Mass Spectrometry: A 1 to 2 ul aliquot was
analyzed by GC/MS using the following conditions:
1. Gas Chromatography
Instrument: Varian Model 1440
Column: 2 mm ID x!0' - Glass 6% 0V-101 on 60/80 mesh GC-Q
Carrier Gas: Helium
Flow: 20 ml/min
Temperatures:
Injector: 230°C
Column: Temperature Program 80-220°C @6°C/min
2. Mass Spectrometry
Instrument: Finnigan Model 1015 EI
Temperatures:
Separator: 250°C
Transfer Line: 230°C
Head: 100°C
Mass Range: 20-300
Integration Time: 8 ms
Samples/AMU: 1
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APPENDIX G
LABORATORY EVALUATION
-------
G-l
ENVIRONMENTAL PROTECTION AGENCY
OFFICE OF ENFORCEMENT
NATIONAL ENFORCEMENT INVESTIGATIONS CENTER
BUILDING 53, BOX 25227, DENVER FEDERAL CENTER
DENVER, COLORADO 80225
o Chief date August 29, 1977
Chemistry Branch
from J. j. SIovinski
jubject Laboratory Evaluation of Commonwealth Oil Refinery Corporation
Panuelas, Puerto Rico
CORCO performs all of its NPDES chemical monitoring in its laboratory
located on the refinery site. This testing has been performed at the
laboratory since the permit requirements went into effect in December,
1974. On August 10, 1977, the CORCO Laboratory was visited by the EPA
personnel to conduct an evaluation of NPDES permit parameter testing.
The laboratory at CORCO is a very large, modern, well-equipped facility,
designed to perform product quality control testing. About 1000 square
feet of lab space and one chemist are devoted full-time to NPDES anal-
yses. In addition, three to four other technicians perform water
quality analyses on a part-time basis. Mr. Aviles is the chemist in
charge of the water analyses. Mr. Jose Ruiz of CORCO's Environmental
Protection Group supervises all NPDES monitoring activities with regard
to the laboratory.
Mr. Aviles performs the analyses according to prescribed methods as out-
lined in the 14th edition of Standard Methods, except as noted below.
He has an adequate understanding of the test procedures and, in most
instances, uses proper analytical techniques.
All instruments are properly maintained and of acceptable quality. All
reagents are of proper analytical grade and are properly stored except
as noted below.
Permanent records of raw data are kept and were available for inspection,
but are very unorganized in their format and difficult to follow.
The following is a listing of those deficiencies, irregularities, or devi-
ations from standard methods and techniques for analysis.
BOD
No dilution water blank is incubated with samples to determine if the
dilution water presents a BOD load on the sample. If the dilution water
is seeded, this is also a check on the activity of the bacterial population.
-------
G-2
From Extractable Material
Typical blank residues of 6, 8, or even 11 mg have been subtracted from
the FEM results. These large residues are indicative of freon contamina-
tion. The same source of freon was used each day, yet the blank values
showed gross variations. High blank values such as these for freon are
not acceptable. FEM results reported with such large blank values sub-
tracted out are highly questionable.
There is no formalized analytical quality control program in effect nor
any informal quality control procedures such as replicate or spiked
samples being performed. Recovery efficiency or precision data is non-
existant. Though from all appearances most of the NPDES parameters are
performed in a correct manner, there is no way of documenting that cor-
rect values are being reported because several of these tests are sub-
ject to interferences. Quality control information is needed to deter-
mine the validity of the data being reported.
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