-------
(1) 1 to 50 employees
(2) 51 to 100 employees
(3) 101 to 500 employees
(4) 501 to 1,000 employees
Tables 6 and 7, pp. 43 and 44,
By plant age according to state and EPA Region, using the following classi-
fications:
(1) 1 to 4 years
(2) 5 to 30 years
(3) 31 to 50 years
(4) More than 50 years
Tables 8 and 9, pp. 45 and 46.
By product slate according to state and EPA Region. (Product distribution
is not given in terms of refinery type.)
Tables 10 and 11, pp. 47 and 48.
By total crude capacity according to state and EPA Region.
Tables 12 and 13, pp.49 and 50.
42
-------
TABLE 6
DISTRIBUTION OF U. S. REFINERIES BY EMPLOYMENT (STATES)
0
.-! Q
& z
IV
X
IX
VI
IX
vm
i
m
UI
IV
IV
IX
X
V
V
VII
VII
IV
VI
I
m
i
V
V
IV
vn
vm
vn
IX
i
u
VI
n
IV
VUI
V
VI
X
UI
I
IV
VUI
IV
VI
VUI
I
UI
X
m
V
VUI
STATE
Alabama
Alaska
Arizona
Arkansas
California
Colorado
Connecticut
Delaware
Dist. of Columbia
Florida
Georgia
Hawaii
Idaho
Illinois
Indiana
Iowa
Kansas
Kentucky
Louisiana
Maine
Maryland
Massachusetts
Michigan
Minnesota
Mississippi
Missouri
Montana
Nebraska
Nevada
New Hampshire
New Jersey
New Mexico
New York
N. Carolina
N. Dakota
Ohio
Oklahoma
Oregon
Pennsylvania
Rhode Island
S. Carolina
S. Dakota
Tennessee
Texas
Utah
Vermont
Virginia
Washington
W. Virginia
Wisconsin
Wyoming
TOTAL
REFINERY TYPE
I
1
2
4
1
1
9
1
2
2
2
2
1
4
2
1
5
3
1
1
1
7
1
1
3
57
2
2
6
1
2
1
1
2
L
1
1
4
1
23
3
2
5
1
2
1
1
1
2
1
1
17
4
0
5
1
1
U
1
1
1
1
1
2
1
7
2
1
2
1
4
3
2
1
1
3
4
1
1
2
2
1
2
1
2
3
2
2
1
6
3
3
1
3
47
I
4
1
1
1
1
1
1
6
5
1
1
in
i
i
i
2
2
0
3
2
1
3
2
1
2
2
6
1
1
1
22
4
1
3
1
5
5
0
IV
1
1
1
1
1
4
2
1
1
1
3
6
3
1
1
1
2
2
3
1
1
12
4
3
1
2
1
1
2
1
2
13
5
3
1
1
3
1
1
1
1
8
20
STATE
TOTAL
4
4
1
4
34
3
0
1
0
1
2
2
0
11
7
0
11
3
18
0
2
0
6
3
5
1
8
1
0
0
5
6
2
0
2
7
12
1
11
0
0
0
1
40
6
0
1
7
3
1
10
247
Key: 1. 1-50 Employees
2. 51-100 Employees
3. 101-500 Employees
4. 501-1, 000 Employees
5. Over 1,000 or more Employees
------- An error occurred while trying to OCR this image.
-------
TABLE 8
DISTRIBUTION O II. S. RFFINF.RIKS BY PLANT AGE fSTATF.S^
0
O
* O
00 Z
fl) rH
rf
IV
X
IX
VI
IX
VIII
I
in
m
IV
IV
IX
X
V
V
VII
VII
IV
VI
I
in
i
V
V
IV
VII
VIII
VII
IX
i
ii
VI
II
IV
VIII
V
VI
X
HI
I
IV
VIII
IV
VI
VIII
I
in
X
in
V
VUI
STATE
Alabama
Alaska
Arizona
Arkansas
California
Colorado
Connecticut
Delaware
Dist. of Columbia
Florida
Georgia
Hawaii
Idaho
Illinois
Indiana
Iowa
Kansas
Kentucky
Louis iana
Maine
Maryland
Massachusetts
Michigan
Minnesota
Mississippi
Missouri
Montana
Nebraska
Nevada
New Hampshire
New Jersey
New Mexico
New York
N. Carolina
N. Dakota
Ohio
Oklahoma
Oregon
Pennsylvania
Rhode Island
S. Carolina
S. Dakota
Tennessee
Texas
Utah
Vermont
Virginia
Washington
W. Virginia
Wisconsin
Wyoming
TOTAL
REFINERY TYPE
I
1
1
2
1
2
2
3
2
15
1
1
2
1
i
i
i
8
2
2
2
6
2
2
3
4
4
1
1
3
1
1
10
1
2
3
75
3
3
2
4
1
i
1
1
2
1
2
12
2
3
II
1
1
1
2
1
1
3
1
1
1
i ; 2
3
2
1
2
2
1 1
1
1
1
3
1
1
1
2
1
1
8
4
3
1
5
46
1
1
1
1
2
14
4
1
1
1
1
4
in
i
0
2
3
3
2
2
1
1
2
1
1
3
1
1
20
3
1
1
1
1
3
I
8
4
1
1
IV
1
1
1
1
3
2
2
1
1
1
1
3
1
4
1
1
16
3
1
1
1
1
2
1
1
5
5
1
19
4
4
1
2
1
2
2
1
2
1
1
17
STATE
TOTAL
4
4
1
4
34
3
0
1
0
1
2
2
0
11
7
0
11
3
18
0
2
0
6
3
5
1
8
1
0
0
5
6
2
0
2
7
12
1
11
0
0
0
1
40
6
0
1
7
3
1
10
247
Key:
1.
2.
1-4 Years
5-30 Years
3. 31-50 Years
4. Over 50 Years
-------
TABLE 9
DISTRIBUTION OF U. S. REFINERIES BY PLANT AGE (EPA REGIONS)
Region
by
EPA
I
II
in
IV
V
VI
VII
VIII
IX
X
Total
REFINERY TYPE
I
1
1
2
3
ฃ
8
2
3
9
7
23
2
10-
16
5
75
3
2
1
2
4
1
2
12
4
2
1
3
II
1
1
1
2
4
2
8
12
4
11
2
3
46
3
1
1
2
4
3
1
1
1
14
4
1
1
1
1
4
in
1
0
2
1
1
4
6
2
2
3
1
20
3
4
2
H
1
8
4
1
1
IV
1
1
2
3
2
2
1
8
1
1
2
1
16
3
6
2
9
1
1
19
4
1
2
5
4
1
4
17
Region
Total
0
7
18
16
35
80
13
29
37
12
247
Key: 1. 1-4 Years
2. 5-30 Years
3. 31-50 Years
4. Over 50 Years
46
------- An error occurred while trying to OCR this image.
------- An error occurred while trying to OCR this image.
-------
TABLE 12
DISTRIBUTION OF U. S. REFINERIES BY TOTAL CRUDE CAPACITY (STATES)
ป
IV
X
IX
VI
IX
vni
i
m
iii
IV
IV
DC
X
V
V
vn
VII
IV
VI
i
in
i
V
V
IV
vn
vm
vn
DC
i
ii
VI
n
IV
VIII
V
VI
X
III
I
IV
vin
IV
VI
vin
i
m
X
m
V
vm
STATE
Alabama
Alaska
Arizona
Arkansas
California
Colorado
Connecticut
Delaware
Diet, of Columbia
Florida
Georgia
Hawaii
Idaho
Illinois
Indiana
Iowa
Kansas
Kentucky
Louisiana
Maine
Maryland
Massachusetts
Michigan
Minnesota
Mississippi
Missouri
Montana
Nebraska
Nevada
New Hampshire
New Jersey
New Mexico
New York
N. Carolina
N. Dakota
Ohio
Oklahoma
Oregon
Pennsylvania
Rhode Island
S. Carolina
S. Dakota
Tennessee
Texas
Utah
Vermont
Virginia
Washington
W. Virginia
Wisconsin
Wyoming
TOTAL
REFINERY TYPE
I
5.6 (35)
10.5 (66.0)
1.5 (9.0)
2.0 (12)
49.0 (308)
1.4 (9)
0.8 (5)
2.3 (15)
4.8 (30)
0.4 (3)
3.0 (19)
1.3 (8)
0.5 (3)
17.4 (109)
3.7 (24)
6.2 (39)
3.4 (21)
3.0 (19)
5. 5 (34)
0.8 (5)
1. 6 (10)
9.5 (60)
2.2 (14)
30.7 (193)
17.7 (112)
0.8 (5)
1.3 (8)
0.2 (2)
187. 1
(1,177)
U
30.0 (188)
2.8 (17)
6.4 (40)
13.4 (84)
14.6 (92)
19.1 (120)
25.0 (157)
37.0 (233)
15.7 (99)
13.3 (84)
38.2 (240)
6.7 (42)
0.8 (5)
82.8 (521)
3.3 (21)
17.1 (108)
7.6 (48)
24.3 (153)
14.9 (94)
6.1 (38)
4.6(29)
90.0 (566)
20.6 (130)
36.8 (232)
5.9 (37)
17.2 (108)
554.2
(3,486)
III
50.0 (312)
76.0 (478)
24.6 (154)
28.6 (180)
17.0(107)
4.5 (Z9)
16.8 (105)
15.5 (98)
10.7 (68)
56< 8 (357)
8.4 (53)
15.3 (96)
3.4 (21)
327.6
(2,058)
IV
7.0(44)
159.0(1002)
4.8 (30)
22.0(140)
93.3 (587)
70.1 (441)
19.1 (120)
TOTAL
5.6 (35)
10.5 (66)
1.5 (9)
9.0 (56)
288.0 (1810)
9.0 (56)
22.0 (140)
0.8 (5)
2.3 (15)
11.2 (70)
183.1 (1152)
87.7 (552)
64.1 (402)
25.5 (160)
181.48(1135)264.5 (1657)
15.6 (98)
65.2 (410)
41.4 (261)
73.2 (458)
3.7 (24)
21.9 (138)
30.3 (191)
46.1 (290)
16.8 (105)
25.2 (159)
0.8 (5)
98.4 (619)
8.8 (55)
17.1 (108)
8.4 (53)
91.1 (573)
76.5 (483)
2.2 (14)
110.0 (689)
4.6 (29)
429.2 (2700) 593.7 (3735)
0.8 (5)
3. 1 (20)
6.8 (43)
1192.1
(7,494)
21.4 (135)
8.4 (53)
54.2 (341)
3.1 (20)
5.9 (37)
27.6 (174)
2261
(14,215)
Capacity Unit:
1, 000 cubic meters (m /day)
1,000 barrels/day
-------
TABLE 13
OF U. S. REFINERIES BY TOTAL CKUDE
CAPACITY (EPA REGIONS)
Region
by
EPA
I
II
in
XV
V
VI
vii:
vm
IX
X
Total
REFINERY TYPE
I
34.4
(217)
12.6
(79)
11.2
(71)
52.1
(327)
1.3
(8)
6.2
(40)
55.3
(347)
14.0
(88)
187. 1
(1,177)
II
99.9
(629)
6.1
(38)
67.8
(426)
87.2
(549)
145.2
(914)
19.9
(125)
54.9
(345)
36.4
(228)
36.8.
(232)
554.2
(3,486)
HI
8.4
(53)
4.5
(29)
93.0
(585)
96.1
(605)
41.4
(259)
18.9
(119)
50.0
(312)
15.3
(96)
327.6
(2,058)
IV
15.6
(98)
98.3
(618)
228.6
(1438)
659.1
(4140)
19.1
(120)
11.6
(73)
15 %0
(1002)
I 0.8
(5)
1,192.1
(7,494)
Region
Total
115.5
(727)
147.2
(926)
84.9
(534)
420.0
(2643)
952.5
(5986)
81.7
(512)
41.6
(577)
300.7
(1889)
66.9
(421)
2, 2>1
(14,215)
Note: Capacity Unit: 1,000 cubic rreters (m )/day
1, 000 barrels/day
50
-------
2.4 FUTURE TRENDS IN THE PETROLEUM REFINING INDUSTRY
2.4.1 INTRODUCTION
Growth in refinery crude capacity in 1974 amounted to about
600,000 barrels per day, which is roughly comparable to the capa-
city gained in the previous year (5 ). Most of the current gains in
the capacity have resulted from expansion of existing plants, since
by this means the new capacity comes on stream more quickly than
by developing grass-roots facilities. Shortly after the changes in
U. S. petroleum import policy were announced in April 1973, a num-
ber of companies announced plans for added refining capacity totaling
more than 2 million barrels per day. The number of new refineries
slated for construction continued to grow, although more slowly,
through the remainder of the year. Due to higher prices and result-
and decreased demand for petroleum products, plans for new refin-
ery construction were delayed or abandoned during 1974 and 1975.
Furthermore, the sharp rise in new refinery construction costs as
well as the reduced profit margin resulting from current higher
prices, make anew refinery a less attractive investment. Construc-
tion of some of the announced refineries has begun in hopes that
prices will improve.
In the past two years there has been little change in process-
ing intensity of downstream equipment. U. S. refineries continue
to be oriented toward maximum gasoline yield and minimal residual
products, while the foreign centers are geared to high distillate and
residual fuel oil production. As of April 1, 1974, downstream capa-
city of the United States refineries as a percent; of crude capacity
were: hydrogen processes, 40.7%; catalytic cracking, 32.5%;
catalytic reforming, 23.6%; thermal processes, 10.5%; alkylation,
6%; and hydrocracking, 6% (6 ). Catalytic cracking, hydrocracking,
and thermal processes primarily convert residual fuel oil compo-
nents to gasoline and distillate components. Catalytic reforming
and alkylation improve the octane quality of gasoline components.
2.4.2 Forecasting Energy Demands
The following discussion of the energy/hydrocarbon relation-
ship as it shapes future trends in petroleum refining is based upon
a report by the Pace Company of Houston, Texas ( 7 ).
51
-------
Methods
The Pace approach to forecasting energy demand has been to
first determine how people have used energy in the past, and to use
this as a basis for projecting how they will use it in the future. The
household is considered to be the fundamental consuming unit and all
forecasts are made on a per household basis. Using this technique, a
forecast of transportation needs embodies the following information:
(1) forecast of total travel between and within cities, and allocation of
totals among the various transportation modes, i.e. , automobile, bus,
air, train, etc.; (2) occupancy rates for each mode to develop vehicle
miles; and (3) fuel efficiencies for individual types of vehicles and
weighted averages to determine fuel consumption. Appropriate fac-
tors and corrections are applied to account for current trends and for
anticipated changes.
The most difficult challenge currently facing forecasters is to
assess the changes in product demands and spending patterns which
will result from the recent large increases in energy costs. Future
demands for virtually every product will be directly or indirectly af-
fected, but the most basic and important is the demand for energy
itself. When faced with these dramatically higher costs, the individ-
ual consumer can react by changing his consumption pattern in two
basic ways: (1) curtailment of energy-consuming activities, such as
cutting back travel or lowering the temperature of heated spaces; and
(2) shifting of buying patterns toward more energy-efficient items,
such as smaller cars and better insulated houses. The first consump-
tion pattern change is likely to be reflected in a fairly rapid reduction
in energy demand, while the effects of the second pattern change are
likely to be cumulative over a long period of time. Both have been
assessed and integrated into the basic forecasting technique. Quanti-
tative determinations of energy demands with respect to price are at
best difficult and imprecise, but the difficulty is compounded because
significantly higher energy costs have occurred only fairly recently,
i.e. , late 1973, and only limited statistical data are available. They
are further compounded by the Arab oil embargo during late 1973 and
1974 and by the severe economic recession resulting in part from the
energy crisis. Both factors tend to make the statistics inconsistent.
Reaction of consumers to the sharp increases in crude oil and energy
prices is best reflected in a comparison of energy consumption and
economic activity of the third quarter of 1974 with the same quarter
of 1973. The third quarter of 1973 was prior to the embargo and the
third quarter of 1974 was after the embargo, when consumption was
52
-------
not limited by shortages. Table 14 gives a comparative data on energy
consumption and economic activity during these two periods. As can
be seen, the third quarter 1974 records a 2.4% decrease in energy con-
sumption from the consumption of the third quarter 1973, with a simul-
taneous 3.6% reduction in petroleum production. During the same
period the real GNP (1958 dollars) suffered a reduction of 2. 1%. For
reference, the average price of crude oil in the U. S. for the two per-
iods was: $3.60/barrel (1973) and $9.20/barrel (1974). Comparisons
thus do not provide measures of consumer reaction to price alone.
Recognizing these limitations, the available data are used in combina-
tion with judgement in forecasting energy demands.
Demand Projections
The relatively inflexible energy supply/demand balance of 1974
resulting from the Arab oil embargo (beginning November 1973)
prompted the use of two probable economic patterns, i.e. , Case I and
Case II, in forecasting energy demands. Case I is the highest attain-
able energy consumption level consistent with world oil prices. It
assumes recovery from the recession by mid-1976, as well as an ab-
sence of mandatory or punitive government controls to reduce con-
sumption, beyond those already enacted. It reflects the rapid change
in consumption that actually occurred in response to the sudden in-
crease in prices. Case II is the current estimate of the energy con-
sumption level which would result from de-control of U. S. crude oil
prices and retention of the $3.00 per barrel oil import tariff initiated
by the President. It assumes reduced consumption, particularly in
the household/commercial and transportation sectors, as a result of
higher energy costs.
The assessment of energy consumption corresponding with
Case I economic patterns assumes that the trends which have occurred
since the beginning of the sharp price escalations in late 1973, such as
increased use of small cars and reduction in heating and cooling of
homes, represent permanent changes rather than short-term emotion-
al reactions. Two significant events have occurred that affect trans-
portation energy consumption but which are not directly related to
consumer reaction: (1) The addition of catalytic mufflers has resulted
in a significant improvement in efficiency for 1975 model cars. Al-
though previous forecasts had assumed further penalties as catalytic
mufflers were added, EPA data show an average improvement for new
cars amounting to about 15% over 1974 models. (2) Enaction by
Congress of a national speed limit of 55 miles per hour has resulted
53
-------
Table 14
ENERGY rnNSllMPTIQN AND ECONOMIC ACTIVITY: THIRD QUARTER,
1973 and 1974
Third Quarter Third Quarter Percent Change
ENERGY CONSUMPTION 1973 ]974_ (1974 vs. 1973)
Coal
Million Tons 144.5 141.8
MB/Day as COE* 6,127 6,012 i.ป
Natural Gas
Billion Cubic Feet 5,841 5.551
MB/Day as COE* 10,758 10,222 &.u
Petroleum
MB/D as COE* . 15,824 15,254 -3.6
Total Energy
MB/D as COE* 34,272 33,446 -2.4
Electric Power (Billion KWH)
Total Generation 504.8 501.0 ;0.1
Sales to Industry 175.6 178.9 *i.ป
Sales to Residential/ _2 ,
Commercial 266.3 260.7 *.i
ECONOMIC ACTIVITY
GNP (Annual Rates)
Billion Actual Dollars 1,308.9 1.416.3 +8.2
Billion 1958 Dollars 840.8 823.1 -*-i
Constant Dollars per _2 9
Capita 4,033 3,918
Personal Consumption
Expenditures (Constant 1 5
Dollar Basis) - - "''
*Crude Oil Equivalent 5.85 million BTU.
-------
in lower gasoline consumption in intercity travel. Case I projections
assume that travel within cities will remain constant at the 1973 level
and that per household intercity travel will decline in 1974. Growth of
each from 1974 levels is expected to occur at the following rates:
1975 to 1977, 0% per year; 1978 to 1980, 0.5% per year; and 1981 to
1985, 1.0% per year. As a point of reference, total travel per house-
hold increased at an average annual rate of 2.2% between the years of
1969 and 1973. The assumed 1974 decline in travel is based upon a
2. 1% drop in gasoline consumption during the third quarter of 1974
from that of the third quarter of 1973, the reflection of an approximate
6.0% decrease in actual automobile miles driven per household during
this period. In view of this, a 3.0% travel reduction may be conser-
vative. Historical and projected intercity and intracity travel data
for the years 1969 to 1985 are shown in Tables 15 and 16, respectively.
In addition to this basic assumption, the following major as-
sumptions influenced calculations of energy demand in the transpor-
tation section for Case I:
(1) Small car sales will stabilize at the level prevailing dur-
ing the first six months of 1974, about 30% of the total for
the period. Since 1970, small car sales on the West
Coast (Petroleum Administration for Defense (PAD) Dis-
trict 5 in Figure 6) have been notably higher than the
national average, and are assumed to stabilize at the
current level of about 48% of national totals. Table 17
shows recent and projected future automobile sales, by
size, according to Case I and II consumption patterns.
(2) Speed limit reductions will be permanent. The effect of
speed restrictions on automobile gasoline consumption is
shown in Table 18.
(3) There will be no increase in car pooling after 1974. This
is reflected in the passenger per automobile estimates
shown in Table 19, showing the ratio between automobile
and passenger miles traveled.
(4) Increased proportions of total travel will be via bus,
train, and air, resulting in a decline in the percentage
represented by automobile travel. (Tables 15 and 16
reflect these changing modes of travel.)
55
-------
-------
Table 15
TRAVEL BETWEEN CITIES. 1969-1985
(Case I)
TTutomo-
biles
1969 977
1970
1971
1972
1973 (Est.)
1977
1980
1985
,026
,071
,085
,104
,129
,189
,323
Billion Passenger
Ttir-
planes
120
119
120
130
135
154
172
203
Rail-
Buses
25
25
26
26
26
37
50
82
roads
12
11
9
9
11
15
19
25
Miles
Hater-
ways
3.8
.4.0
4.1
4.2
4.3
4
4
5
Thousand
House- Miles per
Total
1,138
1,185
1,230
1,254
1,280
1.339
1,434
1,638
holds Household
62,073
63,143
64,293
65,464
66,656
71 ,878
75,847
82,426
18,333
18,767
19,131
19,156
19,203
18,630
18,910
19,870
Per Cent of Total
1969
1970
1971
1972
1973 (Est.)
1977
1980
1985
85.9
86.6
87.1
86.5
86.3
84.3
82.9
80.8
10.5
10.0
9.8
10.4
10.5
11.5
12.0
12.4
2.2
2.1
2.1
2.1
2.0
2.8
3.5
5.0
1.1
1.0
0.7
0.7
0.9
1.1
1.3
1.5
0.3
0.3
0.3
0.3
0.3
0.3
0.3
0.3
100.0
100.0
100.0
100.0
100.0
100.0
100.0
100.0
57
-------
TABLE 16
TRAVEL WITHIN CITIES^ 1969-1985
"
1969
1970
1971
1972
1973 (Est.)
1977
1980
1985
Automo:
biles
652
692
735
795
830
873
910
969
(Case 1)
Buses
UM ซ**"**
*h n
31
on
30
29
/\c\
28
28
44
63
116
Billion
Street
cars
1
i
i
1
1
1
1
Passencjer Miles
Trolley- Subway/Sur-
ra rs face Rail Total
i
i
i
1
1
i
1
1
1
1
1
23
21
21
21
22
32
44
76
708
. 745
787
846
882
951
1,091
1,163
Thousand
House-
holds
(July 1)
62,073
63,143
64,293
65,464
66,656
71 ,878
75,487
82,426
Miles per
Household
11,406
11,799
12,241
12,923
13,232
13,230
13,430
14,110
Per Cent of Total
1969
1970
1971
1972
1973 (Est.)
1977
1980
1985
92.1
92.9
93.4
94.0
94.1
91.8
89.3
83.3
4.4
4.0
3J
3.3
3.2
4.6
6.2
10.0
0.1
0.1
0.1
0.1
0.1
0.1
0.1
0.1
0.1
0.1
0.1
0.1
0.1
0.1
0.1
0.1
3.3
2.9
2.7
2.5
2.5
3.4
4.3
6.5
100.0
100.0
100.0
100.0
100.0
100.0
100.0
100.0
58
-------
TABLE 17
1970
1971
1972
1973
1974 (6 mos.)
1975
1977
1980
1985
Small
21.8
26.0
25.9
28.2
30.1
30.1
30.1
30.1
30.1
(Percent of
CASE I
Intermediate
36.4
32.0
33.9
36.1
42.4
42.4
42.4
42.4
42.4
U.S. Total
Large
41.8
42.0
40.2
35.7
27.5
27.5
27.5
27.5
27.5
Small
21.8
26.0
25.9
28.2
30.1
32
36
40
40
CASE II
Intermediate
36.4
32.0
33.9
36.1
42.4
44
42
40
40
Large
41.8
42.0
40.2
35.7
27.5
24
22
20
20
59
-------
Table 18
EFFECT OF SPEED RESTRICTIONS ON AUTOMOBILE
GASOLINE CONSUMPTION. 1969-1985
Factor Change Due to Speed Restrictions
1.000
1.000
0.978
0.977
0.977
Notesi
The nationwide speed limit of 55 miles per hour will increase
average miles per gallon for automobile journeys between cities
but will not affect fuel usage within cities. The best current
information is that the average fuel saving will be about 5 per-
cent if all drivers slow down from the previous average speed
of 62 miles per hour to an average of 55 miles per hour. If the
average speed is less than 55 miles per hour, a greater fuel
saving will be realized.
The above calculations assume a 5 percent saving on journeys be-
tween cities. The factor declines because driving between cities
is expected to gain slightly within total driving.
The change is relative to fuel usage without the speed restrictions,
NOT to 1969 average fuel use as in the case of the emission control
penalty factors. (Table 3-7)
60
-------
Table 19
RATIO OF AUTOMOBILE MILES/PASSENGER MILES
FOR INTERCITY AND INTRACITY TRAVEL FOR THE
YEARS 1969. 1972. 1977. 1980. AND 1985 (Case I)
1969
Billion Passenger Miles
Passengers per Automobile
Billion Automobile Miles
Between Cities
977
2,487
393
Within Cities TOTAL
652 1,629
1.4
466 859
Billion Passenger Miles
Passengers per Automobile
Billion Automobile Miles
Billion Passenger Miles
Passengers per Automobile
Billion Automobile Miles
1980
Billion Passenger Miles
Passengers per Automobile
Billion Automobile Miles
1985
Billion Passenger Miles
Passengers per Automobile
Billion Automobile Miles
1,085
2,489
436
1,129
2.5
452
1,189
2.5
476
1,323
2.5
529
795
1.4
568
873
1.4
624
910
1.4
650
969
1.4
692
1,880
1,004
2,002
1,076
2,099
1,126
2,292
1,221
Note: The automobile occupancy rate of 1.4 persons on trips within cities was
determined by a survey made by the Department of Transporation. As indi-
cated this rate has been held'constant for Case I. For Case II, we have
assumed that the occupancy rate for travel within cities increases to 1.6
by 1980 as a consequence of car pooling, stimulated by higher gasoline
prices. The occupancy rate for between city travel has not been changed
since this form of travel does not generally lend itself to car pooling.
61
-------
(5) Present exhaust emission reduction schedule will be re-
laxed. It is assumed that beginning in 1977 (1975 in
California) automobile emissions must be controlled at
2.0 grams per mile. Increases in fuel consumption re-
sulting from use of control devices on the average auto-
mobile (exhaust emission penalty factors) are shown in
Table 20.
(6) The negative effects of automobile weight and power
options on gasoline mileage will continue to increase
gradually, leveling off at the early 1980's (see Table 21).
(7) The seat load factor in commercial aircraft will remain
at the 1974 level. Reductions in number of scheduled
flights and substitution of smaller aircraft have approach-
ed a practical maximum.
Average automobile gasoline consumption associated with both
case I and Case II consumption patterns is shown in Table 22. De-
mands for petroleum for use in all modes of travel and representing
Case I and Case II consumption patterns, are given in Tables 23 and
24 respectively. Figures represent thousands of barrels per day
(MBPD).
In the household/commercial sector, calculations of energy
demand are based on the following major assumptions:
(1) A reduction of 1 F in spacing temperature will occur and
there will be a 1 F increase in air conditioned space.
Since the saving in electricity between third quarter "73
and third quarter '74 is equivalent to an increase of 2 F
in the temperature of air conditioned space, the assumed
1 F change in heating and cooling may be conservative.
(2) Energy consumption for electric heating is held constant
at a level of 35%.
(3) Relative amounts of gas and fuel oil used for space heat-
ing will not change from the average of the 1965 to 1970
period.
(4) Demand for space heating energy has been discounted to
allow for the effect of improved insulation according to
62
-------
Table 20
AUTOMOBILE EXHAUST EMISSION PENALTY FACTORS
Registration
Period CASE I CASE II Existing Law
1969 and Earlier^
(Base Period) 1.00 1.00 1.00
1970 - 1974(2) 1.13 1.13 1.13
1975 - 1976*3) 1.05 . 1.05 1.05
1977 - 1980^4^ 1.10 1.05 1.43
1981 - 1985(5) 1.05 1.00 1.37
Notes:
The penalty factor is the increase over base period fuel requirement
caused by engine adjustments to conform to Federal automobile emission
regulations. The increase applies only to automobiles registered after
the initiation date of the regulations. The factors used derive from
discussions with U.S. automobile manufacturers and government agencies
concerning actual and anticipated performance. ,
A limit of 2 grams per mile on NO/ emissions went into effect in
California in 1975. This will increase gasoline usage by about 5 per-
cent and has been taken into account in calculating gasoline demand.
Under existing law, nationwide NOx controls at a level of 0.4 grams
per mile will go into effect in 1977. This will have a drastic effect
on gasoline demand, as shown above. We have, therefore, assumed that
the law will be changed to the California standard (2.0 grams/mile) in
calculating Case I demand.
For Case II, we have assumed that emission control standards beyond those
in effect in 1975 will not be enacted. This means that there will be
no NOx limits except those already existing in California.
(1) This was the last full year before Federal emission
regulations took effect.
(2) Lower compression ratios and controls on carbon and hydro-
carbon emission.
(3) Catalytic oxidation devices added.
(4) Nationwide NOX controls scheduled.
(5) Transmission/aeorodynamic/weight changes improve efficiency.
63
-------
Table 21
EFFECT OF AUTOMOBILE WEIGHT AND
POWER OPTIONS ON FUEL REQUIREMENT
Factor (times 1969 base)
1969 (base year) * 1.000
1972 1.037
1977 K103 .
1980 1.100
1985 1.113
Notes: This factor reflects change in fuel requirement due to the
added weight of various safety features (e.g. collision
resistent bumpers) and the energy used by power options
(mainly air conditioning). The overall factor is influ-
enced by the size of new cars because the fractional effect
is greater on a small car than on a large car. Thus an
increase in small car registrations tends to increase the
factor.
The change indicated above includes the effect of vehicle
size, according to the schedule of new automobile registra-
tions given in Table 3-5.
64
-------
Table 22
AUTOMQBIL&eASOUNE CONSUMPTION AVERAGES
ies per Gallon]
1969
1970
1971
1972
1973
1974
1977
1980
1985
Case I
13.79
13.83
13.79
13.79
13.28
12.76
12.SS
12.68
13,08
Use II
13.79
13.83
13.79
13.79
13.28
12.76
12.70
13.32
13.87
-------
Table 23
TRANSPORTATION SECTOR DEMAND FOR
PETROLEUM - CASE I
GASOLINE
Automobiles
Light Trucks
Heavy Trucks/Buses
Aviati on/Non-Highway/
Losses
Total
DIESEL
Heavy Trucks/Buses
Railroads
Bunkers/Military/
Non-Highway
Total
JET FUEL
Commercial
Military
Total
RESIDUAL FUEL OIL
Bunkers
Lubes
Military/Railroads
Total
LPG
All Uses
(MBPD)
1970
4,274
1,014
314
312
5,914
373
236
256
865
666
290
956
241
75
85
401
87
1972
4,751
1,298
247
296
6,592
515
248
250
1,013
735
263
998
209
77
70
356
96
1977
5,450
1,537
137
265
7,389
771
279
313
1,363
756
206
962
279
80
56
415
63
1980
5,660
1,650
109
236
7,655
891
301
356
1,548
833
219
1,052
308
81
60
449
41
1985
5,970
1,871
95
209
8,145
1,084
367
414
1,865
940
219
1.159
332
87
60
479
22
TOTAL
8,223 9,055 10,192 10,745 11,670
66
-------
Table 24
TRANSPORTATION SECTOR DEMAND FOR
PETROLEUM - CASE II
(MBPD)
GASOLINE
Automobiles
Light Trucks
Heavy Trucks/Buses
Avi ati on/Non-Hi ghway/
Losses
Total
DIESEL
Heavy Trucks/Buses
Railroads
Bunkers/Military/
Non-Highway
Total
JET FUEL
Commercial
Military
Total
RESIDUAL FUEL OIL
Bunkers
Lubes
Military/Railroads
Total
LPG
i
All Uses
1970
4,274
1,014
314
312
5,914
373
236
256
865
666
290
956
241
75
85
401
87
1972
4,751
1,298
247
296
6,592
515
248
250
1,013
735
263
998
209
77
70
356
. 96
1977
5,087 *
1,528
137
261
7,013
771
279
313
1,363
685
206
891
279
80
56
415
63
1980
4,781
1,613
109
226
6,729
891
301
356
1,548
755
219
974
308
81
60
449
41
1985
4,713
1,732
95
197
6,737
1,084
367
414
1,865
852
219
1,071
332
87
60
479
22
TOTAL
8,223 9,055 9,745 9,741 10,174
67
-------
the following schedule:
Percent Reduction
Residential Commercial
1975 to 1977 Construction 10 15
1978 to 1981 Construction 25 25
Pre-1975 Structure in 1980 2 no change
Pre-1975 Structure in 1985 4 no change
The household /commercial energy demands associated
with Case I consumption patterns are summarized in
Table 25. Those associated with Case II consumption
patterns, which assume additional reductions in energy
used within the household, increased small car sales,
and increased carpooling for travel within the cities,
appear in Table 26.
Total U. S. energy demands corresponding to Case I and
Case II, respectively, are shown in Tables 27 and 28.
2.4.3 Consumption/Production in the United States
The need to evaluate the total energy supply/demand balance
led to the development by the Pace Company of a comprehensive com-
puter model which simulates the complete energy /hydrocarbon system
in seven geographical areas of the U. S. This "Energy-Hydrocarbon
Model" is used to determine required new capacities, optimum loca-
tions, product slates, feedstock and energy sources for new plants,
and potential shortages as well as means to offset them.
Table 29 shows the U. S. consumption and annual growth
rates of major fuel products in the United States between the years
1965 and 1974, and projected consumption and growth rates asso-
ciated with Case I and II consumption patterns for the years 1977,
1980, and 1985. Table 30 shows, for each demand sequence, aver-
age refinery major product slates required by the Pace energy/
hydrocarbon model. These product slates are independent of imports,
which are summarized in Table 31. Because of the inter-dependence
of nations, there is a strong economic driving force in the energy/
hydrocarbon model for balanced production slates among the United
States, Europe, and other western hemisphere nations.
68
-------
Table 25
HOUSEHOLD/COMMERCIAL SECTOR
ENERGY DEMAND - CASE I
Consuming Element
Space Heating
Air Conditioning
Water Heating
Cooking
Refrigeration
Clothes Drying
Sub-Total
Asphalt/Road 011
TOTAL
Consuming Element
Space Heating
Air Conditioning
Water Heating
Cooking
Refrigeration
Clothes Drying
Lighting/Small
Appliances
Miscellaneous
Sub-Total
Public Authority/
Street Lighting
TOTAL
THERMAL ENERGY
(Trillion BTU)
1965
8,964
103
1.469
383
8
49
10,976
891
11,867
1965
25
78
79
28
154
7
112
483
31
514
1970
10,329
244
1,691
425
4
70
12,763
1,082
13,845
ELECTRIC
(Billion
1970
70
151
97
33
200
19
191
761
49
810
1972
10,858
316
1,763
424
4
77
13,442
1,156
14,598
POWER
KWH)
1972
113
187
114
38
222
22
177
873
55
928
1977
12,467
432
1,934
371
3
126
15,333
1,348
16,681
1977
153
280
136
50
244
28
281
1,172
75
1,247
1980
12.724
525
2,045
384
3
144
15,825
1.497
17,322
1980
192
312
153
54
263
32
334
1,340
90
1,430
1985
13,511
668
2,230
405
3
171
16,988
1,783
18,771
1985
270
351
179
61
298
38
420
1,617
115
1,732
69
-------
Table 26-
HOUSEHOLD/COMMERCIAL SECTOR
ENERGY DEMAND - CASE II
Consuming Element
Space Heating
Air Conditioning
Water Heating
Cooking
Refrigeration
Clothes Drying
Sub-Total
Asphalt/Road Oil
TOTAL
Consuming Element
Space Heating
Air Conditioning
Water Heating
Cooking
Refrigeration
Clothes Drying
Lighting/Small
Appliances/
Miscellaneous
Sub-Total
Public Authority/
Street Lighting
TOTAL
THERMAL ENERGY
(Trillion BTU)
1965
8,964
103
1,469
383
8
49
10,976
891
11,867
1965
25
78
79
28
154
7
112
483
31
514
1970
10,329
244
1,691
425
4
70
12,763
1,082
13,845
ELECTRIC
(Billion
1970
70
151
97
33
200
19
191
761
49
810
1972
10,858
316
1,763
424
4
77
13,442
1,156
14,598
POWER
KWH)
1972
113
187
114
38
222
22
177
873
55
928
1977
11,974
410
1,837
352
3
120
14,696
1,348
16,044
1977
146
263
129
48
244
27
267
1,124
75
1,199
1980
12,222
500
1,943
364
3
137
15,169
1,497
16,666
1980
184
293
145
51
263
30
317
1,283
90
1,373
1985
12,977
635
2,119
385
3
162
16,281
1 ,783
18,064
1985
258
331
170
58
298
36
399
1,550
115
1,665
70
-------
Table 27-
U.S. ENERGY DEMAND - CASE I
Sector
Household/Commercial
Transportation
Utility Power
Industrial
Petrochemical
Refinery Fuel &
Synthetics Production
TOTAL
Sector
Household/Commerci al
Transportation
Utility Power
Industrial
Petrochemical
Refinery Fuel &
Synthethics Production
TOTAL
(Quadrillion BTU)
1965
12.6
12.7
10.9
17.9
54.1
1970
14.7
16.5
16.5
20.4
68.1
U.S. ENERGY DEMAND -
(Crude Oil
1965
5,916
5,946
5,096
8,383
n
Equivalent -
1970
6,902- 7
7,725 8
7,715 8
9,554 9
1972
15.3
18.0
18.5
-
20.9
72.7
CASE I
MBPD
1972
,183
,427 .
,650 1
,788
1977
16.7
21.2
25.4
15.4
3.8
3.2
85.7
1977
7,816
9,913
1,881
7,228
1,777
1,546
1980
17.3
22.4
29.8
16.0
4.4
3.6
93.5
1980
8,113
10,440
13,956
7,516
2,067
1,690
1985
18.8
24.2
' 36.8
18.1
5.8
4.9
108.6
1985
8,812
11,353
17,222
8,486
2,702
2,280
25,341 31,896 34,048 40,161 43,782 50,855
71
-------
Table 28
U.S. ENERGY DEMAND - CASE II
Sector
Household/Commerci al
Transportation
Utility Power
Industrial
Petrochemical
Refinery Fuel &
Synthetics Production
TOTAL
Sector
Household/Commerci al
Transportation
Utility Power
Industrial
Petrochemical
Refinery Fuel &
Synthethics Production
TOTAL
(Quadrillion BTU)
1965
12.6
12.7
10.9
17.9
54.1
1970
14.7
16.5
16.5
20.4
68.1
U.S. ENERGY DEMAND
(Crude Oil
1965
5,916
5,946
5,096
8,383
n
Equivalent
1970
6,902
7,725
7,715
9,554
1972
15.3
18.0
18.5
20.9
72.7
- CASE II
- MBPD
1972
7,183 7
8,427 9
8,650 11
7
9,788 1
1
1977
16.0
20.3
24.7
15.4
3.8
3.2
83.4
1977
,516
,508
,587
,226
,763
,493
1980
16.7
20.3
29.0
16.2
4.4
3.4
90.0
1980
7,808
9,527
13,598
7,580
2,063
1,570
1985
18.0
21.3
36.0
18.3
5.8
4.4
103.8
1985
8,451
9,990
16,854
8,552
2,713
2,056
25,341 31,896 34,048 39,093 42,146 48,616
-------
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-------
Table 30
AVERAGE REFINERY PRODUCT SLATES
(Major Products)
High Demand Sequence(I)
Refined Products
Total Gasoline
Total Naphtha
Kerosene/Jet A
No. 2 Fuel/Diesel*
Low Sulfur Residual
High Sulfur Residual
+ Asphalt/Bunkers
Total
Aromatics
Benzene
Toluene
Xylenes
Total
Average Slates
1977
MBPD %
734 5.3
13951 100.0
1980
1985
MBPD
MfiPD %
6875
659
1133
2801
1749
49.3
4.7
8.1
20.1
12.5
7515
673
1332
3186
2219
48.0
4.3
8.5
20.3
14.2
7960
608
1338
3674
1794
48.6
3.7
8.2
22.5
11.0
739 4.7
15664 100.0
988 6.0
16362 100.0
80.1
69.4
60.7
38.1
33.0
28.9
87.3
109.2
97.3
29.7
37.2
33.1
121.6
139.4
157.5
29.1
33.3
37.6
210.2 100.0 293.8 100.0 418.5 100.0
Reduced Demand Sequence(II)
Refined Products
Total Gasoline
Total Naphtha
Kerosene/Jet A
No. 2 Fuel/Diesel*
Low Sulfur Residual
High Sulfur Residual
+ Asphalt/Bunkers
Total
Aromatics
Benzene
Toluene
Xylenes
Total
6576
646
1033
2742
1746
48.6
4.8
7.6
20.3
12.8
6589
672
1148
3126
2116
45.8
4.7
8.0
21.7
14.7
6552
693
1156
3486
1743
44.9
4.7
7.9
23.9
11.9
793 5.9
13536 100.0
741 5.1
14392 100.0
973 6.7
14603 100.0
80.2
60.7
58.7
40.2
30.4
29.4
87.6
62.8
62.8
41.0
29.5
29.5
115.9
78.5
108.0
38.3
26.0
35.7
199.6 100.0 213.2 100.0 302.4 100.0
(*) No. 2 Fuel/Diesel does not include 0.3 wt. % Sulfur Residual.
74
-------
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75
-------
2.4.4 Petroleum Demand in Other World Areas
To insure against the pitfall of "solving" energy shortages
through imports, the energy balances of other world areas were
evaluated, and those of Europe, Central and South America, and the
Caribbean are included in the model. Respective proportions of the
total energy demand which must be contributed by petroleum was
determined, and the requirements of individual geographic areas for
specific products was surveyed. This information is incorporated in-
to the model, which ultimately determines the amount and location of
new U. S. refining capacity consistent with U. S. energy demands, as
well as the subsequent flow of petroleum products among these geo-
graphic areas.
2.4.5 New U. S. Refinery Capacity
The number and location of new refineries and expansions
which have been scheduled in the United States through the year 1977
has already been announced, and Table 32 provides a listing of these
additional facilities. Companies and incremental capacity are speci-
fied and locations shown by PAD districts (see Figure 6, p. 56 for
the years 1974 through 1977.
Table 33 shows the total new U. S. refinery capacity for the
periods 1974-1977, 1978-1980, and 1981-1985, which is required to
meet needs reflected in the energy/hydrocarbon model. Both region-
al demands and potential sources of incremental crude oil such as
Alaskan North Slope crudes were influencing factors in determining
locations. This required new capacity is summarized as follows:
Case I Case II
High Demand Reduced Demand
1974-1977 1583 1576
1978-1980 1464 103
1981-1985 860 349
Figures represent thousands of barrels per day, and include addi-
tional capacity required to process Alaskan North Slope crude oil
assuming decreased utilization of 3% and 6% respectively, in the
high and low demand sequences, it appears that the average annual
capacity additions required between the years 1978 and 1985 amount
76
-------
Table 32
NEU REFINERIES AND EXPANSIONS SCMCOUUO li TNI
UNITED STATES BY PAPO DISTRICTS
(Ibis/Day of Crude Distillation)
iv/Loeation
1SZ1
Arneo Steel (Zanosville. Ohio)
Delta Refining Co. (Memphis. Tena.
Clark (Hartford, 111.)
Conoco (Ponea City. Okla.)
ORA (Phillipsburg. Kan.)
Skelly Oil Co. (El Dorado. Kan.)
Hunt Oil (Tuscaloosa, Ala.)
Pride Refining (AbiTene, Tex.)
Tesoro Petroleum (Spring, Tex.)
Farnariss (Lovington, H. Hex.)
Caribou Four Comers (Words Cross,
Husky (Salt lake City, Utah)
?*
4,000
14.000
45.000
Utah)
19.000
1.300
I.OM
2.500
15.750
15.775
3.500
30.000
B.W5
171.12$
1975
BP Oil (Marcus Hook, Pa.)
Exxon (Linden. N. J.)
Standard of Calif. (Perth Amboy, N. J.)
Crystal Princeton (Princeton. Ind..)
Apco 011 Corp. (Arkansas City. Kan.)
fcerr-Mctee Corp. (Uynnewood, Okla.)
Vickers Petroleum (Ardmore. Okla.)
Crystal Oil Co. (Longvitw. Tex.)
Exxon (Baton Rouge. La.)
Marion Corp. (Mobile Bay. La.)
Standard of Calif. (Pascagoula, M1ss.)
Vl-011 Company (Glenrock, Wyo.)
Douglas Oil Co. (Paramount. Calif.)
Htm County (Bakersfield, Calif.)
Newhill Refining (Newhall, Calif.)
Standard of Calif. (El Segundo. Calif.)
Standard of Calif. (Richmond, Calif.)
45.000
30.000
80.000
7.000
n.ooo
u.ooo
tt.000
4.000
4.SOO
14.000
4.000
40.000
155.000 7.000 'B.BU U.5H
14.000
1.000
11,000
1M.OOO
817.500
3,976
Atlantic Richfield (Houston. Texas)
Caribou Four Corners (Kirkland, N. H.)
Chanplin Petroleum (Corpus Chrlsti, Tex.)
Exxon (Baytotm, Texas)
Thrlffetay Oil Co. (Bloomfleld. N. N.)
WO.OOO
800
M.OOO
IfO.OOO
1321
Texaco (Lockport. 111.)
Eeol. Ltd. (fiaryville. La.)
155.000 n.OOO
1.4Xf675
Source: ItorldMlde Construction". October 7. 1*74, Oil ซM Cซt
Mdffled by Pace.
77
-------
Table 33
NEW U.S. REFINERY CAPACITY OVER 1974
(RTBPD)
High Demand Sequence (I)
1974-1977
1978-1980
1981-1985
Sub-Total
1978-1985
Total
S=3
Low Demand Sequence (II)
1974-1977
1978-1980
1981-1985
Sub-Total
1978-1985
Total
1
163
0
0
0
163
163
0
___27
27
190
2A
114
484
299
783
897
107
103
26
129
236
PADD
3
778
731
426
1157
1935
' 778
0
0
0
778
2B/4
118
12
3J?2
384
502
118
0
_j?9JL
296
414
5
410
237
(237)
0
410
410
0
0
0
410
Total
1583
1464
860
2324
3907
1576
103
349
452
2028
78
-------
to only 282,000 barrels per day in the high demand sequence, and
53,000 barrels per day in the reduced demand sequence.
79
-------
3. 0 THE ANALYTICAL PROGRAM
3. 1 INTRODUCTION
The purpose of the analytical program was to identify potentially
hazardous constituents of refinery solid waste streams, to determine
whether they are present in refinery wastes, and to measure their levels of
concentration. Suitable laboratory techniques were developed, and decisions
were made regarding reasonable limits of detection and required degree of
analytical accuracy.
3. 2 CRITERIA FOR IDENTIFICATION OF POTENTIALLY HAZARDOUS
SUBSTANCES
An initial listing of potentially hazardous substances requiring identi-
ficatioi. by the analytical program was contained in the original RFP issued
by the Office of Solid Waste Management Programs. The list included the
following trace elements:
Arsenic Lead
Beryllium Mercury
Cadmium Selenium
Chromium Silver
Copper Zinc
Also listed were certain groups of organic compounds including carcinogens,
pesticides, and chlorinated hydrocarbons. In-house knowledge of the petro-
leum refining industry prompted addition to this list of four other potentially
hazardous constituents of waste, i. e. , nickel, vanadium, cobalt, and moly-
bdenum. A total of 14 trace elements, most of which had not previously
been sought in refinery residues, were thus selected for identification, and
for subsequent measurement of concentration levels in refinery waste
streams. A discussion of the characteristics of these elements appears
in Appendix A. Examination of potential chemical combinations of the
selected elements to determine whether they are organic or inorganic
compounds was not included in the program. Generation of this data would
require separation of the samples into oil, water, and solid fractions, and
the analysis of each of the three fractions separately. This would have
tripled the magnitude of the program, and time limitations precluded these
studies.
80
-------
The identification of potentially hazardous organic compounds pre-
sented an entirely different problem. The number of potentially dangerous
organic compounds is simply too great for detailed analysis. The toxic sub-
stance list (Z ) has over 70, 000 entries, and while many are the product of
a sophisticated chemical industry, there may be an equal number of naturally
occurring organic compounds in petroleum, and refinery wastes. The con-
clusion of the Booz Allen Report (1), in which this problem is reviewed, is
that "oil" is potentially hazardous regardless of its individual constituents.
The transient environmental damage which has resulted from oil spills lends
credence to the correctness of this conclusion. It was therefore decided
that oil should represent a composite of hazardous organic substances and
all refinery samples were analyzed to determine their constituent percent-
ages of oil, water, and solids. In addition to providifig the quantity of oil,
these data also give insight into the physical characteristics of each waste.
This information is invaluable in projecting handling costs, in designing
future treatment and disposal techniques, and in evaluating the adequacy of
current disposal practices.
Review of various published lists of hazardous substances (2, 3)
prompted our adding to the program phenolic compounds, ammonium com-
pounds, fluorides, and strong acids and alkalis, substances which had been
a focal point of many environmental concerns. The acids and alkalis were
characterized by the pH of the aqueous fraction. Pesticides are not included
in the program, since they are not present in petroleum and are not pro-
duced by refineries. Trace amounts of chlorinated hydrocarbons are known
to be present in crude oil, however unlike DDT and its derivatives and
PCB's, they are not the type that are damaging to the environment. Further-
more, they tend to be degraded in the refinery processes, particularly if
the refinery has a catalytic reformer, and hence do not appear in the waste
stream. Nonetheless, the first fourteen waste samples obtained were sub-
jected to direct analysis for chlorinated hydrocarbons, using gas-liquid
chromatography. Identifiable chlorinated compounds were not found in the
samples. To verify these results, the waste streams from the chromato-
graphs were submitted to mass spectroscopy and again the results
confirmed an absence of chlorinated hydrocarbons from refinery wastes.
This class of compounds was therefore eliminated from subsequent
analytical considerations.
The chemical classes of nitrogenous hydrocarbons and polynuclear
aroma tics, commonly considered to be carcinogens, have been extensively
studied because of concerns related to automobile exhaust emissions.
Examinations of various studies concerned with these chemical
81
-------
groups (*) led to the conclusion that the nitrogen compounds in petroleum
are not of the cancer-forming type, viz. , the amines and nitrosamines.
There is, furthermore, no evidence that the naturally occurring nitrogen
compounds are transformQfiLto Carcinogens, either by combustion or by
natural processes. Nitrogen compounds were therefore eliminated from
further consideration. Polynuclear aromatics, on the other hand, are
known to occur in crude oils at levels as high as 0. 1%, although only a
small fraction is carcinogenic (8 ). For example, 3:4 benz-A-pyrene
occurs at a concentration of only 0. 4 to 1. 6 mg/1 (9 ). It was decided that
polynuclear aromatics should be included in the analytical program. Of the
potentially hundreds of isomers, only benz-A-pyrene has been studied
sufficiently to enable a creditable analysis to be performed. The analytical
program, in the case of polynuclear aromatics, was therefore limited to
benz-A-pyrene. It is probable that a near constant ratio exists between
benz-A-pyrene and total polynuclear aromatics. If this is so, benz-A-
pyrene can be used as an indicator of polynuclear aromatics and may prove
valuable in establishing the relationship of this compound to the total
carcinogenity of oily wastes.
3. 3 ANALYTICAL PROCEDURES FOR DETECTION OF HAZARDOUS
SUBSTANCES
Figure 7 is a schematic representation of the analytical program.
Analytical methods employed in the program are detailed in Appendix B,
and in general are standard methods recognized by the American Petro-
leum Institute (API), the American Water Works Association (AWAA), and
the American Organization of Analytical Chemists (AOAC). Oxidation of
the organic matter present without loss of the more volatile trace elements,
particularly mercury and selenium, was achieved by the use of a previously
unpublished method obtained through communication with an industry source
(**). Slight modifications of this method produced satisfactory results
(Procedure 4(a), Appendix B).
The need to establish reasonable detection limits required a judge-
mental decision regarding when a potentially hazardous material becomes
frankly hazardous. The detection limits selected as a standard against
which to measure trace element concentrations are based upon those levels
(*) Source: Chevron Research, Richmond, California;(private communi-
cation.)
(**) Source: E. N. Davis, Manager, Analytical Dept. , Atlantic-Richfield
Co. , Harvey, Illinois.
82
-------
FIGURE 7
SCHEMATIC REPRESENTATION OF THE
ANALYTICAL PROGRAM
SAMPLE
_L
Homogenize Measure Bulk
Density Proportion for:
(A) Wet oxidation:
trace elements
by atomic ab-
sorption, Se
and Hg by wet
chemistry
L
(B) Benzene
extract:
benz-A-pyrene
by GLC
(C) Physical
separation:
% water
(PH, mfi
% oil
% insolubles
(D) Disti
from
.llation
original
material:
cyanid e and
phenols
83
-------
occurring in nature. Natural concentration levels of the collected trace
elements are shown in Table 34. Since these data are somewhat variable,
and there is a lack of agreement regarding precise numbers, concentrations
in refinery wastes are measured against a background level equal to the
average of the numbers shown in the table.
The relevance of leachate analysis to the study of potentially hazard-
ous refining industry wastes was carefully considered, and it was concluded
that such analyses are not within the scope of this study. While many indi-
viduals within the study team, as well as in the EPA and industry consider
leachate analysis to be highly desirable, it was concluded that leachability
of inorganic substances in standard laboratory leachate determinations is
neither an accurate indicator of their solubilization potential in the bio-
logical environment, nor is it a measure of ultimate hazard. Ultimately,
hazard is determined by the presence of a toxic substance, rather than by
its chemical state. For example, mercury is acutely toxic if discharged
to the environment in a form which can readily enter the biological environ-
ment, it is potentially chronically hazardous if disposed of as an "insoluble"
inorganic compound whose entry to the life cycle can only occur after con-
version to methyl mercury. Thus, if mercury did not leach into water in a
standard laboratory test, it might have been concluded that mercury was
bound in an insoluble form which would never leach, before discovering
that several microorganisms have the ability to convert insoluble mercury
to methyl mercury. The complexity of geochemical processes thus pre-
cluded leachate analysis from the analytical program.
3. 4 EVALUATION OF THE ACCURACY OF LABORATORY RESULTS
Sources of error are inevitable in laboratory procedures, and are
particularly apparent when determining trace quantities of toxic elements
in the presence of large quantities of organic matter. The non-homogeneity
of some of the samples, inherent inaccuracies associated with the methods,
equipment limitations, and limitations in our knowledge introduce scatter
into the results. Methods for obtaining accurate data for trace elements in
organic sludges are still being improved, and when detection limits are
pushed downwards, a greater degree of error often results. Determin-
ations of the metals were made on ten gram portions, and it was generally
necessary to bring the prepared solutions to 250 milliliters. Concen-
trations actually measured were thus about 1/25 of those reported for the
original sample. Since many of the values are close to the limits of
detection by standard procedures, background interference is a significant
factor.
84
-------
. . TABLE 34
CONCENTRATION LEVELS OF SELECTED TRACE ELEMENTS
FOUND IN NATURE
(mg/kg dry basis)
Silver (Ag)
Arsenic (As)
Beryllium' (Be)
Cadmium (Cd)
Cobalt (Co)
Chromium (Cr)
Coppe.r (Cu)
Mercury (Hg)
Molybdenum (Mo)
Nickel (Ni)
.Lead (Pb)
Selenium (Se)
Vanadium (Y)
Zinc .(Zri)
Fluorine
Av. <38>
0.1
5
6
0.2'
25
200
200
0.1
i
80
16
0.5
140
'200
800
Igneous 1JJ
Pvocks
ป
1.
2.
0.
25
100
55
1,
.75
12
0
135
. 70
625
07
8.
8
2
,08
.5
,5 '
.05'.
> Sed. ^Jl
Rocks !
.07
1
1
0.05
0..3
35
5
0.03
0.2
2
7 ' .
0.-05
20'
16
27.0
Shales (
13
;.- 3
0.3
19
90
45
0.4.
2. 6
68
2.0
0.6
130
95
740
39)Soil^
5
6.
0.
8
200
20
. 0.
0
' 4.
10
.0.
100
50.
-
;/>.
5
o:
0
0
-------
(mg/kg dry basis)
Silver (Ag)
Arsenic (As)
Beryllium (Be)
Cadmium (Cd)
Cobalt (Co)
Chromium (Cr)
Copper (Cu)
Mercury (Hg)
Molybdenum (Mo)
Nickel (Ni)
Lead (Pb)
Selenium (Se)
Vanadium (V)
Zinc (Zn)
x.
Fluorine
Soils
(28)
1 /
I /
' 13
3
-------
To improve interpretation accuracy, data scatter was quantified in
intra-laboratory control studies. Three methods of monitoring were empl-
oyed. In the first, known concentrations of trace elements were prepared
in water and subjected to the same digestion and preparative procedures as
refinery samples. Four groups of samples were evaluated, and the results
are a measure of the error introduced by extensive pre-treatment steps
required prior to actual determinations. Results are shown in Table 35
for this first series of control tests run during the program. A second
method of evaluating laboratory accuracy involved the addition of known
quantities of the selected elements to refinery samples. Comparison of
concentration levels found with those calculated to be present in spiked
original samples provided a measure of laboratory error. The third
method involved performing duplicate determinations, and was carried
out routinely on ten percent of these samples. Three types of samples
were examined - the oily sludges, aqueous samples, and solid samples.
The data obtained in the second and third series of control studies are
shown in Appendix C. The data are insufficient for rigorous statistical
analyses, but certain trends emerge. Inaccuracies appear to occur in
the direction of lower rather than higher values, but results are accurate
within the 70 to 100 percent range.
Some of the refineries analyzed identical or "split" samples, and the
results provided an additional comparison standard against which to
evaluate accuracy of results. Discrepancies in inter-laboratory results
may reflect sampling errors as well as analytical errors, however a
broad measure of agreement is found in values reported. These data are
presented in Appendix D.
86
-------
TABLE 35
RECOVERY OF KNOWN CONCENTRATIONS OF
TRACE ELEMENTS FROM CLEAN WATER
(mg/1)
Constituent
Arsenic
Mercury
Beryllium
Vanadium
Chromium
Cobalt
Nickel
Copper
Zinc
Silver
Cadmium
Lead
Molybdenum
Amount
Added
0.05
0. 003
0.20
4.0
0.80
0.80
4.0
0. 80
0.40
0.40
0.40
0. 80
2.0
Amount Recovered from Samples
1234
0.09
0.002
0. 13
2.7
0. 77
0.70
3.5
0.57
0.35
0. 12
0.36
0.60
1. 0
0.04
0. 002
0.00
3. 7
0.25
0.83
2.3
0. 80
0.29
0.24
0.35
0. 80
2. 0
0.09
0.003
0.18
3.1
0.57
0.65
4.8
0. 66
0. 54
0.34
0.40
0. 70
1.7
0.09
0.003
0. 17
4.0
0.70
0.90
3.3
0.62
0. 34
. 0.32
0.40
0.43
2.5
Average
Error
+0. 028
-0. 0005
-0. 080
-0.63
-0. 228
-0. 030
-0.52
-0. 138
-0. 02
-0. 145
-0. 022
-0. 168
-0.20
87
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4. 0 WASTE CHARACTERIZATION
4. 1 INTRODUCTION
This section describes the waste streams generated by the petroleum
refining industry. These streams were examined to determine their com-
position and to measure their constituent parts. Potentially hazardous and
non-hazardous constituents of refinery wastes were identified, and quantities
of each were calculated for each waste stream. The results were extra-
polated to the total industry for the year 1974, and are presented according
to states and EPA Regions. In addition, projections are made of potentially
hazardous waste generation for the years 1977 and 1983. Projected
quantities are based upon changing production patterns within the industry
as well as upon the effects of future air and water regulations.
4. 2 WASTE GENERATION DATA DEVELOPMENT
4. 2. 1 Site Selection
Sixteen refineries were visited for data collection and waste
sampling. Selection criteria included: (1) refinery type (representa-
tive sample from each category: see Table 36); (2) geographical
location; (3) refinery age; (4) refinery size. Permission to visit
these refineries was obtained with the help of the American Petroleum
Institute (API) Solid Waste Task Force. In all cases, refinery
personnel were most cooperative in making information available to
us.
4. 2. 2 Data Sources
Information sheets were mailed by the API to the sixteen
participating refineries in order to obtain data regarding sources of
waste generation, annual waste quantities of each stream, types of
discharge, i.e., continuous or intermittent, disposal methods, dis-
posal costs, and, if possible, chemical analyses. A copy of this
information sheet is found in Appendix E. Additional data were
obtained during field visits, in discussions with the API Solid Waste
Task Force, from information reported in the literature, and from
in-house knowledge of Jacobs Engineering Co.
88
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4. 2. 3 Refinery Field Visits
During each refinery field visit, the following procedure was
utilized:
(1) The completed information sheet was reviewed by the study
teams with refinery personnel.
(2) Plant operations were discussed, and information obtained
concerning solid waste generation and sample collection.
(3) Generalized refinery process flow diagrams showing waste
flow were sketched. These flow diagrams are included in
Appendix F.
(4) A tour of the refinery was conducted to examine the various
sources of solid waste and to collect samples.
4. 2. 4 Sample Collection
Both grab and composite samples were obtained. Grab
samples were generally taken from intermittent waste sources and
are considered appropriate since the accumulation of material over
a long period of time is an effective compositing process. Composite
samples taken over a period of four to five hours, were made from
continuous waste sources. In the case of a pond or land disposal
area, four to five grab samples were taken at various locations and
then combined to form representative samples of waste sludges.
Dusts and similar materials were collected in large samples (50
pounds or more), and sub-divided for analysis. In all cases, refinery
personnel assisted in the sampling operation, making sure a parti-
cular process was running normally and that the waste was as
representative as possible. In all cases samples were taken in a
large container, thoroughly mixed, and then divided between the
study team and the refinery for analysis. Sampling instructions
issued to each refinery team are found in Appendix G.
4. 3 REFINERY WASTE STREAMS
Following is a listing of individual refinery waste streams with
accompanying brief descriptions of their origin. A detailed characteri-
zation of each stream is given in A,pper;dix H.
90
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Crude Tank Bottoms - Solid sediment from incoming crude oil
accumulates at the bottom of the crude oil storage tanks. These tanks are
cleaned periodically to remove the sediment and the frequency is determined
by the presence of sediment in the crude oil .sent to the process units. In
those refineries in which mixers are used in the storage tanks, this waste
source is non-existent. Contaminants in crude oil tank sludge vary with
+ype of crude oil as well as with handling and shipping methods employed
prior to delivery to the refinery. Settled sludge consists of a mixture of
iron,rust, clay, sand, water, sediment, and some occluded oil and wax.
Usually this mixture is a tightly held emulsion which does not separate on
settling. Frequency of crude oil tank sludge removal varies from once a
year to once every ten years.
Leaded or Non-Leaded Tank Bottoms - Solids settle to the bottoms of
product tanks, where they remain pending removal. This accumulated
sludge is removed whenever the tank service is changed, the sediment ex-
ceeds specifications, or the tank itself needs repair. The characteristics
of the deposited sludge will vary with the type of product stored in the tank.
It is removed at intervals varying between once a year and once every five
to seven years.
API Separator Sludge - Solids which settle in the API separator during
primary wastewater treatment are periodically removed with a vacuum
truck. Refinery API separators are usually connected to the oily water
plant sewer. The bottoms, therefore, containa mixture of all sewered
wastes, such as tank bottoms, boiler blow-down, and de-salter wastes,
as well as a certain amount of all chemical elements that enter a refinery.
Neutralized HF Alkylation Sludge - Alkylation sludges are produced
by both the sulfuric acid and the hydrofluoric acid alkylation processes. In
the sulfuric acid alkylation process, the spent acid, which is approximately
80% sulfuric acid, is usually regenerated by an offsite producer of sulfuric
acid, and it accumulates in storage tanks for batch transportation to the
reclaimer. The sludge which contains polymerized hydrocarbons, tank
scale, and sulfuric acid, accumulates on the bottom of the storage tank
and is removed when the tank is either cleaned or repaired. It is usually
neutralized with lime and disposed of to land. Unlike the sulfuric acid
alkylation process, all spent acid from the hydrofluoric acid process is
neutralized with lime (usually spent lime from the boiler feedwater treat-
ment process) producing an insoluble calcium fluoride sludge, which is
removed intermittently to final disposal.
91
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Kerosene Filter Clays and Lube Oil Filter Clays - Treatment with
fixed bed clay is used to remove color bodies, chemical treatment residues,
and traces of moisture from product streams such as gasoline, kerosene,
jet fuel, and light fuel oil. Clay is also used to treat lube oils, a process
in which the clay is mixed with the oil and subsequently removed with a
rotary vacuum filter. Since clay is used in treatment of highly refined pro-
ducts, the spent clay from either of the above processes is reasonably free
of oil and can be disposed of in a landfill. Various clay treatment processes
are discussed in Appendix H. Spent clay is produced in significantly greater
quantities from the clay contacting process than from the fixed bed process.
Once-Through Cooling Water Sludge - Water pumped from a nearby
source is passed through primary settling tanks prior to usage for once-
through cooling. Sludge is periodically removed from these tanks.
Dissolved Air Flotation Float - In some refineries, following pro-
cessing by separators, additional oil and solids are removed by the
process of dissolved air flotation. The process takes place in a circular
tank with or without chemicals, bringing the finely divided solids and oil
particles to the surface, where they are skimmed off for disposal.
Slop Oil Emulsion Solids - Skimmed oil from the API separators is
usually pumped into a slop oil tank where the mixture is separated into
three fractions - oil, water and emulsion. The oil is returned for repro-
cessing, and the water is recycled back to the API separator. The emulsion
layer may be disposed of as a sludge, or it may be further treated, i. e. ,
demulsified. Demulsification is carried out by chemical or by physical
treatment. The former employs the use of special agents, heat and settling
tanks. The latter involves removal of suspended solids by centrifugation or
vacuum filtration, while water and oils are effectively resolved in settling
tanks. In either process, the oil is reprocessed, the water is returned to
the wastewater treatment system, and the solids are disposed of as a solid
waste.
Spent Lime from Boiler Feedvvater Treatment - Spent lime from cold
or hot lime softening and from the clarification of boiler feed water is
continuously discharged, de-watered in a settling basin, and disposed of
to land. The quantities and composition of the spent lime sludges are
dependent upon the characteristics of the raw makeup water.
-------
Cooling Tower Sludge - sludge which settled in the cooling tower basin
is removed whenever the cooling tower is out of operation. It is either
washed into the process sewer system or shoveled out and disposed of to
land.
Exchanger Bundle Cleaning Sludge - Heat exchanger bundles are
ieriodically cleaned during plant shutdown. Scale and sediment resulting
irom such cleaning are collected in sumps, from which they are either
flashed into the process sewer system or shoveled out and disposed of to
the land.
Waste Bio Sludge - In the process of biological treatment of refinery
aqueous waste streams, excess bio sludge is created which, for efficient
operation, must be controlled by wasting. The waste bio sludge has a very
high water content (99%) and is dewatered prior to disposal. This waste is
generated non-continuously at a rate dependent upon activated sludge process
variations, desired level of process efficiency, and the raw waste load.
Storm Water Silt - Silt which collects in the stormwater settling basins
in some refineries is periodically removed, de-watered, and disposed of
to land. The quantity of silt is usually a function of the amount of rainfall
and of refinery paved area, rather than of process complexity.
Fluid Catalytic Cracker (FCC) Catalyst Fines - Fluid catalytic
cracker (FCC) catalyst is continuously regenerated by burning off the coke
formed on the catalyst during the cracking process. The flue gas from the
regenerator passes through a series of cyclones that recover most of the
catalyst. This recovered catalyst is then returned to the reactor vessel.
Because of current and future air pollution regulations, more refineries
have installed electrostatic precipitators or an equivalent device to remove
any catalyst fines which would otherwise be released to the atmosphere
with the regenerator flue gas. These catalyst fines are either wasted to
land or in some cases sold. They are generated on a continuous basis,
but are generally disposed of intermittently.
Coke Fines - Coke which is produced in the course of various refinery
operations, such as fluid coking and delayed coking, is sold as solid indus-
trial fuel. Coke fines are generated intermittently, and their quantity is a
function of handling techniques. A certain amount of spillage and consequent
contamination with dirt results in the course of loading operations onto
trucks and railroad cars.
93
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Spent Catalysts - A number of refinery processes require the use of a
fixed-bed catalyst. These processes include catalytic reforming, hydro-
desulfurization, hydrotreating, hydrocracking, steam hydrocarbon reform-
ing for hydrogen production, sulfur production from HJS and/or SO ,
sulfuric acid production, and others. These catalysts eventually become
inactive (viz, six months to three years) and are replaced in the reactors
with fresh catalyst during a unit shutdown. Many of these catalysts con-
tain valuable metals which can be recovered economically. Some of these
metals, such as platinum and paladium, represent the active catalytic
component; others are contaminants in the feed which are adsorbed on the
catalyst during use. After the more valuable metals are recovered, a
service performed by several companies, spent catalysts are disposed
of by these companies as solid waste.
Chemical Precipitation Sludge - Chemical coagulation is used at some
refineries to remove suspended matter from aqueous waste streams. The
chemical coagulants which are added for this purpose form a gelatinuous,
porous precipitate in which the suspended matter, both oil and solids,
becomes enmeshed. The settled sludge is then removed continuously by
appropriate equipment and disposed of. The composition of the sludge de-
pends upon the type of coagulant used as well as upon the characteristics
of the wastewater.
Vacuum Filter or Centrifuge Cake - In order to reduce sludge volume,
some refineries concentrate certain waste streams through use of a common
dewatering system. The dewatered cake from these processes is disposed
of to land, while the filtrate or centrate is returned to the wastewater
treatment system.
Silica Gel - Most refineries use a silica gel dessicant to remove
water from the instrument air. Spent silica gel is usually disposed of to
land.
4. 4 FACTORS AFFECTING SOLID WASTE LOADS
Factors that affect the composition and quantity of specific solid
waste streams are listed in Table 37. Some of the important factors are
discussed below:
94
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TABLE 37
FACTORS AFFECTING THE COMPOSITION
AND QUANTITY OF SPECIFIC SOLID WASTE STREAMS
Waste.
Factors Affecting
Composition and Quantity
Crude tank bottoms
Leaded tank bottoms
Non-leaded tank bottoms
API separator sludge
Type of crude
Treatment given to crude prior
to storage
Slop oil processing method
Refinery size
Mixing, if any
Storage time
Degree, if any, of sludge
emulsion breaking
Type and quantity of chemical
additives
Plant and tank metallurgy
Type of product treatment used
Type of processes used in
producing gasoline and/or
other products
Refinery size
Type and quantity of chemical
additives
Plant and tank metallurgy
Type of product treatment, used
Type of processes used in
producing gasoline and/or
other products
Refinery size
Composition and quantity of
process wastewater
Composition and quantity of
spills and leaks
Composition and quantities of
blowdowns
Refinery housekeeping
Refinery size and age
Segregation of refinery sewers
95
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TABLE 37 (continued)
FACTORS AFFECTING THE COMPOSITION
AND QUANTITY OF SPECIFIC SOLID WASTE STREAMS
Waste
Factors Affecting
Composition and Quantity
Neutralized HF alkylation sludge
Spent filter clays
One-through, cooling water sludge
DAF float
Slop oil emulsion solids
Composition of fresh HF acid
Composition of lime
Feedstock composition
Process operating conditions
HF alkylation process metallurgy
Size of HF alkylation unit
Type and number of clay treating
processes used
Type and number of products
treated
Composition and quantity of
products treated
Type and amount of clay used
Refinery size
Composition and quantity of raw
water
Cooling system metallurgy
Size and nature of process leaks
Refinery size and complexity
Same factors as API separator
Residence time
Amount and time of flocculating
chemical used
Efficiency of API separator
Composition and quantity of
individual oil spills and
oil leakages
Composition of wastewater
emulsions
Nature of emulsion breaking
treatment and degree of success
Refinery size and complexity
Quantity of oil in wastewater
and degree of removal
-------
TABLE 37 (continued)
FACTORS AFFECTING THE COMPOSITION
AND QUANTITY OF SPECIFIC SOLID WASTE STREAMS
Waste
Factors Affecting
Composition and Quantity
Spent lime from boiler feedwater
treatment
Cooling tower sludge
Exchanger bundle cleaning sludge
Waste bio sludge
Composition of raw water
Degree of hardness removed
Type of treatment (hot or cold)
Refinery size
Boiler blowdown rates
Percent condensate recovered
and returned to boilers
.Make-up water composition
Type of chemical treatments
employed
Metallurgy of cooling water system
Nature of contaminants introduced
by process leaks
Blowdown rate
Make-up water rate
Quantity of treatment chemicals
used
Composition of shell and tube side
fluids
Equipment metallurgy
Effectiveness, of desalter
Refinery size .and complexity
Effectiveness of corrosion in-
hibitor systems
Composition and quantity of
wastewater treated
Type of biological treatment
Efficiency of prior treatment
units
Operating conditions and practice
Dewatering and/or treatment
97
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TABLE 37 (continued)
FACTORS AFFECTING THE COMPOSITION
AND QUANTITY OF SPECIFIC SOLID WASTE STREAMS
Waste
Factors Affecting
C ompos ition and Quantity
Storm water silt
FCC catalyst fines
Coke fines
Plant housekeeping
Amount .of rain
Amount of refinery area paved
Segregation of surface drainage
Catalyst composition
Oil compos ition
Type of process
Process operating conditions
(temperature, percent conver-
sion, recycle feed rate)
Catalyst make-up rate
Process metallurgy
Oil feed rate
Number of cyclones
Use of precipitators
Use of elutriators
Oil composition
Type of process
Operating condition (temperature,
pressure, time)
Process metallurgy
Method of coke removal
Method of handling and shipping
Number of cyclone stages
Oil feed rate
-------
Type of Crude Feed Stock - The constituents of crude oil can vary
widely. The heavy metal content, for example, is of major importance in
determining the hazardous or potentially hazardous metal content in crude
oil storage tank bottoms, in waste FCC fines, and in the various waste -
water treatment plant sludges. It is therefore reasonable to expect that
solid wastes will contain different concentrations of potentially hazardous
materials, and that such differences may even be reflected in the solid
waste loads of two refineries of equal capacity which produce the same
products but utilize different crude mixes.
Variations of Process Type - Although the petroleum industry has been
divided into four categories by process type, there is variation in process
units within each category. Differences in wastewater and air pollution
control processes will affect the quantity as well as the composition of
potentially hazardous waste material. For example, refineries which
employ a hydrofluoric alkylation unit produce a sludge high in fluoride,
while those employing a sulfuric acid alkylation unit do not generate large
quantities of fluoride in their waste sludge. There are differences also in
the degree and type of wastewater treatment processes employed by
refineries. A refinery using an extended aeration sludge activation system
will generate smaller quantities of biological sludges than will a refinery
which uses a conventional activated sludge system. Refineries using only
primary wastewater treatment before discharging into a municipal treat-
ment system do not generate the biological sludges which are associated
with secondary treatment.
Age of Processes - Process age refers to the general technology used
in the process rather than to the length of time the process has been in
service. This technology includes methods that will increase or decrease
the quantity of solid waste. Examples of the former are air and water
pollution control systems, i. e. , a catalytic cracker electrostatic pre-
cipitator which increases solid waste quantity by removing particulate
matter which would otherwise be an air pollutant. Examples of solid
waste decreasing technology are: (a) use of air instead of water cooling,
thus reducing or eliminating cooling tower sludges; (b) use of a Bender
treater or hydrotreating instead of clay filters to treat kerosene; (c) use of
mixers in storage tanks to prevent sludge from accumulating in the tank
bottoms; and (d) processing the wastewater treatment sludges for reuse.
Certain solid waste reduction processes which reduce waste mass without
decreasing the quantity of potentially hazardous components are the
following: (a) sludge dewatering, e. g. , centrifuging or vacuum filtering;
(b) digestion of waste biological sludge; and (c) reducing crude tank bottom
99
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sludges by using emulsion breakers prior to removing the sludge.
Operational Practices and Controls - Refinery operational methods
have a significant impact on the final solid waste load. Among the more
obvious practices which affect the quantity of solid waste are: (1) reclaim-
ing spent catalysts for metal recovery; (2) use of filter clay not contami-
nated with oil for road construction; and (3) improved mate rial-handling
procedures to reduce coke fine spills. Reclaiming FCC catalyst fines is
an especially important practice since these fines probably represent one
of the largest single solid waste sources in a refinery with an electrostatic
precipitator on the catalytic cracker. The use of corrosion inhibitors free
from chromium or zinc will also affect the quantities of these potentially
hazardous waste constituents generated.
4. 5 DEFINITION OF POTENTIALLY HAZARDOUS WASTES
An evaluation of potentially hazardous petroleum refinery wastes to
determine which among them are frankly hazardous is dependent upon a
definitiion of "hazard. " While a hazard is a reflection of potential damage,
it can only be measured within a qualified context. For example, in
relation to toxicity in ecosystems, it will vary from species to species,
and from one individual member to another. Ultimately, however, a hazard
to the biosphere is present if toxic substances are present, and the extent of
their toxicity is directly related to their level of concentration. Concen-
tration levels of refinery waste constituents must therefore be examined
against a standard for toxicity. Because most refinery wastes are destined
for land disposal, for purposes of this study the selected standard against
which to measure toxicity is the average concentration of these substances
which is found in the natural soil environment. Hazardous wastes are thus
defined as those wastes which have at least one component with a
concentration level higher than that found in the natural soil environment.
It is recognized that other definitions employing widely varying
criteria may be applicable. Consideration might well be given to the use
of such standards as air pollution, surface or ground water contamination,
fire and explosion, or disturbances of the food chain. However, since the
ultimate fate of wastes in, the environment is highly complex and poorly
elucidated, a more comprehensive definition would be well beyond the
scope of this study. Within the framework of the definition employed in
this study, waste constituents with low levels of concentration will repre-
sent a minimial hazard, regardless of the total quantity which is generated.
100
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Conversely, although certain refinery wastes may contain a number of
components with concentration levels greater than the standard, if the
total quantity generated is low, the hazard will be low in spite of these
levels of concentration.
4. 6 HAZARDOUS WASTE STREAMS
4. 6. 1 Listing by Refinery Category
A listing of the types of solid wastes discharged from typical
refineries in each of the four established categories is given in
Table 38. It is apparent from Table 38 that similar waste streams
are generated within refineries of each category. This is a direct
outgrowth of the method in which the refinery categories were
developed (see Section 2. 2 of this report).
4. 6. 2 Quantification of Hazard
4. 6. 2. 1 Measurement of Concentration Levels of Waste
Stream Constituents
Analysis of each waste sample taken at the parti-
cipating refineries was carried out in order to determine
the concentration of each of twenty identified potentially
hazardous constituent of each waste stream. These values
were recorded as mg/kg, and a range of concentration levels
was established. Appendix P contains a record of concen-
tration levels found in each sample. From individual
concentration ranges, median levels were determined. The
median is that value which is exceeded by one-half the indi-
vidual values in the series and which exceeds the remaining
values. In the case of a series with an even number of values
the arithmetic mean of the central pair is utilized. Table 39
lists the concentration ranges which were found, as well as
median concentration values for each potentially hazardous
component of all refinery waste streams. Values are ex-
pressed as milligrams per kilogram (mg/kg).
01
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4. 6. 2. 2 Identification of Hazardous Streams
Since each of the process streams contains a
minimum of three potentially hazardous components with
concentration levels exceeding those in soil, all are con-
sidered to be potentially hazardous. Table 40 presents a
listing of waste streams associated with refineries of each
of the established categories. Those waste streams which
are more generalized in nature, characteristically contain
greater numbers of components with median concentration
levels exceeding those found in soil. "Generalized" waste
streams are those which represent a composite of several
individual process streams, and which therefore reflect the
hazardous constituents of several streams. Examples of
such streams are the API separator bottoms, which result
from the plant oil sewer, and slop oil emulsion solids skimmed
from the API separator. As can be seen in Table 40, spent
lime contains the lowest number of components with median
concentration levels over background. Although this sludge
is generated in larger quantities than any other refinery
waste, it is a waste which results from a single process -
refinery water treatment - rather than from a process which
generates a combination of process waste streams, such as a
waste treatment process.
4. 6. 3 Data Extrapolation
4. 6. 3. 1 National Totals
Using the established median levels of concentration
of waste stream constituents shown in Table 39, calculations
were made of quantities of these constituents in specific waste
streams. Actual waste quantities generated by each stream
(per 1000 barrels per stream day (BPSD) of crude or process
capacity) were recorded, and median quantities were
established. It is assumed in these series that the median
represents the best estimate of the true mean, and multi-
plication of median concentraion values by median waste
quantities provides an approximation of the average quantity
of each hazardous component in each waste stream. Totals
shown in Table 39 thus represent an approximation of the
105
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average quantity of all hazardous constituents in each waste
stream. For most streams values are expressed as metric
tons (dry weight) per 1,000 barrels per stream day (BPSD)
of crude capacity. For lube oil filter clays, coke fines, HF
alkylation sludge, and FCC catalyst fines, values are ex-
pressed as metric tons (dry weight) per 1,000 barrels of
process capacity.
To determine the total quantity of each hazardous
component generated nationally in each waste stream (1974),
the average quantity of each which is generated in each stream
per unit of capacity is multiplied by the total number of
refinery units (total capacity) in the United States. The
resulting values (in metric tons dry weight) for each identified
component in each waste stream in the United States (1974)
were then adjusted using correction factors described in
Appendix J to account for existing differences in refinery
waste production capability. These values are shown in
Table 41, and represent the total quantities of each hazardous
component in each waste stream generated in the United
States (1974). Column totals show the total weight of all
hazardous components. Also shown in Table 41 are total
quantities of hazardous components combined with inert
solids. All figures are given in metric tons (dry weight).
4. 6. 3. 2 State and EPA Regional Totals
Using the national totals which appear in Table 41
corrections are made to account for current individual and
regional differences in process use within refineries. It is
assumed, for example, that if refineries with dissolved air
flotation units comprise 20% of total U. S. crude oil capacity,
then this percentage will appropriately represent the pro-
portion of total crude oil capacity of such refineries in each
state. Table 42 represents a listing of refinery waste streams
according to the four established refinery categories, with
total quantities generated by each, and the percentage which
this quantity represents of waste generated by all streams.
Table 43 shows the total quantities of all hazardous wastes
and of each hazardous constituent which was generated by
the petroleum refining industry in 1974. Values are given
in metric tons (dry weight) by states and by EPA Regions.
107
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4. 6. 4 PROJECTIONS FOR 1977 AND 1983
Quantities of potentially hazardous wastes and hazardous waste
constituents projected for the years 1977 and 1983 are arrived at by
methods similar to those used to extrapolate totals for 1974, as
follows: The values in Table 41 were adjusted by multiplication with
certain factors (described in Appendix J) which are based upon the
following considerations:
(a) Additional refineries are expected to use secondary biological
treatment and air flotation systems in 1977 and 1983.
(b) Certain wastes, such as slop oil emulsion solids, are
expected to be reduced in quantity as a result of increased
oil recovery.
(c) Environmental regulations are expected to result in reduced
use of such elements as chromium and zinc in cooling towers,
and of lead in gasoline.
(d) Projected increase in crude oil capacity are expected to
result in parallel increases in waste production associated
with fluid catalytic cracking, coking, hydrogen fluoride
alkylation, and lube oil processing.
These projections assume that only those states which presently have
petroleum refineries will have refineries in 1977 and 1983. The
effects of expected changes on waste quantities generated by each
waste stream is reflected in Tables 44 and 45, which show projected
total quantities for 1977 and 1983 respectively, of potentially
hazardous wastes and their hazardous constituents generated by all
waste streams in the United States. All values for each year are
expressed as metric tons (dry weight) and are given by states and
by EPA Regions.
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5. 0 TREATMENT AND DISPOSAL TECHNOLOGY
5. 1 INTRODUCTION AND BACKGROUND
Petroleum refineries generate an estimated 625,000 metric tons per
year of waste (dry weight) in the course of distilling crude petroleum and
processing of petroleum products. The volume of waste generated as well
as the economics of material recovery are determined to a large degree by
the type, age, and condition of process units and the market for product
"mix. " In addition, refineries in different geographic areas encounter
widely varying requirements and problems associated with their individual
solid waste streams. Treatment and disposal methods used by the industry
are contingent upon the nature, concentration, and quantities of waste gen-
erated, as well as upon the presumed hazardousness of these materials.
They are further affected by geographic conditions, transportation distances,
disposal site hydrogeological characteristics, and regulatory agency
requirements.
Much of the material wasted by refineries only 20 to 25 years ago has
either been eliminated by process changes, is now processed into market-
able products, is recycled for reprocessing, or is sold to secondary
material processors for extraction of valuable constituents. Noble metal
catalysts, caustic solutions containing recoverable quantities of phenolic
compounds, and some alkylation sludges reprocessed for sulfuric acid are
examples of such waste streams, although these are not within the scope of
this study. The types of wastes requiring disposal have been listed and des-
cribed in Section 4. 3 of this report. They include: crude tank bottoms,
leaded or non-leaded tank bottoms, API separator sludge, neutralized HF
alkylation sludge, kerosene filter clays, once-through cooling water sludge,
dissolved air flotation (DAF) float, slop oil emulsion solids, spent lime
from boiler feedwater treatment, cooling tower sludge, exchanger bundle
cleaning sludge, waste biosludge, storm water silt, fluid catalytic cracker
(FCC) catalyst fines, coke fines, lube oil filter clays, spent catalysts,
chemical precipitation sludge, vacuum filter or centrifuge cake, and silica.
gel.
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5. 2 DATA DEVELOPMENT METHODOLOGY
5. 2. 1 California Sources
An initial data base was established with information gathered
within the State of California, a. major oil-producing state, with the
help of the following agencies and other sources:
California State Water Resources Control Board
Los Angeles Regional Water Quality Control Board, Region 4
San Francisco Regional Water Control Board, Region 2
Los Angeles County Engineers Department - Planning
Commission on Liquid Waste
Los Angeles County Sanitation District
California Solid Waste Management Board
California Department of Health, Vector Control Section
Los Angeles Office of United States Department of
Transportation
California State Traffic Department, Hazardous Materials
Section
Public Utilities Commission
Governmental Refuse Collection and Disposal Association
(GRCDA)
California Vacuum Truck Haulers Association
Vacuum truck waste hauling firms in Southern California
Browning-Ferris, Incorporated
Chemical companies which reclaim materials and by-
products from refinery waste material
California Division of-Oil and Gas
Western Oil and Gas Association
Private consultants who have specialized in various aspects
of petroleum refinery waste disposal
Information obtained through these sources and from know-
ledgable individuals in private indxistry proved useful in shaping
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study methodology and objectives.
5. 2. 2 General Sources
More generalized data regarding waste management in the re-
maining states was obtained as follows:
Solicitation of local, state, and federal regulatory agencies
with refineries within their jurisdictional boundaries.
Contacting refuse haulers and/or disposal firms in various
parts of the country to determine regional differences in
collection and disposal methods.
Contacting and/or visiting businesses especially engaged in
reclamation or processing of refinery waste materials.
Enlisting the assistance of the API special Solid Waste Task
Force in obtaining the use of the many resources available
through its parent organization, the API.
Examining petroleum refining industry statistics recorded by
various governmental agencies, such as the U.S. Bureau of
Mines, U. S. Department of Commerce, and the Federal
Energy Administration.
Contacting petroleum refining industry representatives.
5. 3 CURRENT TREATMENT AND DISPOSAL TECHNOLOGIES
i
The various technologies for trea.tment and disposal of potentially
hazardous wastes which are in current use are the following:
5. 3. 1 Landfilling
Landfill ing is presently the most widely used method for dis-
posing of all types of petroleum refinery waste products. The envi-
ronmental adequacy of this method is contingent not only upon the
types and characteristics of generated wastes, but also upon methods
of operation and on specific site geologic and climatologic conditions.
Of all the land dispoal methods used by the refining industry, per-
haps the greatest variations in operations and in site suitability are
experienced with landfills. Landfilling operations range from open
dumping of construction and refinery debris to controlled disposal in
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secure landfills in certain Western states. California employs a
system of waste categorization and site classification for the regula-
tion of landfill operations which has been used as a model by other
states. Since these California waste designations and site classifi-
cations will form the basis of all subsequent comparisons and
evaluations of landfill operations of the petroleum refining industry,
brief descriptions follow.
Waste Categorization:
Group I Wastes - Wastes which contain toxic and/or hazardous
substances with potential chemical reactivities capable of
significantly impairing the quality of useable waters. Exam-
ples of Group I wastes are: toxic and hazardous fluids from
industrial operations, rotary drilling muds containing toxic
materials, pesticides, chemicals, and industrial brines.
Group II Wastes - Wastes which contain chemically or bio-
logically decomposable materials but which do not include
toxic substances or those capable of significantly impairing
the quality of useable waters. Examples are garbage,
rubbish, construction and demolition material, sewage treat-
ment sludges,, wafer treatment sludges, ash, and pyrophoric
materials.
Group III Wastes - Wastes consisting entirely of non-water
soluble, non-decomposable inert solids.
Site Classification:
Class I Landfill - A disposal facility which has no possibility
of discharge to user.ble waters. Only where natural geology
prevents hydraulic continuity between the disposal area and
the water can a Class I site lie over a useable ground water
area. Run-off and overflow must be contained in the disposal
area, and flooding and washout must not occur. All types of
wastes may be received, including all designations of hazard-
ous wastes. (A Class I site designation will be used synony-
mously with the term "secure landfill" throughout this report.)
The following criteria are usually used to measure the
permeability of naturally occurring soils or equivalent
synthetic materials in Class I sites;
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- 8
(a) Permeability of less than 10 cm/second.
(b) CL, CH and OH soils per the United Soil Classification
system.
(c) Greater than 30 percent by weight passes a No. 200
U. S. Standard sieve.
(d) Liquid limit of greater than 30 percent (ASTM test
423).
(e) Plasticity index of greater than 15 percent (ASTM
test D424).
Limited Class I Landfill - A disposal facility which places
limitations on the types and amounts of hazardous wastes
which may be accepted because of the existing possibility of
inundation by flooding more frequently than every 100 years.
Class II - 1 Landfill - A site which can be located over or
adjacent to useable groundwater. Containment may be
achieved with artificial barriers where natural conditions
are insufficient. Protection against floods occurring at 100-
year intervals must be provided. Group II and II wastes are
accepted, and under special conditions, Group I wastes may
also be accepted. The permeability of the natural soil or
equivalent artificial barriers should be 10~" cm/second and
soil criteria specified for Class I disposal sites should also
be fulfilled. Infiltration into adjacent non-water bearing
sediments may be allowed if there is no hydraulic continuity
with useable water aquifiers.
Class II - 2 Landfill - Sites which allow vertical and lateral
continuity with useable groundwater, but which have hydraulic
and geologic features which will assure some protection of
the^quality of useable groundwater underneath or adjacent to
the s*ite. These requirements may be based upon soil type,
artifical barriers, depth to groundwater,*1 or other factors,
for which considerable site-to-site variation may exist.
Class III Landfill - Sites with inadequate protection of water
quality, where wastes would enter directly into ground or
surface waters. Only Group III wastes may be accepted.
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The environmental adequacy of a refinery waste landfill is
affected by the following operational and management
practices:
(1) The extent of segregation of wastes to prevent mixing
of incompatible compounds, such as solids containing
heavy metals with acids, or solutions with other
wastes which together produce explosions, heat, or
noxious gases.
(Z) The extent to which liquid or semi-liquid wastes are
blended with soil or refuse materials to suitably
absorb their moisture content and reduce their fluid
mobility within the landfill.
(3) The extent to which acids or caustic sludges are
neutralized to minimize their reactivity.
(4) Selection of sites in which the active fill area is large
enough to allow efficient truck discharging operations,
as well as to assure that blended wastes may be
spread, compacted, and covered daily with approxi-
mately six inches of cover soil. A site operated in
this manner is called a sanitary landfill.
(5) The routing of ground and surface waters around the
landfill site and sloping of cover soil to avoid on-site
runoff and erosion.
Several on-site refinery landfill operations were observed to
employ the best current practices. Special problems were
noted in Gulf State refineries where water table levels were
near the surface. The major problems associated with most
landfill operations, as well as other disposal technologies,
were related to soil suitability, facility design, operation,
and site development for disposal of potentially hazardous
wastes. Many of the landfill sites observed would probably
be designated Class II-2.
5. 3. 2 Landspreading
Landspreading is a relatively inexpensive method of disposal
of petroleum refinery wastes, which is being used by a growing
number of refineries. The success of landspreading in the warm
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Southwestern states has prompted many U. S. refineries in colder
climates to experiment with this method of disposal. The majority
of refineries contacted which employ landspreading have done so for
only one to three years; only a few have a working experience with
this process for a longer period of time. One of the first demon-
strations of this process was the degradation of refinery oily wastes
at Shell Oil Company's Deer Park, Texas refinery several years ago
(10).
Considerable research has been done on methods of land dis-
posal of oil skimmed from oceans or beaches, or from accidental
truck, train, tank car or barge spills within the country (1.1-18).
Results of this research revealed that landspreading of such material
is an economical and efficient disposal method, and it became apparent
that this method might be well suited for disposal of refinery-gener-
ated wastes as well.
More than 100 species of bacteria, yeast, and fungi, repre-
senting 31 genera, are known to attack one or more types of petro-
leum hydrocarbons (19-25). Straight chain paraffins are the least
toxic to soils and plants, while olefins, naphthenes or cyclopa raff ins,
and aromatics are increasingly phytoxic (26). Within each of these
groups, smaller molecules are more toxic than are larger molecules
(27). Studies indicate that pseudomonous bacteria quickly become the
predominant microbial species in the soil (13). Soil moisture
appears to be a significant factor in the rate of growth of these
bacterial populations; growth is inhibited when the soil moisture
content falls below 20 percent. The effect of oil applications to land
on soil productivity, soil pH, microbial population changes, and
plant toxicity is complex. In temperate regions, changes in soils
following contamination by petroleum hydrocarbons are directly
related to soil microbial activity, which increases with the addition
of oils or gases (28-30). Bacteria quickly degrade the oil using the
hydrocarbons as a substrate for their growth. As the degradation
process proceeds, the material changes from an oily, odorous black
sludge to a dried, cracked, cakey, soot-like material which
crumbles easily. The oily characteristics of the sludge are lost
after a short period of time. The microbial by-products may change
the soil moisture available to plants, reduce iron and aluminum
which may accumulate to injure plants, or release nutrients which
stimulate plant growth. Various salt marsh species have entirely
different tolerances to oil (31, 32).
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Soil productivity may actually be enhanced by light applications
of oils. Plice observed that petroleum additions of 0. 5 to 1 percent by
weight produced more luxurious plants than those grown on control
plots where no oil was added (28). Carr noted that soybean growth
was improved by adding a small amount of oil (20). A number of
organic acids from petroleum wastes stimulate plant growth. Weak
solutions of napthenic acids increase the root length of cotton, cucum-
bers, onions, and winter wheat significantly. Even large doses of
oil will eventually be degraded by the microorganisms to produce an
organically rich and productive soil (20). Heavy applications of oil
are often toxic to plants. The volatile fractions, which have great
penetrating power, enter plants and seeds and have a narcotic effect
on all living organisms. The reduction of manganese, iron, and
aluminum to the lower oxidation states increases the toxicity. How-
ever, most of the damage to plants appears to result from their in-
ability to obtain sufficient moisture and air due to physical obstruc-
t?on (28).
The landspreading process is suitable for disposal of almost
any oily waste material generated within the refinery. Waste
material is pumped into a vacuum truck and conveyed to a disposal
site. The oily waste is pumped from the truck through a hand-held
discharge hose, which the truckdriver guides in spreading the dis-
charged material as evenly as possible on the assigned land area.
The actual depth of application is determined by experience, and
varies with the oil composition of the discharge, the soil's moisture
and nutrient content, climatologic conditions, and amount of avail-
able land. The application rates for oily sludge vary from one to
two inches in thickness in the Northwestern U. S. to as much as 3"
and 4" in the warmer, subtropical climates of the Southwestern
United States. The rate of degradation and disappearance of oil
requires between one and six months, depending upon the thickness
of the sludge deposit, percent by weight oil content, amount of
fertilizer used, and frequency of tilling. Successive loads are
handled in the same manner, with each load applied in approximately
the same thickness to an immediately adjacent plot. The process is
continued until a large area is covered by the oily sludge or waste
material. After much of the water has evaporated, a tractor-drawn
plow or rototiller is used to break up the oily crust and mix it with a
surface layer of soil. The frequency of rototilling, plowing and
aeration varies from one location to another. A common practice is
to plow the material into the ground to a depth of about six to eight
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inches and to periodically aerate and blend the oily sludge with the
soil. In the Southern United States, a rototiller may go as deep as
eight to fourteen inches to entrain air in the subsurface layers of the
soil. While some of the hydrocarbons are evaporated as a result of
landspreading, there is no noticeable odor, nor is there grounds for
concern about spontaneous combustion or flammability.
A Northwestern U. S. refinery which had specific information
available calculated that between 1, 500 and 2, 500 gallons of oily
sludge material of approximately 1 to 1.5 percent by weight oil could
be disposed of per acre at each application. For this particular geo-
graphic area, as many as two or three applications per year appear
to be possible. Another West Coast refinery applied approximately
3, 600 gallons per acre per year of a heavy sludge of unspecified oil
content. Both of these values appear to be average application rates
commensurate with individual refineries' specific wastes, method of
operation, and local conditions. Some rudimentary laboratory
analyses for one refinery indicated that a maximum of 6 percent by
weight oil could be applied to their particular soil, and that pre-
scribed amounts of fertilizer should be applied concurrently with the
oily sludge. Fertilizer is necessary in order to accelerate the rate
of degredation and provide essential nutrients where they are lacking.
Oily sludges consist primarily of carbon-hydrogen molecules, and
microorganisms using this material as a substrate often require
additional nitrogen which is not normally available in sufficient
quantities in the soil for their growth. Many refineries do not use
fertilizers; most of those that do use only about 25 percent of the
stoichiometrically required amount.
Soil characteristics in areas used for landspreading are
reported to change with time. In one instance, the initial bentonite
clay which had previously dried to a very hard cake changed to a
soft, loamy soil, presumably due to increased organic and moisture
content. The oily sludge material apparently does not decompose
and disappear completely, since a small fraction of the oil remains
combined with or interspersed between the individual soil particles.
The oil-conditioned soil appears to have a higher moisture content
than the native soil. In the case observed, a spontaneous and very
luxuriant growth of grass quickly appeared in the area where oil was
applied. It grew quickly to a height of two feet,ป which was far higher
than any other plant growth in the area. This grass was also able to
grow in dry periods when other plants were unable to survive, pro-
viding additional confirmatory evidence for reports in the literature
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suggesting that at low concentrations oil may act as a plant stimulant
(20,28 ).
A number of refinery-sponsored studies designed to evaluate
the landspreading procedure or its effect on plant growth are planned
or underway. One refinery is planning to plant agricultural crops on
oil spreading areas in an effort to determine mineral uptake and plant
ability to grow in this medium. . Alfalfa has been selected to be the
first experimental crop because it has deep roots, and water is known
to exist lower in the soil at this site. A refinery in Texas is planning
to investigate landspreading in order to determine optimum operating
procedures. A statistical experimental design using as many as
twenty different experimental plots, each measuring approximately
twenty feet square (37. 16 m L is planned to test the main effects
and interactions of different oil application rates, aeration frequen-
cies, fertilizer application rates, sludge thicknesses, and oil concen-
t'-ations. A refinery in Pennsylvania has already initiated a controlled
experimental testing program to evaluate the landspreading method.
Their well-designed test site employs numerous safeguards and
utilizes various upstream and dQwnsfereasr",well-monitoring stations.
Some early results may already be available. Another East Coast
refinery, with the cooperation of the faculty of Cornell University,
has conducted an extensive two-year study to evaluate landspreading
procedures. A report of the results of their study may already be
available.
Up to this time, refineries have been concerned largely with
possible oil contamination of ground and surface waters which may
result from landspreading. Not many of the petroleum companies
have considered other environmental effects which may result from
this operation. The real concern is not only the recognized short-
term oil problem and incomplete treatment of organic acids and
other intermediate by-products, but the long-term implications of
trace metal accumulation in the soil over long periods of operation.
The problem posed by disposal of heavy metals on or in land is the
same for all treatment and disposal technologies. The major
difference is a quantitative one, with repeated applications of oily
wastes to the same land areas potentially producing greater concen-
trations of heavy metals than result from other disposal methods. In
a confined secure disposal area, these heavy metals and other
hazardous organic acids or degradation products do not pose the same
level of hazard to the environment, Concentration levels of trace
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metals and other hazardous components of refinery wastes are shown
in Table 39. (Section 4. 6). -
An assessment of the environmental adequacy of landspreading
for disposal of oily wastes can perhaps best be made in comparison
with alternative methods. The desirability of burial of these wastes
in a landfill is called into question by the fact that petroleum is not
degraded appreciable under anaerobic conditions. If it were, there
would be no oil present in the world today. Conversely, hydro-
carbon seepages at the earth's surface are not known to exist in
large concentrations or to be very old geologically, since aerobic
bacteria quickly degrade petroleum fractions to residual waxes and
paraffins. Oily fractions deposited in a landfill are merely seques-
tered for a period of time until they percolate or leach out. It thus
becomes important that a landfill be of a secure type to prevent this
outward migration of oil and other hazardous constituents.
Even incineration, while destroying most of the organic pet-
roleum fraction, can volatilize certain trace metal constituents and
organic compounds, and then release them into the atmosphere,
where they can represent a significant and dangerous contaminant.
As progressively more oil is removed from refinery waste streams,
disposal by incineration will become an endothermic process requir-
ing the application of additional energy to sustain the combustion pro-
cess. Landspreading does not require the use of external energy to
degrade marginal fractions of oily material, since these substances
are effectively destroyed through natural aerobic degradation. The
problems presented by conservative trace elements once in the
ground are very similar whether they are present in residual ash as
a result of incineration, in a sanitary landfill, or as a result of land-
spreading. It would appear, therefore, that landspreading may be
emerging as an important method for the disposal of refinery oily
wastes. Industry personnel indicate complete satisfaction with
related costs, effort, and with the surprising reliability and effi-
ciency of oil degradation. At the present rate of two to three
applications annually, the amount of land space actually required is
comparatively small.
5.3.3. Lagoons, Ponds, Sumps, and Open Pits
Lagoons, ponds, sumps and open pits have been used for
many decades by the petroleum refining industry for the disposal of
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liquid and semi-solid waste. In the past, convenience and easy
accessibility rather than environmental considerations dictated dis-
posal site locations. It was thus not uncommon to find sumps and
ponds near the refinery process units or at the back of the refinery
property. Tank bottoms, slop oil, API separator sludge, and other
waste materials were usually allowed to congeal, thicken, percolate,
or evaporate in place. Depending on geographic location and climato-
logic conditions, the extent of weathering, degradation, and volume
reduction varied widely. Such sumps were continual receptors of
waste materials and with time many of the available sites within the
refinery were filled up, the sites simply abandoned or forgotten, and
the progressively larger volumes of such waste materials were
hauled to nearby off site locations which were either owned or leased
by the refineries.
The expediency of past disposal by simply dumping wastes
into lagoons or sumps has turned into a major disposal problem in
many parts of the country (33). The demand for elimination of these
unsightly sumps has been prompted by many factors, among which
are the following: (1) the need for additional land for refinery
expansion; (2) increasing land values which demand that land be put
to a higher and more profitable use; (3) the envelopment of these
lands by urban areas, and the resulting increased potential dangers
to people, particularly small children who may stumble into the
often unfenced and unprotected lagoon; (4) increasingly stringent
regulatory agency requirements; and (5) the desire to eliminate
potentially catastrophic situations which may arise as a result of
flooding rivers carrying large amounts of petroleum sludge with
them. Action is now being taken by a number of states, including
California, Oklahoma, Texas, and Pennsylvania, to phase out the
use of sumps and lagoons as permanent disposal methods, allowing
them to be used only as temporary retention or treatment ponds.
They are thus being relegated to use as wastewater treatment units,
such as primary and secondary clarifiers, biostabilization or oxi-
dation ponds, or thickening basins. Other uses included evaporation
ponds or emergency diversion basins. As wastewater treatment
requirements have become more stringent, many simple facultative
and anaerobic lagoons have been converted into aeration basins by
the addition of mechanical aerators. Because of their simplicity
and ease of construction, many of the newer refineries make con-
siderable use of earthen or lined lagoons as primary or secondary
sedimentation chambers , aeration basins , oxidation ponds, storm
runoff ponds, and emergency oil spill retention basins.
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Of the refineries visited, only one made use of a lagoon for the
disposal of the majority of its wastes. Two others had recently
instituted the use of sumps as a temporary expedient method of dis-
posing of tank bottoms and spilled oily material. Presumably, this
material will be scooped up after evaporating and weathering in
place, and will be disposed of in a sanitary landfill or by landspread-
ing. Those ponds being used for purposes of equalization, retention,
or treatment are periodically emptied with a clam shovel or by
vacuum truck, and the material transferred to a permanent disposal
facility.
The environmental acceptability of lagoons for any of the pre-
scribed purposes is very much dependent upon the method and
materials of construction, specific local hydrogeologic conditions,
and the types of waste which are handled. Unfortunately, the poten-
ial for significant contamination of underlying water aquifers from
many inadequately lined lagoons, both old and new, is appreciable
because of improper location and inadequate safeguards. While many
of the units are perfectly acceptable, some attention needs to be paid
to insuring that adequate design and construction practices are
followed in areas with high water tables, very porous soil, or other
adverse conditions.
5. 3. 4 Leaded Gasoline Sludge Treatment and Disposal
Because organic lead vapors are known to be toxic at very
low concentrations (approximately 0. 075 to 0. 15 mg/m , depending
on lead compound), special procedures have been developed
exclusively for the treatment and disposal of leaded gasoline sludges
which accumulate in aviation and motor gasoline storage tanks. A
broad variety of lead alkyl additives are njfclMftmi* in the manufacture
of gasoline, the most common being tetraethyl lead. Others are
tetramethyl lead, triethylmethyi lead, diethyldimethyl lead, and
ethyltrimethyl lead.
During storage, gasoline is exposed to the action of air and
diurnal variations in temperature. An unstable gasoline will undergo
oxidation and polymerization reactions under these conditions. In
the early stages of formation, these polymerization reaction pro-
ducts may remain in solution in the gasoline, but later, further
chemical changes cause them to precipitate from solution. This is
the material that forms a sludge at the bottom of product storage
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tanks. The sludge is formed from the olefinic material present which,
because of its unsaturated characteristic, is more reactive to the other
constituents. The chemical reactions are accelerated by light and heat.
It is a chain reaction initiated by the formation of peroxides and cataly-
zed by the presence of metals, particularly copper, which may be u
picked up in the refining and handling operations in the refinery.
Various trace metals in the gasoline itself may play a part in this re-
action. Other contaminants are sulphur, polysuphides, thiophenols,
and nitrogen compounds (34).
The survey team encountered two basic procedures for the dis-
posal of leaded-gasoline sludge from gasoline product storage tanks.
The procedures were developed and disseminated to the refineries by
the two primary manufacturers, the Ethyl Corp. and DuPont. The
first procedure is the older of the two and has largely been superseded
by an improved method which assures faster and more complete de-
gradation. Both procedures basically involve the construction of a
dike surrounding the tank to be cleaned. After the tank contents
(except sludge) is pumped to another tank, the remaining sludge is
either pumped into the dike for weathering and degradation or is
transported to a weathering pad elsewhere within the refinery. It is
subsequently rotodisked into the soil or buried on refinery property.
These procedures are described in Appendix K. The volume of
leaded-gasoline sludge generated is quite small and the frequency of
cleaning is subsequently low - on the order of every one to ten years.
Even then, the frequency of tank cleaning is dictated more by required
tank maintenance than by need for sludge removal.
5. 3. 5 Incineration
Incineration of semi-solid and solid organic and inorganic
refinery-generated wastes requires a special type of system which
provides adequate detention times, stable combustion temperatures,
sufficient mixing, and high heat transfer efficiency. A fluidized bed
is one of the few systems which can satisfy all these criteria. In
addition, the fluidized bed of heated solids serves as a heat sink to
ignite volatilized hydrocarbons, thereby reducing or eliminating the
possibility of creating an extremely dangerous explosive mixture of
unburned gaseous hydrocarbons and air. The material to be incin-
erated can be injected either into the fluidized bed or immediately
above it. Refinery wastes known to be incinerated by such systems
include spent caustic solutions, API separator bottoms, DAF float,
waste bio sludge, and slop oil emulsion solids. Experience has shown
that the reaction is self-sustaining if the thermal content of the total
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wastes incinerated exceeds about 29,000 BTU per gallon. Normal
range of operating temperatures is 1300 to 1500 F. Loss of fluidi-
zation and plugging of the bed is still a major problem in the operat-
ion of these units. The only refinery visited which had an incinerator,
mentioned that mechanical problems with the unit were responsible
for significant periods of "down" time. Storage pumps and basins
had been provided to handle the waste during these periods.
A jointly sponsored American Oil Company and EPA pilot
demonstration of the fluidized bed incineration of refinery wastes
was conducted during 1969 and 1970 at American Oil Company's
(AMOCO) Mandan, North Dakota refinery (*). The results were
encouraging enough for the American Oil Company to construct a
larger fluidized bed incinerator of improved design at their Whiting,
Indiana refinery. This use, coupled with the operation of incinerators
by other oil companies, has demonstrated that incineration is a
viable treatment and volume reduction method. The use of incin-
erators, however, appears to be confined to certain parts of the
country, i. e. , the Midwest, the Great Lakes Region, and the North-
east. There are a multiplicity of reasons for this:
Hydrogeologic and climatologic conditions preclude the use
of methods used successfully in other parts of the country.
The shortage or high cost of land excludes land intensive
treatment and disposal methods.
Certain reclaimable wastes, because of volume and/or ship-
ping distances, become uneconomical to handle any other way.
Thermal energy contained in the oily wastes can be used to
destroy certain other waste streams not easily treated using
any other method.
Other parts of the country are prevented from using incin-
eration because of air pollution considerations.
Because several of the trace metals under consideration in
this study are volatile at temperatures normally encountered during
(*) Source: EPA Water Quality Office Report No. 12050, 1971
129
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incineration, expensive air emission control devices are required
where air pollution emission requirements are stringent. During
combustion, organic and metallic materials are converted into a
multidue of compounds. Some are partially oxidized or reduced and
their structure and properties substantially changed. Others remain
chemically unaltered, changing only physically from a solid to a gas.
Recent incineration studies have shown that volatilized metals are
absorbed to a large degree by fine particulate matter. This material
is so fine that many of the conventional air emission control devices
remove only a small percentage of it. Presently unspecified quanti-
ties of metals and certain gases or combustion products not removed
by the air pollution cleaning devices are dis.djar.ged into the atmo-
sphere each day. Metals of most concern which are emitted from
these incinerators (as well as fluid catalytic cracker regenerators)
are beryllium, nickel, and vanadium. The solid residue from com-
bustion is sometimes quenched with water, producing a contaminated
aqueous waste stream which is routed to the wastewater sewer..
Water scrubbing of incinerator gases produces a similar contaminated
waste stream.
Disadvantages associated with the incineration process which
were expressed by several refinery managers and plant engineers
are the following:
The process has a high capital cost as well as high reoccurring
annual operation and maintenance costs.
Because of the increased value of oil, as much oil as possible
is now extracted from all refinery waste streams. Thus, the
thermal value of the various sludges (particularly those that
had to be blended with oily wastes) is decreased to such a
point that the combustion reactions are either no longer self-
sustaining or only marginally so. Continued operation of
incinerators thus requires either that valuable oil is left in
the various wastes or that additional thermal energy is
supplied to the process, further increasing actual operating
costs.
The implementation of increasingly stricter air pollution
regulations may mandate extremely expensive and compli-
cated air pollution control devices at some future date.
130
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More economical and equally efficient treatment and disposal
methods are becoming available.
5. 3. 6 Deep Well Disposal
Subsurface or deep well injection is an ultimate disposal
method which originated with the oil and gas extraction industry.
Connate brines, separated from the extracted gas and oil, are pump-
ed back into the formations from which the fluid is originally taken,
thus restoring the formation pressure and facilitating the extraction
of additional gas and oil. Gradually the injection practice has been
extended to include a multitude of wastes which would be difficult to
dispose of by any other means.
Only one of the sixteen refineries visited practiced deep well
injection of waste solutions. Approximately 186.5 million gallons
per year are injected, consisting of sulfidic solutions generated by
caustic washing of crude cracking and hydrotreating streams, sour
water from a hydrotreating unit, brines from the desalter operation,
and other weak solutions from crude processing and pretreating. The
sulfidic solutions are neutralized with catalytic regenerator flue gas,
and before injection into the subterranean formation, all of the
solutions are pumped through an upflow mixed media filtration unit
consisting of anionic and other unidentified media, possibly sand.
One of the gulf state refineries ships large quantities of
refinery waste solutions to a processing and reclamation plant. This
firm was of interest because it disposes of certain types of residual
wastes by deep well injection. The plant, located in Texas, handles
approximately 30, 000 barrels per month of petroleum refinery wastes.
Approximately 15, 000 barrels are oily wastes, and 8,000 barrels are
waste acids and caustics. The oil is recovered wherever possible.
Economically recoverable materials are separated from these
solutions and the residual aqueous and solid wastes treated by acti-
vated sludge or incineration. If the treated effluent is relatively
innocuous in nature, it is discharged to a receiving surface body of
water. Noxious solutions and wastes are injected in the company's
single deep well. It was reported that this facility would be shut
down in 1975 for undisclosed reasons.
Several refineries in the Southern California area are known
to inject waste brines into deep wells. Deep well injection capital
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and operating costs can be considerable. The future of deep well
injection has been clouded by recent legal and regulatory agency
decisions (35, 36).
5. 3. 7 Ocean Disposal
The 1971 Dillingham report (37) for the EPA on ocean dis-
posal of barge-delivered liquid and solid wastes reported that approxi-
mately 500. 000 tons of refinery wastes have been dumped into the
ocean. Many petroleum refineries located in coastal areas discharge
their aqueous waste streams after treatment into the ocean through
deep water dispersion conduits under National Pollution Discharge
Elimination System (NPDES) permits. Sporadic records obtaasfted:
from Southern California refineries indicated than on random
occasions small quantities of barge transported alkaline or acid
solutions have been disposed off the California coast. This practice
was terminated some time during the late 1960's. It was reported
that until recently, certain petroleum refinery wastes in 55 gallon
drums were still being dumped in the Gulf of Mexico by one or more
gulf state refineries.
The Marine Protection Act of 1972 (PL 92-532) has trans-
ferred regulation and control of all ocean dumping from the district
office of the U. S. Corps of Engineers to the Environmental Protect-
ion Agency. Ocean disposal of certain prescribed hazardous wastes
is prohibited, while permits for other less hazardous wastes are be-
coming increasingly difficult to obtain as alternative methods of
ultimate disposal become available. Present trends indicate that
ocean disposal will be gradually eliminated.
5. 3. 8 Special Treatment and/or Disposal Practices
A procedure for reducing the volume of crude tank bottoms
which was observed in at least one of the refineries visited is the use
of polyelectrolytes. The process is performed prior to cleaning the
tanks, at which time any crude oil remaining in the tank is pumped
out to the sludge layer and replaced with approximately 5, 000 to
6,000 barrels of "Canadian Condensate" or "off-gas" from field
wells. The material in the tank is heated with steam and mixed
with the crude tank bottoms to a temperature of approximately 130 F.
Two kinds of polyelectrolytes are added and the contents mixed for
approximately two days. The types of polyelectrolytes and their
132
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actual concentrations are determined by laboratory tests. (It has been
reported that this procedure does not work well for all types of crude
oil.)
The results exceeded expectations. The crude sludge was
broken down into a very distinct oil fraction and an underlying clear
water fraction, both of which could be separately decanted from the
tank. The total quantity of residual sludge which required removal
from a 125,000 barrel tank following the use of this treatment
amounted to seven barrels. It was found, furthermore, that when
this oil fraction was pumped into a different crude oil storage tank,
it helped to effect a separation in that tank as well.
The same refinery observed that crude tank bottoms and API
separator sludge exposed to alternate freezing and thawing during
winter months in an open sump had a considerable layer of oil on the
surface the following spring. Subsequent laboratory tests revealed
that alternate freezing and thawing does indeed break the emulsions
to a considerable degree. The refinery is planning to expand the
facility and to perform a controlled study of the method.
Another special practice which was observed in treatment of
both liquid and solid wastes is that of chemical fixation. Among the
chemical fixation methods which are in use in the petroleum refining
industry are the following:
(1) Use of chemical coagulants to create an insoluble
precipitate. Only one waste stream in the refineries
visited is deliberately treated to produce a chemically
inert precipitate. This is the routing of cooling tower
blowdown containing hexavalent chromium through the
API separator where available sulfides bring about the
reduction of hexavalent chromium to trivalent
chromium. From the API separator, the now-reduced
chromium ion is routed through the spent lime slurry
tank where it is further precipitated by lime to
chromium hydroxide. The lime sludge containing the
precipitated chromium hydroxide is usually removed
by vacuum truck.
(2) Sorption of solvent-like hydrocarbons on imbiber
beads.
133
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(3) The use of a variety of chemical systems have been
devised to overcome the fluidity of certain petroleum
wastes. These chemical systems react with various
components of the waste to form a semi-solid material
which effectively encapsulates or otherwise ties up the
harmful constituents. The majority of these methods
tend to isolate the material from the environment by
either isolating the waste component as a solid mass,
drying out the liquid, or achieving some form of
chemical bonding or sorption. Chemical fixation or
solidifcation is used by a few refineries to solve specific
disposal problems, such as the permanent disposal of
environmentally unacceptable lagoons filled with API
separator bottoms or crude tank bottoms. The Chem-
fix Process (*) is an example of such a chemical
system. It consists of adding metered quantities of
reactants to 300 to 500 gallons of waste slurry at
intervals of one minute, and mixing to obtain homo-
geneity. The volume of reactant added to the waste is
usually less than ten percent and often below five per-
cent by volume. If cement were used to solidify the
same waste, a volume increase of about 100% would
typically be required to obtain a solid waste containing
the entire liquid portion. The process is continuous
and occurs at ambient temperature and pressure.
One of the Texas refineries visited had an accumulation of
API separator bottoms "Chemfixed" in February of 1974. This was
the only refinery which had material available for observation.
Although samples previously tested by the Texas Water Quality
Control Board had not produced a significant leachate problem, the
Board had nonetheless insisted that the material be placed in a land-
fill with a large dike around it to prevent surface runoff. The Board
also required that approximately two feet of cover dirt be placed over
the waste as a precautionary measure, however, this had not yet been
done at the time of the survey team visit. The treated material had
(*) Chemfix Division, the Carborundum Co. Note: Mention of trade
names does not constitute endorsement or recommendation by EPA.
134
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the appearance of oil-stained dirt. It had rained heavily the previous
day, but there were no visible indications of oil leaching from the
material. The Chemfix process can reportedly stabilize materials
of up to about 38% solids, using different amounts of proprietary
additives. Leaching of various ions is controlled largely by the
amounts of silicates added. As the coagulated material dries, the
pores reportedly shrink, confining the wastes within the matrix. It
is still too early to say exactly how stable these wastes are under
actual environmental conditions. To date, approximately 20 million
gallons of petroleum refinery wastes consisting primarily of API
separator bottoms and crude tank bottoms have been processed using
the Chemfix method. Details of this method appear in Appendix L.
5.4 ONSITE VS. OFFSITE DISPOSAL
Offsite treatment and disposal methods employed by the petroleum
refining industry are landfilling/dumping (i. e. , private, municipal, etc.)
and lagooning. Onsite treatment and disposal methods include landfilling/
dumping, lagooning, landspreading, deep well injection, and incineration.
A summary of onsite and off site disposal methods used by nineteen
refineries appears in Table 46. Information for these tables was obtained
primarily from the sixteen refineries visited as well as from the records
of three California refineries. For each refinery, waste quantities for each
disposal method are given in metric tons. Parenthetical values represent
percentages of total refinery waste generated.
At least three of the newer refineries (refineries No. 7, 12 and 13)
have not yet instituted routine cleaning of their process units. Data in
Table 46 should, therefore, not be construed to suggest that the newer
refineries generate lower quantities of waste for comparable production
levels and unit processes. Since unit processes employed at these
refineries are generally similar to those used in the older refineries
within their companies, there is no reason to believe that waste generation
rates would differ appreciably for any reasons other than variations in
crude oil types or various process or technical innovations which increase
or decrease unit charges of processing materials. A record of disposal of
wastes generated by four California refineries (refineries No. 14, 17, 18,
19 in Table 46) between the years 1968 and 1973 is tabulated in Appendix
M.
135
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The distribution of industry wastes according to the various disposal
methods is further broken down as follows:
Onsite landfilling 16.8%
Onsite landspreading 8. 4%
Onsite lagooning 18. 3%
Onsite incineration 0. 8%
Off site landfilling 34. 3%
Off site lagooning 21. 4%
Table 47 shows quantities of waste generated by each of 19 refineries,
which are listed according to established classification types. These data
are provided for comparison purposes.
Comparison of data in Tables 46 and 47 allows evaluation of relation-
ships between waste quantities generated and refinery type, as well as
between those quantities and individual refineries. The data in Table 47
indicate a considerable range of values within each refinery classification,
as well as an "apparent" general trend of increased waste generation with
increasing refinery complexity. It is important to note however that:
(1) At least three of the refineries are relatively new and
have not yet started routine cleaning of all process
units - resulting in lower than normal waste generat-
ion rates.
(2) Refineries No. 15 and 16 are old established plants
located close to suitable Class I secure disposal
facilities. Their hauling and disposal costs are
among the lowest in the country.
(3) Several of the refineries with high generation rates
use low API crudes (high viscosity, low API gravity
number) and/or have large volumes of water treatment
sludges.
(4) Several of the refineries completed extensive plant-
wide cleaning operations during the reported time
period. Some of the process units will not be cleaned
again for 5 to 10 years.
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TABLE 47
SOLID WASTE GENERATION RATES
BY REFINERY CATEGORY
Metric tons/year
1000 bbl capacity
Type II Type III Type IV
(12) 6.1*
(2 ) 8
(13) 11.5*
(9) 96.5
(18) 168.8
( 4) 276.6
x=94. 6+110. 3 x = 187. 3+_ 304. 68 x = 365.4 + 236. 9
*New refineries which have not yet started to clean all process units
(11)
( 7)
(19)
( 5)
(6)
(17)
(15)
12. 2
15.3*
36.1
38.7
60,4
235.4
912.7
(3)
(1)
(14)
(16)
(8)
(16)
52.5
161.9
300
415. 2
474.3
788. 2
139
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(5) Removal of peripheral statistical values significantly
alters the results and subsequent conclusions.
(6) The mean values and associated standard deviations
for the refinery classifications reveal considerable
overlapping of the groups.
(7) At least one of the refineries has made a concerted
attempt to reduce the amount of solid waste generated
through a process of experimentation, process modifi-
cation, and reuse.
From the tabulation which appears earlier in this section, it is
apparent that onsite methods are employed by the petroleum refinery
industry to dispose of 44. 3% of all generated wastes. Offsite methods
account for 55. 7% of all wastes. On the basis of disposal practices in the
four major refining states of California, Illinois, Louisiana, and Texas,
data has been extrapolated to estimate onsite and offsite disposal distri-
bution methods for the years 1973 and 1983. Figures are presented in
Table 48 and represent approximate percentages of total quantities of
refinery wastes which are disposed of by each major method. Offsite
landfilling and offsite lagooning (primarily for evaporation or skimming of
oil) are the only two significant offsite disposal methods and represent 34%
and 21% respectively of the national total. One refinery employed the land-
spreading services of a parivate contractor to dispose of certain wastes at
an offsite facility, however in proportion to the national total, the quantity
was inconsequential, and therefore appears in the table as a zero under
offsite landspreading. Landfilling and lagooning represent major onsite
disposal methods as well, accounting for approximately 17% and 18%
respectively of the national total.
Discussions with refinery and corporate engineering personnel as
well as with other industry experts provided the basis for projections for
the year 1983 of waste disposal distribution for the various disposal
methods. The projected figures indicate a dramatic decrease in the
amount of offsite disposal with a concommitant shift to onsite methods,
particularly landspreading and landfilling. Lagooning is expected to de-
crease slightly, and minor increases are expected in incinceration and
special onsite disposal practices. Waste destined for offsite disposal is
expected to decrease from 56% in 1973 to 27% in 1983, with a large portion
of the anticipated decrease being reflected in increased onsite landspread-
ing.
140
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TABLE
ESTIMATES OF REFINERY WASTE DISPOSAL
- METHODOLOGIES UTILIZED .FOR
THE YEARS 1973 ANB 1983
Disposal
Procedure
Landfilling
Lagooning
Incineration
Landspreading
Total
1973
Onsite Off site
1983
Onaite
Qffsittet
16.8
18.3
0.8
8.4
44. ^
34. 3
21.4
0
0
55.7
24
12
3
34
73
20
7
0
0
27
141
7-37
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This anticipated dramatic decline in offsite disposal in the space of a
decade is reflective of the dynamic interactions between emerging environ-
mental regulations and restrictions, the development of new disposal
technologies (the most prominent being landspreading and modifications of
the coke and fluidized bed incinerator for disposal of various combustible
refinery wastes), and the effects of energy shortages which encourage re-
clamation of oil as well as other unit process and disposal changes. Even
before the energy crisis, a variety of factors compelled the refineries to
convert to onsite land disposal of their waste. These factors can be
delineated as follows:
The closure of many sumps, lagoons, and dump sites over
the last several years has seriously reduced the availability
of nearby disposal sites for the disposal of petroleum
refinery wastes.
* The present trend is one of increasingly stringent require-
ments by regulatory agencies surrounding disposal of
industrial waste materials to outside municipal or private
landfills. Oily wastes are a highly visible and publicized
industrial waste, and disposal of petroleum wastes in muni-
cipal landfills is gradually being prohibited.
* Regulatory agencies may eventually control the hazardous
constituents in petroleum refinery wastes and possibly limit
their discharge.
* The costly transporting of large volumes of refinery wastes
long distances to federal or state certified secure hazardous
waste disposal sites would bring about significant economic
and price dislocations to a segment of the industry, and place
certain refineries at an immediate disadvantage. The only
secure hazardous waste disposal site in one northwestern
state, for example, was located some 3QO miles from the
refineries - a trip at least 10 times the typical offsite
hauling distance.
* The emerging stringent water and air emission requirements
dictate that increasing volumes of concentrated and possibly
hazardous wastes may need to be discharged to the land,
since land disposal is not as stringently regulated at the
present time.
142
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No doubt there is some recognition of the legal rights, privi-
leges and precedents afforded by private property laws as they
presently exist. This has been observed in a review of the
solid waste laws as they apply to private onsite versus public
offsite disposal facilities. This legal protection surrounding
the use of private property sometimes allows industry to dis-
pose of industrial wastes on their own property without the
necessity of permit, monitoring, or supervision and control
by regulatory agencies over their disposal operation.
The trend in petroleum companies today is toward self-sufficiency in dis-
posal practices. When building new refineries efforts are made to avoid
encumbrance of future regulations by purchasing land areas sufficient to
accommodate adequate disposal facilities.
5. 5 WASTE HANDLING BY PRIVATE CONTRACTORS
The quantity of refinery-generated waste which is handled by private
contractors is closely correlated with offsite disposal quantities, which re-
present approximately 56% of the total (1973). Hauling/disposal contractors
were generally reluctant to divulge information regarding quantities of waste
transported, and this information was obtained directly from the refineries.
Within the state of California, private waste hauling contractors are re-
quired to complete a permit form for each load of industrial waste material
transported to a disposal facility. This permit system was included among
the provisions of State Senate Bill 598 which was designed in an effort to (1)
assure that industrial wastes are disposed of at approved facilities, (2)
monitor the quantity of industrial wastes generated, and (3) minimize
environmental hazards which result from improper waste disposal manage-
ment. The hauler must provide the name of the firm generating the waste,
the address of the site of waste origin, and the quantity and type of waste.
Copies of the permit form including this information are forwarded to the
State Water Resources Control Board and to the state disposal site regula-
ting agency. It is the former agency which ultimately regulates the state
water quality, and this is achieved through a system of regional boards,
each of which is responsible for enforcement of quality standards. State
licensure is mandatory for all potential industrial waste haulers, and
applications for license are filed with regional offices of the State Water
Resources Control Board.
Within the County of Los Angeles, requirements governing industrial
143
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waste disposal are stringent. Past problems with ground water contami-
nation resulting from improper disposal practices led to close monitoring
by the Los Angeles Department of County Engineers of industrial waste dis-
posal within their area of jurisdiction. For all solid waste material remo-
ved to offsite disposal facilities, four major refineries within the County
are required to submit monthly reports describing waste types and quantit-
ies, point of origin, disposal facility used, and name of waste hauler.
As many as six different waste hauling firms may be simultaneously
under contract to a single refinery, although on the average, contracts
with three firms are adequate to meet the needs of one refinery. These
firms dispose of wastes primarily in sanitary landfills (California Class I
site) or in lagoons.
Costs for the services of private waste hauling contractors within the
state of California are based upon rates established under Tariff 13 (for
vacuun: truck hauling operations) by the California Public Utilities Commis-
sion. These rates (1974) are $19/hour for a vacuum truck with a capacity
of 50-90 barrels, and $21/hour for a truck with a capacity of more than 95
barrels. Both figures include the cost of the driver. Rate adjustments may
be made if additional manpower is required, or if overtime periods are in-
volved in completion of waste removal.
A listing of some of the private waste hauling and disposal contractors
providing service to petroleum refineries within and without the state of . -
California appears in Appendix N.
5. 6 SAFEGUARDS EMPLOYED IN TREATMENT AND DISPOSAL
The environmental adequacy of treatment and disposal methods emp-
loyed by the petroleum refining industry varies widely, not only with the
criteria against which it is assessed, but also with the chemical and physio-
logical characteristics of the discarded waste, their concentrations, their
background levels and their chemical and physical mobility in the biological
environment. The industry employs various precautionary measures to
guard against immediate or future injury to the environment resulting from
treatment and disposal practices. Among those commonly encountered
during the course of the petroleum refinery field investigations were the
following: (1) careful site selection with comprehensive consideration of
site geology, soil permeability, soil ion exchange capacity, depth and
distance to local groundwater aquifers, and water quality and hydrology;
144
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(2) site utilization and operations, involving adequate use and compaction of
impermeable cover materials to prevent excessive infiltration and percolat-
ion, sound use of ground sloping to achieve appropriate surface runoff, the
use of waste neutralization or degradation prior to final burial, and where
applicable, planting of grasses, shrubs and trees for soil stability and
water withdrawal by evapo-transpiration; (3) the use of site construction
techniques such as the installation of site liners, leachate collection systems,
gas migration barriers or venting systems, monitoring wells, protected
berms and dikes, and upstream runoff diversion ditches; (4) the use of pre-
treatment measures such as chemical precipitation or neutralization, de-
watering, composting, dilution with municipal refuse or other less hazardous
constituents, incineration, and others.
For offsite landfilling, the use of a site classification system is one
of the most comprehnsive methods presently employed to safeguard ground-
water quality and the surrounding environment. Mandatory minimum
requirements for site management and operation are generally monitored
by state or local regulatory agencies, and sites typically operate under re-
newable permits. In California, Texas, and a few other states, petroleum
refinery wastes must be placed in a secure Class 1 or conventional Class II
landfill site, and there appears to be a trend toward mandatory offsite
monitoring of groundwater quality. Several other states are in the process
of enacting enabling legislation which would provide for suitable environ-
mental safeguards.
The major safeguards employed in onsite landfilling are the use of
hydrogeologically suitable sites, and the construction of storm runoff
diversion ditches, as well as careful adherence to accepted operating
practices. Two of the visited refineries used bentonite clays, which are
presumed to have high ion exchange capabilities and low permeability,
under the onsite landfill areas. Both sites provided for excellent surface
drainage surrounding the sites, using a small exposed working surface and
an impermeable clay covering mounded in the center to shed runoff water.
Landspreading is a relative innovation in the petroleum refining
industry, and its use during the past one to three years has been
essentially on a trial basis. The safeguards which are employed in land-
spreading appear to be limited to the construction of dikes or low-level
berma surrounding the spreading surface. The majority of refinery land-
spreading sites observed had not as yet instituted controls of transportable
oil or other hazardous constituents of refinery wastes in surface water run-
off. Only one of the experimental facilities employed upstream and
145
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downstream monitoring wells for the detection of leachates and analysis of
intermediate degradation by-products.
Few of the lagoons and sumps used for disposal of refinery wastes
employed adequate safeguards. The majority of lagoons and sumps are
constructed from native earth materials, and the only safeguard which was
observed was the use of concrete, plastic, or clay liners to reduce or
impede the exfiltration of potentially hazardous liquids. This safeguard
was employed in few facilities.
Only one example of deep well injection was actually observed during
the course of refinery field visits. Two major safeguards were employed
by this facility, i. e. , those of location and depth selection. A description
of construction plans and geological reports confirming the suitability of
the site were required by the state regulatory agency. The three disposal
wells discharge into unusable saline subterranean formations between 2100
and 4000 feet in depth.
Incineration units employ the use of various types of air pollution
scrubber systems as an environmental safeguard. The use of devices for
the detection and control of excess oxygen, or of temperature monitoring
systems in hearths, stacks, and combustion zones, are additional safe-
guards sometimes employed. One of the units observed employed specially
designed burners and a special injection feed system for controlled.
burning of the very viscous sludge residues and other types of petroleum
refinery wastes. Limited safeguards were employed by the smaller units;
even a rudimentary scrubber system was not present in some of the
systems.
Special precautions are exercised in the disposal of leaded gasoline
sludges and residues. Breathing equipment and tank ventilation systems
are used to protect men working within the tanks against toxicity from
vapor inhalation. Once the sludge is outside'the tank, the vapor concen-
tration is gradually reduced to below the threshold toxicity level. A sump
is excavated around the tanks, and entrance to the surrounding diked area
is generally prohibited until the vapor concentration has been reduced to
levels below twenty parts per million. At those plants where the degraded
leaded gasoline sludge is subsequently removed to another part of the
refinery for final disposal, the disposal area is surrounded by a locked
chainlink fence. The concrete weathering pads employed in the newer
disposal procedure are typically enclosed behind locked chainlink fences
and elevated one or more feet above the surrounding terrain to minimize
146
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the quantity of storm runoff which washes across the pad. The sludge on
the concrete slab is contained by a peripheral curbing of at least six inches
in height, and the entire slab is sloped to assure drainage to the plant
wastewater collection system. All tools such as shovels, rakes, spatulas,
hoses, and others, are maintained in a shed within an enclosure and are
washed after each application. Gloves and working smocks are also pro-
vided within the enclosed area.
Safeguards such as encapsulation in plastic or concrete, burial in
steel drums, or leachate collection and treatment specifically for petro-
leum refinery wastes was not observed. The industry simply believes that
this type of treatment and/or handling is not warranted or economically
justified. The little material presently discharged to the ocean is currently
regulated by the Environmental Protection Agency and permits for ocean
disposal represent a safeguard against the use of hazardous practices.
5. 7 THREE LEVELS OF TECHNOLOGY FOR TREATMENT AND
DISPOSAL OF PETROLEUM REFINERY WASTES
Because of the many factors which affect the ultimate fate of petro-
leum refinery wastes, the course and extent of the ultimate degradation
process is largely speculative. In identifying three levels of technology
(defined in Section 1. 2) for the treatment and disposal of petroleum
refinery wastes, two major criteria have been used. The first is environ-
mental adequacy under varied geologic and climatologic conditions, and
the second is the long-term environmental stress on ground water supplies.
Tables 49 through 65 contain a description of three levels of treatment and
disposal technology associated with each of 17 waste streams generated by
the petroleum refining industry. Engineering experience and judgement
are combined with a knowledge of basic principles in the assessment of
these treatment and disposal technologies. Experienced soil scientists,
microbiologists and consulting engineers working the field of petroleum
geology and treatment and disposal, were consulted as needed regarding
toxicology, epidemiology, chemistry, microbiology, hydrogeology, soil
science and sanitary engineering. Appendix O describes the potential of
these metals for inter-media transfer.
147
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6. 0 COST ANALYSIS
6. 1 INTRODUCTION
The petroleum refining industry generates a total of 1, 756, 633
metric tons of waste annually (1974), and hazardous constituents of
refinery wastes represent approximately 6% of total refinery industry
emissions. Approximately 40% of refinery wastes are managed onsite;
60% are managed offsite. Nearly all waste destined for offsite disposal
are hauled by private contractors, and final disposition of the wastes is
primarily by landfilling and lagooning. For purposes of this study, the
cost to industry for treatment and disposal is based upon the waste
generation and practices of a typical 20-year old U.S. refinery with a
capacity of 100,000 barrels per day. They are further calculated on the
basis of three different levels of technology: Level I - treatment and
disposal practices commonly in current use; Level II - environmentally
best treatment and disposal practices currently used in the industry;
Level III - most environmentally adequate treatment and disposal
practices achievable. Industry costs for implementation of each of
these levels of technology within the typical refinery are then extrap-
olated to the entire petroleum refinery industry. These costs have
been calculated to include present waste management practices, as well
as those projected for 1977 and 1983. Data wese obtained directly from
industry representatives in the course of refinery visits, from waste
treatment and disposal contractors, from state public utility commis-
sions, from the Federal Interstate Commerce Commission, and from
available literature. Wherever possible, costs are based on actual
installations, or on price quotations from waste treatment and disposal
contractors. In the absence of such information, cost estimates are
developed on the basis of plant-supplied costs for similar treatment
and disposal operations.
6. 2 COST RATIONALE AND REFERENCES
All cost estimates are based on fourth calendar quarter 1973
prices. Capital costs include expenditures for the engineering, design
purchase, and installation of treatment/disposal facilities, as well as
land costs when applicable, buildings, special startup costs, equipment,
and contractor profits and contingencies. Annualized capital costs
assume a ten-year depreciation schedule, and therefore represent 10%
174
-------
of total capital investment. Interest costs have been calculated at 10%.
Depreciation costs have been calculated on the straight line method and
are based upon the useful service life of all treatment and disposal
equipment as follows:
Estimated Useful
Equipment/Mate r ial Service Life, Yr.
(1) General Process Equipment 10-15
(2) Incineration Equipment 15
(3) Lined Ponds 20
(4) Trucks, Bulldozers, Loaders, 10
& other such materials hand-
ling & transporting equipment
In view of the extreme variability in land costs, land value has
been held constant at $12,350 per hectare (2.471 acres), or
approximately $5,000 per acre throughout. In many instances, the
market value of land used for waste disposal is reduced because of the
limited usage for which it is subsequently available. Cost estimates
have therefore assumed land values and capital recovery on the
following basis:
(1) Where onsite land requirements are significant and
storage and/or disposal of wastes does not affect ultimate
market value, the estimated costs reflect only interest on
invested capital,
(2) For significant onsite land requirements where ultimate
market value and/or availability of land for subsequent use
has been seriously reduced, estimates include capital
depreciation as well as interest on invested capital.
(3) Offsite treatment/disposal land costs are assumed to be
included in contractor's fees and therefore are not
added.
The selected land value is further based upon the following
estimates: Secure landfilling and landspreading operations requiring
special preparation are reflected in a constant land cost of $19, 760 per
hectare ($8,000 per acre); use of additional special safeguards increases
calculated constant land values to $24, 000 per hectare (approximately
$10,000 per acre).
175
-------
Annual operating costs, including labor, supervision, materials,
maintenance, taxes, insurance, and power and energy are combined with
annualized capital costs to give total costs for treatment and disposal
operations. Labor and equipment costs are calculated at $10 per hour
for a 90 to 100 barrel vacuum truck with an operator, or $20 per hour
for the use of a bulldozer or other earthmoving equipment for waste
disposal. Labor and supervision for treatment equipment varies from
0 to 0.25 operators/shift at $10 per hour with maintenance ranging from
1% to 4% of the capital costs. Power costs were assumed to be $.03 per
killowatt hour. Landfills are assumed to be 25 feet deep with a total
volume capacity of 1,089,000 cu. ft. (or 30,818.7 cu. meters) per acre.
Landspreading costs assume two applications per year, each of two
inches in thickness. The specific gravity of materials disposed of to
land is assumed to be 1.0. Equipment rental charges are based on
an assumed utilization period and on estimated depreciation, main-
tenance, and fuel costs for each.
Transportation costs for onsite disposal assume that the use of
a 100 barrel vacuum truck requires three man-hours for filling,
hauling, and discharge of contents. Transportation costs for offsite
disposal are based on the actual number of 100 barrel vacuum trucks
arriving at the facility and the average number of man-hours required
to complete the disposal procedure in an eight-hour period. Since
most refinery-generated wastes are conveyed in a vacuum truck to the
disposal site, available disposal cost data is often limited to the invoices
of private contractors employed for offsite disposal. Fees typically
range from about $3 a ton to $7 per ton, with private disposal rates
being generally somewhat higher. Waste hauling firms which provide
disposal and/or reclamation services as well as transport services are
often able to defray some of the costs of their operations by profits from
reclamation of waste materials. Among the major items recovered are
oil, metals, and extracted chemicals such as cresols and phenols
contained in the caustic solutions. Most reclamation operations con-
centrate primarily on recovery of oil. Treatment/disposal costs
associated with individual refinery waste streams are shown in Tables
66 through 82.
Apparent cost variations for specific wastes are primarily a
reflection of differences in transportation hauling distances, differences
in disposal technology, type 01 facility from which the material was
collected (closed tank, open basin, dry stockpiles on ground or stat-
ionery closed containers ready for hauling), as well as of the physical
characteristics of the waste material,
176
-------
6. 3 MANAGEMENT COSTS FOR SPECIFIC WASTE STREAMS
Tables 66 through 82 present detailed costs associated with three
levels of technology for treatment and disposal of each of seventeen
hazardous waste streams generated within a typical refinery with a
capacity of 100,000 barrels per day. Each waste stream represents
a certain percentage of the total waste generated within the refinery, and
costs are reflective of this quantity. Each of the tables includes the
following information:
(1) The quantity in wet and dry weight (metric tons per year)
of each potentially hazardous waste as well as of each of
its hazardous components.
(2) Treatment and disposal costs associated with present and
alternative levels of technology.
(3) Investment costs for land or equipment.
(4) Annual costs for capital, operations, energy and power,
and outside contractors.
(5) Unit cost of treatment and disposal (per metric ton of
waste, dry weight).
A description of each of these waste streams appears in Section 4. 3 of
this report.
177
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REFERENCES
1. Booz-Allen Applied Research, Inc. A study of hazardous waste
materials, hazardous effects and disposal method. U. S.
Environmental Protection Agency Contract No. 68-03-0032.
Bethesda, Md. , June 1972. 3v.
2. Toxic substance list, U. S. Department of Health, Education and
Welfare, Public Health Service Publication for Occupational
Safety and Health.
3. Hazardous Substance Act. State of California Senate Bill No. 598,
1973.
4. Development document for proposed effluent limitations guidelines
and new source performance standards for the petroleum refining
point source category. U. S. Environmental Protection Agency
Contract No. 440/1-73/014, Dec. 1973.
5. Trends in refinery capacity and utilization. Federal Energy
Administration Publication No. G-75/368, Washington, D. C. ,
June 1975.
6. Annual refining survey. The Oil and Gas Journal, April 1974.
7. Energy and hydrocarbons in the United States to 1975. The Pace
Company, Houston, Texas, Jan. 1974.
8. ZoBell, C. D. Sources and biodegradation of carcinogenic hydro-
carbons. Proceedings; Joint Conference on Prevention and Control
of Oil Spills. Washington, D, C. , American Petroleum Institute
Publication, 1971. pp. 441-451.
9. Robichaux, T. J. and H. N. Myrich. Offshore Technology Conference
Paper No. OTC-1377, 1974.
10. Kincannon, C. B. Oil waste disposal by soil cultivation process. EPA
Environmental Protection Technology Series (EPA R2-72-110),
Washington, D. C. , Office of Research and Monitoring, Dec. 1972.
195
-------
11. Schwendinger, R. B. Reclamation of soil contaminated with oil.
Journal of the Institute of Petroleum 54:535, 1968.
12. Gilmore, G. A. , D. D. Smith, A. H. Rice, E. H. Shenton and
W. H. Moser. Systems study of oil spill cleanup procedures
Vol. I: Analysis of oil spills and control materials. American
Petroleum Institute Publication No. 4024, 1970.
13. The Torrey Canyon report of the committee of scientists on the
scientific and technological aspects of the Torrey Canyon
disaster. London, H. M. Statistics Office, 1967.
14. Swift, W. H. et al. Review of Santa Barbara Channel oil pollution
incident, National Technical Information Service Publication No.
191-712, Washington, D. C. , 1969.
15. Walker, J. D. , L. Cafone and J. J. Cooney. Microbial petroleum de-
gradation: the role of chadosporium resinal. Proceedings; Joint
Conference on Prevention and Control of Oil Spills, May 13-15,
1973, Washington, D. C. pp. 821-825.
16. Proceedings; 1975 Conference on Prevention and Control of Oil
Pollution, March 25-27, 1975, San Francisco, California,
American Petroleum Institute Publication, Washington, D. C.
17. Kim, B. C. et al. Support systems to deliver and maintain oil
recovery systems and dispose of recovered oil. Battell
Laboratory Publication AD-778-941, Columbus, Ohio, June 1973.
18. Dotson, G. K. Et al. Landspreading: a conserving and non-polluting
method of disposing of oily wastes. FWQA Advanced Waste
Treatment Research Laboratory, Cincinnati, Ohio, July 1970.
19. Ellis, R. and R. S. Adams. Contamination of soils by petroleum
hydrocarbons. Advanced Agron 13:192, 1961.
20. Davis, J. B. Petroleum microbiology. New York, Elsevier Publishing
Company, 1967.
21. Beerstecher, E. Petroleum microbiology; an introduction to micro-
biological petroleum engineering. Houston, Elsevier Publishing
Company, 1954.
196
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22. Byron, J.A. , S. Beastall, and S. Scotland. Bacterial degradation of
crude oil. Marine Pollution Bill, 1970.
23. Gossen, R. G. and D. Parkinson. The effect of crude oil spills on the
microbial populations of selected arctic soils. Biomass and
Respiration, (Canadian) Journal of Microscience, 1973.
24. McKenna, E. F. and R. E. Kallis. The biology of hydrocarbons.
Annual Review of Microbiology, 1965.
25. McCowan, B. H. , J. Brown, and R. P. Murrmann. Effect of oil
seepages and spills on the ecology and biochemistry in cold-
dominated environments. Hanover, N. H. , U. S. Army CRREL,
1971.
26. Currier, H. G. and S. A. Peoples. Phytotoxicity of hydrocarbons.
Hilgardia 23:155, 1954.
27. Overbeek, J. and R. Blondeau. Mode of action of phtotixoc oils.
Weeds 30:55, 1954.
28. Plice, M. J. Some effects of crude petroleum on soil fertility.
Proc. Soil Sci. Soc. Am. 13:413, 1948.
29. Adams, R. S. and L. Ellis. Some physical and chemical changes in
the soil brought about by saturation with natural gas. Proc. Soil
Sci. Am. 24:41, I960.
30. Johnson, D. R. and L. R. Frederick. Effect of injections of propane
into soil on microbial activity. Agronomy Journal 63:575, 1971.
31. Cowell, E. B. The effects of oil pollution on salt marsh communities
in Pembrokeshire and Cornwall. Journal of Applied Ecology 6:133,
1969.
32. ZoBell, C. E. Microbial modification of crude oil in the sea.
Proceedings; Joint Conference on Prevention and Control of Oil
Spills, Washington, B.C., Dec. 1969, pp. 317-326.
33. California project turning sump to soil. Oil and Gas Journal,
Sept. 11, 1972.
197
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34.
35.
36.
37.
Hobs on, G. D. et al. Modern petroleum technology. New York,
John Wiley and Sons, 1973.
Ricci, L. J. Injection wells iffy future. Chemical Engineering
81(16) :58, AugV 1974.
Ruckelshaus, W. D. Administrator's decision statement no. 5: EPA
policy on subsurface emplacement of fluids by well injection.
Feb. 6, 1973.
Smith, D. D. and R. P. Brown. Ocean disposal of barge-delivered
liquid and solid wastes from U. S. Coastal cities. EPA OSWMP
Report No. 5W-lac,\Dillingham Corporation, La Jolla, Calif.,
1971.
198
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34. Hobs on, G. D. et e.1. Modern petroleum technology. Mew York,
John Wiley And Sons, 1973.
35.* Ricci, I... J. Injection wells iffy fxiturc. Chemical Engineering;
81(16):58, Aug. 1974.
36. Kxickelshaus, W. D. Administrator's decision statement no. f>: EPA
policy on subsurface emplacement of fluids by well injection.
Feb. 6, 1973.
37. Smith, D. D. and R. P. Brown. Ocean disposal of barge-delivered
liquid and solid \vastes from U. S. Coastal cities. EPA OiSY/MP
Report No. 5W-lac, Dillhrgham Corporation, La Jolla, Calif, ,
1971.
38. Heslop, R.B. and P.L. Robi.nson, Inorganic Chemistry.
Amsterdam, Elsevier Publishing Co., 1950. 555 p.
39. Bowen, H.ซ3, M. Trace elements in biochemistry. London, Academic
Press, 1966. 241 p.
>
*
40. Hawkes, H.E., and J.S. Webb. Geochemistry in mineral explora-
tion. New York/ Harper and ROVJ, 1962. .
198
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APPENDIX A*
CHARACTERISTICS, OCCURRENCE, AND TOXICOLOGY OF TRACE
ELEMENTS AND OTHER IDENTIFIED HAZARDOUS
SUBSTANCES IN PETROLEUM REFINERY WASTES
The identification of materials known to be toxic to many life pro-
cesses if present in sufficient quantity, has guided the rationale of the
analytical program. It is assumed that these materials are "potentially
hazardous" and may become truly hazardous if disposed of in an unaccept-
able fashion. Their toxicity is addressed in this appendix. These notes
amplify a version of those prepared in a recent report by Pomeroy and
Lofy (1). For a fuller treatment of this topic, reference may be made
to the Versar Report (2).
AMMONIUM SALTS
Ammonia is a gaseous compound with a formula NH_.
"Ammonium" refers to the univalent cation NH . This radical behaves in
its inorganic state like any other ionic species, forming a series of salts
with the negatively charged acid anions. Substituted organic compounds
(quaternary ammonia compounds) are environmentally important (act as
algicides, etc.), but are not included in this discussion as they do not
occur in petroleum.
Occurrence: Ammonium salts occur quite widely in nature, often associ-
ated with the degradation of protein in decomposition processes. It forms
part of the nitrogen cycle and is important to the associated biosphere. It
is readily oxidized and so does not accumulate.
Toxicology: One of the most significant compounds of ammonia is the
hydroxide. This is highly caustic and an irritant, which if ingested, causes
poisoning. The symptoms of poisoning are due to local irritation which
causes severe pain in the mouth, throat, and stomach, with vomiting and
collapse from the severity of the gastritis. Ingestion of ammonia solution
may cause oedema of the larynx, though this may not develop for an hour
or two. Inhalation of ammonia vapor in high concentration causes so
*References for Appendix A: Pซ 218
199
-------
severe an irritation of the throat as to produce immediate spasm and closure
of the glottis, resulting in asphyxia. High concentrations of vapor are
injurious to the lungs and death may result from pulmonary oedma. Ammonia
burns have resulted from treating insect bites and stings with the strong
solution, or even with the dilute solution, especially if a dressing is
subsequently applied.
Ammonia Toxicity and pH: In most biological fluids, ammonia exists in two
forms, the relative proportions of which are determined primarily by the pH
of the solution. Since toxicity depends on the'ammonia which enters the
organism, and hence the cell, it is important that the cell membranes be
relatively impermeable to one form (ionized ammonia) and the other form
(non-ionized) easily passes tissue barriers. Toxicity of ammonium com-
pounds to plants is reduced by lowering the pH with nitric acid. The
influence of pH on the toxicity of ammonia has also been studied in fish,
parasites, ruminants, dogs, mice, and human subjects. The effect appears
to be universally comparable throughout nature. In a medium of low pH
ammonia is toxic only in high volumes whereas in a medium of high pH far
smaller amounts may be lethal.
Ammonium salts are generally less toxic than ammonium hydroxide. McKee
and Wolf ( 3 ) report that dogs can ingest 24, 000 mg/kg of body weight.
Toxicity towards maine life is extremely complex and depends upon pH,
the presence or absence of bicarbonate, and other factors.
ARSENIC (As)
Arsenic is a steel-grey, brittle solid with a metallic luster. It sublimes on
heating with a characteristic garlic-like odor. On heating in a free supply
of air, arsenic burns with a blue flame yielding white fumes of arsenious
oxide As O,. All arsenic compounds are poisonous and hence, are poten-
tially hazardous. The element is insoluble in hydrochloric acid and in
dilute sulfuric acid. It dissolves readily in dilute nitric acid yielding
arsenious oxide, and in concnetrated nitric acid, aqua regia, or in a
sodium hypochlorite solution forming arsenic acid.
Two series of compounds of arsenic are commonly encountered: (a) the
arsenious compounds may be regarded as being derived from the ampho-
teric arsenious oxide As O, which yields salts with strong acids, e. g. ,
arsenious chloride AsCl , or with strong bases, e.g. , sodium arsenite
NaAsO ; and (b) the arsenic compounds corresponding to the pentoxide
ฃป
200
-------
As O,; they are usually salts of the tribastic ortho-arsenic acid, e. g* ,
NaHAsO and
4
Occurrence: In the earth's crust, arsenic concentrations range from 1 to
13 mg/kg, with an average concentration of about 5 mg/kg (4). In the
ocean, the values quoted are around 0. 003 mg/1 ( 5), while in fresh water
they range from 0. 003 to 0. 050 mg/1 ( 6).
The U. S. Public Health Service standard for arsenic in drinking water is
0. 05 mg/1, while the California standard is 0. 01 mg/1. Typical standards
for foods are 0. 1 mg/1 for beverages and 1 mg/kg for foods ( 7 ).
In crude oil, arsenic is reported in the range of 0. 05-1. 0 mg/kg with a
median value of 0. 26 ( 8).
Toxicology: The ingestion of 100 to 300 mg of arsenic (as arsenious oxide)
is usually fatal to humans , however the toxicity depends upon its chemical
state. The body is able to metabolize arsenic, and if ingested in small
quantities it is deposited in the hair and fingernails without chronic
symptoms appearing.
Toxicity toward fish varies from 1 mg/1 to as high as 234 mg/1, while most
lower biotic forms are not affected by arsenic up to 30 or 40 mg/1 ( 3 ).
Radioactive Properties: None
BERYLLIUM (Be)
Beryllium has a greyish metallic luster which melts at 1283C. All the
common mineral acids attach beryllium with the exception of cold
concentrated nitric acid.
Occurrence: Beryllium is reported at various levels, up to 6 mg/kg in the
earth's crust. It is not reported in the sixty most abundant minerals in
seawater, and Bowen gives its concentration there as low as 0. 0000006
mg/1. In fresh water he quotes less than 0. 001 mg/1. It occurs at a
concentration of 0. 002 mg/kg in some animal tissues.
There are no drinking water standards for beryllium.
Toxicology: Beryllium is very toxic to plants, and also to mammals if
injected intravenously. Absorption of beryllium from the alimentary tract
201
-------
is slight (about 0. 006% of the ingested) and it is excreted rapidly. This
fact, combined with the insolubility of the carbonate accounts for the
absence of this element from the drinking water standards.
Radioactive Properties: None
CADMIUM (Cd)
Cadmium is a silvery-white, malleable and ductile metal. It dissolves
slowly in dilute hydrochloric and sulfuric acids with the evolution of
hydrogen. The best solvent for the metal is nitric acid. Only one series
of salts, derived from the oxide CdO, is of chemical importance.
Occurrence: Cadmium occurs in the earth's crust at levels of 0. 2 mg/kg
( 4) while in the ocean it ranges in concentration from 0. 001 to 0. 003 mg/1
( 5). Reported concentrations for water supplies range from 0.001 to
0. 012 mg/1 ( 6 ). Foodstuffs contain cadmium at levels of a few tenths
mg/kg in cereals, meat, and fish.
The USPHS standard for cadmium in drinking water is 0. 01 mg/1, which is
identical with the California standard.
In crude oil, cadmium is reported at about 0. 03 mg/kg ( 8 ).
Toxicology: The ingestion of 10 to 15 mg of cadmium in food or drink can
cause nausea. Generally, 5 to 10% of the cadmium taken internally is
absorbed from the intestinal tract, while 10 to 40% of cadmium breathed
into the lungs in dusts is absorbed. The greatest hazard arises not from
acute poisoning but from accumulation over a period of time. The half-
life of absorbed cadmium in the human body is reported to be 50 to 130
days. Excessive amounts cause serious and painful osteomalacia. Live-
stock have been poisoned by vegetation on which airborne cadmium from a
smelter had settled. In the Jintsu Valley of Japan, mining wastes carry-
ing cadmium, lead, and zinc so polluted a river that rice crops were
damaged and people were poisoned by drinking the water. Two hundred
people were severely affected, of which half died. Cadmium was judged
to be the principal cause, however the other metals no doubt contributed.
The fatal dose of cadmium for animal life is reported at a range of 0. 15 to
0. 3 mg/kg body weight, while the tolerable limit for fish is 0. 01 to 10 mg/1
depending on the test animal, the type of water, temperature, and time of
exposure. Cadmium acts synergistically with other substances to increase
toxicity ( 3).
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Radioactive Properties: None
-CHROMIUM (Cr)
Chromium, is a white crystalline metal which is not appreciably ductile or
malleable. The metal is soluble in hydrochloric acid yielding the blue
chromous chloride CrCl if air is excluded, otherwise chromic chloride
CrCl is formed, and hydrogen is evolved. Dilute sulfuric acid reacts
similarly forming chromous sulphate in CrSO in the absence of air, and
chromic sulphate Cr (SO ) in the presence of air. Concentrated sulfuric
acid, dilute and concentrated nitric acid induce passivity.
The normal oxide of chromium is the green sesquioxide Cr O from which
the chromic salts are derived. Chromous salts, corresponding to the
oxide CrO, are readily oxidized in air to chromic salts; the former are
rarely encountered. An acidic oxide, chromium trioxide CrO , which gives
rise to the colored chromates and dichromates.
Occurrence: Abundance in the earth's crust is reported in the range 35 to
200 mg/kg, with the metal being relatively concentrated in igneous rocks.
In the ocean chromium only occurs at a level of 0. 0005 mg/1 while the
USGS survey ( 6 ) showed a general range for surface waters of 0. 006 to
0. 05 mg/1 of hexavalent chromium (trivalent chromium salts are insoluble,
and hexavalent salts tend to be reduced).
Both the USPHS and the California standard for hexavalent chromium in
drinking water supplies is 0. 05 mg/1.
In crude oil, chromium is reported at a median value of 0. 008 mg/kg and
a range of 0. 002-0. 017 mg/kg ( 8).
Toxicology: Chromium is an essential nutrient for animals, being required
along with insulin for the metabolism of carbohydrates. The daily re-
quirement for humans is not known, but the amount of chromium in an
average diet is of the order of a milligram per day. An excess is rapidly
eliminated.
Hexavalent chromium is toxic. Contact with chromates used industrially
may cause ulceration of the skin and other membranes. Concentrations
high enough to damage the tissues may cause cancer. The drinking water
containing hexavalent chromium at a concentration of 10 mg/1 has been
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found to cause nausea, and a slight effect was noted at a concentration of
5 mg/1, but not at 3. 5 mg/1. Chromium is not cumulative in the body.
Most fish appear to tolerate several mg/1 of hexavalent chromium, but
various phytoplankters and zooplankters are harmed by fractions of a mg/1.
On the other hand, the only evidence for the toxicity of trivalent chromium.
that was uncovered in this study, was that reported in fish bioassays, in
which it seems likely that a. chromic salt used in pure water caused a low
pH and held some chromium in solution. Bioassays with aluminum salts
give similar results, yet no toxicity is attributed to aluminum in water
under ordinary conditions. More tests should be made to ascertain whether
there is any hazard of toxicity from trivalent chromium.
Radioactive Properties: None
COPPER (Cu)
Copper is a light red metal, which is soft, malleable, and ductile. It is
unaffected by hydrochloric acid and by dilute sulfuric acid, but is readily
attacked by dilute nitric acid and by warm concentrated sulfuric acid.
There are two series of copper compounds: Those which may be regarded
as derived from cuprous pxide Cu_O (red), known as cuprous compounds
and containing the ion Cu , and those similarly derived from cupric oxide
CuO (black), known as the cupric compounds and giving rise to the ion Cu
Occurrence: Copper is reported in the range of 5 to 200 mg/kg in surface
rocks, with the highest concentrations appearing in igneous rocks and
shales. In fresh water, it is reported at levels of 0. 04 mg/1 in rainwater
( 9 ) to 0. 01 mg/1 in surface rivers (10).
Vegetation normally concentrates copper from the environment in varying
degrees. On a dry-weight basis, most vegetation contains 1 mg/kg or
more of copper, ranging up to about 20 mg/kg. It is concentrated further
in the bodies of animals, especially in the liver, where the amount may
reach several hundred mg/kg.
Both the USPHS and the California standard for copper in drinking water
supplies is 1. 0 mg/1.
In crude oil, copper is reported at a median level of 1.32 mg/kg and at a
range of 0. 13-6. 33 mg/kg ( 8 ).
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Toxicology: Copper is an essential nutirent for plants and animals. It is
sometimes added to fertilizers for application to copper-poor soils. There
is no evidence that the storing of copper in normal amounts in plants and
animals has any harmful effec
-------
is known to affect the hemoglobin content of the blood. In waters of 1 to 30
mg/1 cobalt compounds appear to be toxic toward various plants ( 3 ).
Aquatic biota are stimulated by levels below 1 mg/1, and poisoned by
levels greater than 10 mg/1.
Radioactive Properties: None
CYANIDE
Cyanide is the general name for the --CN radical in its inorganic combi-
nations. "Free cyanide" means hydrocoyanic acid, HCN, and the cyanide
ion. In neutral water, free cyanide is almost all HCN, and only in alkaline
solutions do substantial amounts of the cyanide ion appear. There are also
insoluble metallic cyanides and complex cyanides soluble in the presence of
an excess of cyanide, as for example, NaAg (CN ). Very little cyanide
remains in solution in the presence of an excess of metallic ions. HCN is
a liquid, boiling at 26C (79 F). It is miscible with water in all proportions.
Occurrence: Unlike the chemical elements which are present on the earth
in constant amounts, cynaide is produced and destroyed by both natural and
man-made processes. Many species of plant life produce cyanide in small
amounts so that it is widely dispersed in the biosphere. It is readily
oxidized biologically; therefore, it does not accumulate. The amounts found
in the environment represent the balance between input and degradation.
Toxicology: The high toxicity of cyanide is well known. The volatility of
HCN makes it especially potent. A concentration of 100 parts per million
by volume in air is enough to cause death. However, because it is so
soluble in water, low concentrations in solution do not produce dangerous
atmospheres.
A concentration exceeding 100 mg/1 in solution would be necessary to pro-
duce a lethal atmosphere of HCN, even in a closed space. By way of
comparison, a solution of 1 mg/1 of H_S is equally dangerous. In the
animal body, cyanide is detoxified by conversion to thiocyanate. Thus, it
is not cumulative. A daily intake of a few milligrams is believed to be
harmless. However, exposure for several hours to concentrations of a few
ppm in the air causes irritation of the eyes and respiratory passages.
Fish are much more seriously affected by cyanide in the water, because it
causes irritation of the gills and loss of the oxygen-supplying function.
Concentrations less than O.-lmg/l may be fatal.
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Radioactive Properties: None
FLUORIDE (F")
Fluorine is a toxic gas, which by reduction forms a univalent amin, fluoride.
This amin forms a series of metallic salts, commonly referred to as
luorides. Hydrofluoric acid, HF, is a highly toxic and hazardous material.
Occurrence: Fluorine is never found free in nature. It occurs as a consti-
tuent of fluospar (calcium fluoride) in sedimentary rocks, and as cryolite
(calcium aluminum fluoride) in igneous rocks.
Bowen reports levels of 330-740 mg/kg in rocks, 0-9 mg/1 in freshwater,
and 1. 3 mg/1 in sea water (4). Marine plants and land animals tend to
concentrate fluorides (as much as 150-500 mg/kg may accumulate in
mammalian soft tissues, and 1500 mg/kg in bones).
The USPHS has a range of fluoride standards (0. 6-1. 7 mg/1) effective for
varying average annual temperatures.
Toxicology: Fluorides in sufficient quantity are toxic to humans, with doses
of 250 to 450 mg, giving severe symptoms and 4. 0 grams causing death.
The fatal dose has also been reported as 0. 5 gms per kg of body weight
and as 2. 5 grams.
There are numerous articles describing the effects of fluoride-bearing
waters on the dental enamel of children and a few papers pertaining to the
skeletal damage. The effects reported in many of these references lead
to the generalization that water containing less than 0. 9 to 1. 0 mg/1 of
fluoride will seldom cause mottled enamel in children, and for adults,
concentrations less than 3 or 4 mg/1 are not likely to cause endemic
cumulative fluorosis and skeletal effect.
The effects of fluoride in drinking water for terrestrial mammals is
analogous to those for humans. General toxicity has been reported ( 3 ).
Hamsters 70-80 mg/kg body weight
Daphnia 270 mg/kg
Esheria Coli 180 mg/1
Protozoa/Rosifen 1000-1700 mg/1
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LEAD (Pb)
Lead is a bluish-grey metal with a density of 11. 48. It is readily dis-
solved by dilute nitric acid.
With concentrated nitric acid, a protective film of lead nitrate, which is
insoluble in this acid, prevents complete solution. Dilute hydrochloric
acid and dilute sulfuric acid have little action due to the formation of
protective films of lead chloride and sulfate, respectively. Lead is both
divalent and tetravalent. In addition to forming plumbous and plumbic
salts, it also forms plumbites and plumbates.
Occurrence: Lead is reported in the range of 7-20 mg/kg for its occurrence
in the earth's crust (4). In water, levels of 0. 00003 mg/1 are reported in
the ocean ( 5 ), while a range of 0. 006 to 0. 050 mg/1 was reported in
surface fresh waters (6).
Published findings on lead in vegetation show a wide range; values are
generally lower in fruits and seeds and higher in the roots and outer leaves.
In edible parts the amounts are generally a few tenths of a mg/kg. The
concentration of lead found in meats appears to be similar or somewhat
lower than in vegetation.
Both ths USPHS and the California drinking water standard for lead is
0. 05 mg/1.
Yen reports lead at a median level of 0. 24 mg/kg in crude oil, and a
range of 0. 17-0. 31 mg/kg ( 8 ).
Toxicology: Lead serves no useful function in plant or animal bodies, but
it is a serious hazard to health because it is cumulative. It is believed
that chronic toxicity can result from a daily intake of 0. 6 mg per day. By
contrast, 10 mg per day of arsenic or of cyanide would not be harmful.
Lead is lethal for fish in concentrations of a. few tenths of a milligram per
liter, and at 0. 1 mg/1 in soft water.
Radioactive Properties: Natural lead is composed of four isotopes with
atomic weights of 204, 206, 207 and 208. The latter three are the decay
products of the radioactive compounds. The relative abundance of these
isotopes are 1.48, 23.6, and 52.3%, respectively. Lead 204 is radio-
active, decaying by alpha radiation with a half-life of 1. 4 x 10 years, and
if isolated is an extremely hazardous material.
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MERCURY (Hg)
Mercury is a. silvery-white, liquid metal at ordinary temperatures, and has
a density (d ) of 13. 595. It is unaffected by treatment with dilute hydro-
chloric or dilute sulfuric acid, but reacts readily with nitric acid.
Adercury forms two series of salts. The mercurous compounds and the
mercuric compounds.
Occurrence: Mercury in elemental form is reported in the range of 0. 03
to 0. 1 mg/kg in the earth's crust. In the oceans it has been reported at
levels of 0. 00003 mg/1 (5), and the USGS survey reported a range of
0. 0001 to 0. 004 mg/1 in surface waters ( 6 ). Generally, 0. 001 to 0. 01
mg/kg occurs in vegetation, while some meats and fish carry up to 0. 3
mg/kg and occasionally, 1. 0 mg/kg.
The USPHS does not currently set s drinking water standard for mercury,
however the California standard is 0. 005 mg/1.
Yen reports the crude oil median concentration of mercury at 3, 24 mg/kg,
and the range as 0. 023-30. 0 mg/kg ( 8).
Toxicology: The poisonous character of mercury compounds and the
occupational hazard to men working in the mercury mines of Spain were
recognized in ancient times. Nevertheless, mercurous chloride (calomel)
was long used as an internal medicine, and mercuric chloride as a disin-
fectant. It has long been reported that adults could safely drink water
containing from 4 to 12 mg of mercury per day, provided it is not in
certain metallo-organic combinations. The toxicity of methylated mercury
compounds is environmentally important. They accumulate in the food
chains, and cause irreversible damage to nerve and brain cells. It is
known that inorganic mercury can be methylated by bacteria, and that
damage to wildlife has resulted in this way.
When using the very sensitive analytical methods now available, traces of
mercury are found everywhere. Evidently, plants and animals can
tolerate the small amounts occurring in nature.
Bioassay tests have indicated that fish may be harmed by mercury at con-
centrations as low as 0. 01 mg/1, and possibly even lower. McKee &t Wolf
report partial inactivation of photosynthesis in giant kelp by concentrations
of 0.05 mg/1 ( 3).
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Radioactive Properties: None
MOLYBDENUM (Mo)
Metallic molybdenum is grey in color with a melting point of 2610 C. It is
chiefly valued for this latter property and its natural resistance to
corrosion. Molybdenum forms six series of salts corresponding to the
valency numbers of 0, 2, 3, 4, 5, or 6. Consequently, the chemistry
of molybdenum is complex.
Occurrence: Molybdenum occurs only in small concentrations in the earth's
crust (average 1. 0 mg/kg). Mero reports levels of 0. 01 mg/1 in seawater
(5).
There are no drinking water standards presently in force for molybdenum.
Yen reports a median concentration in crude oil of 0. 031 mg/kg, and a
range of 0. 008-0. 053 mg/kg ( 8).
Toxicology: Generally, molybdenum presents a low toxicity hazard to
animal life. At low concentrations (0. 1 mg/1 in irrigation water) it is
reported as an essential nutrient for plants, but at levels of 5 mg/1 it
becomes toxic. Plants tend to concentrate molybdenum which can lead to
I toxic effects on ruminants grazing in molybdenum-rich areas. Mckee &
Wolf report toxicity towards fish in a range of 7-370 mg/1, towards alga
at 54 mg/1, but show that E. Coli and Daphnia tolerated concentrations of
1000 mg/1 ( 3 ).
Radioactive Properties: None
NICKEL (Ni)
Nickel is a hard, ductile, malleable, and very tenacious silvery-white
metal. Hydrochloric and sulfuric acids, both dilute and concentrated,
attack it slowly. Dilute nitric acid dissolves it readily, but the concen-
trated acid induces passivity.
Only one stable series of salts, the nickelous salts, which maybe re-
garded as derived from the green nicklous oxide NiO, is known.
Occurrence: Nickel occurs in the range of 2 to 80 mg/kg in the earth's
crust ( 4 ). In the ocean it has been reported at levels of 0. 002 nig/1 (5) and
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0. 005 mg/1 ( 4 ). Surface waters are reported to contain up to 0. 01 mg/1
( 4).
In. plants, a few tenths of a tng/kg appear to be common, with up to several
mg/kg in the leafy parts.
Compared with other metals, nickel is relatively abundant in crude oil. Yen
i eports median levels of 166 mg/kg and a range of 49-345 mg/kg. (8)
Toxicology: Towards humans, nickel is not a cumulative poison, and it
appears that substantial amounts can be ingested without harmful conse-
quences. However, nickel compounds inhaled as sprays or dusts have
caused serious damage to the lungs. Certain plants and aquatic life are
reported to show toxic effects starting at concentrations of 0. 5 or 1. 0 mg/1.
The toxic dose for dogs is reported to be 10-20 mg/kg of body weight, and
the desirable limit for fish is considered to be 1. 0 mg/1 (3).
Radioactive Properties : None
OIL
By common consent, the term oil is used to denote a large group of complex
hydrocarbons, which occurs widely in nature. Predominantly, these hudro-
carbons include both the aliphatic and aromatic series and many substituted
compounds. Their nature and distribution is too large a subject for this
appendix. This discussion is limited to a general appraisal of the kinds of
toxicity that might occur. These compounds have other attributes which
are also of concern, principally, explosiveness and flammability.
Toxicology: No one simple statement can be made for such a large group
of compounds. Their carcinogenity has already been discussed (see benz-
A-pyrene), and only typical examples will be given below.
In the environment the toxicity of "oil" is often manifested by its coating
action. Thus, fish kills result if oil coats the gills. Water fowl are killed
if oil coats their feathers and they lose the protection of the air layer
trapped beneath.
Toxic effects of light hydrocarbons when ingested are typified by the effects
of gasoline on humans. If swallowed, it produces an intense burning
sensation in the mouth and esophagus, with vomiting and diarrhea.
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Restlessness, uncoordination, and cyanosis may occur. Recovery takes
place within a few hours unless the petroleum has been aspirated into the
lungs, in which case death follows rapidly from haemorrhagic pneumonia.
The usual fatal dose for adults is said to be about 500 ml.
Acute poisoning from the inhalation of high concentrations of the vapor causes
headache, nausea, and giddiness, proceeding in severe cases to unconsci-
ousness, muscular tremors, convulsions, dyspnoea, cyanosis, and death.
Chronic poisoning from continuous exposure to lower concentrations causes
dullness, pain in the limbs, and other disturbances of the nervous system.
It is much less liable than benzene to give rise to changes in the haemo-
poietic system.
McKee and Wolf (3) have an extensive discussion on oil, from which the
following is taken:
Fish and Other Aquatic Life: Oily substances may possibly be
harmful to fresh-water aquatic life in the following manners:
(1) Free oil and emulsions may act on the epithelial surfaces of
fish, i. e. , they adhere to the gills and interfere with respi-
ration. Within limits, however, fish have a defensive
mechanism to combat such action. They can secrete a
mucous film to wash away irritants. If the concentration of
oil is too heavy, oil will accumulate on the gills and cause
asphyxia.
(2) Free oil and emulsions may coat and destroy algae and other
plankton, thereby removing a source of fish food. The coated
organisms may agglomerate, with suspended solids and settle
to the bottom of the stream.
(3) Settleable oily substances may coat the bottom, destroy
benthal organisms, and interfere with spawning areas.
(4) Soluble and emulsified material, ingested by fish, taint
the flavor of the flesh.
(5) Organic materials may deoxygenate the waters sufficiently
to kill fish.
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(6) Heavy coatings of free oil on the surface may interfere with
the natural processes of reaeration and photosynthesis. Very
light coatings would not be detrimental in this respect because
of the wave action and other turbulence.
(7) Water-soluble principles may exert a direct toxic action on
fish or fishfood organisms. Such toxicity may be acute or
chronic. Acute toxicity will produce death or debility in 96
hours or less. Chronic toxicity exerts a long-time effect,
through an accumulative action or through subtle changes in
the ecology. By its very nature, chronic toxicity is difficult
to prove. The material presented below deals primarily with
acute toxicity attributable to soluble principles.
Certain petroleum products appear to have no soluble poison-
ous substances, but when emulsified and agitated with water,
such oils prove deadly to fish. Chipman and Galtsoff (11)
report that crude oil in concentrations as weak as 0. 4 ml per
liter (i. e. , about 0. 3 mg/1) is extremely toxic to fresh-water
fish. The lethal limit of gasoline for rainbow trout has been
reported as 100 mg/1. After 15 minutes exposure at 50 mg/1 ,
rainbow trout show irritation and after 60 minutes they are
tired. The toxic threshold is about 40 mg/1.
PHENOL
Phenol is the precursor in a series of organic compounds characterized by
the formula R-OH; where R is an aromatic radical of varying degrees of
complexity. The simple phenols (R = C,H , C.H , CH , etc.) are more
toxic than the complex condensed phenols which occur in nature as tannins
and other vegetable substances.
Occurrence:. As in the case with cyanide, phenol is a compound that is both
produced and destroyed by natural processes. To a smaller extent it is also
produced and destroyed by human activities. The amounts found in the
environment are the result of balances between inputs and losses. It is a
normal constituent of surface waters, usually in amounts of a few thousand-
ths of a mg/1. The normal concentration in human urine is about 30 mg/1.
The cresols, as methyl derivatives of phenol, also occurring in nature but
in smaller amounts, have similar properties. They also react in part in
the analytical test, which is accordingly called "phenols. "
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The USPHS standard for drinking water (0. 001 mg/1) is based mainly upon
the undesirable taste forming chloro-phenols which result when phenolic
waters are chlorinated.
Toxicology: Phenol in drinking water is toxic to man or other terrestrial
animals at concentrations of several hundred mg/1. The data regarding
fish are somewhat conflicting. The threshold concentration for adverse
effects on fish may be around 1 mg/1, but some observations indicated that
it may be as low as 0. 2 mg/1. Other aquatic animal, planktonic or benthic,
appear to be less sensitive. The cresols are more toxic, and the chlori-
nated phenols still more so to the same species.
POLYNUCLEAR AROMATIC HYDROCARBONS
Occurrence: This group of compounds, composed of fused benzene rings,
has been given several names, of which polynuclear aroma tics (PNA) and
polyaromatic hydrocarbons (PAH) appear to be the most common. PNA's
occur widely in nature. Up to 0. 1% has been reported for the total PNA in
crude oil (12), and Graf and Winter (13) reported levels of 0. 4 to 1. 7 mg/1
of benz-A-pyrene in crude oil. Grimmer and Hildebrandt (14) have reported
a range of . 001-0. 044 rug/kg in vegetable oils. Telgner (15) reported levels
of 0. 0002-0. 02 mg/kg in foods. PNA's have also been reported in
industrial and municipal waste effluents, solid, ground and surface waters,
sediments, and biota (16).
Toxicology: The carcinogenity of some PNA's was discovered after
observing that individuals in specific occupations involving prolonged
exposure to coal tar products tended to show an abnormally high incidence
of skin cancer. Research established that benz-A-pyrene (occurring at the
1. 5% level in coal tar) produced skin carcinoma in laboratory animals, and
subsequently, many other PNA's were shown to have that property. For
mice, as little as 0. 25 mg of benz-A-pyrene has produced tumors when
injected subcutaneously.
SELENIUM (Se)
Selenium occurs in many different allotropic forms. Thus, it has no one
set of physical constants. Since it has several oxidation states, several
series of salts occur. Dilute acids do not react well with selenium.
Occurrence: Selenium occurs most commonly in shales (0. 6 mg/kg) and
to a lesser extent in igneous and sedimentary rocks. Mero reports.levels
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of 0. 004 mg/1 in seawater, but Bowen gives concentrations of 0. 00009 mg/1.
Probably the spread of data reflects some analytical difficulty. The most
recent data (17) gives the following:
Rocks 0.008 - 1.48 mg/kg
Black Shales 1.0-7.0 mg/kg
Crude Oil 0.03 -1.4 mg/kg
Coal 0. 56 - 5. 14 mg/kg
Surface Water 0. OOOl^-O. 0004 mg/1
Seawater 0.0001 mg/1
Vegetation 0. 01 - 0. 50 mg/kg
Meat & Fish 1.0-4.6 mg/kg
Both the USPHS and the California standard for drinking water is 0. 01 mg/1.
Toxicology: Selenium is one of a group of elements which is both an
essential nutrient and a poison. It is necessary for good health at a level
of 0. 04 - 0. 1 mg/kg and toxic at levels as low as 4 mg/kg in the diet.
Stock and wildlife show similar reactions to selenium, and for cattle the
lethal dose is about 1 mg/kg of body weight. McKee and Wolf report that
sublethal doses of selenium cause pathological changes in fish (3).
Radioactive Properties: None
SILVER (Ag)
Silver is a white, malleable and ductile metal. It is insoluble in dilute
hydrochloric and sulfuric acids, but dissolves readily in nitric acid
(2:1) and in boiling concentrated sulfuric acid.
Occurrence: Silver occurs at levels of 0. 1 mg/kg in the earth's crust.
In the ocean it occurs at levels of 0. 0003 mg/1 and in fresh water at levels
of 0. 00013 mg/1 (5). Silver is accumulated by plants and animals in
concentrations up to several mg/kg.
The USPHS standard for drinking water is 0. 05 mg/1.
Little is known of the occurrence of silver in crude oil. "Traces" are
reported in certain Mexican crude ( 8 ).
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Toxicology: Very small concentrations of silver ion are lethal to most
bacteria. For this reason, silver has been used for water sterilization.
Unfortunately, the ion soon loses its activity under most conditions due to
the formation of insoluble compounds. Concentrations of a few hundredths
of a mg/1 are lethal to zooplankton and fish. Terrestrial animals can
tolerate the ingestion of quite large amounts. For example, the toxic dose
for humans is reported at a high ten grams. When small quantities of
silver are regularly injected, it accumulated in the body, but in an inert
form, the only objectionable effect is a grey coloration of the skin and
eyes, a condition that has resulted from certain medicinal uses of silver.
Radioactive Properties: None
VANADIUM (V)
Vanadium is a ductile lustrous metal, with relatively low strength and
hardness. It has the ability to form several series of salts, generically
analogous to ortho, meta, pyro, and polyacids.
Occurrence: Vanadium occurs in shales and igneous rocks at levels of
140 mg/kg. Similar levels occur in crude oils, mainly as an organic
metallic porphyrin complex. In seawater vanadium occurs in the range of
0. 002-0. 003 mg/1 and in fresh-water at levels of 0. 001 mg/1. It is
present at 106 mg/kg in plants, 0. 15 mg/kg in land animals, and up to
2 mg/kg in the tissues of marine animals.
There are presently no public health drinking water standards for
vanadium.
Toxicology: Vanadium is highly toxic to humans if ingested as an aerosol
or if injected intravenously. No evidence has been published to suggest
that vanadium compounds are absorbed in the gastro-intestinal tract, and
it appears to have no biological role in animal metabolism. There is some
evidence that in small quantities, it simulates plant growth and that it
resembled molybdenum in promoting growth and activation os azotobacter.
Radioactive Properties: There are two naturally occurring isotopes of
vanadium (atomic weights 50 and 51). Vanadium 50 occurs at an abun-
dance of 0. 24% and decays by ^ radiation with a half-life of 6 x 10 years.
If isolated, V50 is an extremely hazardous material.
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ZINC (Zn)
Zinc is a fairly malleable and bluish-white metal ductile at 110-115 C. The
pure metal dissolves very slowly in acids and in alkalis, although the
presence of impurities or contact with platinum or copper, produced by the
addition of a few drops of the solutions of these metals, accelerates the
reaction. This explains the solubility of commercial zinc. The latter
aissolves readily in dilute hydrochloric and in dilute sulfuric acid, with the
evolution of hydrogen. Solution takes place with very dilute nitric acid, but
no gas is evolved; with increasing concentration of acid, nitrous oxide or
nitric oxide is evolved, depending upon the concentration; concentrated
nitric acid has very little action owing to the very slight solbulity of zinc
nitrate. Sulfur dioxide is evolved with hot concentrated sulfuric acid. Zinc
also dissolves in solutions of caustic alkalis with the evolution of hydrogen
and the formation of zincates.
Occurrence: Zinc is reported in the range of 16-95 mg/kg in the earth's
crust (18). It is relatively soluble in water, being reported at levels of
0. 01 mg/1 in the ocean ( 5) and at levels of 5 mg/1 in surface streams ( 6).
Zinc is an essential nutrient and is the most abundant of the metals reviewed
in this project. The concentrations in vegetation vary widely, generally
being higher in the seeds than in other parts, and often exceeding 50 mg/kg.
It seems to be present quite consistently in meats in concentrations
generally ranging from ZO to 80 mg/kg, but ranging above 1,000 mg/kg in
some seafoods.
Both the USPHS and the California standard for drinking water is 5 mg/1.
Zinc occurs at median levels of 29. 8 mg/kg in crude oil, and in a range of
3. 6 - 85. 8 mg/kg.
Toxicology: The normal daily zinc intake of humans is estimated to be
about 10 milligrams. At sufficient concentrations in drinking water,
probably above 30 mg/1, zinc may cause nausea. At concentrations of
several hundred mg/1 it serves as an emetic.
Fish are far more sensitive towards zinc than mammals because of inter-
ference with the action of the gills. Reports of bioassay tests vary widely,
probably because of the effect of other constituents in the water. In waters
of high alkalinity, the zinc is mostly converted to insoluble forms. Some
fish have withstood 10 to 15 mg/1 in hard water, but concentrations of a few
hundredths have been reported to be fatal to sensitive species in soft water.
217
-------
References (Appendix A):
1. Pomeroy, R. D. and R. J. Lofy. Source controls of hazardous sub-
stances in sewage. For California State Water Resources Control
Board, January 1974.
2. Versar, Inc. Assessment of industrial hazardous waste practices,
inorganic chemical industry. For Environmental Protection Agency
Office of Solid Waste Management Practices, 1975.
3. McKee, I.E. and H. N. Wolf. Water quality criteria. 2d ed.
Resources Agency of California Publication No. 3-A, California,
State Printing Office, 1963. 548 p.
4. Bowen, H. J. M. Trace elements in biochemistry. London, Academic
Press, 1966. 241 p.
5. Mero, J. L. Mineral resources of the sea. N. Y. American Elsevier
Publishing Co. , 1964. 312 p.
6. Reconnaissance of selected minerals or elements in surface waters
of the United States. U. S. Geological Survey Circular 643,
Oct. 1970.
7. Arsenic in food regulation. S.I. No. 831, London, H. M. Stationery
Office, 1959.,
8. Yen, T. F. The role of trace metals in petroleum. Ann Arbor,
Ann Arbor Science Publishers, Inc. , 1975. 221 p.
9. Lazarous, A. L. , E. Lorange, and J. P. Lodge, Jr. Lead and other
metal ions in United States precipitation. Environmental Science
and Technology 4(1): 55-58, Jan. 1970.
10. Livingstone, D. A. U. S. Geological Survey Professional Paper
440G, 1963.
11. Chipman, N. A. and P. S. Gaits off. Effects of oil mixed with
carbonized sand on aquatic animals. Department of Interior
Special Science Report: Fish No. 1, Aug. 1949.
218
-------
References (Appendix A) (Continued):
12. Robichaux, T. J. and H. N. Myrich. Offshore Technology Conference
Paper No. OTC-1377, 1974.
13. Graf, W. and C. Winter. Archiv fur Hygieneund Bakteriologie
152:289, 1968.
14. Grimmer, G. and A. Hildebrandt. Ibid 152:255, 1968,
15. Telgner, D. J. Food manufacture. Nov. 1970.
16. Andleman, J. B. and M. J. Suess, Polynuclear aromatic hydrocarbons
in the water environment. World Health Organization Bulletin
No. 43, 1970.
17. Kothny, E. L. , Trace elements in the environment. Advances in
Chemistry Series 123. Washington, D. C. , the Am. Chem.
Society, 1973. 149 p.
18. Heslop, R. B. and P. L. Robinson, Inorganic Chemistry.
Amsterdam, Elsevier Publishing Co. , I960. 555 p.
219
-------
APPENDIX B*
METHODS EMPLOYED IN THE ANALYTICAL PROGRAM
1. SAMPLE RECEIPT
Upon receipt, the samples were logged on a master control sheet
according to the numbers and codes assigned by the field sampling teams.
The samples were examined and their appearance and odor recorded.
2. PRELIMINARY SEPARATION
The samples were thoroughly mixed and appropriate portions
withdrawn for analysis. After weighing, each sample was mixed with
benzene, and then allowed to stand to enable the phases to separate.
The liquid phases were separated and both portions filtered to obtain the
water and benzene insoluble. All three fractions were finally measured
or weighed and the data recorded. Subsequent analysis was as follows:
(a) Aqueous Fraction
If the sample contained a measurable aqueous fraction, the pH
of the fraction was determined by the glass-electrode method (1).
If the sample size permitted, ammonia nitrogen was then
determined by distillation followed by titration with standard acid
(2). When the sample was too small to permit distillation,
ammonia nitrogen was determined by nesslerization (3).
(b) Benzene Fraction
The benzene layers were separated, dried over anhydrous
sodium sulfate, and cleaned up if necessary prior to analysis by
gas-liquid chromatography (see section 3(d) on Benz-A-pyrene).
(c) Proximate Analysis
In order to report the percentages of the three important phases,
'^References for Appendix B: p. 225
220
-------
the solid residual was weighed and the aqueous phase measured
volumetrically. For the purpose of this study "oil" was defined
as the benzene solubles, but it proved impractical to measure this
quantity directly. Consequently, the Freon method of analysis for
oil and grease was adopted (4).
3. INDIVIDUAL DETERMINATIONS
(a) Phenolic Compounds
Representative samples of the original sample were weighed as
in (2) above. If samples contained oily matter, benzene was added
to aid solution. Phenolic compounds were extracted with portions
of IN NaOH. The caustic layers were combined, acidified with H,PO
and distilled. Phenolic compounds were then determined in the
distillates by the aminoantipyrene method (5).
(b) Cyanides
An aliquot of the original sample was weighed and transferred
to the distillation apparatus, and the evolved hydorcyanic acid was
absorbed in IN NaOH (6). Depending upon the cyanide concentration,
the determination was carried out either by the pyridine-pyrazalone
method (low concentrations) or by the silver nitrate titration method
(high concentrations) (7).
(c) Selenium
A representative portion of the original sample was digested
with a mixture of nitric-sulfuric acids (8), and distilled as the
tetrabromide. The selenium was then quantified as the piazselenol,
using the diaminobenzidine method (9).
(d) Benz-A-pyrene
Benz-A-pyrene was determined on the benzene extract of the
original sample. For the gas-liquid chromatography (10,11,12) the
following instrumentation was used:
(1) G. C., Varian Model 1200, H flame ionization detector.
Column: 10' x 1/8" SS, 2% SE^-30 on 80/100 mesh
Chromosorb W.
221
-------
(2) G. C., Jarrell-Ash Model 700, electron capture (H )
detector.
Column: 4' x 1/4" SS, 0.75% SE-30 on Chromosorb W.
I n the determination of benz-A-pyrene, the hydrogen flame
ionization detector instrument was used primarily for identification
purposes, the relative retention time of unknown peaks being
compared to known benzene solutions of benz-A-pyrene. Quantification
was accomplished with an electron capture (H source) detector taking
advantage of: (a) this detector's relative insensitivity to hydrocarbons,
and (b) the electron affinity of benz-A-pyrene. Peaks identified as
benz-A-pyrene were quantified by comparison of the area under the
peak of the unknown to the area of a know standard benz-A-pyrene
peak.
(e) Chlorinated Hydrocarbons
A modification of method to detect chlorinated hydrocarbons in
pesticides (13).
4. TRACE ELEMENTS
(a) Digestion
Weighed portions of the original sample were digested with a
mixture of sulfuric and nitric acids in an apparatus designed to
prevent volatilization losses of trace elements during the decomposition
of organic matter (14).
(1) Apparatus
All glassware was cleaned with chromic acid followed by 1:1
nitric acid rinses. The digestion apparatus consisted of a 500-ml,
2-neck flask; a distillation receiver equipped with 2-way glass
stopcock; an additional funnel; and a Friedrichs condenser (see
Figure 1-B). All joints were lubricated with concentrated
sulfuric acid.
(2) Procedure
To the weighed sample in the digestion flask, 25 ml of
sulfuric and 50 ml of nitric acid were added. The mixture was
refluxed until no more nitrous fumes were evolved. More nitric
222
-------
FIGURE 1 - B
APPARATUS FOR THE WET OXIDATION OF OILS
All Joints
Ground Glass
(24/40)
1. 125 ml Additional Funnel
2. Distillation Receiver (SGA Scientific Inc., JF 8240)
3, 500 ml 2-neck Flask
4. Friedrichs Consenser
223
-------
acid was added, as required, to maintain oxidizing conditions.
The mixture was then evaporated until sulfuric acid fumes
appeared, and was allowed to fume for five minutes, the distillate
being collected in the receiver. The mixture was then allowed to
cool. When cool, 25 ml of nitric acid were added dropwise and
the dig estate was again allowed to fume sulfuric acid for five
minutes.
Upon cooling, the distillate was returned to the flask and the
mixture was refluxed for 15 minutes. The flask contents were
again distilled, the distillate being collected in the receiver.
Upon cooling, the distillate was returned to the flask, the mixture
was refluxed briefly, then allowed to cool. The condenser and
receiver were rinsed with D. I. water.
The digested mixture was filtered through glass (GFC) paper.
The flask was rinsed with de-ionized water, followed by three
portions of ammonium-acetate solution (to dissolve water insoluble
metallic sulfates, if present). The filtrate and washings were
combined and made up to volume.
(b) Determination
(1) Arsenic
An aliquot of the filtrate from 4(a)(2) was fumed to SO fumes
to remove nitric acid. Arsenic was determined by the arsine
generation method, the arsine being reacted with silver diethyl-
dithiocarbamate. The red complex was read on a photometer at
535 mu (1$.
(2) Mercury
Mercury was determined on an aliquot from procedure 4(a)(2)
(above) by the cold-vapor (flameless) atomic absorption method
(16). (Digestion: modification of 4(a) above.)
(3) Trace Metals
Beryllium, vanadium, chromium, cobalt, nickel, copper,
zinc, silver, cadmium, lead, and molybdenum were determined on
the filtered digestate by atomic absorption spectrophotometry.
224
-------
In most cases, the filtrate could be aspirated directly, dilutions
were made when the concentration exceeded the linear working
range. Although standards were made up to approximate the
sample matrix, the use of Deuterium background correction was
required for some elements (17, 18, 19).
(4) Blanks and Spiked Samples
Blanks and actual samples spiked with known amounts of the
trace elements to be determined were routinely carried through
the extraction and digestion procedures. Recoveries are
tabluated in the main body of the analytical report
References (Appendix B):
1. Standard methods for the examination of water and wastewater. 13th
ed. New York, American Public Health Association Publication
Office, 1971. Section 144A, p. 276-280.
2. Ibid Section 132A, p. 224-226.
3. Ibid Section 132B, p. 226-231.
4. Methods for chemical analysis of water and wastes. Environmental
Protection Agency Publication 625/6-74-003. U. S. Government
Printing Office, 1974. p.226.
5. Standard methods for the examination of water and wastewater. 13th
ed. New York, American Public Health Association Publication
Office, 1971. Section 222B, p. 502-503.
6. Ibid Section 207A, p. 399-402.
7. Ibid Section 207B and 207C, p. 402-406.
8. Methods of analysis of the Association of Official Analytical Chemists
(AOAC). llth ed. Washington, D. C. , AOAC Publications, 1970.
Method 3.073, p. 46-48.
9. Standard methods for the examination of water and wastewater. 13th
ed. New York, American Public Health Association Publication
Office, 1971. Section 150B, p. 298-299.
225
-------
10. Searl, T. D. , F. J. Cassidy et aUAn analytical method for
polynuclear aromatic compounds in coke oven effluents by
combined use of gas chromatography and ultraviolet absorption
spectrometry. Analytical Chemistry 42(9): 954-958, Aug. 1970.
11. Dawson, Jr., H. J. Detection of traces of polynuclear aromatics
in hydrocarbons by gas chromatography. Ibid 36(9): 1852-
1853, Aug. 1964.
12. Davis, H. J. Gas Chromatographic determination of benz-A-pyrene
in cigarette smoke. Ibid 40(10): 1583-1585, Aug. 1968.
13. Standard methods for the examination of water and wastewater. 13th
ed. New York, American Public Health Association Publication
Office, 1971. Section 113A.
14. Personal communication. E. N. Davis, Mgr. , Analytical Depart-
ment, Atlantic Richfield Company, Harvey, Illinois.
15. Standard methods for the examination of water and wastewater. 13th
ed. New York, American Public Health Association Publication
Office, 1971. Section 104A, p. 62-64.
16. Methods for chemical analysis of water and wastes. Environmental
Protection Agency Publication 16020-07/71. U. S. Government
Printing Office, 1971. p. 121.
17. Standard methods for the examination of water and wastewater. 13th
ed. New York, American Public Health Association Publication
Office, 1971. Section 129, p. 210-215.
18. Operating manual for Model 303 atomic absorption spectrophotometer.
The Perkin-Elmer Corporation, Norwalk, Connecticut, Jan.
1969.
19. Analytical methods for atomic absorption spectrophotometry. The
Perkin-Elmer Corporation. Norwalk, Connecticut.
226
-------
APPENDIX C
ANALYTICAL QUALITY CONTROL DATA
FOR QUANTIFICATION OF LABORATORY ERROR
Refinery waste samples were analyzed to determine their concentration
levels of various identified hazardous constituents. After the addition of
known quantities of these substances to the samples, concentration levels
were measured again. Comparison of the results made possible the
evaluation of laboratory accuracy. (Discussion of control methodology and
data significance appears in Section 3. 4 of this report.)
227
-------
APPENDIX C
ANALYTICAL QUALITY CONTROL DATA
FOR QUANTIFICATION OF LABORATORY ERROR
Arsenic (As)
No.
~A-r~i
A-4 !
';
A- 5 ';
C2-8 |
C4-6 ,
C4-3
B2-1
B4-7
B5-5 .
Cl-7
C3-1
A4-3
C2-2
A2-9
B2-2
.
Sample
Centrifuge cake
Slop oil emulsion
solids
Spent lime
Soil farm compos.
Sulf onation waste
Centrifuge cake
API separator
sludge
Lube oil clarif.
bottoms
Lube oil clarif.
bottoms
Waste bio sludge
Spent lime
Kerosene filter
clay
Slop oil emulsion
solids
DAF float
Vacuum filter
cake
Leaded tank
bottoms
.
Found in
Original
Sample
mg/kg
23.5
3.5
0.05
8.2
<0.5
2.5
5.4
3.8
3.8
2. 0
1.0
1.4
7.8
<0. 5
47.5
525.0
.
1 '
Amount
of Spike*
mg/kg
2.3
2.5
0.5
0.0
5.0
4.6
5.0
5.0
5.0
0. 0
5.0
0.0
5.0
5.0
0.0
0.0
Calculated
Spiked Sam-
ple Concen.
mg/kg
25.8
6. 0
0.55
8.2
5.5
7.1
.
10.4
8.8
8.8
2.0
6.0
1.4
12.8
. 5.5
47.5
525.0 1
f
|
i
-
,
1
i
i
i
;
Found in
Spiked
Sample-
mg/kg
26.4
6.0.
0.74
8.2
4.4
11.7
10.8
7.8
10.0
2.0
8.2
2.0
13.2
8.5
45.5
.
455.0
Error
mg/kg
+0.6
0.0
+0. 19
0.0
-1. 1
+ 4.6
+0.4
-1.0
1
+ 1.2
0. 0
i
+ 2.2
+ 0. 6
+ 0.4
+ 3.0
t
-2. 0|
-70.0
i
1
I
i
*0. 0 in this column indicates a duplicate analysis
228
-------
Beryllium (Be)
No.
A-l
A-4
A-5
A3-3
C2-8
C4-6
C4-3
B2-1
B4-7
B5-5
Cl-7
C3-1
A4-3
B4-11
C2-2
Sample
Centrifuge cake
Slop oil emulsion
solids
Spent lime
API separator
sludge
Soil farm compos.
Sulfonation waste
Centrifuge cake
API separator
sludge
Lube oil clarif.
bottoms
Lube oil clarif.
bottoms
Waste bio sludge
Spent lime
Kerosene filter
clay
Slop oil emulsion
solids
Kerosene filter
clay
DAF float
Found in
Original
Sample
mg/kg
0.50
0.38
<0. 1
0.24
1.9
<0. 12
0.22
<0. 25
<0. 13
<0. 13
<0. 13
<0. 13
0.50
<0.25
<0. 25
<0. 25
1
Amount
of Spike*
mg/kg
2.3
2.4
0.5
4.9
0.0
5.0
4.6
5.0
5.0
5.0
0.0
5.0
0.0
5.0
0.0
5.0
Calculated
Spiked Sam-
ple Concen.
mg/kg
2.8
2.78
0.6
5.14
1.9
5.12
4.82
5.25
5. 13
5.13
<0. 13
5.13
0.50
.
5. 25
i
\ <0. 25
5.25
i
!
Found in
Spiked
Sample
mg/kg
2.3
1
f
2.4
0.3
i
5. 2
1.9
5. 3
4.9
5.0
4.3
4.3
<0. 13
4.5
<0. 25
4. 3
<0. 25
4.3
Error
mg/kg
-0.5
-0. 38
-0. 3 j
+o. 06 ;
.0. 0 ;
f 0. 18
+ 0. 08 ป
-0. 25 ;
.
-0.83 :
-0. 83;
0.0
-0.63
-0. 25
-0.95;
0. 0
-0.95
'
1
'
t
i
,
i
0. 0 in this column indicates a duplicate analysis
229
-------
Cadmium (Cd)
No.
A-l
A-4
A-5
A3 -3
C2-8
C4-6
C4-3
B2-1
B4-7
B5-5
Cl-7
C3-1
A4-3
B4-11
C2-2
C4-4
Sample
Centrifuge cake
Slop oil emulsion
solids
Spent lime
API separator
sludges
Soil farm compos.
Sulfonation waste
Centrifuge cake
API separator
sludge
Lube oil clarif.
bottoms
Lube oil clarif.
bottoms
Waste bio sludge
Spent lime
Kerosene filter
clay
Slop oil emulsion
solids
Spent clay
DAF float
Spent lime
Found in
Original
Sample
mg/kg
0. 12
0.30
0.03
<0. 24
2.0
<0. 1
0.5
0.5
0.3
0.3
0. 3
0.3
1.5
<0. 25
<0. 25
<0. 25
0. 1
'
Amount
of Spike*
mg/kg
4.5
4.9
1.0
9.8
0.0
10.0
9.2
10.0
1-0.0
10.0
0.0
10.0
0.0
10.0
0.0
10. 0
0.0
Calculated
Spiked Sam-
ple Concen.
mg/kg
4. 62
5. 2
1.03
,10.04
2.0
10. 1
9.7
10.5
,
1
10.3 !
,
10. 3
0. 3
10.3
. r
; 1
1.5 !
t
10.25 j
I <0. 25 j
\ 10. 25 |
i o.i !
' *
^ i
i t
i i
i
i j
i
j
i
1 i
;, i
J
\
Found in
Spiked
Sample
mg/kg
1.9
4.7
0.39
3.4
1.3
1.0
4.6
9.0
10.0
10.0
0.3
10.0
1.5
7.0
<0. 25
7.0
0.25
Error
mg/kg
-2.72;
i
i
-0.5 i
. -0. 64 '!
,
' '
-6.641
f
-0.7 ;
-9.1 j
-5. 1 !
1
-1.5 ;
-0. 3 i
-0.3 !
0.0 i
-0.. 3
0.0
-3. 25
0.0
-3. 25
+ 0. 15
\
\
i
i
i
i
i
i
i
*0. 0 in this column indicates a duplicate analysis
230
-------
Chromium (Cr)
No.
A-l
A-4
j
A-5
f
A3-3
C2-8
C4-6
C4-3
B2-1
B4-7
B5-5
Cl-7
C3-1
A4-3
B4-11
C2-2
B2-5
C2-5
C4-2
C4-4
C3-3
C3-5
Sample
Centrifuge cake
Slop oil emulsion
solids
Spent lime
API separator
sludge
Soil farm compos.
Sulfonation waste
Centrifuge cake
API separator
sludge
Lube oil clarif.
bottoms
Lube oil clarif.
bottoms
Waste bio sludge
Spent lime
Kerosene filter
clay
Slop oil emulsion
s olids
Kerosene filter
clay
DAF float
DE filter cake
Centrifuge cake
DAF float
Spent lime
API separator
sludge
Cooling tower
sludge
Fourid in
Original
Sample
mg/kg
850.0
444.0
0.07
6790.0
288.0
0.2
536.0
445.0
40.0
40.0
475.0
0.5
45.0
380.0
1.3
28.0
1750.0
1175.0
117.5
28.0
285.0
i
i
343.0
Amount
of Spike*
mg/kg
9.1
9.8
2.0
20.0
0.0
20. 2
18.0
20.0
20.0
20.0
0.0
20.0
0.0
20.0
0. 0
20.0
0. 0
0.0
0.0
0. 0
0.0
0.0
Calculated
Spiked Sam-
ple Concen.
mg/kg
859.1
453.8
2.07
6810.0
288. 0
20. 2
554. 0
465.0
i
60.0
t
60.0 !
475. 0 |
20.5
i
i
45.0 |
i
400. 0 |
(
ซ 1.3
i
48.0 i
1750. 0 j
1175.0 j
117.5 j
28.0 j
\
I
285.0 i
l
I
343.0 j
i
|
l
1
i
, , , "i
Found in
Spiked
Sample
mg/kg
625.0
478.0
1.2
6860. 0
338. 0
16.5
551.0
405.0
48.0
55.0
475.0
14.3
45.0
393.0
1.3
42.0
2100.0
1250.0
123.0
29.5
220.0
376.0
Error
mg/kg
-234. 1
+ 24. 2
rO. 87
+ 50. 0
+ 50.0
-3.7
-3.0
-6Q. '0
-12.0 i
-5.0 !
0. 0
-6. 2
0. 0
-7.0
0. 0
-6.0 '
+350.0 .
+75. 0 ,
+5. 5 ''
+ 1.5 [
(
-65.0 ;
+ 33. 0 .
,
'
*0. 0 in this column indicates a duplicate analysis
231
-------
Copper (Cu)
No.
A-l
A-4
A-5
A3-3
C2-8
C4-6
C4-3
B2-1
B4-7
B5-5
Cl-7
C3-1
A4-3
B4-H
1
1
C2-2
A3-3
i
A2-6
!
;
Sample
_____ 1
Centrifuge cake
Slop oil emulsion
solids
Spent lime
API separator
s olids
Soil farm compos.
Sulfonation waste
Centrifuge cake
API separator
sludge
Lube oil clarif.
bottoms
Lube oil clarif.
bottoms
Waste bio sludge.
Spent lime
Kerosene filter
clay
Slop oil emulsion
solids
Kerosene filter
clay
DAF float
API separator
sludge
Kerosene filter
clay
Found in
Original
Sample
_mg/kg
27.5
15.9
0.22
514/0
112.0
6.3
111.0
29.0
3.0
3.0
9.5
2.0
8.0
31.5
0.5
0.5
i
5 514.0
9875.0
i
i
i
1
1
Amount
of Spike*
mg/kg.
9.1
9.8
2.0
20.0
0.0
20.0
18.0
20.0
.
20.0
20.0
0.0
20.0
0.0
20.0
0.0
20. 0
0.0
0.0
Calculated
Spiked Sam-
ple Concen.
mg/kg
36.6
25.7
2.22
534.0
112.0
26.3
129,0
'
49.0
1 23.0
,
J 23.0
i 9.5
i 22.0
;
' 8.0
;
1 51.5
i
I 0.5
' 20. 5
i
i
i 514.0
;
' 9875.0
; ' ;
' t
; i
1
i 1
i
t 1
i <
Found in
Spiked
Sample
mg/kg
141.0
27.0
1.7
515.0
112.0
17.0
124.0
46.5
17.5
17.5
9.5 -
18.5
7.5
47.8
0.5
15. 5
500.0
14780.0
Error
mg/kg
+ 104.4 '
i
1
1
+ 1.3 I
-0.52]
;
-19.0 \
0.0
-9.3 ;
-5.0
'
-2.5
-5.5
-5.5
0.0
-3'5
-0.5 >
;
' -3. 7 :
1 ;
1 ;
! o.o,1
| -5.0
I !
! -14.0 ;
J '
+4905.0!
\
I
t
i
i !
i i
i i
j i
i
i i
*0. 0 in this column indicates a duplicate analysis
232
-------
Cobalt (Co)
No.
A-l
' A-4
A-5
A3-3
i
G2-8
C4-6
C4-3
B2-1
B4-7
B5-5
Cl-7
C3-1
A4-3
C2-2
C4-2
Sample
Centrifuge cake
Slop oil emulsion
solids
Spent lime
API separator
sludge
Soil farm compos.
Sulfonation waste
Centrifuge cake
API separator
sludge
Lube oil clarif.
bottoms
Lube oil clarif.
bottoms
Waste bio sludge
Spent lime
Kerosene filter
clay
Slop oil emulsion
solids
DAF float
DAF float
Found in
Original
Sample
mg/kg
25.0
4. 2
0. 18
26. 2
14.0
<0. 2
74.0
<1. 0
<0. 5
<0. 5
0.5
<0. 5
5. 0
5.0
2. 0
67.5
,
i
1
Amount
of Spike*
mg/kg
9.1
9.8
2.0
20.0
0.0
20.0
18.0
20.0
20.0
20.0
0.0
20.0
0.0
20. 0
20.0
0.0
Calculated
Spiked Sam-
ple Cone en.
mg/kg
34.1
14.0
2. 18
46. 2
14.0
20.2
92.0
21.0
20.5
i
20.5 ;
0.5 i
f
20.5 !
i
\
i
5.0 ;
i
25.0
22.0 ;
67.5 '
!
i
i
i
i
i
i
1
\
\
i-
i
i
i
1
!
i
i
\
Found in
Spiked
Sample
mg/kg
50.0
14.0
1.7
42. 2
17.5
24.0
87.0
15.5
16.3 '
16.3
0.5
17.3
. 5.0
15.0
15.0
10.3
Error
mg/kg
+15.9 ;
i
0. 0 i
-0.43;
I
I
-4.0 :
+ 3.5 ,
+ 3.8 '
-5. 0 \
-5.5
-4. 2;
-4. 2 .
0.0 ;
-3.2
0.0,
-10. 0;
-7.0;
-57. 2;
i
I
1
;
*0. 0 in this column indicates a duplicate analysis
233
-------
Cyanide
No.
C4-9B
C4-6
B5-5
B4-7
A4-3
i
C2-2
A3-3
C4-10
Al-1
Al-2
C4-11
Sample
Leaded tank
bottoms
Found in
Original
Sample
mg/kg
<0. 08
Sulfonation waste j <0. 08
Waste bio sludge
Lube oil clarif.
bottoms
Slop oil emulsion
solids
DAF float
API separator
<0. 10
Amount
of Spike*
nig/kg
1. 17
200.0
0.80
<0. 10
0.80
1
-
0.40
1.00
<0. 1 1.00
.
sludge j 51.4 0.0
Loading tank sludg4 17. 2 0.0
Sludge facult pond
Centrifuge cake
19.5 0.0
54.4 0.0
Storm water silt 0.34 \ 0.0
!
i
' !
\
\
i ;
i
j
j
1
i
1 !
Calculated
Spiked Sam-
ple Concen.
mg/kg
1.25
200. 08
'0.90
0.90
1.40
1. 10
i
51.4
17. 2
19.-5
54.4
0. 34
i
i
*,
i
t
|
\
f(
;
*
1
j i
t (
i j
i
i
t
\
Found in
Spiked
Sample
mg/kg
1.46
141.0
1.05
0.83
1.62
0.77
36.2
10.8
19. 0
50.5
0. 61
Error
mg/kg
;
+ 0. 21 j
-59.08 i
+ 0. 15 ซ
I
t
-0.07 ?
'
;
+ 0. 22 ,
-0.33 :
-15.2 '.
-6.4 i
-0.5 i
-3. 9 ;
+ 0. 27
:
i i
i
1 1
:
\ ;
\
1 ;
'
\ >
i
1
\ ?
i
^ t
< i
i
I
i
t
'; 1
1 i
:
i
*0. 0 in this column indicates a duplicate analysis
234
-------
(Pb)
!
1 i
No, Sample !
: " 1
-' 5
A 3 - 3
".2-8
04-6
C4-3
, B2-1
; B4-7
B5-5
Cl-7
C3-1
. A4-3
1
I
Centrifuge cake >
Spent lirae i
API separator !
sludge i
Soil farm rompcs '
Sulfonation wasi.e j
Centrifuge cake j
API separator j
sludge ;
Lube oil clarif.
bottoms '
Lube oil clarif.
bottoms |
Wa.ste bio sludge i
Spent lime ;
Ke r os ^ ne 1'iite r
clay ;
Slop oil emulsion j
solids |
64-11 Kerosene filter \
A3-7
clay (
FCC cataly s i fine s
A3 -8 Combined lime &. \
B2-5
B4-1
B4-2
FCC sludge |
DE filter cake 1
Flotator .
|
Amount
of Spike5''4
i.-'ri/l^ i mg/kg
1 :'.,. Ci
-,,0, i
,'>, f
it V~>. ::
'. ';
28. i
10. 0
I >
i. 1
:.. o
/.. '.':
<2, r>
10. a
2. 3
195. 0
19H. 0
275. 0
1250, 0
388. 0
12,90. o
6. 8
94,. 8
1420. 0
59. o
i. 2
9.1
i 2. 0
!- 19.6
0.0
20. 0
18.3
20.0
; 20. o
j
20. 0
0.0
20. 0
0.0
20.0
0.0
0.0
0.0
0. 0
0.0
0. 0
0.0
0.0
0.0
0. 0
0.0
0.0
Calculated
Spiked Sam-
ple Concen.
mg/kg
21. 1
2. 1
80.2
1100. 0
29-5 \
46.4 !
;
30.0
1
21. 3 !
t
;
21.3 ;
5.0 !,
22.5 :
,
<2.5 :
t
30.8 i
!
2.3 |
195.0 j
(.
198. 0
275.0 |
1250.0 ;
388. 0 !
j
1290.0
6.8 j
94. 8 j
j
1420.0 j
59-0 j
i
1.2 [
Found in
Spiked
Sample
mg/kg
91.0
0. 1
61. 3
750. 0
27.5
51.5
50.0
18. 8
18. 5
5.0
13.8
ซC2. 5
7.8
2.3
355. '0
145. 0
39. 0
1390. 0
258.0
69.0
2. 3
68.0
780. 0
39.0
4.4
Error
jrig/kg
+ 69, 9
-2. 0
-18 9
-350. 0
-. C
+ 5. I
+20. e
-2.5
-?.. ฐ
0 . 0
-P.,7
0. r,
-23.0
+ j. t "j C
_ ; - :, r
-2':>h i
+ :
-------
Mercury (Hg)
No.
A3-3
C2-8
C4-6
B2-1
B4-7
B5-5
Cl-7
A-4
A-5
A-l
C2-2
B4-11
"A-8
B5-3
C3-5
C4-4
Sample
API separator
sludge
Soil farm compos.
Sulfonation waste
API separator
sludge
Lube oil clarif.
bottoms
Waste bio sludge
Spent lime
Slop oil emulsion
solids
Spent lime
Centrifuge cake
DAF float
Kerosene filter
clay
Bundle cleaner
sump
API separator
sludge
Cooling tower
sump
Spent lime
Found in
Original
Sample
mg/kg_
0.32
2.00
0.07
0.05 .
0.10
1.28
<0.04
0.88
<0. 01
2.50
0.07
<0. 04
20.0
6.2.
3.35
2.73
'
Amount
of Spike*
mg/kg
0.29
0.0
0.3
0.30
0. 30
0.0
0.30
0. 15 ^
0.03
0. 14
0.30
0.0
0.0
0.0
0. 0 '
0.0
Calculated
Spiked Sam-
ple Concen.
mg/kg
0.61
2.00
0.37
0.35
0.40
1.28
0.34
1.03
0.04
2.64
0.37
<0. 04
20.0
6.2
, 3.35
2.73 i
i
f
i
i
i
;
j
j
i
! i
Found in
Spiked
Sample
mg/kg
0.50
1.82
0. 22
0. 65
0. 37
1.08
0.32
1.34
<0.01
5.23
0.38
<0. 04
23. 3
7.9
0.09
<0.04
Error
mg/kg
-0. 11 ]
-0. 18 I
]
-0. 15 i
'
+ 0. 30
--0. 03
-0. 20
-0.02
+ 0. 31
-0. 03
+ 2.59
+ 0.01
i
0.0
1
+ 3.3
+ 1.7
i
!
-3.26
I- -2.69
i
j
i
'
,
|
i
!
0. 0 in this column indicates a duplicate analysis
236
-------
: i
" J ;if in ;
i
Ly >~ ifji , i i ' A\o. damoK 3a .'vue j of Spike:>-
1 ! nv, ' K.?
A - 5
Sun p','. trials i"i:
S Olid,1-: -"> S
Sperd" lirno. =CU, ?,:>
A3 -3 API c;e;jarator ;
blur'ge i 1 V. 4
C2-8
C4-6
Soil ฃ? t-.n compc s. <5,, 0
Sulfonatioii waste : x5, 0
1
C4-3 i Centrifuge cake ; ] G. C
B2-1 A PL separator ';
134-7
.,35-5
C-17
C3- 1
A.4-3
B4-11
C2-2
i'ju-lgrt . 5.0
J_,ube oil claxif.
bottoms j <2, 5
I. ube oil claril.
bottoms i 'C2. 5
Waste bio sludge j <2. 5
Spent liro.e 'C2, 5
Kerosene filter
clay <.'5, 0
Slop oil emulsion
solids i
';:0. 0 ii; this column indicates a duplicate analysis
ZV7
-------
Nickel (Ni)
No.
A-l
A-4
A-5
A3-3
C2-8
C4-6
C4-3
B2-1
B4-7
B5-5
Cl-7
C3-1
A4-3
B4-11
C2-2
A4-7
Cl-2
C4-4
Bl-3
Bl-5
Sample
Centrifuge cake
Slop oil emulsion
s olids
Spent lime
API separator
sludge
Soil farm compos.
Sulfonation waste
Centrifuge cake
API separator
sludge
Lube oil clarif.
bottoms
Lube oil clarif.
bottoms
Waste bio sludge '
Spent lime
Kerosene filter
clay
Slop oil emulsion
solids
Kerosene filter
clay
DAF float
Vacuum filter cakq
FCC catalyst fine^
Spent lime
Aerated pond
sludge
FCC catalyst fines
Found in
Original
Sample
mg/'kg
288.0
35.0
1.0
150.0
60.0
15.0
129.0
7.5
<2.5
<2.5
2.5
1.3
22.0
60.0
2.5
<2.5
1100.0
1000. 0
19.4
<2. 5
586.0
Amount
of Spike*
mg/kg
50.0
49.0
10.0
98.0
. 0.0
100.0
97.0
100.0
100.0
100.0
0.0
100.0
0.0
100.0
0.0
100.0
0.0
0.0
0.0
0.0
0.0
Calculated
Spiked Sam-
ple Concen.
jng/kg
338.0
84.0
11.0
248.0
60. 0
115.0
226.0
107.5
102.5
102.5
2.5
101. 3
22.0
160.0
2.5 i
102.5
1100.0 j
f
1100.0 1
19.4 !
<2. 5
586. 0 j
I
i
i
\
t
Found in
Spiked
Sample
mg/kg
341.0
368.0
6.8
250.0
65.0
92.5
216.0
1
97.5
93.0
100.0
2.5
113.0
16.0
138.0
2.5
82.5
950.0
925.0
20.0
17.1
411.0
Error
mg/kg
+ 3. 0
+ 284.0
-4.2
+ 2. 0
+ 5.0
-22.5
-10.0
-10.0
-9.5
-2.5|
0. Oi
+ 11.7
;
-6.0
',
-22.0!
0.0
-20. Q
+ 150. Oj
-75.0;
+0. 6:
\
+ 14.6!
-175.0;
1
t
t
i
*0. 0 in this column indicates a duplicate analysis
238
-------
Phenolic Compounds
1
i
No.
B2-1
i
B4-7
B5-5
Cl-7
C3-1
A3-8
A2-16
C4-8
A4-3
B2-9
B4-11
Bl-4
Al-10
Bl-1
Al-10
A-2
A3-2
A2-14
A3-7
B4-2
Sample
API separator
sludge
Lube oil clarif.
bottoms
Waste bio sludge
Spent lime
Kerosene filter
clay
Lime & FCC fine
slidges
Soil farm comp.
Tergol filter clay
Slop oil emulsion
solids
Coke fines
Spent clay
Cooling tower
sludge
Crude tank
bottoms
Holding basin
Crude tank
bottoms
API separator
sludge
Neutralized HF
alkylation
sludge
Crude tank
bottoms
FCC catalyst fines
Crude tank
bottoms
Found in
Original
Sample
mg/kg
6.5
2.1
4.5
2. 3
6.4
4.4
7.9
2.0
33.6
2.5
<0. 5
4. 1
21. 0
32.0
21. 0
157. 0
14. 6
15. 0
72. 0
16.5
Amount
of Spike*
mg/kg
I
48. 5
i
48. 5
48. 5
48. 5
48. 5
85. 0
85.0
85. 0
47. 4
0. 0
0. 0
10. 6
10. 3
10. 6
0. 0
0. 0
0. 0
0. 0
0.0
0. 0
Calculated
Spiked Sam-
ple Concen.
mg/kg
55.0
50. 6
53.0
50.8
54.9
,
89.4
92.9
87. 0
'
81.0
2.5
<0. 5
14.7
31.3
42. 6
,
21. 0
157. 0
14.6
15.0
72.0
'
16.5
i
Found in
Spiked
Sample
mg/kg
,
50.0
45.0
; 47. 6
| 50.5
! 40.8
86. 0
56.0
60. 0
74. 2
1.5
<0. 5
14.5
22. 0
24. 0
10. 2
72.4
16. 2
11.6
10.5
37.8
Error
mg/kg
-5. o ;
i
-5.6 '
-5. 4 :
-0. 3
-14.1 ',
-3. 4
-36.9
-27.0
-6.8
-1. 0 ,
0. 0 i
-0.2
-9.3
-18.6 ,:
-10.8 ;
1
-84. 6
(
+ 1. 6 '
-3.4
-61.5 .
4-21.3
*0. 0 in this column indicates a duplicate analysis
239
-------
Phenolic Compounds (continued)
No.
B5-4
Bl-1
Bl-3
Bl-4
C4-9A
Sample
Slop oil emulsion
solids
Holding basin
Aerated holding
pond
Cooling tower
sludge
Nonleaded tank
bottoms
;
i
i
Found in Calculated Found in
Original Amount Spiked Sam- Spiked
Sample of Spike* pie Concen. Sample Error
mg/kg mg/kg mg/kg ' mg/kg mg/kg
i
i
68.0 0.0 68.0 i 78.5 -1-10.5
32.0 0.0 32.0 8.9 -23.1
1 j
1
<
10.3 0.0 10.3 6.2 -4.1
i
4. 1 0.0 j 4. 1 3.6 -0.5
'
1.7 0.0 . 1.7 i 1.5 -0.2
1
i
j
'
.
<;
i
i
*
,
1 ' i
i i
! ; ;
i
' i
i } [
i i
i
t i
!
*
t
\
' '
< -ta
t
:0. 0 in this column indicates a duplicate analysis
240
-------
Selenium (Se)
No.
A4-3
C2-2
B5-5
C3-1
Cl-7
A-9
C4-3
i
Bl-1
1
.
Found in
Original Amount
Sample Sample of Spike*
1 mg/kg mg/kg
Slop oil emulsion |
solids i <1.0 10.0
DAF float 2. 0 10. 0
Waste bio sludge <1. 0 10.0
Kerosene filter ;
clay 2.1 10.0
Spent lime <1.0 10.0
Sulfur spill clean-
up <2. 0 10.0
Centrifuge cake 8.8 0.0
Centrifuge cake 8.8 0.0
Holding basin 7.6 0. 0
| ,
i
i
;
:
;
;
'
i
; 1
;
i
1
Calculated
Spiked Sam-
ple Concen.
mg/kg
11.0
,12. 0
11.0
12. 1
11.0
12. 0
8.8
8.8
7.6
Found in
Spiked
Sample j Error
mg/kg hng/kg
j
9.6 1 -1.4 s
4.1 j -7.9 i
9.2 -,1.8
i
l '
10.1 j -2.0
<1.0 I-.10. 0
i
; i
9.2 j -2.8 :
6.7 -2.1
5.8 ; -3.0
2. 3 1-5.3 ;
j
j
t
\
I
l
! :
i
1
*0. 0 in this column indicates a duplicate analysis
241
-------
Silver (Ag)
No.
A-l
A-4
A-5
C2-8
C4-6
C4-3
! B2-1
Sample
Centfifuge cake
Slop oil emulsion
solids
Spent lime
Soil farm compos.
Sulfonation waste
Centrifuge cake
API separator
sludge
B4-7 Lube oil clarif.
i bottoms
! Lube oil clarif.
B5-5
Cl-7
C3-1
A4-3
B4-11
C2-2
C4-3
bottoms
Waste bio sludge
Spent lime
Kerosene filter
clay
Slop oil emulsion
solids
Kerosene filter
clay
DAF float
Centrifuge cake
i
5
. Found in
Original
Sample
mg/kg
0.8
0.2
0.05
0.5
0. 25
20. 1
0. 5
0. 3
0. 3
0.5
0.5
1.0
<0. 13
<0. 13
0.50 '
20. 1 '
i
i
I
Amount
of Spike*
mg/kg
4. 5
4.9
0.95
0. 0
10.0
9.2
10.0
10.0
10. 0
0. 0
10.0
0.0
10. 0
0.0
10.0
0. 0
Calculated
Spiked Sam-
ple Concen.
mg/kg
5.3
5.1
1.0
0.5
10.25
29.3
| 10.5
10.3
10.3
0.5
10.5
1.0
;
; 10.13
1 <0. 13
; 10.5
20. 1
i-
Found in
Spiked
Sample
mg/kg
2.5
4.1
1.05
0. 5
8.9
27.5
10.0
8.0
3.8
0.5
5. 3
1.0
7. 5
<0. 13
5.0
17.0
Error
mg/kg
-2.8
-1.0 i
+ 0.05!
0.0 [
-1. 35 :
-1.8 .
-0.5 ;
;
-2.3
>
-6.5 ;
0.0
'
-5.2 :
0. 0
-2.63;
0.0 '
-5. 5 ;
i -3. 1 '.
\
\
\
{
1
,
5
t '
*0. 0 in this column indicates a duplicate analysis
242
-------
Vanadium (V)
- O.
A-l
,-4
A-5
\3-3
C2-8
04-6
C4-3
B2-1
84-7
S5-5
Cl-7
C3-1
\4-3
Sample
Centrifuge cake
Slop oil emulsion
solids
Spent lime
API separator
sludge
Found in
Original
Sample
mg/kg
66.0
11. 0
<0.7
48.5
Soil farm composl 90. 0
Sulfonation waste 7. 5
Centrifuge cake
API separator
sludge
Lube oil clarif.
bottoms
Lube oil clarif.
bottoms
Waste bio sludge
Spent lime
Kerosene filter
clay
Slop oil emulsion
i solids
B4-11) Kerosene filter
clay
C2-2 DAF float
Al-4
A4-9
C4-2
Soil (control)
75.0
15.0
<5.0
<5.0
5.0
<5. 0
65.0
5.0
<5.0
<5.0
115.0
FCC catalyst fine ฃ 82.5 \
DAF float
C4-4 Spent lime
C4-10J Crude tank
bottoms
i
15.0
31. 6
35.0 i
i
Amount
of Spike*
mg/kg
45. 0
49. 0
10. 0
98.0
0.0
100. 0
92. 0
100. 0
100.0
100. 0
0. 0
100.0
0.0
100. 0
Calculated
Spiked Sam-
ple Concen.
mg/kg
Found in
Spiked
Sample
mg/kg
111.0 j 116.0
60. 0
10.7
146.5
90.0
107. 5
167.0
115.0
105. 0
105.0
5.0
105. 0
65. 0
105. 0
0.0 ( <5.0
100.0
0. 0
0. 0
0. 0
0. 0
0. 0
105.0
115. 0
82.5
15. 0
31. 6
35. 0
i
64.0
<10. 0
167.0
85. 0
115. 0
161. 0
125. 0
90. 0
90. 0
<5. 0
103. 0
70. 0
115.0
<5.0
110. 0
115. 0
70. 0
10. 0
25. 0
48.8
i
t
i -
Error
mg/kg
+ 5. 0
i
+ 4. 0
-0.7 ;
i
;
+ 20.5 '
-5.0
+7.5
-6.0
:
+ 10. 0 ;
,
-15. 0
-15.0 ;
0. 0
+ 2. 0 ;
+ 5.0
+ 10. 0
0. 0
+ 5. 0
0. 0
-12.5
-5.0
-6. 6
+ 13.8
0 in this column indicates a duplicate analysis
243
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APPENDIX D
COMPARISON OF INTER-LABORATORY ANALYTICAL DATA
To evaluate analytical quality control, .samples collected at the
various refineries were split into identical pairs. One sample was
left at the refinery for analysis within their laboratories. The results
of analyses of five participating refineries are shown here with those
of identical samples analyzed in the laboratories of Jacobs Engineering
Co.
244
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APPENDIX E
SAMPLE INFORMATION SHEET
(API QUESTIONNAIRE)
(JEC Project 02-1033)
This information sheet was developed after a trial visit to a. West
Coast refinery, and was mailed by the API to each participating refinery.
It was designed to provide certain refinery information required to carry
out this industry study..
Each company was requested to nominate two or more of their
refineries in different geographic areas. From the nominations, the Task
Force selected 17 which best represented the sample distribution outlined
by Jacobs. It was recognized that all of the seventeen refineries* selected
by Jacobs Engineering Co. might not be available for the survey.
The attached Table 1-E lists the solid waste streams which may
be present in the refineries. The definition of a solid waste stream in
this case is any identifiable refinery waste stream (excluding trash) that
is not subject to control under either air or water environmental regula-
tions.
Instructions for Completing
the Questionnaire
1. Complete the general information sheet to identify and character-
ize the refinery. Under products, list only the broad categories
of products such as gasoline, kerosene, lubes, etc.
2. Complete a. separate Solid Waste Stream Data Sheet for each
solid waste stream, that is disposed of off site or onsite. Do not
include such things as reformer catalyst in which the noble metal
is reclaimed. Describe in general terms the principal sources of
the wastes, particularly if it is a mixture of several streams. If
the stream is disposed of offsite, give the name of the contractor,
the cose of the offsite disposal, and if known, the location of the
site of ultimate disposal.
*List of seventeen refineries is not included because of a confidentiality
agreement with the industry.
248
-------
3. Prepare a block diagram (similar to the attached sample)
showing the origin of the various solid waste streams.
The purpose of the diagram is to assist Jacobs in under-
standing the origin of the streams and their relationship
to each other. Jacobs would appreciate having a copy of
the wastewater flow sheet which was filed with your NPDES
permit application. They should also appreciate receiving
a copy of the PR brochure for the refinery usually given to
visitors. The Jacobs representatives will have with them a
copy of the Annual Refining Survey from the April 1, 1974,
Oil and Gas Journal. They will ask if any of the units
shown were not in operation at the time of the sampling.
All of this information will assist Jacobs in their study of
the data collected while not revealing any unpublished data
concerning the processing scheme.
4. Complete the questionnaire prior to the Jacobs visit and
furnish a copy to Jacobs during the visit. Arrangements
for the visit will be made by Jacobs with the Refinery Con-
tact.
5. Samples of each solid waste stream should be collected
jointly with the Jacobs representatives. Duplicate samples
should be collected and one of them analyzed by the
refinery. After the Jacobs visit, a copy of the completed
questionnaire should be furnished to the Corporate Contact
who will in turn, furnish it to the Task Force Chairman.
249
-------
Company Name
Refinery Location
Solid Waste Stream Data Sheet
Identifying Name
// Continuous Stream
/ / Intermittent Stream
Quantity (previous 12 mo.)
(monthly range)
Source (Describe)
Method of Disposal (Describe)
(off-site, on-site, reclaimed, costs, contractor)
Analysis (if available) :
Asbestos
Arsenic
Beryllium
Cadmium
Copper
Cyanides
Lead
Mercury
Vanadium
Nickel
PNA's
Organic Amines
Halogenated Hydrocarbons
Pesticides
Selenium
Zinc
Chromium
Other
(List of components furnished by Jacobs)
250
-------
TABLE I-E
Refinery Sources of Solid Wastes
A. Utility Sludges
Water Treatment & Power Generation Wastes
B. Waste Treatment Residue
Bio Sludges
DAF - Floated and Bottoms
API Separator Bottoms
Chemical Sludges
C. Tank Bottoms
Crude
Products
D. Catalyst Fines or Rejects
E. Filter Clays
Driers
Filters
F. Process Chemical Wastes (e.g. acids & caustics)
G. Solid Incinerator Wastes
H. Cleanup, Maintenance, and Spills
I. Air Pollution Abatement Sources
J. Other
251
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APPENDIX F
FLOW DIAGRAMS OF REFINERY SOLID WASTE
TREATMENT PROCESSES AND WASTE FLOW
This Appendix contains block flow diagrams of the solid waste
treatment system of each of the refineries visited in the study. These
diagrams show the origin of the solid waste, the treatment processes,
and the disposition of residual solid waste and sidestreams. Also shown
is the type of stream, continuous or intermittent, and the sample loca-
tion. The sample numbers indicate the order in which the samples were
taken, and the letters identify the survey team. The refinery number
completes identification of sample origin.
253
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APPENDIX G
SAMPLING INSTRUCTIONS
ISSUED TO PARTICIPATING REFINERIES
1. Each sample container will have a label (see below) affixed.
POMEROY, JOHNSTON and BAILEY
Pasadena Ventura
660 S Fair Oaks Ave. 29 North Olive
(21 3) 681-46SS (80S) 648-2735
Client
uab No
Date
Sample ID
Analyze lor
On the label enter the following information:
Client Enter Project No. (02-1033)
Date Enter date sample was taken
Lab. No. Leave blank
Sample ID Enter identification code
Analyze for Use this space for any additional identity data
2. In addition to filling out the label, maintain a log on each sample. As a
minimum, the following information should be recorded:
2. 1 Sample origin (where taken)
2. 2 When taken
2.3 Type of sample (i.e., grab sample, composite sample, etc.)
2.4 History of the sample (i.e. , is the sample an accumulation over a
period of time, or is it a recurring daily/weekly waste that may
be variable)
270
-------
3 . Obtaining Representative Samples
The obtaining of homogeneous samples that are truly representative of
an entire operation will, no doubt, be difficult in some cases, and im-
possible in others.
In the case of liquid or semi-solid wastes, a procedure of taking
numerous small grab samples over a period of time will yield a more
representative sample.
For dusts (such as catalyst fines) or other solids, it is recommended
that a large (50 Ibs. or more) sample be taken. The sample is to be
thoroughly mixed by means of a shovel or trowel. After mixing, the
sample is "quartered". Three of the "quarters" are discarded and
the mixing and quartering is continued until the sample is reduced to
the desired size.
For sizable solids, no firm recommendation can be made and each
situation must be judged on its own merits.
4. Splitting the Samples
The refineries may wish to run all or part of the analyses on the same
samples. To assure that analytical results can be compared, it is
essential that the samples be as nearly identical as possible.
For all the cases in (3) above, it is suggested that the samples be
taken in a large container, thoroughly mixed, and then divided.
Your team will be provided with sufficient one-gallon plastic sample
containers, but you will not have an excess. Let the refineries pro-
vide their own sample containers (make a note of what type they are
using). DO NOT give away our containers.
5. Shipping
After taking and properly labeling the samples, put each in the plastic
bag (provided) and seal.
Wherever possible, ship via UPS "Blue Label" service to the
Pasadena address shown on the labels.
If no UPS service is available, use Air Freight.
271
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APPENDIX H
CHARACTERIZATION OF SPECIFIC SOLID WASTE STREAMS
This appendix is included to enable the general reader to obtain
a clearer concept of the nature of the -wastes being discussed.
Filter clays
Clays are used for treating a number of products. One use, re-
presented by samples from refineries C-3 and B-4, is the final treating
of lubricating oil base stocks to improve color and, if any are present,
to remove acidic compounds. This type of operation is being phased out
at most lube oil manufacturing operations and being replaced by mild
hydrogenation or hydrotreating. The hydrotreating does a better job of
improving color, increasing stability against oxidation, has no yield
loss (the oil measured in the filter clay represents a loss of some of the
most costly products produced in a refinery) and eliminates the problem
of disposing of the spent clay. Since the lubricating oils treated with
clay have been highly refined (i. e., deasphalted, liquid-liquid extracted
and dewaxed) there should be very little material removed by the filter
clay. Measured quantities of potentially hazardous materials probably
were in the original clay.
Another clay treating operation represented by a sample from
refinery A, is fixed bed treating of an aromatic petrochemical extract
such as the benzene, toluene, and xylene (BTX) fraction extracted from
catalytic reformate. This treatment is used to improve the acid wash
color test, and basically, removes any trace olefins or diolefins present
in the extract. Eventually, this clay becomes coked or is not sufficiently
active to remove olefins and must be dumped from the tower and dis-
posed of. Again, the material being treated has been highly refined
(distilled, hydrotreated, reformed, and liquid-liquid extracted) and the
only materials removed by the clay are traces of extraction solvent and
hydrocarbons. Most of the potentially hazardous materials shown in the
analysis were probably present in the original clay.
The clay sample from refinery C-4 was used to give a final
treatment to a lubricating oil additive. The clay treating is carried out
after a sulphonation operation and removes traces of unreacted sulfuric
acid or oleum. Most of the measured materials probably were present
in the clay, although some might come into the operation with the
272
-------
or SO, used in the sulphonation step.
The clay from refinery A-2 is used to treat kerosene. It appears
that this kerosene is treated prior to filtration with a copper-containing
compound. The filter clay is then used to remove excess copper car-
ried out with the kerosene. Other potentially hazardous materials were
probably present in the fresh clay.
The spent filter clays have high oil adsorption qualities which
make them ideally suited for use on in-plant oil spills. These clays are
used typically from the filtration of light-end distillates and lube oils.
Rather than immediately disposing of this spent clay, the refineries
stockpiled them within the diked areas around the refinery until used.
Stockpiling of the clay also allows the distillates to evaporate and the
hydrocarbons to degrade by microbial action.
Spent clays constitute one of the largest waste streams in
several of the Type IV refineries. At least one of these refineries has
mentioned that it will attempt to recycle this clay. It is not known what
type of process will be used, but previous work on the regeneration of
clay by burning the residual oil with air, using oil roasting kilns or
similar equipment, has rarely been satisfactory. Close temperature
control is necessary for the clay to maintain its activity, and with the
variations in the amount of residual oil left on the clay this becomes
extremely difficult. The Socony-Mobil Oil Company has developed their
Thermofor kiln for the regeneration of non-activated clay. The equip-
ment is rather complex. The process consists of washing the spent
clay with naphtha to free it from oil and render it mobile. It is dried by
steam heating and fed to the clay burning kiln where it is regenerated by
controlled combustion of the absorbed impurities. The unit process is
quite complex, and a considerable amount of auxiliary equipment is
required. This type of unit process has been in use for many years on
a batch basis, but has as yet never been integrated into a continuous
process.
Coke fines
In a Delayed Coking Unit, residuum from the fractionation of
crude petroleum is heated to a high temperature (880-930 F. ) and
passed into large drums with a high residence time. The heaviest
materials form a layer of coke on the inside of the drums. When the
drums are full of coke, the feed is switched to another drum and the
coke is removed by high pressure water sprays. The water cuts the
273
-------
coke into fairly large chunks but also produces some fine materials.
Some of these fines remain in the water which is usually recycled to the
cutting operation. Some of these fines settle out in the water storage
vessels and are removed intermittently. Some of the fines remain with
the coke and will drop to the ground or pavement during handling of the
coke. These fines are also collected and disposed of.
All non-volatile metals contained in the crude petroleum remain
in the residues from crude distillation and are concentrated in the coke.
These metals are predominately vanadium and nickel along with traces
of other elements as shown in the coke fines samples from refineries A
and A-6.
Fluid Coking uses the same feed stock, but after heating, it is
sprayed onto a flowing mass of fine coke particles. The new coke is
formed on the coke particles which are then transferred to a burner (or
regenerator) where the new coke is partially burned to provide heat for
the reactor. Some of the coke is removed from the system and repre-
sents the net coke production. The fluidized coke contains relatively
fine particles and includes a. much greater proportion of dust or coke
fines than in delayed coker coke. As in the case of delayed coking, the
coke will contain most of the non-volatile metals from the original crude
as shown in the samples from refinery C-l.
A new type of coking unit, called a Flexicoker, is essentially a
Fluid Coking Unit with an added gasifier vessel in which the net coke
production is gasified with steam and oxygen or air to produce a low to
medium BTU fuel gas. It is not possible to gasify all the coke. Some
10-20% of the net production must be removed from the gasifier in order
to remove the metals. The removed coke contains all the non-volatile
metals from the crude but in an even more concentrated form, as shown
by the sample from refinery B-2.
Fluid catalytic cracker (FCC) catalyst fines
The major contaminating metals found on catalytic cracking
catalysts are vanadium, nickel, copper, chromium, and iron. Small
amounts of these metals are present in the crude petroleum and except
for some of the iron, all are in the form of metal-organic compounds.
Some of these compounds are volatile and when the vacuum gas oil feed
to catalytic cracking units is prepared, they appear in the gas oil. Most
of the iron and probably the chromium found on the catalyst is the result
of erosion and corrosion either in the lines, equipment, or tanks
274
-------
through which the gas oil passes.
When the feed comes in contact with the catalyst, most of the
metal compounds are tightly adsorbed on the catalyst. In the catalytic
cracking unit regenerator, where coke is burned off the spent catalyst,
the organic portion of these molecules is burned and the metals are
oxidized to an inorganic oxide and remain on the catalyst. Corrosion
and erosion products may be mixed with the catalyst as fine particles or
may also be adsorbed on the catalyst surface.
The heavy metals, vanadium and nickel, and to a lesser extent,
iron and copper, act as dehydrogenation catalysts and produce excessive
quantities of undesirable coke and light gases (especially hydrogen). In
many cases, these metal contaminants are the primary reason for dis-
carding parts of the equilibrium catalyst. Fresh (uncontaminated)
catalyst is then added to maintain a reasonable average level of con-
taminants.
j>
One recent series of analyses"' of catalysts from most of the
fluid catalytic cracking (FCC) units in the United States showed the fol-
lowing mean concentration values and significant ranges (in mg/kg):
Metal Mean Range
Vanadium 445 122 - 1626
Nickel 242 76 - 772
Copper 14 4-57
Most of the analyses reported in the analytical program of this study
fall within these ranges. The variations between the samples are pri-
marily due to the different crude sources used to prepare the feedstock.
A mild hydrogenation or hydrotreating process is used on the
catalytic cracking feed to some units. This feed treatment removes
some of the metal compounds and has other good effects on the catalytic
cracking operation (i. e. , removing sulfur which reduces the amount of
sulfur emissions from the regenerator and in the products, increasing
conversion to desirable products such as gasoline, etc.). Among the
samples analyzed, the three from refineries C-4, B-2, and B-4 used
the hydrotreating process. The hydrotreating step reduces the metal
* Analyses carried out by the Davison Chemical Division, W. R. Grace Co.
275
-------
content of the FCC feed, allowing the FCC to operate with less makeup of
fresh catalyst. The catalyst used for hydrotreating is usually cobalt and
molybdenum on a silica alumina base. The catalysts from both refineries
C-4 and B-4 contain larger than normal concentrations of cobalt and
molybdenum.
It is interesting to note that lead was found as a constituent in the
catalyst when analyzed. The only explanation we can offer for this is
that possibly some alkyl-lead compounds may find their way into the
FCC feed via slop oil reprocessing.
The total weights of catalyst fines produced by the several units
sampled varies considerably. The amount of discarded catalyst fines is
low for those units which do not have an electrostatic precipitator (re-
fineries B-l, A-5, A-3 , A-4 and C-l). A major portion of the fines
from these units are lost from the regenerator stack. Those units which
do have electrostatic precipitators (a, C-4, C-3, and B-4) produce
larger quantities of waste FCC fines which must be disposed of. The one
exception to this is refinery C-4 which has a low discard rate, and
hence, a higher concentration of metals on the catalyst fines. This may
be the result of hydrotreating all of the FCC feed in this refinery.
Neutralized HF alkylation sludge
The two samples collected represent the sludges produced when
vent gases produced from hydrofluoric acid (HF) alkylation units are
neutralized with the spent lime from boiler feedwater treatment. Both
sludges contain appreciable quantities of fluorides, however, they are
probably entirely in the insoluble calcium fluoride form as indicated by
the high pH (12. 9 and 9. 5) of the aqueous fraction of the sludge. Other
potentially hazardous materials in these sludges probably were present
in the fresh HF or lime, or in the water prior to its treatment.
Cooling tower sludge
The analytical results for all constituents shown would appear to
be in a range that one could reasonably expect with the exception of
cyanide from refinery C-4 and selenium from refinery A. The concen-
tration of cyanide of 17. 2 mg/kg is high for this service, most likely the
result of a leak from the process into the cooling water system. Sele-
nium at a level of 24 mg/kg is also high. Unless the selenium is present
as an impurity in the treating chemicals, it cannot be accounted for.
276
-------
Slop oil emulsion solids
The analytical results for this waste appear reasonable except in
a few instances. At refinery A-1 , the concentration of cyanide (54.4
mg/kg) is either an error or a large leak from the cracking unit and
should be discounted. In addition, chromium from refinery A-6 at 1. 0 ppm
is unusually low even for a refinery using non-chromate water treatment.
Once-through cooling water sludge
All results appear reasonable except for the concentration of
selenium at refinery A- 5. A level of 10. 4 ppm indicates an unusual
degree of contamination in the silt for once-through cooling water.
Spent lime from boiler feedwater treatment
All results appear reasonable except for the concentration of
selenium at refinery A-4. This high value is possibly present in boiler
feedwater treatment chemicals. This refinery is also recycling its
wastewater, which may account for the high quantities of arsenic, mer-
cury, vanadium, chromium, copper, and zinc that appear. However,
these contaminants may also be present in the boiler feedwater treatment
chemicals.
Exchanger bundle cleaning sludge
All results appear reasonable. The level depends on the service
of the exchangers that were cleaned.
API separator sludge
All results appear reasonable except for the sample taken at
refinery A-3 where the constituent levels are high because the sludge
has been centrifuged. If the values are normalized by adding oil and
water in the same proportion found in other sludges, the numbers will
reduce to that which might normally be expected. Chromium and zinc
concentrations for this sample are very low due to the non-chromate
water treatment. This type of treatment is not typical.
Dissolved air flotation (DAF) float
All numbers appear reasonable except for the lead concentration
at refinery B-4. A level of 1250 mg/kg is either an analytic error or
Z77
-------
the result of a plant spill/leak. This is approximately the concentration
of lead in gasoline, and in any case is not typical.
Leaded tank bottoms
All results appear reasonable except for a. few instances. The
phenol concentration at refinery C-4 appears to be very high since most
phenols are eliminated by hydrotreating.
Arsenic levels in the leaded tank bottoms at refineries C-4 and
B-2 are also high. Arsenic in gasoline is normally present only at levels
of 1 mg/kg or less with the arsenic usually removed by hydrotreating.
Possibly, the arsenic is a contaminant of the gasoline additives.
Zinc in the samples from refineries C-4 and B-2 for leaded tank
bottoms is also present in unusually high quantities. Possibly, this
might be the precipitated product of brass corrosion (dezincification) in
exchangers. If so, this should be verified since brass is no longer com-
monly used. The zinc quantity is not typical.
Crude tank bottoms
All results appear reasonable except for the concentration of lead
from refinery B-4. This cannot be accounted for unless the refinery is
recycling their slop oil to the crude tank.
In reviewing all refinery B-4 waste streams, a number of them
seem to have excessively high lead contents. It is possible that this is a
uniquely high lead-bearing crude.
Non-leaded tank bottoms
All constituent levels appear reasonable except for the concentra-
tion of copper and zinc from refinery C-4, which cannot be explained. If
this is the result of product additives, then it is typical only of a specific
sludge.
278
-------
APPENDIX J
FACTORS UTILIZED IN EXTRAPOLATING
REFINERY WASTE QUANTITIES FOR 1974*
Waste
Factor Based on Utilization
Factor. Based on
Cleaning Frequency
Waste bio sludge
From the Clean Water Report (1),
90% of the refineries have a
secondary biological system in
1974
None
Storm water silt
From field visits and Jacobs
Engineering in-house knowledge,
it is estimated that 25% of all
refineries have a separate storm
water sewer system which would
collect silt
None
Spent lime from
Boiler feedwater
treatment
From field visits and Jacobs
Engineering in-house knowledge,
it is estimated that 75% of refin-
eries employ lime softening to
treat boiler feedwater
None
Kerosene filter
clays
From field visits and Jacobs
Engineering in-house knowledge,
it is estimated that 30% of the
refineries generate waste filter
clays from treating kerosene
products
None
Non-leaded tank
bottoms
From field visits and Jacobs
Engineering in-house knowledge,
it is estimated that 100% of the
refineries generate this waste
Once every
10 years
(*) References for Appendix J: p. 289
279
-------
1974
Waste
Factor Based on Utilization
Factor Based on
Cleaning Frequency
API separator
sludge
From field visits and Jacobs
Engineering in-house knowledge,
it is estimated that 100% of the
refineries generate this or an
equivalent waste
None
Leaded tank
bottoms
From field visits and Jacobs
Engineering in-house knowledge,
it is estimated that 100% of the
refineries generate this waste
Once every
6.5 ye ar s
Cooling tower
sludge
From field visits and Jacobs
Engineering in-house knowledge,
it is estimated that 25% of the
refineries generate this waste
as a separate source
None
Crude tank
bottoms
From field visits and Jacobs
Engineering in-house knowledge,
it is estimated that 75% of all
refineries generate this waste--
the remaining utilize mixers
which eliminate this waste
Once every
3 years
Dissolved air flota-
tion (DAF) float
From the Clean Water Report (I),
20% of the refineries utilize
some form of dissolved air
flotation
None
Exchanger bundle
cleaning sludge
From field visits and Jacobs
Engineering in-house knowledge,
it is estimated that 10% of all
refineries generate this waste or
an equivalent as a separate
source
None
Z80
-------
1974
Waste
Factor Based on Utilization
Factor Based on
Cleaning Frequency
Slop oil emulsion
solids
From field visits and Jacobs
Engineering in-house knowledge,
it is estimated that 100% of the
refineries generate this waste
None
Once-through cool-
ing water sludge
From field visits and Jacobs
Engineering in-house knowledge,
it is estimated that 15% of the
refineries generate this waste
None
Lube oil filter
clays
From field visits and Jacobs
Engineering in-house knowledge,
it is estimated that 100% of the
refineries producing lubes gen-
erate this waste
None
Fluid catalytic
cracker (FCC)
catalyst fines
From field visits and Jacobs
Engineering in-house knowledge,
it is estimated that 100% of the
refineries having an FCC unit
generate this waste
None
Coke fines
From field visits and Jacobs
Engineering in-house knowledge,
it is estimated that all refineries
producing coke generate this
waste
None
Neutralized HF
alkylation sludge
From field visits and Jacobs
Engineering in-house knowledge,
it is estimated that all refineries
having an HF alkylation unit gen-
erate this waste
None
281
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APPENDIX K
TWO PROCEDURES FOR THE DISPOSAL OF LEADED-GASOLINE
SLUDGE FROM GASOLINE PRODUCT STORAGE TANKS
Two basic procedures for the disposal of leaded-gasoline sludge
from gasoline product storage tanks -were developed and disseminated to
the refineries by the Ethyl Corporation (1, 2) and duPont. The older
procedure involves the construction of a large, shallow dike around the
gasoline product storage tank which is to be cleaned. The excavated
material is placed around the periphery of the dike to make a berm. The
tank is opened, and the contents, down to the sludge layer, pumped to
another storage tank. The leaded-gasoline sludge is pumped into the
dike, where in the presence of sunlight and air, it rapidly evaporates
and weathers.
After a suitable period of time, which is largely dependent on the
climate, the contents of the dike are covered with the surrounding soil.
A modification of this procedure is relocation of the material elsewhere
on the refinery property for burial. Many of the refineries had com-
pletely fenced and locked areas of land set aside exclusively for the
burial of leaded-gasoline sludge. Only one of the refineries contacted
disposed of this material in an off-site municipal sanitary landfill.
The observation that leaded-gasoline sludge which had been
buried for many years still indicated potentially-toxic levels of tetra-
ethyl lead resulted in the development of an alternate procedure for its
disposal. Using the new procedure, the leaded gasoline sludge is
(a) pumped from the storage tanks onto the ground in the diked area in
which the storage tank is located, or (b) is transported to a weathering
pad elsewhere within the refinery. The material is spread in layers ,
two to four inches thick, and allowed to weather and evaporate for a
period of at least four weeks. In some northern climates, as much as
four months may be required for this weathering. The leaded-gasoline
sludge is sampled at regular , periodic intervals to determine the
tetraethyl lead concentration. After the concentration falls to a level
of below 20 parts per million, which is considered a safe level, the
material is either thinned and rotodisked into the soil in the tank dike
area or scooped up and buried somewhere on the refinery property.
-^References for Appendix K: p. 291
290
-------
*
A technical communication from the Ethyl Corporation pointed
out that degradation of buried sludge is very slow and probably not com-
plete. They suggest that the sludge be spread on the soil surface and be
allowed to weather for an indefinite period of time, if possible. This
allows greater evaporation of volatile fractions and greater weathering
in the presence of sunlight and air.
References (Appendix K):
1. Procedures for disposal of sludge from leaded gasoline storage tanks
from Section 6 of Ethyl Corp. Tank Cleaning Manual.
2. Ball, H. D. Methods of disposing of sludge from leaded gasoline
storage tanks. An Ethyl Corp. publication.
(*) Source: K. C. Jost, Manager Product Service and Safety, Ethyl
Corp. , January 1975.
291
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APPENDIX L
A DESCRIPTION OF THE CHEMFBC PROCESS
(For the chemical fixation and solidification of complex waste
mixtures to be used as landfill)
The Chemfix process utilizes a two-part, inorganic chemical
system which reacts with all polyvalent metal ions and with certain
other waste components; it also reacts within itself to form a chemi-
cally and mechanically stable solid. This system, now patented, is
based on the reactions between soluble silicates and silicate setting
agents which react in a controlled manner to produce a solid matrix.
The matrix itself, as produced, is actually a pseudo-mineral. It is
based on tetrahedrally coordinated silicon atoms alternating with oxygen
atoms along the backbone of a linear chain. The charged side groups -
in this case oxygen - in reaction with polyvalent metal ions result in
strong ionic bonding between adjacent chains to form a cross-linked,
three-dimensional, polymer matrix which is very much like many of
the natural pyroxene minerals. This type of structure displays pro-
perties of high stability, high melting point, and a rigid, friable struc-
ture, very similar to many soils.
Three classes of interactions take place in such a system. First
are the very rapid reactions between soluble silicates and nearly all
polyvalent metal ions, producing very insoluble metal silicates. These
insoluble compounds are non-toxic and cannot easily be resolubilized
later on. In some cases, of course, they are similar to the minerals
from which the metals were originally extracted, and it is claimed that
they are quite resistant to breakdown under environmental conditions.
The second set of reactions occurs between the soluble silicate
and reactive components of the setting agent. The setting agent is
usually so formulated or chosen that the cross-linking ions have
limited solubility but a high reserve capacity, allowing the reaction to
take place slowly under controlled conditions. (This is analogous to
buffering capacity in acid-base reactions. ) In addition to operational
requirements which are served by such controlled reaction rates, the
gel structure which is thus formed is more suitable to producing good
solid properties, especially in waste which has a high water content.
The gel acts as a sort of sponge and has the unique property of being
able to hold very large quantities of water while acting in all respects
like a solid. The gel reaction can occur quickly enough, for example,
292
-------
in seconds or minutes, to prevent the settling out of solids which one
wants to contain in the structure. Because of its properties, the gel
holds ions in place by various chemical and physical bonding mechanisms
and thereby acts much as an ion exchange resin. Other waste compo-
nents such as oils are also entrapped in the structure and thereby immo-
bilized. The third class of reactions (depending upon the setting agent
used) occurs bet-ween the setting agent and the waste and/or water, as
it undergoes a series of hydrolysis, hydration and neutralization reac-
tions.
A typical operating unit consists of a mobile van 40' long and 8'
wide, which contains the chemical storage, metering and mixing equip-
ment to operate the process at flow rates of 300 to 500 gpm. The process
is continuous and occurs at ambient temperature and pressure. Process
control is maintained by automatic equipment which meters the required
ratios of chemical reactants into the waste as it flows through the unit.
293
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APPENDIX M
EXAMPLES OF REFINERY WASTE GENERATION RATES:
A RECORD OF DISPOSAL OF FOUR CALIFORNIA RE-
FINERIES BETWEEN 1968 and 1973
Wastes that need disposal to a landfilling operation may be
produced continuously within the refinery, however disposal is a
discontinuous process dependent upon a number of variables. These
variables include size of the equipment.storing the sludges, seasonal
demands, process changes, etc. The attached data represent a record
of waste disposal of four refineries in the Los Angeles area between the
years 1968 and 1973. This record is presented to indicate the variabil-
ity in disposal practices, and not necessarily as typical examples. The
data presented in Section 4.0 should be interpreted against this background.
All quantities are given in barrels unless otherwise indicated.
294
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APPENDIX N
PARTIAL LIST OF PRIVATE WASTE HAULING AND DISPOSAL
CONTRACTORS HANDLING PETROLEUM REFINERY WASTES
Pollution Control, Inc.
American Oil Rd.
.Little Rock
ARKANSAS
CALIFORNIA
All American Oil Co.
3655 S. Main St.
Los Angeles 90003
Angelas Pumping Co.
2453 E. 25th St.
Los Angeles 90058
Argo Petroleum Corp.
10880 Wilshire Blvd.
Los Angeles 90024
Atlantic Richfield Co.
5.15 S. Flower St.
Los Angeles 90071
B & H Vacuum Pump Service
16260 Placid Dr.
Whittle r 90604
Barnett Trucking, Inc.
P.O. Box 416
Fillmore 93015
J. S. Brower & Assoc. , Inc.
2040 N. Towne Ave.
Pomona 91767
Browning Ferris Industry,
Chemical Services Div.
P. O. Box 44
Wilmington 90744
Capri Pumping Service
3128 Whittle r Blvd.
Los Angeles 90023
Julian Galindo Carrasco, Inc.
6959-1/2 E. Olympic Blvd.
Los Angeles 90022
Carrasco Vacuum Truck Service
P.O. Box 1043
Wilmington 90744
Geo. F. Casey Pumping Co.
10052 Miller Way
South Gate 90280
Geo. F. Casey Pumping Co.
21801 Barton Rd.
Colton 92324
Chancellor and Ogden, Inc.
3031 East "I" St.
Wilmington 90744
323
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Chemical Disposal Co.
1138 Princeton, Suite C
Santa Monica 90403
City of Industry Disposal Co.
420 N. Del Valle St.
City of Industry 91744
Crosby and Overton, Inc.
1620 W. 16th St.
Long Beach 90813
D & J Transportation Corp.
15728 Garfield
Paramount 90723
Ecology Control, Inc.
215 E. Rocklite Road
Ventura 93001
Oscar E. Erickson, Inc.
249 Tewksbury Avenue
Richmond 94801
Falcon Disposal Service
3031 E. "I" Street
Wilmington 90744
Federal Prison Industrial,
Terminal Island
San Pedro 90731
Inc,
Findly Chemical Disposal, Inc.
12192 Morrie Lane
Garden Grove 92640
Fix & Brain Vacuum Truck
Service
233 East "D" Street
Wilmirgton 90744
Getty Oil Co.
133 West Santa Clara Street
Ventura 93001
W. E. Gilliard Vacuum Tank
Service
P. O. Box 584
Torrance 90508
H & S Vacuum Trucking
Service
P. O. Box 401
Wilmington 90744
Hapco Co.
13724 Chadron Avenue
Hawthorne 90250
Holbrook & Son Trucking,
Oil Field and Vacuum
12637 Los Nietos Road
Santa Fe Springs 90670
Humble Oil and Refining Co.
2755 Orange Avenue
Long Beach 90807
W. H. Hutchison & Sons
Service Co. , Inc.
P. O. Box 3202
Olympic Station
Beverly Hills 90212
324
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Industrial Tank Inc. of
. Martinez
Martinez*
John Preston Nash
101 W. Fremont Square
Montebello 90640
Ray E. Karns Co.
3006 San Emidio
Bakersfield 93304
King Pumping Co.
7436 1/2 Laura Street
Downey 90241
Kyle O. Mayes Co. , Inc.
800 West 15th Street
Long Beach 90806
Maymanian Disposal Co.
3420 E. Olympic Boulevard
Los Angeles 90023
Arch T. McCoy
4657 Glen Arden
Covina
Mobil Oil Corp.
612 S. Flower St. Rm. 551
Los Angeles 90017
Robert H. Morrison
1176 East 25th Street
Signal Hill 90806
Newhall Refining Co. , Inc.
22674 Clampitt Road
Newhall 91321
M. C. Nottingham Cot
Southwest
2926 West First Street
Santa Ana 92703
M. C. Nottingham Co. of
Southern California
4928 N. Walnut Grove Ave.
San Gabriel 91778
Oil and Solvent Process Co.
P. O. Box 907
Azusa 91702
Oil Fields Trucking Co.
1601 South Union Avenue
Bakersfield 93307
Ott's Vacuum Truck Service
1430 East Bastanchury Road
Fullerton 92635
industrial Tank, Inc. of Martinez is the major hauler of petroleum re-
finery waste materials in the San Francisco area. They handle approx-
imately 80% of all the solid wastes generated by the six petroleum
refineries in the area. Industrial Tank operates four Class I sanitary
landfills in the area located in San Jose, Martinez and environs, and a
fifth site is proposed at Antioch. The remaining 20% of the material
hauled from the refineries is handled by another firm which disposes
of the material at one of Industrial Tank's Martinez facilities.
325
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Randy's Pumping Service
2402 Troy Avenue
South El Monte 91773
Roberts Liquid Disposal
14708 Studebaker Road
Norwalk 90650
Routh Transportation
800 W. 15th Street
Long Beach 90813
Rubbish Haulers, Inc.
8520 Fishman Road
Pico Rivera 90660
Rich Sand Service Co.
P. O. Box 2403
Orcutt 93454
Shell Oil Co. - West Coast
E & P Division
1008 W. Sixth Street
Los Angeles 90017
Soupy's Pumping Service
3409 Santa Ana Street
Huntington Park 90255
Southland Drain Oil and Vacuum
Service
13219 Goller Avenue
Norwalk 90650
The Superior Oil Co.
State Highway 43 & 7th Standard Rd.
Bakersfield 93302
Union Oil Co. of California
9654 S. Santa Fe Srpings Road
Santa Fe Springs 90670
United Pumping Service
6059 1/2 E. Olympic
Los Angeles 90022
John E. Walden
21700 Dial-Way Ct.
Corona
W. L. Watson & Son
16741 Saticoy Street
Van Nuys 91406
Western Disposal Co.
1017 Gladstone
Azusa 91702
Standard Oil Co.
225 Bush Street
San Francisco
of California
Steverson Bros.
18062 Gothard
Huntington Beach 92648
326
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ILLINOIS
Clearing Disposal, Inc.
5245 W. 38 Cicero
Chicago
General Refuse Disposal Co.
11641 S. Ridgeland
Worth
Kankakee Industrial Disposal
P. O. Box 742
Kankee 60901
INDIANA
Calumet Waste Systems
7337 W. 15th Ave.
Gary
Home Sanitation Service
5607 W. 101st Ave.
Crown Point
Midwest Disposal Co.
6514 E. 109th Ave.
Crown Point
Mr. Frank, Inc.
201 W. 155th St.
So. Holland
Independent Waste Systems, Inc.
1020 Kennedy
Schererville
Superior Waste Systems, Inc.
1046 Sample
South Bend
LOUISIANA
B & M Trucking
P. O. Box 51957
Lafayette
Browning Ferris Industries
7850 Plank Road
Baton Rouge
Groendyke Transport
1907 St. Bernard Hwy.
Meraux
Gulf Coast Pre-Mix Trucking
Inc.
P. O. Box 51271 O. C. S.
Lafayette
Matlack, Inc.
Mason Ave.
Baton Rouge Terminal
Merichem Co.
P. O. Box 61529
Houston
(Convent Area)
327
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MICHIGAN
A. A. F.O. Disposal, Inc.
14491 Ronnie
Livonia
Fairall Trucking
18472 Allen Rd.
So. Gate
Kramer Waste Material Co.
9588 Greeley
Detroit
Falesto Bros.
200 Merseles St.
Jersey City
Interstate Waste & Removal
208 Patterson Ave.
Trenton
M. E. Trucking Co.
14740 Plymouth Rd.
Detroit
S. C. A. Services, Inc.
2151 Livernois
Troy
NEW JERSEY
Tri-County Disposal Service
Hiway 130
Robbinsville
NEW MEXICO
American Waste Removal
Jemez Dam Rd.
Bernalillo
(Albuquerque Area)
Commercial Oil Services
3600 Cedar Point
Oregon
(Toledo Area)
OHIO
Ohio Sanitation Systems,
Buckeye Road
Lima
Inc.
328
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OKLAHOMA
Atco Fuels, Inc.
5200 S. Harvard
Tulsa
B & C Tank Truck, Inc.
RFD 2, Box 532
Stroud
Bacon Transport
Box 1134
Ardmore
Banner, Inc.
Box 3306
Tulsa
Bigheart Crude Oil Corp.
Box 376
Tulsa
Roger K. Graves
Box 1125
Ardmore
Jack Ha skin
Gushing Hot Oil Treating Co.
Box 769
Gushing
H. L. Henderson
Henderson's Oil Field Service
Stroud
Victor Hiebert
2201 Meadowbrook
Enid
J-B Tank Trucks, Inc.
Enid
Buster's Transports, Inc.
202 E. Market
Box 1681
Enid
Lola M. Cain (Mrs.) Executrix
Of Estate of A. O. Cain
RFD 1,
Ponca City
Chaparral Transports, Inc.
505 S. Hayes
Enid
Ray I. Jones Service Co.
2710 S. Van Buren
Enid
John R. Martin
John R. Martin Tank Truck
Service
Box 383
Gushing
Tom Mason & Carl Mason
Midway Tank Trucks
Stroud
Kenneth F. Fackrell
421 "K" S. W.
Ardmo re
Groendyke Transport, Inc.
2510 Rock Island Ave.
Enid
Vernon Richardson
Richardson Tank Trucks
Gushing
Rogers Trucking,
Box 573
Stroud
Inc.
329
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Tom Scherer, Inc.
5200 S. Harvard
Tulsa
Target Service Co. , Inc.
2409 Sherwood Dr.
Enid
Transportation Services,
Box 6703
Tulsa
Inc.
A. F. Wass
Lumber and Hardware, Inc.
12 W. Main
Cyril
PENNSYLVANIA
Ace Service Corp.
123 Wilder St.
Philadelphia
Amo Pollution Services
2743 Nobletown Rd.
Pittsburg
Charles Crumbley
2334 N. 24
Philadelphia
Kasper Bros.
4579 Torresdale Ave.
Philadelphia
A. Marininn's Sons, Inc,
3301 Tulip St.
Philadelphia
Tri-County Hauling
1777 Calcon Hook Rd.
Sharon Hill
TEXAS
Bio Ecology Systems, Inc.
4100 E. Jefferson
Dallas
Coastal Vacuum Tank Service
8412 Hansen
Houston
Force Oil & Vacuum Company
5707 Polk
Houston
Gulf 8r Metallurgical Co.
Hiway 519
Box 2130
Texas City
Liberty Waste Disposal Co
Box 3370
Bay town
Merichem Co.
P. O. Box 61529
Houston
(Baytown Area)
Rollins Environmental Services
Deer Park
Texas Industrial Disposal, Inc.
920 S. Lamar
Dallas
330
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Western Refuse of Texas, Inc.
129 North Shaver
Houston
Ace Disposal Co.
945 Hyland Lake Dr.
UTAH
Reliable Waste Systems
1550 West
North Temple
(Salt Lake Area)
WASHINGTON
Airo Services, Inc.
2103 112th St.
Tacoma
Liquid Waste Disposal Co.
1318 4th
Seattle
Resource Recovery Corp.
5501 Airport Way
Seattle
331
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APPENDIX O
POTENTIAL FOR INTER-MEDIA TRANSFER OF SOME
COMMONLY OCCURRING METALS
Throughout this report the environmental consequences of waste
disposal have been treated as an indeterminate. Generally, the variety
of environmental situations that might arise are too complex to enable
simple categorization. In particular, the various mechanisms of inter-
media transfer are unknown, except in specific well-investigated situa-
tions. However, it is useful to have some generalized picture of the
fate of important trace metals. The following notes are a preliminary
evaluation.
332
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APPENDIX P
CONCENTRATION LEVELS OF HAZARDOUS
COMPONENTS OF REFINERY WASYE STREAMS
The attached tabulation presents analytical data that were obtained
from the sampling and analysis program, performed by the contractor.
From these data the concentration ranges used in the data extrapolations
in Section 4. 6 were derived.
337
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