WATER POLLUTION CONTROL RESEARCH SERIES • 12130 FJQ 06/71
         Pollution Abatement
     and By-Product Recovery
in Shellfish and  Fisheries Processing
      U.S. ENVIRONMENTAL PROTECTION AGENCY

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          WATER POLLUTION CONTROL RESEARCE SERIES

The Water Pollution Control Research. Series describes, the
results and progress in the control and abatement of pollu-
tion of our Nation's waters.  They provide a central source
of information on the research, development, and demon-
stration activities of the Environmental Protection Agency
through inhouse research and grants and contracts with
Federal, State, and local agencies, research institutions,
and industrial organizations.

Inquiries pertaining to the Water Pollution Control Research
Reports should be directed to the Head, Publications Branch,
Research Information Division, R&M, Environmental Protection
Agency, Washington, D.C. 20460.

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         POLLUTION ABATEMENT AND BY-PRODUCT RECOVERY
             IN SHELLFISH AND FISHERIES PROCESSING
                                 by
                       CRESA, a joint venture of
              Food, Chemical and Research Laboratories, Inc.
                     4900 Ninth Avenue Northwest
                      Seattle, Washington 98107
                                 and
                      Engineering-Science of Alaska
                       326 "I" Street, Suite 31
                      Anchorage, Alaska 99501
                              for the
              ENVIRONMENTAL PROTECTION AGENCY
                        Project # 12L30F JO
                       (Formerly 11060FJQ)
                            June  1971
For sale by the Superintendent of Documents, U.S. Government Printing Office, Washington, D.C. 20402 - Price $1

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                   EPA Review Notice
This report has been reviewed by the Environmental
Protection Agency and approved for publication.  Approval
does not signify that the contents necessarily reflect
the views and policies of the Environmental Protection
Agency, nor does mention of trade names or commercial
products constitute endorsement or recommendations for
use.
                              ii

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                         ABSTRACT
Laboratory and pilot plant studies show that utilizable by-products
can be obtained from shell fish wastes produced at Kodiak, Alaska.
Alkali extraction of the contained protein leaves a matrix of chitin
and calcium carbonate (CaCO  ).  The chitin-CaCO matrix can be
converted chemically into its components.

Other fishery wastes found at Kodiak; salmon waste and small fish
associated with shrimp can be liquified by alkali treatment, partially
neutralized with acid,  and converted into oil, bone meal and 50%
solubles.

The economics and pollution abatement capabilities of a proposed
plant  are discussed.  The construction and operation of this plant
would reduce the yearly pollution load from the present 22. 1 million
Ibs per year of C. O. D. being dumped into Kodiak Harbor to 6, 6
million Ibs per year of C.O.D.

Preliminary  designs are  submitted for the implementation of this
process, together with indicated markets and plan of operation.

This report was submitted in fulfillment of Project Number 11060 FJQ,
under the (partial) sponsorship of the Water Quality Office, Environ-
mental Protection Agency.
                                iii

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                        CONTENTS

Section                                                Page
 I        Conclusions                                    1
 n       Recommendations                               3
 III       Introduction                                    5
 IV       The Present Pollution Problem                  9
 V       Process Description                           19
 VI       Pollution Abatement                           23
 VII      Laboratory Investigations                      27
 VIII     Markets                                       51
 IX       Proposed Facilities                            55
 X       Economic Considerations                      65
 XI       Pro Forma Business Structure                 71
 XII      Alternate Disposal Methods                    73
 XIII     In-House Improvements at Processing Plants    75
 XIV     Acknowledgments                              77
 XV      References                                    79
 XVI     Publications                                   81
 XVII    Appendix                                      83

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                         FIGURES


.No.                                                     Page

 1        Map:  State of Alaska                            6

 2        Processing Plant Locations at Kodiak Harbor     10

 3        Shrimp Production at Kodiak,  Alaska            13

 4        Composition of Wastes by Percent               28

 5        Extraction Rates for Shellfish Wastes            36

 6        Oxygen Consumption by Shellfish Waste          40

 7        Map:  Location and Topography - Near Island     56

 8        Dock and Trestle for the Proposed By-Product
          Recovery  Plant                                 58

 9        Plan:  By-Product Recovery Plant Process
          Building                                        59

10        Schematic Flow Diagram - Scrap Fish from
          Shrimp Processors,  Crab Butchering Waste
          and Salmon Fisheries Waste,  Processing Unit    61

11        Schematic Flow Diagram - Shrimp Waste
          Processing Unit                                62

12        Schematic Flow Diagram - Crab Picking Line
          Waste Processing Unit                          64
                                 VI

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                        TABLES


No.                                                    Page

 1        Crab Production in 1970 for the Kodiak Area     14

 2        1970 Salmon Production at Kodiak               17

 3        Pollution Load                                 23

 4        Water Usage by Processors at Kodiak           24

 5        Amino Acid Composition of Spray Dried
          Shellfish Waste Proteins    '                   33

 6        C.O.D.  Values of Shellfish Waste               39

 7        Waste Distribution in Shrimp Processing
          A.  Raw Peeling                               42

 8        Waste Distribution in Shrimp Processing
          B.  Peeling after Steaming                      43

 9        Cooking Whole Crab                            45

10        Live Butchered Crab                           46

11        Sales/Year - Income from Disposal Fee         67

12        Yearly Operating Expenses                      68

13        Plant Investment - June 1971 Prices             69
                                Vll

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                        SECTION I

                       CONCLUSIONS
1.  The present pollution load discharged to Kodiak Harbor as wastes
from  shellfish and fish processing is about 22. 1 million Ibs of C. O, D.
per year.  This is roughly equivalent to the domestic wastes from a
city of 250, 000 population.

2.  A plan for collection and treatment of solid wastes to produce
marketable by-products  has been developed.

Wastes  would be collected in barges and transported to a site on Near
Island for by-product recovery.  Shellfish wastes would be extracted
with dilute alkali to yield a high quality protein and a chitin-CaCO
residue as products.   The protein would be marketable as a pet food
additive or for industrial applications.   The chitin-CaCO  residue
could be exported for conversion to chitin and  derived products  or
could be used in Alaska as a soil liming and fertilizer material.

Fish wastes would also be alkali extracted to yield a concentrated
protein  product similar to fish solubles,  oil and bone meal.

3.  The proposed plan would accomplish a 70% reduction in the
present pollution load and is shown to be practical and economically
sound.

4.  Any rational plan for complete pollution abatement by secondary
treatment of liquid wastes would require prior  separation and disposal
of solid wastes.

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                        SECTION II
                   RECOMMENDATIONS
1.  A pollution control district comprising all of the seafood process-
ing plants should be established.

2.  A board of directors should be elected and managements should
be appointed.

3.  A decision to construct a by-product recovery plant for solid
wastes, using processes developed in this  study, should be made.

4.  A plan for financing the enterprise should be developed.

5.  Consultants should be retained for design, construction and
operation of the facility  and for marketing  of its products.

6.  A schedule for construction of the facility should be prepared  to
comply with Federal and State of Alaska regulations.

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                       SECTION III
                     INTRODUCTION
The City of Kodiak, Alaska,  located on the northeast shore of Kodiak
Island (Figure 1),  has been an important center for fish and shellfish
processing for many years.  Starting in 1963,  with development of the
Alaska King crab fishery,  very  rapid expansion of operations in Kodiak
occurred.  Also a serious pollution problem developed.

Processing plants, now numbering 15,  are spread over  2 miles of
waterfront and are generally located on docks or moored vessels.
Usual practice is to discharge all wastes into harbor waters adjacent
to the plant.  In 1967  about 50 million Ibs of  King crab waste were
so handled.  Since then the King crab fishery has declined to 20% of
its peak but shrimp processing has increased to  the extent that over
70 million Ibs of waste were discharged into Kodiak Harbor  in 1970.

Food, Chemical and Research Laboratories, Inc.  became acquainted
with the Kodiak pollution problem in 1966 as a result of discussions
with principals in  the major processing companies for which the
Laboratories performed quality control services on products shipped
via Seattle.  Several of these companies had, in  the past,  considered
recovery  of solid wastes from shellfish processing by production of
a dried crude shellfish meal.

Economic analysis of costs and  markets for  such products led to the
conclusion that production costs in Kodiak and freight to Puget Sound
ports or other possible markets would  be prohibitive.

As an alternate, Food, Chemical  and Research Laboratories, Inc.
independently explored the possibilities of upgrading shellfish waste
by separating it into its principal  components; protein,  chitin and
calcium salts.  It  was found that a protein of high nutritional value
could be extracted from the shell  by mild alkali treatment and that
chitin, after conversion to chitosan, was useful as a coagulant and
coagulant-aid in water and waste treatment.   Possible return from
the waste  was thus increased from about $20 per ton for dry crab
meal  F. O. B. Kodiak to perhaps $200 per ton (500 Ibs protein at
$0. 15, 500 Ibs  chitin at $0. 25).

One of the King  crab producers, Pan Alaska Fisheries,  supported
additional work  on the proposed process and further studies were
supported by contracts from the U. S.  Bureau of Commercial Fisheries,

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PT. BARROW
                                     FIGURE 1
                                      MAP
                                 STATE OF ALASKA

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now National Marine Fisheries Service.  These studies concluded that
extraction of protein from shellfish waste was economically practical
at Kodiak but that further processing of the residue, chitin and CaCO
to obtain chitin should be done in areas where low cost hydrochloric
acid (HC1) was available.  Alaska markets for the residue as a soil
liming agent and fertilizer appeared practical as an alternate disposal.

In 1969 the severity of the pollution problem  at Kodiak and the imminent
need to comply with Federal and State  of Alaska laws regarding waste
discharges prompted application to the Water Quality Office,  Environ-
mental  frotection Agency for a research, development and demonstra-
tion grant to the  City of Kodiak. Objectives  stated in the application
were:

a.  To design and construct a facility to effect abatement of primary
pollution from shellfish waste  in Kodiak Harbor.

b.  To demonstrate a shellfish by-product recovery process for
conversion of waste.  The process may also  be applicable in other
processing localities.

c.  To develop in-house  measures at shellfish processing plants for
reduction of  secondary pollution levels.

The plan of  work for the project initially was divided into seven tasks
as follows:

Task 1  - An  engineering survey at Kodiak to:

a.  Determine character, extent and distribution of pollution loads.

b.  Obtain all basic data needed for preliminary design of waste
collection and recovery facility including optimum  site location,
collection equipment and procedures,  site improvements, probable
costs for fuel,  labor,  freight,  power,  water, etc.

c.  Review operating practices and facilities at individual processing
plants  to determine possibilities for in-house improvements and
changes needed to permit handling of wastes  by the recovery facility.

Task 2  - Pilot plant and chemical studies at  Seattle to obtain design
parameters for the recovery facility and to characterize  wastes and
possible products.

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Task 3 - A market development study to determine acceptability of
products for possible end uses,  potential sales volumes and prices.

Task 4 - Preparation of a Pre-construction Summary Report.

Task 5 - Engineering Design of Facilities.

Task 6 - Construction of Facilities.

Task 7 - Operation of system for 1 year with demonstration of pollution
abatement,  economic feasibility and training of personnel for continua-
tion  of operation.

On April 6,  1970,  Tasks 1,  2 and 4 of the application were funded
through a grant to the City of Kodiak  with CRESA, a joint venture
between Food, Chemical and Research Laboratories,  Inc.  and
Engineer ing-Science of Alaska,  as contractor.  Task 3 was disallowed
as not within the allowable scope of EPA support.  Tasks 5, 6 and 7
were deferred pending completion of  Task 4 and approval.
                                  8

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                        SECTION IV
           THE PRESENT POLLUTION PROBLEM


Plant Locations

Figure 2 is a map of Kodiak Harbor  showing locations of processing
plants.  Starting at the southwest end of the harbor, these are:

 1.  American Freezerships  (at Gibson Cove)

 2.  Alaska Ice  and Cold Storage Inc.

 3.  East Point  Seafoods Co.

 4.  King Crab  Inc.

 5.  B and B Fisheries

 6.  Kinnear and Wendt Inc.

 7.  Ursin Seafoods, Inc.

 8.  Pan Alaska Fisheries, Inc.

 9.  Roxanne Fisheries, Inc.

10.  Northern Processors, Inc.

11.  Point Chehalis Packers,  Inc.

12.  Martins King Crab

13.  Alaska Packers Association

14.  Columbia-Ward Fisheries

15.  Whitney-Fidalgo Seafoods, Inc.

The plant at Gibson Cove is on a converted ferry.  The ferry is
moored below a rocky hill  that makes land access difficult.  The
site is about  1 mile southwest of the next plant in the line.  Plants
2 through 10  are along a 1/2 mile  stretch of waterfront southwest
of the breakwater for the small boat harbor.  There are three plants,

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O      D
  /
A
                                                                    K
1.  American Freezer Ships (at Gibson Cove)
2.  Alaska Ice and Cold Storage
3.  East Point Seafoods
4.  King Crab, Inc.            10. Northern Processors
5.  B and B Fisheries          11. Point Chehalis Packers, Inc.
6.  Kinnear and Wendt         12. Martins Fresh King Crab
7.  Ursin Sea Foods           13. Alaska Packers
8.  Pan Alaska Fisheries, Inc.    14. Columbia-Ward Fisheries
9.  Princess Roxanne, Inc.      15. Whitney-Fidalgo Sea Foods
  )   I)  I   .1

   SPISt
                                                        >  /\ ^
                                                         t)  V-   (15
                                                         r  /~*\    —'
                                                   + */    ©
   BY-PRODUCT RECOVERY
            -  PLANT   	
                                                                               FIGURE 2
                                                              *T        PROCESSING PLANT
                                                                              LOCATIONS
                                                                                    at
                                                              KODIAK   HXRBOR
                                                 Sc.iU- 1:10,000

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11 through 13,  just northeast of the boat harbor and the last two are
about a 1 /2 mile farther to the northeast.

Operations in the processing plants differ widely as to species handled,
size and type of pack.  Some operations are more seasonal than others
so that the pollution load varies widely throughout the year as to
character, volume and distribution.

Shrimp Processing

Alaska shrimp are smaller than shrimp caught in most other areas
with counts of 350 to 450 per Ib on a peeled weight basis.  Processing
consists of sorting out small scrap fish and debris (caught in the trawls
with the  shrimp) and mechanical peeling with or without a quick steam
precook.  The precook requirement depends on the type of peeler used.

After peeling and washing the shrimp are packed for freezing or
canning.

Since 1969 shrimp processing has been by far the major operation at
Kodiak and its relative importance is still increasing in 1971.  There
are now six shrimp processors, all in the group southwest of the boat
harbor with major producers at the southwest end of the line.  While
both canning and freezing operations are  conducted,  from a pollution
standpoint there is little difference in the character or amount of
waste  generated as a fraction of the live weight.  All plants use
mechanical peelers which typically recover about 18% of the live
weight as salable product leaving  82% as  waste.  Water usage averages
about 7. 5 gals, per Ib of live weight processed but varies from 5 to 10
gals, depending on peeler design and operation and the production rate.

To evaluate the pollution load from shrimp processing,  laboratory
studies were conducted (see SECTION VII) on the distribution of
suspended and dissolved solids and Chemical Oxygen Demand (C. O. D.)
of waste fractions generated in different processing operations.  This
was  done simulating procedures with both old and new style peelers.
The  former peel raw shrimp after a preliminary aging period and the
latter use a rapid  steam cook without aging before peeling.  It was
found that with old  style peelers only 60% of the total waste solids
and 57. 2% of the total waste C. O.  D. is recoverable in the shell portion
with most of the remainder as  solubles in the peeler water.   With new
style peelers 70% of the waste  solids and C. O. D.  is  recoverable in
the shell portion.  Apparently the  precook reduces soluble losses.
                                 11

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The total C. O. D. in shrimp waste was found to be 0. 21 Ibs per Ib of
live weight for both types of peelers.  Five day Biochemical Oxygen
Demand (B. O. D. ) for the solid portion of shrimp waste approached
an  ultimate value under laboratory conditions and amounted to 48%
of the C. O. D.  How rapidly the waste may be consumed under Kodiak
Harbor conditions has not been established.

Figure 3 presents 1970  production data for  shrimp at Kodiak.  The
four plants operating in 1970 show roughly the same  seasonal variation
in pack with a minimum in May,  the molting season,  and a maximum
in July.  The monthly average for 1970 was 5.21 million Ibs live weight.
For June, July,  August and September the monthly average was 7. 20
million Ibs live weight.   The total for 1970  was 62. 6  million Ibs live
weight.  In 1971 two new processors,  one with production about equal
to the largest operator for 1970,  and another  smaller operator entered
the field, and a 50% increase in production  was planned by one other
plant.  The  projected increase for 1971 is 75% of 1970 production.

From above data the 1971 pollution load from shrimp processing at
Kodiak can be calculated at 16. 6  million Ibs of C.O.D. or 8 million
Ibs of B. O. D. per year.  Removal of solid  wastes would reduce this
load by 70%. The remaining 30% solubles are contained in 750 million
gals,  of process water per year.

Crab Processing

Since the peak of King crab production in 1967,  which amounted to
about 50 million Ibs live weight at Kodiak, this fishery declined to
about 9. 7 million Ibs in 1970.  There has been an increase, however,
in the production of smaller species,  Tanner  and Dungeness crab,
with a total  for all species of 20. 47 million Ibs in 1970 (Table  1).

King crab fishing is now restricted to the period from August through
January.  Dungeness  crab are not fished during the period January
through April and Tanner crab production is at a very low level from
June through December.  In 1970 total crab production showed a high
of 3. 58 million Ibs per month in  September with a low in May of 0. 74
million Ibs and June of 0.73 million Ibs.

In 1970 there were nine plants processing crab at Kodiak and these
were scattered along  the full length of the waterfront.  Crab process-
ing differs from shrimp in that the amount of  waste generated depends
on the type of product.  Some of  the crab is picked from the shell and
marketed as canned or frozen crab meat.  Some crab is marketed
as whole leg sections in shell and some as frozen whole crab.   Data

                                  12

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(9
8
5!
2
S
                                           SHRIMP PRODUCTION
                                                    at
                                             KODIAK, ALASKA
                                                  TOTAL FOR

                                                  FOUR PLANTS
    Jan   Feb   Mar   Apr   May  Jun   Jul    Aug   Sep   Oct

                      YEAR of RECORD
Ncv   Dec
                                                        FIGURE 3
                            13

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                             TABLE 1

          CRAB PRODUCTION IN 1970 FOR THE KODIAK AREA
                     Millions of Lbs - Live Weight
              (Source - Alaska Department of Fish and Game)
           Kodiak Area
                                       Citv of Kodiak (80%)
Month
Jan.
Feb.
Mar.
April
May
June
July
Aug.
Sept.
Oct.
Nov.
Dec.
King
1.29
-
-
-
-
-
-
1.69
3.69
2.47
1.73
1.22
Tanner
0.71
1.21
2.73
1.74
0.76
0.18
0.14
-
0.01
0.01
0.12
0.14
Duneeness
-
-
-
-
0.16
0.73
1.91
1.51
0.78
0.49
0.13
0.02
King
1.03
-
-
-
-
-
-
1.35
2.95
1.98
1.38
0.98
Tanner
0.57
0.97
2.19
1.39
0.61
0.14
0.11
-
0.01
0.01
0.10
0.11
Dungeness
-
-
-
-
0.13
0.59
1.53
1.21
0.62
0.39
0.10
0.02
Total
1.60
0.97
2.19
1.39
0.74
0.73
1.64
2.56
3.58
2.38
1.58
L1L
Total
11.81
7.75
5.73
9.67
6.20
4.58    20.47
                                 14

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from individual plants indicate that in 1970 about 69% of the total crab
marketed was as frozen or canned meat, 25% as leg sections and 6%
as frozen whole crab.  Solid wastes generated by the three different
products are 63%, 47% and 1% of live weight respectively.

To determine the total pollution load from crab processing and the
amounts of wastes generated in the principal operations of butchering,
cooking and picking a series of experiments similar to those on shrimp
processing was conducted  (See SECTION .VII). Live Dungeness crab
from Westport, Washington were used for these studies.  It is  believed
that  very nearly the same results would be obtained with other  species.
To simulate different plant practices,  some crab were cooked whole
before butchering and picking and others were butchered first,  cooking
only deviscerated bodies and leg sections.

Very nearly the same results were obtained by the two procedures.
The  total yield of meat was 31% in the first case and 33% in the second
compared with an average of about 25% in practice.  The total C. O. D.
of wastes was 0.16 and 0. 14 Ibs C. O. D. per Ib of live weight for the
two treatments.  Soluble losses in cooking and picking water were in
both cases 12% of the total C. O. D. of the waste.  Of this only about
6. 7% was cooking losses.  This is  notably much less than found for
shrimp.  Backs and viscera account for about 49%  to 50% of the total
waste C. O. D.  and the remainder,  39% is in the shell  from the picking
lines. Some studies  in 1968 on cooking King and Tanner crab showed
a similar distribution of solids and presumably of C. O. D.  (1).

The  total pollution burden,  due to  crab processing in 1970, may be
calculated  as follows:

Product                                         C. O. D.  (Ibs)
Whole crab  (20. 4 x  10  ) (0. 06)(0. 15)(0. 067 ) =       12,400
Leg  section  (20.4x10  ) (0. 25)(0. 15)(0. 56)  =     430,000
Picked meat  (20. 4x  10  ) (0. 69)(0. 15)(1.00)  =   2.110. OOP
Total                                           2, 550, 000

Of this, over 85% could be eliminated by recovery of backs, viscera
and picking line shell.

Salmon Processing

In 1970 there was a very large pack of salmon at Kodiak.  It amounted
                                 15

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to about 200, 000  48 Ib cases of canned salmon and about 2. 6 million
Ibs of frozen salmon (Table 2).  The live weight of fish processed per
case is about 83 Ibs leaving 35 Ibs of waste per case.  Total waste
from canned salmon was thus about 7 million Ibs.  Since salmon are
frozen eviscerated with heads, wastes generated from this source
would be about 750,000 Ibs in 1970.  Total salmon waste was thus
about 7. 75 million Ibs.

As indicated in Table 2 the season extended from  June 13 to September
13 with 90% of the production during July and August.  There was a
pronounced peak from July 12 to August 9 with production averaging
5, 000 cases per day and 46, 500 Ibs per day of frozen salmon for this
4 week period.  This  would amount to about 185, 000 Ibs of salmon
waste per day.

Salmon are processed at points extending the full  length of the water-
front.  From the  City  of Kodiak records water usage is about 1. 75
gals, per  Ib of salmon processed.  During the  peak season water used
for salmon processing would thus be about 830, 000 gals, per day.   The
C. O. D. of screened salmon waste can be estimated as follows:

Representative analysis:  solids, 20%; protein, 40% of solids; fats,
30% of solids.

C.O.D. of protein  (0. 20)(0. 40) 1. 35 =  0.1041b

C.O.D. of fat      (0.20)(0.30) 2. 95 =  0.177 Ib
Total  C.O.D. per Ib of drained weight=  0.281 Ib

For the 1970 season this would be 2. 2 million Ibs of C. O. D. with
50, 000 Ibs per  day during the peak period.

The volume of water associated with salmon packing and the extended
distribution of processing plants along the waterfront indicate that
complete elimination  of the pollution load by collection and processing
of both liquid and solid wastes would be impractical at this time.
Studies conducted at a salmon cannery operation at La Conner,  Wash-
ington  during the  1970 season indicate (2) that screening (40 mesh
screen) of wastes at the processing plants with collection of solids
would remove 80% to  85% of the C. O. D.  load.

Scrap Fish and Other Fishery Wastes

The principal scrap fish source is small fish caught in the shrimp
trawls. These are sorted out prior to peeling  and generally amount

                                 16

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              TABLE  2
1970 SALMON PRODUCTION AT KODIAK
             Cases Packed
Frozen Salmon
Week Ending
6-13
6-21
6-28
7-5
7-12
7-19
7-26
8-2
8-9
8-16
8-25
8-30
9-6
9-13
Total
48 Ibs each
1,781
1,232
17,508
789
14, 774
37,838
34,835
40, 006
26, 714
10.612
13, 131
5,314
514
-
205, 048
Ibs
-
95,280
74,664
27,270
77,402
257,356
392, 827
371,214
275,276
19,829
61,164
562,417
-
399, 709
2,614,408
                     17

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to 3% of the shrimp weight.  For the year 1971 this would be 3 million
Ibs.   Other sources,  such as herring and halibut trimmings, are of
minor significance.  Crab butchering waste would probably be collected
with scrap fish, but it has already been considered  in the previous
discussion.

Assuming a C. O. D. load for  scrap fish equal to that of salmon waste,
the total would be 800,000 Ibs of C. O. D.  per year.

The  Total Pollution Load
In summarizing data for individual sources, indications are that the
total pollution burden discharged into Kodiak Harbor as shellfish and
fishery wastes in 1971 will be as follows:

                                             Lbs.  C. P.P. /year
Shrimp waste                                   16, 600, 000
Crab waste                                      2, 500, 000
Salmon waste                                    2, 200, 000
Scrap fish                                         800.000
Total Pollution Load                             22, 100,000

These  figures assume that total shrimp production for the year will
be 75% greater than in 1970,  and that crab and salmon processing
would be about the same as in 1970.  The increase in shrimp is based
on the  number of new peelers and may not materialize in actual
production.
                                 18

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                        SECTION V

                  PROCESS DESCRIPTION
The Collection System

The dispersion of processing plants, the diverse character of wastes,
the seasonal variation of waste generation and the  volume of wastes to
be handled during peak periods all point to a barging system  as the
most practical solution to the waste collection problem.  Other possi-
bilities such as truck hauling, fluming or pneumatic pipe lines for
transport to a processing site have  been considered but appear to
involve either much greater initial investment or much greater operat-
ing cost.  It is believed that the load could be handled by a fleet of 1 2
small barges with 1 work boat for towing to the by-product recovery
site.  Solid decked  barges with bins would be used.  Where possible,
barges would be spotted at processing plants to collect wastes as
generated.  Insofar as possible  wastes would be segregated into three
classes:

1.  Shrimp peeler waste.

2.  Crab picking line waste.

3.  Fishery waste (includes crab butchering waste).

Barges could be compartmented where simultaneous collection of more
than one class of waste was needed.  Scrap fish from shrimp trawls
and crab butchering waste would be collected on a  total recovery basis.
Salmon wastes would require screening  at the  processing plants before
collection.

It appears likely that the entire  barging  operation could be contracted
to one  of the towing companies.   Existing small barges could probably
be used so that deck bins  would be the only investment.

Site Location

Criteria for site location  used in the study have been as follows:
1.  Availability of land.

2.  Adequate size to accommodate recovery plant,  fuel and product
storage and dock facilities with possible expansion to include secondary
liquid waste treatment.

3.  Location compatable with collection  system to  minimize  transporta-
tion costs.

                                 19

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4.  Availability of utilities.

There appeared to be no site along the Kodiak waterfront which would
meet all of these criteria.  The site which has been selected is at the
southern tip of Near Island directly opposite the breakwater at the small
boat harbor.   This site is owned by the City of Kodiak and  is presently
unimproved.   The available area is ample for the by-product recovery
plant and any foreseeable expansion.  The topography is reasonably flat
with an average elevation of 20 - 45 ft above low tide level. Site im-
provement costs should therefore be reasonable.

There is water on Near Island which by impounding  should be adequate
for the by-product recovery plant.  If supplementation becomes neces-
sary barge transport is feasible.  A diesel generator installation is
planned for electric power.  Waste  heat from the generator would
supply a substantial part  of heat needed for the protein extraction
process.

By-Product Recovery Process

Crab and shrimp shell would be unloaded from barges by pneumatic
pipe line.  It would be coarsely ground with a hammer mill and passed
to continuous  alkali extraction units in which the shell proteins would
be  solubilized and extracted by dilute NaOH passing through the units
countercurrent to the  shell. Final  sections of the units would  be used
to wash the extracted  shell and the NaOH would  be added at several
points to maintain sufficient alkalinity for complete  protein extraction.
Average extraction temperature v»uld be 140°F and residence times
would be about 2 hours for crab waste and 1 hour for shrimp waste.
Laboratory and pilot plant  studies indicate that these conditions repre-
sent an optimum balance  between efficient protein extraction and
minimum protein degradation.  Other factors such as equipment
design, alkali concentration and liquor-to-solids ratio will be  of
influence in actual plant operation.

The sodium proteinate extract liquor would be clarified and treated
with dilute HC1 to a pH of about 4. 0 precipitating the protein.   The
slurry of precipitated protein  would pass to a centrifuge for dewatering
and washing;   the washed cake would be dried and bagged.

The extracted shell would be  dewatered with a screw press and shipped
in  bulk to either a Puget  Sound port for conversion to chitin and
calcium chloride or to Alaska ports for use as a soil fertilizer and
liming agent.  Burning to yield heat and lime is also possible.
                                  20

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Centrifugate liquor from protein recovery containing 2% to 3% of the
C. O. D. of collected wastes would be discharged to harbor waters  or
ultimately be subjected to secondary treatment.

Fishery wastes would also be pneumatically unloaded and  wet ground
to a gurry.   This would be processed with dilute NaOH in  a concurrent
unit to dissolve the protein.  The treated waste would be screened to
remove bone and centrifuged to remove oil.  These products would be
further processed to meet  market requirements. The clarified
protein liquor would be neutralized and evaporated to about'50%  solids.
The product  would be similar to the "fish solubles" now produced from
fish meal operations.
                                 21

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                        SECTION VI

                 POLLUTION ABATEMENT
The collection system and waste processing plan described previously
would completely eliminate  discharge of solid fish and shellfish wastes
into Kodiak Harbor.   The effect on the pollution load would be as shown
in Table 3.

                         TABLE 3
                     POLLUTION LOAD
                        Lbs per Year

                                  C. O. D. Removed     Residual
  Waste        Total C.O. D.         In Solids	      C. O. D.
Shrimp Waste    16,600,000          11,100,000        5,500,000

Crab Waste       2,500,000           2,000,000          500,000

Salmon Waste     2,200,000           1,870,000          330,000

Scrap Fish          800.000             800,000        	-0;	

      Totals     22,100,000          15,770,000        6,330,000

Without secondary treatment of effluents from the protein recovery
process, about 2% of the C. O. D. in solid shrimp and crab waste
would be discharged as nonprecipitated protein.  This would amount
to 260, 000 Ibs of C.O.D.  per year.  Overall pollution abatement
would thus be 15. 770.000 - 260. OOP  = 70% of the present pollution
                   22, 100, 000
load.   This is essentially all that could possibly be accomplished  by
elimination of solid waste discharge.

If elimination of the  residual 30% of the C. O. D. becomes obligatory,
by new Federal  and  State of Alaska  laws,  collection and secondary
treatment of  liquid wastes would be required.  Table 4 shows the
volume of the water  used  by processors which would be roughly
equivalent to liquid wastes.  This would involve an industrial sewer
the full length of Kodiak waterfront.   Possibly a separate system
could be constructed at Gibson Cove.

Also the sewer and treatment plant could be combined with a sanitary
sewer  system for the City of Kodiak.  These possibilities are beyond
the scope of the present study.   It can be said, however,  that the


                                  23

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                                           TABLE  4


                    WATER USAGE BY PROCESSORS AT KODIAK

                                     Millions of Gals./Mo


                                     1969                                       1970              T°*f
          Mar  Apr   May  June  July  Aug   Sept  Oct   Nov   Dec   Jan   Feb   Mar   Apr   May  15 Mo


East
  Point   13.4  10.6   9.0  18.1  18.1  20.7  17.8  12.8  19.0  11.4   19.4  23.2   24.4   28.1   14.1  256.2
                                           Shrimp Canning Only

King
  Crab
  Inc      3.1  11.2  11.8  11.7  12.0   3.1   1.8   6.9   3.8   0     0     0     0     0     0     70.4
                         Crab             Salmon Canning                 Herring

B&B Fish-
  eries    10.2  10.5  10.1   3.3   6.0   8.8   9.3   8.9   5.9   4.9    9.3   6.2    7.9    9.8    3.0  114.1
                        All species                                    Herring

Reefer
  King     0.5   9.2  10.5   5.3   0     1.5   2.9   1.9   1.6   2.4   10.3  10.8   11.4   11.9    2.7    82.9
                                         ,  Mostly Shrimp

Ursln Sea
  Foods   2.3   1.2   0.2   0.2   0.3   1.9   1.8   2.0   0.5   2.5    2.4   0.8    2.1    1.0    0     19.2
                                              Crab

Princess
  R ox-
  anna     2.8   4.2   3.3   2.1   3.9   3.0   3.8   3.2   0.5   3.5    5.6   5.8   11.8    3.3    1.1    57.9
                                              Crab

Klnnear &
  Wendt   8.0   5.6   3.6   7.5  11.0  10.2   7.8   4.0   7.0   4.6   10.0   8.4    9.3   10.3    4.0  111.3
                                       Shrimp freezing and canning

Northern
 Processors 0     0     0     0.6   2.1   2.8   2.7   1.4   0.2   0.6    0.6   0     0     0     0.2    11.2
                                       All species except Shrimp

Martins
  King
  Crab     1.5   1.6   1.2   0.7   0.7   1.0   1.1   1.1    0.2   1.7    1.8   0.7    1.9    2.4    0.4    18.0
                                             Crab

Pt. Che-
  halls     0.7   1.1    1.8   0.6   3.3   3.8    3.1   1.5    0.6   1.0    1.2   1.2    1.7    1.6    0.3    23.5
                                      Dungeness Crab Mostly

Alaska
  Packers  0     0     0     0     0     0     5.7   6.4    1.2    0     0     0     0.1    0     0     13.4
                                              Salmon

Columbia
 Ward     0.1   0     0.1   0.6   1.7   3.2    1.1   2.1    0.5   0.5    1.1   0.1    0.2    0.1    0.2    11.6
                                             Canned King Crab Only

Whitney
  Fldalgo  2.3   4.2    2.6   0.1   1.5   4.3    3.2   1.7    0.1    0     0     0     1.0    6.4    4.9    32.3
                                             Crab and Salmon

Total     44.9  53.2   53.6  47.0  60.3  73.2   63.4  48.8   44.2   36.9   61.7  57.2   71.8   74.9   30.9  822.0
                                                     24

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problem would be insolvable,  or at least exceedingly difficult, without
prior elimination of solid wastes.
                                   25

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                         SECTION VII
                 LABORATORY INVESTIGATIONS
Information presented in this section covers typical experimentation
which has been conducted in the laboratories at Seattle, Washington.
Much of the data is taken from progress reports submitted during the
course of the study.  Some  data from prior reports is included to
illustrate investigative procedures.

Laboratory investigations included protein recovery from King crab
butchering waste and King crab picking line waste.  Losses in wash
water from the screening of crab wastes were measured.   Similar
investigations were conducted on Dungeness crab picking line waste.

The recover ability of protein from NaOH-protein rich solution  by
isoelectric precipitation with HC1 was investigated.

Factors influencing protein quality and rate of protein extraction from
crab and shrimp waste have been investigated.  C. O. D., B. O. D.
and soluble waste  losses have been determined for shellfish waste.

Salmon offal was investigated for protein extraction and solids losses
on screening.

Figure 4, a ternary diagram showing approximate shellfish waste
compositions, is a useful representation for calculation of changes
in extraction operations and comparison of product yields.   The point
shown for Red crab represents the whole animal.  It is not pertinent
to the Kodiak situation but illustrates possible application of the protein
extraction process in other localities.  Red crab is a small pelagic
crustaceous species occurring in large swarms in temperate and sub-
tropical ocean waters.  Harvesting for human food has been proposed  (3),

King Crab Butchering Wastes

About 200 Ibs of King crab butchering waste were collected by one of
the processing plants in Kodiak,  frozen and sent to Seattle.  Analyses
and processing experiments on this material have been conducted.

The material as received (frozen in 30 gal. plastic pails) was very
inhomogeneous,  consisting  of carapaces,  gills, blood and viscera,
all in unground condition.  To obtain an approximate analysis, about
                                  27

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                                                           Chitin
                                                                         FIGURE 4
                                                                  COMPOSITION  OF WASTES
                                                                        BY PERCENT
00
               CaC03
              & Other
                                                                                        Protein

-------
1/2 Ib of material was selected, using ratios previously determined
from  butchering whole crab,  to represent the entire waste.   This was
ground with a measured volume of water in a Waring blender and
analyzed with results as follows:

    Solids:  (corrected for added water)
                 26. 6            26. 1        Average 26. 3%

    Ash: (dry basis)
                 32.4            32. 0        Average 32. 2%

    Nitrogen: (dry basis)
                  8.00    7.96   8.06        Average 8.0%

    Fat: (dry basis)
                  8.17           8.36        Average 8.3%

The probable composition of  the waste on a dry basis can be calculated
from  above  data to be:

    Ash         32%             Fat        8%
    Protein     48%             Chitin      11%

This assumes 6. 9% nitrogen  in chitin and 15. 0% nitrogen in protein.

Previous studies (4) on crab  picking line wastes (all species) have
indicated that these materials can be wet-ground to 1/8 to 1 /4 mesh
and collected on a 40 mesh screen with very little loss  (less than 1%)
of suspended solid materials.

Two Ibs of King crab butchering waste were wet-ground in a Hobart
garbage grinder and collected on a 40 mesh screen.   Material passing
through the  screen and solids collected on the screen were separately
analyzed with results as follows:

Total Solids:
                 Retained on 40 mesh         1 36. 0  grams
                 Through 40 mesh            100.5  grams
                 Percent through              42. 6  %

Fat:
                 Retained on 40 mesh           1. 7  grams
                 Through 40 mesh              8. 8  grams
                 Percent through              83. 7  %
                                 29

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Protein:
                 Retained on 40 mesh
                 Through 40 mesh
                 Percent through
60. 0 grams
62. 7 grams
51.1 %
B. O. D. of Effluent (estimated from analysis) = 13, 000 ppm

It is apparent from the analyses that crab butchering wastes could
not be handled in the above manner if a high degree of pollution abate-
ment is to be achieved.   Accordingly,  an experiment was conducted
on the whole  waste to determine its  behaviour in the alkaline extraction
process.

Selected frozen waste, 250 grams [protein =  250(0. 263)(0.48) = 31 grams]
was mixed with 400 grams of water  and ground a few seconds in a
Waring  blender.  A solution of 10% NaOH (79 grains) was then added
and the  slurry was stirred mechanically at 60° C for 1 hour.   The solid
matter was then collected on a Buchner funnel.  Water and NaOH were
again added to the solid residue  and it was re extracted at 60 °C for
1 hour as before.  Solids were again collected and  washed.  Extract
fractions from the treatment were analyzed with results as  follows:
                 1st extract (565 ml)
                    Total nitrogen
                    Fat

                 2nd extract (485 ml)
                    Total nitrogen
                    Fat
5.49  mg/ml
3. 75  mg/ml


0.75  mg/ml

0.02  mg/ml
The solid residue was not analyzed.  Protein extracted in the first
treatment amounted to:
                 5.49/1000 x 565/0.15
20. 7 grams
and in the second:
                 0.75/1000x485/0.15   =     2. 44 grams

About 90% of the total extracted protein was obtained in the first
treatment.   The second treatment probably could have been omitted
and the residual protein removed by simple washing.  Total protein
recovery was only 75% of that calculated from the waste analysis.
This probably represents nonprotein nitrogen in viscera.  Similar
                                 30

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results have been obtained on salmon waste.

Fat removed in the first treatment was 2. 12 grams and in the second
0.0097 grams.  The first treatment was practically quantitative.

The amount of alkali consumed in the extraction treatment was
determined by potentiometric titration of a sample of the first extract.
Fourteen ml of 1.0389N HC1 were required to the isoelectric point
(pH = 4. 0) for a 50 ml sample.  From this a NaOH consumption of
13. 6 Ibs per 100  Ibs of protein in the waste may be calculated.

Protein recovery by isoelectric precipitation from butchering waste
extracts shows lower recovery than from picking line waste extracts.
Fat appears to be thoroughly emulsified in the alkaline extract,  but
may be separable by centrifugation at some intermediate pH between
that of the extract (about 13.0) and that at which protein precipitation
begins (about 5. 5).

Dungeness Crab Protein

During August, 1970, an extended study of the alkali extraction process
as applied to Dungeness crab picking line waste  was  conducted.  Nine
extraction runs were conducted using three mixer charges with 45 Ibs
of crab waste per mixer in each run.  Each batch was subjected to
two extraction treatments using 6. 75 Ibs of 10%  NaOH solution,  0. 75
Ibs of sodium bisulfite and 50 Ibs  added  water per extraction^   The
first extraction was at 60° C for 1. 5  hours.  Following this the extract
was drained from the shell, a new charge of 6. 75 Ibs 10% NaOH and
50 Ibs  water was added and extraction conducted for  1 hour at 60° C.
The second extract was drained to the sewer  in these studies since
trial experiments showed that its  protein content did not warrant
recovery in pilot plant operation.

Following the second extraction the  shell was washed with water four
times in the mixers, drained and  refrozen for possible chitin isolation
at a later date.  The first extract liquor was  neutralized to pH 4. 0 with
dilute HC1 to precipitate protein.   This was allowed to settle overnight
under refrigeration.  The supernate, amounting to about 3/4 of the
total volume,  was decanted and the precipitate was twice washed with
water by reslurrying,  settling and decantation.  The washed precipitate
was collected on  a Buchner funnel and frozen in  bricks 8x10x2 inches
for storage.  About 150 Ibs of frozen cake were  obtained from the  nine
runs with an average solids content  of about 20%.  Ash on a representa-
tive sample amounted to 1. 02%.   This material was used for spray
                                 31

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drier performance studies, feeding experiments,  and evaluation in
pet food formulations.

Recoverability of Protein by Isoelectric Precipitation

Results from earlier experiments in July,  1969, and prior indicated
that the solubility of alkali extracted protein at its isoelectric point
would be about 5 grams per liter (0. 5%).  To attain 95% protein re-
covery would thus require a protein concentration in the extract of
10%. This placed emphasis on the need for countercurrent treatment
in order to build up the protein concentration in the extract to the
desired level.

Subsequent studies have shown that protein solubility at the isoelectric
point (actually,  the pH of minimum solubility) is to some degree
affected by the severity of the alkali treatment and to a very large
degree is a linear function of the salt concentration.  Since there is
a minimum alkali combining capacity of about 10% for the extracted
protein equivalent to  about 14. 6% of the protein as salt on neutraliza-
tion, it is not possible to increase the protein  concentration without
increasing the salt concentration proportionally.  One could,  of
course, consider desalting procedures such  as dialysis,  reverse
osmosis or ion exchange, but these would not be economic in the
process.   In addition, the added time of treatment to achieve high
protein concentrations in the  effluent would result in more degradation
and more isoelectric protein solubility.

Preceding conclusions point to an extraction process in which alkali
concentration,  total alkali used and time of contact are all minimized.
In recent  experiments these objectives have  been  approached and
results have  been encouraging.  In one experiment an isoelectric
protein solubility of 0. 25% was attained at a  salt concentration of
1. 3%.  This  would amount to  a protein recovery of 97. 2% from an
8, 9% protein solution, assuming minimum alkali consumption.

The use of sodium hexametaphosphate to complex and precipitate
additional protein from the  supernate as suggested by Mr. John
Spinelli (5) of the Seattle  National Marine Fisheries  Service also
shows  considerable promise.  In one experiment protein  solubility
was reduced  to 0. 07% representing a recovery of  96. 5% from a 2. 37%
protein solution.

Factors Influencing Protein Quality
In Table 5 data are presented on amino  acid  composition  of spray dried

                                  32

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               TABLE  5
        AMINO ACID COMPOSITION
OF SPRAY DRIED SHELLFISH WASTE PROTEINS

Sample
Duneeness crab protein
As received
Basis %
100% protein
Basis %
Shrimp protein
As received [ 100% protein
Basis % 1 Basis %
Casein (6)
100% protein
Basis
Lysine*
Histidine*
Arginine*
Aspartic Acid
Threonine*
Serine
Glutamic Acid
Proline
Glycine
Alanine
Cystine
Valine*
Methionine*
Isoleucine*
Leucine*
Tyrosine
Phenylalanine*
Tryptophan*
Total
*essential
5.4
2.21
5.5
10.3
3.57
2.7
12.3
4.33
4.2
4.6
0.24
5.5
1.97
4.7
6.6
4.0
4.07
1.0
6.35
2.60
6.47
12.1
4.20
3.18
14.5
5.10
4.94
5.41
0.28
6.47
2.32
5.53
7.78
4.70
4.80
1.18
97.9
6.24
2.22
6.04
6.46
2.93
3.51
13.3
3.40
5.63
5.35
not deter-
mined
4.21
1.95
3.87
6.10
2.70
3.78
0.55
8.34
2.97
8.06
8.63
3.91
4.69
17.8
4.54
7.52
7.14
-
5.62
2.60
5.17
8.14
3.61
5.05
0.73
104.52
6.02
2.31
2.41
4.45
3.81
5.88
21.90
15.71
1.16
1.47
not deter-
mined
7.91
2.75
3.91
11.07
2.72
5.46
1.00
99.94
                    33

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crab and shrimp waste proteins in comparison with casein (6).  It was
found that the compositions of the two shellfish waste proteins were
quite  similar although determined by two different laboratories using
different procedures.   They both  compare favorably with casein in
total essential amino acid content.  The  percentages of arginine and
isoleucine are significantly higher for the shellfish proteins while
casein shows higher values for valine and leucine.

Feeding tests have been conducted on rats using both the  shrimp and
crab waste proteins.   Both show marked deficiency in sulfur-containing
amino acids  which can be corrected by supplementation with  either
cystine or methionine.   Otherwise the shellfish waste proteins were
found to be equal to casein in nutritional value and there were no  toxic
effects noted.

A sulfur  balance on crab waste and on the extracted protein indicated
that most of  the sulfur  in the waste is still present in the spray dried
protein.   It  should be noted, however, that a very slight odor of  hydro-
gen sulfide has been detected during  neutralization of alkaline extracts.
Based on assays for cystine and methionine, only about Half of the sulfur
found in the protein can be accounted for. It thus appears that sulfur-
containing amino acids were present before extraction at about twice
the  level found by assay on the isolated protein.

Review of the literature (7)(8)(9)(1D)  on effects of  alkaline treatment
on methionine and cystine in proteins suggests that methionine should
be relatively stable in the treatment  but  that cystine can be largely
and irreversibly converted to lanthionine which presumably has no
nutritional value as a sulfur source.   The exact mechanism for the
reaction is not clear but the overall effect is the rupture  of disulfide
bonds with elimination  of 1  atom of sulfur and recombination of residues
in a thio  ether linkage.
Cystine:        HOOC-CHNH  -CH-S-S-CH CHNH -COOH
                            Lt    £         L*      Lt
Lanthionine:    HOOC-CHNH  -CH2-S-CH2CHNH2-COOH + S

The form of the eliminated sulfur was not clearly established.
Normally,  there is an equilibrium between cystine and cysteine
residues in proteins determined by the presence of oxidizing or
reducing conditions in the system.  The formation of cysteine with
free sulfhydryl groups may be an intermediate step in lanthionine
reaction.  If it is not, or if the sulfhydryl group can  be blocked from
combining as thio ethers,  the presence of a reducing agent should

                                  34

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be beneficial in preventing lanthionine formation.  Sulfite ion,  either
by shifting the equilibrium toward cysteine or by blocking recombina-
tion through formation of s-sulfo cysteine groups might serve  this
purpose.

Experiments by Food, Chemical and Research Laboratories, Inc.
indicate that the presence of sodium sulfite during extraction does
exert beneficial influences.  There were noted in increased  extraction
rate (rupture  of disulfide crosslinks?) and in improved color and odor
of the extracted proteins.  Analytical results suggest that reduction in
extent of cystine destruction may also have been achieved.

Cystine determinations (6) showed 1.05% in Dungeness crab protein
extracted in the presence of sodium sulfite and 0.23%  in Dungeness
crab protein extracted in the absence of sodium sulfite.  It would
appear that cystine destruction was reduced in the sulfite experiment.

Factors Determining Rate of Protein Extraction

Rate studies have been conducted on extraction of Dungeness crab and
shrimp wastes using two different procedures.  In one,  the rate at
which protein concentration approaches an equilibrium value is
measured in a batch treatment, at constant alkali concentration and
temperature.   The procedure has been found most useful to  characterize
the behavior of different wastes and to determine effects of pretreatment,
alkali concentration and temperature.  Calculation of rate constants
assumes that  the rate of change of protein concentration at the inter-
face between  shell particles and ambient liquid is proportional to a
driving force  equal to the difference between protein concentration in
shell interstices (P )  and that  at the interface (P.).
                   8                           1
                       d P./dt = K(P  - P.)
                          i          si
Further assumptions are that P. is equal to the protein concentration
in the ambient liquid and P  is equal to the total unextracted protein
dissolved in a constant interstitial volume equal to the  water content
of the moist shellfish  waste.  Values for P  can thus be calculated
from those for P. and numerical integration can be employed to obtain
the rate constant.  This is equal to the slope of the line:
loe  (P - P.)/P  /  - •  ..versus time. Typical data plots are shown
  &10  s    i    s(ongmal)                1C          c
in Figure  5  for shrimp and Dungeness crab waste using different
extraction conditions.

It was found that both  shrimp and crab wastes show an initial period
of very rapid  extraction amounting to 30% to 50% of the total protein

                                  35

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I
OH
•^_
 cs



 &
                                    EXTRACTION RATES  for  SHELLFISH WASTES
                                                         O Dungeness 1% NaCH, 60 JC
                                                           Dungeness 0.25% NaOH + Na,SO,

                                                                          55aC  2  3
                                                           Dungeness 1.2% NaOH, 80C



                                                         C Shrimp 1% NaOH,
     1.C
     0.75
                   25
                               50
   75         100


TIME IN MINUTES
125
150
                                          FIGURE  5

-------
followed by a rather sharp break and a slow extraction period which
fits the diffusion mechanism outlined above.  This is undoubtedly an
oversimplification of the true mechanism,  but serves to give a
numerical  index of the waste behaviour.  It is noted that rate constants
obtained for shrimp waste are considerably higher than for Dungeness
crab shell particles of the same size, probably reflecting the density
of the  shell. It is also noted that temperature effects are higher than
would  be expected for strict diffusion dependence of the rate constants.
Note:  Curves for Dungeness crab in 1. 0% and 1. 2% NaOH in Figure  5
are at nearly equal alkali concentrations but with 20° centrigrade
difference in temperature.   This  suggests chemical activation such
as rupture  of bonds between chitin and protein as being involved in
the process.  Based upon pilot plant extraction runs alkali concentration
does not appear to be  an important variable.  Sufficient alkali to
satisfy the base binding capacity of the protein is necessary. This
appears to be about 10 grams of NaOH per 100 grams of protein.   Also
a pH level of 12.5 or higher appears necessary for the extraction  since
sodium carbonate  solutions with concentrations up to 5% are relatively
ineffective.  Addition of sodium sulfite to the alkaline extraction liquor
may have a specific effect in increasing the extraction rate as well
as other beneficial effects.

The other  procedure for study of extraction rates has been the deter-
mination of protein levels in elution from percolation experiments
in a fixed bed diffuser type reactor.

Results from this  type of experiment are more difficult to interpret
because more variables have to be  considered such as flow rate and
alkalinity.  Alkalinity is not constant during the extraction because
unextracted protein absorbs alkali during early  stages of the experi-
ment.   A mathematical analyses of the elution process has been de-
veloped (11)(12) which allows prediction  of elution rates from rate
constants determined by the "approach to equilibrium" procedure.
The treatment would be generally applicable to any fixed bed extraction
process which is diffusion controlled and may prove to be of value
should such types of  processing become  indicated.

C. O. P.. a"d B. O. D.  oJLShellfish Wastes

In previous reporting, C. O. D. values for wastes were estimated for
chemical compositions assuming theoretical values for combustion  of fat,
carbohydrates and protein.  It is of interest to compare these with
values determined by the usual dichromate oxidation procedure (13).
                                   37

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C. O.D. values were obtained on samples of shrimp waste, crab waste,
chitin isolated from shrimp waste by alkali and acid extraction and
protein isolated from crab waste by alkali extraction and isoelectric
precipitation.  Data are presented in Table 6.

Values found are somewhat higher than those used in earlier reports.
They would indicate an even higher present pollution load to the harbor
but do not significantly affect  estimates of abatement by the by-product
recovery process.

While C. O. D. values give a measure of the oxygen consumed in
complete oxidation of organic matter it is of interest to determine
the actual extent and rate of organic breakdown by micro-organisms.

Normally,  B.O. D. values are determined by 5  day incubation of very
small waste samples in water with added mineral nutrients seeded
with micro-organisms normally present in receiving waters.  The loss
in dissolved oxygen is  determined for the 5 day period  and is taken
as a measure of the oxygen consuming capacity of the waste sample.

With solid shellfish wastes there is no a priori  reason  to assume that
wastes would be entirely consumed in 5 days.  The organic matter
(chitin and protein) is distributed throughout a more or less dense
shell matrix  which may be only slowly attacked by micro-organisms.
Further, the digestion of  chitin requires special enzyme systems
(chitinases) that may not be present in predominating micro-organisms.

To investigate some of these factors,studies of  the rate of oxygen
consumption  by  shrimp and crab shell have been conducted.  To permit
use of larger  samples  and minimize variation due to their heterogeneous
character,  experiments were conducted using 5 liter volumes of seeded
dilution water and about 200 mg solid waste.  Dissolved oxygen in the
closed system was determined at  several elapsed times up to 120 hours.
A Yellow Springs Instrument Company Model 54 Oxygen Meter  was
used.

Results are presented  in Figure 6.  For comparison,  weights of waste
used are shown on a dry basis.  With 52 mg  of shrimp  waste the rate
of oxygen consumption is  very low at 120 hours.

The dissolved oxygen consumed was (8. 5 - 3. 9) (5) equal 23. 0 mg for
(52) (0. 68) =  35. 2 mg of chitin plus protein.  This would be a 5 day
B.O. D. of 23/35. 2 = 0. 653 mg 0  per mg of organic matter or 48%
                                 38

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           TABLE 6




C.O.D. VALUES OF SHELLFISH WASTE
Weight
Sample mg
Shrimp Waste
» V
»5 >»

Crab Waste
» n
»» »»

Shrimp Chitin
5» >»
»» >»

Crab Protein
» »»
»» »»

101
110
101

109
101
112

19.5
27.0
20.5

10.2
10.2
10.2

Solids
%
25.9
25.9
25.9

67.5
67.5
67.5

93.1
93.1
93.1

100.0
100.0
100.0

CaCO3
dry basis
%
32.0
32.0
32.0

50.0
50.0
50.0

< 1.0
< 1.0
< 1.0

< 1.0
< 1.0
< 1.0

Chitin+Protein
dry basis C.O.D.
% mg 02/mg Organic Matter
68.0
68.0
68.0
Average
50.0
50.0
50.0
Average
100.0
100.0
100.0
Average
100.0
100.0
100.0
Average
1.27
1.42
1.44
1.37
1.03
1.12
1.05
1.06
1.22
1.24
1.27
1.24
1.40
1.40
1.37
1.3.8
                 39

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I
X
O

a
Ul
                                                           I	•

                                                       FIGURE 6

                                       OXYGEN CONSUMPTION BY SHELLFISH WASTE
                                                        Weights are on a dry basis
                                         48      60


                                             TIME IN HOURS
108
120

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of the C. O. D. ratio in Table 6.

With 101 mg of crab waste some oxygen was still being consumed at
120 hours.  The 5 day B.O. D.  would be (8.70-2.35)(5)  equal 31. 8 mg
for 50. 5 mg of chitin plus protein or 0. 63 mg 0  per mg of organic
matter.  The ratio of B. O. D. to C. O. D. would be 0. 59.

Soluble Waste Losses in Shrimp and Crab

Fresh raw shrimp obtained from Kinnear and Wendt in Kodiak on
March 9,  1971,  were frozen and sent to the Seattle  Laboratory by
air for immediate processing.

In one experiment following practice with old style (Laitram Model  A)
peelers, 4. 0 Ibs of thawed raw  shrimp were peeled by hand using
4. 25 Ibs of water for waste preparation.  The recovered meat was
boiled 2 minutes in water,  cooled in water and collected on a 40 mesh
screen.  Cooking and cooling waters were  combined.  The  solid waste
was washed by slurrying twice in  water  and draining on a 40 mesh
screen.  The shell wash water and original peeling  water were com-
bined.  Weights, total solids, suspended solids,  C. O. D.,  B.O. D.
and nitrogen were determined on significant fractions and material
balances were computed.   Data are  shown  in Table  7.

The yield of picked meat was 24. 1%  of live weight which is higher than
usually obtained with mechanical peelers (18%).  B. O. D. and C.O.D.
values on peeling and wash water  and cooking and cooling waters were
very high,  reflecting the use of only 0. 5 gals,  of total processing
water per Ib of raw shrimp as opposed to about 7. 5 gals,  per Ib of
shrimp as an average of operating practice at Kodiak.  This suggests
that considerable reduction in water consumption might be affected
by more efficient peeler design.

The percent of the waste solids recoverable in washed shell was only
60% (57. 2% of the  C. O. D.).  A surprisingly high loss of waste solids
(28. 7%) and of C. O.D. (33. 1%) occurred in peeling  and washing water.
This should be compared with results  obtained on shrimp which were
steamed 2 minutes before peeling.

The shrimp were steamed 2 minutes before hand peeling.  Shell and
process waters were handled as in the previous experiment.  Data
are presented in Table 8.

The yield of meat was 25. 8% of the live weight, again showing im-
provement over  mechanical peeling.   C.O.D. and B. O.D.  values

                                 41

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                               TABLE 7
             WASTE DISTRIBUTION IN SHRIMP PROCESSING
                         A.  Raw Peeling
                               Analysis
 Sample

 Raw shrimp
 Washed  shells
 Cooked meat
 Cooking and
 cooling water
 Peeling and
 washing water
Sample
Raw shrimp
Washed shell
Cooked meat
Cooking and
cooling water
Peeling and
washing water
Weight
1,815
1,292
439
1,046
6,248


grams
467
236
87
44.5
113
Total
Solids
25.7
18.3
19.8
4.26
1.81

Solids
total
100
50.5
18.6
9.5
24.2
Suspended
Solids



0.43
0.49
Distribution

waste
60.0

11.3
28.7
C.O.D.
ppm
304,000
173,000
267,000
36,300
23,900


grams
552
224
117
38
130
5 Day
B.O.D. N
ppm ppm



18,000 5,850
9,800 2,180

C.O.D.
waste

57

10
33
                                     42

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                  TABLE 8
WASTE DISTRIBUTION IN SHRIMP PROCESSING
           B. Peeling after Steaming
                 Analysis

Sample
Raw shrimp
Washed shells
Cooked meat
Cooking and
cooling water
Peeling and
washing water

Weight
grams
1,818
1,325
470
2,563
5,865
Total
Solids
25.7
20.1
21.4
1.58
1.24
Suspended
Solids
%



0.37
0.63

C.O.D.
304,000
173,000
267,000
19,200
17,500
                                           5 Day
                                           B.O.D.    N
                                             3m    ppm
                                           9,600   2,500
                                           7,800   1,680
                Distribution
          Solids
C.O.D.
Sample
Raw shrimp
Washed shells
Cooked meat
Cooking and
cooling water
Peeling and
washing water
grams
467
267
101
40.5
72.8
total
100
57.2
21.6
8.7
15.6
waste

70.2

10.7
19.1
grams
505
254
136
34
84
waste

70

10
23
                        43

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for process waters were considerably lower than for raw peelings.
Total soluble losses were  30%  of the initial solids as compared
with  40%  for raw peeling.  It appears that the initial steaming
coagulates and prevents loss of some solubles.   In this experiment
70% of the initial solids or C. O. D. was recovered  in the washed
shell.

Three whole live Dungeness crab were brought to the laboratory from
Westport, Washington.  They were cooked 15 minutes in 2 liters of
water using 50 grams of salt.  The cooked crab were drained hot,
then cooled in a refrigerator and weighed.  After cooling, the crab
were  butchered and weights of  different portions were determined.
These were then analyzed for solids, C. O. D. and other factors.
Data  are presented in Table 9.

The yield of picked meat amounted to 31. 2% of live weight which
is higher than normal plant practice.  Total solids  recovered, in all
fractions, after correction for added salt, amounted to 27. 2% of live
weight indicating full recovery.  Solids in waste  fractions amount to
74. 6% of the total with only 2. 4% in picking wash water.  The remainder
would be recoverable either as butchering waste to be processed with
scrap fish or as shell.

C. O. D. values as Ibs per 100 Ibs live weight for backs and picking
line shell have been calculated from previous experimental data
reported in  Table 6.  Values for other  waste fractions are calculated
from present data.   The total C. O. D.  load in all waste fractions
amounts to 15. 8  Ibs of C. O. D. per 100 Ibs of live weight.   Of  this,
5.9 Ibs or 37.4% would be recovered as picking line shell and 7.9 Ibs
or 49. 8% as backs and viscera.  The remainder  2.  0  Ibs or 12. 8%
would be lost in cooking and wash water.

Preceding data indicate that pollution abatement  from crab processing
by recovery of shell and viscera is considerably more effective than
collection of solids in shrimp processing.   Parallel experiments
on King and Tanner crab have not been conducted but there  is no
reason to expect that significantly different values  would be obtained.

In another experiment,  3 Dungeness crab were butchered live and
only legs and bodies were cooked.  Data for this experiment are
presented in Table 10.  They are in substantial agreement with the
whole cooked crab experiment.  Solids recovered were 27. 5% of live
weight.  Total C. O.D. of waste was 15.35 Ibs C.O. D. per  100  Ibs
of live weight  of which 13. 54 Ibs or 88% is recoverable in backs,
viscera and picking line shell.

                                 44

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     TABLE  9



COOKING WHOLE CRAB
Live
Weight
Sample grams
Whole crab
No. 1 1,090
No. 2 1,045
No. 3 965
Total 3,100
Legs and
Bodies
Backs
Viscera
Picking Line
Shell
Leg Meat
Body Meat
Cooking Water
Viscera + Wash
Water
Picking Water
Total
Cooked
Weight
grams

982
973
900
2,855
1,743
190
530
615
563
404
2,150ml
2,280 ml
4,000 ml

Total
Solids C.O.D.
% ppm




(27.2%
of live
weight)

60.2

55.8
22.6
21.4
2.2 13,600
6.3 80,400
0.5 8,400

Solids C.O.D.
grams






114.3

353.0
127.0
86.5
47.3
143.7
20.0
891.8
%of Ib/lOOlbs
total Live Weight





13.6 ( 1.96)

41.8 ( 5.90)
15.1
10.3
5.6 0.94
(mostly
salt)
17.1 5.90
2.4 1.08
105.9 15.78
        45

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                               TABLE 10

                       LIVE BUTCHERED CRAB
Viscera +
 Water

Cooking
 Water

Picking
 Waste

Wash Water

Leg Meat

Body Meat

  Total
                Live    Cooked    Total
                Weight    Weight   Solids   C.O.D.
                                          ppm
                                      Solids
Sample
Whole crab
No. 1
No. 2
No. 3
Total
Backs
grams

815
923
980
2,718
183
grams '


& 	 .

1,413
(legs & bodies)
27.5 of
live weight
57
.8
2,280
         2,520ml  1.1


          540ml 55.8

         4,000 ml  0.3

          465    23.3

          322    21.6
                                   grams
                                                  106
5.3     67,200   121
         7,600    28


                302

         7,600    12

                109

                JZQ_

                748
                         %of
                         total
16.2


 3.7


40.3

 1.6

14.6
           C.O.D.
         Ib/lOOlbs
         Live Weight
                                           14.2     (  2.07)
  5.60


  0.70


( 5.87)

  1.11
                                          100.0
          14.35
                                   46

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Salmon Offal

Samples of salmon offal as discharged into Kodiak Harbor by Columbia
Ward Fisheries and B & B Fisheries were sent to the laboratories in
frozen condition.  This material was used for processing studies.

A sample of thawed waste was ground in a home-size garbage disposal
unit without added water.  The gurry obtained was analyzed for solids,
fat,protein and ash.   Results were as follows:

          Solids          20. 6%        (as received)
          Fat             30. 3%        (dry basis)

          Protein         40.0%        (dry basis)

          Ash            21.0%        (dry basis)

A mixture was prepared from 1, 109 grams gurry, 200 ml 10% NaOH
and 691 ml water.  This was heated for 1  hour at 60° C with a mechan-
ical stirrer.   The solid residue was then collected on a filter, washed
with 100 ml of water and  dried.  Yield 38. 8 grams.  It consisted of
fine bone fragments with  a small amount of clam and mussel shells.
The extract solution (1, 800 ml) contained 8. 57 mg nitrogen per ml
or 15. 4 grams total.  This is equivalent to 96. 5 grams of protein
(N x 6. 25) or 100% of that calculated for the starting material.

A 50 ml sample of the extract solution was titrated conductimetrically
with standard HC1.  It showed an alkali consumption of 18 grams of
NaOH per 100 grams of protein.  Also, about 37% of the added alkali
was unconsumed.  Accordingly a second extraction was conducted in
the same manner with 0. 75% NaOH instead of 1% as used before.
Titration of the resulting extract showed a slightly lower alkali
consumption per unit of protein with 21. 5% of the added alkali un-
consumed.  Protein in the extract liquor was 107. 8 grams or 98%
of the initial protein.

Extract liquors were adjusted to pH 4.  0 with dilute HC1 yielding a
good protein precipitation which filtered readily with a clear filtrate.

Additional grab samples of salmon waste collected during the run at
Kodiak were sent to Seattle frozen in 3 gal. plastic pails.  They varied
widely in solids content from nearly 0% to about 21%.  A  sample
containing a maximum of solids was ground in a garbage  disposal unit
and analyzed for solids yielding 20. 7%. The  dried material was
analyzed with results as follows:


                                  47

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          Fat             30. 3%
          Protein         42. 8%

          Ash             21.0%

          Calcium         3. 4%
          Phosphate       10.5%

The ground wet material was slurried with 700 ml of 1% NaOH and
digested for 1 hour at 60° C using mechanical stirring.  It was then
filtered yielding 1, 800 ml of extract and 38. 8 grams of residue (dry
weight).  The extract contained 53. 5 mg protein and 27. 2 mg of fat
per ml.  A material balance for the extraction shows  98% recovery
of protein and 70% recovery of fat with 81% of the ash in the dried
residue.

The extract was adjusted to pH 4. 0 with HC1, to cause isoelectric
precipitation of protein,  and filtered.  Analyses of the filtrate showed
the following:
          Total volume     2, 085    ml

          B. O. D.         11,750    ppm

          C.O. D.         11,920    ppm
          Protein             21. 4 mg/ml

          Phosphate          800    ppm

Protein recovery by isoelectric precipitation was found to be only
53. 5%.

This is much lower than recoveries which have been obtained from
alkali extracts of crab and shrimp waste which consistently show
85% to 90% recovery.  Attempts to improve recovery by precipitation
of a polyphosphate complex or by lime addition were only  slightly
effective (visual appraisal).   It was concluded that autolysis of the
waste by action of visceral enzymes was probably responsible.  It is
also possible that a substantial part of the nitrogen in the  filtrate was
nonorganic nitrogen.  This is supported by B.O. D. and C.O.D. values
which are only about  1/2 of values calculated from the assumed protein
content.

For comparison with data on Kodiak salmon waste, a sample of waste
from a La Conner, Washington operation was  subjected to similar
treatment.
                                48

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Analyses of a ground slurry prepared as with Kodiak waste was as
follows:

          Solids          21.8 % (as received)

          Fat             20. 4 % (dry basis)

          Protein         61. 2 % (dry basis)


Thirty two Ibs of this waste was extracted with 1% NaOH for 1 hour at
60° C and passed through a 40 mesh screen.   Thirty four Ibs of extract
and washings and 162 grams (dried) of residue  were obtained.  The
residue contained 5. 0% nitrogen (31. 3% protein) and 62. 9% ash.  It
amounted to only 5.1% of the original  solids.

The extract contained 16. 3% solids, 110. 6 mg protein per ml and
33. 5 mg fat per ml.  Total recoveries of 88% of original protein
and 80% of original fat are indicated.  These results probably reflect
sampling  error  since the ground slurry was not homogenous and there
should be no losses in the digestion treatment.

Precipitation tests were conducted on small aliquots of the extract
with results even less satisfactory than on Kodiak salmon waste.

Experiments on fat removal using a continuous Westplalia separator
were more successful.   After adjusting to pH 6. 0 and passage through
the separator the fat content of  the extract was reduced from 3. 35%
to 0.48%.  Small scale laboratory centrifuge tests indicated  that
better separation might have been achieved at pH 8. 0.

To summarize results obtained on salmon waste to date, it is con-
cluded that alkali digestion followed by isoelectric protein precipitation
or precipitation of protein as a  phosphate complex or a calcium
proteinate will not achieve a reasonable level of pollutant removal
from effluents.  The alkali digestion does appear to be of value in
homogenizing the waste so that  solid residues (bond,  etc. ) can be
removed on 40 mesh screens and  so that fat removal  can be  accom-
plished by centrifugal treatment.  This refining can be conducted at
relatively high total solids content (16%) which  is not far below that
of the dewatered waste (20% to 21%).

Evaporation of the refined extract to about 50% solids using triple
effect evaporators would yield a product similar to the "concentrated
fish solubles" already an article of commerce.   There would be no
liquid effluent from the process.  The product would be biologically
                                  49

-------
stable and could be shipped in drums or tanks to market areas.

To estimate the effectiveness of solids removal by screening, recourse
is again taken from a La Conner,  Washington operation with which we
are familiar.  This cannery operated during July,  August,  and Septem-
ber, 1970,  primarily on silver salmon.  Due to the larger  size of these
fish only about 68 Ibs are processed per 48 Ib case as compared with
83 Ibs of Kodiak operation on Bristol Bay red salmon.  Heads and
roe are separated from the waste during butchering and are separately
handled for oil and caviar production.   Spent heads are hauled to  a
dump.  Remaining solids are collected with a 20 mesh flat  type screen
and are sold without further treatment for pet food manufacture.
Effluent from  the screen is discharged into the Swinomish Slough, a
tidal estuary,  discharging into Padilla Bay or Skagit Bay depending
on the tidal flow.

A summary of the season's operations shows the following:
                               % of fish (live weight)

          Fish packed                  71.0

          Eggs packed                  3. 0
          Oil  produced                 0. 5

          Solid wastes to dump         5. 7

          Waste sold as pet food        14.1

          Waste lost to sewer          5. 7

While the waste lost to the sewer was 5. 7% of fish processed it was
5. 7/29 =19. 6% of the total waste, i. e. of the fish not packed in the
can.
                                 50

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                        SECTION VIII
                          MARKETS
As the isolation of recoverable by-products from shellfish wastes is
a new process the salability of these materials in the quantities
anticipated must be considered thoroughly.

The proposed plant will be capable of producing at least 7 million Ibs
of shellfish protein plus other fisheries products.   The shellfish
portion will have a protein content of at least 90%,  and ash content
of less than 5% with the remainder being moisture.

Feeding tests have shown this protein to be of high quality,  and  ex-
ceedingly palatable to pets.

According to one major pet food manufacturer,  who conducted exten-
sive feeding tests on cats, it is a preferred protein.  This manufacturer
has indicated  a desire to purchase at least 5 million Ibs of the shell-
fish protein at from $0. 12 to $0. 20 per Ib F. O. B. Kodiak.

As a protein competitive with fish meal, which is the largest volume
high grade protein sold,  the following comparisons can be made:
There  were 458, 000 tons of fish meal (14)  available for sale in the
United States  during 1970, at an average price of $196. 50 per ton
for anchovy (65% protein).   This is $300.00 per ton ($0. 15 per Ib)
on a 100% protein basis.  While 90%  protein material calculates  to
be $270. 00 per ton or $0.135 per Ib  on an equivalent basis, the palat-
ability, low oil and ash content will make the selling price at least
$0. 15 per Ib,  with a price floor equivalent to fish meal protein.

Production of 3, 500 tons per year of protein will represent 0. 8% of
the total fish meal available for sale in the United States.

Because of the carotenoid pigment astaxanthin,  which  gives shrimp
and crab their red color, there is great interest in the use of ex-
tracted shellfish protein for hatchery trout feed. This pigment when
fed to hatchery trout causes their flesh to turn salmon  color,  a
desirable effect.  Presently limited  quantities of dried shrimp meal
are being sold to trout hatcheries for this purpose.

A concentrated supply of protein plus astaxanthin will  command a
premium price over other protein sources.
                               51

-------
A large market exists for food quality shrimp protein.  Present selling
price for this material is $0. 90 per Ib on a bond-dry basis.  The pro-
posed plant is not being designed  to manufacture products for human
consumption, however,  it is felt that  by proper  handling certain portions
of the waste load can be converted to  food grade products provided
clearance from the Food and Drug Administration can be obtained.

The use  of shellfish protein has not been fully investigated as an
industrial chemical.

There are approximately 50 million Ibs of soya  isolate (90% protein)
consumed each year in the United States at a selling price of from
$0. 22 to $0. 24 per Ib   (15). The paper coating field requires 70% of
this market while the paint, adhesive, ink and miscellaneous industries
consume the rest.

Limited  tests with a regional ink manufacturer have shown that they
can replace soya isolate with deoderized shellfish protein.  Should
this be the case in the paper coating field the potential profit of this
plant could  rise by 30% to 35%.  Further development work must be
done to establish these markets.

The markets for salmon oil are well established with fish oil presently
selling for $0. 1015 per Ib.  Over  200  million Ibs of fish oil were pro-
duced in the United States in 1970  (14). Production of 300, 000 Ibs at
Kodiak is an insignificant increase.

The market for fish solubles is also well established.   There were
90,  700 tons (14) produced in the United States during the first 10
months of 1970.  These  solubles sold  at an average price of $51. 90
per ton F. O. B.  East Coast plants.

The production of 2,000 tons represent 2.7% of the United States  produc-
tion.  Using $30.00 per ton as an  estimated selling price  F. O. B.
Kodiak and an indicated freight cost to Puget Sound ports  of $20.00
per ton,  the  F. O. B. Puget Sound  price becomes $50. 00 per ton.

Other than a small production of tuna  solubles produced at Astoria,
Oregon,  there are no other local sources  of solubles available to
Northwest consumers.  Northwest consumers import from California,
Gulf or East Coast suppliers.  The freight to the Northwest from these
points would place the product in a preferred price position.

The garden  specialty market can readily absorb the 200 tons of fish
bone meal which will result from  the production of the solubles.


                                 52

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The only other product requiring a market is the 6, 600 tons  (bone-dry
basis) of chitin-CaCO, complex.  Because of the distance between
Kodiak and the Continental United States the cost of transportation
appears to be a problem.  To help resolve this problem this material
is to be pressed to 50% solids with a bulk  density of 60 Ibs per cu
ft.  Using $10. 00 per ton bone-dry basis F.O. B. Kodiak the complex
can be shipped to the Pacific Coast ports at a delivered price of $50. 00
per ton of solids.   This delivered price could make conversion of the
complex to chitin and its  derivatives economically possible.

There are several  companies looking at the possibility of building a
plant  in the  Puget Sound area to convert the complex to chitin de-
rivatives.  It is likely that such a plant will be  built once  a source
of raw materials is guaranteed.  The Alaska market for the  complex
exists as a liming agent - soil amendment.  Test runs at the Palmer,
Alaska, experiment station (16) show that this material is useful on
the acid soils of Alaska.

A price of $10. 00 per  bone-dry tone  F. O.  B. Kodiak might induce the
Alaska agriculturists to use the nitrogen-phosphorous-calcium
containing complex on their gardens  and farms.

Ready markets for the production of  this plant exist at attractive
economic returns.  Chitin derivatives have huge potential world
markets and if made competitive with other soluble polymeric
materials can sell  in the  range of $0.65 to $1.65 per Ib.  Competitive
products are carboxymethylcellulose,  polyvinylpyrrolidine,  poly-
acrylamides and others.  The markets could be proved if isolation
of chitin at Kodiak  were possible.  Work on this project should be
initiated.
                                 53

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                          SECTION IX

                  PROPOSED FACILITIES
 The proposed facilities consist of: waste collection at the shrimp,
 crab and salmon processors; transportation of the waste material
 to the by-product recovery plant;  and the by-product recovery plant.

 Kodiak has limited sites available for the by-product recovery plant.
 The sites proposed by Kodiak were inspected.  Two sites located in
 close proximity to the processing plants were too small. A third
 site located 4 miles from the processors would not permit easy
 disposal of liquid products produced in the by-product recovery.

 The site selected and recommended is located on Near Island directly
 opposite the shrimp,  crab and salmon processors (Figure 7).  The
 by-product recovery plant is to be located on Kodiak city-owned  land.
 The selected site must be no less than 2. 5 acres.  The site must
 lend itself to the construction of secondary treatment facilities.
 The site must be readily accessible for transportation of the waste
 and recovered products.

 Trucking of waste is estimated to be more costly than barging.   The
 use of barges as holding tanks for shrimp waste  reduces the invest-
ment required for storage of shrimp waste prior to transporting
 to the by-product recovery plant.

 The barging of the waste from the processors to the by-product
 recovery plant will be handled by long term contract.  The barge
 contractor will supply a minimum of 12 small flat barges and the
 required power  equipment.  The by-product  recovery plant will
 supply containers permanently mounted on the  barge.  The processors
will supply the required holding tanks and collection systems within
their own plant.   The barge contractor will handle the personnel
transportation to the Near Island site.

A barge with free draining containers will  be located at each shrimp
processor.  The shrimp processor will pump his wet shrimp waste
directly into the barge.  The barge will be removed and replaced once
or twice a day as production requires.  No holding tanks for shrimp
waste will be required at the shrimp processing plant.

Crab picking line waste will be dewatered by the  crab processor  and
held in holding tanks adjacent to the barge transfer area. No

                                 55

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Ul
                                                                                           DEPTH 20' AT END
                                                                                                   PROPOSED
                                                                                                  8" OUTFALL
                                                                                          PROPOSED
                                                                                          BY-PRODUCT
                                                                                           RECOVERY PLANT
   PROPOSED,
TRESTLE & DOCK
                                                                           MAP
                                                                  LOCATION & TOPOGRAPHY
                                                    FIGURE 7

-------
 significant deterioration of wastes in 12-24 hours is anticipated.
 The holding tank will be emptied by gravity into the barge.   Barge
 pickup will be once or twice a day as production requires.

 Scrap fish from shrimp processing and crab butchering waste will be
 held in holding tanks adjacent to the  barge transfer area.  Scrap fish,
 crab butchering waste and salmon fisheries waste may be combined
 and held in the same holding  tank.  Pickup will  be once or twice a
 day as required.

 A pier and crane will be built at the  Near Island site (Figure 8).  This
 pier will accommodate 5 small barges.   The pier will be equipped
 with a 5 ton crane.  The pier will accommodate a 3 ton capacity fork
 lift.

 The barges will be unloaded by a pneumatic unloading system.  The
 pneumatic unloading system will transfer the waste from the barges
 into holding tanks at the by-product recovery plant.  A similar system
 will be used to transfer finished bulk product directly from the by-
 product recovery plant into cargo vans on barges at the pier.

 A 500 KW diesel generator and 600 HP packaged boiler will  be located
 at the recovery plant.  These units will use No.  2 diesel as  fuel.  A
 plant and instrument air  system is included.

 The by-product recovery plant will be located in a  steel and masonry
 building 120 ft wide by 180 ft  long.  The building will be on 2 levels
 to take advantage of the  natural contour of the land.  The building will
 have a concrete slab floor.  Within the building  are the sanitary
 facilities, lunchroom, office,  laboratory and boiler room (Figure9).

 Fresh water for the plant will be obtained from  the roof of the building
 and from a holding pond constructed approximately 300 ft from the
 building.  The water will be treated as required.  The liquid effluent
 from the recovery  plant contains less than 5, 000 Ibs per day of B. O. D.,
 based on best estimate.   The dissolved material is essentially protein.
 Secondary treatment of the plant effluent is not considered at this time.
An outfall to *20 ft should be installed into the more swiftly  moving
 waters of the narrows.

 The processing facilities would consist of: a process line for scrap
fish,  crab butchering waste and salmon fisheries waste; a process
line for the shrimp waste; and a process line for the  crab picking
line waste.
                                 57

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.X
 «5>
 v£

 M
   ^fDolphin
   «0
   KH
    -I    \
     _

SM
             u
                                  NOT FOR CONSTRUCTION


                                     NOT TO SCALE

                                —
                             PLAN
                          ^-
                             Timber Decf<
                        El   \\   FT
                        ~T
                                     Cap
                               ~7
                                               -Trea+ecf
             TJ
TJ         U
                           SECTION
                           FIGURE 8


                       DOCK &  TRESTLE


               FOR THE PROPOSED BY-PRODUCT RECOVERY PLANT
                               58

-------
Ol
        m
        O
        3D
        O
        m
O
3
Si
            8
CRAB
SHELL
PRODUCT
SHRIMP
SHELL
PRODUCT
                NaOH (HO
                   O
                    P
                                                                                                 P = PUMP
                                                                                                 C=CONVEYOR
                                                                                                 S = SURGE TANK
                                                                                                  CE = CENTRIFUGE
- NEUTRALIZING
?  TANK
i)
                                                                     BAGGER
        PLAN
BY-PRODUCT RECOVERY PLANT
  PROCESS  BUILDING
                        RAMP UP
                                                           FLOOR ELEV. 40.00
                                                                                              m
                                                                      LUNCH-
                                                                       ROOM
                                                                                                                LABORA-
                                                                                                                  TORY
                                                                                                                 OFFICE
      NOT FOR CONSTRUCTION
                          FIGURE 9

-------
 The combined scrap fish,  crab butchering waste and salmon fisheries
 waste will be fed to the process unit from a 12 ft square x 14 ft high
 tapered bottom tank (Figure 10).  A variable rate screw conveyor will
 feed a grinder.  The waste after grinding is conveyed to a 5 ft  diameter
 x 20 ft long cooker where 50% NaOH is added to  solubilize the protein.
 The quantity of NaOH added is equivalent to 1% by weight of solids.
 The cooker is maintained at 60° C.

 The cooker product is pumped to a mixer equipped tank where  31%
 HC1 is added to  reduce the pH to 8. 5.  The pH adjusted waste is centri-
 fuged first to remove the oil and then to remove bone.   The oil is
 collected in drums for shipment.  The bone is dried to 6% moisture
 and bagged for shipment.

 The liquid from the bone centrifuge is reduced in moisture content to
 50% in a triple effect evaporator.   The 50% moisture material is loaded
 into drums for shipment.  A solids content of 50% has been arbitrarily
 chosen to equal  that of commercial fish solubles.  The solids content
 could be varied  to meet  trade preferences.

 The dewatered shrimp waste will be fed to the process unit from two
 12 ft square x 14 ft high tapered bottom tanks (Figure 11). A variable
 rate screw conveyor at each holding tank will feed a grinder.   From
 the grinders the waste is conveyed to parallel reactors.   Each  reactor
 line has two reactors 5 ft diameter x 20 ft long.

 In the reactors the waste is treated countercurrently with 50% NaOH.
 NaOH is added at a rate equivalent to 1 Ib of NaOH for each 10  Ibs of
 protein.   The contact time in the reactor is about 1  hour.  The reactors
 are heated with  steam and the  exhaust from the diesel generator.  A
 water wash section is provided within the second stage reactor.

 The solids product from both reactor lines is combined and conveyed
 to a heated screw press where the deproteinized shrimp waste  is
 pressed into a cake with a moisture content of 50%.  The  pressed
 cake is pneumatically conveyed either into storage or directly into
 vans on barges at  the pier.  Stabilization by removal of protein should
 permit storage and shipment of the material without significant
 deterioration.

 The NaOH-protein  rich solution from both reactor lines is combined
 with the NaOH-protein solution derived from crab shell and treated
 in a mixer equipped tank with 31% HC1.  The pH is reduced to 4. 0 to
precipitate protein.  The slurry is filtered.   The solids are water
                                 60

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    WASTE, from Barge
    unloading System
                                                                                                 50% Solids
                                                                                                 50%
       Variable rate
       Screw
       CONVEYOR
                    31% HCI
                    from Storage
                                             Oil. Storage
                                                                                                               Into 55 Gal. Drums
                                                                                                                   BONE MEAL
                                                                                                                   to Storage
                                                                                                        Bagger
                                                               P    Into 55 Gal. Drums
    LEGEND
 P = PUMP
 C = CONVEYOR
 S = SURGE TANK
 R = REACTOR ( COOKER )
 G = GRINDER
           SCHEMATIC FLOW  DIAGRAM

SCRAP FISH FROM SHRIMP PROCESSORS. CRAB BUTCHERING WASTE
       & SALMON FISHERIES WASTE, PROCESSING UNIT
NOT  FOR CONSTRUCTION
                     FIGURE  10

-------
                             EXHAUST
                 Screen
      r&
                                                                   50% NaOH
                                                                   Storage
                                                                                               H20
                                                                                               Storage
       V
           Rootes
            Blower
CYCLONE
I
1
C
Z
5
o
i
                             To  CRAB SHELL
                             Processing
                           Holding
                           TANK 1
GE . ,


-------
washed and conveyed to a steam-heated roller dryer where the protein
is reduced to 6% moisture.  Dry protein is bagged for shipment.  The
filtrate liquid from the screw press is collected and disposed of through
the outfall.

The dewatered crab picking line waste will be fed to the process unit
from a  12 ft square x 14 ft high tapered bottom tank (Figure 12).  A
variable rate screw conveyor will feed a grinder.  From the grinder
the waste is conveyed to the reactor section.

The reactor section consists of two 5 ft diameter x 20 ft long reactors
in series.  In the reactors the waste is treated countercurrently with
an NaOH solution.  NaOH is added  at a rate equivalent to 1 Ib NaOH
to 10 Ibs protein.  The contact time in the reactors is about 2  hours.
The reaction takes place at 60°C.  The reactors are heated by steam
and diesel generator exhaust.  A water-wash section is provided in
the second stage reactor.

The solids product from the reactors is conveyed to a heated screw
press where deproteinized shrimp is pressed into a cake with  a mois-
ture content of 50%.   The pressed cake is pneumatically conveyed
either into storage or directly into  vans on barges  at the pier.

The NaOH protein-rich solution derived from the crab shell is combin-
ed with NaOH protein-rich solution derived from the shrimp waste.
The combined steam processing is  described in the preceding  paragraphs.
                                 63

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                                                               o
                          50% NaOH
                          Storage
 WASTE from Barge
 unloading  System
H20
Storage
      Variable Rate
      Screw Conveyor
                                                                                                                       50% H20
                                                                                                                       Deproteinized
                                                                                                                       CRAB SHELL
                                                                                                                       to Storage
                                                                                                       LIQUID to
                                                                                                       Collection System
                                                      pH 12.5
                                                                      NaOH Protein-rich Solution
                                                                      to Neutralization Tank
    LEGEND
P = PUMP
C = CONVEYOR
S = SURGE TANK
R = REACTOR ( COOKER )
G = GRINDER
   SCHEMATIC FLOW DIAGRAM
CRAB PICKING LINE WASTE PROCESSING UNIT
NOT FOR CONSTRUCTION
              FIGURE  12

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                          SECTION X

                ECONOMIC  CONSIDERATIONS
 Based on the 1970 production figures,  13. 6 x 10  Ibs of shellfish solids
 could be collected in,Kodiak.  From this waste load,  8. 8 x 10  Ibs are
 shrimp and 3.9 x 10  are crab solids.

 However,  the number of peelers put into operation when this report
 was written has increased by 75%.  It is assumed in this study that
 they  will operate at the  same rate per peeler the others did in  1970.
 Therefore, there will be at least 15. 4 x 10  Ibs of collectable shrimp
 solids available for processing.

 Using an average of 38% recoverable protein, from shrimp  and  30%
 recoverable protein from the crab,  5. 8 x 10  Ibs of shrimp protein
 and 1.2x10  Ibs of crab protein per year can be recovered by using
 this process.  The indicated market price for  this protein  is $0.15
 per Ib F. O. B. Kodiak on a 100% solids  ba.sis making the market price
 for this product $1, 050, 000.

 The salmon waste of 1. 3 x 10  Ibs would produce 300, 000 Ibs of oil
 worth $24, 000; 200 tons of bone meal worth $40. 00 per ton, or $8, 000;
 and 900 tons of 50% solids salmon solubles worth $30. 00 per ton or
 $27,000.

 Crab  butchering waste and scrap fish associated with the shrimp
 trawls of 0. 87 x 10  solids would produce an additional 1, 600 tons
 of solubles worth  $48,000.

 The residual chitin-CaCO complex of 6, 600 tons (dry) has a minimum
 value of $66, 000 F. O. B. Kodiak for  its  lime value, and will be worth
more when markets open up for chitin as an industrial chemical.

 The total worth of these  products is  $1, 223, 000 per year.

As it  is anticipated that this facility  is to be set up along the lines
 similar to a local improvement district  and will enjoy government
financing, it therefore is necessary  to require the users to pay a
fee for waste disposal.

Many different formulae have been proposed for such fees throughout
the world.  Some are based on B.O.D. , C.O. D., or total  solids
while  others are based on water handled.
                                 65

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At Kodiak a reasonable fee should be equivalent to the annual cash
reserve required for 7-year depreciation of the plant.  The 7-year
period was chosen in consideration of the erratic history and un-
certainties of the industry and commonly accepted engineering
practice for installations of this type.  This amounts to $225,000
per year and can be based on the number of pounds of collectable
solids handled by the plant at $0. Oil /lb dry basis.

This is estimated to be 20. 6 x 10  Ibs, and is summarized on Table 11.

The costs of operating the plant (are  as follows and) are based on the
barge handling of waste to the Near Island site which will be donated
by the City of Kodiak.  The  direct manufacturing expenses as shown
on Table 12 amount to $692, 000 per year,  and are based on a plant
investment of $1, 592, 000.  Table 13.

The indirect expenses amount to $531, 000. They are figured on
20-year, 7% bonds,  with interest paid at 8% on a $500, 000 line of
credit, a cash reserve for depreciation of $225, 000 per year and
consultant and management fees of $99i 000.

The estimated profit based on these figures will be $219, 700, which
is $5, 300 less than the disposal fee of $225, 000.  This means that
this $219, 700 per year could be returned to the processors paying
the dumping fee  in its entirety,  as adequate provision has been made
by means of the  cash reserve for depreciation to completely rebuild
the entire plant in 7 years or enlarge it as the industry grows.

An alternative use for this money would be to use part of the dumping
fee and part of the cash  reserve  for depreciation to build an industrial
sewer system to treat the processing waters not handled by this  plant.

All costs estimated for this report are based on June  1971 prices.
                                 66

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TABLE 11
.SALES/YEAR
Shrimp Protein
Crab Protein
Salmon Oil
Fish Bone
Fish Solubles
Chitin-CaCO
5.8 x 106 Ibs
1.2 x 106 Ibs
3.0 x 105 Ibs
200 tons
2, 500 tons
6,600 tons
@ $
@
@
@
@
@
.15 =
.15 =
.08 =
40.00 =
30.00 =
10.00 =
$ 870, 000
180,000
24,000
8,000
75,000
66,000
$ 1,223,000
INCOME FROM DISPOSAL, FEE
Collectible Shrimp
Solids
15.4 x 106 Ibs
Collectible Crab Solids
3.9 x 106 Ibs
Collectible Salmon

Solids
1.3 x 106 Ibs

@$
@
@

0.011 =
0.011 =
0.011 =
(Use
$ 169.400
42,900
14,300
$ 226,600
$ 225,000)
       Total Income

       Total Costs
Profit Before Taxes
$1,448,000

 1,228, 300
$  219,700
                                 67

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                  TABLE 12
     YEARLY OPERATING EXPENSES
Barge
Labor
Maintenance
Electricity
Heat
Chemicals
G & A
                     DIRECT
$  132,000
   179,800
    50,000
    30,600
    58,000
   152,000
    89,900
$  692,300
Retire bonds 20
  years       $
Bond Interest
  7%
Sales  Costs
Management
Consultants
Op Capital,
  interest @ 8%
Cash reserve for
  depreciation
       INDIRECT

    80,000

    56,000
    31,000
    75,000
    24,000

    40,000

   225, OOP
Total
$
$1,
531,000
223, 300
                     Plant Cost
                        $1, 592,000
                     Operating Credit Line
                        $  500,000
                            68

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                                          TABLE  13
                       PLANT INVESTMENT - JUNE 1971 PRICES
                    (Based On 9-Month Engineering Design and Construction Schedule)
  Major Process Equipment (all prices delivered Near Island)
  NO.  ITEM
  2
  2
Baggers
Centrifuges
 20    Conveyors (installed)
  2    Driers
  1    Evaporator
  1    Filter
  4    Grinders
  2    Mixers
 19    Pumps
  7    Reactors (blenders and cooker)
  2    Screw Presses
 17    Tanks and Vessels (erected)
                                                SUBTOTAL
 Other Major Equipment (all prices delivered Near Island)

      600 HP Steam Generator with Boiler Feedwater System and Treatment
      500 KW Diesel Generator and Motor Control Center
      Instrument and Plant Air Compressor and Tank
      Water Treating Unit
      Pneumatic Unloading, Dried Shell Transfer and Loading Astern
         Installed Complete (less wiring)
      Dock Crane
      Sump Pump for Liquid Waste Collection System
      Dust Collection System
      Heat Recovery from Diesel Generator
      Small Tools (includes 3 ton fork lift and welding equipment)
Major Construction Items (Estimated)

     Building
     Pier and Approach Ramp
12   Containers for Barges (installed)
     Fresh Water Pond and Transmission Line
     Liquid Waste Outfall
                                               SUBTOTAL
                                               SUBTOTAL
     Instrumentation (for those items not included with equipment - installed)
     Millright (equipment setting)
     Electrical (labor and materials)
     Piping (labor and materials)
     Soils
     Civil (included with individual items)
     Painting, Plumbing, Carpentry (included with individual items)
     Contingency (15%)

     Engineering and Construction Management

     Process Consultants
                                              TOTAL
DOLLARS
  5,800
 56,000
 31,000
 46,000
 28,000
 17,000
  7,200
  1,200
 18,400
108,000
 80,000
 34,200
                                                                     29,200
                                                                     64,500
                                                                      3,500
                                                                      2,200

                                                                     84,200
                                                                      2,500
                                                                      3,500
                                                                     10,700
                                                                      8,000
                                                                     30,000
                                                                   152,000
                                                                    82,000
                                                                    54,000
                                                                    14,400
                                                                    14.100
                                                                                             DOLLARS
                                                                                              432,800
                                                                                             238,300
                                              GRAND TOTAL
                                                                                      316,000
                                                                                       22,000
                                                                                       59,600
                                                                                       38,800
                                                                                       68,000
                                                                                       22,000
                                                                                    1,198,000
                                                                                     180,000

                                                                                     168,000

                                                                                      46.000

                                                                                    1,592,000
                                                   69

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                        SECTION XI
            PRO FORMA BUSINESS STRUCTURE

The establishment of a pro forma business structure is necessary
to implement this study.

It is proposed that an industrial sewage disposal district similar to
local improvement districts normally used to build sewer lines and
pave streets should be formed using the offices of the City Attorney,
City of Kodiak, Alaska.

This district would be composed of the processors, each of whom
would have 1 vote, plus the City Manager of Kodiak who would have
a vote.  They would form a board of directars who would contract with
a management firm to arrange the financing,  erect the plant and hire
the plant personnel and operate the business.

The City of Kodiak would donate the land necessary for the require-
ments of the plant.  With this land the sewage disposal district can
borrow the funds required to finance  the plant by morgaging the land
and the plant.

This money could be  obtained through the  Small Business Administra-
tion, Economic Development Administration, or the Agency of the
State of Alaska empowered to make such loans.

The management firm would make recommendations to the board of
directors regarding the establishment of dumping fees and other
matters concerning the group which would be voted upon by their
board.

This district would be formed immediately so that continuity of effort
is maintained and £he time necessary to build a plant capable of
reducing the pollution load to  satisfy  Federal and  State of Alaska laws
is minimized.
                                 71

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                         SECTION XII
             ALTERNATE DISPOSAL METHODS
 Handling of the entire industrial waste load by dumping at sea has
 been mentioned as an alternate possibility.

 An economic analysis shows that it would require ocean-going barges
 and tugs.  The 12 barges required plus 1 ocean-going tub have been
 quoted by experienced towboat operators at $1, 500 per day.  With 2
 tugs it would be $2, 000 per day.

 Based on a 350-day season, the nonrecoverable costs would be
 $525,000 per year and $700,000 per year respectively.

 Another possibility, the hauling of the  waste to a sanitary landfill,
 has been explored.

 There are  50, 000 tons per year of wet waste to dispose of.

 Trucking costs are $0. 20 per ton mile.   The present landfill is
 approximately 6 miles from the waterfront.  The trucking costs
 to haul this waste would be  $60, 000 per year.  The present 120-acre
 landfill, according to the Kodiak Island Borough Comprehensive Plan (1),
 states that, "Drainage courses passing through the fill will cause
 erosion and drainage problems and increase the likelihood that Monashka
 Bay will be contaminated. "

 The 50,000 tons of wet proteinaceous waste is approximately 15  times
 the present waste load and according to recent studies, will cost $3. 50
 per ton or  $170, 000 per  year to comply with present solid waste manage-
 ment standards.

 The cost to the processors in providing the necessary dewater de-
 vices and holding hoppers is estimated to be at least $25, 000 per
 plant or  $375, 000.

 The total annual direct cost of sanitary landfill disposal would be
 approximately $230, 000.  This figure does not include any costs by
the processors for dewatering  and  holding hopper nor does it include
 any hauling costs for cover  material or treatment of fill leachate.

 The third possibility,  the welding of a sewer line connecting the
processors' plants to a primary treatment plant, is not a part of this

                                73

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contract.   However, in discussions with sanitary engineers, a capital
outlay of at least $3, 000, 000 will be required to treat the 5 million
gals,  per  day of effluent.  This does not include the costs of disposing
of the 50, 000 tons of wet solids captured by the treatment plant.

Considering the above alternate disposal methods it would appear that
the by-product recovery method is clearly the most desirable.
                                 74

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                        SECTION XIII

    IN-HOUSE IMPROVEMENTS AT PROCESSING PLANTS
Since the inception of this project, periodic visits by assigned
engineering personnel have been made to all seafood processors
operating in the City of Kodiak to discuss improvements to their
plants that would make waste collection less costly and more
efficient.

The more efficient plants use flumed water as the carrying agent for
their  wastes to a submerged outfall.   Others have multiple waste
discharges from various points without a common collection system.

The proposed plan for solid waste collection would necessitate
elimination of multiple outfalls with all wastes being collected for
dewatering and transfer to the barging system.   This would facilitate
ultimate connection to an industrial sewer  system for the remaining
liquid wastes.

Another area  where in-house improvements were  suggested is in
economy of water  usage.  The City of Kodiak does not have an
inexhaustible  water supply and shortages have been periodically
encountered.  Some plants do not adjust flow of fluming and washing
water with variation of the throughput of materials.  During periods
of slack operation water consumption per unit of material processed
can be excessive.  Automatic controls on water lines keyed to
instantaneous  production rates should be installed where feasible.
Automatic shutoff  valves on hoses used for wash down were also
discussed. In some plants flume sizes are not properly scaled to
production rates and  arrangements to minimize water needs  have
not been given proper consideration.   With possible  increased
water rates or liquid waste dumping charges on a volume basis,
these  factors would be of even greater importance.
                                 75

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                         SECTION XIV

                    ACKNO WLEDGMENTS
 The assistance of the following persons in furtherance of this project
 is gratefully acknowledged:

 The Honorable Peter Resoff,  Mayor of the  City of Kodiak,  Alaska.

 Mr. Holland Jones, City Manager for the City of Kodiak, Alaska.

 Dr.  Murray Hayes, Associate Regional Director of the National
 Marine Fisheries Service of Kodiak.

 Dr.  Winston M. Laughlin,  Research Soil Scientist for the Alaska
 Agricultural Experiment Station at Palmer.

 Mr. John Spinelli,  Research Chemist for the National Marine
 Fisheries Service in Seattle,  Washington.

 Dr.  Sidney M.  Cantor,  Consultant F. A. O.  United Nations,
 Haverford,  Pennsylvania.

Mr. Kenneth A. Dostal, EPA Project Officer, Pacific Northwest
 Water Laboratory,  Corvallis,  Oregon.

Also many of the managers and personnel of processing plants in
Kodiak have made valuable contributions.
                               77

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                           SECTION XV

                          REFERENCES
  1.  Tryck,  Nyman & Hiyes, Kodiak Island Borough Comprehensive
      Plan 1968 - 1999. Part 2:  Kodiak Urban Area Transportation
      and Utilities Plan,  Anchorage, Alaska (1969)

  2.  Perkins, C.  E.,  Private communication.

  3.  National Marine Fisheries Service,  Private communication.

  4.  National Marine Fisheries Service Contract No.  14-17-0007-960
      Progress Report No. 4, October 10,  1968

  5.  Spinelli, John, Private communication.

  6.  Block,  R, J., Amino Acid Composition of Proteins and Foods.
      Springfield, Illinois (1945)

  7.  Horn, M. J., Jones, D. B. and Ringel,  S.  J. , J.  Biol Chem.
      138:141  (1941)

  8.   Cuthbertson,  W.  R.  and Philips,  H.,  Biochem. J. . 39:7(1945)

  9.   Lindleg,  H. and Philips, H.,  Biochem. J..  39:17(1945)

10.   Blackburn,  S. and Lee, G.  R., Biochemica et Biophysica Acta.
      19:505 (1956)

11.   Schuman, T.  E. W. .  J.  Franklin Institute.  208:405(1929)

12.   Furnas,  C. C.,  Trans American Society of  Chemical Engineers.
      24:192

13.   American Public Health Association,  Standard Methods for the
      Examination of Water and Waste Water. 12th Edition, pp 510-514
      New York,  New York (1965)

14.   U.  S. Department of Commerce, Industrial  Fishery Products.
      Situation and Outlooks (Feb. 1971)

15.   Sidney M. Cantor Associates,  Inc., Private communication.

16.   Laughlin, Winston,  Private communication.

                                 79

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                         SECTION XVI
                        PUBLICATIONS
1.  Johnson, Edwin Lee,  and Penis ton, Quintin P., "Pollution
    Abatement and By-Product Recovery in the Shellfish Industry, "
    Proceedings of the 2nd Symposium on Food Processing Wastes.
    Denver,  Colorado (March 23-26, 1971)

2.  Johnson, Edwin Lee,  and Peniston, Quintin P. , "Pollution
    Abatement and By-Product Recovery in the Shellfish Industry, "
    Proceedings of the 26th Annual Purdue Industrial Waste Conference.
    West Lafayette, Indiana (May 4-6, 1971)
                               81

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                         SECTION XVII

                          APPENDIX


 Analytical Methods and Investigative Procedures

 C. O. D. - "Standard Methods for the Examination of Water and
 Waste water, " 12th edition (1965), page 510,  American Public Health
 Association,  Inc., 1790 Broadway, New York, New York 10019.

 B. O. D. - 5 Day -  "Standard Methods" loc. cit,,  page 415.

 Solids - Shellfish Waste - 16 hours drying in air  oven at 105° C.

 Solids - Fish Wastes, Extracts,  etc.  - 16 hours,  vacuum oven, 60° C.

 Fat  - Ether extraction on dried sample in Soxhlet apparatus.

 Ash - Burn at low  temperature in platinum.  Complete ignition at
 600° C in muffle furnace to constant weight.

 Sulfated Ash - Ash as above to complete combustion of carbon, cool,
 moisten with  sulfuric acid and reheat in muffle to 600° C.

 Calcium - Ash as above, dissolve ash in dilute HC1, add ammonium
 oxalate solution and slight excess of ammonia. Digest on hot plate
 until excess ammonia is dispelled.  Cool, filter on asbestos pad in
 Gooch crucible.  Wash,  transfer  to beaker,  add dilute sulfuric acid,
 heat and titrate with standard potassium permanganate solution.

 Total nitrogen - Kjeldahl procedure - Sodium sulfate-copper sulfate
 catalyst.  Biuret Protein Analysis,  adaptation of  Technicon Auto-
 analyzer procedure N-14b for total protein to permit manual colori-
 metric tests.   Used for  protein extraction rate studies.  Standardized
 for each run against  specific protein involved using Kjeldahl procedure.

 Chitin in Shellfish  Waste - Grind  1 gram dry  samples to about 1 /8 inch
mesh.   Digest in about 100 ml 2% NaOH at 100° C 1 hour.  Filter on
medium tared sintered glass crucible.   Transfer to beaker  and repeat
 NaOH extraction.   Refilter on same crucible.  Retransfer to beaker
 and treat 12 hours  at room temperature with  100 ml 5% HC1.  Refilter
on sintered glass.  Wash with hot distilled water until  no test for
 chloride.  Dry at 110°C 16 hours  and weigh.  Check for ash and nitro-
 gen content.   Should be less  than  1. 0% and 6.  9% respectively.
                                 83

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Protein in Shellfish Waste - Determine total nitrogen.  Determine
chitin as above.  Subtract chitin nitrogen from total nitrogen and apply
factor.   (15% nitrogen in shellfish protein)

Cystine in Shellfish Protein - Protein is hydrolyzed by heating in 6N
HC1 under reflux for 24 hours.   Cystine is determined in the hydrolyzate
by Vassel's modification of the Flemming reaction  (2).

Protein Extraction Rate Studies - A sample of shellfish waste of desired
particle  size and known protein content is suspended in distilled water
contained in a round bottom flask fitted with a reflux condenser, a
mechanical stirrer, a thermometer and a sampling port.  The flask
is heated by an electric mantle controlled by a variable transformer.
When the aqueous sample suspension has attained the desired reaction
temperature, a preheated NaOH solution in amount calculated to bring
the sample suspension to the desired alkali concentration is quickly
added and  timing is started.  Small  samples (3 to 5 ml) of the suspen-
sion are withdrawn at noted times.   These are immediately filtered
and analyzed for protein by the biuret colorimetric procedure (loc. cit.).
One or more of the samples are also analyzed by the Kjeldahl procedure
for standardization.  Extraction rate constants are calculated as
described  in Section VII, page 35 and 37.

Calculation of Waste Composition - Analytical values for solids,  fat,
Kjeldahl nitrogen, and sulfated ash or  calcium are converted to a
dry basis calculating calcium or sulfated ash to CaCO ,  The following
equations are then used to obtain percent chitin and percent protein.

% Chitin + % Protein =  100 - %Fat - %  CaCC>3
(0. 069)% Chitin + (0. 150)(% Protein) =  % Kjeldahl nitrogen

A nitrogen content of 1 5% for shellfish waste protein is in better
agreement with actual analyses than the usual 16% (Protein = 6. 25 x N).
Calculated chitin values can be compared with actual yields by isolation.

Pilot Plant Extraction Studies  -  Wastes are held  frozen in a nearby
cold storage warehouse.   Sufficient waste for a pilot plant run (30 to
90 Ibs) is brought to the laboratory and ground with water using a
restaurant size Hobart garbage grinder.  The ground waste is drained
on a 40-mesh stainless screen and  transferred to one or more of
four small portable  cement mixers.

The mixers are externally heated with gas burners.   They  are equipped
with screens for  draining and thermometers.  They can be operated
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singly for batch processing or as a four stage countercurrent system.

The charge to the mixers is made up with calculated amounts of water
and 10% NaOH solution to give a desired liquor to solids ratio (usually
6 to 1} and a desired alkali concentration (usually 0. 5 to 1. 0%).   The
mixers are rotated and held at the desired temperature (50° C to 80° C)
for the desired reaction time (0. 5 to 2. 0 hours).  On completion of the
extraction stage, mixers are tilted to drain through screens  clamped
to the face.  Samples of the  sodium proteinate liquor are analyzed for
protein content (Kjeldahl nitrogen) and for unconsumed NaOH (conducti-
metric titration).  The liquor may be processed for protein recovery
by isoelectric precipitation or be advanced to another extraction stage.

Extracted solids are transferred to a Bock laundry  reclaimer centrifuge
for further dewatering and washing.  Samples are analyzed for solids
and residual protein.  Solids may be advanced without washing to another
extraction stage or may be treated for chitin recovery.
                                  85

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      i'ff union Number
                            Subject Field &. Group
                                05D
                                          SELECTED WATER RESOURCES ABSTRACTS
                                                INPUT  TRANSACTION FORM
     Organization
     Food, Chemical  & Research Laboratories,  Inc., Seattle, Washington  and
     Engineering-Science of Alaska, Anchorage, Alaska
     Title
     Pollution Abatement and By-Product Recovery in Shellfish and Fisheries Processing
 10
Authors)
Johnson,  Edwin Lee
Peniston,  Quintan P.
Braun, F.  W. , P.E.
16
    Project Designation
                                   21
                                            EPA Project #12130 FJQ (Formerly 11060FJQ)
                                       Note
 22
     Citation
 23
Descriptors (Starred First)

     Industrial Wastes*, Waste Treatment*, Water Quality Control*,  Pollution
     Abatement*, By-Product recovery*
    Identifiers (Starred Firs')
          Alaska Fisheries  and Shellfish Processing Waste Treatment & By-Product
          Recovery*   Protein recovery by alkali extraction Economics of Treatment*
 27
Abstract
Laboratory and pilot plant studies show that utilizable by-products can be obtained
from shellfish wastes produced at Kodiak, Alaska.  Alkali extraction of the
contained protein leaves a matrix of chitin and calcium carbonate.  The chitin-calcium
carbonate matrix can be converted chemically into its components.

Other fisheries' wastes found at Kodiak; salmon waste and small fish associated
with  shrimp can be liquified by alkali treatment,  partially neutralized with acid,
and converted into oil,  bone meal and 50% solubles.
The economics and pollution  abatement capabilities of the proposed plant are dis-
cussed.  The construction and operation of this plant would reduce the  yearly
pollution load from the present 22. 1 million Ibs per year of C. O. D. being dumped
into Kodiak Harbor to 6. 6 million Ibs per year of C.O.D.

Preliminary  designs are  submitted for the implementation of this process,
together with indicated markets and plan of operation.
Abstractor
     Edwin Lee Johnson
                         Institution
                          Food, Chemical  &t Research Laboratories.  Inc.
 WR:1G2 (REV JULY 19691
 WRSI C
                                                WATER RESOURCES SCIENTIFIC INFORMATION CENTER
                                                U.S. DEPARTMENT OF THE INTERIOR
                                                WASHINGTON. D. C 20240

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