Reuse of Fermentation Brines in the Cucumber Pickling …infohouse.p2ric.org/ref/15/14362.pdf ·...

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RESEARCH REPORTING SERIES

4 Environmental Monitoring 5 Socioeconomic Environmen!a! Studies 6 ? 6 Special Reports ? !J,scellant.ous Repfx ts

Scientific and Technical Assessment Reports ISTAR, interagency Energv-Enviror8rtent ResParc? 3nC De le,oL.7Yr:

Thts report has been assjgned 10 !he EY'JIRONMENTAL F NOLOGY sertes This series descr.bes rssearch performed I opsiraie lnstrumen!ation equipmep! ana methodology lo r v,ronmer;!aI &?gradatton lrom poin! an< non-poinl Sources 0 prc'rldes the new or impro.ied techr,oioc;y requNred for the Contrg! ar'3 :reatce-I c ' ooiiil:Non sources to meei erivironmer!al qualitv sta.!darOs

pi,.w m.i TECHNICAL Inruxrrons 00 REPORT rhr rctrrS? DATA heforc colnplrnnpl

I' 3 REClPl REPORT N O

5 REPcmT DATE EPA-600/2-78-207 T I T L E A N O S U S T T L E

REUSE OF FERMENTATION BRINES I N THE CUCUMBER September 1978 issuing date

E P E R F O R M I N G ORGANIZATIOH CODE

8 P E R F O R M I N G ORGANIZATION REPORT NO. PICKLING IWSTRY A U T H O R I S I

R. F. kFee ters and U. Coon*; M. P. P a l n i t h r and I 10. P R O G R A M ELEMENT NO. b l . Veltin *** N. Fehrin er***

Pickle Packers International II.CONTRACTICRANT N O 108 East Hain Street P.O. Box 31 5-803825

PLRFoRhrlNG ZRG;NIZATION N A W f A N D ADDRESS lBB610

60174 St . Charles , I L 13. T V i E OF R E P O R T A N O P E R l O D C O V E R E D _-____________----..-

I. S P O N S O R I N G A G E N C Y N A M E A N D A D O R E S Industrial Environmental Research Laboratory

U.S. Environmental Protection Agency EPA/600/12 Cinciunati, Ohio 45268

Final ReDOrt 5/75 - l.2177 Office of Research and Development 14. S P O N S O R I N G A G E N C Y CODE

i. SUPPLEMENTARY NOTES *Department of Food Science and Human Nutrition, M S t . Univ., East Lansing,MI4882&

**Vlasic Foods, Inc, West Bloomfield, M I 48033 **Detroit District Office U.S. M 48826

feas ib i l i ty of recycling spent cucunbek fermentation brine. procedures, heat treatment and chemical treatment, were used. tha t brine recycling w a s practical on a comerical scale. procedure resulted i n salt stock which were equivalent i n quality t o contkol cucumbers.

Studies were conducted t o determine the adequacy of the brine treatment

i. ABSTRACT

The project evaluated on a comerical scale the technological and economic Two brine treatment

The results showed Either brine treatment

procedures employed. s e c . was scf f ic ien t t o assure inactivation of pectinlses from nolds found to be ccTnon OF. cu:uaber f r u i t s and flowers. temperature of 7 P F or higher w a s required. tained a t 11.0 o r higher f o r a t l eas t 36 h r t o assure 99% inactivation of pectinases from the molds which were investigated.

An eco;iomic evaluation of the recycling procedures snowed a sa211 net savings

The data confirmed tha t a heat treatment of 175°F for 30

For effective cnenical treatment a brine In addition, the pH had to be main-

f o r the heat treatment procedure and a small net cost for chemical treatment. Selection of the process fo r a particular plant w i l l depend upon the local conditions

Food Processing f'(,"'.f '9' Pi

B r i n a ~ Circulation Economic Analysis Treatment

Y

- 8 O l S T R l B U T l O N S T A T E U E N T le S E C U R I T V CLASS [Tliit RIPPI]

-lo. SECURITY CLASS (Thtl P W l Unclassified

Unclassified Release to Public

I

EPA-60012-78-207 September 1978

REUSE OF FERMENTATION BRINES IN THE CUCUMBER PICKLING INDUSTRY

by

R. F. McFeeters and W. Coon Department of Food Science and Human Nutrition

Michigan State University, East Lansing, Michigan 48824 and

M. P. Palnitkar and M. Velting Vlasic Foods, Inc., West Bloomfield. Michigan 48033

and N. Pehringer

Detroit District Office, U.S. Food and Drug Administration Detroit, Michigan 46826

Grant No. 5-803825

Project Officer

Harold W. Thompson Food and Wood Products Branch

,Industrial Environmental Research Laboratory Corvallis Field Station

Corvallis, Oregon 97330

INDUSTRIAL ENVIRONMENTAL. RESEARCH LABORATORY OFFICE OF RESEARCH AND DEVELOPMENT

U . S . ENVIRONMENTAL PROTECTION AGENCY CINCINNATI, OHIO 45268

DISCLAIMER FOREWORD

This report has been reviewed by the Industrial Environ- mental Research Laboratory-Cincinnati Food and Wood Products Branch, U . S . Environmental Protection Agency, and approved for publication. Approval does not signify that the contents necessarily reflect the views and policies of the U . S . Environ- mental Protection Agency, nor does mention of trade names or commercial products constitute endorsement o r recommendation for use.

When energy and material resources are extracted, processed, converted, d used, the related pollutional impacts on our environment and even on our alth often require that new and increasingly more efficient pollution ntrol methods be used. The Industrial Environmental Research Laboratory- ncinnati (IERL-Ci) assists in developing and demonstrating new and improved thodologies that w i l l meet these needs both efficiently and economically.

This report shows the results of a comercinl evaluation of the reuse "spent brine" in the cuctnnber pickling industry. It appears that the

This can lead to important cumber pickling industry can economically recover nnd reuse most of the rmentation brines generated in tank yards. ductions in waste generation in this industry vithout significant changes the quality of the products produced. of interest to the processors in this industry,and environmental regula-

For further informntion on this project contact the Food and

As a result, this report should

ry agencies. od Products Branch, Induetrial Pollution Control Division, Industrial vironmental Research Laboratory-Cincinnati.

David C. Stephan Industrial Environmental Director Research Laboratory

Cinc idnat i

ii iii

. e

. . . . * - . I .

ABSTRACT

The p r o j e c t e v a l u a t e d on a couanercial scale the technolo- g i c a l and economic f e a s i b i l i t y of r e c y c l i n g s p e n t cucumber fe rmenta t ion b r i n e . 'pwo b r i n e t r e a t m e n t procedures , h e a t t reatment and chemical t r e a t m e n t , were used. The r e s u l t s shaved t h a t b r i n e r e c y c l i n g was p r a c t i c a l on a commercial scale. b r i n e t r e a t m e n t procedure r e s u l t e d in s a l t s t o c k which were e q u i v a l e n t i n q u a l i t y t o c o n t r o l cucumbers.

S t u d i e s were conducted t o determine the adequacy of the b r i n e t r e a t m e n t procedures employed. h e a t t r e a t m e n t o f 175'F f o r 30 sec. w a s s u f f i c i e n t t o asBure i n a c t i v a t i o n o f p e c t i n a s e s from m o l d s found to be common on cucumber f r u i t s and f lowers . For e f f e c t i v e chemical t r e a t m e n t a b r i n e tempera ture o f 72'F or h i g h e r w a s requi red . t h e pH had t o b e main ta ined a t 11.0 or h i g h e r for a t l e a s t 36 h r to a s s u r e 99% i n a c t i v a t i o n of p e c t i n a s e s from t h e molds which were i n v e s t i g a t e d .

small n e t s a v i n g s f o r the h e a t treatment procedure and a s m a l l n e t c o s t f o r chemical t rea tment . S e l e c t i o n o f the p r o c e s s f o r a p a r t i c u l a r p l a n t w i l l depend upon the l o c a l c o n d i t i o n s .

by P i c k l e Packers I n t e r n a t i o n a l , Inc. , under the p a r t i a l spon- s o r s h i p of the U.S. Environmental P r o t e c t i o n Agency. report covers a p e r i o d from May, 1975 t o December, 1977; d a t a c o l l e c t i o n was completed as of October , 1977.

E i t h e r

The d a t a confirmed t h a t a

I n a d d i t i o n ,

An economic e v a l u a t i o n of t h e r e c y c l i n g procedures showed a

This report was submi t ted in f u l f i l l m e n t of G r a n t S-803825

This

CONTENTS

Foreword . . . . . . . . . . . . . . . A b s t r a c t . . . . . . . . . . . . . . . F i g u r e s . . . . . . . . . . . . . . . Tables . . . . . . . . . . . . . . . . Conversion F a c t o r s and Metric P r e f i x e s

Acknowledgment . . . . . . . . . . . . 1. I n t r o d u c t i o n . . . . . . . . . 2 . Conclusions . . . . . . . . . . 3 . Recommendations . . . . . . . . 4 . Experimental Design . . . . . . 5. R e s u l t s and Discussion . . . .

References . . . . . . . . . . . . . . Appendix . . . . . . . . . . . . . . .

. . . . . . . . . . . iii

. . . . . . . . . . . i v

. . . . . . . . . . . v i

. . . . . . . . . . . v i i

. . . . . . . . . . . x i

. . . . . . . . . . x i i i

. ( . . . . . . . . . 1

. . . . . . . . . . . 4

. . . . . . . . . . . 5

. . . . . . . . . . . 6

. . . . . . . . . . . 2 3

. . . . . . . . . . . 6 8

. . . . . . . . . . . 71

iv V

FIGURES

Number

1 Schematic diagram o f t h e b r i n e recovery u n i t . . . . 8

2 Regenera t ive h e a t exchanger system used f o r t h e

3 General des ign of t h e commercial e v a l u a t i o n

4 Score sheet f o r taste p a n e l e v a l u a t i o n of

5

b r i n e recovery unit . . . . . . . . . . . . . . . 9

o f b r i n e r e c y c l i n g . . . . . . . . . . . . . . . . 1 2

hamburger d i l l c h i p s . . . . . . . . . . . . . . . 15 ..

E f f e c t of pH on h e r t i n a c t i v a t i o n of P e n i c i l l i u m l a n t h i n e l l u m p e c t i n a s e . Experiments were done i n brine c o n t a i n i n g 12% N a C 1 , 0.6% lac t ic a c i d and 0.1% Ca++ i o n . . . . . . . . . . . . . . . . . . . . . 6 4

TABLES

Number

1 C h a r a c t e r i s t i c s of 1st c y c l e s p e n t b r i n e i n t h e s p r i n g of 1975 b e f o r e and a f t e r h e a t or chemical t rea tment . The t r e a t e d b r i n e s were used as cover b r i n e s f o r 2nd c y c l e f e r m e n t a t i o n s . . . . . . . . . . . . . . . . . . 2 4

t h e s p r i n g o f 1976 b e f o r e and a f t e r h e a t o r chemical t r e a t m e n t . The t r e a t e d b r i n e s were used as cover b r i n e s f o r 3rd cycle f e r m e n t a t i o n s . . . . . . . . . . . . . . . . . . 25

3 Summary d a t a on fe rmenta t ion tanks, 1975 . . . . . 2 8

4 Summary d a t a on fermenta t ion t a n k s , 1976 . . . . . 28

5 A n a l y s i s of s p e n t b r i n e remaining i n t h e

2 C h a r a c t e r i s t i c s of 2nd c y c l e s p e n t b r i n e i n

fe rmenta t ion tanks i n the winter a f t er removal of e a l t s t o c k cucumbers from the 2nd c y c l e (1975) and 3rd c y c l e (1976) fe rmenta t ion t a n k s . . . . . . . . . . . . . . . . . . . . . . 30

6 Analys is of spent b r i n e remaining i n t h e fe rmenta t ion tanks in t h e w i n t e r a f t e r removal of s a l t s t o c k cucumbers from t h e 2nd c y c l e (1975) and 3rd c y c l e (1976) f e r m e n t a t i o n tanks . All d a t a a r e expressed a s mg/l o f b r i n e . . . . . . . . . 3 1

7 Q u a l i t y of 2nd c y c l e s a l t s t o c k cucumbere

8 Q u a l i t y of 3rd c y c l e s a l t s t o c k cucumbers

9 Comparison of 2nd c y c l e product wi th t h e

fermented in recyc led b r i n e , 1975 . . . . . . . . 32

fermented i n recyc led b r i n e , 1 9 7 6 . . . . . . . . 32

c o n t r o l (averages) , 3 samples/group, 9 judges and 7 groups . . . . . . . . . . . . . . 34

. . ..

vi v i i

,

Number * 10 Comparison of 3rd c y c l e product w i t h the

c o n t r o l (averages) , 3 samples/group, 11 judges and 5 groups . . . . . . . . . . . . . . 35

11 Analys is o f v a r i a n c e t a b l e f o r t e x t u r e d i f f e r e n c e s of hamburger d i l l c h i p s made from 2nd c y c l e s a l t s t o c k cucumbers . . . . . . . . . . . . . . . . . . . . 36

Analys is o f v a r i a n c e t a b l e f o r f l a v o r d i f f e r e n c e s of hamburger d i l l c h i p s made from 2nd c y c l e s a l t s t o c k cucumbers . . . . . . . . . . . . . . . . . . . . 37

1 3 Analys is o f v a r i a n c e t a b l e f o r t e x t u r e d i f f e r e n c e s of hamburger d i l l c h i p s made from 3rd c y c l e sa l t s t o c k

1 2

cucumbers . . . . . . . . . . . . . . . . . . . . 38

1 4 Analys is of v a r i a n c e t a b l e f o r f l a v o r d i f f e r e n c e s of hamburger d i l l c h i p s made from 3rd c y c l e s a l t stock cucumbers . . . . . . . . . . . . . . . . . . . . 39

Analys is o f variance table f o r o v e r a l l q u a l i t y d i f f e r e n c e s of hamburger d i l l c h i p s m a d e from 3rd c y c l e s a l t s t o c k

16 S a l t s t o c k cucumber a n a l y s i s . D i s t r i -

15

cucumbers . . . . . . . . . . . . . . . . . . . . 40

b u t i o n o f minera l l e v e l s i n commercial s a l t s t o c k d u r i n g t h r e e c y c l e s of fe rmenta t ion . A l l d a t a are expressed a s mg/kg of cucumbers . . . . . . . . . . . . . . 4 2

1 7 Desa l ted cucumber a n a l y s i s . D i s t r i b u t i o n o f m i n e r a l l e v e l s i n d e s a l t e d cucumbers d u r i n g three c y c l e s of fe rmenta t ion . All d a t a are expressed as mg/kg of cucumbets . . . . . . . . . . . . . . . . . . . . 43

1 8 Savings from r e c y c l i n g 1 , 0 0 0 g a l of

1 9 Economic e v a l u a t i o n of chemical t rea tment

Operatkng costs and savings us ing h e a t

s p e n t b r i n e . . . . . . . . . . . . . . . . . . . 45

of s p e n t b r i n e s . . . . . . . . . . . . . . . . . 45 20

t r e a t m e n t f o r s p e n t b r i n e s . . . . . . . . . . . . 46

2 1 N e t p r e s e n t va lue c a l c u l a t i o n f o r comparison of chemical t rea tment w i t h h e a t t r e a t m e n t of b r i n e . The d i f f e r e n c e between t r e a t m e n t costs p e r 1,000 g a l f o r chemical compared t o h e a t t r e a t m e n t of b r i n e was $16.43 i n 1976. For 1.7 m i l l i o n g a l this is a t o t a l d i f f e r e n c e i n t r e a t m e n t cost of 1700 x $16.55 - $27,931. With a maintenance cost o f $500/yr f o r t h e u n i t t h e n e t d i f f e r e n c e is $27,431 . . . . . . . . . . . . . . . . . . 48

22 Raw waste l o a d summary . . . . . . . . . . . . . . . 50

23 EPA e f f l u e n t g u i d e l i n e s - 1977 . . . . . . . . . . . 50

2 4 EPA e f f l u e n t g u i d e l i n e s - 1983 . . . . . . . . . . . 51 25 T h e o r e t i c a l s a l t use and d i s c h a r g e d u r i n g

fe rmenta t ion , s t o r a g e , untanking and d e s a l t i n g of cucumbers. R e s u l t s are expressed as t h e l b of s a l t r e q u i r e d ger bu (50 lb) of f r e s h cucumbers . . . . . . . . . . 53

26 Recoveries (0 ) of added p e s t i c i d e s . . . . . . . . . 56

27 L o w e s t l e v e l s a t which r e s i d u e s were

28 E f f e c t of h e a t and NaOH t r e a t m e n t on



31 E f f e c t of h e a t o r NaOH t r e a t m e n t on PCNB

32

q u a n t i t a t e d . . . . . . . . . . . . . . . . . . . 57

c a r b a r y l i n p i c k l e b r i n e . . . . . . . . . . . . . 59

p a r a t h i o n i n p i c k l e b r i n e . . . . . . . . . . . . 60

endosul fan i n p i c k l e b r i n e . . . . . . . . . . . . 6 1

and PCA i n p i c k l e b r i n e . . . . . . . . . . . . . 62

de te rmina t ion of thermal s t a b i l i t y of p e c t i n a s e s i n b r i n e s . . . . . . . . . . . . . . . 63

thermal s t a b i l i t y i n p r e l i m i n a r y experiments . D-values w e r e o b t a i n e d a t pH 3.3 i n 12% NaC1, 0.6% l ac t i c a c i d and 0.1% Ca++ i o n . . . . . . . . . . . . . . . . . . 63

Sources and i d e n t i t y of fungi used f o r

33 D-values of p e c t i n a s e s with the g r e a t e s t

v i i i

5 i x

A*:& c 'r +"-

34 E f f e c t of NaCl concentration on the heat inact ivat ion o f pectinase from Penic i l l ium janthinellum a t 7 5 O C . . . . . . . . 6 5

35 Inactivation of pect inase from Penici l l ium a t high pH i n spent br ine .

22OC ( 7 1 . 6 O F ) . S a l t concentration 8.0% . . . . . . . . . . . . . . . 6 5

CONVERSION FACTORS AND METRIC PREFIXESa

. . To ccnvert from

Degree Fahrenheit (OF)

inch (in)

foot (ft)

gallon (gal)

bushel (bu)

3.8 gal/bu

grain (pr)

ounce (02)

pound (lb)

gallons per minute (gal/min)

ounces per gallons (oz/gal)

pounds per ton (lb/ ton)

pounds per 1000 pounds (lb/1000 lb)

tons per year (ton/yr)

gallons per ton (gal/ton)

CONVERSION FACTORS

to

Degree Celsius (OC)

metre (m)

metre (m)

metres (m3)

metre3 (m3)

0.408 m3/m3 1

kilogram (kg)

kilogram (kg)

kilogram (kg)

metre3/second (m3/s)

(kg/m3)

(kg/kkg)

(kg/kkg)

(kkg/yz)

(m3/kkg)

kilogram/metre3

kilogram/kilokilogram

kilogram/kilokilogram

kilokilogram/year

metre3/kilokilogrars

Multiply by

t°C = 0.56 (t0~-32)

2 . 5 4 x l o - *

3.048 x 10-1

3.784 10-3

3.524 x IO-*

1.0

6 . 4 8 x 10-5

3.11 x

4.536 x lo-'

6.308 x l o - ;

8.218

4.643 x 10-1

1.0

9.074 x 10-1

4.17 x 10-3

X xi

To convert from to

pounds per gallon kilograns/metre3 ( W g a l ) W m 3 )

pounds per 1000 (lb/ 1000

cost per pound ($/lb)

cost per gallon ($/gal)

cost per 1000 gallon cost/metre3 ($/lo00 gal) (S/m3)

cost per ton ($/ton)

Prefix Symbol

kilo k

centi C

cost/kilokilogram (S/kkg)

METRIC PREFIXES

Multiply by

1.1984 x lo2

1.1984 x 10-I

4.536 x lo-'

2.642 x lo2

2.642 x 10-1

1.102

Multiplication factor Example

103

10-2

2 kg = 2 x 103 grams

2 cm = 2 x 10-2 metre

ACKNOWLEDGMENTS

P i c k l e Packers I n t e r n a t i o n a l , I n c . , a p p r e c i a t e s t h e coopera t ion of t h e Department of Food Science and Human N u t r i - t i o n , Michigan S t a t e Univers i ty : Vlasic Foods, 1nc. i and t h e P P I Ecology Committee i n t h e p lanning , a d m i n i s t r a t i o n and e x e c u t i o n of this p r o j e c t . The D e t r o i t Dis t r ic t O f f i c e of t h e U.S . Food and Drug Adminis t ra t ion w a s very h e l p f u l i n provid ing a s s i s t a n c e on p e s t i c i d e a n a l y s i s .

M r . Herman B l u m ' s a s s i s t a n c e i n i n i t i a t i o n of t h e p r o j e c t and h i s advice and l e a d e r s h i p d u r i n g t h e p r o j e c t were p a r t i c u - l a r l y va luable . M r . Michael V e l t i n g , Mr. Richard Bowman, M r . Scott Smith, M r . Maury K i t t e l , and M r . Charles S a n t e r r e were o t h e r members of Vlasic Foods, Inc. , who made s i g n i f i c a n t c o n t r i b u t i o n s t o t h e o p e r a t i o n of the p r o j e c t . The a s s i s t a n c e of p l a n t personnel a t Imlay C i t y , Michi#an is a l s o acknowledged.

P e c t i n a s e i n a c t i v a t i o n s t u d i e s were done by Ma. Suparath Chavana and M r . Nicholas Pa lamidis . A s s i s t a n c e with cucumber b r i n i n g , sample c o l l e c t i o n , and a n a l y s i s a t MSU w a s provided by Mr. Michael F i s h e l , Ms. Debra P a t t e r s o n , W. Luci Chua and Ms. Patr ic ia Fodel l . Members of the Michigan S t a t e U n i v e r s i t y Cucumber Research Committee provided t r a n s p o r t a t i o n , r e p a i r s e r v i c e s , and advice throughout t h e p r o j e c t .

W e f u r t h e r acknowledge M r . Harold Thompson of t h e I n d u s t r i a l Environmental Research Laboratory of t h e Environ- mental P r o t e c t i o n Agency f o r his guidance and numerous h e l p f u l s u g g e s t i o n s i n a l l phases of t h e p r o j e c t .

aStandard for Mezric Practice. kLISI/ASTM Designation: E 380-76', IEEE Std 268-1976, American Society for Testing and Materials, Philadephia, Pennsylvania, February 1976. 37 pp.

xli xiii

I . , ". . . _ I . . .. - "... I . . ,

SECTION 1

INTRODUCTION

P e r c a p i t a p i c k l e consumption i n t h e United S t a t e s h a s shown s t e a d y i n c r e a s e s s i n c e 1930 from 1.07 kg to 3.75 kg i n 1976. There are two major classes of cucumber p i c k l e s , f r e s h pack a i d p r o c e s s pack. Fresh pack products a r e prepared by p r o c e s s i n g f r e s h cucumbers d i r e c t l y i n t o f i n a l p roducts . The process pack r e q u i r e s i n i t i a l fe rmenta t ion of cucumbers, s t o r a g e a t h igh s a l t c o n c e n t r a t i o n s , and subsequent d e s a l t i n g p r i o r t o p r o c e s s i n g i n t o consumer or i n s t i t u t i o n a l products . I n 1975 t h e p r o c e s s pack o p e r a t i o n u t i l i z e d 206,000 metric t o n s o f green s t o c k o r 6 4 % of t h e green s t o c k purchased by p r o c e s s o r s (1). This d i s t r i b u t i o n of product u t i l i z a t i o n makes t h e tank y a r d I '

a major source o f waste i n t h e i n d u s t r y . Kirk ( 2 ) r e p o r t e d t h a t . s p e n t b r i n e accounted for 8% o f t h e to ta l h y d r a u l i c load, 4 4 % of t h e BOD and 59% o f t h e s a l t genera ted i n t h e manufacture of p r o c e s s pack products .

t i o n s . These i n c l u d e s p i l l a g e , t ank overf low dur ing r a i n y p e r i o d s , l eakage from wooden t a n k s , s p e n t fe rmenta t ion b r i n e and " p r o c e s s w a t e r " genera ted d u r i n g d e s a l t i n g o p e r a t i o n s . This p r o j e c t was designed t o e v a l u a t e r e c y c l i n g of s p e n t b r i n e s a s a means f o r c o n t r o l of this s o u r c e of waste.

There are s e v e r a l sources o f w a s t e s from tank y a r d opera-

U6ual fe rmenta t ion p r a c t i c e s w i l l r e s u l t i n product ion of about 40% by volume spent b r i n e i n a fe rmenta t ion tank . The cucumber fe rmenta t ion is normally done a t 6.5% NaCl ( 3 ) . How- e v e r , when t h e fe rmenta t ion i s completed, a d d i t i o n a l s a l t i s added t o i n s u r e a g a i n s t d e t e r i o r a t i o n of t h e f r u i t d u r i n g tank y a r d s t o r a g e . As a r e s u l t , s p e n t b r i n e s u s u a l l y c o n t a i n 9-15% NaC1, the BOD w i l l be 10,000-15,000 mg/l and t h e pH w i l l b e 3.2-3.5. These c h a r a c t e r i s t i c s make b i o l o g i c a l t r e a t m e n t of w a s t e r e l a t i v e l y d i f f i c u l t . Discharge of b r i n e s produced by tank y a r d , o p e s a t i o n s may n o t be p o s s i b l e i n some l o c a t i o n s wi th limits on t o t a l d i s s o l v e d s o l i d s .

I n a s s & s i n g environmental c o n t r o l s t r a t e g i e s a v a i l a b l e for managing these b r i n e s one may wonder i f it is f e a s i b l e t o either r e c l a i m t h e s a l t conta ined t h e r e i n , or t o r e c y c l e t h e s p e n t s o l u t i o n .

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Durkee e t a l . ( 4 ) has developed a procedure f o r s a l t recovery from fermenta t ion b r i n e s by e v a p o r a t i o n of t h e water and i n c i n e r a t i o n of t h e o r g a n i c m a t t e r . S a l t recovered by t h i s method has been used s u c c e s s f u l l y i n cucumber f e r m e n t a t i o n s (5). However, t h i s technique has n o t been adopted commercially due t o t h e high c o s t o f equipment and energy.

One i s t h e p o t e n t i a l f o r l o s s of product q u a l i t y i f p e c t i n a s e s were c a r r i e d over i n t h e recyc led b r i n e a t l e v e l s s u f f i c i e n t t o s o f t e n cucumbers dur ing months of fe rmenta t ion and s t o r a g e i n t h e b r i n e . I t is a l s o p o s s i b l e t h a t p roducts of fermenta- t i o n could i n h i b i t subsequent fe rmenta t ions o r cause abnormal fe rmenta t ions . There could a l s o be a b u i l d u p o f t o x i c compounds. The d e s t r u c t i o n of t h e s e products might r e q u i r e i n c i n - e r a t i o n o r o t h e r d r a s t i c techniques. Pa thogenic organisms w i l l n o t , however, be a problem due t o t h e low pH and h igh s a l t c o n t e n t of t h e b r i n e .

When cons ider ing b r i n e r e c y c l i n g , many concerns arise.

Geisman and HeMe ( 6 , 7) developed a chemical t r e a t m e n t procedure f o r rec la iming s p e n t fe rmenta t ion b r i n e s . Their procedure r e q u i r e s r a i s i n g t h e pH o f s p e n t b r i n e to 10 or 11. This t r e a t m e n t c l a r i f i e d t h e b r i n e , s i n c e a p r e c i p i t a t e formed which occluded suspended cells. It was a l s o presumed t o i n a c t i v a t e p e c t i n a s e a c t i v i t y . A f t e r a 48-hr h o l d i n g p e r i o d , the pH was a d j u s t e d t o 7 and t h e b r i n e used as a cover b r i n e f o r fe rmenta t ion . Normal fe rmenta t ions r e s u l t e d from use of t h i s b r i n e . This showed t h a t i n c i n e r a t i o n was n o t r e q u i r e d f o r r e u s e of s a l t and provided a p r a c t i c a l a l t e r n a t i v e t r e a t m e n t .

P a l n i t k a r and McFeeters ( 8 ) showed t h a t chemica l ly t r e a t e d b r i n e could be used f o r m u l t i p l e fe rmenta t ion c y c l e s w i t h o u t loss of s a l t s t o c k q u a l i t y . They a l s o sugges ted t h a t h e a t i n g of b r i n e could be used a s an a l t e r n a t i v e t r e a t m e n t and sugges ted 175'F f o r 30 sec . a s a reasonable h e a t t r e a t m e n t .

The r e c y c l i n g procedures were compared t o c o n t r o l s i n which cucumbers were fermented i n f r e s h s a l t b r i n e . The c o n t r o l fe rmenta t ions were done accord ing t o normal commercial b r i n i n g procedures . The commercial fe rmenta t ions were c a r r i e d o u t a t

. t h e Imlay C i t y , Michigan p l a n t of V l a s i c Foods, I n c .

C r a n f i e l d ( 9 ) had previous ly r e p o r t e d on a system f o r p a s t e u r i z a t i o n of b r i n e , s a t u r a t i o n of t h e t r e a t e d b r i n e by a d d i t i o n of s a l t and reuse of t h e t r e a t e d b r i n e a s a s a t u r a t e d s a l t s o l u t i o n . 8

The primary o b j e c t i v e s of t h i s p r o j e c t were t o e v a l u a t e t h e commercial , t e c h n o l o g i c a l , and economic f e a s i b i l i t y of b r i n e r e c y c l i n g by both h e a t and chemical t r e a t m e n t s and t o determine t h e r e l a t i v e merits of t h e s e two procedures .

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SECTION 2

CONCLUSIONS

1. Br ine r e c y c l i n g i s an e f f e c t i v e procedure f o r reduct. ion of waste i n the manufacture o f s a l t - s t o c k p i c k l e s .

2 . Both the h e a t and chemical t r ea tmen t s f o r s p e n t b r i n e are p r a c t i c a l f o r use i n c u r r e n t commercial tank ya rd o p e r a t i o n s .

a t l eas t 99.98% d e s t r u c t i o n of p e c t i n a s e s from f u n g i which were found t o be common on cucumber f r u i t s and f lowers .

4 . R a i s i n g the pH o f ->72'F s p e n t b r i n e t o 1 1 . 2 o r h i g h e r f o r .,' a t l e a s t 37 h r w i l l dec rease P e n i c i l l i u m ' a n t h i n e l l a n p e c t i - nase a c t i v i t y i n s p e n t b r i n e s t o <1% of i b c t i v i t y : T h i s shou ld be an adequate t r e a t m e n t f o r b r i n e r e c y c l i n g .

3 . Heating s p e n t b r i n e f o r 30 sec. a t 1 7 5 ' F w i l l a s s u r e

5. S a l t - s t o c k cucumbers produced from fe rmen ta t ions us ing r e c y c l e d b r i n e s are e q u i v a l e n t t o c o n t r o l s a l t s t o c k i n b l o a t e r losses, t e x t u r e , and f l a v o r . Consumers have n o t d e t e c t e d any s i g n i f i c a n t d i f f e r e n c e s i n p roduc t s p repa red from s a l t s t o c k fermented i n r ecyc led b r i n e .

6 . No s i g n i f i c a n t accumulations of me ta l s or p e s t i c i d e s occur as a r e s u l t of b r i n e r e c y c l i n g .

7 . The r e s u l t s show tha t b r i n e can b e reused f o r a t least three f e r m e n t a t i o n c y c l e s on a commercial b a s i s . There are also no i n d i c a t i o n s o f adverse e f f e c t s o f r e c y c l i n g on s a l t - s t o c k q u a l i t y o r bu i ldup o f t o x i c c o n s t i t u e n t s . This s u g g e s t s t h a t b r i n e can con t inue t o b e r eused beyond t h r e e c y c l e s .

8. Under the c o n d i t i o n s o f t h i s p r o j e c t , h e a t t r e a t m e n t o f b r i n e r e s u l t e d i n a sma l l n e t s av ings wh i l e t h e r e was a s m a l l ne t c o s t f o r chemical t r ea tmen t . The r e l a t i v e economics o f these t w o r e c y c l i n g procedures may vary wi th i n d i v i d u a l c i rcumstances. However, the use o f r e c y c l i n g i s an economical ly f e a s i b l e means f o r reducing the waste from t ank y a r d o p e r a t i o n s .

SECTION 3

RECOMMENDATIONS

1. a r i n e r e c y c l i n g should b e adopted by t h e processed cucumber p i c k l i n g i n d u s t r y as a means t o reduce was te s .

2 . Both h e a t and chemical t r e a t m e n t s of t h e spen t b r i n e a r e e f f e c t i v e from a t e c h n i c a l viewpoint . S e l e c t i o n o f a procedure can be based upon economic c o n s i d e r a t i o n s and upon :he r e l a t i v e compa tab i l i t y o f t h e procedures x l t h each p a r t i c u l a r t a n k ya rd o p e r a t i o n .

3 . Care should be t aken t o i n s u r e p rope r design of a r ecyc l ing system, proper t r a i n i n g of o p e r a t i n g personnel and p rope r supe rv i s ion of t h e p rocedure , s i n c e improper r e c y c l i n g t echn iques ho ld t h e p o t e n t i a l f o r s i g n i f i c a n t economic l o s s e s .

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4 . Undertake an e v a l u a t i o n o f calcium hydroxide as a p a r t i a l o r t o t a l replacement o f sodium hydroxide i n the chemical t r ea tmen t procedure. The use o f calcium hydroxide would s i g n i f i c a n t l y reduce t h e a c c i d e n t r i s k s a s s o c i a t e d with this procedure.

5 . Evaluate t h e need t o remove the p r e c i p i t a t e formed dur ing chemical t r ea tmen t . I f p r e c i p i t a t e removal i s unnecessary, it would reduce b r i n e l o s s e s and reduce handl ing of t h e b r i n e .

6 . E f f o r t s should be made t o reduce t ank leakage and overf low, s i n c e s i g n i f i c a n t b r i n e losses occur from t h e s e sou rces .

7 . A major e f f o r t i s needed t o develop s a l t - s t o c k s t o r a g e technology, which w i l l allow reduc t ion i n t h e s a l t l eve l s maintained i n b r i n i n g t a n k s , s i n c e wastes gene ra t ed i n t h e d e s a l t i n g o p e r a t i o n are second only t o spen t b r i n e a s a sou rce of waste i n t ank y a r d o p e r a t i o n s .

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SECTION 4

EXPERIMENTAL DESIGN

B R I N E TREATMENT PROCEDURES

Chemical Treatment of Brine

Chemical t r e a t m e n t of s p e n t b r i n e was c a r r i e d o u t by t h e a d d i t i o n o f Food Grade NaOH p e l l e t s t o a tank of s p e n t b r i n e ( 8 , 0 0 0 - 1 0 , 0 0 0 g a l ) t o r a i s e t h e pH of t h e b r i n e t o 11 o r g r e a t e r .

determined by t i t r a t i n g a 32-02, s p e n t b r i n e sample from a w e l l mixed tank w i t h 1 0 % NaOH s o l u t i o n t o a pH of 11.5. Approximately 80% of t h e c a l c u l a t e d NaOH requirement w a s added t o t h e tank and the b r i n e was c i r c u l a t e d . A eample of t h i s p a r t i a l l y a d j u s t e d b r i n e w a s t i t r a t e d t o pH 11.5, and t h e NaOH requirement c a l c u l a t e d . This amount of NaOH was added and the tank w a s c i r c u l a t e d w i t h a pump. A characteristic change i n c o l o r of t h e s p e n t b r i n e t o d a r k e r ye l low, development o f an ammonia-like odor and formation of a p r e c i p i t a t e occurred as t h e pH was r a i s e d . This two-step NaOH a d d i t i o n procecure provides i n s u r a n c e a g a i n s t major errors i n t h e amount of NaOH added and a t t a i n m e n t of t h e proper f i n a l pH.

A p r e c i p i t a t e formed when t h e b r i n e pH was r a i s e d . This p r e c i p i t a t e s e t t l e d i n the tank . A f t e r s e t t l i n g , t h e c l e a r b r i n e was pumped i n t o a c l e a n tank. d i scarded . The pH o f t h e NaOH t r e a t e d b r i n e w a s a d j u s t e d t o pH 4 . 5 - 4 . 7 w i t h 300 g r a i n v inegar . The amount of v i n e g a r requi red was determined by t i t r a t i o n of a sample wi th a c e t i r ac id . Addit ion was done by t h e same procedure as t h e a d d i t i o n of NaOH. A f t e r a c i d i f i c a t i o n of t h e b r i n e , it was h e l d u n t i l it was used as a cover b r i n e .

The m u n t of NaOH r e q u i r e d f o r each b a t c h of b r i n e was

The p r e c i p i t a t e l a y e r was

Grea t c a r e must be e x e r c i s e d when us ing sodium hydroxide for pH adjus tments . fol lowing precaut ions :

I n j u r i e s were prevented by use of t h e

2 . These people were s p e c i f i c a l l y t a u g h t the problems and dangers a s s o c i a t e d wi th handl ing NaOH.

goggles , acid-base r e s i s t a n t g l o v e s , and r a i n s u i t was r e q u i r e d f o r handl ing NaOH.

4 . A water hose was turned on when NaOH was be ing handled so any s p i l l s could be r a p i d l y washed. r e a d i l y a v a i l a b l e .

5. NaOH was slowly added by manual a d d i t i o n w h i l e t h e b r i n e tank was mixing t o minimize t h e p o s s i b i l i t y of l o c a l h igh concent ra - t i o n s o f NaOH on t h e s u r f a c e of t h e t a n k ,

3. P r o t e c t i v e c l o t h i n g i n c l u d i n g wrap around

Eye wash equipment was

Heat Treatment of Spent Br ine

recovery system developed by t h e APV Company, Inc . o f Tonawanda, N e w York and V l a s i c Foods. A schemat ic diagram of the u n i t is shown i n f i g u r e 1. Figure 2 shows a drawing of t h e h e a t exchanger system. The u n i t has a t i t a n i u m a l l o y h e a t exchanger t o resist b r i n e c o r r o s i o n , a 200 g a l s t a i n l e s s s teel hold ing t a n k , and a s c r e e n i n g system t o remove p a r t i c u l a t e m a t e r i a l s from t h e b r i n e b e f o r e it e n t e r s t h e h e a t exchanger .

68OC (155'F) by r e g e n e r a t i o n from t h e hea ted b r i n e . Heat ing from 68OC up to 90.5OC (195'F) i s done wi th h o t water hea ted by b u r n i n g propane. This s y s t e m al lows up t o 60% of t h e h e a t i n g t o be o b t a i n e d by c o o l i n g t h e t r e a t e d b r i n e t o a tempera ture o f 35OC (95OF).

The e n t i r e u n i t i s mounted on a 6 x 1 6 f t t r a i l e r so i t can be moved between tank rows. I n r o u t i n e o p e r a t i o n i t was most e f f i c i e n t to pump b r i n e from nearby rows of t a n k s t o minimize t h e number of t i m e s t h e u n i t had t o be moved. The u n i t can b e loaded on a t r u c k and t r a n s p o r t e d t o o t h e r tank y a r d l o c a t i o n s . I n t h i s way one u n i t has been used t o s e r v e more than one l o c a t i o n . The u n i t has r e q u i r e d r e l a t i v e l y l i t t l e maintenance and does n o t appear t o be d e t e r i o r a t i n g s i g n i f i c a n t l y even though s e v e r a l m i l l i o n g a l l o n s of b r i n e have been t r e a t e d .

Spent b r i n e was hea ted wi th a t ra i lef- mounted b r i n e

The h e a t exchanger h e a t s b r i n e from ambient tempera ture t o

1. Only c o l l e g e s t u d e n t s who had taken i n t r o d u c t o r y chemistry handled t h e sodium hydroxide.

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PROPAhE GAS SUPPLY

F i c u r e 1. Schematic diagram of t h e b r i n e recovery u n i t .

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B o t t l e d propane gas was used as the f u e l source. The h e a t exchanger had a h e a t c a p a c i t y of 50 gal/min. To p rov ide an e x t r a margin o f s a f e t y , t h e b r i n e i n this p r o j e c t was t r e a t e d t o 190'F f o r 30 sec. Whenever f e a s i b l e , t h e h e a t i n g o f b r i n e w a s done on warmer days (>2loC o r 70°F) s i n c e w a m r b r i n e r equ i r ed less f u e l f o r t r ea tmen t .

An o p e r a t o r con t inuous ly monitored t h e h e a t i n g o p e r a t i o n t o a s s u r e p r o p e r t r e a t m e n t o f t h e b r i n e and t o p r o t e c t the equipment i n case o f malfunct ion. A second person was r e q u i r e d on a pa r t - t ime b a s i s t o a s s i s t i n pumping b r i n e t o t h e u n i t .

The f l a t - b o t t o m des ign of c u r r e n t wood tanks made it i m p r a c t i c a l t o remove a l l t h e b r i n e from t anks . Usual ly abou t a 6 inch l a y e r o f b r i n e c o n t a i n i n g d i r t , p i c k l e d e b r i s , and o t h e r r e s i d u e s remained. This b r i n e was d i sca rded through t h e 5ung h o l e i n t h e bot tom o f t h e t anks . I t was necessa ry t o thoroughly c l e a n t h e t anks p r i o r t o f i l l i n g with t r e a t e d b r i n e . Though the t anks canno t b e s t e r i l i z e d and t h e b r i n e w i l l be open t o the a i r , the contaminat ion o f the b r i n e by pumping i n t o a d i r t y t ank i s a e s t h e t i c a l l y unpleasing and cou ld r e s u l t . , I

i n c o n s i d e r a b l e y e a s t growth i n the b r i n e b e f o r e use, The b r i n e comes froio t h e h e a t exchanger a t a temperature o f 90-10O0Ft The re fo re , i t w i l l n o t s a n i t i z e a poorly cleaned t ank p r i o r t o cool ing. Tanks were c l eaned by manually sc rubb ing the t anks w i t h 0.5 oz /ga l calcium h y p o c h l o r i t e s o l u t i o n fol lowed by washing w i t h h y d r a t e d l ime and r i n s i n g w i t h f r e e h water. I f tanks were n o t used immediately f o r b r i n e s t o r a g e , t h e y were f i l l e d w i t h f r e s h water t o p r e v e n t the wood from c o n t r a c t i n g .

The t r e a t e d b r i n e was h e l d a t i t s o r i g i n a l pH, u s u a l l y a t pH 3.2-3.5. J u s t p r i o r t o u s e , t he pH was r a i s e d t o 4.5 w i t h NaOH p e l l e t s u s ing t h e procedure desc r ibed ear l ier . E t c h e l l s e t a l . (10) have recommended a similar pH adjustment f o r f r e s h b r i n e used i n c o n t r o l l e d f e rmen ta t ion . I n l a b o r a t o r y experiments this pH ad jus tmen t was found t o b e necessa ry i n o rde r t o minimize b l o a t i n g problems and t o o b t a i n a normal a c i d development d u r i n g f e rmen ta t ions . The q u a n t i t i e s o f N a O H r equ i r ed f o r t h i s ad jus tmen t have been s a f e l y handled i x normal commercial o p e r a t i o n s us ing t h e p recau t ions p r e v i o u s l y desc r ibed . I t would b e worthwhile t o o b t a i n d a t a on t h e use of l i m e , C a ( O H ) 2 , f o r t h i s adjustment . Calcium s a l t s have been added t o p i c k l e s as f i rming agen t s . L ime would be cons ide rab ly less expens ive than NaOH and easier t o handle .

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Cont ro l s f o r Fermentat ions W i t h Recycled Br ine

Commercial p r a c t i c e f o r cucumber f e rmen ta t ions has h i s t o r i c a l l y been t o cover the f r e s h cucumbers wi th f r e s h l y p repa red b r i n e . A t the conc lus ion o f f e n n e n t a t i o n and s t o r a g e , t h e b r i n e r e a a i n i n g a f t e r s a l t s t o c k w a s removed from tanks w a s termed " s p e n t b r i n e " and d i s c a r d e d . To e v a l u a t e the e f f e c t s o f b r i n e recyc1ir.g it was necessa ry t o compare the s a l t s tock and b r i n e s frcm fe rmen ta t ions wi th r ecyc led b r i n e s with fermentat ions i n xhich green s t o c k cucumbers were covered with f r e s h l y prepared s a l t s o l u t i o n s .

CO."IMEFlCIAL E' . 'XGATION OF BRINE RECYCLING

Fermenta:ion b r i n e s were r ec l a imed and reused through t!!ree c m p l e t e fer:e?.tation c y c l e s p e r t r e a t m e n t as shown i n f i g a r e 3 . i h e p r o j e c t kegan i n 1975 w i t h t h e s e g r e g a t i o n of f i r s t cyc le s p e n t b r i n e from the g e n e r a l t ank y a r d b r i n e s . A f t e r h e a t i n g or chemical t r ea tmen t , it w a s used f o r second c y c l e fermenta- t i o n s i n 1975. The second cycle b r i n e was saved and t r e a t e d i n the s p r i n g of 1976 f o r t h i r d c y c l e f e rmen ta t ions . Con t ro l f e rmen ta t ions i n which cucumbers were covered w i t h f r e s h s a l t b r i n e were rui! i n both 1975 and 1976.

S i z e 3A-3B :3.8-5.1 c m d i m ) rmixed cucumbers were used f o r a l l t anks . These s i z e s of cucumbers are fermented i n g r e a t e s t volume commercially. In a d d i t i o n , t h e l a r g e s i z e cucumbers are most s u s c e p t i b l e t o b l o a t i n g . One o b j e c t i v e o f the p r o j e c t w a s t o determine i f b r i n e r e c y c l i n g would s i g n i f i c a n t l y a f f e c t b l o a t i n g . Tank s i z e s v a r i e d from 800-1,200 bu capac i ty . For t h e c o n t r o l f e r n e n t a t i o n s , f r e s h l y p repa red , 6.6% NaCl cover b r i n e was use<. aecycled b r i n e was added t o cucumbers wi thou t d i l u t i o n . The s a l t c o n c e n t r a t i o n s v a r i e d from 1 0 - 1 2 % NaC1. .p.e s a i t concen t r a t ion d e c l i n e d a s t h e b r i n e e q u i l i b r a t e d with t h e water i n the cucumbers. I n a l l t anks dry e a l t w a s added i o 'he t anks 35 r equ i r ed t o m a i n t a i n t h e s a l t concen t r a t ion of 0.5% (25' SI :;rinq the f e rmen ta t ion . A t t he end o f t h e fermentat ior . ge r iod , s a l t was added accord ing t o t h e usua l s chedu le t o s ; T d l y r a i s e t h e s a l t t o 11%.

Tanks were f i l l e d i n groups o f t h r e e c o n s i s t i n g o f a c o n t r o l t a m , 3 tank i n which h e a t e d b r i n e was used and a tank i n t o which ck.?r,ically t r e a t e d b r i n e was added. During the 1975 season , n i n e complete groups o f t anks were fermented t o give n i n e r e p l i c a t e s p e r t r ea tmen t . During the 1976 season , e i g h t groups o f tar.i.5 were fermented. I n this i n s t a n c e , t he number of groups was i i m i t e d by the amount o f the second cyc le chemical ly t r e a t e d b r i n e a v a i l a b l e .

m.

11

Fresh Salt Brine

1974 1st Cycle Fermentation

1 1 s t Cvcle Spent Brine

Treatment Treatment c 1975 2nd Cycle Fermentation

1 1975 2nd Cycle

F ermenta t i on

1 2nd Cycle 2nd Cycle

S p e n t Brine Spent Brine

C hmical Treatment Treatment

1 Pasteurization

I I + 1976 3rd Cycle

.) 1976 3rd Cycle Fennenta tion Fermentation

3rd Cycle Spent Brine

1 3rd Cycle

Spent Brine

1975 Control Fermentation

1 1s t Cycle

Spent Brine

1976 Control Fermentation

1st Cycle Spent Brine

1

Figure 3. .General design of t h e commercial e v a l u a t i o n of b r i n e r e c y c l i n g .

When groups of tanks were f i l l e d , 1 ,000- lb t o t e boxes o f . cucumbers were dumped a l t e r n a t e l y i n t o t h e tanks t o assure s i m i l a r cucumbers were p u t i n each tank . Fresh cucumber samples were e v a l u a t e d f o r mechanical damage, c a r p e l s e p a r a t i o n , loose seed c a v i t i e s , and o t h e r d e f e c t s .

Recycled b r i n e was sampled i n t h e s p r i n g b e f o r e and a f t e r t r e a t m e n t p r i o r t o use i n t h e fe rmenta t ions . These samples were used f o r s a l t , pH, a c i d , reducing s u g a r , suspended. s o l i d s , BOD, COD, K j e l d a h l n i t r o g e n and m i n e r a l a n a l y s e s . Addit ion of s a l t was recorded throughout t h e fe rmenta t ion , Br ine from each tank was sampled f o r t h e same a n a l y s e s l i s t e d above i n the w i n t e r when cucumbers were removed f o r process ing . Two 5-gal p a i l s of cucumbers were taken from each tank f o r a n a l y s i s of n i t r o g e n and minera l components. One p a i l of cucumbers was d e s a l t e d i n t h e l a b o r a t o r y wi th t a p water . A 1 0 k 5 sampie of s a l t s t o c k and d e s a l t e d cucumbers was d i c e d w i t h a vege tab le d i c e r and homogenized wi thout a d d i t i o n of water w i t h a Bronwill Poly t ron homogenizer. A 1 l i te r sample of each homogenate was k e p t f o r a n a l y s i s .

The b r i n e and cucumber samples w e r e T e f r i g e r a t e d when they were c o l l e c t e d i n t h e tank yard. The samples were frozen i n t h e l a b o r a t o r y . For minera l and K j e l d a h l n i t r o g e n a n a l y s e s , t h e samples were h e l d from 1-6 months p r i o r t o a n a l y s e s . Brine samples f o r de te rmina t ion of BOD, COD, suspended s o l i d s , t i t r a t a b l e a c i d i t y , and NaCl were r e f r i g e r a t e d . The BOD was run w i t h i n 3 days of r e c e i p t of the samples. The o t h e r a n a l y s e s were completed w i t h i n 1 week.

To e v a l u a t e t h e commercial q u a l i t y of s a l t s t o c k produced wi th recyc led b r i n e , samples of 200 cucumbers were taken from each tank. They were c l a s s i f i e d i n t o t h r e e c a t e g o r i e s by tank yard personnel . Good cucumbers were t h o s e wi th no i n t e r n a l d e f e c t s . Commercially a c c e p t a b l e cucumbers inc luded t h e good cucumbers p l u s t h o s e w i t h s l i g h t b l o a t e r o r honeycomb d e f e c t s which could be s l i c e d i n t o d i l l c h i p s wi th only smal l l o s s e s . Commercially unacceptable s t o c k had s e v e r e b l o a t e r o r hor.Pycomb d e f e c t s which made it s u i t a b l e only f o r less va luable r e l i s h s t o c k . T h e t e x t u r e Qf d e s a l t e d cucumbers was eva lua ted by a puncture t es t w i t h a 5/16 inch d iameter probe. This was similar t o t h e t es t developed by B e l l and E t c h e l l s (11) ':sin9 a Magnus-Taylor manual p r e s s u r e tester. The test was d0r.e w i t h an I n s t r o n Universa l t e s t i n g ins t rument ( I n s t r o n Corp., Canton, M A ) . The f o r c e r e q u i r e d t o puncture the cucumber was determined by running a 5 /16 inch d iameter probe v e r t i c a l i y i n t o t h e f r u i t a t a speed of 50 cm/min. The r e c o r a e r was set t o record 20 kg p r e s s u r e f u l l scale. Twenty cucumbers from each tank were punctured. The average peak f o r c e requi red to puncture t h e cucumbers was c a l c u l a t e d .

12 13

A taste panel e v a l u a t i o n of t h e f i n a l p roduct made from 2nd and 3rd c y c l e s t o c k and t h e cor responding c o n t r o l s t o c k was conducted. Hamburger d i l l c h i p s from t h e 2nd and 3rd c y c l e s were prepared by d e s a l t i n g t h e s t o c k and u s i n g commercial procedures Of Vlasic Foods, Inc.

t h e taste test e v a l u a t i o n ( 1 2 ) ("Reference Guidebook f o r Sensory T e s t i n g , " 3rd e d i t i o n , 1 9 6 6 , C o n t i n e n t a l Can Co., I n c . , Chicago, I L ) . The s c o r e s h e e t is d i v i d e d i n t o three p a r t s . In t h e f i r s t p a r t t h e c o n t r o l sample i s e v a l u a t e d f o r f l a v o r , t e x t u r e and o v e r a l l q u a l i t y i n an " e x c e l l e n t " t o "poor" r a t i n g . I n t h e second p a r t t h e judges compare t h e h e a t and chemical t r e a t m e n t s w i t h t h e c o n t r o l on t h e scale of 0 (no d i f f e r e n c e ) t o 5 (very l a r g e d i f f e r e n c e ) . P a r t I11 compares o v e r a l l q u a l i t y of t h e t r e a t m e n t s wi th t h e c o n t r o l product on t h e s c a l e of 1 (much worse) t o 4 (same) t o 7 (much b e t t e r ) . The d a t a were analyzed us ing a n a l y s i s of v a r i a n c e procedures .

analyzed f o r s a l t , pH and t i t r a t a b l e a c i d i t y . These were t h e , normal a n a l y s e s performed i n commercial o p e r a t i o n s . S a l t w a s measured u s i n g a hydrometer t o de te rmine the p e r c e n t s a t u r a t i o n of a s a l t s o l u t i o n . I n a d d i t i o n , s a l t w a s measured by t i t r a t i n g b r i n e samples wi th 0 . 1 7 1 N AgN03. expressed as degrees sa lometer . A 1% change i n s a l t concen- t r a t i o n i s approximately e q u i v a l e n t t o a change o f 4 * salometer. The pH was measured w i t h a g l a s s e l e c t r o d e . Ti t ra table a c i d i t y w a s determined by t i t r a t i o n of a b r i n e sample wi th NaOH t o phenolphtha le in end p o i n t o r pH 8. R e s u l t s were expressed as p e r c e n t l a c t i c a c i d .

B l o a t e r damage was e v a l u a t e d on each commercial tank of cucumbers accord ing t o t h e c r i t e r i a used i n s t a n d a r d commercial o p e r a t i o n s a t V l a s i c . The t a n k s were emptied from October t o March. The s a l t s t o c k was d e s a l t e d t o approximately 4 % NaCl according t o the commercial p r a c t i c e of V l a s i c Foods, L:c. and processed i n t o f i n a l p roducts , p r i m a r i l y hamburger dill c h l p s .

s o l i d s (15) us ing s t a n d a r d methods. Reducing s u g a r was determined wiLth t h e d i n i t r o s a l i c y l i c a c i d r e a g e n t ( 1 6 ) . Nitrogen was measured using a microKjeldah1 procedure ( 1 7 ) .

The d i f f e r e n c e test s c o r e s h e e t ( F i g u r e 4 ) was used f o r

During the fermenta t ion of t h e cucumbers, t h e b r i n e s w e r e

The r e s u l t s were

Br ine was analyzed f o r BOD ( 1 3 ) , COD (14), and suspended

Brine and cucumber sampLes were assayed f o r l e a d , cadmium and chromium by atomic a b s o r p t l o n spec t rophotometry . A method d e s c r i b e d by Sprague and S l a v i n (18) and by Thomas e t a l . (19) was used w i t h q u a n t i t i e s of samples a p p r o p r i a t e f o r cucumbers and b r i n e . A 40 m l a l i q u o t of b r i n e or a 4 0 g sample of ground cucumbers w a s added t o a 250 m l Erlenmeyer f l a s k t o g e t h e r wi th 35 m l of c o n c e n t r a t e d n i t r i c a c i d . The sample was b o i l e d

T e s t Sample No.

DIFFERENCE TEST

Name: Date:

I . Sample K is t h e s t a n d a r d , o r r e f e r e n c e sample. P l e a s e r a t e K below:

O v e r a l l Q u a l i t y of K Come n t s ( c i r c l e one) F lavor Texture

E x c e l l e n t E x c e l l e n t E x c e l l e n t Good Good Good F a i r F a i r F a i r Poor Poor Poor

11. Please compare t h e samples t o iC f o r t e x t u r e and f l a v o r d i f f e r e n c e s . T e s t samples may o r may n o t be d i f f e r e n t from the r e f e r e n c e sample. R a t e each sample accord ing t o this d i f f e r e n c e scale:

R a t i n q Dif fe rence from Standard

0 No d i f f e r e n c e 1 Very s l i g h t d i f f e r e n c e 2 S J i g h t d i f f e r e n c e 3 Moderate d i f f e r e n c e 4 Large d i f f e r e n c e 5 V e r y l a r g e d i f f e r e n c e

Dif fe rence Rat ings Comments Texture 1 Flavor Texture 1 Flavor

I 1

111. Q u a l i t y of samples compared t o K :

T e s t Sample # T e s t Sample #

Much worse Moderately worse S l i g h t l y worse Same S l i g h t l y b e t t e r Moderately b e t t e r Much b e t t e r

F i g u r e 4 . Score s h e e t f o r t a s t e pane l e v a l u a t i o n of hamburger d i l l ch ips .

14 15

i

g e n t l y on a h o t p l a t e f o r approximately 3 h r u n t i l it turned clear and had reached a volume of 1 0 m l . The sample was then cooled t o room tempera ture and t h e pH a d j u s t e d t o 3.0 w i t h ammonium hydroxide. A f t e r cool ing aga in to room tempera ture , 5.0 m l o f 2 % ammonium p y r i l i d i n e d i th iocarbamate was added. The f l a s k was s w i r l e d and then al lowed t o s t a n d f o r 1 0 min. Then 1 0 o r 20 m l o f methyl i s o b u t y l ke tone (MIBX) was added. The s o l u t i o n was shaken f o r 2 min and al lowed t o s t a n d u n t i l it became clear. The MIBK phase was then removed and analyzed.

Mercury a n a l y s i s was based on t h e method developed by Hatch and O t t ( 2 0 ) . I n determining mercury l e v e l s , 4 0 ml of b r i n e o r 40 g of ground cucumber w a s t r a n s f e r r e d t o a 2 5 0 m l Erlenmeyer f l a s k and d r i e d on a h o t p l a t e a t 71°C f o r approx- imate ly 20 h r or u n t i l t h e sample appeared mois ture f r e e . The sample was cooled t o -1B0C, then 20 m l c o n c e n t r a t e d n i t r i c a c i d was added and t h e sample was allowed t o s t a n d f o r 1 h r a t room temperature . A f t e r h e a t i n g on a steam b a t h f o r 4 h r , 1 5 m l o f c o n c e n t r a t e d s u l f u r i c a c i d was added and h e a t i n g w a s cont inued u n t i l t h e brown n i t r o u s fumes were d r i v e n o f f (approximately 1 1/2 h r ) . w/v) w a s added. The sample w a s h e a t e d on a s team b a t h for 30 min t o complete t h e sample p r e p a r a t i o n . cooled t o room temperature , t h e mercury c o n c e n t r a t i o n was measured w i t h a Coleman model MAS-50 mercury a n a l y z e r .

Phosphorus, calcium, magnesium, manganese, i r o n , copper , boron, z i n c , and aluminum l e v e l s were determined by atomic emission spec t roscopy (21). Brine or ground cucumber samples were d r i e d i n p o r c e l a i n c r u c i b l e s on a h o t p l a t e a t < l O O ° C over a 32-hr p e r i o d . furnace a t 4 O O O C f o r 7 h r . Michigan S t a t e U n i v e r s i t y Leaf Analys is Labora tory .

The sample was cooled on ice and 1 5 m l o f KMnO4 ( 5 %

When t h e s o l u t i o n was

The d r i e d samples w e r e ashed i n a muff le Samples were ana lyzed by t h e

SPECIAL STUDIES

C e r t a i n s t u d i e s were done s e p a r a t e from commercial b r i n e r e c y c l i n g t o e v a l u a t e p o t e n t i a l d i f f i c u l t i e s w i t h r e c y c l i n g . These i n c l u d e d an e v a l u a t i o n of p e s t i c i d e b u i l d u p w i t h m u l t i p l e reuse of b r i n e , de te rmina t ion of t h e tempera ture and pH s t a b i l i t y of f u n g a l p e c t i n a s e s which are m o s t l i k e l y t o occur in f e r m e n t a t i o n b r i n e s and a measurement of l y s i n o a l a n i n e i n chemical ly t r e a t e d b r i n e .

'.* .

E f f e c t of Br ine Recycl ing on t h e Buildup of P e s t i c i d e Residues

S e l e c t e d cucumber p l o t s were t r e a t e d wi th twice t h e recommended dosage of p e s t i c i d e s a t h a l f o f t h e recommended i n t e r v a l s b e f o r e h a r v e s t . T e r r a c h l o r Super X ( p e n t a c h l o r o a n i l i n e ) , Demesan ( c h l o r o n e b ) , p a r a t h i o n , Thiodan ( e n d o s u l f a n ) , and Sevin ( c a r b a r y l ) . Demesan was n o t a p p l i e d i n 1 9 7 7 because it was dropped from cons ider - a t i o n f o r use on cucumbers.

The p l a n t s were t r e a t e d wi th

The cucumbers were shipped t o Michigan S t a t e Univers i ty and b r i n e d w i t h o u t s i z i n g or washing. Approximately 110 l b of cucumbers were p laced i n each of seven tanks and covered w i t h b r i n e t o g i v e a pack-out r a t i o of 57:43 by weight of cucumbers t o b r i n e . For t h e f i r s t c y c l e a l l seven tanks of f r e s h cucumbers were covered w i t h f r e s h 6.6% NaCl s o l u t i o n . I n subsequent c y c l e s t h e c o n t r o l tank was covered wi th f r e s h b r i n e , t h r e e tanks were covered wi th h e a t t r e a t e d b r i n e from t h e previous c y c l e , and three tanks were covered wi th chemical ly t r e a t e d b r i n e .

The fe rmenta t ions were c a r r i e d o u t d n d o o r s under u l t r a - v i o l e t l i g h t s to r e t a r d t h e growth of f i l m y e a s t s . Dry food- grade s a l t was added t o t h e tanks a s r e q u i r e d t o main ta in t h e s a l t c o n c e n t r a t i o n a t 6 .6%.

A t t h e end of the f e r m e n t a t i o n , u s u a l l y 3-4 weeks, t h e cucumbers were removed from t h e t a n k s , t h e b r i n e s were t r e a t e d and used as a cover b r i n e on t h e n e x t b a t c h of f r e s h cucumbers.

Samples were taken f o r p e s t i c i d e a n a l y s i s of f r e s h washed and unwashed cucumbers, b r i n e d cucumbers, and b r i n e b e f o r e and a f t e r h e a t o r chemical t r e a t m e n t . The cucumbers f o r t h e washed sample were sprayed wi th t a p water from a spray nozz le f o r 2 min. The water f low rate w a s 10 kg/min. For f r e s h and b r i n e d cucumber samples, 1 0 kg o f cucumbers were d iced on a v e g e t a b l e s l icer and then homogenized wi th a Bronwil l Poly t ron t i s s u e g r i n d e r .

Br ines and cucumbers were analyzed by e x t r a c t i o n of p e s t i c i d e m a t e r i a l s ' f o l l o w e d by g a s - l i q u i d chromatography. S o l v e n t s used i n t h e a n a l y s i s were methylene c h l o r i d e , ace tone , e t h y l a c e t a t e , and petroleum e t h e r ( b o i l i n g range 30-60OC). These s o l v e n t s were o b t a i n e d commercially, d i s t i l l e d i n g l a s s , from Burdick and Jackson L a b o r a t o r i e s , I n c . , Muskegon, Michigan 49422 . Chloron b , PCNB,#entachloro i l i n e (PCA) , p a r a t h i o n , paraoxon, Bravo%, Dathal , D i f o l a t s endosulfan I , endosul fan I f , endosul fan s u l f a t e , and c a r b a r y l were obta ined from P e s t i c i d e Reference S tandards Sec t ion , Chemistry Branch, R e g i s t r a t i o n Div is ion , room 5 1 7 5 , South Agr icu l ture Bui ld ing , Environmental P r o t e c t i o n Agency, Washington, DC 20460 .

16 17

Bio Beads 5-X3-200-400 mesh, c o n t r o l no. 13127 , c a t a l o g no. 154-2750, were purchased from Bio-Rad L a b o r a t o r i e s , Richmond, C a l i f o r n i a 9 4 8 0 4 .

Two gas chromatographs were used f o r t h e a n a l y s i s . The ins t ruments , columns and o p e r a t i n g c o n d i t i o n s were a s follows:

(1) Perk in Elmer model 910 equipped wi th ni t rogen-phosphorus d e t e c t o r ( N P D ) . Columns - 1 . 8 m x 4 mm i d g l a s s columns packed w i t h 108 OV-101 and 10% OV-101 + 15% OV-210 (1 + 1) , both on Chromosorb W-HP, 80-100 mesh, condi t ioned 48 h r a t 250 O C wi th c a . 20 ml/min N 2 flow.

Opera t ing c o n d i t i o n s - temperatures ( " C ) - column 210 , i n j e c t o r 230 , d e t e c t o r 250; n i t r o g e n c a r r i e r g a s , 60 ml/min; N P D bead temperature - 1 0 t u r n p o t s e t t i n g 630 or t o g i v e approximately 5 0 % f u l l s c a l e d e f l e c t i o n (FSD) f o r S ng c a r h r y l on 1 mv r e c o r d e r , b u t n o t t o exceed a d u l l r e d glow of d e t e c t o r bead. D e t e c t o r gas f lows - hydrogen 3 ml/min, a i r 38 ml/min. Ni t rogen and phosphorus c o n t a i n i n g compounds can both be determined under t h e above c o n d i t i o n s , however, t h e response f o r phosphorus i s ex t remely h igh . To circumvent making l a r g e d i l u t i o n s , t h e phosphorus compounds w e r e q u a n t i t a t e d with a flame photometr ic d e t e c t o r .

e l e c t r o n c a p t u r e d e t e c t o r (ECD) and flame photometr ic d e t e c t o r (FPD) connected i n p a r a l l e l wi th column e f f l u e n t s p l i t t e r .

Column - 1 .8 m x 4 nun i d g l a s s column packed w i t h 1 0 % OV-101 on Chromosorb W-HP, 80-100 mesh condi t ioned f o r 4 8 h r a t 250'C with ca . 23 m l / min N 2 flow.

Opera t ing c o n d i t i o n s - temperature ("C) - column 200 , i n j e c t o r 230 , d e t e c t o r s 350 (ECD) , 2 2 0 (PPD) . Argon c a r r i e r gas - 60 ml/min, s p l i t a t column e x i t w i t h 1 p a r t t o ECD and 19 p a r t s t o FPD. P u r g e ' g a s t o ECD - 70 ml/min argon-methane (95 + 5 ) . ECD a t t e n u a t i o n set t o g ive 40-60% FSD f o r 1 ng i n j e c t e d h e p t a c h l o r epoxide wi th s i g n a l f e d t o 1 mv r e c o r d e r . FPD o p e r a t i n g c o n d i t i o n s - hydrogen 50 ml/min, a i r 80 ml/min, e l e c t r o m e t e r s e t t i n g s so t h a t 2 ng of i n j e c t e d p a r a t h i o n g i v e s 40-60% FSD i n t o a 1 mv recorder .

( 2 ) Tracor model MT 222 equipped wi th l i n e a r i z e d 6 3 N i

Gel permeation chromatography was performed with d GPC Autoprep 1001 ( A n a l y t i c a l Bio Chemistry L a b o r a t o r i e s , I n c . , Columbia, Missouri 65201) equipped wi th a 2 . 5 x 50 CIT. column packed wi th Bio Beads S-X3. Methylene c h l o r i d e a t B 5 m l / m i n flow r a t e was used as t h e s o l v e n t . Usual p r a c t i c e was to d i s c a r d t h e e f f l u e n t f o r 29 min and then t o c o l l e c t the sample f o r 2 4 min. However, dump and c o l l e c t i o n times may vary depending upon flow r a t e , column packing , e t c . Each cclumn and ins t rument should be c a l i b r a t e d wi th t h e compounds of i n t e r e s t b e f o r e a n a l y s i s of samples i s begun.

samples were concent ra ted w i t h a 500 m l Kuderna-Danish c o n c e n t r a t o r f i t t e d w i t h a t h r e e - b a l l Snyder column (Kcntes G l a s s Co. , K-570000 o r e u i v a l e n t ) . The lower j o i n t of t h e c o n c e n t r a t o r must f i t a f 19 /22 of a 1 0 m l Mil ls- type graduated tube (Kontes Glass Co., K-570050 o r e q u i v a l e n t ) .

a 500 ml, s t a i n l e s s steel cup ( Ivan S o r v a l l , I n c . , Newton, CT 0 6 4 7 0 or e q u i v a l e n t ) .

Br ine s o l u t i o n s were shaken b e f o r e sampling t o o b t a i n an even d i s t r i b u t i o n of any s e t t l e d m a t e r i a l . Raw and b r i n e d cucumbers were chopped i n a food chopper t o g ive a homogenous mass. Samples were e x t r a c t e d accordi,ng t o t h e procedure of Luke e t a l . ( 2 2 ) . Brine ( 4 0 g ) was Weighed i n t o a 1 2 5 m l , g l a s s s toppered Erlenmeyer f l a s k , 80 m l of ace tone was added, and t h e sample was thoroughly mixed. For raw o r br ined cucumbers a 1 0 0 g chopped sample was added t o t h e b lender cup, 200 m l ace tone was added and t h e sample was blended a t high speed for 2 min. The s l u r r y was c e n t r i f u g e d and t h e super - n a t a n t decanted through a g l a s s wool plug i n t o a 303 ml g l a s s s toppered Erlenmeyer f l a s k . A l t e r n a t e l y , t h e sample could be f i l t e r e d w i t h s u c t i o n through a 12 cm Buchner funnel f i t t e d w i t h s h a r k s k i n f i l t e r paper .

Samples were blended w i t h a S o r v a l l b lender equipped w i t h

E ighty m l of e x t r a c t s , whether from b r i n e o r cuc.xmbers, w a s t r a n s f e r r e d t o a 1 l i t e r s e p a r a t o r y f u n n e l , One hlmdred ml each of petroleum e t h e r and methylene c h l o r i d e were added. The f u n n e l was shaken v igorous ly f o r 1 min , t h e l a y e r s were al lowed t o s e p a r a t e and t h e lower aqueous phase was dra ined i n t o a 2 5 0 m l s e p a r a t o r y f u n n e l c o n t a i n i n g 7 g NaC1. This funnel was shaken f o r 30 sec t o d i s s o l v e most of t h e NaC1. The upper phase from t h e 1 l i t e r s e p a r a t o r y funnel was passed through a 5 cm column of anhydrous g r a n u l a r Na SO4 i n t o a 500 m l Kuderna-Danish c o n c e n t r a t o r f i t t e d w i t h a 1 0 m? graduated tube. The 1 l i t e r s e p a r a t o r y funnel was r i n s e d wi th 1 0 0 ml methylene c h l o r i d e . This s o l v e n t was then added t o t h e 250 ml separa tory funnel t o r e - e x t r a c t t h e aqueous phase. The funnel was shaken for 1 min and t h e lower methylene c h l o r i d e phase was dra ined through t h e Na2S04 column i n t o the Kuderna-Danish concent ra tor .

18 19

The aqeous phase w a s e x t r a c t e d wi th another 1 0 0 ml p o r t i o n of methylene c h l o r i d e . A f t e r e x t r a c t i o n , this s o l u t i o n was a l s o d r i e d and added t o t h e concent ra tor . The combined =e thylene c h l o r i d e e x t r a c t s were evaporated t o about 2 m l wi th t h e a i d of a t h r e e - b a l l Snyder column. I t was necessary t o t a k e care t o p r e v e n t s o l v e n t from b o i l i n g i n t o t h e column a t the beginning o f t h e evapora t ion .

The c o n c e n t r a t e d e x t r a c t was d i l u t e d t o 7.0 ml w i t h methylene c h l o r i d e i n t h e graduated tube. The sample (5.0 m l ) was loaded i n t o the sample loop of t h e Autoprep 1001 and chromatographed by dumping 29 min (145 m l ) and c o l l e c t i n g f o r 2 4 min (120 m l ) . "Cleaned up" e x t r a c t was c o l l e c t e d and c o n c e n t r a t e d i n t h e Kuderna-Danish c o n c e n t r a t o r t o approximately 2 m l . The tube conta in ing sample w a s removed from t h e c o n c e n t r a t o r . The sample was evapora ted t o dryness w i t h a s l i g h t c u r r e n t of a i r o r n i t r o g e n and minimal h e a t . The d r i e d sample was d i s s o l v e d i n 3.0 m l e t h y l a c e t a t e f o r i n i t i a l i n j e c t i o n on the gas chromatograph equipped w i t h the NPD f o r q u a n t i t a t i o n o f c a r b a r v l . Appropriate d i l u t i o n s were made f o r i n j e c t i o n on the ECD/FPD equipped chromatograph.

was Sample r e p r e s e n t e d i n t h e f i n a l e t h y l a c e t a t e e x t r a c t s

Cucumbers: 100 g/(200 m l + 9 4 ml - 1 0 m l ) x 5 m 1 / 7 m l ; where 94 ml w a s t h e volume of water p r e s e n t i n t h e cucumbers, 10 ml w a s t h e water-acetone c o n t r a c t i o n f a c t o r and 5 m1/7 m l w a s t h e q u a n t i t y of sample used f o r GPC cleanup.

Br ine : 40 g/80 m l + 34 m l - 2.5 m l x 5 m1/7 m l : where 34 m l was t h e volume o f water i n t h e b r i n e sample c o n t a i n i n g 15% s o l i d s and 2.5 m l w a s t h e water-acetone c o n t r a c t i o n f a c t o r .

c a l c u l a t e d a s fol lows:

P e c t i n a s e I n a c t i v a t i o n

The p o s s i b i l i t y f o r i n t r o d u c t i o n of p e c t i n a s e s i n t o s p e n t b r i n e s , e i t h e r from t h e previous fe rmenta t ion o r dur ing p e r i o d s of b r i n e s t o r a g r , was a major concern i n the development of r e c y c l i n g procedures . c o n t r o l l e d , s e r i o u s s o f t e n i n g of cucumber s a l t s t o c k could result.

I f t h e s e enzymes were n o t p r o p e r l y

E t c h e l l s e t a l . ( 2 3 ) d i d a survey of t h e f u n g i p r e s e n t on cucumber f r u i t s and f lowers . They i d e n t i f i e d t h e most common molds and found t h a t a l l of t h e s p e c i e s i n v e s t i g a t e d produced p e c t i n a s e a c t i v i t y . I t was t h e i r op in ion t h a t enzymes from t h e dominant molds would b e t h e usua l cause of commercial cucumber s o f t e n i n g .

P e c t i n a s e was produced by growing each of t h e organisms s t u d i e d on t h e fo l lowing medium ( 2 4 ) : NH4N03 (1 g / l ) , MgS04 (0.3 g / l ) , y e a s t e x t r a c t (Difco) ( 0 . 1 g / l ) , KH PO4 ( 0 . 0 1 M) and c i t r u s p e c t i n (Sigma) (5.0 g / l ) . The pH was a 8 j u s t e d t o 6 .4 wi th 4 N NaOH p r i o r t o s t e r i l i z a t i o n of the medium. Fernbach f l a s k s c o n t a i n i n g 1 l i t e r o f media were i n o c u l a t e d wi th a p p r o p r i a t e organisms and shaken a t 1 1 0 r p m on a r o t a r y shaker . C u l t u r e s were grown a t room tempera ture ( 2 1 - 2 4 O C ) u n t i l enzyme a c t i v i t y reached i ts maximum l e v e l .

f o r 5 min a t 12,000 x g. The s u p e r n a t a n t was f i l t e r e d through a 0.45 u pore d iameter M i l l i p o r e f i l t e r . The ce l l f r e e f i l - t ra te , c o n t a i n i n g p e c t i n a s e a c t i v i t y , was concent ra ted with an Amicon model 4 0 2 u l t r a f i l t r a t i o n ce l l using a UM-10 membrane wi th a molecular weight c u t o f f of approximately 1 0 , 0 0 0 d a l t o n s .

For thermal i n a c t i v a t i o n s t u d i e s p e c t i n a s e c o n c e n t r a t e s were added t o b r i n e s o l u t i o n s such t h a t dur ing i n a c t i v a t i o n 1 2 % NaC1, 0 . 6 % l ac t ic a c i d and 0.1% Ca++ ion were p r e s e n t i n t h e b r i n e . The b r i n e pH w a s a d j u s t e d t o 3.3 t o 4.7 depending upon t h e p a r t i c u l a r experiment . Br ines were haa ted f o r s p e c i f i c time i n t e r v a l s i n 4.5 mm I . D . test t u b e s s e a l e d w i t h p a r a f f i n and cooled i n an ice b a t h . The enzyme a c t i v i t y remaining was measured by the rate of v i s c o s i t y change i n a 1 . 0 % p e c t i n s o l u t i o n i n pH 4.0, .015 M lactate b u f f e r . The t i m e r e q u i r e d f o r 90% i n a c t i v a t i o n o f enzyme a c t i v i t y (D-value) w a s d e t e r - mined from the l i n e a r p o r t i o n o f a p l o t of t h e logar i thm of t h e p e r c e n t a c t i v i t y remaining as a f u n c t i o n of t i m e .

Fungal cells were removed from t h e medium by c e n t r i f u g a t i o n

I n a c t i v a t i o n of p e c i i n a s e a t h igh pH was done i n s imula ted s p e n t b r i n e s i n which C a of a p r e c i p i t a t e . Glycine (0.02 M) was added t o provide b u f f e r c a p a c i t y a t high pH i n the b r i n e . I t was necessary t o f l u s h wi th n i t r o g e n gas and t i g h t l y c l o s e t e s t tubes with corks o r rubber s t o p p e r s t o p r e v e n t t h e b r i n e pH from dropping dur ing incubat ion . The pH drop was a p p a r e n t l y a r e s u l t of C02 a b s o r p t i o n dur ing i n c u b a t i o n .

The pH of t h e h igh pH b r i n e s was a d j u s t e d t o 4 . 0 with 1 N H C 1 p r i o r t o measuring t h e remaining enzyme a c t i v i t y . A c t i v i t y was determined a s d e s c r i b e d above. The i n a c t i v a t i o n of p e c t i - nases a t h igh pH d i d n o t fo l low f i r s t o r d e r r e a c t i o n k i n e t i c s . A s a r e s u l t , D-values could n o t be determined.

i o n w a s omi t ted t o avoid formation

20 21

Enzyme c o n t a i n i n g b r i n e s f o r i n a c t i v a t i o n experiments i n commercial s p e n t b r i n e s were prepared by d i a l y z i n g enzyme c o n c e n t r a t e i n a l a r g e excess of s p e n t b r i n e . This was done t o p r e v e n t d i l u t i o n of b r i n e c o n s t i t u e n t s by the enzyme s o l u t i o n .

Lys inoa lan ine Content of Chemically Trea ted Br ine

Formation of l y s i n o a l a n i n e by base t r e a t m e n t of p r o t e i n had been r e p o r t e d by DeGroot and Slump ( 2 6 ) . Woodward and S h o r t ( 2 7 ) had r e p o r t e d t h a t f r e e l y s i n o a l a n i n e was t o x i c t o r a t s . Though cucumber brines are low i n p r o t e i n , t h e h i g h pH r e q u i r e d f o r chemical treatment provided t h e p o t e n t i a l f o r formation of this compound.

To de termine whether s i g n i f i c a n t amounts of l y s i n o a l a n i n e could be formed by chemical t r e a t m e n t a f i r s t c y c l e , commercial spent sample b r i n e was used. The b r i n e was a d j u s t e d t o pH 1 1 . 4 and h e l d a t room tempera ture (23OC) f o r 8 days. The c l e a r s u p e r n a t a n t b r i n e w a s r e m v e d anc?.the pH a d j u s t e d t o 4 .6 wi th g l a c i a l acetic a c i d . Samples of u n t r e a t e d and base t r e a t e d b r i n e were d i a l y z e d a g a i n s t w a t e r t o r e m v e s a l t and low molecular weight components. The d i a l y z e d samples were concent ra ted on a f l a s h e v a p o r a t o r w i t h t h e water b a t h hea ted t o 40’12. A l i q u o t s of t h e c o n c e n t r a t e s were hydrolyzed a t 1 0 0 ° C wi th 6 N HC1. The h y d r o l y s a t e w a s chromatographed on a Beckman , l20C amino a c i d a n a l y z e r using the column f o r b a s i c amino a c i d . Authent ic l y s i n o a l a n i n e w a s chromatographed t o v e r i f y the p o s i t i o n on t h e chromatogram and f o r q u a n t i t a t i v e s t a n d a r d i z a t i o n o f t h e column.

2 2

SECTION 5

RESULTS AND DISCUSSION

CHARACTERISTICS OF RECYCLED BRINES

Br ine samples were c o l l e c t e d b e f o r e and a f t e r h e a t and chemical t rea tment f o r t h e f i r s t c y c l e b r i n e s i n 1 9 7 5 and f o r second c y c l e b r i n e s i n 1976. Tables 1 and 2 show t h e m e a n v a l u e s f o r t h e resul ts of t h e a n a l y s i s done on t h e s e b r i n e samples. The d a t a were analyzed by an a n a l y s i s of v a r i a n c e procedure t o determine t h e changes which occur a s a r e s u l t of h e a t o r chemical t rea tment .

There were no s i g n i f i c a n t d i f f e r e n c e s between t h e u n t r e a t e d b r i n e s used f o r t h e f i r s t c y c l e h e a t t r e a t m e n t and chemical t r e a t m e n t i n 1975. This was expected s i n c e t h e s e b r i n e s were randomly s e l e c t e d from t h e tank yard and ass igned t o e i t h e r t h e h e a t o r chemical t rea tment . A more l j m i t e d a n a l y s i s of b r i n e samples was done previous ly ( 8 ) . The l e v e l s observed i n t h i s p r o j e c t for the mineral components of t h e b r i n e s were s i m i l a r t o t h o s e obta ined i n t h e e a r l i e r s t u d y .

Heat t rea tment caused few changes i n t h e b r i n e . The pH and t i t r a t a b l e a c i d i t y were i n c r e a s e d and decreased , r e s p e c t i v e - l y . NaOH w a s added a f t e r h e a t t r e a t m e n t t o e f f e c t those changes. There was approximately a doubl ing of t h e aluminum l e v e l .

Chemical t rea tment caused a number of changes i n t h e b r i n e s . The pH and t i t r a t a b l e a c i d i t y changed a s expected. Reducing s u g a r s dec l ined under t h e a l k a l i n e c o n d i t i o n s . Formation and removal of a p r e c i p i t a t e reduced t h e suspended s o l i d s . BOD and COD i n c r e a s e d as a r e s u l t of v inegar a d d i t i o n f o r pH adjustment . S e v e r a l of t h e minera l components of b r i n e , i n c l u d i n g P , Ca, Mg and F e , d e c l i n e d a s a r e s u l t of chemical t r e a t m e n t . I t was found p r e v i o u s l y (8) t h a t t h e p r e c i p i t a t e formed c o n s i s t e d ’ p r i m a r i l y of minera l m a t e r i a l . t h e only minera l component t o show an i n c r e a s e .

Aluminum was

23

TABLE 1. CHARACTERISTICS OF 1ST CYCLE SPENT BRINE I N THE SPRING OF 1975 BEFORE AND AFTER HEAT OR CHEMICAL TREATMENT. THE TREATED BRINES WERE USED AS COVER BRINES FOR 2ND CYCLE FERMENTATIONS

Parameter Heat t r e a t m e n t Chemical treatment Unt rea t ed T r e a t e d Unt rea ted T r e a t e d

Acid % l ac t ic S a l t %

PH Sugar mg/l Suspended solid8 m g / l BOD mg/l COD mg/l Kjeldahl N m g / l C d mg/l Hg W/ l P mg/l C a mg/l Mg mg/l t4.n mg/l Fe mg/l Cu mg/l

Zn m g / l A1 mg/l C r mg/l

B mg/l

0.45 B* 13.1

3.58 A

405 B 254 B

10300 b 14200 b

594 . 0 15 0

130 B 1010 B

1 4 1 B 2.7 6.2 B 1 .6 1.4 4.9 5.3 a

.003

0.17 A

12.5 4.63 B 272 AB 204 B

9700 b 12800 b

507 .038 0

111 B 978 B 130 B 2.5 6.7 B 1.6 1 .3 4.3

10.7 b .003

0.47 B 13.2

3.53 A

392 B 231 B

10600 b 14000 b

564 .093 0

116 B 1020 B

130 B 3.4 7.2 B 2.0 1 . 4 5.0 6 . 1 a

.003

0.23 A 12.7

4.80 B

190 A 55 A

14000 a 17200 a

523 .058

0 26 A

714 A 12 A

1.9 2.5 A 1 .3 1.2 3.2

11.6 b .001

*Samples w i t h d i f f e r e n t letters are s i g n i f i c a n t l y d i f f e r e n t . With upper case letters, d i f f e r e n c e s are s i g n i f i c a n t a t t h e 1% l e v e l . W i t h lower case letters, d i f f e r e n c e s are s i g n i f i c a n t a t t h e 5% level.

TABLE 2. CHARACTERISTICS OF 2ND CYCLE SPENT BRINE I N THE SPRING OF 1976 BEFORE AND AFTER HEAT OR CHEMICAL TREATMENT. THE TREATED BRINES WERE USED AS COVER BRINES FOR 3RD CYCLE FERMENTATIONS

Heat t r e a t m e n t Chemical t r ea tmen t Unt rea ted T r e a t e d U n t r e a t e d Trea ted

Parameter

A c i d % l ac t i c S a l t %

PH Sugar mg/l Suspended solids mg/l BOD mg/l COD mg/l Kjeldahl N mg/l Cd m g / l Hg mg/l P m g / l Ca m g / l Mg mg/l Mn m s / l Fe mg/l Cu mg/l B m g / l Zn mg/l A 1 mg/l

0.62 B* 1 1 . 4

3.52 C 263 B 298

12500 b 18600 b

583 0.013 0.003

139 A

1042 A 173 A

1 . 4

9.3 1 . 4 1 . 4 4.8 8.3 A

0 .21 A 11.8

4.55 A 222 B 206

14000 ab 19300 b

621 0.012 0.003

128 AB

1123 A 183 A

1 .7 11.2

1 . 6 1.6 5 . 6

12.3 A

0.63 B 0.26 A 11.0 10.8

3.66 B 4.95 A 258 B 115 A 15 8 87

14500 ab 17400 a 19500 b 22700 a

601 507 0.012 0.015 0.003 0.003

100 B 11.0 C

960 A 652 B 140 B 5 c 1 . 0 0 .6

17 .5 4.9 1 . 0 1.6 1 . 3 1 . 5 4.2 3.6 7.1 A 31.2 B

*Samples w i t h d i f f e r e n t le t ters are s i g n i f i c a n t l y d i f f e r e n t . With upper case le t te rs , d i f f e r e n c e s are s i g n i f i c a n t a t t h e 1% level. With lower case le t te rs , d i f f e r e n c e s are s i g p i - f i c a n t a t the 5% l e v e l .

24 25

In 1 9 7 6 the second cyc le s p e n t b r i n e s were t r e a t e d p r i o r to the t h i r d c y c l e fe rmenta t ions . P r i o r t o t r e a t m e n t , a few d i f f e r e n c e s w e r e observed between t h e b r i n e s which had been h e a t t r e a t e d and chemical ly t r e a t e d the prev ious y e a r . The pH of t h e chemical t r e a t m e n t b r i n e was 3.66 compared t o 3.52 f o r the h e a t treatment b r i n e . This d i f f e r e n c e was s i g n i f i c a n t a t t h e 1% l e v e l . I t is thought t o be the r e s u l t o f v inegar a d d i t i o n which caused an i n c r e a s e i n b u f f e r c a p a c i t y i n the chemical t r e a t m e n t b r i n e . Phosphorus and magnesium were a l s o reduced i n t h e chemical t r e a t m e n t b r i n e s .

Heat t r e a t m e n t of t h e second c y c l e b r i n e r e s u l t e d i n no s i g n i f i c a n t change i n b r i n e composition except f o r t h e i n c r e a s e i n pH and decrease i n t i t r a t a b l e a c i d i t y . t rea tment caused s i g n i f i c a n t changes i n t h e same components and i n t h e same d i r e c t i o n s i n 1 9 7 6 and 1975 wi th the except ion of BOD and Fe . I n t h o s e two i n s t a n c e s t h e r e were d i f f e r e n c e s i n the same d i r e c t i o n s a s were observed i n 1975. However, t h e d i f f e r e n c e s were n o t s i g n i f i c a n t a t t h e 5 % l e v e l .

Chemical

Comparison of the h e a t t r e a t e d f i r s t and second c y c l e b r i n e s showed an i n c r e a s e i n BOD from 9700 mg/l t o 1 4 , 0 0 0 mg/l and COD from 1 2 , 8 0 0 mg/l t o 19,300 mg/l. In a d d i t i o n , there were s m a l l i n c r e a s e s i n t h e c o n c e n t r a t i o n of P , C a and Mg. For chemical t r e a t m e n t t h i s f i r s t and second c y c l e comparison showed t h a t BOD and COD i n c r e a s e d . Though the l e v e l s of P , Ca and Mg were lower i n t r e a t e d b r i n e s , t h e l e v e l s i n 1975 were a c t u a l l y s l i g h t l y h i g h e r than i n 1 9 7 6 . This may have been a r e s u l t o f more e f f i c i e n t removal of p r e c i p i t a t e i n 1976.

The r e s u l t s of t h e s e experiments showed t h a t h e a t t r e a t m e n t had no e f f e c t upon t h e b r i n e c o n s t i t u e n t s , except f o r aluminum and t h e pH and t i t r a t a b l e a c i d i t y , which were i n t e n t i o n a l l y a l t e r e d . Chemical t r e a t m e n t r e s u l t s i n a d e c l i n e o f many, b u t n o t a l l , o f the minera l c o n s t i t u e n t s of b r i n e . The BOD and COD are i n c r e a s e d as a r e s u l t of v inegar a d d i t i o n . Aluminum l e v e l s i n c r e a s e d a f t e r completion of b r i n e t r e a t m e n t wi th both t h e chemical and h e a t techniques . I t may be t h a t t h e food grade NaOH, which was used i n both procedures , c o n t a i n s some aluminum a s an impur i ty .

Thi rd c y c l e b r i n e s were removed from cucumber fe rmenta t ion The composi t ion of t a n k s a f t e r t h e t h i r d c y c l e fe rmenta t ions .

t h e t h i r d c y c k b r i n e s i s given i n T a b l e s 5 and 6 . The c o n c e n t r a t i o n s of, m i n e r a l c o n s t i t u e n t s were similar t o t h e c o n c e n t r a t i o n s b e f o r e t rea tment of t h e f i r s t and second c y c l e b r i n e s . S i n c e t h e p r o j e c t was concluded a t t h e end of t h e t h i r d c y c l e of f e r m e n t a t i o n , the t h i r d c y c l e b r i n e s were n o t t r e a t e d .

CHARACTERISTICS OF CUCUMBERS AND FERMENTATIONS

Tables 3 and 4 summarize t h e numbers of tanks opera ted i n this p r o j e c t and t h e amount o f cucumbers and b r i n e s used. The c o n t r o l tanks were covered w i t h 6.6% (25' S ) NaCl b r i n e a t t h e beginning of cucumber fe rmenta t ion . This w a s t h e usua l commercial p r a c t i c e f o r using f r e s h b r i n e s . Recycled b r i n e s were used a t whatever s a l t c o n c e n t r a t i o n was p r e s e n t a f t e r b r i n e treatment. This averaged about 12.5% i n 1975 and 11% i n 1 9 7 6 . The a b i l i t y t o use a high s a l t cover b r i n e is a necessary p a r t o f s u c c e s s f u l r e c y c l i n g , s i n c e d i l u t i o n of b r i n e t o 6 .6% would r e q u i r e d ischarge of a l a r g e f r a c t i o n of s p e n t b r i n e due t o t h e excess volume genera ted .

water i n t h e cucumbers. To main ta in t h e s a l t concent ra t ion a t 6 . 6 % dur ing fe rmenta t ion , dry s a l t was added t o t h e tank head- boards . These tanks were fermented a s nonpurged, n a t u r a l fe rmenta t ions . This was t h e u s u a l fe rmenta t ion procedure a t t h e time this p r o j e c t was i n i t i a t e d . Recent ly Cost i low e t a l . ( 2 8 ) r e p o r t e d on a n i t rogen-purg ing procedure which was des igned t o r e m v e C 0 2 from n a t u r a l fe rmenta t ions . The technique was shown t o s i g n i f i c a n t l y reduce b l o a t e r s dur ing cucumber fe rmenta t ions . The p r o s p e c t i s t h a t a s i g n i f i c a n t p r o p o r t i o n of commercial f e r m e n t a t i o n s w i l l be using t h i s tech- n ique i n the immediate f u t u r e . V l a s i c has used t h e purging technique i n combination wi th r e c y c l e d b r i n e wi thout d i f f i c u l t y i n fe rmenta t ion t a n k s which w e r e n o t p a r t of this p r o j e c t . No v a r i a t i o n s i n b r i n e composi t ion would b e a n t i c i p a t e d as a r e s u l t of us ing purging, s i n c e t h e only e f f e c t of the technique i s t o c i r c u l a t e t h e b r i n e d u r i n g the fermenta t ion per iod i n such a way t h a t COz genera ted by t h e microorganisms and t h e f r u i t can be e f f i c i e n t l y removed.

The cover b r i n e was d i l u t e d a s it e q u i l i b r a t e d w i t h t h e

26 27

. . . .

TABLE 3. SUMMARY DATA ON FERMENTATION TANKS, 1975

Contro l Heat Chemical t r e a t m e n t t r e a t m e n t

Number of t a n k s 1 0 11 1 0

Bushels of cucumbers 7660 8668 7388

Gallons of b r i n e 34321 31418 30881

Gallons o f b r i n e / b u s h e l 4.48 3.62 4.18

Pack-out r a t i o 57:43 62: 38 59:41

TABLE 4. SUMMARY DATA ON FERMENTATION TANKS, 1976

Contro l Heat Chemical trea.tment t r e a t m e n t

Number o f tanks 8 8 8

Bushels o f cucumbers 5727 5604 5727

Gallons of b r i n e 19832 20780 19960

Gallons of br ine /bushe l 3.46 3.71 3.49

Pack-out r a t i o 63: 37 62: 38 63: 37

Tables 5 and 6 show t h e composi t ion of s p e n t b r i n e s a t t h e t i m e cucumbers were removed from the fermenta t ion tanks . The c o n t r o l b r i n e s i n 1975 and 1976 were f i r s t c y c l e s p e n t b r i n e s . “%e tanks which c o n t a i n e d h e a t and chemical ly t r e a t e d b r i n e s were second c y c l e fe rmenta t ions i n 1975 and t h i r d c y c l e fermen- t a t i o n s i n 1976. When second c y c l e b r i n e s were compared t o the 1975 f i r s t c y c l e c o n t r o l b r i n e s , t h e only s i g n i f i c a n t d i f f e r e n c e s were a h i g h e r f i n a l pH i n t h e recyc led b r i n e tanks and a h i g h e r aluminum l e v e l i n t h e h e a t t r e a t e d b r i n e than i n t h e c o n t r o l . The h e a t and chemical t r e a t e d b r i n e s d i f f e r e d from each o t h e r i n suspended s o l i d s , b u t n e i t h e r was s i g n i f i - c a n t l y d i f f e r e n t from t h e c o n t r o l .

c o n t r o l b r i n e s showed an i n c r e a s e i n pH, reducing s u g a r , BOD and COD i n t h e chemical ly t r e a t e d b r i n e s . The h e a t t r e a t e d b r i n e s d i f f e r e d from t h e c o n t r o l o n l y i n pH, BOD and COD. The

I h e a t t r e a t m e n t b r i n e s had a h i g h e r Ca and Mg c o n t e n t than t h e chemical t r e a t m e n t . However, t h e c o n t r o l tanks showed i n t e r -

’ mediate l e v e l s which were n o t s i g n i f i c a n t l y d i f f e r e n t from e i t h e r the h e a t o r chemical t r e a t m e n t b r i n e s .

The rise i n f i n a l pH i n r e c y c l e d b r i n e t a n k s was expected because t h e b u f f e r c a p a c i t y of t h e r e c y c l e d b r i n e s would r e t a r d the drop i n pH d u r i n g fe rmenta t ion . BOD and COD l e v e l s i n b r i n e s were also expec ted t o i n c r e a s e because of t h e car ry- over o f o r g a n i c matter when b r i n e s were recyc led . None of t h e changes a f f e c t e d t h e course of fe rmenta t ion to any p r a c t i c a l degree. Observa t ions of the p r o g r e s s of fe rmenta t ions and t h e tank y a r d o p e r a t i o n s w i t h r e c y c l e d b r i n e showed t h a t r e c y c l i n g can be done w i t h o u t changing the t a n k y a r d o p e r a t i o n dur ing t h e fe rmenta t ion p e r i o d .

Comparison o f t h i r d c y c l e b r i n e s wi th t h e 1976 f i r s t cyc le

A

28 29

Y

, . 3 . TABLE 6. ANALYSIS O F SPENT BRINE REMAINING I N THE FERMENTATION TANKS I N

THE WINTER AFTER REMOVAL OF SALT STOCK CUCUMBERS FROM THE 2ND CYCLE (1975) AND 3RD CYCLE (1976) FERMENTATION TANKS. ALL DATA ARE EXPRESSED AS mg/l OF BRINE*

Element C o n t r o l H e a t t r e a t m e n t Chemical treatment 2nd cycle 3rd cycle 2nd cycle 3rd c y c l e

1975 1976 1975 1976 1975 1976

N Cd

H g P Ca

4 Mn Fe

c u B

Zn A 1

Pb C r

582 543 656 .008 -012 .006

0 .008 0

1 2 8 252 134 1180

137 213 ab 142

3.0 1 .3 3.1 8.9 11.9 10 .0

2.9 0.4 1.8 1 . 3 1 . 4 1.4

4.3 2 . 8 4.7 7.3 b 1 2 . 1 12.6 a

-. 1130 958 ab

0 0 0 0 0 -

755 .020 -010

322 1391 a

261 a 2.0

17.9

1.1 1 . 8

4.7 22.3

0 -

665 692 .005 . 0 19 .001 . 005

127 165 1120 774 b

120 146 b

2.3 1.4 11.0 9 .8

1 .3 1.3 1 . 3 1 . 3 3.9 2 .8 9.9 ab 25 .1

0 0

0 - 'Treatments were compared w i t h i n the same year by ana lys i s of variance.

w i t h d i f f e r e n t le t ters are s i g n i f i c a n t l y d i f f e r e n t . W i t h l ower case letters, d i f fe rences are s i g n i f i c a n t a t the 5% leve l . W i t h upper'case let ters, d i f f e r e n c e s are s i g n i f i c a n t a t the 1% level.

Samples

S a l t s t o c k q u a l i t y was e v a l u a t e d f o r cucumbers fermented i n recyc led b r i n e s . Bloa t ing h a s t r a d i t i o n a l l y been a major source of d e f e c t s i n fermented f r u i t . B l o a t i n g r e s u l t s i n sig- n i f i c a n t economic loss because s e r i o u s l y b l o a t e d f r u i t can only be u t i l i z e d i n lower p r i c e r e l i s h products . t h e r e s u l t s of b l o a t e r e v a l u a t i o n s on second and t h i r d c y c l e s a l t s t o c k . I n both 1975 and 1976, t h e c o n t r o l w a s f i r s t c y c l e s a l t s tock . No s i g n i f i c a n t d i f f e r e n c e s were found between f r u i t fermented i n recyc led b r i n e s and t h e c o n t r o l s . This showed t h a t b l o a t e r d e f e c t s w i l l n e i t h e r i n c r e a s e nor d e c r e a s e a s a consequence o f r e c y c l i n g . A ~ I s t a t e d above, i f fermenta- t i o n s were p r o p e r l y purged, s i g n i f i c a n t d e c r e a s e s i n b l o a t e r d e f e c t s could be obta ined .

T a b l e s 7 and 8 show

TABLE 7. QUALITY OF 2ND CYCLE SALT STOCK CYCUMBERS FERMENTED I N RECYCLED BRINE, 1975

~ ~~~

Contro l Heat Chemical t r e a t m e n t t r e a t m e n t

Good s t o c k ( 0 ) 72.0 72.8 73.0 C o m e r c i a l l y a c c e p t a b l e ( 8 ) 85.3 86.5 86.5

Commercially unacceptab le ( % ) 14.7 13.5 13.5 ~

'No s i g n i f i c a n t d i f f e r e n c e s among t r e a t m e n t s .

TABLE 8. QUALITY OF 3RD CYCLE SALT STOCK CUCUMBERS FERMENTED I N RECYCLED BRINE, 1976*

Cont ro l Heat Chemical t r e a t m e n t t r e a t m e n t

Good s t o c k (%) 52.1 46.0 54.0 Commercially a c c e p t a b l e ( % ) 84.9 80 .2 8 2 . 6

Commercially unacceptab le ( % ) 15.1 19.9 17.4

I n a d d i t i o n t o b l o a t e r d e f e c t s , the s a l t s t o c k was r o u t i n e l y e v a l u a t e d f o r o v e r a l l commercial a c c e p t a b i l i t y a t t h e t i m e o f p r o c e s s i n g . Cucumbers fermented i n recyc led b r i n e were judged t o have normal t e x t u r e , color and odor . I n s t r o n p r e s s u r e test e v a l u a t i o n of the d e s a l t e d s t o c k from second c y c l e f e r m e n t a t i o n s showed no s i g n i f i c a n t d i f f e r e n c e s i n t h e s t o c k from r e c y c l e d b r i n e s . The average p r e s s u r e t es t was 17.5 l b f o r t h e c o n t r o l , 18.4 Ib f o r t h e s t o c k from h e a t t r e a t e d b r i n e and 18.3 l b f o r e t o c k from chemical ly t r e a t e d b r i n e . On t h e s c a l e proposed by B e l l e t a l . ( ll), t h e f r u i t would be r a t e d very f i rm.

Taste p a n e l e v a l u a t i o n s were done on hamburger d i l l c h i p s p r e p a r e d from c o n t r o l s a l t s t o c k and from s a l t s t o c k from second and t h i r d c y c l e fe rmenta t ions . Tables 9 and 1 0 show t h e average scores f o r second and t h i r d c y c l e products and cor responding c o n t r o l samples. The l a s t column shows t h e cumulat ive averages . The c o n t r o l samples were r a t e d f a i r t o good when e v a l u a t e d f o r f l a v o r , t e x t u r e and o v e r a l l q u a l i t y .

Tables 11-15 show the r e s u l t s o f q n a l y s i s of v a r i a n c e of t h e d i f f e r e n c e s i n t e x t u r e , f l a v o r and o v e r a l l q u a l i t y of producte p r e p a r e d from c o n t r o l and r e c y c l e d fe rmenta t ions . There were no s i g n i f i c a n t d i f f e r e n c e s between t h e c o n t r o l and p r o d u c t prepared from s a l t s t o c k fermented i n e i t h e r h e a t t r e a t e d or chemica l ly t r e a t e d , recyc led b r i n e .

t o be any s i g n i f i c a n t d e t e r i o r a t i o n or improvement i n t h e q u a l i t y of products o b t a i n e d from fermenta t ion i n recyc led b r i n e . There have been no complaints from either i n s t i t u t i o n a l o r i n d i v i d u a l consumers of t h e s e products which have been r e l a t e d t o use of recyc led b r i n e .

Based upon commercial exper ience , t h e r e does n o t appear

*No s i g n i f i c a n t d i f f e r e n c e s among t r e a t m e n t s .

32 33

w VI

TABLE 1 0 . COMPARISON OF 3FW CYCLE PRODUCT WITH THE CONTROL (AVERAGES), 3 SAMPLES/GROUP, 11 JUDGES mn 5 GROUPS

Groups Cumula t ive 1 2 3 4 5 a v e r a g e

I. E v a l u a t i o n of c o n t r o l 2.54 2.73 3.0 2.73 2.45 2.69 3.26 3.09 3.0 2.64 2.09 2.84 2.36 2.36 2.73 3.0 2.55 2.60

O v e r a l l q u a l i t y T e x t u r e Flavor

X I . T e x t u r e differences H e a t t r e a t m e n t Chemical t r e a t m e n t

1 .54 1.36 1.09 2.63 2.72 1.87 1.18 2.45 1.45 2.72 3.45 2.25

111. Flavor d i f f e r e n c e s H e a t t r e a t m e n t Chemical t r e a t m e n t

2.36 2.27 1.82 2.0 1.45 1.98 3.64 3.18 2.10 3.64 1 . 7 3 2.84

IV. O v e r a l l q u a l i t y d i f f e r e n c e s 4.18 4.45 3.73 4.02 4.09 . 4.25

3.64 3.64 4.09 3.45 4.0 3.76 H e a t t r e a t m e n t Chemical t r e a t m e n t

TABLE 9 . COMPARISON OF 2ND CYCLE PRODUCT WITH THE CONTROL (AVERAGES), 3 SAMPLES/GROUP, 9 JUDGES AND 7 GROUPS

Cumula t ive average

Group 1 2 3 4 5 6 7

I . E v a l u a t i o n of c o n t r o l

O v e r a l l q u a l i t y 2.89 2.22 2.44 1.89 3.00 2.11 2.89 2.49 w T e x t u r e 3.56 3.11 2.89 3.22 3.67 2.00 3.00 3.06

F l a v o r 2.89 2.33 2.55 2.11 3 .00 2.22 2.78 2.56 &.

11. T e x t u r e d i f fe rences

Heat t r e a t m e n t 1.56 1 .78 1.33 1 . 5 5 1.11 2.00 1.22 1 . 5 1 Chemical t r e a t m e n t 2.78 1.44 1.11 2.67 0.78 2.78 1 .33 1 . 8 4

111. F l a v o r d i f f e r e n c e s

Heat t r e a t m e n t 1.44 1 . 7 8 3.67 3 . 0 0 1.56 1.67 3.22 2.33 Chemical t r e a t m e n t 4.11 1.67 3.33 2.67 2.11 2.11 2.22 2.62

TABLE 11. ANALYSIS OF VARIANCE TABLE FOR TEXTURE DIFFERENCES OF HAMBURGER D I L L CHIPS MADE FROM 2ND CYCLE SALT STOCK CUCUMBERS*

Source df 8s Ms F

Treatments 1 3.50 3 .50 1 . 6 4

Groups 6 33.16 5 . 5 3 2 . 6 0

Treatments x groups 6 1 2 . 7 8 2 . 1 3

Judges 8 23 .59 2 . 9 5 1 . 0 0

Judges x treatments 8 2 . 8 6 0 . 3 6 0 . 1 2

Judges x groups 4 8 1 4 1 . 9 1 2 . 9 6

Judges x groups x treatments 4 8 59.86 1 . 2 5

*No s i g n i f i c a n t d i f ferences

TABLE 1 2 . ANALYSIS OF VARIANCE TABLE FOR FLAVOR DIFFERENCES OF HAMBURGER D I L L CHIPS MADE FROM 2ND CYCLE SALT STOCK CUCUMBERS*

Source df ss Ms F

Treatments

Groups

1 2 . 5 7 2 . 5 7 0 . 4 1

6 4 6 . 6 5 7 . 7 0 1 . 2 4 1

Treatments x groups 6 3 7 . 7 6 6 . 2 9

Judges 8 1 2 . 2 9 1 . 5 4 0 .70

Judges x treatments 8 7 . 4 3 0 . 9 3 0 . 4 2

Judges x groups 48 1 0 5 . 4 9 2 . 2 0

Judges x groups x treatments 4 8 4 0 . 2 4 0 . 8 4

*No s i g n i f i c a n t d i f ferences .

36 37

TABLE 1 3 . ANALYSIS OF VARIANCE TABLE FOR TEXTURE DIFFERENCES OF HAMBURGER DILL CHIPS MADE FROM 3RD CYCLE SALT STOCK CUCUMBERS

Source d f SS us F

Treatments 1 4.0 4.0 2 . 3 0

Groups 4 5 6 . 6 8 14.17 8 . 1 4 *

Treatment x groups 4 6 . 9 6 1.74

Judges 10 2 6 . 0 5 2 . 6 1 0 . 8 2

Judges x t r e a t m e n t s 1 0 1 2 . 1 0 1 . 2 1 0 . 3 8

Judges x groups 40 1 2 7 . 3 2 3 . 1 8

Judges x groups x tre atments 4 0 5 9 . 5 4 1 . 4 9

~~~ ~~ ____ ~-

* S i g n i f i c a n t l y d i f f e r e n t a t p = .05.

&& I--

TABLE 14. ANALYSIS OF VARIANCE TABLE FOR FLAVOR DIFFERENCES OF HAMBURGER DILL CHIPS MADE FROM 3RD CYCLE SALT STOCK CUCUMBERS'

~~

Source d f 98 MS F

Treatments 1 2 0 . 0 8 2 0 . 0 8 9 . 2 1

Groups I 3 3 . 8 1 8 . 4 5 3 . 8 8

Treatments x groups 4 ' 8 . 7 0 2 . 1 8

Judges 1 0 1 6 . 2 9 1 . 6 3 0 . 7 4

Judges x t r ea tmen t s 1 0 1 5 . 0 2 1 . 5 0 0 . 6 8

Judges x groups 40 8 7 . 9 9 2 . 2 0

Judges x groups x t r e atments 40 3 6 . 7 0

*No s i g n i f i c a n t d i f f e r e n c e s

38 39

'

TABLE 15. ANALYSIS OF VARIANCE TABLE FOR OVERRLL QUALITY DIFFERENCES OF HAMBURGER D I L L CHIPS MADE FROM 3RD CYCLE SALT STOCK CUCUMBERS'

Source df ss us F

Treatments 1 6.64 6.64 2.74

Groups 4 0.86 0.22 0.09

Treatments x groups 4 9.68 2.42

Judges 10 22.70 2.27 0.72

Judges x t r e a t m e n t s 10 13.26 1.33 0.42

Judges x group8 40 126.94 3.17

Judges x groupe x t r e a t m e n t s 40 64.92 1.62

*NO s i g n i f i c a n t d i f f e r e n c e s .

The c o n c e n t r a t i o n s of s e v e r a l m i n e r a l s i n t h e s a l t s t o c k and t h e d e s a l t e d cucumbers were analyzed t o determine t h e degree of b u i l d u p o f t h e s e m a t e r i a l s which might r e s u l t from r e c y c l i n g br ine . R e e u l t s of t h e s e a n a l y s e s a r e summarized i n Tables 1 6 and 17. The second c y c l e s a l t s t o c k showed no s i g n i f i c a n t d i f f e r e n c e s i n t h e m i n e r a l c o n t e n t compared t o t h e c o n t r o l f i r s t c y c l e s a l t s t o c k except t h a t a t the 5% s i g n i f i c a n c e l e v e l , t h e l e v e l of A 1 i n the h e a t t r e a t m e n t s a l t s t o c k was h i g h e r than f o r the c o n t r o l or chemical ly t r e a t e d samples. The t h i r d c y c l e samples from h e a t t r e a t e d b r i n e had h i g h e r l e v e l s of ~ g , m and Fe than t h e c o n t r o l . There were no s i g n i f i c a n t d i f f e r e n c e s between the samples from chemical ly t r e a t e d b r i n e and t h e c o n t r o l samples.

A f t e r d e s a l t i n g the s a l t s t o c k cucumbers i n t h e second c y c l e samples , t h e only S i g n i f i c a n t d i f f e r e n c e was a h igher Mn l e v e l i n t h e samples from h e a t t r e a t e d b r i n e and a lower A 1

, l e v e l i n samples from chemical ly t r e a t e d b r i n e compared t o h e a r t r e a t e d b r i n e samples. The t h i r d c y c l e samples shaved no

L d i f f e r e n c e s between t h e c o n t r o l and e i t h e r r e c y c l e d b r i n e technique . The only d i f f e r e n c e s i g n i f i c a n t a t t h e 5% l e v e l was a h i g h e r Mg c o n c e n t r a t i o n i n samples from h e q t t r e a t e d b r i n e s compared t o samples from chemical ly t r e a t e d b r i n e s . I n s e v e r a l i n s t a n c e s there were lower l e v e l s of m i n e r a l s i n the d e s a l t e d cucumbers i n 1975 compared t o 1976 i n a l l t h r e e groups of samples. This w a s a t t r i b u t e d t o the f a c t t h a t i n 1975 t h e cucumbers were d e s a l t e d t o (1% N a C l . done t o b r i n g the s a l t c o n c e n t r a t i o n down t o 4%. This w a s closer t o a c t u a l conrmercial p r a c t i c e .

The r e s u l t s of t h e minera l a n a l y s i s d i d n o t show any b u i l d u p o f e lements to i l l e g a l o r p o t e n t i a l l y t o x i c l e v e l s i n t h e s p e n t b r i n e s (Table 6 ) , t h e s a l t s t o c k (Table 1 6 ) or t h e d e s a l t e d cucumbers (Table 1 7 ) . The Pb was below d e t e c t a b l e l e v e l s . The lowes t d e t e c t a b l e l e v e l was e s t i m a t e d t o be approximately 0.05 ppm. Samples were ana lyzed f o r chromium i n 1975. Most samples conta ined no d e t e c t a b l e chromium. A s a r e s u l t , t h i s a n a l y s i s was n o t done i n 1976.

composi t ion of s p e n t b r i n e s b e f o r e and a f t e r t r e a t m e n t , on t h e course of fe rmenta t ion and on t h e minera l components of cucumbers b e f o r e and a f t e r d e s a l t i n g l e d t o t h e fo l lowing conclus ions regard ing t h e t e c h n o l o g i c a l a s p e c t s of b r i n e r e c y c l i n g .

1. Major changes i n tank yard p r a c t i c e were n o t r e q u i r e d f o r

* 2 . Fermentat ions proceeded normally. The same c r i t e r i a used t o

I n 1976 d e s a l t i n g was

The d a t a on t h e commercial q u a l i t y of s a l t s t o c k , on t h e

b r i n e r e c y c l i n g .

judge completion of f r e s h b r i n e f e r m e n t a t i o n s could be used t o judge fe rmenta t ions wi th r e c y c l e d b r i n e .

- 41 40

. . . " TABLE 17. DESALTED CUCUMBER ANALYSIS. DISTRIBUTION OF MINERAL LEVELS I N

DESALTED CUCUMBERS DURING THREE CYCLES OF FERMENTATION. ALL DATA ARE EXPRESSED AS m g / k g OF CUCUMBERS*

Element C o n t r o l Heat t r e a t m e n t Chemical t r e a t m e n t 1st cycle 1st cycle 2nd cycle 3 r d c y c l e 2nd c y c l e 3 r d cycle

1975 1976 1975 1976 1975 1976

N 399 589 364 678 348 626 Cd .039 .013 .081 -009 .064 .017 H g .015 .004 .019 .004 .009 .006 P 56 210 58 216 53 2 60 C a 372 6 7 1 32 7 912 331 564 M9 59 156 a b 56 186 a 53 102 b

Mn 0.06 b 0.9 0..29 a 0.8 0.06 b 1.0 Fe 6.1 18.8 7.8 16.1 6 .0 11.6 c u 0.7 1.2 0.7 1 .2 0.6 1.6 B 0.6 1.3 0.6 1 .5 0.6 1 .3 Zn 0.3 1.6 1.2 1.7 0.2 1.7 A 1 7.0 ab 23.7 7.1 a 17.9 4.9 b 12.9 Pb 0 0 0 0 0 0 C r .016 - .012 - .018 -

p. W

c- N

*Treatments w e r e compared w i t h i n the same y e a r by a n a l y s i s of v a r i a n c e . Samples w i t h d i f f e r e n t let ters are s i g n i f i c a n t l y d i f f e r e n t . With l o w e r case' let ters, d i f f e r e n c e s are s i g n i f i c a n t a t the 50 l e v e l . With upper case le t te rs , d i f f e r e n c e s are s i g n i f i c a n t a t the 1% level.

- 1

TABLI.: 16. SALT SWCK CUCUMBER ANALYSIS. DISTRIBUTION OF MINERAL LEVELS I N COMMERCIAL SALT STOCK DURING THREE CYCLES OF FERMENTATION. ALL DATA ARE EXPRESSED AS mg/kg O F CUCUMBERS*

Element C o n t r o l Heat t r e a t m e n t Chemical t r e a t m e n t 1st cycle 1st cycle 2nd c y c l e 3 rd c y c l e 2nd c y c l e 3 r d cycle

1975 1976 1975 1976 1975 1976

N C d

Hg P C a

M9 Mn Fe c u B

Zn A 1

592 74 6 466 79 6 .057 -014 .032 .015 .006 .004 .009 . O O 3 130 248 ab 145 321 a 924 954 ab 920 1308 a 134 198 b 136 275 a

1 .7 1.5 B 1 .8 2.5 A

9.5 13.5 b 13.0 22.3 a

1.1 1.6 1 .3 1.7 1 . 4 1 .7 1 .5 2.1 3.3 3.0 3.4 3.9 7.2 b 14.7 11.5 a 22.8

726 .06 1

-019 ,136 992 113

2.4 11 .0

1 .6 1.6 4 . 1 8.4 b

814 .021 .006 168 b

810 b

1 4 1 b 1 .2 B

11.1 b 1.1 1.6 3.4

11.7

Pb 0 0 0 0 0 0

C r .010 - -012 - .017 - *Treatments w e r e compared w i t h i n the same y e a r by a n a l y s i s o f v a r i a n c e . Samples with d i f f e r e n t letters are s i g n i f i c a n t l y d i f f e r e n t . With lower case le t ters , d i f f e r e n c e s are s i g n i f i c a n t a t t h e 5% l e v e l . With upper case l e t t e r s , d i f f e r e n c e s are s i g n i f i c a n t a t t h e 10 l e v e l .

c

3 .

4.

5.

Trea ted b r i n e which conta ined 12.5% NaCl could be used with- o u t d i l u t i o n a s a cover b r i n e . This y i e l d e d s a l t s t o c k e q u i v a l e n t i n q u a l i t y t o c o n t r o l tanks .

Changes i n b r i n e o r cucumber composi t ion as a r e s u l t o f r e c y c l i n g were small. of t o x i c e lements i n b r i n e s o r cucumbers which would i n d i c a t e t h a t r e c y c l i n g should n o t be done o r t h a t t h e number of b r i n i n g c y c l e s would need t o be l i m i t e d .

From a t e c h n i c a l p o i n t o f view, r e c y c l i n g t h e b r i n e was p r a c t i c a l and r e s u l t e d i n f i n a l p roducts which were commer- c i a l l y e q u i v a l e n t t o t h e c o n t r o l s .

There were no s i g n i f i c a n t bu i ldups

ECONOMIC ANALYSIS OF BRINE RECYCLING

The economics o f b r i n e r e c y c l i n g must be analyzed f o r each p a r t i c u l a r case . The c o s t s and sav ings r e a l i z e d f o r t h i s p r o j e c t are summarized i n Tables 18 , 19 and 20. T a b l e 18 shows the savings t o b e r e a l i z e d as a r e s u l t o f r e c y c l i n g b r i n e . S a l t which w a s reused r e p r e s e n t e d a d i r e c t sav ings . The c a l c u l a t i o n was done on t h e b a s i s o f 1 2 % s a l t i n s p e n t b r i n e . The s a v i n g s i n t r e a t m e n t costs can be q u i t e v a r i a b l e . I n t h i s p r o j e c t waste was t r e a t e d i n an o n - s i t e , a e r a t e d lagoon. A c o s t o f P‘Jlb BOD t r e a t e d w a s e s t i m a t e d . N o d o l l a r cost could be p laced upon t h e f a c t that l e s e sa l t w a s d i scharged as a r e s u l t of r e c y c l i n g . However, the p l a n t had a s t r i n g e n t l i m i t upon i ts d iecharge of sa l t . Reduct ion o f N a C l l e v e l s i n t h e e f f l u e n t w a s e s s e n t i a l t o cont inued o p e r a t i o n o f the p l a n t . A small cost sav ing was r e a l i z e d as a r e s u l t of r e u s e of water.

The c o s t s of t h e chemical t r e a t m e n t procedure a r e shown i n T a b l e 19. The l a b o r c o s t was d i f f i c u l t t o e v a l u a t e because o f t h e smal l scale o f t h e chemical t r e a t m e n t o p e r a t i o n . S ince the t i m e r e q u i r e d was i n t e r m i t t e n t rather than cont inuous , as was t h e case w i t h the h e a t t r e a t m e n t procedure, the labor cost w a s es t imated t o be 50% of t h e labor c o s t f o r p a s t e u r i z a t i o n . The major c o s t s were NaOH and v inegar . I n 1975 an average of 4 4 l b NaOH/1,000 g a l of t r e a t e d b r i n e was requi red . I n 1976 t h i s i n c r e a s e d t o 52 l b . The v i n e g a r use, c a l c u l a t e d on t h e b a s i s of e q u i v a l e n t g l a c i a l acetic a c i d , a l s o i n c r e a s e d from 30 l b / 1 , 0 0 0 g a l i n 1975 t o 36 lb/1,000 g a l i n 1976. These i n c r e a s e s may r e f l e c t an i n c r e a s e i n b u f f e r c a p a c i t y of t h e second c y c l e s p e n t b r i n e compared t o f i r s t c y c l e b r i n e . The h igh c o s t of chemicals r e s u l t e d i n a small n e t cost f o r chemical t rea tment . No c a p i t a l inves tment w a s r e q u i r e d f o r t h e p r o j e c t . However, if chemical t r e a t m e n t w e r e used as t h e s o l e b r i n e t r e a t m e n t procedure i n a t a n k y a r d , t h e q u a n t i t i e s r e q u i r e d might make it necessary t o purchase s t o r a g e tanks f o r t h e NaOH and a c e t i c a c i d a long wi th meter ing equipment.

TABLE 18. SAVINGS FROM RECYCLING 1 ,000 GAL OF SPENT BRINE ~ ~~

D o l l a r s saved I t e m

NaC1 , 1 .08 l b / g a l @ $2O/ton 10.76

BOD, 12,000 mg/l a t 8C/lb 8.00

Water, 47C/1,000 g a l .45

T o t a l s a v i n g s 19.21

TABLE 19. ECONOMIC EVALUATION OF CHEMICAL TREATMENT OF SPENT BRINES

1975 Cost 1976 Cost ($/i,ooo g a l ) ($/l,OOO g a l )

I t e m

0.84 1.32 Labor I! $ 4 / h r

N a O H , 1975 19.5C/lb 8.58 8.84 1976 17C/lb

Vinegar , 1975 $ l .Ol /ga l 11.87 13.32

Total c o s t 2 1 . 2 9 23.48 T o t a l s a v i n g s 19 .21 1 9 . 2 1 N e t cost 2.08 4 . 2 7

1976 94C/gal

44 45

TABLE 20. OPERATING COSTS AND SAVINGS U S I N G HEAT TREATMENT FOR SPENT BRINES

I t e m 1975 Cos t 1 9 7 6 Cost ($/1,000 g a l ) ($/1,000 g a l )

L a b o r @ $ 4 / h r 1.67 2 .64

Propane 1.23 1.29

Pumping 0.71 0.71

NaOH, 1975 19.5C/lb 2.76 2 . 4 1 1976 17C/lb

T o t a l o p e r a t i n g c o s t s 6.37 7.05

T o t a l s a v i n g s 1 9 . 2 1 1 9 . 2 1

N e t s a v i n g s based upon o p e r a t i n g c o s t s 1 2 . 8 4 1 2 . 1 6

46

3

The o p e r a t i n g c o s t s f o r h e a t t r e a t m e n t were cons iderably lower t h a n f o r chemical t r e a t m e n t . A major cost was the purchase of a $44,575 APV t i t a n i u m a l l o y r e g e n e r a t i v e h e a t exchanger wi th a b r i n e t r e a t m e n t c a p a c i t y of 50 gal/min. This f i r s t h e a t exchanger has been used f o r t h r e e b r i n i n g seasons w i t h o u t showing signs of major d e t e r i o r a t i o n . I n 1976 t h e c o s t cf a new 50 gal/min c a p a c i t y h e a t exchanger u n i t , wi th some improvements and r e v i s i o n s of t h e f i r s t model, was approximately $60,000. c a p a c i t y of 50 gal/min wi th minimum i n s t r u m e n t a t i o n and convenience f e a t u r e s i s $50,000. A similar u n i t wi th a 35 g a l / min c a p a c i t y c o s t s approximately $40,000.

An e s t i m a t e of whether it is worth purchas ing a h e a t exchanger u n i t , cons ider ing t h e d i f f e r e n c e i n o p e r a t i n g c o s t s between chemical and h e a t t r e a t m e n t of b r i n e , was made by doing a c a l c u l a t i o n of the n e t p r e s e n t va lue (29) of t h e d i f f e r e n c e i n o p e r a t i n g cos- between chemical and h e a t t rea tments . Such an estimate is highly dependent upon t h e aaeumptions used f o r t h e c a l c u l a t i o n . Each company c o n s i d e r i n g b r i n e r e c y c l i n g must make the d e c i s i o n between t r e a t m e n t s based upon t h e i r p a r t i c u l a r c i rcumstances.

i n Table 21. c a l c u l a t i o n .

1. A h e a t exchanger u n i t wi th a t r e a t m e n t c a p a c i t y of 35 gal/min

The p r e s e n t cost of a b a s i c turn-key u n i t wi th a

The r e s u l t s of t h e n e t p r e s e n t v a l u e c a l c u l a t i o n a r e shown The fo l lowing assumptidns were used i n making the

w i l l be purchased f o r $40,000.

1 4 hr /day, 20 days/month f o r 3 months to t r e a t 1 . 7 m i l l i o n g a l of b r i n e .

2 . The h e a t exchanger u n i t w i l l be u t i l i z e d a t f u l l c a p a c i t y

3. The i n t e r e s t r a t e w i l l be 8.5%.

4 . The d i f f e r e n c e between t h e o p e r a t i n g c o s t s of chemical and h e a t t rea tments w i l l remain c o n s t a n t .

5. The maintenance c o s t of t h e b r i n e r e c y c l i n g h e a t exchanger

6. The u s e f u l l i f e of t h e h e a t exchanger u n i t w i l l be 5 yr.

7. The va lue of t h e u n i t w i l l be zero a f t e r 5 y r .

8. The c a p i t a l c o s t of t h e chemical t r e a t m e n t w i l l be zero.

w i l l be $500/yr.

47

TABLE 21. NET PRESENT VALW CALCUWTION FOR COMPARISON OF CHEMICAL T-T WITH HEAT TREATMBNT OF BRINE. THE D I E T E R E " BETWEEN TREATMENT COSTS PER 1,000 GAL FOR CHMCAt COMPARED TO BEAT T R E A m T OF BRINE WAS $16.43 IN 1976. FOR 1.7 MILLION GAL TBSS IS A TOTAL DIFF'ERENCE I N

W I T E A MAINTENANCE COST OF $500/YR FOR THE UNIT TEE NET D I m R E H C E IS $27,431.

TREATMENT COST OF 1700 X $16.55 $271931.

Years of use of t h e . h e a t exchanger unit

P r e s e n t v a l u s of $27,431 a t 0.5%

i n t e r e s t

1 25,282

2 23,301

21,476

1 9 , 794

18,243

T o t a l p r e s e n t va lue of d i f f e r e n c e i n c o s t s between chemical and h e a t t r e a t m e n t s 108,096

P r e s e n t v a l u e o f h e a t exchanger u n i t

N e t p r e s e n t va lue

40,000

. Based upon t h e s e assumptions, t h e p r e s e n t va lue of t h e

sav ings to be r e a l i z e d over a 5-yr p e r i o d by us ing h e a t t r e a t - ment is o v e r $108,000. w i l l be about $40,000, r e s u l t i n g i n a n e t p r e s e n t va lue o f over $68,000, t h e h e a t t r e a t m e n t procedure would be t h e t r e a t m e n t of choice. This c a l c u l a t i o n was r e p e a t e d making t h e same assumptions as b e f o r e except t h a t on ly 50% a s much b r i n e was t r e a t e d . va lue o f o v e r $13,000 when h e a t t r e a t m e n t was used,

I n summary, i t appears t h a t e i t h e r chemical or h e a t treatment can be u t i l i z e d w i t h o u t making t h e c o s t of b r i n e r e c y c l i n g p r o h i b i t i v e . I t appears t h a t i n many s i t u a t i o n s , t h e h e a t t r e a t m e n t procedure would be economical ly advantageous. However, an a n a l y s i s must be made f o r each p a r t i c u l a r s i t u a t i o n c o n s i d e r i n g l o c a l economic and p h y s i c a l cond i t ions .

POTENTIAL FOR RBDUCTION OF WASTE

Since t h e c o s t of t h e h e a t exchanger

In t h a t ca se there was s t i l l a p o s i t i v e n e t p r e s e n t

T a b l e 22 shows t h e raw was te loads f o r f r e s h pack, process pack and p i c k l e s a l t i n g s t a t i o n s a8 publ i shed by EPA ( 3 0 ) . On A p r i l 16 , 1976 t h e EPA publ i shed i n k h e F e d e r a l R e g i s t e r (31) a n o t i c e o f e f f l u e n t g u i d e l i n e s f o r e x i s t i n g sources and pre- t r e a t m e n t standards f o r new and e x i s t i n g sources cover ing t h e canned and p r e s e r v e d f r u i t and v e g e t a b l e p o i n t source category. T a b l e 23 shows t h e e f f l u e n t g u i d e l i n e s which must be m e t as o f J u l y 1, 1977 w i n g "best p r a c t i c a l c o n t r o l technolcgy c u r r e n t l y a v a i l a b l e " (BPCTCA) . The " b e s t a v a i l a b l e technology economical- l y achievable" (BATEA) must be in p lace by J u l y 1, 1983 to meet t h e e f f l u e n t l i m i t a t i o n s shown i n T a b l e 24 .

EPA has n o t developed l i m i t a t i o n s on t o t a l d i s s o l v e d s o l i d s ( s a l t ) . However, many s t a t e s have placed l i m i t s on s a l t d i scha rge . T h e r e f o r e , i n t h e des ign of waste r educ t ion systems, p r o c e s s o r s must c o n s i d e r r e d u c t i o n s i n s a l t a s w e l l a s BOD, TSS and f low r a t e s .

The problem o f s p e n t b r i n e d ischarge from a tank yard must be cons idered both i n terms of d i r e c t BOD and TSS discharge and its d e t r i m e n t 4 1 e f f e c t s upon t h e waste t rea tment system. I f t h e s p e n t b r i n e is t o be accomodated i n an e x i s t i n g waste t r e a t m e n t f a c i l i t y , it can cause s e v e r a l problems. The i n c r e a s e d sa l t l e v e l s w i l l reduce oxygen s o l u b i l i t y , thus lowering t r e a t m e n t e f f i c i e n c y , and t h e i n t e r m i t t e n t na tu re of t h i s h igh BOD, h i g h s a l t wastewater w i l l cause a shock e f f e c t t o most b i o l o g i c a l t r e a t m e n t systems. The u l t ima te r e s u l t w i l l be h i g h e r c o s t s f o r t h e t r e a t m e n t ope ra t ion .

I

48 49

TABLE 22. RAW WASTE LOAD SUMMARY*

I t e m TSS l b / t o n F;E7ga;;;n l;(33 lbi;;; 1977 1983

TABLE 24. EPA EFFLUENT GUIDELINES - 1983"

Fresh pack 2051 1878 19.0 5.89 3.82 1.91

Process pack 2298 1481 36.7 17.2 6.54 1.57

S a l t i n g s t a t i o n s 253 77 15.9 3.17 0.83 0.43

*EPA 440/1-75/046, p. 197. Development DoCUment for I n t e r i m F i n a l and Proposed E f f l u e n t L i m i t a t i o n s G u i d e l i n e s and New Source Performance Standard.

TABLE 23. EPA EFFLUENT GUIDELINES - 1977*

I t e m Raw (lb/1,000 Ib) Dai ly 30 Day Annual

maximum average average

- - . - '

\

Fresh pack BOD TSS

1.22 0.75 0.53

2.19 1.54 0.99

Process pack

BOD TSS

S a l t s t a t i o n s

BOD

1.45 2.63 I

0.92 0.68 1 .91 1.28

0.18 0.12 0.09

TSS 0.33 0.25 0.18

* B e s t P r a c t i c a l Control Technology C u r r e n t l y Available (BPCTCA) . E f f e c t i v e 7/1/77.

50

I t e m l b / l , O O O l b D a i l y 30 Day Annual

m a x i m u m average average

F r e s h pack

BOD mediyt large

0.639 0.461 0.213 0.639 0.461 0.213

Processed pack

1.139 0.606 0.429 0.639 0.461 0.213

0.692 0.511 0.313 0.652 0.511 0.313

1.208 0.784 0.643 0.652 0.511 0.313

S a l t station. 0.084 0.072 0 .OS4 0.084 0.072 0.054

0.163 0.125 0.113 0.084 0.072 0.054

*Best Available Technology Economically Achievable (BATBA).

'Medium - 2,000 t o 10,000 tons /y r .

'Large - UI,OOO tons or more/yr.

E f f e c t i v e 7/1/83.

51 c

TABLE 25. THEORETICAL SALT USE AND DISCHARGE DURING FERMENTATION, STORAGE, MTANKING AND DESALTING OF CUCUMBERS. RESULTS ARE EXPRESSED AS THE LB OF SALT REQUIRED PER BU (50 LB) OF FRESH CUCUMBERS

S t a g e of processing F i n a l s a l t c o n c e n t r a t i o n O S

2 5 30 35 40 45 50 55 60

1. 2.

3.

s 4.

5.

6.

7.

8.

9.

25O S cover br ine D r y s a l t added to maintain 25O S during fermentation R a i s i n g s a l t concen- t ra t ion f r o m 25O S t o f i n a l l eve l T o t a l s a l t u t i l i z e d ,

Spent b r i n e (3.8 ga l /bu ) Cucumbers upon removal f r o m tanks Cucumbers after de- s a l t i n g , 4% f i n a l sa l t concentration i n f r u i t

P r o c e s s water

T o t a l losses w i t h o u t br ine recycling sum of 5 and 8

suu of 1-3

1.84

3.46

0

5.30

2.19

3.11

2.21

0.90

3.09

1.84 1.84 1.84

3.46 3.46 3.46

1.12 2.26 3.42

6.42 1.56 8.72

2.65 3.12 3.60

3.17 4.44 5.12

2.21 2.21 2.21

1.56 2.23 2.69

4.21 5.35 6.51

1.84

3.46

4.60

9.90

4.09

5.81

2.21

3.60

7.69

1.84

3.46

5.80

11 -10

4.58

6.52

2.21

4.31

8.89

1.84

3.46

7.00

12.30

5.10

1.20

2.21

4.99

10.09

1.84

3.46

8.27

13.51

5.60

1.91

2.21

5.76

11.36

m a a 0

p .a

a a 0 d 0) '5

N YI

It appears t h a t b r i n e r ecyc l ing i s an economically attractive o p e r a t i o n f o r i n c l u s i o n i n t o process packers ' environmental c o n t r o l systems. However, e f f l u e n t problems can n o t be solved simply by i n t r o d u c t i o n of b r i n e r ecyc l ing i n t o t h e tank yard ope ra t ion . Kirk ( 2 ) r epor t ed t h a t spen t b r i n e accounted f o r 8% of t h e t o t a l h y d r a u l i c l oad , 4 4 % of t h e BOD and 59% of the s a l t gene ra t ed i n a p i c k l e s a l t i n g s t a t i o n . Even i f complete r e c y c l i n g of s p e n t b r i n e w e r e achieved, it would be necessary t o g r e a t l y reduce tank leakage , tank overf low, s p i l l a g e and most impor t an t ly , d e s a l t i n g water (process water ) i n o rde r t o meet the 1983 l i m i t a t i o n s . Therefore , a cont inuing development of new technology must occur i f t h e p i c k l i n g indus t ry i s t o remain v i a b l e . E f f e c t i v e a p p l i c a t i o n of b r i n e recyc l ing technology w i l l be one s t e p i n t h i s process .

RESULTS O F SPECIAL STUDIES

P e s t i c i d e D i s t r i b u t i o n i n Br ine Recycling

The s tudy was performed t o e v a l u a t e cond i t ions r e p r e s e n t i n g the extreme misuse of p e s t i c i d e s . on a s e l e c t e d p l o t of l and and w e r e t r e a t e d a t t w i c e t h e recommended dosage w i t h p e s t i c i d e s normally used by cucumber growers. In a d d i t i o n , t h e cucumbers w e r e harves ted a t h a l f t h e pos t - ha rves t i n t e r v a l recommended by t h e Environmental P r o t e c t i o n Agency.

Methodology t o determine t h e s e l e c t e d compounds s imultan- eous ly could n o t be found. However, t h e procedure of Luke e t a l . ( 2 2 ) e x t r a c t s many more p e s t i c i d e s than are inc luded i n t h i s s tudy and is r a p i d and easy t o perform. The d e c i s i o n was made t o expand t h i s e x t r a c t i o n i n t o a s u i t a b l e method f o r t h e s e l e c t e d compounds. q u a n t i t a t i o n us ing ECD and s i n c e s e v e r a l of t h e compounds a r e not recovered through t h e PAM F l o r i s i l c leanup (351, g e l permeation chromatography w a s i nves t iga t ed .

and methylene c h l o r i d e mobile s o l v e n t was t r i e d . The s e p a r a t i o n between t h e sample e x t r a c t i v e s and t h e p e s t i c i d e s w a s b o r d e r l i n e a t b e s t and t h e d e c i s i o n was made t o t r y a 50 cm column. Separa t ion was improved a l though some of t h e e x t r a c t i v e s had t o be c o l l e c t e d t o i n s u r e good r ecove r i e s of pa ra th ion and paraoxon. q u a n t i t a t i o n by ECD.

The cu=umbers were r a i s e d

S ince t h e e x t r a c t was too d i r t y f o r d i r e c t

I n i t i a l l y a 2.5 x 25 cm column packed wi th Bio Beads S-X3

These e x t r a c t i v e s d i d no t i n t e r f e r e wi th t h e GLC

The e f f e c t of d i r e c t evapora t ion of t h e GPC e l u a n t of methylene c h l o r i d e from the c o l l e c t i o n beakers was compared t o evapora t ion us ing a Kudema-Danish concen t r a to r (Table 2 6 ) .

sample s u b s t r a t e i s a l s o shown i n Table 26. The unusual ly low recove r i e s of Bravo@ and DifolatanO i n t h e Kuderna-Danish evapora t ion compared t o t h e h ighe r r ecove r i e s through the proposed method could no t be expla ined . The f i n a l evapora t ion t o dryness i s c r i t i c a l . removed: however, i f t he tube i s allowed t o remain under t h e a i r o r n i t rogen je t a f t e r dryness , l o s s o& r e s idues can occur, e s p e c i a l l y chloroneb, PCNB, PCA and Bravo . harves t ed , analyzed f o r r e s idues and b r ined i n seven 55-gal drums. b r i n i n g s o l u t i o n was removed from each of t h e seven druns and saved f o r a n a l y s i s a s un t r ea t ed b r i n e . b r i n e s i n drums 1, 3 and 4 w e r e sc reened t o remove l a r g e deb r i s and pas t eu r i zed a t 175OC f o r 25 sec i n a h e a t exchanger. A f t e r t r ea tmen t , t h e b r i n e s were pumped back i n t o t h e i r r e s p e c t i v e drums and the pH of t h e b r i n e was ad jus t ed w i t h NaOH j u s t p i r o r t o reuse.

NaOH t o r a i s e t h e pH t o 11.0 and al lowed t o s t a n d f o r 48 hr . The pH w a s then ad jus t ed wi th a c e t i c a c i d and t h e l a r g e d e b r i s was screened o u t j u s t p r i o r t o reuse .

The t r e a t e d b r i n e i n each drum was then reused w i t h ano the r ba tch of p e s t i c i d e t r e a t e d cucumbers. r epea ted f o r each cyc le . and an a d d i t i o n a l t h r e e cyc le s were completed i n 1976. The same b r i n i n g s o l u t i o n s were used throughout t h e s i x cyc les .

a s a "con t ro l " and was n e i t h e r pas t eu r i zed nor chemicai ly t r e a t e d except t o r e a d j u s t t h e s a l t con ten t o r t h e pH.

'The recovery of p e s t i c i d e s from cucumbers, b r i n e s and with no

The methylene c h l o r i d e must be

. The cucumbers f o r p e s t i c i d e d i s t r i b u t i o n s t u d i e s were

A t t h e end of each b r i n i n g cyc le , a po r t ion of t he

The remainder of t h e

The remainder of t h e b r i n e s i n drums 5-7 were t r e a t e d w i t h

This process was Three cyc le s were performed in 1 9 7 5

The b r i n e i n drum no. 2 was c a r r i e d through t h e s i x cyc les

The e f f e c t s of t h e p a s t e u r i z a t i o n and chemical t rea tments r i n i n g so u t ions can e seen i n Tables on t h e r e s idues i n t h e

28-31. Chloroneb@, Bravo', Dacthal', Difolatan', and paraoxon showed no more than t r a c e r e s idues i n any of t h e samples run through t h e s tudy and were not inc luded i n any of t h e t a b l e s excep t Table 27, which g ives t h e sc reen ing l e v e l s f o r each of t h e p e s t i c i d e s . I n i t i a l i n j e c t i o n s of sample e x t r a c t equiva- l e n t t o 40 mg were necessary t o a t t a i n these s e n s i t i v i t i e s . Any peak less than 10% FSD was cons idered a t r a c e and was no t q u a n t i t a t e d .

54 55

TABLE 26. RECOVERIES ( 8 ) OF ADDED PESTICIDES*

Evapora t ion Evapora t ion Through Spiked Spiked from beaker from K-D method cucumbers b r i n e

Chloroneb PCNB PCA P a r a t h i o n Paraoxon Bravo Dacthal D i f o l a t a n

@ Q

@

0 1 5 47 90 96 88

10 5 46

77 94 96 98

100 65

105 70

78 92 96 99 87 99

1 0 1 92

92 96

104 10 8 106

86 9 8 95

86 85 9 1 87 71 -9

Endosulfan I 95 - 92 10 5 87

Endosulfan 11 Endosulfan SO4

98 -- 98 107 92 97 -- 97 95 9 1

-- -- 94 10 6 94 C a r b a r y l

*Recoveries r e p r e s e n t an average r e s u l t of t h r e e or more d e t e r m i n a t i o n s .

m w w w 1 g E ! 2 8 D P

R E : o r 1 0

1

0 o o p . . . 0 0 0 0 O N I - 0 N W

cl "ts o 1 1 s e a a a , " g o o 4 E 5 E

& B E I- m m m

m w n o n e 1 0 0 0 0

R

TABLE 28. EFFECT OF HEAT AND Naon TREATMENT ON CARBARYL IN PICKLE BRINE(PPM)

Produce ana lyzed Cycle 1 Cycle 2 Cycle 3 Cycle 4 Cycle 5 Cycle 6

t Raw cucumbers (unwashed)* 2.98 5.50 0.10 0.31 N.D. 1 .01

(washed) 2.13 5.19 0.10 0.27 N.D. 0.97 * Br ined cucumbers 2.76 3.43 0.27 0.20 t r § 1 .18 (av. t a n k s 1, 3-7) Un t rea t ed b r i n e (av. t a n k s 1, 3-7) Heat t r e a t e d brine (av. t a n k s 1, 3, 4 ) t r e a t e d

(av. t a n k s 5-7) t r e a t e d

Br ined cucumbers 2.66 2.46 tr tr tr 0.53 ( c o n t r o l t a n k 2)

Untreated b r i n e 0.93 1.15 tr Sample tr 0.54 ( c o n t r o l t a n k 2) l o s t

0.93 1.37 0.10 N o s p l e N o s p l e 0.74

0.59 1.46 N.D. 0.10 t r N o t

$ Chemical ly t r e a t e d b r i n e N.D. N.D. N.D. N.D. N.D. N o t

#

#

*Unwashed cucumbers used f o r b r i n i n g .

'N.D. = none d e t e c t e d .

*Tank #2 was c o n t r o l t a n k and r e c e i v e d no treatment.

Jtr = trace.

c 0 4 CI

.4 CI d c U

k '

" n c .4 c, 0) I&

b m dp

W

m v)

4'

TABLE 29. EFFECT OF HEAT AND NaOH TREATMENT ON PARATHION I N PICKLE BRINE (PPM)

Product ana lyzed Cycle 1 Cyc le 2 Cycle 3 Cycle 4 Cycle 5 Cycle 6

t Raw cucumbers (unwashed)* 0 . 0 7 0.04 0.04 t r tr + ;::: (washed) 0.09 0.03 0.03 tr N.D.

Brined cucumbers' 0.07 0.03 0.02 tr tr 0.23 (av. t anks 1, 3-7) Untrea ted b r i n e 0.01 tr t r N o s p l e No s p l e 0 . 0 7 (av. t a n k s 1, 3-7) Heat t r e a t e d brine' tr t r N.D. N.D. N.D. Not (av. t a n k s 1, 3, 4) t r e a t e d

8 Chemically t r e a t e d b r i n e N.D. N.D. N.D. N.D. N.D. Not t r e a t e d (av. tanka 5-7)

Brined cucumbers 0.09 0.02 0.03 N.D. N.D. 0.15 (control t ank 2)

(control t ank 2 )

*Unwar'hed cucumbers used f o r b r i n i n g .

Unt rea ted b r i n e t r t r t r N.D. N.D. 0.01

I

f . D . = none d e t e c t e d .

'Tank # 2 w a s c o n t r o l t ank and r ece ived no t r ea tmen t .

TABLE 30. EFFECT OF HEAT AND NaOH TREATMENT ON ENDOSUL!?AX I N PICKLE BRINE (PPM)

Product h l y r e d Cycle 1 Cycle 2 Cycle 3 Cycle 4 Cycle 5 Cycle 6

tr. tr , tr tr, t r , tr 0.30. 0.27, 0.06 RBw cucumbera (unwashed)’ 0.14, 0.12, 0.02 0.12. 0.21. 0.03 0.03. 0.02, tr (washed) 0.14, 0.13, 0.06 0.13, 0.17. 0.04 0.03. 0.01, tr tr, tr. tr tr. tr. tr 0.25. 0.23, 0.07

Brined cucrnbere 0.18. 0.15. 0.07 0.12, 0.20, 0.02 0.04, 0.03. tr t r , tr, tr N.D.. N.D.. N.D. * 0.31. d.28. 0.09

* f

0.01. 0.01, tr tr, 0.02, tr tr, tr. tr No Sample 0.08. 0.09. 0.06 No Sample J Untreated brfne (Av . Tanb 1.3-7)

tr , tr. tr tr. 0.01. N.D. N.D., N.D., N.D. N.D., N.D., B.D. N.D., N.D., N.D Not Treated h t treated brine ~ A v . Tanka 1.3.4)

C h a r i d l y treated brine N.D.. N.D.. N.D. N.D., N.D.. N.D. N.D.. N.D., N.D. N.D., N.D., N.D. N.D., N.D., N.D. Not Treated

Brined cucumberr 0.20. 0.16, 0.07 0.12, 0.21, tr 0.04. 0.02, tr N.D., N.D., N.D. (Control Tank 2)

Untreated brine 0.01, 0.01, tr tr. tr. N.D. N.D.. N.D., N.D. N.D., N.D., N.D. (Control Tank 2)

P

Q\ I-

JAv. T a b 5-7)

N.D.. N.D., N.D. 0.22, 0.25. 0.03

N.D.. N.D., N.D. 0.01, 0.02, N.D.

*Umraabed euccnberr uaed for brining. t Values repreaent realduu of Endomulfan I. 11, urd S O 4 respectively.

tr - Trace.

Tank 12 wam control tank and received no treatment.

N.D. - none detected.

: §

x

TABLE 31. EFFECT OF HEAT OR NaOH TREATMENT ON PCNB AND PCA IN PICKLE BRINE (PPM).

Product Analyzed Cycle 1 Cycle 2 Cycle 3 Cycle 4 Cycle 5 Cycle 6

0.170. tr §

N.D.. N.D. . t f Raw cucumbare (ruueebed) 0.105. 0.003 0.080, 0.053 0.016. 0.013 tr, tr

(vuhed) 0.120. 0.009 0.043. 0.055 0.017. 0.013 tr, tr N.D., N.D. 0.140. N.D.

Brined cucumbers 0.039, 0.030 0.057. 0.078 0.018, 0.030 N.D., N.D. 3 i . D . . N.D. 0.015, N.D. JAv. Tank# 1.3-7)

# Untreated brine (AV. T d u 1.3-7)

h a t t rutd brio.

#

N.D., N.D. tr, 0.003 N.D., tr No Spl No Sple 0.005, N.D.

Not hutd N.D., U.D. tr. tr N.D., N.D. N.D., N.D. N.D., N.D. #

OI (Av. Tank# 1.3.4) hJ

Chuically treated brine N.D.. N.D. tr, tr N.D., N.D. N.D.. N.D. N.D.. N.D. Not hea ted _(Av. T M L 5-7)

Brined cucumber# 0.037, 0.033 0.062, 0.088 0.015, 0.024 N.D., N.D. N.D., N.D. 0.010, N.D. (Control T u & 2)

Untreated brine tr, tr 0.005, tr tr, tr N.D. . N.D. N.D., N.D. N.D., N.D. _(Control Tank 2)

+Oaradd cucwaberr u e d for brining. t

'tr - Trace.

V d u m rcprceent reeiducs of PCNE and PCA respectively.

N.D. .I none detected. 5

%auk 42 vas control tank and received no treatment.

TABLE 32. SOURCES AND IDENTITY OF FUNGI USED FOR DETERMINATION OF THERMAL STABILITY O F PECTINASES I N BRINES

O r g a n i s m Source*

A l t e r n a r i a t e n u i s

Cladosporium cladosporioides

Fusarium oxysporum

Fusarium roseum

Fusarium solani

P e n i c i l l i u m janthinellum

P e n i c i l l i u m oxalicum

Trichoderma vir ide

NRRL 2169

MSU

NRRL 1943

MSU

N R R L 3078

NRRL 2016

NRRL 790

MSU

,

"RRL - USDA Northern Regional Research Labora tory , P e o r i a , I L

MSU - Michigan S t a t e University, Department of Botany and P l a n t Pathology.

TABLE 33. D-VALUES OF PECTINASES WITH THE GREATEST THERMAL STABILITY I N PRELIMINARY EXPERIMENTS. D-VALUES WERE OBTAINED AT p H 3.3 I N 12% NaC1, 0.6% LACTIC ACID AND 0.1% Ca++ ION

Organism Temperature D-value ("C) ( s e c )

P e n i c i l l i u m janthinellum 78 4 75 1 8

P e n i c i l l i u m oxalicum 70 1 8

Fusarium solani 70 5 Fusarium oxysporum 70 4 Alternaria t enu i s 65 25

Trichoderma v i r i d e 65 1 0

63

PH Figure 5 . E f f e c t of pH on h e a t i n a c t i v a t i o n of P e n i c i l l i u m

j an th ine l lum pec t inase . Experiments were done in b r i n e con ta in ing 12% N a C l , 0.6% lac t ic a c i d and 0.1% Caw ion.

TABLE 34. EFFECT OF N a C l CONCENTRATION ON THE HEAT INACTIVATION OF PECTINASE FROM PENICILLIUM JANTHINELLUM AT 75OC

NaC1, % D-values a t 75OC (eec)

pH 3.5 pH 3.7

8 2 4 31

1 2 29 33

1 6 30 37

TABLE 35. INACTIVATION OF PECTINASE FROM PENICILLIUM JANTHINELLUM AT HIGH pH I N SPEN'F BRINE. -22'C (71.6OF). SALT CONCENTRATION 8.08

pH of Time for 90% Time for 99% i n C u b a t ion i n a c t i v a t i o n i n a c t i v a t i o n

(h r ) ( h r )

10.6 50% i n a c t . i n 70 h r

11.0 34 * 11.2 5.0 37

11.3 6.5 27

11.6 2.5 1 3 (est.)

*99% i n a c t i v a t i o n of 'he enzyme w a s n o t reached i n 4 0 hr .

64 65

A t 78OC (172.4OF) , t h e maximum D-value observed under any of t h e condi t ions i n v e s t i g a t e d was 8 sec. Curren t ly , t h e minimum recommended p rocess f o r b r i n e t r ea tmen t is 79.4OC (175OF) f o r 30 sec i n a p l a t e h e a t exchanger. This w i l l r e s u l t i n a t l e a s t a 30 sec/8 sec = 3.7 D process . Therefore , a t 79.4OC f o r 30 sec, the e x t e n t of i n a c t i v a t i o n w i l l be 103-7 o r about 5,000-fold. S ince the suggested h e a t i n g temperature i s 1 . 4 O C h ighe r than t h e h i g h e s t temperature i n v e s t i g a t e d i n t h e s e experiments and t h e p e c t i n a s e was s i g n i f i c a n t l y less s t a b l e i n commercial s p e n t b r i n e s , t h e e x t e n t of enzyme i n a c t i v a t i o n i n commercial b r i n e would be expected t o be considerably g r e a t e r than 5,000-fold.

P e c t i n a s e s are known which a r e cons ide rab ly more r e s i s t a n t t o thermal i n a c t i v a t i o n than E. ' an th ine l lum enzyme. A commercial enzyme from A s er i l l i s niger was found t o have a D-value of 34 s e c a t 80*-in pH 3.6 s imulated spent b r i n e ( 8 ) . Archer and F i e l d i n g (32) repor ted a polygalacturon- a s e from S c l e r o t i n i a f r u c t i ena which caused d i s i n t e g r a t i o n of f r u i t s a f t e r canni&Jd a D-value near 3.5 h r when heated a t 90°C i n pH 7 .0 , 0.02 M phosphate b u f f e r . Therefore , t h e p o s s i b i l i t y e x i s t s t h a t a h i g h l y stable s o f t e n i n g enzyme could occur i n f e rmen ta t ion b r i n e s . However, h e a t i n g a t 79.4OC (175OF) f o r 30 sec w i l l be s u f f i c i e n t t o p r o t e c t a g a i n s t s o f t e n i n g from p e c t i n a s e s which are l i k e l y t o be p r e s e n t on cucumber f r u i t s and f lowers .

Experiments were a l s o done t o determined the s t a b i l i t y of

It was found t h a t t h e enzyme could n o t P. Tur!ng base t rea tment . be adequately i n a c t i v a t e d i f t h e temperature was he ld a t 10°C (SOOF). I n no r the rn l o c a t i o n s , such a s Michigan, chemical t rea tment should n o t be done u n t i l t h e b r i n e s have warmed up. In a l l cases p e c t i n a s e i n a c t i v a t i o n a t h igh pH d i d n o t show f i r s t o r d e r d e n a t u r a t i o n k i n e t i c s . The r a t e of i n a c t i v a t i o n dec l ined wi th t i m e . A s a r e s u l t , meaningful D-values could n o t be c a l c u l a t e d . T a b l e 35 shows t h e e f f e c t of d i f f e r e n t pH l e v e l s a t 22OC ( 7 2 O F ) on t h e t i m e r e q u i r e d f o r 90% and 99% enzyme i n a c t i v a t i o n . Based upon t h e s e r e s u l t s , it is recommended t h a t b r i n e be he ld a t 72OF o r h ighe r during chemical t rea tment . The pH should be r a i s e d t o 11 .2 o r h ighe r and he ld f o r a t least 37 h r a t t h a t pH b e f o r e a c i d i f y i n g t h e b r i n e .

'anthinel lum p e c t i n a s e a t t h e high pH levels encountered

Enzymatic s o f t e n i n g i n Michigan i s n o t common. Ana lys i s of spent b r i n e s , according t o t h e procedure developed by B e l l and E t c h e l l s (ll), a f t e r cucumbers were removed from fe rmen ta t ion tanks , showed no measurable p e c t i n a s e a c t i v i t y . AS a r e s u l t , it was n o t p o s s i b l e t o e v a l u a t e t h e e f f e c t of h e a t and chemical t rea tments on t h e Lnac t iva t ion of p e c t i n a s e a s they occurred i n commercial b r i n e s .

66

Lys inoa lan ine i n Base Trea ted Brine

l e a d t o formation of l y s i n o a l a n i n e (26) and it had been r e p o r t e d t h a t f r e e l y s i n o a l a n i n e was t o x i c t o r a t s ( 2 7 ) , an experiment was done t o determine whether l y s i n o a l a n i n e was formed dur ing base t r ea tmen t of s p e n t b r i n e . c y c l e br ine was adjus ted t o pH 11.4 and h e l d a t room tempera- t u re f o r 8 days. t o pH 4.6 wi th a c e t i c ac id . Th i s t r e a t m e n t w a s a severe t r e a t m e n t r e l a t i v e t o t h a t r e q u i r e d f o r p e c t i n a s e i n a c t i v a t i o n . Lysinoalanine w a s found i n t h e s p e n t b r i n e b e f o r e t r ea tmen t a t a level of 1 5 ug/l . The r e s u l t s i n d i c a t e d t h a t s i g n i f i c a n t amounts of l y s i n o a l a n i n e weme n o t formed a s a consequence of base t rea tment . a l a n i n e has been found i n a number of foods and food p r o t e i n s (33, 34) . The l e v e l i n p i c k l e b r i n e would appear t o be q u i t e low compared t o t h e l e v e l s i n processed foods which con ta in S i g n i f i c a n t l e v e l s of p r o t e i n .

Since it was known t h a t base t r e a t m e n t of p r o t e i n could

A sample of f i r s t

The c l e a r supe rna tan t w a s removed and ad jus ted

A f t e r t rea tment , 1 2 pg / l were de tec ted .

Lysino-

67

1.

2.

3.

4.

5.

6.

7.

8.

9.

. .. ..

, .

10. E t c h o l l s J J. L., B e l l , T. A.,.Fleming, H. P. , . I (a l l inq , R. E., and TbQPPson, R. L. Suggested Procedure f o r the C o n t t p l l a d Fexmentaedon of C a a w r c i a l l y Brined P i c k l i n g Cucumbqs - - th~ Uso of S t a r t e r Culmres and Reduction of Carbon Dioxide A c c u m u l a t i o n . P i w e Pak mi. 314, 1973.

Anonyroru. Oc-r 1, 1975. S t . C h u l o s , I l l i n o i s 60174, 1977.

Annual Report of Intsk. and Inventow as of Pi&& P a d u r s International, hc.,

K i r k , D. G. Managomexit of Wastowator Problems i n the P i c k J e Indus t ry . ?int Intunational Congns. on Enc4nooring and Food, D i g o s t o f P a p o n . Bng imors , S t . Josoph, Wchigan 49085, 1976, pp. 151.

Amriaan S o c i e t y o f Agricultural

E t d w l l . , J. L. . n d Noom, W. R., Jr. ?acton I n f l u s a c i n g tbm B r i n i n g of. D i a l c l i n g CucP.bus--Qtwst ioru urd Answus. Pi-. P.k Sof. 111, 1971.

-,E. L., fAm,IC. , Ikk . r , K. E., u r d B u t g . s s , J . W . P i o l d Wt8 of S a l t Reoovory S y s t a f o r S p t B r i m . J. Food Soi. 381507, 1973.

hrrk.. 1. L.. bm. IC. urd Tooebak. E. A. U n of 1L.Oycl.d Salt -&tadoh of cucrrb.t S a l t Stoak. J. rood ki. 3911032, 1974.

Gois", J. R. urd Ha", R. E. Reaycling ?ood Brino ~ l i r i n a t u P o l l u t i o n . ?oed E g r . 45 ( l ) t l l P , 1973.

G o i s m ~ , J. 1. and Honno, R. E. RoayCUnP B r i n e fm Piakling. Ohio Report 58176, 1973.

Palnnftku, n. P. and nmooters, R. F. Recycl ing S p u r t B r i m s in Cua"r P e m o n t a t i o n s . J. Food Sci . 4011311, 1975.

C r u r f i o l d , D. Cucrnrkr Br in ing and S a l t R e ~ o V O r y . P i c k l e P 8 c L . n I n t o r n a t i o n a l 8.rLnu on P i c k l e Procamsing W a s t e s , 1973.

11. Bell, T. A., Etcha l lm, J. L. and Jones, I. D. A b t h o d for Te8t ing Cucmbor S a l t Stock B r i n e f o r Sof ten ing A c t i v i t y . U.S. Dept. of Agric., ARS 72-5, 1955, pp. 1-15.

12. C o n t i n e n t a l C a n ColppMy. Inc. Reforenae Guidebook f o r Sonsory Tes t ing , 3rd ed , , Chicago, Illinois, 1966.

13. S t a n d a r d Wethods f o r the Examination of Water and Wastewater, 1 4 t h od., see. 507. American P u b l i c Heal th Assoc ia t ion , New York, 1975, pp. 543-550.

1 4 t h ad., sec. 508, American P u b l i c Heal th Assoc ia t ion , W o w York, 1975, pp. 515-554.

15. S tandard Methods f o r t h e Examination of Water and Wastewater, 1 4 t h ad., sac. 208D, American P u b l i c Heal th Assoc ia t ion ,

14. Standard Hothods f o r the Examination of Water and Wastewater,

WOW YOrL, 1975, p. 94.

16. nillor, 0. L. O n of D i n i t r o s a l i c y l i c Acid f o r Dotermfn- ation O f R.aucing S ~ U S . Anal. Qrm. 311426, 1959.

17. L i l l o v f k , E. A. Tha Dotormination of T o t a l O r g a n i c U i t r o g o n . hthod. in ?ood Analysis , 2nd od., Joslya, 1. A., od., " i o Prom, UOW York, 1970, pp. 601-616.

18. Spragua, S. urd Slavin , W. Dot.&tfon o f Vory Small Amount. of Copper and Load in KCl by O r g u r i c Extraation urd h a c AbwrptiOn S p . c t r o p a o t a w t r y . A W c Absorpthn U m & t t U 3137, 1964.

19. Rromu, B., Rough-, J. A. and Wattors, E. Load and C a d " Contoat of Sop. Vogotablo M t u f f s . J. Sci . Food Agr. 2311493. 1972.

20. Hatch, W. R. and O t t , W. L. Dotemination of Sub-Microgram Quntitiam of Mercury by A t o m i c Absorpt ion Spectrophoto- metry. Anal. Chm. 40:2085, 1968.

21. Chaplfn, M. 8. and D i x o A. R. A Hothod for Analysis of P l a n t Tissues by D i r e c t k a d i n g Spark Emission Spectroscopy. Appl. Spectroscopy 28:s. 1974.

22. Luke, W. A., Pxoimrg, J.. E., and thsumoto, H. T. E x t r a c t i o n . . . - and.CleMup of. OrgMochlorine, Organopho8phate, Organoni- . . .

trogetn, and Hydrocarbon P e s t i c i d e s in Produce f o r Determin- i

a t i o n by --Liquid Chromatography. JAOAC 58:1020, 1975,

69

. .

Activity. Ilgsologia 43:656, 1951.

25. Chavana, S. and Weetor., R. F. Thermal I n a c t i v a t i o n of Fungal P e c t h e r in C u c e r Brine.. Lebensm.-Wiss. U. Tocbaol. 1 0 ~ 2 9 0 , 1977.

26. DoGraot, A. P. and Slump, P. Effectm of Severe Alkali Treatment O f Protein. Amino ACicccmpo.itiOn and Nut r i t i ve V a l u e . J. N u t r i t i o n 98145, 1969.

8oy Pr0iA.n in Rata. J. N u t r i t i o n 103x569, 1973.

Purg ing of N a t u r a l Sa l t -S tock P i c k l e N-tatloar: to R O d W B l o a t e r Damage. J. Food Sci . 42x234, 1977.

4 t h ad., Prent ice-Hal l , Englewood Cliff., blew Jersey, 1977.

Kievelo-t Documat for Interim Final and P r a p o r d E f f l u e n t L i m i t a t i o n s G u i d e l i n e . and New Source Performance Standard . for the F N t . , Vegetables and Spac ia l t iem Segment of the Canned and Preserved *nits and Vegetable. P o i n t Source Category.

27. Woodward, J. C. and Shor t , D. 0. T o x i c i t y of Alka l i -Trea ted

28. Co8t i law, R. Io., Badford, C. L., Hixqus, 0. and Black, D.

29. HOMgra, C. T. Co.tAcoDWthg--a Xan.garial m h m i . .

30. United S t a t u Environmental P r o t e c t i o n Agency.

EPA 440/1-75/046, 1975.

31. Anon-. Canned and Premerved F r u i t s and Vegetables P o i n t Sourco Category. F e d e r a l Register 41 (751r16272, 1976.

32. A r c h e r , S. A. and F i e l d i n g , A. H. Rurrmo8table Polygalac- turonama S e c r e t e d by S c l e r o t i n i a f r u c t i g e n a . J. Food Sci . 408423, 1975.

32. A r c h e r , S. A. and F i e l d i n g , A. H. Rurrmo8table Polygalac- turonama S e c r e t e d by S c l e r o t i n i a f r u c t i g e n a . J. Food Sci . 408423, 1975.

33. S t e m b e r g , M., Kim, C. Y. and Schwende, F. J. Lys inoa lan iner Presence8 i n Fooda and Food I n g r e d i e n t e . 19 75.

Science 190:992,

ri

APPENDIX

TABLB A-1. COIBOSITION OF FIRST CYCLE SPENT BRIUE BEIORE HEAT TREA-T, 1975 DATA

Tank nkmber Parameter K7 X l l K41 LE L39 L40 L43

.319 .577

12.10 12.96

3.52 3.52

325 585

238 240

7550 14000 12745 15900

517 738 ,031 --

0 0

119 154

1010 980 130 150

3.6 3.0 4.9 7.5 -- 1.8

1.4 1.8 6.8 5.4

.360 .I20

10.92 14.02

3.57 3.68

306 404

200 300

8250 10500 11235 14195

499 597 .013 0

0 0

102 131 910 980 130 130

3.3 2.4 4.9 7.5 1.7 1.7 1.3 1.4 5.1 4.7

A 1 %ng/l . 34. m u , H. T., P B l l e t t , P. L. and Near, W. W. E f f e c t of Alkali Treqtumnt on the Formation o f Lys inoa lan ine i n Corn. J. Ag. Foeti Chm. 24:1084, 1976. I: C r w/1

.480 .412 .501

14.10 13.64 14.28

3.58 3.57 3.68

391 427 403

300 185 320

9800 10450 11700 16500 13855 15025

712 612 530 .016 .005 .027

0 0 0

142 114 148

1090 930 1170 160 140 150

1.9 1.1 3.6 6.9 3.7 8.1 1 .5 0.9 2.0 1 . 3 1.0 1.6 3.8 2.8 5.6 5.3 4.2 6.3

0 0 -010

35. PerticideAn&lyticalXMual, vol. I, Food and Drug Adsnh- i s t r a t i o n , Waahington, DC, Rev. March, 1977, a e c . , 2 l l . l 4 d , 1968.

TABLE A-2. COUPOSITION OF FIRST CYCLE SPENT BRINE AE'TER HEAT TREATMENT, 1975 DATA

Tank number Parameter K7 K41 K41 L8 L39 L40

Acid % lactic .087

Salt % 12.50 PH 4.72 Sugar mg/l 228

ss mg/l 138 BOD mg/l 10375

COD mg/l 13080 _ _ Cd ms/l ,008 H9 W l 0 p 4 1 119

Kjeldahl N mg/l 559

Ca mg/l 1060 Mg ms/l 130

t4t-l W l 3.6 Fe mg/l 8.7 Cu mg/l 1.8

B mg/l 1.7 Zn mg/l 5.8 A1 mg/l 17 Cr mg/l 0

.lll

11.00 4.73 273

273 8700

11560 495 0 0

102

910 120

3.3 7.5 1.8 1.3 5.1 9.0 .003

.208

11.16 4.39 276

195 9250

11815 500 .016 0

91

810 120

1.1 5.8 1.2 1.0 2.6 7.4 .003

.074

12.20 5.02 123

100 7825

10825 395 0 0 80

960 10 0

3.3 4.9 2.1 1.0 5.1

13.8 0

.229 .331

14.38 13.96 4.45 4.76 271 463

336 185 12000 10300

15460 13910 -- 585 .179 .027 0 0

14 8 131

1060 1040 150 150

3.3 1.9 9.0 6.4 1.6 1.2 1.7 1.5 4.4 3.3

15.9 11.6 .OlO 0

TABLE A-3. COMPOSITION OF FIRST CYCLE SPENT BRINE BEFORE CHEMICAL TREATMENT, 1975 DATA

Tank number Parameter K10 L6 L9 L4 2 M8

Acid 8 lactic Salt %

PH Sugar mg/l

SS mg/l BOD mg/l COD mg/l Kjeldahl N mg/l

Cd ms/l Hg mg/l

.398 13.29 3.48 408 125

9850 13620

486 .162 0

.334 13.39 3.46 305 300

7850 10545

0

.410 14.11 3.66 490 310

10200 13820 600 .013 0

.563 14.66 3.58 484 267

12300 16135

637 .179 0

.650

10.86 3.50 280 155

12560 16085

5 36 .019

0

p ms/l 114 102 125 114 125 Ca mg/l 930 1040 1060 1010 1060 Mg mg/l 120 130 130 130 140

4 1 2.7 3.3 2.7 3.8 4.4 Fe mg/l 4.6 7.8 6.9 8.1 8.4 Cu mg/l 2.0 1.9 1.6 2.2 2.3 B mg/l 1.2 1.5 1.3 1.3 1.6

Zn mg/l 4.2 4.9 4.4 5.6 5.8 A1 mg/l 5.3 5.3 4.7 7.9 7.4 Cr mg/l .012 0 0 .003 0

12 73

TABLE A-4. COMPOSITION O F FIRST CYCLE SPENT BRINE AFTER CHEMICAL TREATMENT, 1975 DATA

Tank number Parameter L41 L42 L47 M45 L7

A c i d % l ac t ic S a l t %

PH Sugar m g / l

ss ms/l

COD m g / l Kjeldahl N m g / l Cd m g / l

Hg ms/l p m d l Ca ms/l Mg m s / l Mn mg/l Fe m g / l Cu m g / l

B mg/l Zn m g / l

A 1 mg/l C r mg/l

BOD mg/l

.415 .289 10.38 10.60

4.60 4.55

151 170 35 55

12300 15750 15665 18265

457 516

.023 .001 0 0 11 28

570 470 1 0 20

0.5 0.5 1 .7 2.9 0.7 0.4 1.0 0.7

1 . 7 1.3

6.4 1.9 0 0

.208

14.07 5.10

349 22

16625 21620

616 .009

0 34

810 10

2.4

2 . 0

1.4 1.6

3.8

6.3 0

.OS8 .192 13.50 14.37

5.25 5.00

194 2 4 2

110 5 3 8750 16650

12700 17795 4 32 594

.098 .159 0 0 1 7 40

810 910 10 1 0

2.2 4.1 1.4 4.6 1.6 2 .2

1.1 1.8

3.8 5.4

13.8 23.5 .003 0

TABLE A-5. CO;lPOSITION OF 2ND CYCLE SPENT BRINE BEFORE AND AFTER tEAT TREATHENT, 1976 DATA

Tank nuvber

A f t e r t reatment Parameter Before t reatment

L46 M4 M8 M10 N49 f.14 M3 L44 Acid % l a c t i c -57 .66 .63 .61 .20 .22 .30 .12 S a l t % 10.7 11.5 11.9 11.6 12.3 11.8 11.8 11.5 PH 3.52 3.55 3.52 3.50 4.58 4.49 4.33 5.10 Sugar m g / l 230 276 319 227 232 205 262 189 SS mg/l 157 160 252 622 220 100 194 313

10700 13400 13500 12400 13200 12363 14000 16600 BOD mg/l U)D ms/l 17592 19768 19504 17576 18724 18720 20128 19616

Kjeldahl N mg/l 540 641 614 540 631 571 669 613 Cd mg/l -03 .03 -01 .03 -02 .02 .03 .025 Hg mg/l .003 .003 .003 .003 .003 -004 .003 .003 p mg/l 119 165 159 114 159 108 137 108 Ca mg/l 910 1090 1110 1060 1220 1220 1140 1010 Mg W 1 170 180 180 160 190 ieo 180 180 Mn mg/l 0.5 1.1 2.4 1.6 1.6 1.6 2.4 1.1

3.4 14.7 11.7 7.5 9.9 5.8 23.9 5.2 Fe mg/1

Cu mg/l 0.8 1.1 2.0 1.7 1.8 1.5 1.6 1 .4 B mg/l 1.1 1.3 1.5 1.5 1.5 1.6 1.7 1.5

A 1 mg/l 3.2 9.0 10.0 11.1 20.2 7.4 14.3 6.3 Zn mg/l 2.8 4.0 6.6 5.6 5.4 5.4 7.3 4.4

74 75

--

TABLE A-6. COMPOSITION OF ZND CYCLE SPENT BRINE BEFORE AND AFTER CHEMICAL TREATMENT, 1976 DATA TABLE A-7. ANALYSIS OF 1ST CYCLE CONTROL SPENT

BRINES AFTER REMOVAL OF SALT STOCK

Parameter Before t r e a t m e n t A f t e r t r e a t m e n t L47 M6 M43 M48 L47 M5 M I 1 M5

Acid % l ac t ic .65 .57

S a l t % 9.6 11.3 PH 3.60 3.82 Sugar m g / l 292 259

ss w/1 179 167 BOD m g / l 13300 12700 COD m g / l 18552 19544 Kjeldahl N m g / l 453 608

Cd m g / l .025 .02

Hg m s / l .003 .003

p m s / l 85 97 C a m g / l 760 1010

Mg mg/l 100 160

l4I-l mg/l 0.5 1.1

Cu mg/l 0.8 0.8 Fe mg/l 20.5 15.9

B m s / l 0.9 1.5

Zn mg/l 3.1 4.4

A 1 mg/l . 4.2 4.7

.57 .74 .04 .31 12.3 11.2 10.0 10.4

3.58 3.67 6.65 4.80 228 253 87 90

117 170 104 208 13600 18400 18817 14800 18032 21704 18667 23152

590 832 465 543

.03 .02 .01 .os -003 -- .003 .003

102 114 11 11 1010 1060 640 590

140 160 10 10

1.1 1.1 0.5 0.3 17.7 15.9 1.1 2.3

1.7 0.8 1.7 1.3 1 . 4 1.5 1.3 1 .5

4.7 4.4 3.3 2.6

14.8 4.7 32.0 21.3

.24 .43 11.6 1 1 . 4

4.90 4.80 104 178

1 4 22 15921 19840 22368 26952

489 531

.03 .03

.003 .003

11 11 810 570

0 0

1.1 0.5 2.6 13.5 1 . 4 2.0 1.5 1.7

4.2 4.4

36.1 34.4

Tank no. Acid S a l t pH Reducing BOD COD Suspended -1975- % % suga r mg/l mg/l s o l i d s

m s / l m g / l

L36 M2 M5 1 M 1

M 5 2 M9 M I 2 M35 M 3 3 L4 8

-1976- M7 M50 M47 M 4 6 M6

M 4 3 M9 M8

.670 8.6

.742 9.7

.640 10.5

.657 12.1

.669 8.5

.761 10.2

.649 8.4

.718 9.6

.716 9.7

.498 8.7

.568 9.3

.514 8.1

.782 10.2

.557 7.7

.579 9.4

.520 7.6

.415 6.7

.629 9.5

3.30 3.40 3.35 3.32 3.39 3.29 3.38 3.38 3.37 3.50

3.52 3.62 3.57 3.60 3.50

3.60 3.50 3.49

378 575 571 125 19 3 493 4 8 1 505 168 176

172 134 258 208 20 3

166 140 210

11480 15736 15900 20296 15010 15864 13800 17520 13657 16525 17000 18880 11375 18500 17200 19260 21400 18575 10000 14825

14000 16990 10800 14309 18800 23550 14558 18116 12000 17184

11612 15131 6600 12210

12000 19066

227 540 463 4 88 160 311 -- 388 288 213

347 820 4 80 7 30 9 61

420 12 7 535

76 77

TABLE A-8. ANALYSIS OF ZND AND 3RD CYCLE HEAT TREATMENT SPENT BRINES AFTER REMOVAL OF SALT STOCK

~

Tank no. A c i d S a l t pH Reducing BOD COD Suspended -1975- % % s u g a r m g / l m g / l solids

(2nd c y c l e ) mg/l mg/l

L37 M 3

M49 M47

M 5

M7 M10 M41 M 1 1

M8 L46

-1976- (3 rd c y c l e )

M 1

M 5 2 M 3 M44 M49 M42 M4 L48

.628

.892

.564 ,732 .623 .534 .749 .852 .645 .702 .551

.751

.767

.833

.738

.E87

.750

.E24

.371

10.2 3.43 8.8 3.50

12.2 3.50 10.2 3.60

8.7 3.67 9.0 3.51

12.0 3.52 12.2 3.25 11.3 3.45

9.3 3.48 7.7 3.55

7.3 3.64 12.6 3.62

9.7 3.62 9.9 3.64 9.6 3.80

11.5 3.60 10.1 3.55

6.5 3.83

467 479

527 76

420 370 499 361 531

431 402

179 1 8 1 192 186 172 186 19 1 119

13480 16584 20200 25600

13600 16730 19000 21695

6820 17824 9320 15584

21400 23535 10200 11390 18700 20170 12720 19112 12400 17180

18763 22935 20400 25555 20400 27184 18400 24506 23800 27776 21400 25396 19600 24850 11000 12846

76 967

1025 675 765 124 500 330 750 207 660

175 771 617 732 271 230 185

53

TABLE A-9. ANALYSIS O F 2ND AND 3RD CYCLF, CHEMICALLY TREATED SPENT BRINES AFTER REMOVAL OF SALT STOCK

Tank no. Acid S a l t pH Reducing BOD COD Suspended -1975- % % s u g a r mg/l mg/l so l id s

(2nd cycle) m g / l ms/l

L44 M4 M5 0 M4 8 M6 M4 3 M4 0 M39 M4 5 L47

-1976- (3 rd c y c l e )

MZ

M5 1

M4 8 M 4 5 M 5 M 4 1 M 1 1

L47

.852 10.6 3.50

.787 8.8 3.62

.642 10.0 3.65

.E90 10.8 3.65

.755 9.6 3.63 -697 8.4 3.58 .723 9.6 3.38 .636 10.1 3.60 .594 9.1 3.70 .750 7.3 3.59

.937 7.7 3.78

.507 9 .1 3.73

.978 10.6 3.78

.538 7.6 3.70 1 . 1 4 10.2 3.65 .505 7.2 3.72 .770 8.6 3.41

.EO6 8.8 3.58

512 169 380 431 410 442

69 71

342 420

258 162 350 208 32 8 184 311 274

17600 23288 17000 23490 15800 18910 20300 24815 14520 22104 13250 18732 17300 18945 17000 18055 14800 16604 15600 19670

21000 26082 13000 15667 25400 32323 13275 16351 27200 30784 13600 15028 21000 23508

22600 25068

172 --

457 417 136 --

2 75 380 144 139

36 7 1610

880 660 820 387 90 80

70 79

TABLE A-Ll. SALT STOCK QUALITY OP CUCUMBERS FERMENTED I N FRESH SALT BRINE, HEAT TREATED 2ND CYCLE BRINE AND CHEMICALLY TREATED 2ND CYCLE BRINE--1975 SEASON

Group Fresh b r i n e c o n t r o l Heat t r e a t e d b r i n e Chemically treated b r i n e no.* Good7 CA' cus Good CA CU Good CA cu

9 % % 9 9 % % % 9

1 30.0 46.1 53.9 52.7 76.3 23.7 54.8 71.4 28.6 2 73.8 91.5 8.5 77.8 84.1 15.9 56.8 71.8 28.2 3 74.5 87.0 13.0 87.1 97.5 2.5 82.8 96.5 3.5 4 84.3 96.3 3.7 66.6 85.6 14.4 75.9 89.6 10.4 5 71.0 84.0 16.0 68.7 88.0 12.0 58.2 72.3 27.7

OD 6 79.8 89.1 10.9 69.0 77.6 22.4 -- -- -- t-

7 78.6 92.1 7.9 85.9 96.5 3.5 88.6 93.6 6.4 8 71.3 87.0 13.0 85.3 96.3 3.7 82.1 95.0 5.0 9 82.4 91.6 8.4 87.0 97.2 2.8 68.1 88.1 11.9

-- 52.2 78.1 21.9 75.3 90.0 10 .o l o 11 82.0 88.3 11.7 68.0 74.3 25.7 87.8 96.9 3.1

-- --

* A l l t a n k s i n a group were f i l l e d on the same day. 'Good s t o c k i s f r e e o f i n t e r n a l defects. 'CAI coimnercially acceptab le . d e f e c t s .

fCU, commercially unacceptable . S tock w i t h severe i n t e r n a l d e f e c t e . Useful o n l y f o r r e l i s h products .

I n c l u d e s sum o f good s t o c k and s t o c k w i t h s l i g h t

TAaLg A-10. SALT STOCK QUALITY OF CUC-RS "TED I N FRESH SALT BRINE# HEAT TREATED 3RD CY- BRINE AND -cALLY TIUUTgD 3RD CYCLE BRINE--1976 SEASON

-,,up F r e s h b r i n e c o n t r o l lbat treatod brhe no.* GoodT CAS CUC Good

Chemical ly treated b r i n e CA cu

I I 0 I a I u I e

1 29.3 72.6 21.4 3L.O 75.6 24.4 47.9 84.4 15.6

2 73.8 95.9 4.1 48.4 82.9 17.1 10.2 94.1 5.9

3 73.9 91.3 0.7 50.7 85.5 14.5 64.3 89.9 10.1

4 49.5 82.6 17.4 32.6 62.8 37.2 34.8 69.0 31.0

30.0 74.2 25.8 65.0 91.5 8.5 55.5 80.8 19.2

6 35.3 77.0 23.0 22.1 64.5 35.5 54.5 78.3 21.1 8 5

7 71.4 98.5 1.5 74.3 94.3 5.7 67.4 100 0

8 53.4 87.1 12.9 45.3 80.8 19.2 38.0 86.8 13.2

' A l l tmka i n a group were f i l led on the m a m e day. 'Good a t o c k is f r e e of i n t e r n a l &facts. (CA, u m u m r c i a l l y acceptab le .

ECU, c o m a e r c i a l l y unacceptab le . S t o c k with severe i n t e r n a l d e f e c t s . Usefu l

Includes a m of good stock and stock w i t h a l i g h t d e f e c t s .

o n l y €or relish products .

TABLE A-13. MINERAL COMPOSITION OF SPENT BRINE FROM 2ND CYCLE HEAT TREATED FERMENTATION--1975 DATA. W RESULTS ARE EXPRESSED IN mg/l IN BRINE

Group N Cd Hg P Ca Mg Mn Fe Cu B Zn A1 Pb Cr

1 625 .002 0 137 1110 140 3.3 6.1 1.5 1.5 4.9 4.7 0 0

2 1013 .017 0 202 1060 160 2.4 25.8 1.4 1.4 5.6 30.5 0 0

3 504 .001 0 137 1220 150 4.4 15.3 2.4 1.7 6.3 17.5 0 0

4 886 .005 0 182 1060 160 2.2 21.4 1.8 1.3 4.2 21.8 0 0

5 705 .036 0 159 1040 160 2.7 12.6 1.6 1.3 4.7 12.2 0 0

6 605 .016 0 131 930 140 1.6 8.1 1.0 1.0 3.1 6.3 0 0

7 849 .016 0 173 1020 160 3.1 8.4 1.9 1.4 5.1 11.3 0 0

8 221 0 0 68 1250 105 3.4 6.0 2.4 1.6 4.9 7.1 0 0

9 769 0 0 154 1170 150 4.4 12.0 2.3 1.6 5.4 18.1 0 0

10 524 .038 0 134 935 150 1.9 9.3 1.1 1.1 4.9 6.8 0 0

11 515 0 0 102 710 130 1.1 3.7 0.7 0.8 2.2 6.8 0 0

no.

OD w

TABLE A-12. MINEPAL COMPOSITION OF SPENT BRINE FROM 1ST CYCLE CONTROL FERMENTATION--l975 DATA. ALL RESULTS ARE EXPRESSED IN mg/l IN BRINE

Group N . Cd Hg P Ca Mg Mn Fe Cu B Zn A1 Pb Cr no.

1 467

2

3 560

4 5 89

N 5 603

6 644

7

8 641

9 611

---

0

---

10

11 543

.002

.lo7

0

.004

.040

.024

--- .007

0

0

0 114 910

0 165 1490

0 91 1060

0 153 1480

0 148 1110

0 159 1220

002 --- --- 0 119 1050

0 159 1330

120 3.0 5.5

170 3.5 14.2

120 2.2 5.8

160 3.3 20.3

140 2.7 7.2

160 2.7 9.0

--- --- --- 140 2.1 6.8

150 4.7 10.5

1.2 1.2

1.8 1.6

1.1 1.1

1.7 1.6

1.4 1.2

2.0 1.5

--- --- 1.1 1.0

2.0 1.7

4.2 5.3 0 0

5.3 12.2 0 - 3.5 4.7 0 0

4.9 10.9 0 0

4.4 6.8 0 0

3.8 10.0 0 0

--- --- - - 3.4 7.3 0 0

6.1 9.0 0 0

0 114 960 130 2.7 6.4 1.3 1.2 3.5 6.8 0 0

TABLE A-15. MINERAL COMPOSITION OF SALT STOCK CUCUMBERS FROM 1ST CYCLE CONTROL FERMENTATION--1975 DATA. ALL RESULTS ARE EXPRESSED AS mg/kg I N CUCUMBERS

Group N Cd H g P Ca Mg Mn Fe Cu B Zn A 1 Pb C r no.

~ ~~

1 822 .167 . 002 114 960 120 1.1 3.7 0.6 1.3 2.2 1.0 0 0

2 852 .066 .005 159 1440 160 3.3 16.5 2.0 2.0 4.7 13.8 0 .023

3 788 .040 .005 125 1220 130 1.6 8.7 1 .3 1 .5 4.0 8.4 0 0

4 688 0 . 005 119 1110 130 1.4 18.9 1.0 1.5 3.1 13.2 0 0

5 735 .073 .003 148 60 130 2.7 8.1 1.6 1.7 4.4 6.3 0 .003

6 1 8 1 -069 .002 148 1125 140 2.3 9 . 1 1.5 1 . 7 4.1 2.7 0 .018

7 83 .045 .002 151 1170 165 1.9 8.5 1.3 1.6 3.4 7.1 0 -018

8 326 .030 .010 125 1050 130 0.8 7.8 0.8 1.2 2.2 8.4 0 0

9 732 .039 . 020 1 3 1 1330 130 1.9 11.1 1.2 1.5 3.5 9.0 0 0

1 0

11 709 .038 0 125 910 130 1.4 7.5 0.9 1 .3 2.6 5.3 0 .031

TABLE A-14. MINERAL COMPOSITION OF SPENT BRINE FROM 2ND CYCLE CHEMICAL TREATMENT FElWENThTION--1975 DATA. ALL RESULTS ARE EXPRESSED I N mg/l I N BRINE

Group N Cd H g P Ca M g Mn Fe Cu B Zn A 1 Pb C r no.

1 839 .004 .005 80 810 90 1.4 3.4 0.8 0.9 2.2 9.0 0 0

--- --- - 0 0 2 -- --- -- 2.2 --- --- 1.9 --- --- - - 2

3 647 0 .015 119 1060 130 1.9 10.2 1.2 1.3 4 . 0 9.5 0 0

4 835 .002 0 162 1025 130 2.5 2.6 1.6 1.4 4.1 --- ' 0 0

5 711 .020 0 1 3 1 910 110 2.4 5.8 1.2 1.2 4.0 21.5 0 0

6

7

8 292 0 0 137 1300 130 2.2 14.1 1.6 1.5 3.8 4.3 0 - 9 603 0 0 137 1190 130 3.8 12.0 1.9 1.7 6.1 9.5 0 0

10 5C6 .022 . 002 102 910 100 1.4 5.5 1.0 1.0 2.2 6 .8 0 0

11 886 -006 0 125 860 120 1.9 6.9 1.0 1.1 2.8 7.4 0 0

I

2.0 --- 4.7 7.9 - --- --- ---- --- ---- --- --- --- -

TABLE A-17. MINERAL COMPOSITION OF SALT STOCK CUCUMBERS FROM 2ND CYCLE CHEMICAL TREATMENT FERMENTATION--1975 DATA. ALL RESULTS ARE EXPRESSED AS mg/kg IN CUCUMBERS

Group N Cd Hg P Ca Mg Mn Fe Cu B Zn A1 Pb Cr no.

~~- ~

1 700 .062 .012 32 1090 110 2.2 5.5 1.4 1.7 3.8 3.2 0 .003

2 130 .062 .002 116 1270 140 2.2 12.6 1.4 1.9 4.4 11.6 0 .069

3 863 .035 .087 74 1110 120 3.0 11.7 1.8 1.9 4.7 7.4 0 0

4 839 .040 .010 132 810 100 2.2 23.9 1.2 1.5 3.8 13.2 0 0

5 881 -155 .012 93 980 100 2.4 7.5 1.4 1.7 4.0 9.3 0 .012

6

7 1006 .041 .007 84 1010 130 2.7 8.4 2 . 0 1.7 4.7 8.4 0 .043

8 303 .020 143 1040 100 1.6 12.6 1.2 1.5 3.5 14.3 0 -- 9 760 .041 .001 90 1040 120 1.6 9.6 1.2 1.5 3.5 9.0 0 .006

10 1036 ,034 0 143 880 100 1.1 8.1 1.2 1.3 2.4 14.3 0 .002

11 773 .050 .007 84 910 110 3.0 8.4 2.5 1.7 4.4 8.4 0 .021

TABLE A-16. MINERAL COMPOSITION OF SALT STOCK CUCUMBERS FROM 2ND CYCLE HEAT TREATMENT FERMENTATION--1975 DATA. ALL RESULTS ARE EXPRESSED AS mg/kg IN CUCUMBERS

Group no. N . Cd Hg P Ca M g Mn Fe Cu B Zn A1 Pb Cr

1 167

2

3 85

4 1090

5 779

6 292

7 386

8 39 7

9 769

10 340

11 350

--- .032 .001 154

---- ---- --- .032 .010 137

.021 .010 211

.012 .022 171

.034 0 148

.042 .007 74

.045 .002 80

.063 .010 154

.048 .010 133

-023 -002 114

1140

---- 1170

1220

1060

1250

320

1110

1040

825

495

150 2.2 5.8

--- --- --- 140 2.7 12.6

190 2 . 2 25.5

150 2 . 2 14.1

160 2.7 8.4

40 0.5 15.0

90 2.7 7.8

150 1.6 8.7

130 1.9 9.0

135 1.2 7.8

1.2 1.7 3.8 3.7

1.3 1.4 5.6 30.5

1.7 1.7 4.2 12.2

1.5 1.8 4.7 17.5

1.9 1.8 3.8 12.2

1.7 1.7 4.9 7.4

0.7 0.9 1.1 19.7

1.6 1.7 4.2 9.0

1.5 1.6 3.5 9.0

1.1 1.3 2.8 8.2

0.7 1.3 2.5 6.5

0 0

- - 0 0

0 0

0 0

0 0

0 .018

0 .006

0 .069

0 .031

0 0

TABLE A-19. MINERAL COMPOSITIW OF DESALTED CUCUMBERS FROM 2ND CYCLE HEAT TREATMENT FERMENTATION--1975 DATA. ALL RESULTS ARB EXPRESSED I N mg/kg I N CUCUMBERS

Group N C d Hg P Ca Mg Mn Fe Cu B Zn A 1 Pb C r no.

1 398 .138 .005 6 3 360 70 0 7.9 0 0.5 0 0.5 0 .031

2 355 .020 .010 80 430 60 1.1 10.8 1.3 0.9 1 .3 7.9 0 0

3 361 .022 . 005 57 380 50 0.3 9.9 0.8 0.7 1.1 7.4 0 0

4 390

5 568

6 454

7 82

8 323

9 311

1 0 409

11 351

a0 rD

.018

.352

.215

.020

.017

.019

-190

-125

. 0 0 8 60

-030 80

.037 68

-007 3 4

. l o0 40

.005 57

0 60

0 5 1

2 60

430

4 30

120

410

250

350

300

50 0.2 11.1 0.6 0.5

80 0.3 8.4 0.9 0.7

70 0 4.0 0.7 0.6

20 0 11.7 1.2 0.4

50 0.5 5.8 0 . 8 0.7

60 0 5.2 0 0.4

60 0 5.5 0.5 0.6

60 0.3 4.6 0 . 8 0.6

0.6

1.1

0.9

0

0.6

0

0.1

0.9

9.8

5.3

3.7

12.2

4.2

3.2

6.0

13.8

0

.064

0

0

0

0

.032

.002

TABLE A-18. MINERAL COMPOSITIW OF DESALTED CUCUMBERS FROM 1ST CYCLE CONTROL PEmTATION--1975 DATA. ALL RESULTS EXPRESSED IN mg/kg I N CUCUMBERS

Group N C d H g P Ca Mg Mn Fe Cu B Zn A 1 Pb C r no.

1 409 ,026 .007 40 275 55 0 2.0 0 0.4 0 0 0 .003

2 404 .019 -045 62 440 65 0 7.5 0.6 0.6 0 5.0 0 0

3 452 .045 .007 68 500 80 0 5.8 0.2 0.6 0.2 3.7 0 .028

4 372 .017 .040 57 380 60 0 13.5 1.5 0.6 0.4 8.4 0 0

5 378 .066 -008 68 430 60 0.5 6.7 0 . 8 0.7 0.9 31.1 0 .064 t

6 451 .117 .010 63 470 60 0.5 5.8 1.6 0.6 0.9 5.8 0 0

7 448 .018 .010 6 8 430 70 0 5.5 1.0 0.7 0.4 4.2 0 0

8 385 .025 0 34 210 30 0 5.8 0.5 0.4 0 5.3 0 0

9 379 .020 .010 57 360 50 0 4.9 0.7 0.6 0.4 5.3 0 0

10

11 312 .113 -011 5 1 320 60 0 3.4 0.7 0.6 0 4.2 0 -064

b

TABLE A-21. MINERAL COMPOSITION OF SPENT BRINE FROM 1ST CYCLE CONTROL FERMENTATION--1976 DATA. ALL RESULTS ARE EXPRESSED IN mg/l IN BRINE

Group N Cd Hg P Ca Mg Mn Fe Cu B Zn A1 Pb no.

~

1 445 ,035

2 574 .010

3 813 .005

4 553 .010

5 428 0

6 659 .010

7 386 ---- 8 483 .013

.007 80 610 110 1.1

.011 336 1150 250 1.7

.001 389 1560 310 2.3

-002 114 610 130 0.8

.011 232 820 200 0.1

,013 232 870 220 0.3

.009 286 1030 220 1.1

.011 322 1010 270 2.8

7.2

9.5

17.9

7.5

5.4

5.7

32.2

10.1

0 . 7 1.1 3.5 8.4 0

0.1 2.0 3.0 20.2 0

0.01 2.1 3.9 13.3 0

0 . 7 0.9 2.8 8.4 0

0.01 0.9 0.5 5.1 0

0.7 1.3 2.1 6.9 0

0.01 1.4 2.0 27.8 0

1.0 1.6 4.9 6.9 0

TABLE A-20. MINERAL COMPOSITION OF DESALTED CUCUMBERS FROM 2ND CYCLE CHEMICAL TREATMENT FERMENTATION--l975 DATA. ALL RESULTS ARE EXPRESSED IN mg/kg IN CUCUMBERS

Group N Cd Hg P Ca Mg Mn Fe Cu B Zn A1 Pb Cr no.

1 391 .129 .002 46 430 60 0 2.9 0.4 0.6 0.4 3.2 0 0

2 377 .029 .020 57 320 50 0 9.3 0.5 0.4 0 5.3 0 .031

3 350 .008 .350 57 360 60 0 6.1 0.3 0.6 0.2 4.7 0 0

4 314 .026 .002 57 300 50 0 16.2 0 . 7 0 . 8 0 8.4 0 0 (D 0 5 318 .201 .027 57 360 50 0 2.9 1.2 0.6 0.4 3.7 0 .090

6

7 430 .041 0 46 270 50 0 2.9 0.8 0.6 0 6.8 0 0

8 286 .032 .007 46 320 50 0.5 5.8 0.8 0 . 7 0.6 4.2 0 0

9 398 .028 .007 46 300 50 0 4.0 0.5 0.4 0 3.2 0 0

10 206 .097 -017 40 320 40 0.7 5.2 0.6 0.5 1.0 12.4 0 .064

11 410 .079 0 63 320 60 0 4.0 0.4 0.6 0 4.2 0 0

a

TABLE A-23. MINERAL COMPOSITION OF SPENT BRINE FROM 3RD CYCLE CHEMICAL TREATMENT FERMENTATION--1976 DATA. ALL RESULTS ARE EXPRESSED IN mg/l IN BRINE

Group N Cd Hg P Ca Mg Mn Fe Cu B Ln A1 Pb no.

~ ~ ~ ~~ ~ ~~~ ~

1 506 .005 .013 80 660 120 0.5 7.2 1.2 1.3 2.8 10.6 0

2 882 .010 0 232 1310 200 1.9 16.7 2.0 1.8 3.0 65.7 0

TABLE A-25. MINERAL COMPOSITION IN SALT STOCK CUCUMBERS 3RD CYCLE HEAT TREATMENT FERMENTATION--1976 DATA. ALL RESULTS ARE EXPRESSED IN mg/kg IN CUCUMBERS


896 .020 .005 357 1700 270 2.8 25.1 1.9 2.4 5.6 26.5 0

863 . 0 2 0 0 277 1470 310 3.4 24.2 2.4 2.0 5.2 29.7 0

707 .013 .005 398 1400 330 4.0 26.3 2.0 2.6 4.4 18.9 0

788 .020 .003 331 1330 280 2.6 18.5 1.3 2.2 5.4 16.4 0

0 .007 349 1540 300 2.3 lg.8 1.7 2.2 4.4 15.2 0

843 -005 .001 357 1380 290 2.3 13.7 1.6 2.2 4.3 16.4 0

946 .015 .002 366 1290 330 1 . 7 47.1 2.2 2.1 0 55.6 0

971 .015 ,003 131 360 90 0.8 4.6 0.5 0.8 2.2 3.7 0

TAELE A-24. MINERAL COMPOSITION IN SALT STOCK CUCUMBERS FROM 1ST CYCLE CONTROL FERMENTATION--1976 DATA. ALL ReSULTS ARE EXPRESSED IN mg/kg IN CUCUMBERS


540 .010 .001 91 745 110 1.1 9.3 1.0 1.4 3.7 9.3 0

802 .005 ,003 384 1010 240 1.7 14.9 1.7 2.0 0.5 17.0 0

1008 .015 .002 393 1260 300 2.3 20.0 1.8 2.1 3.9 16.4 0

642 .013 .012 108 720 125 0.8 10.3 0.9 1.3 3.4 8.0 0

5 699 .030 .001 295 1010 250 1.4 9.5 1.2 1.8 3.2 13.9 0

616 .020 .005 241 1010 190 1.7 8.9 1.3 1.8 3.0 15.9 0

855 .010 .003 152 570 100 1.1 12.8 1.8 1.3 1.4 15.2 0

806 .010 .001 322 1310 270 2.0 22.4 3.4 2.1 4.7 22.1 0

TABLE A-27. MINERAL COMPOSITION IN DESALTED CUCUMBERS FROM 1ST CONTROL FERMENTATION--1976 DATA. ALL RESULTS ARE EXPRESSED IN mg/kg IN CUCUMBERS


1 542 .008 .005 170 520 120 1.7 11.9 1.3 1.4 3.3 15.2 0

2 440 .015 .005 246 520 140 0.1 6.6 1.3 0.8 0 11.4 0

W 3 675 .015 0 214 820 170 1.1 10.1 1.1 1.6 2.4 10.7 0

4 600 -013 .012 170 570 140 0.6 11.0 0.9 1.1 1.7 12.0 0

5 527 -010 .005 174 450 140 0.1 7.8 0.2 1.0 0 8.8 0

6 728 0 -002 349 1200 270 2.6 58.8 2.2 2.0 3.3 83.3 0

U

7 602 .025 .002 179 570 140 0.1 29.2 1.3 1.3 0 29.7 0

8 604 .015 0 179 720 130 0.9 14.9 1.4 1.4 2.0 18.9 0

TABU A-26. MINERAL COMPOSITION IN SALT STOCK CUCUMBERS 3RD CYCLE CHEMICAL TREATMENT PERMENTATION--1976 DATA. ALL RESULTS ARE EXPRESSED IN mg/kg IN CUCUMBERS

Group N Cd Hg P Ca Hg Mn Fe Cu B Zn A1 Pb no.

1 640

2 1203

W 3 941 m

4 647

5 924

6 442

7 675

8 1037

.013 .004 246

.025 .003 82

.013 .007 322

.010 .009 91

.020 0 340

.023 - 0 0 2 63

.030 -006 88

.030 .002 114

730

1330

1330

690

1380

5 30

190

300

105

220

240

105

2 70

80

50

60

1.0

1.1

2.8

0.7

2.6

0.4

0.7

0.6 -

8.0 0.9 1.5 3.5

16.7 1.1 2.1 3.3

20.0 2.2 2.4 5.9

9.8 1.6 1.4 2.9

14.0 1.4 2.3 5.6

4.8 0.8 1.1 2.0

11.4 0.5 0.8 2.1

4.4 0.6 0.8 2.0

8.5 0

20.2 0

21.5 0

12.3 0

11.4 0

5.3 0

10.6 0

3.4 0

TABLE A-29. MINERAL COMPOSITION IN DESALTED CUCUMBERS FROM 3RD CYCLE CHEMICAL TREATED FERMENTATION--1976 DATA. ALL RESULTS ARE EXPRESSED IN mg/kg IN CUCUMBERS


1 528

2 835

\o 3 795

4 553

5 777

6 554

7 464

8 499

W

.010

.OlO

-013

.020

.025

.015

.025

.020

.003

.008

.002

.006

b

.017

.004

.003

161 470

214 910

210 870

156 520

228 940

116 530

945 120

54 150

110 1.4

160 1.7

140 1.4

90 1.1

180 1.1

70 0.1

30 --- 40 0.3

8.4

14.3

25.7

13.1

13.7

6.9

6.8

3.8

4.9 1.6 3.2

2.1 1.7 1.9

1.1 1.7 3.0

1.7 1.4 1.4

1.3 1.9 3.0

0.7 1.2 0

0.3 0.4 0.1

0.5 0.4 1.0

12.6 0

24.0 0

13.9 0

13.3 0

12.6 0

12.6 0

9.3 0

5.0 0

TABLE A-28. MINERAL COMPOSITION IN DESALTED CUCUMBERS FROM 3RD CYCLE HEAT TREATED FERMENTATION--1976 DATA. ALL RESULTS ARE EXPRESSED AS mg/kg IN CUCUMBERS


1 843 0 . 0 0 3 268 1060 200 1.7 20.9 1.6 1.8 3.0 16.4 0

2 531 .015 .001 357 1060 240 2.3 13.4 1.9 2.2 4.4 19.6 0

W 3 813 0 .001 219 1360 340 0.1 19.1 0.6 1.6 0.8 14.5 0

4 698 .015 .002 206 790 180 0.9 11.9 1.1 1.4 1.9 10.1 0

5 770 .010 .003 214 870 160 0.3 16.7 1.5 1.5 0 24.0 0

6 571 -005 .002 197 620 160 0.1 9.5 0.9 1.3 1.0 14.5 0

7 696 .015 .006 201 840 170 0.6 33.4 1.3 1.5 1.4 39.8 0

01

8 503 .ole .oil 62 700 40 0.4 3.13 0.5 0.4 1.1 4 . a o

TABLE A-30. ACID PRODUCTION DURING 1ST CYCLE FERMENTATION OF CUCUMBERS USING FRESH CONTROL BRINE--1976 DATA. RESULTS ARE EXPRESSED AS PERCENT TITRATABLE ACIDITY

CALCLlLATED AS LACTIC ACID

Fementation Tank number time (days) M50 M7 M47 M46 M6 M43 M9 M8

--- --- 1

2 .01 .os 3 . 0 4 .05 4 5

6 7 8

9

10 11 12 13

14

15

16

17 18 19

20 21 22

--- --- .13 .16

.17 .23

.24 .30

.29 .39

.33 .39

.I2 .49

. I S .SO

.so .54

.51 .58

.SO .63

.60 .69

.55 .68

.65 .70

.68 .75

.70 . 7 4

.66 .78

.69 .83

.63 .75

--- .02 .02 .04

.06

.21

.25

.29

.32

.36

.38

.50

.55

.60

.62

.64

.76

.68

.71

.75 --- .85

.02 .02

.OS .06

.03 .16

.OS .24

.10 .29

.18 .34

.29 .43

.36 .54

.I2 .64

.46 .76

.52 .77

.54 ---

.56 .83

.67 .78

--- .83

.72 ---

.65 --- --- .82 .66 . a4

--- .92 --- .93 .63 .91

--- .02 .04 .os .22

.07

.16

.21

.25 --- .40 .40 .44 .27

.34 --- .61 . 5 8

.61

.65

.65 ---

--- --- .OS .04

.07 .14

.10 -23 --- .31

.37 -34

.37 ---

.47 ---

.56 .47

.62 .61 --- .64 --- .66

.51 .66

.68 ---

.79 ---

.78 ---

.80 .77 --- .75

.70 --- --- --- . 8 7 --- .84 ---

100

TABLE A-31. ACID PRODUCTION DURING 1ST CYCLE FERMENTATION OF CUCUMBERS USING FRESH CONTROL BRINE--1975 DATA. RESULTS ARE EXPRESSED AS PERCENT TITRATABLE ACIDITY

CALCULATED AS LACTIC ACID

Fermentation Tank nrmrber (daye) L36 M2 M51 M1 M52 M9 M42 M35 M33 LO8 ._ _._

1

2 -03 .03 .06 .03 .03 .06 .03 .03 .03 .03

3 -15 .09 .12 .06 .06 .18 .09 .03 .18 .06

4 -27 -15 -18 e09 -21 -57 -24 .24 -27 -09

.24 .54 .18 .36 .54 .30 .33 .12 .09 5

6 . 4 8 .27 .45 .21 .57 .57 . 4 5 .36 .18 .12 7 .57 . 45 .51 .36 .60 .57 .54 .45 .24 .21

0 .57 .48 .54 .46 - 5 4 .60 .42 .57 .33 .36

---

9 -63 - 5 4 -60 -33 -60 -66 .39 . 4 8 --- --- lo -63 -60 -66 - 4 2 -63 -63 -42 --- .42 --- 11 -60 -66 -63 -51 -63 -69 .57 .57 - 4 8 .54 12 --- 13 -81 -60 -75 -57 -69 -78 -63 .57 .60 .66 14 - 8 4 -66 -75 -63 -78 -81 -63 .60 .63 --- 15 -90 -72 -75 -69 -78 -78 -63 .63 .63 ---

-18 .62 .57 .63 .78 -54 .63 . 54 .63

16 .a7 -78 .78 .75 -81 -81 -54 .66 .69 --- 17 -87 -63 -78 -69 -78 .81 .78 .63 --- --- 18 .90 -81 -66 .72 .78 .90 .75 --- --- .81

20 .93 .7a .ai .69 .87 .ai .78 .a .78 .69 19 -96 - 8 4 .78 .63 .81 .87 .75 --- .72 .72

21 1.02 .69 .69 .75 .87 .93 .69 .72 .78 .69 22 .96 . 7 8 .72 .60 .81 .84 .63 .72 --- ---

101

TABLE A-32. OF CUCUMBER

RESULTS

ACID PRODUCTION DURING ZND CYCLE FERMENTATION USING 1ST CYCLE HEAT TREATED BRINE--1975 DATA. 3 EXPRESSED AS PERCENT TITRATABLE ACIDITY

CALCULATED AS LACTIC ACID

1

2 3

4 5

6 7

8

9 1 0

11

1 2 13 1 4 15 1 6 1 7

18 1 9

20

2 1

.30 .12 .24

.18 .18 . 2 1

.33 . 2 1 .45

.54 .36 .45

.60 .81 .57

.60 .51 .66

.72 .66 .75

.75 .75 .78

.75 .78 .90

--- .81 .87

. 81 .87 .93

.84 .87 .90

.93 .96 .96

. 87 .96 1.02

.90 .99 1.02

.96 .99 .99

.931.02 1.05

i 9 0 1 . 0 2 .96

1,02 1.05 .87

- 9 9 1 . 1 1 .93

.21 .18 .18 .06 .09

.24 . 2 1 .15 .12 .12

.33 .36 .39 .42 .24

.57 .48 .60 .54 .39

.45 .57 .63 .63 .42

.57 - 6 6 .69 .69 .48

.63 .69 .75 . 75 .54

.60 .75 .81 .72 .57

.48 .84 . 75 . 7 2 --- .81 .78 .90 .63

.78 . 81 .87 .84 .66

---

.70 .87 .72 .84 .54

.81 .84 .72 .84 .60

. 8 1 .84 .75 .90 .54

.87 .84 .75 .90 .57

.81 .87 .69 .99 . 63

.84 .87 - 7 5 .96 --- - 7 2 .96 .78 .90 --- .84 .87 . 7 2 .99 . 33

.90 -84 .84 .93 .39

.06 .03

.06 .30

.27 .15

.42 .30

.48 ---

.57 .54

.57 .57

.63 .54 --- -60

.72 . 8 1

.72 .69 - 7 8 . 75 .63 --- . 8 1 --- .81 .78 .78 .75

.84 --- --- --- . 8 1 --- .87 ---

TABLE A-33. ACID PRODUCTION DURING 2ND CYCLE FERMENTATION OF CUCUMBERS U S I N G 1ST CYCLE CHEMICAL TREATED BRINE--

1975 DATA. RESULTS ARE EXPRESSED AS PERCENT TITRATABLE ACIDITY CALCULATED AS LACTIC ACID

Tank number F e r m e n t a t i o n time ~ 4 4 M4 M50 M48 M6 M43 M40 M39 M45 L47

1 2

3

4

5 6 7 8

9

1 0

11

1 2 1 3

1 4

15

1 6 17 1 8

1 9 20

2 1

.24

. a3

.51 --- .69 .75 . 71 .87

.81

.87 --- .96

1 .05 1 .23

* 99 * 99

1.05 1 .05 1.02

1.08

.30 .39

.39 .12

.42 .24

.51 .30

.60 .54

.60 .69

.66 . 72

.75 .75

.78 .81

.81 .75

. 8 7 .84

.84 .90

.90 .90

.93 .99

.96 1.05

1.02 .96 .99 1 .02

1.02 1 .02 1 .05 .96

.96 .99

.15

.12

.21

.42

.36

.66 .15 .81

.90

.96

.99 1 .02

-99 1 .05

1 .08 1.11 1.14

1.05 1.08

1 .17 2 2 1 - 0 2 1 . 0 8 - 8 7 .78 .99 - 7 5 .96 .48 .75 --- --- 22 1 . 0 8 1.05 .99 1 .05

.09 .12 .06 .06 .09 .18

.18 .24 .06 .06 .09 . 2 1

.60 .54 - 2 4 .33 .09 .33

.63 .75 .33 .42 .18 .40

.78 .60 .27 .48 --- .54

.87 .69 .39 .33 .36 .60

.87 .72 .39 .33 .57 .69

.93 -69 .42 .54 .54 ---

.99 .78 --- --- .60 ---

.96 .90 . 51 .63 .66 .84

.93 . 8 1 - 5 4 .69 .66 .90

.96 .93 .60 .57 .54 .93

1.05 .93 .63 .63 --- --- .96 .93 - 6 6 .75 --- --- .99 .90 - 6 9 .78 .75 --- -96 -99 - 6 6 .78 . 8 1 --- .96 .99 --- --- .84 .96

.gg -87 --- --- --- .99 1 .05 1 .08 .84 .60 .75 ---

.99 .99 .96 .69 .84 --- - 8 1 .93 .75 .84 --- ---

102 103

TABLE A-34. ACID PRODUCTION DURING 3RD CYCLE FERMENTATION OF CUCUMBERS USING 2ND CYCLE BEAT TREATED BRINE--1976 DATA.

RBSULTS ARB EXPRESSED AS PERCENT TITRATABLE ACIDITY CALCULATED AS LACTIC ACID

TABLE A-35. ACID PRODUCTION DURING 3RD CYCLE FERMENTATION OF CUCUMBERS USING ZND CYCLE CHEMICAL TREATED BRINE-- 1976 DATA. RESULTS ARE EXPRESSED AS PERCENT TITRATABLE

ACIDITY CALCULATED AS LACTIC ACID

F e r m e n t a t i o n T a n k number M52 M1 M3 M44 M49 M42 M4 L48

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19

--- .26 .23 --- .29 .43 .53 .59 .69 .74 .73 .77 .81 .79 .84 .84 * 88

.90

.91

.24 --- -12 .13 --- ---

.23 .16 .14 .19 .16 .13 --- .15 .12 .34 .17 .13 --- .16 .08 .46 .17 .15 .49 .26 -28 .56 -26 --- .61 .41 .32 .61 .31 .41 .61 .49 .38 .70 .36 .49 -64 -60 -44 -70 -37 -49 .67 .62 .SO .86 .42 .59 -73 -64 -60 --- --- .62

.72 .76 -65 .91 .63 --- -74 .79 -70 .91 .59 --- .77 .79 .69 .96 .66 .73 .78 .89 .75 .69 .49 .76 .84 .91 . S 5 .80 .60 .82 -85 .84 - 8 0 --- --- .84 -83 .go --- --- --- .83

.85 .73 .71 .87 .63 ---

.83 .84 --- .87 .64 ---

F e r m e n t a t i o n Tank number time (days) M51 M2 M48 M45 M5 M41 M11 L4 7

.25 1 2 .23 .24 3 -23 --- 1 --- .41 5 .30 .54 6 .45 .61 7 .54 .75 8 .64 .79 9 .69 .85 lo .80 --- 11 . 7 8 .93 12 .82 .99 13 .84 1.01 14 .88 1.06

15 . 8 7 1.07 16 .78 1.08 17 .80 1.10 18 .83 .1.08 19 .89. 1.06

--- --- .20 .17 .18 .16 .33 .42 .51 .55 .61 .70 .75 .81 .80

.89

.88

.98

.93

.91

.15 .12 .12

.09 .19 .09

.14 .38 .15

.07 .56 .34

.23 .66 .36

.36 .73 .42

.49 .79 .46

.58 .80 .50

.67 -91 ---

.70 --- .75

.71 1.04 .78

.61 1.13 .78

.73 1.06 .62

.80 1.10 .69

--- 1.11 .67 .91 --- . 7 7

.80 --- .90

--- 1.11 .82 .81 1.11 .86

--- --- .12 .21 -13 .35 .16 .48

.63 .46 .63 .47 .82 .56 .79 .63 .91 .71 .88

.81 .91

.88 ---

.98 ---

.97 --- 1.03 . 8 0

.82

.91

---

--- --- --- --- 1.02 ---

104 105

TABLE A-37. SAMPLE CALCULATIONS FOR 1 BUSHEL CUCUMBER SALTING (DESALTING*)

Item Amount

TABLE A-36. INSTIEDN PRESSURE TEST ON 2ND CYCLE SALT STOCK CUCUMBERS AFTER DESALTING. AS kg OF FORCE REQUIRED TO PUNCTURE THE FRUIT WITH

RESULTS ARE EXPRESSED

A 5/16" DIAMETER PROBE

Group no. Control Heated br ine Chemically t r ea t ed br ine

1 6 . 0 7 8.28 8.88

2 8.67 7.98 8.92

3 4.77 8.75 7.35

4 8.63 8.86 8.40

5 8.80 7.87 7 .62

6 9.19 8.67

7 7.65 8.85 7 . 6 1

8 8.60 8.64 9.04

9 8.84 9.24 9.60

l o ---- 7.55 7.40

----

11 8.09 7.08 8.48

~ ~~

l b S a l t Total l b Fermentation ---- l b s a l t i n 3.2 g a l cover br ine a t 25OS

l b s a l t required t o maintain 25's 1 . 0 4 3 .46 -_--

Storage l b s a l t required t o r a i s e sal t concen-

t r a t i o n t o 45OS 4.60 9 .90

Untankinp

lb sal t remaining i n 3.8 g a l spent

lb sa l t in 1 bushel o r 5.4 g a l

4.09 ---- brine

p ick les 5.81 9.90

Desalting

lb s a l t i n desa l ted p ick les 2 .21 ---- lb sa l t l o s t i n process w a t e r 3.60 ----

suppmary to ta l l b s a l t t o 45's

lb s a l t i n spent br ine

No recycling Recyclinl 9.90 9.90

4.09 4 .09

l b s a l t i n process water 3.60 3.60

l b s a l t i n excess b r ine ( a f t e r fermentation) 0.65 0 . 6 5

l b s a l t saved because of recycling ---- 3.44

l b s a l t t o waste t r e a t 7.69 4.25

*Basis: 1. Bushel occupies 6 ga l volume 2. 3 .2 g a l needed t o cover 1 bushel 3. 65 par t s cucumbers, 35 par t s br ine by weight

4 . 10% shrinkage of p ick le stock, thus 10%

5. Stock s to red a t 45OS desa l ted t o 18's. excess b r ine generation

106 107

TABLE A-38. HEAT INACTIVATION OF PUNGAL PECTIWES AT pH 3.3 I N 12% NaCl, 0.6% LACTIC ACID AND 0.1% Ca++ ION

O r g a n i s m Heating Heating A c t i v i t y temperature t i m e r e m a i n i n g

("C) ( s e d ( 0 )

P e n i c i l l i u m j a n t h i n e l l u m 78 20 16 .3 24 1.9 2 5 1.1

40 2.9 40 2.8 4 5 1 .6

P e n i c i l l i u m oxalicum 70 30 32.7

45 3.2 50 3.0

Fusarium solani 70 15 17.0 17 6.0 18 3.5 20 1.5

Fusa r ium oxysporum 70 18 27.0 20 9.0 22 2.6 2 3 1.5

Alternaria t e n u i e 65 20 51.1 30 20.7 45 4.6 60 1.3

Tr i chode rma viride 6 5 30 22.7 35 10.6 40 8.4 45 5.0

P e n i c i l l i u m janthinellum 7 5 30 11 .2

40 9.6

3.1

4.0

4.5

4.7

TABLE A-39. EFFECT OF pH ON INACTIVATION OF P e n i c i l l i u m j a n t h i n e l l u m PECTINASE AT 75°C

Heating A c t i v i t y t i m e ( e e c ) remaining (0 )

PB

3.1 28 6.2 30 4 . 1 33 2.7 35 1 .8

3.3 25 19.0 30 10.7 35 6.6 40 3.3

3.5 30 10 .3 35 6.5 37 5.5 40 4.4 45 3.1

35 10 .3 40 6.9 45 5.1 50 3.6

35 27.9 40 15 .5 45 8.2

30 15 .5 32 10.2 35 4.3 25 33.3 27 19 .9 30 7.7 32 3.2 35 1.4

108 109

r

I '* .,

TABLE A-43 C o n t i n u e d

PH Incubation A c t i v i t y t i m e (hr) r e m a i n i n g ( 0 )

11.6 0 1 3.5 6.5 22

59 22 . 6.1 3.4 ND'

*ND = N o t detectable.

114

TAB= A - 4 4 . INACTIVATION OF P e n i ' c i l l i u m ' a n t h i n e l l u m PECTINASE I N SIMULATED SPENT BRINE AT

SALT CONCENTRATION 12%

Incubation A c t i v i t y t i m e (hr) remaining (a)

Pa

11.0

11.7

0 6 10 2 1 33 45 57 69

71.9 69.8 69.8 63.3 61.3 59.7 56.5 51.6

0 70.1 2 60.4 9 65.3

20 30

~.

55.5 53.5

40 53.9

115

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