Methods for total metal determination onorganic residues containing soil material

Item Type text; Thesis-Reproduction (electronic)

Authors Artiola-Fortuny, Juan, 1952-

Publisher The University of Arizona.

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METHODS FOR TOTAL METAL DETERMINATION ON

ORGANIC RESIDUES CONTAINING SOIL MATERIAL

by

Juan Art iola- 'Fortuny

A Thesis Submitted to the Faculty o f the

DEPARTMENT OF SOILS, WATER AND ENGINEERING

In P a r t i a l Fu lf i l lm en t o f the Requirements fo r the Degree of

MASTER OF SCIENCE WITH A MAJOR IN SOIL AND WATER SCIENCE

In the Graduate College

THE UNIVERSITY OF ARIZONA

1976

STATEMENT BY AUTHOR

This t h e s i s has been submitted in p a r t i a l f u l f i l l m e n t of r e ­quirements fo r an advanced degree a t The Universi ty o f Arizona and is d epos i ted . in the Univers i ty L ib ra ry to be made av a i la b le to borrowers under ru le s o f the Library.

B r ie f quota t ions from t h i s t h e s i s are allowable without specia l permission provided t h a t accurate acknowledgment o f source i s made. Requests fo r permission fo r extended quota t ion from or reproduct ion of t h i s manuscript in whole or in p a r t may be granted by the head of the major department or the Dean o f the Graduate College when in his judg­ment the proposed use of the mater ia l i s in the i n t e r e s t s of s cho la r ­ship . In a l l o ther in s tan ce s , however, permission must be obtained from the author.

SIGNE

APPROVAL BY THESIS DIRECTOR

This t h e s i s has been approved on the date shown below:

Wallace H. F u l le r U DateProfessor of

S o i l s , Water and Engineering

ACKNOWLEDGMENTS

The author wishes to give spec ia l recogni t ion and extend his

personal thanks to Dr. W. H. F u l l e r , d i r e c t o r o f the t h e s i s and major

p ro fesso r . Without his guidance and individual concern expressed , t h i s

study would not have been poss ib le .

Appreciation is a lso extended to the f a c u l ty and s t a f f members

of the Department o f S o i l s , Water.and Engineering fo r t h e i r invaluable

a s s i s tan c e in t h i s study.

A f ina l note of apprec ia t ion i s given to Drs. D. Marx and P.

Johnson, s t a t i s t i c i a n s , fo r t h e i r invaluable help in the s t a t i s t i c a l

ana lys is o f the da ta .

This research i s supported in p a r t by funds from the Regional

Research Technical P ro jec t W-124.

TABLE OF CONTENTS

P a g e

LIST OF TABLES ..................... vi

LIST OF ILLUSTRATIONS . . . . ..................... v i i i

ABSTRACT . . . . . . . . . . .......................... . . . . . . . . . . . ix

INTRODUCTION . . , . .......................... . . . . . . . . . . 1

Object ives .................................................................. . . . . . . . . . . 15

MATERIALS......................... 17

METHODS .......................... 21

Description of Methods . . ............................................................................ 22

The Oxida t ions HgOg Plus Heat Method (Coded 1) . .. ................. 22

Step-wise Procedure .................. . . . . . . . . . . . . . 22

Laboratory Evaluation . . . , . . . . . ......................... . 2 3

The Oxidat ion, HNOg-HgOg Plus Heat Method (Coded 2 ) .................. 23

Step-wise Procedure ......................... 23

Laboratory Evaluation . . ' ..................... 24

The Oxidat ion, HNOg-HClO^ Plus Heat Method (Coded 3) . . . . 2 6

Step-wise Procedure . . . . . . . . . . . . . ................. 26

Laboratory Evaluation ......................... i . . . 27

The Parr Bomb Method (Coded 4) . . . . . . . . . . . . . . . 27

Step-wise Procedure . . . . . . . . . . . . . . . . . . 28

. Laboratory Evaluation . . . . , ............................ . . . . 2 9

The Dry Ashing (HNOg-HF) Method (Coded 5 ) ..................... .... 29

Step-wise Procedure .............................. 31

Laboratory Evaluation . . . . . ' .............................................32

i v

V

TABLE OF CONTENTS — Continued

P a g e

The NagCOg Fusion Method (Coded 6) . ......................... . . . . . . 32

Step-wise P r o c e d u r e ............................................................ 32

Laboratory Evaluation . . . .......................... . . . . . . . . 33

Atomic Absorption Spectroscopy to Determine Metalsin Waste Sample Solut ions .............................. '. . 34

DISCUSSION OF RESULTS ................... . . . . . . . . . 36

SUMMARY AND CONCLUSIONS..................... 53

RECOMMENDATIONS ..................... 55

APPENDIX 1 REPORT ON SODIUM, POTASSIUM, CALCIUM ANDMAGNESIUM OF AN ARIZONA FEEDLOT MANURE . . . . . . . . . . . . . . 56

APPENDIX 2 REPORT ON TRACE ELEMENT CONTENT OF AN ARIZONA FEEDLOT MANURE . . . . . . . . . . . . . . . . . . . . . . 63

LITERATURE CITED . . . . . . . . . . . . . . ............................................... 68

L IS T OF TABLES

T a b l e

1.

2 .

. 3.

4.

5.

6 .

7.

8 .

9.

10.11 .

12.

13.

14.

P a g e

Total and s a tu r a t io n e x t r a c t concentra t ions oft ra ce metals in s lu d g e - t r ea ted so i l ( surface to 25 cm) . . 5

Suggested metal content, of sludge appropria te fo rland a p p l i c a t i o n ............................... ... ............................................... . 6

Trace element concentra t ions of sewage sludges fromthe USA ......................... 8.

Range of some m icronutr ien ts commonly foundin manures ....................................... . 10

Representa t ive chemical composition of beef c a t t l efeed lo t manure from the a r id Southwest . . . . . . . . . . 11

Amounts of major p lan t n u t r i e n t s in sewagesludge dry so l id s . .............................. . . . . . . . . . . . 13

Suggested to le rance leve ls of metals and probable a v a i l a b le form in agronomic s o i l s ..................... 14

C h a r a c t e r i s t i c s of the waste samplesused in th i s study ..................... 19

Elemental composition of the s a tu r a t io n e x t r a c t so f the wastes used in t h i s study . ..................... 20

Weight l o s t a f t e r the HgOg t rea tment . . . . . . . . . . . 24

Weight l o s t a f t e r the HNO3-H2O? treatment . . ................... 24

Weight l o s t a f t e r the HNO3-HCIO4 treatment . . . . . . . . 3 0

Weight l o s t a f t e r the Dry Ashing (HNO3-HF) t rea tment . . . 30

The t o t a l content of Fe, Zn, Ni, Cu and Cr foundin the Tucson manure as revealed by s ix d i f f e r e n tprocedures. Mean values and the h a l f lengths ofthe 95% confidence in t e rv a l s (± tsx ) . . . . . ...................... . 3 7

VI

v i i

LIST OF TABLES - Continued

T a b l e P a g e

15. The t o t a l content o f Co, Cd, Mn and Pb found in Tucson manure as revealed by s ix d i f f e r e n t pro­cedures. Mean values and the h a l f lengths of the95% confidence in t e rv a l s ( ±tsx) . . . . . . . . . . . . . 38

16. The t o t a l content o f Fe, Zn, N i , Cu and Cr found in the Marana manure as revealed by s ix d i f f e r e n t procedures . Mean values and the h a l f lengths ofthe 95% confidence in t e rv a l s (±ts%) . . . . . . . . . . . 39

17. The t o t a l content of Co, Cd, Mn and Pb foundin the Marana manure as revealed by s ix d i f f e r e n t procedures. Mean values and theh a l f lengths of the 95% confidence in te rv a l s (*ts%) . . . 40

18. The to t a l content of Fe, Zn, Ni, Cu and Crfound in the Tucson sludge as revealed by

. s ix d i f f e r e n t procedures . Mean values and theh a l f lengths o f the 95% confidence in t e rv a l s (±ts%). . . . 41

19. .The t o t a l content of Co, Cd, Mn and Pb found inTucson sludge as revealed by s ix d i f f e r e n t pro­cedures. Mean values and the h a l f lengths o f the 95% confidence in t e rv a l s (±ts%) . . ..................... 42

20. The t o t a l content of Fe, Zn, Ni, Cu and Cr foundin the Phoenix sludge as revealed by s ix d i f f e r e n t procedures. Mean values and the h a l f lengths ofthe 95% confidence in te rv a l s (±ts%) . . . . . . . . . . . 43

21. The t o t a l content of Co, Cd, Mn and Pb found inthe Phoenix s ludge as revealed by s ix d i f f e r e n t procedures. Mean values and the h a l f lengths ofthe 95% confidence in te rv a l s (±ts%)................ ........ 44

22. Methods ranked according to the Student-Newman-Keul 's procedure ........................................... 46

23. Total content o f As, Hg, Be and V found in the Tucsonand Marana manures (MT), (MM) and the Tucson andPhoenix sludges (ST), (SP) . . . . . . . . . . ., . . . . 48

LIST OF ILLUSTRATIONS

Figure Page

1. Cycle of heavy metals in man's ecosystem . ■............................ 10

2. Adjusted r a t in g s of the s ix methods t e s t e d fo rmanure waste ana lys is . .................. 51

3. Adjusted r a t in g s of the s ix methods t e s t e d fo rsludge waste ana lys is . . . . . . . . . . . . 52

4. Water so lub le Na content of f eed lo t manure ex t rac ted fo r ten success ive times a t th ree manure/water r a t i o s (A, B and C). Reported as % of the t o t a l Na in themanure 59

5. Water so luble K conten t of f e e d lo t manure ex t r a c ted fo r ten successive times a t th ree manure/water r a t i o s(A, B and C). Reported as % o f the to t a l K in them a n u r e ......................... 60

6 . • Water so lub le Ca content of f e e d lo t manure ex t rac tedfo r ten successive times a t th ree manure/water r a t i o s(A, B and C). Reported as % o f the t o t a l Ca in themanure . . . . . . . . . .................................. 61

7. Water so lub le Mg content o f f e e d lo t manure e x t r ac ted fo r ten successive times a t th ree manure/water r a t i o s (A, B and C ) . Reported as % o f the to t a l Mg in them a n u r e ..................... ...................................................................................... 62

8 . Water so lub le Fe, Zn and Ni content in f eed lo t manureex t rac ted fo r ten successive times a t 1:2 manure/waterr a t i o . Reported as % o f the t o t a l Fe, Zn and Ni foundin the manure . . . . . . . . . . . . . . . . ...................... 66

9. Water so lub le Cu and Mn content in the f eed lo t manureex t rac ted fo r ten success ive times a t 1:2 water/manurer a t i o . Reported a s • % of the t o t a l Cu and. Mn found inthe manure . . . . . .................................. 67

vi i i

ABSTRACT

This study looks a t s ix d i f f e r e n t methods o f p repara t ions of

manure and sludge samples fo r to t a l metal an a ly s is . The methods are

compared in terms of: equipment and time requirements, r e p ro d u c ib i l i ty

and e f fe c t iv e n e s s in s o lu b i l i z in g metals from the waste res idues .

The methods chosen are: peroxide oxidation plus hea t , peroxide-

n i t r i c oxidation plus hea t , p e r c h l o r i c - n i t r i c oxidation plus hea t , Parr

bomb, dry ashing and sodium carbonate fus ion . Sample s iz e cons idera t ions

are a lso included within each of the s ix methods hereby s tud ied . The

waste sample s iz e var ies from .1 g to 2 .0 g. Atomic absorption sp ec t ro ­

photometry is used to q u a n t i t a t i v e l y measure the metals so lu b i l i z e d by

each o f the trea tments considered in t h i s study. The data obtained is

s t a t i s t i c a l l y analyzed and the r e s u l t s in d ica te t h a t the oxidizing

methods have a g re a te r dependency on sample s iz e f o r optimum performance

than the remaining th ree methods do. However, the ox id iz ing techniques

give lower values fo r the twelve metals of i n t e r e s t , namely: Fe, Zn,

Ni, Cu, Cr, Co, Cd, Mn, Pb, Hg. Be, Se, and V. The l im i t a t i o n s of each

method are c l e a r ly ou t l ined and s p e c i f i c recommendations on use and

improvement of the s ix methods conclude the study.

INTRODUCTION

The slow process of man towards food su f f ic ie n c y i s evidenced

by the ra p id ly increas ing world populat ion and the i n e v i t a b le unbalance

and exhaustion of the na tura l resources . This f a c t i s compelling man

to use and recycle the wastes he produces.

The use of farm manures as f e r t i l i z e r s can be t raced to ea r ly

times in the h i s to ry of Homo sap ie n s ; thus , i t i s common method of

recycl ing na tura l elements. Human and in d u s t r i a l wastes , r ecen t ly pro­

duced and accumulated in massive amounts in s ide and around c i t i e s , are

the modern forms of manures. These wastes have a double source of

o r ig i n , one a r t i f i c i a l ( indus t ry d isca rds ) and the o the r n a tu r a l , com­

parable to farm manures (human feces and food d i sc a rd s ) . The al ready

complex nature o f human wastes i s being f u r t h e r modified by the add i t ion

of many organic and inorganic sy n th e t ic products , leading to the develop­

ment of thousands o f s o -c a l le d "sludges".

In view of the shortage of f e r t i l i z e r s , r e c e n t ly brought about

by the misuse and abuse of petroleum-derived p roduc ts , and in view of

the f a c t t h a t accumulations of municipal sludges and manures in dumps,

water streams and l a n d f i l l s are producing major p o l lu t io n hazards, man

must and i s a l ready beginning to recycle such wastes f o r the sake of

his s u rv iv a l . The use of sludges as f e r t i l i z e r s fo r crop production i s

a very new p ra c t i c e which is rece iv ing considerable a t t e n t i o n by farmers

and so i l f e r t i l i t y exper ts in a l l f i e l d s but p a r t i c u l a r l y in tu r f - g r a s s

product ion.

1

2

Within the l a s t , two decades emphasis, has been given to the

trea tment o f c i t y wastes previous t o the app l ica t ion of them to f i e ld s

as f e r t i l i z e r s or t h e i r disposal in to water streams. This i s evidenced

by many s tud ie s published in such jo u rn a ls as Compost Science and Water

and Sewage Works. Also, animal manures are beginning to be used once

more as a supplement to the petroleum-derived commercial f e r t i l i z e r s .

I t may j u s t be a mat ter o f years before these low analyses manures wil l

play a more dec is ive p a r t in the f e r t i l i z e r usage of the world.

The addi t ion of manures and/or municipal sludges to f i e ld s to

be used fo r a g r i c u l tu r a l purposes requ i res a careful eva lua t ion of the

e f f e c t s to be f e l t in the so i l system. T r a d i t i o n a l ly , manures have been

added to s o i l s to rep le n i sh , mostly, the e a s i ly exhausted macronutrients

and/or improve the organic matter content . Such p r a c t i c e , once thought

of as wholly b e n e f i c i a l , or a t l e a s t harmless, i s now being s c ru t in ize d

fo r poss ib le i r r e v e r s i b l e po l lu t io n e f f e c t s harmful to both p lan ts and

animals. Large manure app l ica t ions to s o i l s can produce high concentra­

t io n s o f NO3-N a t subsoil lev e ls (McCalla, E l l i s and G i lber tson , 1972)

with a change in the redox p o t e n t i a l , which in turn a f f e c t s the e q u i l i ­

brium d i re c t io n s of many elements such as Mn (Meek e t a l . , 1974). in the

so i l system. So, the excessive ap p l ica t ion of manure can r e s u l t in the

contamination of underground water when used in excess of the crop needs

(Ayers, 1972) in the case of n i trogen requirements! Meek e t a ! . (1975)

rep o r t t h a t concentra t ion of la rge q u a n t i t i e s of manures in small areas

cannot only c rea te land p o l lu t io n , but a lso a i r p o l lu t io n . A study by

Azevedo e t a l . (1974) supports the previous s tatement by Meek and gives

' . 3

d e ta i l e d composition on such manure p a r t i c u l a t e s . An e a r ly study by the

author of t h i s t h e s i s and reported in Appendix 1 and Amoozegar* F u l le r

and Warrick (1975)s shows the ease of re le a se of Na, K, Ca and Mg from

Arizona f e e d lo t manure; experiment which demonstrates how f a s t s a l t pro­

blems can a r i s e in areas of high manure concentrat ion a f t e r repeated

i r r i g a t i o n . Studied recommendations fo r manure usage and disposal are

a must fo r the farmers (Meek e t a l . , 1975).

Extensive research in the areas of manure and i t s impact in the

environment as well as i t s physical and chemical c h a r a c t e r i s t i c s is

needed today fo r the syn thes is o f sound recommendations on i t s management.

In management of ever l a r g e r amounts of s ludges , man is faced

with problems.s imilar to those assoc ia ted with the use o f animal manure.

Accumulations of Targe q u a n t i t i e s of wastes around the c i t i e s a re well

known to produce i r r e v e r s i b l e environmental upsets (Wagner, 1971,

pp. 107-132) in terms of t h e i r d e s t ru c t iv e impact on the local biosphere.

This i s of ten accompanied by severe growth cur ta i lm ent of the fauna and

f lo r a o f the p a r t i c u l a r areas a f f l i c t e d ; as well as increas ing l i m i t a ­

t io n s on the use o f the resources av a i la b le in such reg ions . Misuse o f

these wastes fo r farming a lso can c rea te problems in the physical prop­

e r t i e s of s o i l s . Carnes and Lossin (1970) repo r t t h a t a 0 day composted

waste has an ac id ic pH e a s i l y changed a t low water concen tra t ions . The

pH value leve ls o f f a t 4 .8 a f t e r the water/compost r a t i o exceeds 1/200.

As the compost becomes old the reac t ion becomes bas ic . Carnes and

Lossin (1970) go on to say t h a t addi t ion o f sludge to s o i l s produces a

very poorly understood b u f fe r system s e n s i t i v e to concentra t ion changes.

During the p rocess ing .o f waste (often cal led, d iges t ion ) through sewage

trea tment p lan ts and composting p l a n t s , the raw form of the mixture of

m a te r ia ls i s changed in to more homogeneous, e a s i ly degraded m a te r ia l .

(Recently developed methods fo r p re treatment and use o f waste are ex ten­

s iv e ly covered by Yen (1974). This mater ia l i s then s u i t a b l e fo r use

as f e r t i l i z e r (Day, 1973). The pre treatment o f wastes increases the

a v a i l a b i l i t y and s o l u b i l i t y o f most t r a c e elements in the s o i l so lu t ion

as reported in Table 1. Page (1974) repo r ts the use of 0.5 N_ HOAc to

e x t r a c t " av a i lab le t r a c e elements to higher p lan ts" and presen ts data

which show a wide range of these e x t r a c ta b le elements with no apparent

c o r re l a t io n with the t o t a l concentra t ions of such elements in the

s ludges . The lack of data concerning the chemical forms of these e l e ­

ments in the sludges Page claims, prevents him from drawing any genera l ­

ized conclusions on the v a l i d i t y of such methods of e x t r a c t io n .

Table 2 r epo r ts the metal content of a sludge sa id to be appro­

p r i a t e fo r land a p p l i c a t io n s ; lev e ls which are e a s i ly surpassed by most

s ludges , (see Table 3 ) . In view of t h i s , harmful le v e l s o f many heavy

metals are normally found in s o i l s a f t e r some years o f sludge a p p l ica t io n s

according to Bradford e t a l . (1975). Micronutr ients such as Zn and Cu

promptly accumulate in s o i l s a f t e r one or two sludge t re a tm e n ts , some­

times to a level of t o x i c i t y fo r p lan ts as reported by King and Morris

(1972) and Page and Chang (1975). S a l t s are not r ep resen ted in high ■

enough leve ls in sludges to o f f s e t the soil , bu f fe r system.

Despite the high leve ls of metals t h a t the add i t ion of manures

and e s p e c ia l ly sludges introduce in to the so i l medium, only very small

percentages or f r a c t io n s of a percent o f these metals are a c tu a l ly

5

Table 1 . Tota l and s a tu r a t io n e x t r a c t concentra t ions of t r a ce metals in a s lu d g e - t rea ted s o i l , ( surface to 25 cm).'

ElementTotal Concentration nSludge-Treated Soil Control

. ----- — ppm

Cd 13 1.0

Co 65 - 18.0

Cu 44 14.3

Cr 64 13.0

Ni 114 19.0

Pb 125 10.0 or le ss

V 25 or less 25.0 or l e s s

Zn 117 50.0

Sa tu ra t ion Extract Concentration

Cd 1.2 0.002 or l e s s

Co 0.03 0.01 or l e s s

Cu 0.09 0.06

Cr 0.40 0.006

Ni 2.0 0.02

Pb 0.22 0.01 or l e s s

V. . 0.03 0.01

Zn 0.11 0.07

1 Bradford e t a l . (1975)? Samples co l le c te d from a sludge-drying pond.

6

Table 2. Suggested metal content of sludgt appropria te fo r land app l ica t ion

Element Content

ppm

Zn 2000 or less

Cu 800 or less

N1 TOO or less

Cd 1 or less

Pb 1000 or less

Hg 15 or less

1 Melsted (1973)

so lu b i l i z e d - See Table 1 and Appendix 2. Furthermore, the s o l id so i l

media, e s p e c ia l ly c la y s , a c t as a t t en u a to rs by adsorbing many of the

metals i n i t i a l l y put in to con tac t with them, as reported by Korte e t a l .

( in p ress , 1976). Leeper (1974) provides a good review of the physical

and chemical reac t ions o f heavy metals with the so i l medium, with

emphasis on r e v e r s i b i l i t y of some re a c t io n s , s o l u b i l i t y and uptake by

p lan ts o f heavy metals.

D if fe ren t types of manures as well as d i f f e r e n t types of sludges

contain a wide range of metals. In the case of manure, t h i s i s due to

the d i f f e r e n t animals t h a t produce i t , p r im ar i ly because o f t h e i r varying

d i e t s , the degree o f composting, and p u r i t y of the manures, Meek e t

a l . (1975). (Note: Most manure data a v a i la b le in the l i t e r a t u r e are

concerned with c a t t l e waste .) No two s ludges , moreover, appear to be

id e n t ic a l in chemical composition. This i s due to the multi complex

accumulation of t h i s waste. I n d u s t r ia l proximity to sewage p lan ts tends

to r a i s e the level of any one or more of p a r t i c u l a r metals above what

municipal waste normally con ta ins . Industry a lso can c re a te a higher

and f a s t e r degree of f lu c tu a t io n of such l e v e l s , causing an almost

unpredic tab le concentra t ion of elements l i k e Pb and Hg, as reported by

Page (1974).

Table 3 repo r ts an average t race-e lem ent con ten t o f sewage

sludges in the USA in 1974 (Page and Chang, 1975). A comparable t ab le

fo r a l l t r a ce elements in manure is not av a i la b le in the l i t e r a t u r e .

However, Brady (1974) r epo r ts ranges of s ix m icronu tr ien ts expected in

farm manures as d isplayed in Table 4. The amounts o f n u t r i e n t s l ik e

8

Table 3. Trace element concentra t ions of sewage sludges from the USA.^

Element Minimum Maximum Median•------------------------------pg /g—— ------------ — -

B 4 680 20

Cd 1 1,100 10

Cr 20 33,000 400

Cu 100 11,700 700

Ni 10 4,500 50

Mo 2 1,000 5

Hg 0.1 50 3

Pb 10 26,000 500

Zn 100 28,500 2,200

As 0.5 30 4

Se < 0.1 81 3

Page and Chang (1975)

9

N, P9 K9 Ca, Mg and Na contained in manures and s lu d g e s , which become

av a i lab le fo r p lan t use have not been underestimated in the l i t e r a t u r e .

Tables 5 and 6 r e p o r t some examples of these n u t r i e n t s and the amounts

found in f eed lo t manure and sewage sludge from the Southwest.

There is a myriad of values and numbers provided among th i s

recent la rge flow of repo r ts in the l i t e r a t u r e . Attempts are made by

the authors to describe one or more physical and chemical c h a r a c t e r i s t i c s

o f wastes . Despite t h i s , the data a re incomplete and f requen t ly leave

one with a f ee l in g fo r the need to s tandard ize methodologies.

Repeatedly t e s t e d methodology fo r p lan t and s o i l ana lys is can

be found in t e x t books, enabling labora to ry and f i e l d techn ic ians to

carry on t e s t s and s tud ie s which produce standard r e s u l t s , Walsh (1971).

As the waste products begin to play a c ruc ia l ro le in the hea l th and

welfare of t h i s c i v i l i z a t i o n , a more complete knowledge concerning the

nature of manure and sludge i s necessary to suggest p rac t ica l , management

of t h i s resource.

In s p i t e of the technological c a p a b i l i t i e s which allow man to

ro u t in e ly probe in to the deepest corners of the atom s t r u c t u r e , s c i e n t i s t s

have not d e l t e f f e c t i v e l y with the complexity of the wastes man produces.

This paradox may be explained by the f a c t t h a t most instruments cannot

d is t in g u ish indiv idual molecules from a crowd of s im i la r molecules very ,

wel l . Thus, the in v e s t ig a to r i s forced to i s o l a t e these molecules and/or

place them in to homogenous media. This allows the measuring instrument

to zero in on a p a r t i c u l a r molecule or concentration o f them while mini­

mizing in te r f e re n c e s from other molecules. To unlock the unique combina­

t ion of each waste produced, we are faced with t h e i r m ul t ip le nature

Table 4. Range of some micronutr ien ts commonly found in manures.

Micronutr ient ppm

Iron 38-446

Zinc 14- 87

Manganese 5- 86

Copper 5- 14

Molybdenum 1- 0.5

1 Brady (1974)

IN O U S T ( U A L P R O D U C T S

O U H N E Uru t i

FEnriLiZf: ns

P L S T I C I U I s

R O C K S -n I A H TM %

C R U S T

H U M A N tirul A N I M A L W A S T E S

- > L - A_ ' " 3 ” >r

■y

- i j o n - J - y - > ) P L A N T S )

>[w7TF;r|-

— >| m n o s ^ j — v

_J?)OMJ l" ."

D O M E S T I C R I A L S

Figure 1. Cycle of heavy metals in man's ecosystem.

11

Table 5. Representative chemical composition of beef c a t t l e f eed !o t manure from the a r id Southwest.!

Const i tuent Composition (oven-dry bas is )% . ppm

Organic m at ter 63.7

Soluble ions 10.0

Total n i t rogen 1.98

no3- n 3.5

nh4- n 1880

Ca 2.80

K 1.12

Mg 1.53

Na 2.84

P 0.27

Meek e t a l . (1975)

• 12

containing products of .everchanging chemical and physical p roper t ie s

and in terdependent combinations. A good example is found in the che­

l a t i n g and l igand binding p roper t ie s o f metals with organic and

inorganic molecules. Such reac t ions are very c lo se ly dependent upon

the medium and the concentra t ions o f the c o n s t i tu e n ts brought toge the r .

These che la t ing p roper t ie s are known to play a major ro le in the mobil­

i t y o f metal ions through the s o i l (Mortvedt, Giordano, and L in s a y . ,

1972); y e t , l i t t l e i s known about them.

In choosing the chemical p ro p e r t ie s th a t are most d es i r ab le in

manure and sludge wastes, the instrumental level o f accuracy and the

importance of the p ro p e r t ie s with re spec t to the management of the wastes

must be evaluated. Not many organic molecules found in wastes , with

the exception of p e s t i c id e s , are d i r e c t l y considered p o l lu ta n t s and/or

necessa ry 'a s p lan t n u t r i e n t s . Furthermore, t h e i r complex s t r u c tu r e and

progress ive d eg rad ab i l i ty (Rogers and Landreth, 1975) make them d i f f i c u l t

to i s o l a t e and c h a ra c te r iz e once they reach the waste streams a n d . s o i l .

On the o th e r hand, many inorganic molecules such as s a l t s and metals

( inc luding the ones found in the s t r u c tu r e s of many p e s t i c id e s ) have

indeed ser ious inf luence on the p o l lu t in g and n u t r i e n t p ro p e r t ie s of

wastes. The importance of common s a l t s and o ther macronutrients on the

po l lu t ion and/or f e r t i l i t y leve ls o f manure and sludges has already been

emphasized in the l i t e r a t u r e . P a r t i c u l a r a t t e n t io n i s now being given

to t r a c e elements, mostly the heavy metals which are being found in

in c reas ing ly l a r g e r concentra t ion in wastes. This f a c t i s pointed out

by Brady (1974, pp. 534-576) in Figure 1 which shows the bas ic cycle of

13

Table 6 . Amounts of major p lan t n u t r i e n t s in sewage sludge dry s o l i d s . ^

Nutr ien t Amount Present {%)Element Minimum Maximum Median

N 1 15 2

P 1 6 1.3

K 0.05 1 0.2

1 Page and Chang (1975)

Table 7. Suggested to le rance level of metals and probable ava i lab le form in agronomic s o i l s '

ElementProbableForm

Common Range in So i ls

ToleranceLevel

ppm PPm

Cadmium Cd++ ' 0.05-0.20 - 3

Cobalt Co++ 0.01-0.30 5

Copper Cu++ 3-40 150

Iron Fe++ 20-300 750

Manganese Mn++ 15-150 300

Mercury Hg++ 0 . 001- 0.01 0.04

Nickel Ni++ 0 . 1- 1.0 3

Lead Pb++ 0 .1 -5 .0 10

Zinc Zn++ 15-150 300

Arsenic AsO" 0 . 01- 1.0 ’ 2

Chromium CrO". 0 . 1- 0 .5 2

Selenium SeO" 0.05-2 .0 3

Vanadium V03 0 . 1- 1.0 2

1 Melsted (1973)

metals in our ecosystem with metal concentra t ions inc reas ing from l e f t

to r i g h t . Some of these elements a re c l a s s i f i e d as m ic ronu t r ien ts ,

o thers s t r i c t l y as p o l lu t a n t s , and s t i l l o thers as chance contaminants

on the bas is o f t h e i r concentrat ion and s o l u b i l i t y . Copper and In are

well known enzyme a c t iv a to r s in l iv in g organisms (Starkey, 1955). Yet,

high leve ls o f I n and Cu can i n h i b i t the uptake of o the r n u t r i e n t s by

p l a n t s , thus causing d e f i c i e n c ie s . Elements l i k e Kg and Pb are essen­

t i a l l y poisonous and l i f e in h ib i to r s above leve ls such as the ones

suggested in Table 7 by Melsted (1973).

There i s , indeed, a very d e l i c a t e balance between the concentra­

t ion leve ls of most metals and hea l th o f a l l l iv in g mat ter . Careful

monitoring of such elements, t h e i r forms and concentra t ions in a l l media

is consequently imperative fo r our fu tu re wel l -being and s u r v i v a l .

Object ives

Sui tab le methods fo r eva lua t ing t o t a l metal content in wastes

remain to be suggested in today 's l i t e r a t u r e . The broad ob jec t ive of

o f t h i s research was to evaluate the cu r ren t chemical methods of p repara­

t ion of samples containing organic and inorganic res idues fo r to t a l metal

ana lys is .

Six procedures o f sample p repara t ion of so i l and p lan t t i s s u e

(some modified) fo r t o t a l elemental ana lys is were used to evaluate the:

1. Effec t iveness fo r s o lu b i l i z in g and e x t r a c t in g metals from

waste re s idues .

2. Reproducib i l i ty of r e s u l t s .

16

3. Completion time.

4. Equipment requirements.

Two manures and two sludges were used in t h i s study. Atomic

absorption spectrophotometry was the primary method employed to d e tec t

the metals. Poss ib le in te r f e ren ces r e l a t e d to the atomic absorption

method are reviewed and incorporated in to the r e s u l t s o f t h i s study.

MATERIALS

Two manures and two sludges were used in t h i s s tudy. The f i r s t

manure (coded MT) came from the f eed lo t o f the Univers i ty of Arizona

Experimental Farm a t Tucson. I t was co l le c te d from a l o t with concrete

f lo o r ; thus , t h i s manure has l i t t l e so i l contamination (except air-blown

' p a r t i c l e s ) . . An a i r - d r i e d sample of severa l kilograms was f in e ly ground

to pass through a 20-mesh screen in a feed-type hammer m i l l . Afterwards,

samples from t h i s r e l a t i v e l y homogeneous stock were ground in a bal l mill

f o r 30 minutes , u n t i l a powder-like mater ia l was obtained. The f ina l

sample was s to red in an a i r - t i g h t con ta ine r throughout the experiment

to avoid moisture v a r i a t io n s . Some c h a r a c t e r i s t i c s o f t h i s manure are

l i s t e d in Table 8 .

The second manure (coded MM) was co l le c te d from a commercial

f e e d lo t a t Red Rock and s to red a t the Marana farm loca ted 25 miles nor th

of Tucson. This manure was co l le c ted from bare ground; consequently,

more so i l contamination was found in t h i s waste. Dif ferences between

the two manures may not only be l im i ted to contaminations, but a lso to

t h e i r natural composition s ince undoubtedly feed r a t io n s were not i d e n t i ­

ca l . The Marana manure (MM) was ground and t r e a t e d the same as the f i r s t

manure sample (MT). The f in a l product had a powder-like c o n s i s t e n c y . ,

The co lo r o f the former was brownish-gray and o f the l a t t e r , s o l id brown,

there being only a visual d i f fe ren ce .

One sludge sample (coded ST) which came from Tucson municipal

sewage system, had been processed in a so l id - s lu d g e processing p lan t

17

1 8

previous to being used as f e r t i l i z e r . I t was co l le c te d from the Randolph

Park Golf Field s tock p i l e s in Tucson, Arizona, as a g ranular s o l id and

a i r d r ied . The sample then was ground in a bal l mill fo r 30 minutes to

a gray powder and used as such in t h i s study. (Col lec t ion date June ,

1975.) See Tables 8 and 9 fo r c h a r a c t e r i s t i c s o f t h i s waste.

A second sludge sample (coded ST) was obtained from Phoenix

Municipal Sewage P lan t . I t had not been processed fo r f e r t i l i z e r use.

Sample homogeneity was obtained by gr inding several hundred grams

through a ba l l mill fo r 30-40 minutes and then mixing thoroughly. Again,

a gray, powder-like s o l id was the end product . Differences in composi­

t ion between these two sludges may be expected s ince they o r ig ina ted

in two d i f f e r e n t c i t i e s and appear to contain varying amounts of so i l

m a t e r i a l . (Col lec t ion da te , summer, 1974 . j See Tables 8 and 9 fo r

waste c h a r a c t e r i s t i c s .

' . 19Table 8 . C h a ra c te r i s t i c s of the waste sample's used in t h i s study.

WastesMT MM ST SP

pH* Sat. paste 6.90 8,85 6.23 6.54

pH* Sat . ext . 6.78 8.81 6.19 6 .44 '

Sat . Ext. ppm + 32,681 33,833 24,000 13,128

O.M. % 62.34 49.99 36.44 48.92

Si02 % 22.37 34.87 41.13 • 29.92

Other** % 15.29 15.14 22.43 21.16

OM + o the r % 77.63 65.13 58,87 70.08

Na % 1.2500 .4500 .3250 .4250

K % 1.5100 1.5200 .3250 .6453

Ca . % 1.9320 2.2350 2.0225 2.0975

Mg % .5870 .3025 .3625 .2725

* pH measured a f t e r two hours s a tu ra te d pas te was prepared

** May include s a l t s (Na, K, Ca and Mg), metals and ions o ther than S i02s and O.M. t h a t r e s i s t e d temperatures over 500°C.

t Total s a l t s

NOTE: All percentages are by a i r -d r y weight.

2 0

Table 9. Elemental composition of the s a tu r a t io n e x t r a c t s of thewastes used in t h i s study.

. ,

WastesElement MT MM ST SP

---------ppm —

Na 6,293 2,215 1,947 1,070

K 6,164 13,330 '421 : 350

Ca . 343 146 746 382

Mg 442 . 53 583 401

Fe 2.0 32.1 1.2 4.3

Zn .5 3.2 7.9 5.0

Ni 1.0 1.0 4.0. 34.5

Go .5 1.1 .9 .6

Cu .7 2.0 22.7 17.3

Cr . 1* . 1* 1.3 . 1*

Cd . 1* .3 .3 . .3

Pb • 5 .7 . 1* . 1*

Mn 1.0 1.4 1.2 . 1*

Means le s s than the number i t fo llows.

METHODS

The methods of analyses o f the metals in wastes , as evaluated

in t h i s s tudy, are chemical in nature and should not be regarded as

the only techniques a v a i lab le . The au thor o f t h i s r e p o r t i s aware t h a t

techniques such as photon a c t iv a t io n ana lys is (Chattopadhyay and J e r v i s ,

1974) may become s tandard methods fo r t race-e lement ana lys is in s o i l s

and wastes. But a t the p resen t time such techniques are e i t h e r in the

experimental s tage or f a r beyond the economic l im i t s o f a g rea t many

research centers and lab o ra to r i e s around the world and even in the

United S ta t e s . I t seems only log ica l t h a t we confront to d ay 's problems

with the p re sen t ly av a i lab le techniques , adapting and exhaust ing t h e i r

c a p a b i l i t i e s .

: The s ix methods described here have t h e i r o r ig in s in p lant

and so i l research programs. Some a lso have been used fo r analys is of

metals in waste waters (Traversy, 1971), but never have they been

applied to t o t a l analyses o f s o l id waste. They are:

1) Oxidat ion, HgOg plus heat

2) Oxidat ion, HNOg-HgOg plus heat

3) Oxidation, HClO^-HNOg plus heat

4) Parr Bomb

5) Dry ashing (HNO3-HF) .

6 ) NagCOg fusion

2 1

. Following these s ix t r e a tm e n ts , atomic absorption spectroscopy

was used to determine the concentra t ion of the metals in s o lu t io n .

Description of Methods

The Oxidat ion, HgOg Plus Heat Method (Coded 1)

The use o f HgOg (30%) as a method to s o lu b i l i z e elements found

in wastes seems reasonable , a t f i r s t hand, s ince being an oxidiz ing

agent , i t should destroy the organic m a t te r , r e lea s in g the metals. .

Hydrogen peroxide may a lso a c id i fy the medium enough to r e le a se some

of the metals adsorbed in the inorganic p a r t (mos t ly ,so i l mater ia l ) of

manure and sludge wastes. The use of HgOg to decolor ize s o i l e x t r ac t s

fo r co lo r im e t r ic s tud ie s has previously been reported by Hesse (1971).

To determine the sample s iz e e f f e c t s , th ree s ize s were se lec ted

(0.5 g, 1.0 g, and 2 .0 g ) .

Step-Wise Procedure.

1. Place samples in to 100 ml ( t a l l form) beakers. Add 2, 4 and

8 ml o f d i s t i l l e d water followed by 2, 4 and 8 ml of HgOg

(30%) r e sp e c t iv e ly , to each sample s ize .

2. Cautiously heat the samples, avoiding excessive foaming (not

. higher than 80°C).

3. The HgOg s tep should be repeated a t l e a s t t h re e times over

a 4- or more-hour per iod, or u n t i l samples have stopped foam­

ing and/or no more deco lo r iza t ion is tak ing p lace.

4. Bring samples to near d ryness , c o o l , and f i l t e r (#42 paper)

in to a 100 ml or less volumetric b o t t l e with 0.2 N_ HNOg.

2 3

T h e s o l u t i o n s may b e s t o r e d i n p o l y e t h y l e n e b o t t l e s . P e r c e n t a g e

w e i g h t l o s t w as d e t e r m i n e d f r o m t h e s o l i d s l e f t . T h r e e s a m p l e s o f e a c h

w a s t e w e r e a n a l y z e d s i m i l a r l y b y t h i s p r o c e d u r e .

Laboratory Eva lua t ion . This procedure has no specia l problems

and no specia l equipment requirements. The completion time is within

a working day, by carefu l supervis ion of the samples a f t e r each increment

o f H2O2 is added. Table 10 repor ts the percentage weight loss fo r each

sample a f t e r the t rea tment . These values in d ic a te t h a t the HgOg oxida­

t ion i s le ss e f f e c t i v e as the s iz e o f the sludge samples increases . The

opposite i s t ru e fo r the manure samples. Comparing the values of Table

11 with the ones l i s t e d in Table 8 (O.M. plus o th e r ) , i t appears t h a t

t h i s t rea tment d issolved approximately 60% of the organic matter and

s a l t s in the waste samples. Hard- to -ox id ize , undigested p la n t f ib e rs

and w ate r - in so lub le so i l p a r t i c l e s were l e f t undissolved.

The Oxidation, HN03-H202 Plus Heat Method (Coded 2)

This procedure i s referenced in most s o i l and p la n t ana lys is

books and seems to be a log ica l sequence in increas ing the s ev e r i ty of

oxidation on the waste samples fo r metal ana lys is . N i t r i c a c i d . i s a

s trong oxidiz ing agent as well as a s trong ac id , thus i t complements

the HgOg oxidat ion and metal s o lu b i l i z a t i o n . To t e s t r e p ro d u c ib i l i t y

and sample s iz e v a r i a t i o n s , again th ree sample s izes were se le c ted ;

namely, 0.5 g, 1.0 g and 2.0 g.

Step-Wise Procedure.

1. Place samples in to 100 ml ( t a l l form) beakers. Add 10, 20

and 30 ml of reagent grade concentrated HNO3 to each sample

2 4

Table 10. Weight l o s t a f t e r the HgOg treatment^

Sample Sample Sizes (%)I d e n t i t y 0.5 g 1.0 g 2.0 g

MT 51.73 54.99 55.72

MM 44.11 43.77 46,84

ST 29.87 28.44 27.20

SP 38.35 37.05 39.99

^Averaged values of the t r i p l i c a t e analyses .

Table ' l l . . ' - Weight l o s t a f t e r the HNOg-HgOg treatment^

Sample Sample Sizes (%)Id e n t i ty 0.5 g 1.0 g 2.0 g

MT 71.44 68.58 70.60

MM 62.57 61.40 60.25

ST 53.89 52.45 47.92

SP 67.16 68.07 62.94

IAveraged values o f the t r i p l i c a t e analyses .

2 5

s i z e , r e sp e c t iv e ly . Cover the beakers with watchglasses

and re f lu x on a hot p la te ( a t 83°C) overnight .

2. Cool samples and add 2 , 4, and 8 ml o f HgSO^free HgOg to

the samples. Repeat the HgOg addi t ion up to th ree times.

Allow to d ig e s t almost to dryness a t 80°C over a hot p l a t e

fo r a period of th ree or more hours.

3. Upon cool ing , wash the beaker contents through a #42 f i l t e r

paper in to a 100 ml or l e s s volumetric f l a s k . Again, the

so lu t ions obtained in t h i s second procedure are s tored in

polyethylene b o t t l e s . The so l id s ind ica ted the percentage

s o lu b i l i z a t i o n of the waste samples. T r i p l i c a t e analyses

were made on each materia l and a t each sample s iz e .

Laboratory Eva lua t ion . This method, l i k e the previous one, uses

s tandard labora tory equipment. The completion time i s well within 24

hours. Careful a t t e n t io n is required only during the add i t ion of H2O2

to avoid foaming when there is f i r s t con tac t with organic matter. I t

i s d i f f i c u l t to determine the poin t where the HgOg has no f u r th e r ox i ­

d iz ing in f luence on the organic matter . Thus, the amounts of H2O2 added

may vary from sample to sample. I t i s recommended t h a t no more ox id iz ing

agent be added when foaming and co lor change s tops . Table 11 reports

the percentage weight losses fo r each sample and sample s i z e . The data

seem to in d ica te t h a t the method loses e f f i c i e n c y with increas ing sample

s iz e . The values a l so in d ica te t h a t most o f the organic matter was des­

troyed and/or s o lu b i l i z e d , s ince a l l o f these values exceed the O.RL %

reported in Table 8 .

2 6

The Oxidat ion, HNO3-HCIO4 Plus Heat Method (Coded 3)

This method i s s tandard pre trea tment procedure fo r t o t a l elemental

ana lys is of p lan t t i s s u e (Jackson, 1958; and Chapman and P r a t t , 1961).

However, i t was developed as ea r ly as 1935 by Gieseking, Snider , and

Cetz (1935). B as ica l ly , the success o f t h i s method r e l i e s on the s trong

oxidiz ing p ro p e r t ie s o f HCIO^, which is reported to des troy most organic

matter a t temperatures above 60°C (Cotton and Wilkinson, 1972). HNOg

helps to preoxidize the organic matter before p u t t in g i t in contact with

the HCIO^, thus minimizing the r i s k o f explosion. Gal laher , .Weldon, and

Tutral (1975) have developed a system of mul t ip le sample ana lys is by

using aluminum blocks temperature co n t ro l l ed up to 375°C to speed up

t h i s ox ida t ion . Waste sample s ize s o f 0.5 g, 1.0 g and 2.0 g were

se le c ted to study the sample s ize e f f e c t s .

Step-Wise Procedure.

1 . Place waste samples in to 100 ml ( t a l l form) beakers. Add

5 , 10 and 20 ml o f ' r e a g e n t grade HNOg in to each beaker with

0 . 5 , 1 . 0 and 2 . 0 g-sample s i z e s , r e sp e c t iv e ly . Allow to

stand overnight .

2 . Place beakers under specia l H C I O ^ hood. Add equal amounts

o f , f i r s t , d i s t i l l e d H g O , then reagent grade H C I O ^ to the

HNOg. (The addi t ion o f H g O f i r s t makes the H C I O 4 addi t ion

s tep s a f e r and allows the HN O g to continue oxid iz ing the

organic m a t te r . ) Place p la in watch g lasses over beakers

and allow to re f lu x over a hot p la te a t 90°C fo r 3-4 hours.

(Boi l ing chips or Pyrex g lass beads are needed to prevent

bumping.)

2 7

3. Uncover beakers to allow the H2O and HNO3 t o d i s t i l l away.

Raise temperature to 140°C to evaporate the HCIO^ (white

fumes appear to near dryness. Cool and f i l t e r in to volu­

metr ic f la sk s with #42 Whatman paper and 2 N_ HNO3 .

These so lu t io n s may be s to red in polyethylene b o t t l e s . T r i p l i ­

ca te analyses o f a l l samples and sample s ize s were made.

Laboratory Eva lua t ion . Safe manipulation o f HCIO^ in labora­

t o r i e s requ ires the use o f a s p e c i a l ly equipped hood with water streams

cons tan t ly washing down the surfaces to avoid acid accumulation. Unlike

the previous two less-demanding methods, the opera tor must follow r i g o r ­

ously a l l the s t e p s , e s p e c ia l ly during the HCIO4 ad d i t io n s . Fai lure to

do so m ay .resu l t in an explosive reac t ion which can produce serious

i n j u r i e s . This f a c to r of ten makes t h i s method undes irab le fo r ana lys is

o f metals in wastes i f o th e r , s a f e r methods y ie ld s im i l a r r e s u l t s . The

completion time is within 24 hours. Table 12 repo r ts the sample weight

losses a f t e r t h i s t rea tment . They in d ica te t h a t almost a l l organic m at te r

and so l id s were destroyed o r , o ther than SiOg, s o lu b i l i z e d . The sample

s iz e made no d i f fe ren ce in the weight losses of the manure and sludge

samples. Comparison of Table 11 with Table 12 in d ica te s t h a t the HCIO^

trea tment i s more complete than the HgOg methods.

The Parr Bomb Method (Coded 4)

This method of sample p repara t ion fo r t o t a l elemental ana lys is

o f so i l samples i s repor ted by Bernas (1968). I t combines the use of

s trong acids ( aqua r e g ia and HF) with a heat- induced high pressure

con ta iner to destroy both organic and inorganic mat ter . The HF

2 8

s o lu b i l i z e s the s i l i c a , allowing the complete breakdown of the inorganic

so i l m a te r ia ls . The Bernas procedure was modified to t r y to decompose

waste samples by p red iges t ing the samples with HNO3 and HgOg to destroy

the bulk of the organic mat ter . In t h i s t e s t we were l im i ted by the

sample s iz e to 0.1 g, so sample s ize e f f e c t s were not s tud ied .

Step-Wise Procedure.

1. Weigh 0.1 g of waste sample in to a Teflon cup (Parr Bomb

sample c o n ta in e r ) . Wet with 2 ml of reagent grade HNO3

and allow to oxidize overnight .

2. Digest to near dryness with gen t le hea t ing , increas ing i t

to 80°C over a hot p l a t e .

3. Allow to cool down before c a r e fu l ly adding 2-4 ml of HgOg

(30%). Avoid any splashing or foaming over the top. Apply

gen t le heat and slowly d ig e s t to near dryness. This s tep

should be repeated severa l t imes. .

4. Cool and add 2 ml of aqua reg ia and 6 ml o f HF. Place cover

on Teflon cup and s l i d e the conta iner in to a Parr Bomb.

Place the Parr Bomb in s ide an oven a t 110oC fo r about 1

hour. Allow to cool before opening. The so lu t io n should

be c l e a r and p a r t i c l e f r e e .

5. Add about 2 g of B(0H)3 (reagent grade) to n e u t r a l i z e the

excess HF before t r a n s f e r r i n g the so lu t ion in to a volumetric

(25 ml) f l a s k .

' ■ ' 2 9

NOTE: B(OH)g reac t s with HF to form BF3 , thus preventing

the HF from d isso lv ing the g lass con ta ine rs . I t a lso

minimizes the HF atomic absorption in te r f e r e n c e s .

Laboratory Eva lua t ion . This procedure ex h ib i t s an inherent

problem of sample s iz e . Samples as small as 0.1 g can hardly be con­

s idered r e p re s en ta t iv e of the wastes, even a f t e r the p re treatment de­

scribed in the m a te r ia ls sec t io n . The author of t h i s t h e s i s i s not

aware o f o ther l a r g e r Parr Bombs t h a t allow d iges t ion of bigger samples.

Even a f t e r repeated HgOg d ig e s t io n , the sludge samples f a i l e d to f u l l y

d isso lve . (Note: HCIO4 oxidation was considered but f a c to rs such as

sample s i z e , o p e ra to r ' s s a f e ty , and poss ib le sample losses due to

sp lash ing , discouraged the author from f u r t h e r modifying t h i s method.

The completion time takes over 20 working hours, r eq u i r in g f u l l o p e r a to r ' s

a t t e n t io n along most s tep s . Overa l l , t h i s method can be considered long

and ted io u s , of ten ending with unreproducible r e s u l t s . )

The Dry Ashing (NHO3-HF) Method (Coded 5)

The ashing of p lan t mater ia l to determine t o t a l ash has been

reported by Jackson (1958). But he suggested v o l a t i l i z a t i o n losses of

some elements including Si . Fugiwara and Nagasaki (1968) make use of

an oxygen bomb to ash p lan t materia l without v o l a t i z a t io n losses and/or

reagent contamination to determine t r a c e elements in organic t i s s u e s .

Korenman (1968) gives s p e c i f i c values fo r minimizing metal losses by

ashing a t temperatures o f 400-6Q0°C. However, Korenman makes c le a r

t h a t v o l a t i l i z a t i o n losses a lso depend on the vapor p ressure o f the

Table 12, Weight l o s t a f t e r the HNOg-HClC^ treatment^

Sample Sample LossI d e n t i t y (All s iz e s )

MT

%

75.32

MM 64.93

ST 55.32

SP 69.41

]Averaged values o f the t r i p l i c a t e analyses

Table 13. Weight l o s t a f t e r the dry ashing (HNO3-HF) t r e a tm e n t1

Sample Sample. LossI d e n t i t y ( 1.0 g s ize )

MT

%

93.25

MM 93.51

ST 96.13

SP .96,50

I. Averaged values of the t r i p l i c a t e analyses

31metal forms and the reagents added p r io r to ashing. F u l le r e t a l .

(1966) used t h i s procedure su ccess fu l ly fo r P, Co, and Sr when they found

t h a t HCIO4 forms inso lub le p r e c i p i t a t e s with Ca and Sr . Addition of

s trong acids seems to minimize Pb lo s se s . The dual na ture of wastes

such as manures and sludges seems t o ru le out a simple ashing technique

fo r t o t a l t r a c e element ana lys is . The fo llowing procedure i s a modified

dry ashing technique, using a p re -ox ida t ion trea tment with HNO3 and

p a r t i a l Si v o l a t i l i z a t i o n with HF. To check sample s iz e e f f e c t s two

s ize s o f 0.5 and 1.0 g were used.

Step-Wise Procedure.

1. Weigh samples in to platinum c ru c ib le s . Add 5 and 10 ml of

reagent grade HNO3 to each sample s i z e , r e sp e c t iv e ly . Allow

to d ig e s t Overnight.

2. Slowly dr ive o f f HNO3 over a hot p l a t e a t 80°C. Increase

hot p l a t e temperature to maximum and dr ive o f f as much HNOg

as poss ib le p r io r to ashing in furnace.

3. Place c ruc ib les in s ide furnace and r a i s e temperature slowly

to 450°C, allowing 1 hour fo r ashing.

4. Cool to room temperature and wet the c r u s t with d i s t i l l e d

water. Add 5-ml amounts o f HF, up to 30 ml per sample to

slowly dr ive o f f the SiFg a t 70°C. Bring to dryness and

c o o l . Redissolve the l e f t - o v e r so l id s with 2 N_ HNO3 p r io r

to f i l t e r i n g them in to 50 ml volumetric f la sk s (#42 Whatman

o r f i n e r f i l t e r p a p e r ) .

Solut ions may be s to red in polyethylene b o t t l e s . T r ip l i c a t e s were

run.

, 32

Laboratory Eva lua t ion . The percentage weight-1oss values reported

in Table 13 in d ica te that , the major p a r t o f the waste samples was so lu ­

b i l i z e d or driven o f f With HF. More than h a l f o f the t o t a l SiOg.in the

samples was v o l a t i l i z e d . Complete loss of the Si would have required

the add i t ion of twice as much HF, increas ing the chance of sample con­

tamination. The time required fo r t h i s t reatment was no more than 24

hours with specia l care required during the HF a d d i t i o n . The use of a

furnace and platinum cruc ib les i s necessary.

The Nag-COg Fusion Method (Coded 6)

Sodium carbonate fusion was f i r s t used by Washington (1930) fo r

rock ana lys is and soon adapted fo r s o i l s . Jackson (1958) describes the

NagCOg fusion fo r so i l an a ly s is . According to Black e t al. (T965), t h i s

method should only be used to determine S i , Al, Fe, T i , Ca, Mg, and Mn

in s o i l s . V o la t i l i z a t i o n losses of most o ther elements found in s o i l s

are unavai lab le s ince the method requ ires sample temperatures up to 1000°C.

However, a review by ToTg (1972) on t r a c e analys is r epo r ts only s i g n i f i ­

cant losses fo r the o the r metals in inorganic m a te r ia l s . Since s ludges ,

o f a l l wastes, contain large amounts of metals , Na^COg fusion could

possib ly produce acceptable values when compared to ac tual to t a l values .

The method used here was ca r r ied out according to Black e t a l . (1965).

Again, sample s ize variance was s tudied by using th ree s iz e s of 0 .5 , 1.0

and 2.0 g.

Step-Wise Procedure.,

1. Place samples in to platinum c ru c ib le s . I g n i t e samples under

a hood with gas burners u n t i l smoking stops (450°C).

33

2. Place c ruc ib les ins ide a furnace and slowly r a i s e the tem­

pera tu re to 900°C fo r no more than 10 minutes. (Burner can

a lso be used.)

3. Add about 4 g o f NagCOg (anhydrous) per gram of sample and

mix thoroughly. Place the c ruc ib les again in s id e a furnace

and r a i s e the temperature to 1000°C for about 30 minutes,

or u n t i l fusion i s completed. Remove the c ruc ib les from

. fu rn ace and cool down ( i f cake c racks , remelt aga in) .

4. Dissolve cake with small por t ions of 6 1 HC1 (avoid excessive

e f fe rvescence) . Place so lu t ions in to 100 ml beakers.

5. Take so lu t ions to dryness over a hot p la te ( a t t h i s point

SiOg c r y s t a l s are v i s i b l e ) . Add 2 ii HNOg to so l id s and

f i l t r a t e in to 50 or 100 ml volumetric b o t t l e s with #42

Whatman f i l t e r paper.

6 . Solut ions may be s to red in to polyethylene b o t t l e s . T r i p l i ­

cate analyses of a l l samples should be made.

Laboratory Eva lua t ion . The res idues from fusion were used to

determine the SiOg percentage in the waste samples and are reported in

Table 8 . This method can be ca r r ied out within 24 hours with no specia l

problems. Most s teps requ ire carefu l a t t e n t i o n , e s p e c i a l l y the HC1

addi t ion during which excessive e f fervescence wil l r e s u l t in s i g n i f i c a n t

sample lo sses . The equipment requirements are s tandard , being: An

e l e c t r i c furnace and/or Meker burner and platinum c ru c ib le s .

3 4

Atomic Absorption Spectroscopy to Determine Metals in Waste Sample Solut ions

Analysis o f mult i-e lement so lu t ions is s t i l l a major problem

with which an a ly t ic a l chemists are s t ru g g l in g today. The f i r s t methods

of de tec t ion of elements in s o i l s and p lan t sample so lu t io n s included

separa t ion of the element via techniques such as p r e c i p i t a t i o n and

chromatography followed by colorometr ic techniques fo r q u a n t i t a t i v e

determination of the element(s) i s o l a t e d . Redox methods such as pola-

rography a lso have been popular but are very s e l e c t iv e . The development

and expansion of atomic absorption and flame emission permits the mea­

surement of over 60 elements (Walsh, 1971, p. 12) without th e use of

separa t ion techniques. Special a t t e n t io n has been given to the use of

atomic absorption spectroscopy fo r ana lys is of metals. Traversy (1971)

gives a complete d esc r ip t ion of metal ana lys is in waste waters using

atomic absorption spectroscopy. He suggests the a c i d i f i c a t i o n of the

sample so lu t ions with HNO3 , p r io r to the .a tomic absorption ana lys is of

any metals. This ac id addi t ion wil l prevent p r e c i p i t a t i o n of s a l t s and

o the r ions over long s torage periods while minimizing metal adsorption

by the p l a s t i c or g lass con ta iners . However, excess ac id addi t ion can

cause matrix in t e r f e r e n c e s . Thus, the use of o ther types of flames

besides a i r - a c e ty le n e may be necessary as suggested by Barnet t (1972).

All sample so lu t ions from t h i s study contained no more than 0.5% HNOg

which, according to Barnet t (1972), should produce n e g l ig ib le matrix

i n t e r f e r e n c e s .

35

Chemical in t e r f e re n c es seem to be very small when determining

metal content in so i l and p lan t e x t r a c t s (Walsh, 1971). Alkal ine ea r th

determination by atomic absorption on such samples i s severe ly hindered.

The use o f re lea s in g agents such as LaClg or higher flame temperatures

(Fassel and Becker, 1969) i s required . Chemical in t e r f e r e n c e s during

metal, determination in waste sample so lu t ions can be ru led out with the

poss ib le exception o f Fe determination.

Most bulk in te r f e ren ces are not a ssoc ia ted with metals s ince no

metal i s presen t in excess of 1%, except A1 and Fe. However, no s i g n i f i ­

cant bulk problems have been reported in the l i t e r a t u r e by these twoI

metals,. Bulk in te r f e re n c es due to excess Na in samples prepared by the

NagCOg fusion method wil l be discussed in another s ec t io n .

All s tandards were prepared according to Brezenski (1971). The

instrument used was a J a r r e l l Ash Atomic Absorption u n i t using an a i r -

acety lene flame.

DISCUSSION OF RESULTS

Several assumptions were necessary f o r the s t a t i s t i c a l an a ly s is :

o f the d a ta . F i r s t* i t was assumed t h a t no s i g n i f i c a n t reagen t contami­

na t ions took place during the t rea tm en ts . Seconds no s i g n i f i c a n t metal

amounts were r e leased and /or adsorbed by the f i l t e r papers , beakers ,

c ru c ib le s and polyethylene b o t t l e s . Such losses and /or contaminations

are indeed a p o s s i b i l i t y t h a t can become s i g n i f i c a n t even a t the micro

leve l and are thoroughly discussed by Korenman (1968). And* t h i r d , no

major chemical , bu lk , or matrix in t e r f e r e n c e s occurred during the metal

analyses using atomic absorpt ion spectroscopy.

Tables 14-21 show the percentage by weight o f metal contained in

the four waste samples obtained by the s i x methods a t the 95% confidence

leve l (Lentner , 1972). S ince , in accordance with the previous assumptions,

the method rep o r t in g the h ighes t values should be the most e f f e c t i v e ,

Tables 14-21 r e p o r t t h a t method 1 (HgOg + heat) and method 2 (HNO3 +

HgOg + heat) gave overa l l the lowest va lues . B e t te r performance among

the o th e r methods i s obvious, thus req u i r in g a c lo se r Took before f u r t h e r

conclusions can be drawn.

In the second p a r t o f the s t a t i s t i c a l eva lua t ion an ana lys is o f

var iance was made. The procedure used was the Student-Newman-Keul' s

(SNK) t e s t (KendalT and S t u a r t , 1968). This i s a m u l t ip le range t e s t

which assumes a normal data d i s t r i b u t i o n and c l a s s i f i e s each method in

o rder o f inc reas ing mean and homogeneous su b se t s . These homogeneous

* :

T a b l e 1 4 . The. t o t a l c o n t e n t o f F e , Z n , N i , Cu a n d C r f o u n d i n t h e T u c s o n m a n u r e a sr e v e a l e d b y s i x d i f f e r e n t p r o c e d u r e s . Mean v a l u e s a n d t h e h a l f l e n g t h s o ft h e 95% c o n f i d e n c e i n t e r v a l s ( ± t s % ) .

Methods* SS** Fe Zn ' Ni Cu Cr

.5 .0440 +.0202

____________ _____

.00 55 +.002 9 0 0 01 1 .0 .0140 +.0178 .0037 ± .0158 0 0 0

2 . 0 .0231 +.0025 .0007 ± .0 02 9 0 0 0

.5 .4600 +.0860 .0106 ± .0044 .0061 ±.0014 0 . 02 1 .0 .4900 +.1940 .0058 ± .0104 .0070 +.005 7 .0018 ±.0019 .0142 ±.0133

2 . 0 .6700 +.2521 .0098 +.0055 .0092 ± .0056 • .0027 ±.0037 .0171 ±.0052

.5 .6800 +.0658 .0123 +.0015 . 0092 ±.0084 .0035 ±.0054 .0157 ±.00913 1 .0 .3733 +.0287 • .0 113 ± .0014 .0123 ±.0029 .0029 ±.0017 .0165 ±.0023

2 . 0 .5600 +.2744 ' .0111 ± .0002 .0126 ±.0027 .0033 ±.0012 .0167 ±.0044

4 .1 1 .0530 + i 1494 . .0079 ±.0041 . .0165 ±.0020 .0027 ±.0116 .0190 ±.0025

• .5 .8541 +.0474 .0095 ± .0012 .0155 ± .0048 . .0037 ±.0017 .0311 ±.01195. 1.0 .8208 +.0646 .0084 ±.0001 ' .0135 ±.0009 .0034 ±.0002 .0338 ±.0035

.5 .9455 +.0707 .0143 + .0038 . .0190 ±.0002 .0037 ±.0008 .0281 ±.00756 1.0 1.2603 +.7518 .0140 ± .0043 .0257 ±.0112 .0068 ±.0080 . .0323 ±.0246

2 . 0 . .8755 +.0431 .0100 ± .0000 . .0187 ±.0029 . 0025 ±.0004 .0260 ±.0159

*1. Oxidation HgOg + heat 4. Parr Bomb

2. Oxidation H2°2 ' HNOg + heat 5. Dry Ashing (HN0--HF)

3. Oxidation hcio4 - HNQg + heat 6. NapCOg Fusion**

Sample s i z e in grams . -

O J

3 8

T a b l e 1 5 . T h e t o t a l c o n t e n t o f C o , C d , Mn a n d Pb f o u n d i n t h e T u c s o nm a n u r e a s r e v e a l e d b y s i x d i f f e r e n t p r o c e d u r e s . Mean v a l u e sa n d t h e h a l f l e n g t h s o f t h e 95% c o n f i d e n c e i n t e r v a l s ( ± t s % )

Methods* ss** Co Cd Mn Pb____ _________ - - % -

.5 0 0 .0133 ± .0 0 0 8 O'

T 1 .0 0 0 0 0

2 . 0 0 0 0 0

.5 .0042 + .00 22 0 .0166 ± . 0 0 5 6 02 1 . 0 .0019 ± .0001 0 .0159 ± . 0 0 5 3 0

2 . 0 .0013 - .0001 0 .0219 ± . 0 2 2 9 0

.5 .0023 ± .0 0 1 0 . 0 • .0216 ± .0 0 3 5 03 1 .0 .0013 ± . 0000 0 .0313 ± . 0 3 3 7 .0

2 . 0 .0016 ± .0 007 0 .0275 ± .0 2 2 2 .0029 ±.0001

4 .1 .0083 + .0026 0 .0276 + .0032 .0187 ± .0361

.5 .0027 ± .0 0 0 4 ' 0 .0332 ± .0075 .0029 ± .00 14

5 1. 0 .0023 ± .0005 .0009 ± .0002 .0328 ± .0 1 0 0 .0040 ± .0 019

.5 .0031 ± .0 010 0 .0289 ± .00 85 .0094 ± .00 78

6 1. 0 .0034 ± .0004 . 0 .0286 ± .0 07 3 .'0064 ± .00172 . 0 .0034 ± .0003 0 .0431 ± .01 44 .0078 ± .0013

* I . Oxidation HgOg + heat 4 . Parr Bomb

2. Oxidation HgOg-HNOg + heat 5. Dry Ashing (NHOg-HF.)

3, Oxidat ion HCIO -HNO + heat 6 . NagCOg Fusion

Sample s i z e in grams.

T a b l e 1 6 . T h e t o t a l c o n t e n t o f F e , Z n , N i , Cu a n d C r f o u n d i n t h e M a r a n a m a n u r e a s r e v e a l e db y s i x d i f f e r e n t p r o c e d u r e s . Mean v a l u e s a n d t h e h a l f l e n g t h s o f t h e 95% c o n f i ­d e n c e i n t e r v a l s ( ± t s % )

Methods* SS** • Fe -Zn Ni . Cu Cr__ _ %________

. .5 .0147 ± .0 160 .0062 ± .00 60 0 0 01 • 1 .0 . 0 0 6 5 ± . 0 0 0 4 .0009 ± .0 0 3 7 0 0 • 0

2 . 0 ' .0097 ± .00 37 0 0 0, 0

.5 .5154 + .2475 .0108 ± .0 0 3 6 0 0 02 1.0 .5952 ± .1 8 7 7 .0 0 8 8 + . 0 0 4 3 • .0013 + .0000 .0015 + .0043 0

2 . 0 . .5373 ± .0993 .0089 ± .0 0 1 9 .0019 ± .0009 .0022 ± .0017 .0 0 4 8 + .0006

' .5 .5947 ± .00317 .0124 + .0013 .0018 + .0013 . 0 0 3 6 + . 0 0 4 7 03 1 .0 ' .3610 ± .0485 .0107 ± .0014 .0026 ± .0013 .0023 ± .0049 - .0052 ± .0008

. 2 . 0 .6033 ± .2113 .0104 ± .0016 . 0 0 3 0 ± .0004 .0026 ± .0006 . 0 0 4 9 ± .0012

4 .1 .9865 ± . 1 0 0 8 .0335 ± .0237 .0101 ± .0025 .0090 ± .0000 . 0 0 9 0 ± .0025

.5 .7500 + .0822 .0105 ± .0 0 6 9 . 0 0 4 8 ± .0018 .0022 ± .0006 .0055 ± .00065 • i . o .7292 ± . 0 4 7 4 .0112 ± .0116 .0040 ± .0007 . 0 0 2 8 ± .0005 . 0 0 5 9 ± .0025

.5 . 8 5 6 5 ± .1532 . 0 1 4 8 ± .0051 .0081 ± . 0 0 3 6 .0056 ± .0046 .0121 ± .00366 1. 0 1.6333 ± .4481 .0143 ± .0 0 6 3 .0088 ± .0052 . 0 0 6 7 ± .0051 . 0 1 4 5 ± .0013

*2 .0 .8755 ± .0638 .0110 ± . 0 0 0 0 .0062 ± .0090 . 0 0 6 4 ± .0021 . 0 1 3 6 ± .0039

1. Oxidation HgOg + heat 4 . Parr Bomb

2. Oxidation HgOg-HNOg + heat 5„ Dry Ashing (HNO - HF)

3 . Oxidation HCIO -HNO + heat 6. NagCOg Fusion

Sample s i z e in grams.

CO<sO

4 0

T a b l e 1 7 . T h e t o t a l c o n t e n t o f C o , C d , Mn a n d Pb f o u n d in' t h e M a r a n am a n u r e a s r e v e a l e d b y s i x d i f f e r e n t p r o c e d u r e s . Mean v a l u e sa n d t h e h a l f l e n g t h s o f t h e 95% c o n f i d e n c e i n t e r v a l s ( ±t s x )

Methods* SS** Co Cd Mni

Pb___________________ % .

.5 0 0 0 ‘ 01 1 .0 0 0 • .0045 + .0165 0

2 . 0 0 0 • . 0 0 6 5 ± .0295 0

.5 . 0 0 4 0 ± .0026 0 .0192 ± .0000 02 1 .0 .0018 + .0010 0 . 0 2 0 3 ± .0029 0

2 . 0 . 0 0 1 0 ± .0005 . 0 . 0 2 0 4 ± .0056 0

.5 .0022 + .0011 o' .0212 ± . 0 0 2 7 03 1 .0 .0013 + .0004 0 . 0 2 1 3 ± .0043 0

2 . 0 . 0 0 1 5 ± .0007 0 .0225 ± .0081 • . 0 0 3 3 ± .0026

4 .1 .0069 ± .0052 0 .02 50 ± .0061 .0128 ± .0129

.5 .0027 ± .0006 0 .0301 ± .0069 .0021 ± .00095 1 . 0 .0022 ± .0001 . . 0 0 0 9 ± .0004 .0332 ± .0077 .0039 ± .0035

.5 .0028 ± .0 0 1 2 0 . .0260 ± . 0 0 3 6 .0093 ± .00026 1. 0 .0036 ± . 0 0 0 6 0 .0326 ± . 0 0 5 6 .0069 ± .0 0 4 2

1, Oxidation HgOg + heat 4. Parr BombZ „ Oxidation HgOg-HNO + heat 5. Dry Ashing (HNO -HF)3. Oxidation HCIO^-HNO + heat 6 . NagCO Fusion

Sample s i z e in grams

T a b l e 1 8 . T h e t o t a l c o n t e n t o f F e , Z n , N i , Cu a n d C r f o u n d i n t h e T u c s o n s l u d g e a sr e v e a l e d b y s i x d i f f e r e n t p r o c e d u r e s . Mean v a l u e s a n d t h e h a l f l e n g t h o ft h e 95% c o n f i d e n c e i n t e r v a l s ( ± t s % ) .

Methods* SS** • Fe Zn Ni Cu Cr__ % ___________

.5 .0065 ± .0004 .0062 ± .0060 .0025 ± .0003 . 0 0 5 8 ± .0034 .0257 + . 0 0 7 71 : 1 . 0 .0173 ± .0217 .0073 ± .0013 .0021 ± .0010 . 0 0 3 9 ± .0037 -.0193 ± .0187

2 . 0 .0077 ± .0 0 1 4 .0062 ± .0060 .0027 ± .0013 .0040 ± .0038 .0177 ± .0123

.5 ' ■ 1 .2275 ± .0968 .3060 ± .0602 .0077 ± .0057 .0495 ± .0194 , .0560 ± .01712 1.0 1 . 1867.± .1879 .2527 ± .1987- .0137 ± .0137 .0176 ± .0108 .0129 ± .0054

2 . 0 1.2725 ± .3075 .3311 ± .0045 ■ . 0 0 9 7 ± .0006 . 0 8 5 8 ± .0054 .0687 ± . 0193

.5 ' ' 1.1066 ± .4971 .3658 ± .1040 .0110 ± .0025 .0982 ± .0330 - .0738 ± ..01313 1.0 .7567 ± .2254 .3773 ± .0160 .0230 ± .0025 .0958 ± .0220 .0692 ± .0185

2 . 0 1 .3530 + .3240 .3643 ± .0 5 2 2 .0117 ± .0010 .1008 ± .0295 .0740 ± .0110

4 .1 1.4150 ± 1 . 6125 .2278 ± .1996 .0152 ± .0243 .0810 ± .0581 .0900 ± .0247

.5, 1 . 5 0 0 0 ± . 1 2 4 0 .3126 ± .0372 .0132 ± .0007 .0938 ± .0039 .0922 ± .0 1845 1.0 1.4167 ± .3583 .2956 ± .0133 .0120 ± .0022 .0954 ±.0031 .0958 ± . 0087

.5 1.6833 ± .4 9 3 3 .3577 ± .1 0 2 5 .0163 ± . 0 1 0 0 .0900 ± .0000 .1100 ± .01146 1.0 1 .753 ± .4 4 2 0 .3607 ± .1 1 0 0 .0157 + .0107 .0942 ± .0208 .0860 ± .000 0

2 .0 1.5566 ± .1 1 2 0 .3505 ± .0452 .0163 ± .0 039 .0770 ± .0065 .0825 ± .0174

1. Oxidation HgOg + heat 4. Parr Bomb

2. Oxidation HgOg-HNOg + heat 5 .• Dry Ashing (HNOg-HF)

3 . Oxidation HCIO -HNO + heat 6. Na^CO Fusion

Sample s i z e in grams.

4 2

Table 19. The t o t a l content of Co, Cd, Mn and Pb found in the Tucson sludge as revealed by s ix d i f f e r e n t procedures. Mean values and the h a l f lengths of the 95% confidence in t e rv a l s( ±tSx)

Methods * ss ** Co Cd Mn Pb

______________ ^

.5 0 O' 0 0

i 1 , 0 0 0 0 0

2 . 0 0 0 0 0

.5 .0036 ± .0000 0 .0189 + . 0 1 9 9 .0355 ± .02672 1 . 0 .0020 ± .0 00 7 .0013 ± .0 0 1 5 .0203 ± . 0111 .0351 ± .0091

2 . 0 .0015 ± .00 03 .0017 ± .0 0 0 9 .0222 ± .0066 .0227 ± .0 2 6 0

. 5 .0023 ± .0 0 0 7 .0010 ± .0 0 1 5 .0220 ± . 0 0 5 0 .0405 ± .0 0 3 7

3 1 . 0 .0020 ± .0 0 0 9 .0019 ± . 0 0 0 8 .0245 ± .0 0 9 7 .019.0 ± . 0 1 0 0

2 . 0 .0020 ± .0005 .0020 ± .0006 .0234 ± .0025 .0191 ± .0 0 1 5

4 .1 .0065 ± .0012 0 .0214 ± ,0 2 6 2 . .0370 ± .0495

.5 .0034 ± . 0 0 1 3 .0046 ± .0 0 0 5 .0366 ± . 0 0 7 0 .046 ± .0041

5 1 . 0 .0026 ± .0 0 0 2 .0037 ± .0001 .0413 ± .0116 .0397 ± .0 1 8 3

.5 .0038 ± .0021 .0014 ± .0015 .0311 ± .0035 .0416 ± .0 0 4 2

6 1 .0 .0038 ± . 0 0 0 9 .0018 ± . 0 0 0 3 .0305 ± .0013 .0436 ± .0 1 1 2

2 . 0 .0039 ± .0001 .0023 ± . 0 0 0 2 .0332 ± .0107 .0458 ± .0 1 2 2

* 1. Oxidation HgOg + heat 4. Parr Bomb

2. Oxidation H g O g - H N O g + heat 5. Dry Ashing ( H N O ^ - H F )3. Oxidat ion H C I O ^ - H N O g + heat 6. NagCOg Fusion

Sample s i z e in grams

T a b l e 2 0 . T h e t o t a l c o n t e n t o f F e , Z n , N i» Gu a n d C r f o u n d i n t h e P h o e n i x s l u d g ea s r e v e a l e d b y s i x d i f f e r e n t p r o c e d u r e s , mean v a l u e s a n d t h e h a l fl e n g t h s o f t h e 95% c o n f i d e n c e i n t e r v a l s ( ± t s % ) .

Methods* SS** . Fe Zn Ni Cu Cr

<v . ___ .

.5 .0285 ± .0108 .0207 ± .0135

h

.0203 ±.0047 .0142 +.0224 .0235 ±.00221 l . o .0120 ±.0066 .0139 ± .0078 .0188 ±.0011 . .0064 ±.0026 ■.0220 ±.0030

2 .0 .0065 ±.0022 .0073 ±.0055 .0165 ±.0015 .0027 ± .0038 .0213 ±.0107

.5 1.5694 ± .0703 .5495 ±.1742 .0625 ±.0151 ■ .1620 ±.0301 .1900 ±.22792 1.0 1.5691 ± .1486 .4433 ±.2361 .0675 ±.0409 .0935 ±.0151 .1226 ±.0374

2 . 0 1.5310 ±.1607 .5950 ±.0215 .0703 ±.0087 .1448 ±.0204 .1090 ±.0151

. .5 1.6300 ± .2416 .6040 ±.1033 .0690 ±.0043 .1453 ± .0387 .1320 +.00833 1.0 .7150 ± .4945 .6200 ±.0657 .1430 ± .0210 .1428 ± .0252 .1145 ±.0000

' 2 . o : 1.2166 ± .2494 .6200 ± .0430 .0730 ± .0758 .423 ±.0312 ,0955 ±.0086

4 . .1 ' 1.2655 ± .2567 .2567 ± .2900 .0610 ± .0430 .0985 ± .0194 .0950 ±.0215

• .5 1.7417 ±.2181 .5107 ± .0529 .0664 ± .0076 .1379 ±.0011 .1555 ±.03155 ' 1 .0 1.6750 ± : 0621 .5138 ± .0177 • .0615 ± .0079 .1396 ± .0084 .1588 ±.0242

.5 1.8830 ± .2432 .6050 ±.1.075 .1043 ±.0592 .1045 ± .0323 .1446 ±.01946 1.0 1.5400 ± .1312 .6100 ± .1080 .0883 ± .0169 .1093 ±.0177 .1370 ± . 0301

2 . 0 1.8700 ± .1720 .6233 ± .0574 .0130 ± .0043 .1460 ± .0516 .1250 ±.0400 ;*

1. Oxidation HgOg + heat 4. Parr Bomb

2. Oxidation H^-HNO^ + heat 5. Dry Ashing (HNO^-HF)

3. Oxidation.HClO^-HNOg + heat 6. NagCO Fusion

** Sample s i z e in grams -

4 4

T a b l e 2 1 . T h e t o t a l c o n t e n t o f C o , C d , Mn a n d Pb f o u n d i n t h e P h o e n i x 's l u d g e a s r e v e a l e d b y s i x d i f f e r e n t p r o c e d u r e s . Mean v a l u e sa n d t h e h a l f l e n g t h s o f t h e 95% c o n f i d e n c e i n t e r v a l s ( ±t S x )

Methods* SS** Co Cd Mn Pb

— —

.5 0 0 0 01 1.0 0 0 0 0

2.0 0 0 0 0

.5 .0042 ± . 0 0 1 7 . 0 0 1 1 ± .0009 .0213 + .0030 .0496 + .000

2 1 . 0 .0028 ± . 0 0 1 8 .0028 ± . 0 0 0 9 .0232 ± .0045 .0347 ± .0241

•2.0 .0021 + .0 0 0 7 .0035 ± .0007 .0239 ± .0021 .0455 ± .0 02 2

. 5 .0033 ± .0 005 .0031 ± .0 01 5 .0207 ± . 0 0 7 3 .0403 ± .0 0 3 03 1 .0 .0026 + .0 007 .0035 ± .0011 .0222 ± .0 0 1 8 .0107 ± .00 00

2 . 0 .0024 + .001 3 .0040 ± .0 00 5 .0216 ± .0 0 4 4 .0241 ± .0109

4 .1 .0074 ± .0 01 3 0 .0188 ± .00 00 .0542 ± .0258

.5 .0037 ± .0017 .0064 ± .0002 .0330 ±.0021 .0572 ± .0000

5 1 .0 .0030 ± .0 004 .0054 ± .000 6 .0380 ± .0050 .0653 ±.0172

.5 .0040 ±.0031 .0019 ± .0012 .0262 ± .0028 . .0531 ±.0059

6 1 . 0 .0044 ± .0015 .0030 ± .0016 .0272 ± .0 04 8 . .0540 ± .0250

2 . 0 ' ,.0046 ± .0002 .0034 ± .0004 .0240 ± .0108 .0478 ±.0112

*1. ■Oxidation HgOg + heat 4. Farr Bomb

2. Oxidat ion H202 -HN03 + heat 5. Dry Ashing (HNOo.-HF)3. Oxidat ion HCIO -HNO + heat 6 . Na2(COj Fusion ,

subsets are groups of methods in which no two methods have means t h a t do

not d i f f e r by more than the s h o r t e s t s i g n i f i c a n t range fo r t h a t p a r t i c u l a r

subset s i z e . For t h i s t e s t the s ix methods were subdivided in to f i f t e e n

groups according to sample s ize so each method and sample s iz e was t r e a t e d

as a d i f f e r e n t method. Nine elements were t e s t e d . Table 22 includes a l l

the methods and rankings given in the l a s t homogeneous subse t of the SNK

procedure fo r each waste sample. The rankings given in Table 22 c l e a r l y

show t h a t methods 4 (Parr bomb), 5 (Dry ashing) and 6 (NagCOg fusion)

gave the h ighes t recovery of t o t a l metal in the wastes .

The Parr bomb method ranks very high fo r Fe, Ni, Co and Pb

ana lys is according to Table 22. Never the less , a c lose look a t the con­

f idence in t e rv a l s in Tables 14-21 shows very wide ranges fo r t h i s p a r t i ­

cu la r method; e s p e c ia l ly fo r the Fe, Co and Pb va lues . The problem of

sample s iz e (0.1 g maximum) was a lready pointed out in the methods sec­

t ion and is c l e a r ly o f g rea t inf luence in the highly v a r ia b le r e s u l t s ,

possib ly due to poor sample homogeneity.

The Dry Fusion Method ranks high fo r Cr, Cd, Mn and Pb determina­

t i o n . The 1.0-g sample s iz e seems to provide more uniform data than

the smal ler one. According to Tables 14-21, the overa l l confidence

i n t e rv a l s are much narrower than the ones reported fo r the Parr bomb

method. Thus, the Dry Ashing Method shows g rea te r r e p ro d u c ib i l i t y than

the Parr Bomb Method does. «

The NagCOg-Fusion Method ranks very high fo r Fe, Ni and Cu

determination. But in te r f e re n c es due to the high sodium content in the

so lu t ions (approximately 10,000 ppm) were detected on blank runs fo r

Table 22. Methods ranked according to the Student-Newman-Keul's procedure.

Methods SS* Fe I n Ni Cu Cr Co Cd Mn Pb1 2 3 4 1 2 3 4 1 2 3 4 1 2 3 4 1 2 3 4 1 2 3 4 1 2 3 4 1 2 3 4 1 2 3 4

H2°2oxid.

.5

1.0

2 . 0 9

H2°2

oxid.

.5

1 .0

2 .0 8

8

9

8

9

11

8

9 9

0

8•

0

10

6

7

11

9

4

8

9

9

10 11

10

57

hcio4

N03h

oxid.

.5

1 .0

2 .0

7

7

7

13

12

3

5

6

3

2

4

5

3

2

1 2 1

6

9

7

2

3

1

2

3

1

7

10

124

7 7

8

12

7

9

Parr Bomb .1 2 1 1 7 2 7 2 1 3 2 9 5 11 1 1 1 1 6 1 1 1 1

Dry

Ashing.5

1 .0

5

6

5

5

6

6

4

10 1

7

8 6

8

5

7

4

4

5

3

1 1

3

2

3

2 1 1

1

2

1

2

2

3

3

1

2

1

2

1 51

fi4

1Na2C03

Fusion

.5

1 .0

2 .0

3

14

1

3

2

4

3

10

4

1

2

3

4

6

51

11

4

1

1

4

3

3

1

2

3

1

4

8

5

8

10

6

9

2

5

1

4

5

1

6

5

6

1

5

2

4 3 3

3

2

4

2

3

4

5

4

2

6

3

81. Tucson manure 3. Tucson sludge

2. Marana manure 4. Phoenix Sludge

* Sample s i z e in grams

4o>

Cd and Nl. These i n t e r f e r e n c e s » although not f u l l y q u a n t i f i e d , exceeded

10% of the h ighest metal leve ls recorded. Although o the r Na i n t e r f e r ­

ences were detected on o th e r metals , none of them exceeded 1%. of the

leve ls recorded. These in te r f e re n c e s coupled with poss ib le v o l a t i l i z a ­

t ion Tosses make the NagCOg Method le ss d es i rab le than previously

expected. O vera l l , the r e p ro d u c ib i l i t y o f the r e s u l t s rank th i s method

second to the Dry Ashing Method.

The HClO^-HNOg + Heat Method should be mentioned as having

performed very well f o r Ni determination. And the confidence in te rv a l s

reported on Tables 14, 16, 18 and 20 are very s a t i s f a c t o r y , in d ica t in g

a good r e p ro d u c ib i l i t y of r e s u l t s . C lea r ly , even the. s t ro n g e s t acid

ox ida t ion , however, i s not enough to re le a se a l l metals from manure and

sludge wastes.

A*third s t a t i s t i c a l t e s t was undertaken to eva lua te any d i f f e r ­

ences between the two manures and between the two sludges r e l a t in g to

the method used. In s h o r t , do the s ix methods give the same e f fe c t s

on the two types o f wastes? A two-way ana lys is o f variance (S te r l in g

and Pollack, 1968) was made; which showed t h a t both manures (MT and MM)

are a f fec ted equal ly by any of the t r e a tm e n ts . But the two sludges did

not s i g n i f i c a n t l y c o r r e l a t e fo r An and Ni c o r re la t io n when submitted to

any of the s ix t rea tments . The author cannot assess any valuable s i g n i ­

f icance to these r e s u l t s , since only two metals, f a i l e d t h i s t e s t with the

r e s t o f them showing high c o r re la t io n numbers.

Table 23 repor ts the sample content of As, Hg, Be, and V. These

data were obtained by sending the sample so lu t ions to an independent

Table 23. Total content of As, Hg, Be, and V found in the Tucson and Marana manures (MT), (MM) and the Tucson and Phoenix sludges (ST), (SP). Mean and - Standard Deviation.

Method Sample* . As Hg .Be V

HC10. MT .0007 + .0003 0 0 O'4

MO U MM .0010 + .0 004 0 0 03 St .0014 + .000 6 0 0 .0088 ± .0015

Oxid. SP .0020 + . 000 9 0 0 .0069 ± .0009

MT .0054 ± .0 0 1 8 0 .0012 + .0004 1 0Parr Bomb MM .0032 + .0010 0 0 0

ST ' - 0 ■ 0 O' 0SP . .0083 + .0067 0 0 0

MT .0023 +.0011 • 0 0 . 0Dry Fusion MM .0036 +.0011 0 0 0

ST .0022 + .0008 0 . 0 .0062 ± .0013SP .0031 + .0016 0 0 .0073 ± .0015

Na9C0o MT .0083 +.0026 .0486 + .0275 .0023 ± .0000 .0048 ± .00002 j Fusion MM

ST ..0092 ±..0025 .0084 +.0027

.0436 + .0314

.0454 +.0454.0021 +.0001 .0030 ±.0001

0.0074 ±.0020

SP .0093 +.0011 .0488 ± .0454 .0024 ±.0001 .0080 ± .0008

Sample s i z e s averaged.

NOTE: Methods 1 (HgOg p x i d . ) and 2 (HgOg + NO H o x i d . ) f a i l e d to g iv e any s i g n i f i c a n t r e s u l t s .

49

l a bo ra to ry where a n i t rous oxide flame burner was used. The author can­

not be held f u l l y responsib le fo r the values reported in Table 23. No

s t a t i s t i c a l t e s t s were made on these data s ince they were very fragmen­

ta ry and obvious in te r f e ren ces occurred in the As and Hg determination.

According to Ando e t a l . (1969), As determination by atomic absorption

spectroscopy i s a f fec te d by j u s t about every metal and s a l t in so lu t ion

with As. No attempt was made to ad ju s t the data fo r i n t e r f e r e n c e s ,

s ince a l l samples had d i f f e r e n t ion concentra t ions . All data in column

1, Table 23 should be regarded as meaningless (unless ad justed) in view

o f such severe in t e r f e r e n c e s . Other de tec t ion methods fo r As determine- :

t ion are av a i la b le (Traversy, 1971). The Hg data are meaningful in t h a t

a l l methods but the NagCOg Fusion Method reported values below 0.05 ppm

in s o lu t io n . Sodium in te r fe re n c es were obvious here and were confirmed

by blank runs. The Be and V values are more r e a l i s t i c : no in te r f e re n c es

were de tec ted and the values are c o n s i s t e n t . However, due to the small

c o ncen t ra t ions , the da ta were highly v a r iab le and s t a t i s t i c a l l y i n s i g n i ­

f i c a n t . Concentrations o f the so lu t ions should be considered for the

determination of V and Be by atomic absorption spectroscopy.

In Figures 2 and 3 the at tempt i s made to combine the s t a t i s t i c a l

t e s t r e s u l t s toge the r with the de tec t ion and v o l a t i l i z a t i o n problems

discussed in the l a s t four paragraphs. The methods are separated fo r

each metal element in to four zones. The zones labeled (50-75) and (75-

100) include methods t h a t had values above average (see Tables 14-21).

The zone labeled (75-100) contains methods se lec ted by the Student-

5 0

Newman-Keul's t e s t as being in the f i r s t homogeneous group. Sample

s iz e i s not included in t h i s ranking because i t has been found to be

only re levan t on the f i r s t th ree oxidat ion methods.

RANG

E -

%

(0 -

25)

(25

- 50

) (50

-

75)

(75

- 10

0)

51

• • □ A□ □

• » O□ □ A O

A A A e □• O A • A

• O O □ •X A

X OO • * •

O A A A A

A O O OX O

X X X X

■ X X

O □

X X X■ ■ n ■ B B B B B Q B

Fe Zn Ni Cu Cr Co Cd Mn Pb Hg Be V

ELEMENT ANALYZED

■ Oxidation, HgOg plus heat x Oxidat ion , HNO3-H2O2 plus heat O Oxidat ion , HCIO4-HNO3 plus heat A Parr Bomb • Dry ashing (HNO3-HF)□ Na2C03 fusion (Ni, Cd, Hg ra t ings not included)

Figure 2. Adjusted ra t in g s of the s ix methods t e s t e d fo r manure waste ana lys is .

52

o

un

LOr--

oLO

CS LO

L OCXJ

LOCXI

O

ELEMENT ANALYZED

■ Oxidat ion , HgOg plus heat x Oxidat ion, HNOg-HgOg plus heat O Oxidat ion , HCIO4 plus heat A Parr Bomb e Dry ashing (HNOg-HF)□ NagCOg fusion (Ni, Cd, Hg ra t ings not included)

Figure 3. Adjusted r a t ings of the s ix methods te s ted fo r sludge waste ana lys is .

SUMMARY AND CONCLUSIONS

The eva lua t ion f o r t o t a l metal con ten t o f manure and sludge

wastes i s in no way a simple mat ter . .

Within the l i m i t s o f the equipment, t echn iques , and informat ion

a v a i l a b l e , the au thor at tempts to p r e s e n t , ca r ry o u t , and discuss methods

fo r p repara t ion and an a ly s is of manures and municipal s ludges . Recom­

mendations on the use and improvement o f these methods w i l l follow t h i s

s e c t io n .

Several conclusions may be drawn from t h i s s tudy and are l i s t e d

« f ol lcws: . ' Z ^ ^

T. Only very s t rong ox ida t ion methods such as HCIO^ t rea tm en t

can e f f e c t i v e l y r e l e a s e 80-90% o f most o f the metals in

s o i l - o r g a n ic m at te r s o l i d waste such as f e e d !o t manure and

municipal s ludges .

2. Sample s iz e markedly a f f e c t s ac id ox ida t ion methods and

should be considered.

3, Methods combining ash ing , v o l a t i l i z a t i o n and fusion techniques

a re most e f f e c t i v e fo r r e l e a s in g 90-100% o f the metals in

s o l i d wastes . ■ V

4, No s in g le method stands out as most e f f e c t i v e fo r p repara t ion

and a n a ly s is o f s o l id wastes . Each has advantages and d i s ­

advantages.

5. V o l a t i l i z a t i o n and contamination problems make some methods

u ndes i rab le f o r ana lys is o f some metals in s o l i d wastes .

' ' 53 ; /V : /■ ' ‘ , ■■ -

Atomic absorption can and should be used to d e te c t metals

in sample waste s o lu t io n s , provided in te r f e re n c e s are

e i t h e r minimized, cancelled out or ad justed fo r .

All methods have varying degrees o f complexity, requirement

t imes, and equipment needs.

RECOMMENDATIONS

Recommendations fo r use o f the s ix methods s tud ied are as

follows:

T. Parr Bomb to be used fo r a l l wastes in metal determination ,

provided:

a. Sample s iz e can be increased to 0.5 or 1.0 g by using

l a r g e r Par r Bombs.

b. Pre-ashing a t low temperatures (450°C) o f the organic

matter in waste sludges is done as p a r t o f the t r e a t ­

ment.

2. Dry Ashing (HNOg-HF) method with 0 .5 -1 .0 g samples be used

fo r most metals except Hg in both types o f wastes. (Note:

; HE addi t ion probably v o l a t i l i z e s a small percentage of metals

as f l u o r a t e s . )

3. The NagCOg fusion with 1.0-g sample s iz e be used in both

wastes and a l l metals except Ni, Cd and Hg. This method

should be avoided i f the f i r s t two are a v a i l a b le .

55

APPENDIX 1

REPORT ON SODIUM, POTASSIUM, CALCIUM AND MAGNESIUM CONTENT OF AN ARIZONA FEEDLOT MANURE

Object ives

The purpose of t h i s experiment was to determine the r a t e of

r e lea se of Na, K, Ca and Mg through success ive water e x t r a c t io n s 'of a

f e e d lo t manure sample from the Tucson, Arizona area.

Material

The manure used in t h i s experiment had been d r ied and f in e ly

ground by passing i t through a 20-mesh screen in a feed-type hammer m i l l .

The manure was thoroughly mixed af terwards to produce a s tock of r e l a ­

t i v e l y homogeneous m a te r ia l .

Methods

Three s e t s o f two 10-g samples were weighed and put in to s tee l

c en t r i fuge tubes. Deionized water was added to obta in manure-water

r a t i o s of 1 : 2 , - 1 : 5 , and 1:10.

The above s teps were followed by approximately 4 hours of shaking

a t medium speeds to avoid foaming and/or gas accumulation ins ide the

tube. All samples were centr i fuged a t 9000 rpm for 45 minutes and the

e x t r a c t s c o l l e c te d , taking care not to remove any s o l id s from the tubes.

I den t ica l volumes of water to the ones ex t rac ted were replaced in to the

con ta ine rs .

56

, 57

The s teps descr ibed in the l a s t two paragraphs were repeated

a t o t a l o f ten times on each manure sample during a period of ten days.

All ex t rac ts , were subsequently r e f r i g e r a te d to avoid unnecessary decom­

p o s i t io n , Aliquots of these e x t r a c t s werd decolorized with hydrogen

peroxide (301) on a hot p la te a t 80°C in p repara t ion fo r t h i s an a ly s is .

Atomic absorption spectrophotometry was used to determine the Ca and Mg

leve ls and Flame emission was used fo r Na and K. See following

Figures 4-7.

Discussion of Results

Figures 4 and 5 fo r Na and K, r e sp e c t iv e ly , show t h a t over 90%

of these two elements was removed a f t e r 10 e x t r a c t io n s . Over 50% of

the s a l t s was removed a f t e r the f i r s t 3 e x t r a c t io n s . This f a s t r a t e o f

e x t r ac t io n was expected s ince these elements are very mobile and e a s i ly

removed from the surface of the s o l id s . Figures 6 and 7 fo r Ca and Mg

show, unlike K and Na f ig u re s , a very e r r a t i c behavior in t h e i r e x t r a c ­

t ion r a t e s . Calcium tends to have the same ex t rac t io n r a t e o f about 1%,

a t 1:2 r a t i o fo r each e x t rac t io n and doubles as the water-manure r a t i o

doubles. Magnesium ex h ib i t s a constancy in the r a te of e x t r a c t io n , too ,

but unlike Ca, i t shows a f a s t e r migration r a t e during the f i r s t th ree

e x t r a c t io n s in the 1:5 and 1:10 r a t i o s . The to ta l amounts removed fo r

both Ca and Mg did not exceed 40% of the t o t a l s p resen t in the manure.

These e f f e c t s may be explained by the f a c t t h a t inorganic Ca and Mg com­

pounds are more inso lub le than s im i la r Na and K compounds; plus the f a c t

t h a t Ca and Mg also r e a c t with organic molecules more r e ad i ly . th a n K and

5 8

Na. The removal of Ca and Mg is probably more time dependent (on micro­

b ia l m inera l iza t ion and slow s o l u b i l i t y cons tants) than manure-water

r a t i o dependents as are K and Na.

RECO

VERY

-

% OF

TOTA

L

1:2 RATIO

20

10

1 2 3 4 5 6 7 8 9 100

90

80

70

60

50

40

30

20

10

0

B - 1:5 RATIO

1 2 3 4 5 6 7 8 9 10

90

80

70

60

50

40

30

20

10

0

C - 1:10 RATIO

1 2 3 4 5 6 7 8 9 10

E X T R A C T I O N - N u m b e rFigure 4. Water so luble Na content of feed lo t manure ex t rac ted for ten successive times a t three manure/

water r a t io s (A, B and C), reported as % of the to ta l Na found in the manure.

cnUD

A - 1:2 RATIO

1 I I rhTh-,1 2 3 4 5 6 7 8 9 10

E X5. Water s o lu b le K content

manure/water r a t i o s (A,

70 — 70

60 -B - 1:5 RATIO

-C - 1:10 RATIO

50 - 50 —

40 - 40 -

30 — 30 -

20 — 20 -

10 — 10 —

- 1 - 1 - . . , . ---------- ,0 1 2 3 4 5 6 7 8 9 10 0 1 2 3 4 5 6 7 8 9 10

■ R A C T I O N - N u m b e r

n f e e d l o t manure ex trac te d for ten s u c c e s s iv e t imes at three and C), reported as % o f the to t a l K found in the manure.

RECO

VERY

-

% T

otal

7 r

6

5

4

3

2

1

A - 1:2 RATIO

7 | -

6

5

4

3

2

1

B - 1:5 RATIO

1 2 3 4 5 6 7 8 9 10 0 1 2 3 4 5 6 7 8 9 10 0

E X T R A C T I O N - N u m b e r

C - 1:10 RATIO

1 2 3 4 5 6 7 8 9 10

Figure 6 . Water soluble Ca content of feed lo t manure ex trac ted for ten successive times a t three manure/water r a t io s (A, B and C), reported as % of the to ta l Ca found in the manure.

cr>

RECO

VERY

-

% T

otal

20 r-

15

10

A - 1:2 RATIO

20 r

15

10

B - 1:5 RATIO

20 n

15

10

1 2 3 4 5 6 7 8 9 10 0 1 2 3 4 5 6 7 8 9 10 0

E X T R A C T I O N - N u m b e r

C - 1:10 RATIO

1 2 3 4 5 6 7 8 9 10

Figure 7. Water so luble Mg content of feed lo t manure ex trac ted for ten successive times a t three manure/water r a t io s (A, B and C), reported as % of the to ta l Mg found in the manure.

ITiPO

APPENDIX 2

REPORT ON TRACE ELEMENT CONTENT OF AN ARIZONA FEEDLOT MANURE

Object ives

This experiment was c a r r ie d out to e s t a b l i s h the r a t e of

r e le a se of some metals such as Fe, Ni, Zn, Cu, Mn, Co, Pb, and Cr. from

Arizona f e ed lo t manure through successive water e x t r a c t io n s .

Materia ls

See Material Section of Appendix 1.

Methods

E s s e n t i a l ly the same e x t r a c t in g techniques and m ate r ia ls were

used fo r t h i s study as fo r s a l t r e lea se reported in Appendix 1. The

obtained samples were a lso r e f r i g e r a te d and a l iquo ts were decolorized

with hydrogen peroxide over a hot p l a t e . Due to the b o i l in g o f f of

some water ( to reduce volume) and d es t ru c t io n of the organic matter

t h a t holds some ions in so lu t io n , some p r e c i p i t a t e was seen in the l a t e

s tage of deco lon iza t ion . The p r e c i p i t a t e was red isso lved with small

por t ions of concentrated n i t r i c acid. (Note: On the average, 2 ml of

n i t r i c acid per 20 ml a l iq u o t were needed to red isso lve the p r e c i p i t a t e . )

The c l e a r so lu t ions were brought to volume without exceeding a d i lu t io n

f a c to r o f 1 :2 .5 .

Atomic absorption was used to d e te c t the metals.

6 3

64 .

Discussion of Results

Fe e x t r ac t io n r a t e s , Figure 8-A, were f a i r l y cons tan t along the

ten e x t r a c t io n s , averaging about 0.04% of the t o t a l Fe in manure. So

l e ss than 0.5% Fe was ex t rac ted during the 10 e x t r a c t io n s . This shows

t h a t Fe i s not only the most abundant m icronutr ien t in manure, exceeding

1% of the t o t a l manure weight, but a lso the slowest in being re leased

from i t , poss ib ly due to the highly inso lub le forms both organic and

inorgan ic , in which i t i s found in manures.

Zinc, Figure 8-B repor ts a s teep drop as the number o f e x t r a c t io n s

inc rease . Despite the low Zn concentra t ion in manure (0.020%/w), approxi­

mately 5% of i t came o f f a t the end of ten e x t r a c t io n s . This may be

accounted fo r by the f a c t t h a t An i s mostly found in the organic pa r t

of manure, thus being more e a s i ly s o lu b i l i z e d than Fe.

Nickel , Figure 8-C repor ts a s im i la r r e leas ing p a t te rn to the

one of Zn, desp i te the even lower concentra t ion of i t in manure (0.013%/w)

and the f a c t t h a t over 5% of i t came o f f a f t e r the e x t r a c t io n s . Again,

the Ni i s probably mostly involved with the organic p a r t o f manure.

Copper, Figure 9-A repo r ts an almost id en t ica l behavior to the

one of Ni, with about 11% of the t o t a l Cu (0.0034%/w) r e leased a f t e r the

ten th e x t r a c t io n . Some f a s t d isso lv ing phosphates and s u l f a t e s may be

the cause o f such an abrupt drop a f t e r the s ix e x t r a c t io n s in the e x t r a c ­

t ion r a t e below the de tec tab le l im i t s .

Manganese, Figure 9-B, was the l a s t metal to be detected in the

ex t rac ted samples. The Mn graph shows an increasing r a t e of re lease

up to a t o t a l o f 9% of the t o t a l Mn presen t in manure (0.03%/w). Since

65

most Mn in manure is probably o rg an ic9 with an increase in pH towards

the bas ic s id e , t h i s may f u r th e r help the Mn s o l u b i l i t y as the number

o f ex t r a c t io n s increase .

RECO

VERY

-

t T

otal

.08

.07

.06

.05

.04

,03

,02

01

IRON - A .4

.3

ZINC - B

. 2

.1

.8

.7

. 6

.5

.4

.3

. 2

.1

NICKEL - C

0 1 2 3 4 5 6 7 8 9 10 1 2 3 4 5 6 7 8 9 10 0 1 2 3 4 5 6 7 8 9 10

E X T R A C T I O N - N u m b e rFigure 8. Water s o lu b le Fe, Zn and Ni content in f e e d l o t manure ex trac ted fo r ten s u c c e s s iv e

times at 1:2 manure/water r a t i o , reported as % o f to ta l Fe, Zn and Ni found in the manure.

CTY

RECO

VERY

-

% T

otal

40

30

20

10

COPPER - A

1 2 3 4 5 6 7 8 9 10

1.6

1. 4

1 . 2

1 . 0

0 . 8

0 . 6

0. 4

0. 2

0

MANGANESE - B

1 2 3 4 5 6 7 8 9 10

Figure 9.E X T R A C T I O N - N u m b e r

Water s o lu b le Cu and Mn content in f e e d l o t manure ex trac ted for 10 s u c c e s s iv e t imes a t 1:2 manure/water r a t i o , reported as % o f t o t a l Cu and Mn found in the manure.

cr>

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