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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.
Rights Copyright © is held by the author. Digital access to this materialis made possible by the University Libraries, University of Arizona.Further transmission, reproduction or presentation (such aspublic display or performance) of protected items is prohibitedexcept with permission of the author.
Download date 17/04/2021 12:32:54
Link to Item http://hdl.handle.net/10150/347874
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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