Effect of sulfuric acid treated mine tailings and elementalsulfur on uptake of iron and copper by sorghum

Item Type text; Thesis-Reproduction (electronic)

Authors Lanspa, Kenneth Eugene, 1932-

Publisher The University of Arizona.

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EFFECT OF SULFURIC ACID TREATED MINE TAILINGS AND ELEMENTAL SULFUR ON UPTAKE OF IRON

. AND COPPER'BY SORGHUM

by

Kenneth "Be Lanspa

A Thesis, Stibmitted to the Faeulty of the

DEPARTMENT OF AGRICULTURAL CHEMISTRY AND SOILS

In Partial Fulfillment of the Requirements

For the Degree of

MASTER OF SCIENCE

In the Graduate College

UNIVERSITY OF ARIZONA

1964

STATEMENT BY AUTHOR

This thesis has been submitted in partial fulfillment or requirements for an advanced degree at The University of Arizona and is deposited in the University Library to be made available to borrowers under rules of the Library.

Brief quotations from this thesis are allowable without special permission, provided that accurate acknowledgment of source is made. Requests for permission for extended quotation from or reproduction of this manuscript in whole or in part may be granted by the head of the major department or the Dean of the Graduate College when in their judgment the proposed use of the material is in the interests of scholarship. In all other instances, however, permission must be obtained from the author.

SIGNED

APPROVAL BY THESIS DIRECTOR

This thesis has been approved on the date shown below:

3 . L - . : d L ^ V - /*/- fayUAT.LArr. h_ rnr.T.FR D a t e IWALLACE H. FULLER DateProfessor of Agricultural Chemistry and Soils

ABSTRACT OF THESIS

EFFECT OF SULFURIC ACID TREATED MINE TAILIHGS AND ELEMENTAL SULFUR ON UPTAKE OF IRON

AND COPPER BY SORGHUM

Kenneth E0 Lanspa

Tailings frbm a zinc mine in Northern Arizona were heated to different temperatures and treated with various amounts of sulfurie aeido Sob® were then ammoniated hy adding ammmia gas to the reacted tailingso • Plainsman and Kafir sorghum grown by the Stanford-DeMent Technique and the standard greenhouse pot tests were used to evaluate the availability of the iron and copper in the reacted tailings.Ferrous sulfate 5, sulfur 9 - .Ionite 9 and Sulfasoil were compared with the V' treatments of reacted tailingSo The results indicated that ammoniation influences the plant uptake, of iron and copper0 The reacted tailings,, which were ammdniated and had additions of elemental sulfur9 produced the greatest total oven dry weight of plant, top as well as the greatest total amount of iron and copper , up’takes .

Using the greenhouse pot method^ elemental sulfur was mixed into the soil at various rates with. Kafir sorghum as the test plant The rates of one ton or less of sulfur per acre did not reduce the soil paste pH values of the soil® Ferrous sulfate was more effective in supplying the plants with available iron and thereby correcting the chlorosis than .sulfdr; at corresponding rates®

ACKNOWLEDGEMENT

, The author wishes to acknowledge the invaluable

help and guidance received from Dr. Wallace H. Fuller

. during the graduate course.work and the preparation.of

this thesis.

'He. also wishes to express his appreciation to

Dr.. Robert H. Maier and Dr. Stanley We Buol for serving

■: on his committee ; and for their help^irf; M s graduate

studies. ' - ■

v

TABLE OF CONTENTS

;:-V . ' Pa§e

IMTROLUOTTOMoo © © @© © © © © © © © © © © © @ © © © © © © © © © © © © © © © © © © © © © © © © © © © © © © © © © X

L X TEII A TORE REVIEW © © © © © © © © © © © © © © © © © © © © © © © © © © © © © © © © © © © © © © © © © © © © © © 3

EXPERIMENTAL MATERXALS AND METHODS© © © © © © © © © © © © © © © ©©.©©©©©©© © © © © © 16

'Preparation of Mine Tailing Produets©© ©o © © © © © © © © ©© ©© © © © © © ©■ 16Some Chemical Charaetex'isties of the Tailing Products

Dseiio © © © © © © © © © © © © © © © © © © © © © © © © © © © © © © © © © © © © © © © © © © © © © © © © © © 13pheMpaIv.Ch'a:ra&teri.3ties ;6fV;tlit@.;@ila Soil Material

• ’•{•• Used© ©©© ©.'©©© © ©.© ©© 0 © 8.0 ■*'©■•© © 9 © © 0.0 © © OS,© ©. o © © O© O ©© © © © © 0 © o © © © © 19S St an ford™De Ment Seedling Culture Technique © © © © © © © © © © © © © © © © 19

(General ■ Treatment of the Sand© © © © © © © © © © © © © © © © © © © © © © © © © © ■ 19General Proce dure Used©© © © © © © © © © © © © © © © © © © © © © © © © © © © © © © © © 21Test to Determine the Best Soil Material for

Ejqjeriment © © © © © © © © © © © © © © © © © © © © © © © © © © © © © © © © © © © © © © © © © © 22. Experiment to Determine Iron Release from the Ottawa ,

Quarts Sand©©©©©©©©©©©©©©©©©©©©©©©©©©©©©©©o©©©©©©©©© 23Experiment to Determine Time Contact Between Plant

Roots and the Soil©© © © © © © © © © © © © © © © © © © © © © © © © © © © © © © © © © 23Determination' of the Normal Field Water-Holding

Capacity of the Soil©© © © © © ©©©©©©©©©©o©©©©©©©©©©©©©©© 24Determination of the Amount of Test Product to be

.■ Applied to the Soil© © © © © © © © © © © © © © © © © © © © © © © © © © © © © © © © © 24

Chemical Methods Used© © © © © © © © © © © © © © © © © © © © © © © © © © © © © © © © © © © © © 25 -Method of Determining Water-Soluble Iron$, Coppers and

Sulfur in the Soil and Reacted Mine Tailings©«©©©©o©©©© 26. Greenhouse Pot-Test Technique to Study Reacted Mine

Tailings © © © © © © ©©.©©©©©©© © © © © © © © © © © © © © © © © © © © © © © © © 6 © © © © © © © , 27Greenhouse Pot-Test Technique to Study the Sulfur

Effect on the Soil and Plants©© © © © © © © © © © © © © © © © © © © © © © © © © - 23

TABLE. OF CONTENTS (Continued)' '

x ; : .•. , < " : W

RESULTS AMD DISQUSSIOM© <$> © © © © © © © © © © © © © © © © © © © © © © © © © © © © © ©©©©©© © © © © 30St 30. f D s M@0t . T 0 St © © © o © © © © O O © ©d*© O © © © 0 6 0 © 0 6- © © O © O O O Q © 0 O © O O 30 ..Gpeenhouse Pot Test to Evaliiate Reacted Tailings© © © © © © © © © © 36;Greenhouse Pot Test to Evaluate Sulfur and Rates of

its App lication © © © © © © O O" O © O © O’ © O O © © © © O O © O O O © © 0 © © © © O © © 0 © © © 8SUMMARY © © © © © © © © © © © © o © © o .© © © d © © © © © © © © © © © © o © o o e © o o © © © © © o © © o o o © o o © © . 59

LITERATURE CITED© o.os©©©©©©©©©©©©©©©© © © ©©©©©©©oo©®©©©© © © oo©®©©©© 61

vii

LIST OF TABLES

Table

1 O-

2.

3o

4o

50

6 0

■ :7e '

. ■ . - ' ' ■ PageThe amount of total and water-soluble iron 8 copper9 and sulfur found in reacted mine tailings8- raw mine tailings $ two commercial products9 and Gila fine sandy loamoo o o 0 o o 0 o o o o o o O O O O O Q e 0 d0 0 0 o o o o o © o o o o O O O O © O 0 0 O O O O O O O 0 17

Some chemical characteristics of Gila fine sandy loam sample used in greenhouse experiment involving the absorption of iron from reacted mine tailing materials " by sorghumo o © © o © © o o © o © ©, © © © © o © © © © © © © o © © o © © © © © © © o © © © o o © ©» 20

A summary of-the iron content and dry weight of plant material of two varieties of sorghum grown under greenhouse conditions in Gila fine sandy loam soil material treated witU reacted mine tailings© © © © © © © © © © © © © 31

A summary, of the iron and copper content of Kafir sorghum grown under greenhouse conditions in Gila fine sandy loam soil material treated with reacted mine tailings andSUlfUr© ©, © e ©.©.©© © © O © O Q © O © © © O © © 0 6 © © o, © 9 © © © ■ 9 o 0 © © © © © © © © © 0 © © © © 6 37

Analysis of variance between treatments as indicatedby Duncan * s Multiple Range Tes t of copper and ironuptake into Kafir sorghum plant tops© © © © © © © © © © © © ©.© © © © © © © 41

The pH values9 Soluble saltSg nitrate nitrogen 9 avail­able phosphate „ and soluble sulfur f omd in Gila fine sandy loam soil material receiving various sulfur bearing soil amendments and-cropped once to Kafir sorghum©©©© ©©© 43

A, summary of the dry weight of the iron, copper, and sulfur content of Kafir sorghum grown under green­house conditions in Gila fine sandy loam soil material treated with sulfur and sulfates ©©•©©©© © ©»© © © © © © © © © © © © © © © 49

Analysis of variance between treatments as indicated by Duncan8s Multiple Range Test cf sulfur uptake into - Kafir Sorghum plant tops© © © © © © © © © © © © © © © © © © © © © © © © © © © © © © © © 50

' viii :

LIST OF TABLES (Cotttinued)

Table

9„

10 o

, : \ . ; . , " v . PageA summary of the iron„ copper, and sulfur contentin the tops of Kafir sorghum grown under greenhouseconditions in Gila fine sandy loam soil materialwith Various sulfur and sulfate treatments0 = 0»»0»e = 0 o » =« 52

Analysis of variance between treatments as indicatedby Duncan's Multiple Range Test of copper9. iron,and sulfur uptake into Kafir sorghum plant tops0„e*.d„ao 53

ix

Figure

1.

■ 2. ■

3»

4,

5.

6»

: ?.

LIST OF FIGURES' ' "

•; . ; ’ : ’ . ■•■■■ ' ; - ■■■' . . BageDiagram illustrating general trend of relation of soil reaction (pH) and associated factors to the availability of the plant nutrient elements, ...Vf,'. t• • ' 9

Total uptake of iron found in" Plainsman and Kafir sorghum tops grown in Gila fine sandy loam soil material supplied with 2gm„ of reacted mine tailings using the Stanford”DeMent Technique« , . , , « , - « » « , « 32

Total uptake of iron found in Flaihsman and Kafir sorghum tops grown in Gila fine sandy loam soil material supplied with 4 gja, of reacted: mine tailings using the S tanford-DeMent Technxque,', o boo ,, e,,,» ,, o o , o # o o et , ®,,,, ®, . 33

Total uptake of iron found in Plainsman and Kafir sorghum tops grown in Gila fine sandy loam soil material supplied with ,6 gm, of reacted mine tailings using the Stanford6®Decent Technxque,,, <> o,,, ©, o,«.»® ,• e o e o,, e o, © e o,»m 34

The dry weight of Kafir sorghum tops grown in Gila fine, sandy loam soil material receiving various reacted mine tailing products, sulfur, iron sulfate,and Sul fa sox 1 e, o ©,, © ©> © © © © © ©x© © © © ©, © @ © © © © © © ©, © a © © © © ©, © o © © © 38

Total uptake of iron found in Kafir .sorghum topsgrown in Gila fine sandy loam soil material receivingvarious reacted mine tailing products, sulfur, ironsulfate, and Sulfasoxl© © © © © © © © © © © © © © © © © © © © © © © © © © ©©©©*© © © 39

Total uptake of copper found in Kafir sorghum tops • xgrown in Gila fine sandy loam soil material receiving ' various reacted mine tailing products, sulfur, iron sulfate, and Sulfasoxl © © © © © © © © © © © © .©©'©©©©© © © © © © © © © © © © © ©»© 40

The dry weight of Kafir sorghum tops grown in Gila fine sandy loam soil material receiving K, Fe, and Mn sulfate and various rates of sulfur, ,.„©,»©«. © © © ©.»© ©. 54

LIST OF FIGURES (Continued)

Figure

90

':'10s

lie '

. '■ ' . ; ■ " , " - ; " pageTotal uptake of iron found in Kafir sorghum topsgrown in Gila fine sandy loam soil material receivingK g Fe3 and Mh sulfate and various rates of sulfur®0 «oe 55

Total uptake of copper found in Kafir sorghum topsgrown in Gila fine sandy loam soil material receivingKs'Fe g and Mn sulfate and various rates of sulfure s eo 0 e ® 56

Total uptake of sulfur found in Kafir sorghum topsgrown in Gila fine sandy loam soil material receivingKg Feg and Mn, sulfate and various rates of sulfur® ®e ® ® ®®' ,,'57

LIST OF PLATES:

Plate

lo

■3.

:

5o

■ . y.< ■ ■ '; v ■ ■ ' - ■ . ■ Page

Gbowth of Kafir sor»ghtim in Gila fine sandy loamsoil material receivings T~800 and sulfra?e.....6 . 4 5

Growth of Kafir sorghum in Gila fine sandy loam :soil material, feeeiving % T-800 and T-800 with ■ . ;sulfur o o o 4 0 o o o » o o © e e » e o- o o o o ti-.* o 6 o o o ;0 o o o o c> o o @ o d o o © o o o o o o o e o" 45

Growth of Kafir sorghum in Gila fine sandy loam soil material receivings 1-800® T-800 with sulfur®T-800NHg wrth sulfur® and T—SOONHgo©0 0 ©©©©©©©©©©©©©©©©©©© 46Growth of Kafir sorghum in Gila fine sandy loam soil material receivings. T-8Q0: with sulfur and • ferrous sulfate © © © © © © © © © © © © © .© © © q © © © o © © © © e © © © 0 © © © © © o o o ® © © o 46

Growth of Kafir.sorghum in Gila fine sandy loamsoil material receivings Sulfasoil® sulfur®, andT-800 with sulfur© © © © © © © ©©©©©©©©©©©©© © © ©©©©©©©©©© © © ® © © © © © 47

INTRODUCTION . ,

There are aeetimulatidns of mine tailings containing sul­

fides of irons manganeise8 eopper9 and zine from Arizona's vast-mining

enterpriseo These tailing dumps pose a ebstly disposal problem and

often threaten to become a nuisance«, Moreover^ they provide no economic

return to the'owners.o Jy"'

v The most prominent sulfides contained in the wastes are those

of iron which appear in the form of ferrous sulfides (FeS)9 double sul­

fides (FeSg)® and pyrrhotite- or polysulfide having iron and sulfur in

ratios of. Fe S >. <, The formulae of the latter usually are given as

FegSy and F e ^ S ^ , , . ' ■ , .. ■ ^

Numerous attempts have been made to findsome agricultural use

for pyrite mine waste0 Todayg there are several pyrite dr pyrite-like

products on the market despite the fact that pyrites oxidize too slowly

to have much influence on the physical condition of the soil and are .

almost wholly ineffective in supplying available micronutrients to plants

If some economical means were provided to oxidize the pyrites to sulfates

or some intermediate product of moderate solubility $, before applying to

the soilg their agricultural value could be better recognized. The

sulfates of iroB9 manganeseg zincs and copper generally have certain '

water-soluble characteristics that make them available to plants. Cer­

tain oxidized pyrites have been demonstrated to be of agricultural

2

importance when applied to soils or to plants where deficiency Symptoms ' are found, - .. • . V

, The Shattuck Denn Mining Company reacted the tailings from the

Iron King Mine Ca Xead^zine mine) at Humboltg Arizonag with sulfuric

•acid and heat treatments in an attempt to make certain elements more

soluble and available for further mineralization by the biological

action of the soil. It was hoped that by using controlled chemical

reactions8 an eeohomical process could be developed to make a product

that could meet the needs of agriculture for certain micronutrients %

the most prominent of which would be iron, An investigation 8 therefore *

was undertaken to determine the iron availability to plants of different

reacted products of mine tailings from the Iron King Mine 8 Humboltg

Arizona,'' ■ . ' VV - ' / .

LITERATURE REVIEW 1

Creasey (40), while with the U. S. Geological Survey, made a

study of the Iron King Mine. He stated that production began at the

Iron King Mine in 1906 from the oxide ores. Mining activities eeased

in 1907 and; except during World War I, the mine remained inactive

until 1936, when production was resumed and continued to date.

In the Iron King Mine and adjacent areas, faults and a pro­

nounced foliation are the dominant structural features,;• The area is .

underlain by the pre-Cambrian Yavapai schist, which, contains beds of

conglomerate,- The strike of the altered shear zone is about N25° E

and is parallel to the foliation^ There were two periods of shearing

and mineralization. The first period localized the early minerals

characterizing the hydrothermal alteration of the hanging wall. The

second period breceiated the early mineralization and facilitated the

introduction of ore forming minerals. The mineralizing processes were

sericitization, silicifieation, pyritization, and the introduction of

carbonates. The deposit is a massive sulfide replacement of schist

along well-defined veins which have sharp contacts with the wall rock.

The principal minerals in the veins are:

Byrihe Iron disulphide FeSg

Arsenopyrite Sulpharsenide FeAsS

4

ChaXeopyrite • Copper-irom sulphide CuFeS2

Sphalerite Zinc sulphide ZnS

Tennantite Sulphcopper-arsexiide SCugS 6 AsgSg

Galena Lead sulphide PbS

Gold . ■ ; . Au

Quartz : i,; V . ; . ' sio2 .

The major ore minerals are sphalerite and galena from which zinc and

lead are extracted* The bulk flotation method is used to extract the

lead and zinc and more recently copper» The gold and silver are being

extracted by the cyanide process => These noble metals are sufficient

to make the mining operation profitable at the present low market

value of zinee ; - : ; ■ ;

The value of pyrite or other sulfides for soil conditioning

and plant nutrition depends on the rate it oxidizes to the sulfate form

while in the soil0 In 19309 Smith (34) showed that copper-bearing

pyrites oxidized at widely different rates depending on their source

when placed in soilso' Most pyrites yielded only traces of sulfate when

incubated for six weeks e McGeorge and Breeze ale (27) j, who compared the

rate of oxidation of elemental sulfurg,, pyrrhotite 8 and pyrite from

several sourcess reported that pyrrhotite and sulfur dxidized to sulfate

very rapidly in the soil at closely equivalent rates and suffibient ly

rapid.to be effective as soil conditionerso The oxidation of pyrite

was very slow and varied with differant sources <> Copiapite 9 a naturally

occurring Oxidation product of pyrite 3 also appeared to have "soil

condltionihg" value. McGeorges Abbotts and Breazeale (26) concluded

5

in another report that waste 'pyrite has little or no “soil eonditioning", ,

value9 whereas pyrrhotite and copiapite. have conditioning values some­

what equivalent to iron sulfatea

Olson (30) worked with iron oxides and the correction of iron

chlorosis in plants* In his 1948 experiment 9 he used three soils$ two

of which were calcareous and under greenhouse eon di tion s0 Olson 9 over

a span of two seasons$ used Early Sumac sorghum to determine the influ­

ence of different iron1 oxide- forms .and acidifying agents for the correc­

tion of chlorosiss The pH values of the soils were 8o09 7o5s and 609

with a calcium carbonate content of 1*0, 0«5g and 0' percent$ respectivelye

The soil treatments and rates of application were as followsi ferrous

sulfate at 590 pounds per acre| sulfur at four tons per acre| sulfuric

, acid9 iron oxides (hematite 9 magnetite 9 and. limmite) at three: to four

thousand pounds per acres A control pot was included and all treatments

were triplicated0' Results of the experiment are given below6 ■

Yield of tops in Total iron inin ppm .

None . 2306 470

Sulfur' ■ : ' /; - 333 : ' V .

Ferrous sulfate 26a4 405

Ma#itite : ' r 2701 459

Limonite - 27*8 566 ■■

Hematite 3004 378

hgSOjj. ■ ■ ■■ ■■ , • ■ '' ’.'-"V : 34a5 : , - 312 ' . 'V . :• y:

Soil treatment leaves

The addition of sulfur, and sulfwic acid lowerid the pH value from 8 0 0

to 5a8 and B a 6 in two of the soils0 In all other treatments and the

third soil$ the pH remained tinehangedo In previous work9 Olson* (29)

f omd that the amount and type of iron oxide was important in iron avail­

ability | however g he was not able to stibstantiate it in this experiments

He found that there was no decrease in chlorosis or increase in iron

uptake by the sorghum plant when iron oxides were applied to the soils

..However$, in the sulfur experiment j chlorophyll content increased9 but

there was no corresponding increase in iron absorptions

Chlorosis is an abnormal condition of plants in which the chloro­

phyll fails to form or is formed in only small amounts0 The color of

the leaves are yellow or almost white? Chlorosis is usually caused by

a deficiency of one or more nutrients? nitrogen9 magnesiums copper9

manganese9 and irOne The symptoms of iron deficiency is the yellowing

of the y o m g leaves« This yellowing begins suddenly because iron $ unlike :

other nutrients such as nitrogen and magnesium^ is not translocated from

the older leaves.to the younger leaves to alter the deficiency patterne

The chlorosis affects the interveinal areas of the leaf 9 Tdiile the veins

renain a darker color and are often relatively greeno Iron is required

in the synthesis of chlorophyll and is an essential prosthetic group of

various enzymese Iron is not bound directly to the protein$ but becomes

a part of a more complex iron porphyrin molecule„ Iron porphyrin enzymes

act as catalysts which make, up essential links in the process of respira-

7

Iron deficiencies generally occur in arid and semiarid regions

where the soils contain accumuiations of lime at1 some .point in the pro­

file. When the zone of lime accumulation occurs within the depth of

high-root concentration, iron may be an important factor in plant

nutrition.

Boischot et al. (6) found that iron was fixed by calcareous soils

where iron was precipitated and was not readily redissolved in the soil

solution. Thorne and Wallace (38) found that the role of lime-inducing

chlorosis is complicated by the fact that there is no consistent difference

in the lime content Of soils where plants are green and where they are

chlorotie, even though such differences may exist within limited areas.

In other words, it was found that there were no specific pH values at

which a plant will suffer an iron deficiency due to iron unavailability.

A number of studies by Thorne (4,37), Haas (15), and Burgess and

Pohlman (7) indicate that chlorosis and the pH values of high-lime soils

are related to soil texture, profile characteristics, and moisture content.

Thorne (5,37) states that the pH values of calcareous soils increase as the

amount of moisture increases. He believes this to be a result of reduction

of COg pressure and a.dilutipa of salts in the soil solution which permits

greater hydrolysis of the calcium clay.

Elements. other: than iron are also made unavailable to plants by

high pH values. Copper, manganese, and zinc are.examples. Truog (39)

designed a diagram, Figure 1, to illustrate the "general trend Of rela­

tion of soil reaction (pH) and associated factors to the availability

- " ■■ 8 ■

ef plant nutrient el@aentiSo Each element is . represented by a band as :

labeled. The width of the band at any particular pH value indicates

the relative favbrableness Of this pH value and' associated factors to

the presence of the elements in question in readily available form

(the wider the band the more favorable the influence)$ but not to actual

’ amounts necessarily present;, this being influenced by other factors,

such as cropping and fertilization," Antipov-Karataev (1) found that

in soil containing montmorilIonite clays with low pH values, copper was

fixed in an unavailable form much more rigidly than the calcium and mag­

nesium, whereas in the case of nonmontmorillonite clays the rigidity of

absorption was reversed, _ . . .■

Perhaps the major problem causing iron chlorosis is the form in

which iron is found in the soil. In other wordsj some forms of iron are

more available to the plant than other forms, Kliman (19). found that •

iron can be,absorbed by plants in only the ferrous state. The results

of research done in this area by Thorne and Wallace (38) support the

concept that ferrous iron is of fundamental importance in plant nutri­

tion and is necessary for the formation Of chlorophyll. They belieVed

that no large quantities of ferrous iron can exist for any period of

time in calcareous soils under common moisture conditions and suggested

the following reaction that may take place in high-lime soils.

- : '■ ; : Pe^** CaG0 3 ^ F e G 0 3 > ca** \ ‘ Y"

4PeC03 4- 02 Ca (HG03)2*-^2Fe2'e (CQ3)3 > Ca (OH)^

Fe2 (C03)3 =f SHgO — ^FegO'S 4- 3H2GO3

EXTREMEACIDITY

STRONGacidity

SLIGHTacidity A

SLIGHT-KALINITY

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Figure 1. ’’Diagram illustrating general trend of relation of soil reaction (pH) and associated factors to the availability of plant nutrient elem ents.” After Truog (39).

CO

They , fomd that iron: was more easily reduced in soils produeing healthy

green plants than in those producing ehloritie plants* Tryog C39)g

workiag on the uptake of iron,' reported that when soil'pH values fall

below 6*5® iron tends to exist in the ferrous state and is soluble in :

earbmie aeidg, and hence readily available => Under strong aeidityg fer­

ric oxides are reduced to ferrous in quantities enough to be available

to plant nutrition* 'He states further that'at-pH values above 6„5g, the

soluble ferrous is oxidized tb the ferric state which is so insoluble

under neutral and alkaline ednditions that iron defieiehey in a plant

deeurs* Truog also found that copper9 manganeseg and zinc are much like

iron in that they become unavailable , at high pH values<> Many others have

studied manganese9 copper, and zinc uptake as a function of pH values*

For example, Bambergs (2) and Bambergs and Balode (3>s in experimenting

with sandy, salty, and peaty soils, found that the absorption of copper,

manganese, and zinc is mostly a function of pH values* They stated that

the levels of these elements in the plant increased, and the levels of

molybdenum decreased with decreasing pH values* However, Burstrom and

Boratynski (8) found that with both copper and manganese, absorption

increased with decreasing acidity over the entire pH range of 3*5 to 7*0

and was greater in the more concentrated than the more dilute treatments*

There has been considerable research undertaken in the field of

soil treatment of calcareous soils to make nutrient cations more avail­

able to the plant* Olson (30) stated that the amount of iron dissolved

in the soil solution tended to increase rapidly with a decrease in pH .

values in soils more acid than 6*5* This tends to indicate that there is a difference in the amount or form of iron in acid soils as compared

11

to neutral or alkaline soils. Olson also found that when soils were

acidified, with sulfuric acid, they showed definite differences in the

amount of iron in solution at any given pH value, and the differences

were proportional to the free iron oxide content of the soils. It is

Olson8s opinion that the soil pH value is not the only factor determin­

ing the solubility of iron in the soils and the ability of the soils

to supply iron to plants. At least one other factor is the amount of

free iron oxide in the soil.

Sulfur plays two important roles in agriculture: as a plant

nutrient and. an acidulating agent. However, it is generally true that

in calcareous soils, sulfur is not a limiting factor in plant nutrition.

In Ariaona, sulfate is generally present in most irrigation

waters and is found in arid and semiarid soils primarily as calcium

suifafe. Sulfur and sulfur products are generally used as soil condi­

tioners in arid regions of southwestern United States.

MeGeotge (23) 'and McGeorge and Green (28) have done a consider­

able amount of work with sulfur and its influence on crops and soils. In

their work on the oxidation of sulfur, they stated that the conversion of

sulfur to sulfuric acid in the soil is brought about by either chemical

or biological means. 'The biological oxidation'of'sulfur'in the soils is

carried out chiefly by the genus Thiobacillus and is of much greater

importance than'the chemical transformation. Thorne (37) of Utah gave

the following reaction for the biological oxidation of sulfur to sulfuric

: . . / ■ -

2S-Kh 2H20 ^ 302 - o 2H2S04

. ■' ■ - ■' ■ v : - ' . 12

The ehemical reaction of sulfuric acid on calcareous soils s

. H2S0^ t CaCOg^CaSO^ + H20 t C02

HgSO^ t 2CaC0g=±CaS0y + Ca (HQ0g)2

' MoGeorge and Green (28) found no evidence of sulfur deficiencies

in crops of Arizdna® They stated that the irrigation waters are well

supplied with sulphates and that there are extensive deposits of gypsumg,

sulphide oreSg and other sources of sulfur in the stateB According to

their experimentat ion $ they eonelude d that the chemical activity of

elemental sulfur increased with the decrease in the particle size of

sulfuro They-found that sulfura at the rate of one ton per acre, oxidized

very rapidly in two or three weeks at optimum moisture and temperature $

whereas heavy:; applications of two to ten tons per acre have a more pro­

longed and pronounced effect' upon the soil $ causing a decrease in pH

values and an increase - in the solubility of calcium$ sulphates g potassium®

and phosphates o. In later work MeGeorge (24), using barley seedlings as

a test plant8 found no evidence that acidifying agents helped in iron

uptake by the plant o Seedlings grown in high-lime soils showed an increase

in iron content of plant tops when sulfur and sulfur-manure uere mixed

with the soilo However® there was no corresponding increase in iron

uptake with increasing, applications of sulfur and sulfur-manure e He con?

eluded that his data were not consistent and that iron uptake was not

definitely influenced one way or the other by the sulfur treatments used®

He did find® however® that copper uptake was increased by additions of

sulfuro MeGeorge (25) found that in a highly calcareous soil the alka-

linity and excess uptake of calcium contribute; to a reduced iron activity

; ■ ■■ ■■ .■/- \ 13

in the roots and aerial, papts of. the plant® He stated that if ample

adtiye iron is maintained in the plant$ excess calcium uptake does not

cause chlorosis0 This can be accomplished by reducing the pH values

of the zone of contact between the roots and the soil; however9 soil

in which linra^indueed chlorosis occurs contains: too much CaCOg to reduce

economically the pH value throughout the entire.,soil mass* , In order to

circumvent this problema MeGeorge suggested applying the sulfur in bands

where a zone of low pH values can be maintained^ To be successful® it

is of great importance■that a sufficient root population be in- contact

with the bands of sulfur0 He stated that soil conditions such as poor

aeration $.poor drainage $ or- any soil condition which will result in

restriction of root respiration may be the initial cause of plant ehloro-

sise ' , - - : ' . ■ ; : : -v' -'Another factor of chlorosis that must be taken, into consideration

is the relationship of one nutrient upon the others Sommers and Shive

(35) found that high ratios of manganese, to iron induced chlorosis by

Oxidizing iron to the. more insoluble ferric forms0 Rediske and Biddulph

(31) reported that phbsphorus exerted a marked negative influence cm the

absorption and utilization of iron* Brown et al0 (10) supported this

belief but found that phosphorus and copper -were much more effective in

causing iron chlorosis if applied together than if either element was

applied alone0 Bambergs (2 > 9 working with acid soils j, found that super­

phosphate fertilizers in excess lowered the coppers zinc, and manganese

uptake in the plant9 whereas nitrate fertilizers had the opposite effect*

The work of Shkol0nik and Makaroua (33) revealed a strong .antagonism

between ' copper' and Iron*," Their test plants .were flax and sunflowers in

: hydroponic eulttireSo The plants developed chlorosis when a low iron :

level was maintained relative to the boppeh present6 With an increase

in iron$ relative to copper9 normal;development occurredo Brown and .

Holms. (9) found that available copper supply in the growth media seemed

to have a marked effect upon the absorption and utilization of iron by

corn® Analysis by Brown showed that the iron accumulated throughout

the copper deficient plant8 especially in the nodes® and the addition

of copper to the soil decreased copper absorption® ’

, The susceptibility of plants to chlorosis varies from species to

species and varieties within a species as was found by Haume and Bouat

(22) and Bbown and Holmes (9)® ,

A summary of the major factors knownto cause iron chlorosis

and the known treatment for iron chlorosis followss

1® The amounts of CaCO. in the soil and the pH value deter­

mine iron chlorosis® However9 there is nd consistent

amount of CaCOg of pH value at which a plant will suffer

irpn chlorosiso • , .; - ■. , V , "-'i . :

2 ® The kfnd and variety of plant o’

3® The amount of moisture in the,soil$ aeration, soil texture3

and profile characteristics are important in iron chlorosis®

4® IrOn oxides and sulfides are of little value in correcting

"'v;/ ' ;yi'>':ifon:::deficieBoies® . ■,-.' ; ' f _ : .

5o Iron in the ferrous form is best suited for plant uptake®

: 6® Sulfur added tO the soil in modest amounts will not always

lower the pH value of the soil®

15

No correlation between sulfur and iron uptake„

No correlation between sulfur applied and iron uptake.

Some elements interfere, with the uptake of iron.

EXPERIMENTAL MATERIALS AND METHODS

Preparation of Mine Tailing Products"*'

In order to oxidize the pyrite tailings to a more available form„

two methods were used: oxidation by heat and reaction with sulfuric acid*•

The tailings were placed in a hdrmal household mixer with a known amount

of sulfuric acid and mixed thoroughlyThe material was then poured onto

drying pans and placed in a drying oven® After the reacted tailings Were

thoroughly dry3 the material was broken up into pellets and screened to

Wise® Various rates9 pounds per tpn® of sulfuric acid were used® The "T"

(T~800) designates tailings and the number following is the number of

pounds of acid per ton of tailings® ■ In one of the treatments8 the iron

in the tailings was concentrated and then reacted with sulfuric acid at ,

the rate of 400 pounds per-ton of concentrate.and heated t o .350° F® This

concentrate: was designated R-350-P-400® Some of the reacted tailings

were treated with ammonium gas®, These.products are distinguished from ■

the others by addition of NH^ to, the symbol9 i6e®g T- 2 0 0 NH^c The per­

cent of nitrogen in these tailings varies from Qe40 to 2®82' percent® .

Some of the characteristics of these faili.ngs. may be found in Table 1®

The mine tailing products were prepared by Mh® Galen Clevenger of the Shattuck Denn Mining Co® a t ' the.Iron King Mine Laboratory g .Rumbolt$,■ ■:Arizona®'; :r:'... V"

16

fable Is -The amount of total and water-soluble if©n$ copper® and sulfur found in reacted mine tailings® raw mine tailin gs ® two commercial products ® and Gila fine sandy loam*

Materials analyzed Total Iron ^

TotalCopper-^

H20-SoioIron^

Gila fine sandy loam Raw mine tailin gs T-200T-200MH •:T=>400 3

T-400HH3'T-500T-SOONH.T-600 3

T-800T-8 OONH3 , R-=350=P-=400 Sulfasoil3

%-3*0 5,0 6 «'H3.

lonate5;

5,3

6o0 5,0

20,5 - 42 oO4

%0,0040,0570,060

0,055 0,046 : 0,134

0,1704

%0,004 0,004 0 , 7000 , 1 6 0

1,400 1,000 1,700 0,470 2,100 2 , 1 0 0

1,470 2,100 5,600

lOeOOO4

HgO-Sol©Copper^

%0,000025

0,00510,00270,0191'

TotalNitrogen^-

%0,01trace

0,40 . .

0,61 :

2,51

2.83

Average of three replicates.

Total sulfur 2,34 percent® HgO-soluble sulfur 0,079 percent.

Not determined.

Guaranteed by company,

3 Trade; names, ,

•IT

• : ' ' ■ ■ ■ ■ ' : 1 8

Some Chemical Characteristics of:the TailingProducts Used " : •

In order to properly evaluate the iron and copper availability

of the reacted tailings to the plantsj, -a chemical analysis was made on

these products and the soil materials Total iron g water-soluble iron,

and total copper were determinedo The results are found in Table la

The nitrogen content of ammonia ted reacted mine tailing products

range from 0640 to 2 082 percent in four different products0 Apparently,

the greater the amount of sulfuric acid used, the greater was the amount

of ammonium ion retained* No doubt ammonium sulfate formed 'as the ammo­

nium' gas" .reacted.with the unspent sulfuric acid used on the tailings®

Ammondating the products substantially reduced the amount of water-soluble

iron and copper found in the extracts, probably by reducing the amount

of free sulfuric acid that could react with these elements and by raising

the pH value of the first product® Data presented in Table 1 also indi­

cate that the two competitive commercial products— Sulfasoil and donate--

have roughly 2 to 5 times$ respectively9 the amount of water-soluble iron

as the reacted tailings product■““TrSOO® The reacted mine tailings product,

T-SOO, had the most water-soluble iron, 2 sl percent, of all the reacted

tailings® The water-soluble iron and copper decreases with ammoniation

because the ammoniatioh ion increases the pH values and causes the iron

and copper to precipitate rather than remaining in solution® Moreover,"

the total iron content of the mine tailings also was found to be very low—

between 4 and 6 percent Iron® . .

The water-soluble and total irons copper’s, and sulfur of the Gila

soil material was determined also for comparative purposes* The water-

soluble iron and copper content 9 as may be seen in Table 2 9 are low

epmpared-with -the test materials* .

Some Chemical Characteristics of the Gila Soil Material Used

' , (isssaass^nsssca ■ •

' " The Gila fine sandy loam material from field ’’T” on the Univer­

sity of Arizona Campbell Avenue Farm in Tucson was taken from the plowed

zaae 'i The field is part of the flood plain of the Rillito river* Some

characteristics of this soil are shown in Table 2* The data show the

soil to be slightly alkalines moderately high in soluble salts& and low

in sodium* It is well supplied with available nitrogen and phosphorus

for plant growth„ The Gila series "occurs on flood plains and low

terraces throughout the southwestern arid regions,M •‘They are distinctly

calcareous with the lime mainly disseminatedg although fine thread-like

segregations are visible in places,M (16) - '

Stanford-DeMent Seedling Cultufe Technique

To determine the availability to plants of the iron in certain "

reacted products9 the Stanford^DeMdntt technique (36) was used®

General Treatment of the Sand- ' . . . — T . ' ' ' ■ ' ■ '

Silica sand was washed to extract the water and acid soluble

iron® The sand from the Ottawa Silica Company$ Illinois9 was soaked in

^ From the Ottawa Silica Co® 8 Ottawa$ 111® Flint shot grade®

20

Table 2. Some chemical characteristics of Gila fine sandy loam sample used in the greenhouse experiment involving the absorption of

, iron from reacted mine tailing materials by sorghum0 '

Soil 8 Loca- Material 8 tion

Gila fine 0 of A sandy farmloam at

Tucson

e1 pH ’ Value

5 7o 6

Soluble salt V N03"N0

trppm2590

ppm

54

P0U"P. i

ppm

38

8

'Sodium Indica*”

9 tion-®-/iTo e d t a

2.53

0. S. Department of Agriculture Giro. 982.

■ ■ ■ ; ■ ; ■ ,; ■■■ , ' ;;; 2 1 ; .

IN. HCl for 24 hours6 The HC1 was removed by washing with watere A second

washing with IN HCl was again added for another 24 hours and the sand was

then washed with tap water until a pH value of 6.5 to f05 was obtained.

The sand was sucked dry of free water a&d leaehed with deionized water. .

It was.then-completely air dried. . ' .V'

General Proeedure Qsed - '■ '

The bottom of a cottage cheese carton was removed and nested in a

second carton with the bottom intact. Seven hundred and seventy grams of

dried9 acid-washed sand was placed in each carton. Fifty seeds of Plains­

man or Kafir sorghum were planted one-half inch beneath the surface» The

containers were brought up to the weight of 860 gnu with deionized water. ,,

This represents about the field water-holding capacity of the sand. The

cartons , were -covered to keep out sunlight0 Each day the cartons were

brought up.to a weight of 860 gnu with more deionised water. Nutrient

solution was made up according to the procedure developed by HOagland and

Amen (17) o Three days after plantings 25, ml. of iron-free nutrient solu­

tion were added to each carton« Six days after planting^ an additional

25 ml. were added to each Container and the plants were uncovered. Eleven

days after plantings the outside.box was cut away and the plants were

transferred to a carton containing 330 gm. of soil material from the sur­

face 6 inches of a Gila fine sandy loam. Each contained either 2$ 4$, or

6 gm, of the test material thoroughly mixed, into the soils The soil mate­

rial had been previously sieved to remove roots9 manure9 rocks9 and other

foreign Objects, Before transferring,, 10 ml0. of nitrogen and phosphorus

solution were added to the soil. The amount of N and P added was based

22

on 50 pounds of P per acre and 300 pounds of N per acre, (An acre-six

inches of soil weighs approximately two million pounds,) Each carton

was brought up to a weight of 1,200 gm. with water. This represents

the weight of the sand, soil,-and the field-moisture-holding capacity, - -

of the sand and the soil. Eight days after transferring, the plant

tops were harvested, dried, and weighed. Drying was at 60® C, for a

three-day period. Total iron analyses were made on each plant sample.

This test was carried out during.the months of June, July, and August,

1961. Z ■ ' ; , ' . ■ "' • : ■ .

Test to Determine the Best Soil Material for Experiment

To determine the best soil material suitable for research, 21

Stanford-DeHent test pots were set up; 12 pots were planted with Plains­

man seed, 5 with soybeans, and 4 with Kafir seed. Three soil samples

were taken from three different locations from Chino Valley, Arizona,

on the advice of the local county agent. An attempt was made to find

the same soil type under varying agricultural situations, i.e., one from

a virgin area, another from an area cultivated to corn and a third from

an area cultivated to alfalfa, A fourth soil sample was obtained from

the Del Rio area near Prescott, Arizona, It had a very high content of

calcium carbonate. No fertilizers were added to the soil samples. Eight

days after transferring, the plants showed no consistent pattern of

chlorosis. However, after harvesting the sorghum the new regrowth gen­

erally showed strong to severe chlorosis. The soybeans showed no iron

chlorosis before or after harvesting. The plants did show modest signs

of a potassium and phosphorus deficiency. The conclusion reached from

23

this experiment was that these soils did not suit our needs6 Another

soil sample"“Gila fine sandy loam obtained from the plowed zone$ the

surfaee 6 inches— was used because it was known to induce iron deficiency

symptoms in. sorghum. ’ ,

Experiment to Determine Iron Release from the Ottawa Quartz SandThree Stanford-DeMenh pots using polyethylene beads $ in place

of the acid^washed sandj, were used to determine the relative release of •

iron from the sand* Kafir, Plainsman, and soybean seeds were planted

in the three pots* The results of the polyethylene vs* sand test showed

conclusively that the plants obtained considerable amounts of iron from

the quartz sand despite the extensive washing with HC1 previously

described* - ..-'■■■■■ ' ■ 1 -

Experiment t° Determine Time Contact Between Plant Roots and the Soil

Using, the Stenford«DeMeat technique 9 eight pots were set up to

determine the most suitable time for contact between the plant roots

and the products to be tested* At the time of transfer, 6 gm* of test

product R-350-P-400 was thoroughly mixed with the soil of four pots*

The remaining four pots received no test product* Two days after con­

tacting the plant roots with the soil, two. plants— one with and one

without R-350-Pr#0— were harvested* An iron analysis was made on. the

dried plant material to determine the amount of iron taken up by the

plants* After four days, two more plants were harvested and a similar

. ' analysis was made*- On the eighth and twelfth days two more plants were

, analyzed for total iron uptake* From the information gathered, on the

: basis of the least amount of time to the greatest amount of iron uptake g ''

the eight-day period was selected as the most suitable root-soi1 contact

timee '■ . : ' y - ' ■ ■, ' ‘ . ... ■ : "

Determination of the Normal Field Water-Holding Capacity of the Soil

■ A definite a m p m t 9 460 gmS 9 of oven-dried-Gila fine sandy loam

material was weighed out and placed in a Buchner funnel. The soil was

super-saturated with deionized water. After the gravitational water

had completely drained from the soils, the sample was weighed^ The fig­

ure obtained by subtracting the dry weight from the wet weight was used

as the normal field water-holding capacity of the soil.

Determination of the Amount of the Test Product to be Applied to the Soil

The number of grams of test product to be used in the experiment

was determined from the amount of water-soluble iron:it contained rather

than from an economical standpoint. It must be understood that the '

Stahford-DeMent technique is utilized solely as, an indication of possible

trends that one might expect to find in the field. In no ease is an

attempt made to suggest that the amount of test material applied to the

individual pots inthegreenhousecan, be used directly as recommendations ,

.for field practice. Because previous investigetors-have found that micro-

nutrient sources can be roughly evaluated on- a basis of water-soluble

. nutrient elements 8 this experiment was designed to take advantage of '

information regarding this characteristice Rates of application were

selected as 2 $./ 4g and- 6 gm0 of the test product. This range of applica­

tion insured an amount of 2 0 pounds of water-soluble iron per acre-six .

inches be supplied frem each product at at least one level of applica­

tion* It has been fotmd that fon most plants this level is sufficient

to prevent ifon deficiency symptoms in the plants0.

Even though the nates of application appear quite high when cal­

culated on an acre six-inches of soil basis9 it was hoped that the iron

supply in g-=power of the products would be tevealed in the proper relation­

ship of one to the other* ThuSg the test would serve to distinguish

between the poorest and the best products with respect to their ability

to supply available iron to plantSo

The test materials used in the Stanford-DeMent technique experi­

ment were as follows; untreated tailings s, „T-200$, T-200MHg» 'T-5Q6,

T-SOONHgg, T™800s T-SOONHgg, R-350-P-4009 and two commercial fertilizers—

Sulfasoil^ and lonate'K A test pot with Soil alone was used as a control

The rate of application was 2® i V and 6 gme of test material* All treat­

ments were replicated three times*

Chemical Methods Used \ : :

In determining the amount of•; sulfur in the soil and plant material®

Shawls.(32) indirect flame photometric method was used*

Copper analysis made on the soil® reacted tailings® and plant

material followed the procedure outlined by Cheng and Bray (11)*

All iron determinations followed the orthophenanthroline method

outlined by Jackson (18) and modified by Maier (21). The modifications

'are as - follows; ' : ; v ' -

1 Trade naims*

• ^ " Y ' . . ' ■ ■ ■ ■■ ' ; ' ' 2 6

To a plant or soil sample aliquot s not more than 10 rnlo .eontaiaa.ng 0--5 0 mierograras Fe $ whose residue has been taken, tp in 0ol HNOg adds •

1® Ten ml® of 1 HAc ~ 1 KfaAc buffer (pH 4®5) g mix

2® One ml® 10% MHgOH „ HC1 soln0 3 mix

■ . : .v 3® Three ml® of 0o20% orthophenanthroline a mix

Make .up to"25 ml® volume0 The pH should be maintained at ' -about 4®0® , ; - . . ..

The transmittancy. was read against water at 500 mjx8 eornr pared with a standard eurve made in the- same manner "aS above 9 using 0™50: jig® Fe per 25 ml® '

The plant material was oxidized with a mixture of eoncentrated

nitric aeid8 water9 and perchloric acid® References for this procedure

are : Gieseking et-- al® (14)4 Earley (13) 9' and Maier (20)®

' . i ; Method of Determining Water-Soluble Iron» Copper9

• and Sulfur in the Soil and Reacted Mine Tailings

The amorat of water-soluble iron, copper9 and sulfur in the soil

and reacted mine failings was found by placing 5 gm® of the material in

an Erlenmyer.flask with 200 ml® of deionized water and placing it on a

Burrell wrist-aetion shaker at half speed for one hour® The solution

was then filtered to bbtaih a ; clear filtrate for the analyses® For. sul™

fur, a k n o w amount of the filtrate was taken down to dryness and treated apeording to Shaw (32)® For total analyses9 the perchloric method was

used on a one-half gm®. sample.® The results may be found in Table 1®

27

Tailings

In order to determine further the availability and effect upon

both the soil and plants from applications of reaeted raine tailings g,

the Usual greenhouse pot test was employed0

The soil material used was the same as that used in the Stanford-

DeMent Teehnique— Gila fine sandy loam.. Like the short-term method, the soil, was sieved and air dried.

The materials tested in this experiment were: Sulfasoil, ferrous

sulfate 9 T-800, ..T-SOONH ', R-350-P-400 9 sulfur 9 T-8 Q0 plus sulfur, T-SOOMg

plus sulfurg, and a control of no treatment 0 All treatments were repli­

cate d. three times. Clean porcelain pots were used in the experiment.

. Each pot contained 2,200 gm. of soil. The test materials were mixed

thoroughly in the soil at the rate of one ton per acre or 2 . 2 gnu in the

2,200 gm. of soil material and the total mixture placed in the pot. The

only exceptions to the rate of application were the T-800 plus sulfur

and the T-SOONH^ plus sulfur. In this case, 2.2 gm. of. sulfur were mixed

with,2o2 gm0 of the tailings and then applied to the soil material. The

sulfur was in.the elemental powered-form. A polyethylene tube $ with an .

inside diameter of five-eighths Of an inch and having numerous holes

drilled into it was placed in the center of each pot. These were used

to facilitate watering, aeration, and to prevent damp-off in the seed­ling stage. Fifty Kafir sorghum seeds were powdered with " O r t h o c i d e .

a captan fungicide3 and planted a quarter of ah indi deep. The pots

were watered to the weights representing about 80 percent field water-

holding capacity with deionized water. Nutrient solution of N and P,

Greenhouse Pot-Test Technique to Study Reaeted Mine

28

at the rate of 300 pounds per acre and 50 pounds per acre3 respectively$

was added to each pot® "Orthocide” was sprinkled over, the surface of

the.soil to prevent damp-offo Vermiculite was placed over the soil to

keep the surface soil moist® The pots were covered to exclude the sun­

light® The cover was removed within five to seven days®. The seeds were

planted on October 5 and the plants harvested on November 138 1961®

From the tiins of uncoveringthe pots were watered daily to about 90 percent:

field water-holding capacity® For statistical analysis9 a random design

was used® After harvestings, the plant material was placed in individual

beakers and put into a drying oven for three days at 60° C® The plant

material was weighed and an iron and copper analyses were made®

Greenhouse Pot-Test Technique to Study the Sulfur Effect on the Soil and Plants ,

There were two large pot experiments carried out to determine the

effect of sulfur on the soil and the uptake of iron and copper®

The procedure and methods used in these two experiments are the,

same as those used in the-previous experiments, except for the materials

tested® The materials tested and rate of application were as follows:

MhSO^ (at the rate of 25 pounds of sulfur per acre or 0,15 gm®)$ F e ^ S O ^ g

(at the rate of One ton per acre of 2 ® 2 gm®); K^SO^ (at the rate of 25

pounds per acre or 0®13 gm®)i and 0 ®1 $ 0® 4, 0® 8 $ 1®6 9 and 2 ® 0 gm® of pow­

dered .elemental sulfur® Seventy-five seeds we're planted on January 1 1 %

and two weeks later thinned to 50 plants® They were harvested on Febru- ' ;

ary 26$, 1962® In the second experiment*.■ ; seeds were planted on Febru­

ary 16 9 thinned to 50 plants9 and harvested on April 11® The methods

were the same9 except in this experiment the pots were watered to above

field wafer-holding capacity and then allowed to reach temporary wilting

point before, again watering to field capacity» In both experiments 9

ireo g copperg and sulfur analyses were made on the plant material0 : ‘, -

RESULTS AND DISCUSSION

;; . V'' , Stanford-DeMent Test ; • -

The advantage of using the.Stanfbrd-DeMent seedling culture

technique, is that many different products can be evaluated in a short

period of timea A high absorption stress is placed on the soil and

the test products by the large number of roots per unit volume of

niaterialo This intense mat of roots provides ah ideal environment to

determine the relative root-supplying power of the test products9

The results of the Stan ford™ DeMent,nutrient-availability test

using two varieties of. sorghum,, Plainsman and Kafir-9 as test crops

are given in Table 3« , The data are presented as an average of three

; .replicates of identleei treatmenfSa The experiment was not designed :

for statistical analysis 8 ibut rather for exploration 0 The different

treatments did not occur concurrently9 but were carried out over a

two-month period,, The greenhouse was entirely constructed by trans­

lucent fiberglass and during the heat of the day in the months of July

and August 8 the air conditioning unit was not always able to keep the

greenhouse at the most desirable temperature. According to the data

in Tables 3. and, Figures 2 8 3S- and 4S it is apparent that there was a

certain amount of variation in total dry weight of the sorghum tops8

but that these, variations were not correlated with, either kind of product

31

Table 3b A summary of the iron content and dry weight of plant material of two varieties of sorghum grown under greenhouse conditions in Gila fine sandy loam soil material treated with reacted mine

: : : t - v . : :: t a i l i n g s b \ : - ' v . t ;.' ,/ .. :

Materials . added

- : St ' ■ ■ , »e Rate ' 9 « applied «,

™ , —™'"=— ™- ■' ... “v"“Plainsman 9

r sorghpm* - Kafirsorghnm*

: »' y.' ; ' ' r r -■Iron s. Dry wt. V : Irongm®/pot gUlo/pOt jMg./pot gm./pot jUg. /pot

None none 0 9 618 185 . 0.715 225

None '■ , . ■ ': ': ,tidhe / , Ob 65 3 ' :177 ' 0.790 ' 195 :'Raw failings 2 0.653 ■ 217 0.549 165

4 0.627 206 , 0.560 1540.599 tv ,J71,:.. ' / . 0.348 1 0 2

T-200 ■ . 2 0.652 2 2 1 0.455 144..-4 0.552 175 0.500 133

6 0.638 207 0.445 1545T^2 0 0 NH3 t.;,: " 2 ’. • 0.636 189 0.531 2 0 1

0.620 • 190 . ■ 0.577 . . 177 : :v 6 0 . 6 8 8 , 243 0.463 151

T-500 2 ■ 6.718 291 0.494 191. . .■■■ 4 " ■ : 0.635 254 0.538 213

. 0.647 . : ■; 236 0.530 . 190T=-50QNH3 ' 2 •■■■'■ ■:

'■ 40.8160.810

296'' 1 245

0.7110.645

174198

• 6 0.800 283 0.753 : 290T-gdO v.v. ; - 0.537 .1V.242;' 0.305 :vl52;

■ ■ 4- ■ ': 0.497 ;; 259 , . , 0.425 143■ : 6 . 0.488 248 0.413 130

T-8Q0NH3 2 ' : . 0.670 223 0.447 1234 0.679 : 236 0.532 157

X ; : ' 6.705 ': \::245: . 6.491 166R-350-P-400 ' 2 6.626 225 0.560 144

4 0.638 227 0.480 144", i ' , 0.615 2 2 0 0.657 174

Sulfasoil', . t,:&^33,. 136:.. , , 0.527 168 ;V 4 ’ 0;639 ' , 227 0.487 149

0.578: 262 6.502 . 199lonate 0.551 ' • 235 ■ , 0.527 248

.z'V'V; ' ;4.;v ■/' V. 0.577 V . . . '278 I' 0.503 259; V : '>V::6 ;;': ■ 0.588: *■ • 4i8: 0.313 \ - 167 : ■

* Average of three replicates of identical treatments0.

400

o>

h- 3000 CL01 Ljj CL0 2 0 0

100

PLAINSMAN

KAFIR

CONTROL RAW T -2 0 0 T - 2 0 0 T - 5 0 0 T - 5 0 0 T - 8 0 0 T - 8 0 0 R-3 5 0 SULFA- 10NATETAILINGS NH3 NH3 NH3 P - 4 0 0 SOIL

Figure 2. Total uptake of iron found in Plainsman and Kafir sorghum tops grown in Gila fine sandy loam soilm aterial supplied with 2 gm. of reacted mine tailings using the Stanford-DeMent Technique.

a>K>

PLAINSMAN

KAFIR

h- 300

ll_ 2 0 0

CONTROL RAW T-2 0 0 T - 2 0 0 T - 5 0 0 T - 5 0 0 T - 8 0 0 T - 8 0 0 R -3 5 0 SULFA- 10NATE TAILINGS NH3 NH3 NH3 P - 4 0 0 SOIL

Figure 3. Total uptake of iron found in Plainsman and Kafir sorghum tops grown in Gila fine sandy loamso il m aterial supplied with 4 gm. of reacted mine tailings using the Stanford-DeMcnt Technique.

COCO

PLAINSMAN

KAFIR

|— 300

%

CONTROL RAW T - 2 0 0 T -2 0 0 T -5 0 0 T - 5 0 0 T - 8 0 0 T - 8 0 0 R -3 5 0 SULFA- I ON ATE TAILINGS NH3 NH3 NH3 P - 4 0 0 SOIL

Figure 4. Total uptake of iron found in Plainsman and Kafir sorghum tops grown in Gila fine sandy loam so ilm aterial supplied with 6 gm. of reacted mine tailings using the Stanford-DeMent Technique.

. : : ; - ' , 3 5

a 4 ded or the ainount of material added9 except where the raw tailingswere applied^ The highest rate of application — 6 gm* — of raw tailings appeared to interfere with maximum, growth as compared with less amounts or no tailings6 As this level is beyond the practical application$ these results have significance only from a fundamental knowledge stand­

point o ' - ' ' ' • ■ - -Iron absorption was calculated on a per-pot basis, rather than

on a go per gnu of dry weight basis9 since the main objective was to

measure the maximum amount of available iron taken up by the plants in

a given amount of tinte0 If iron was measured on a jxg<, per gnu dry weight

basis9 a misconception could easily result» For instance9 a nonchlorotic

plant showing good growth might have an iron content of 15 ^ge and a dry

weight of 5 gnu g whereas a ehlorotic and poorly developed plant might

have an iron content of 5 gg 0 and a dry weight of one gnu If iron absorp­

tion were measured oh j ge per gm0 of dry weight 9 the ehlorotic plmt. would

show 5 jj,gc per gnu of, dry weight* wher’eas the nonchlorotic plant would be

reported as having only 3 pg, per gm» of dry weight. It might be erron­eously concluded that the ehlorotic plant is the healthy plante

: The effect'sof ammoniation of the reacted tailings on the sorghum

plants was to increase the total dry weight produced in all but one of

the comparisons 0 There was a general trend towards an increase in iron

absorptioh in the ammoniated versus the nonammoniated reacted tailings*

but this was not consistent9 This would suggest* however* that nitrogen

could cause an increase in the total absorption df iron in these varieties

of sorghum as well as the growth of the plants^ The pyrite concentrate

(R-350-P-400) might have given better results had if been reacted with

■ more . than-' 400 „ :pQunds:>:.d£\.stil£tiric; .aei<$ .nei ton of eoneentmte. There

seems to be no correlation between iron absorption and the amount of

■ water-soluble: iron, found ‘In ,the;various reacted tailings. This, might ;

'be due tg'the :very low amount of'water-soluble;iron as well as to the. >

small differences in water-soluble iron content between the products.

Greenhouse Pot Test to Evaluate Reacted Tailings -

\ This test was used to evaluate’ the availability and release of '

iron to the plants over, a, longer period of time than is possible by the

Sanford-DeMent test.' The products were mixed into the soil material

at the' tate.- of one ton per' acre 'six inches. . - ' -

The results of* the pot test using Kafir sorghum as a test crop

for evaluating iron availability in the reacted tailing products are

shown in Table 4 and Figures 5, 6 ,, and 7 The data are averages of

three replicates of identical treatments. The experiment was designed

for statistical analysis. A completely random design was employed.

Statistically significant differences were found in dry weight of plant

materials, iron, and copper uptake into the plants, as a result of apply­

ing the various products to the woil. The "Duncan’s Multiple Range Test

(12) was used to test significant differences. Based on the criteria

shown in Table 5 no material, Sulfasoil and ferrous sulfate showed no

significaht differences, whereas significantly better results were

generally obtained with elemental sulfur and T-800 or T-8 OONH3 ^Sulfur.

The mine tailing materials were intermediate in this respect.

The Duncan test is designed to show that A is less significant

37

Table 4 0 A summary of the iron and coppei? content of Kafir sorghum . . grown under greenhouse conditions in Gila fine, sandy loam

•soil material treated with reacted mine tailings and sulfure

Materialstested Ra*® A sorghum applied » ,. «

: «

:"t- °f i fetalirontops

Control

Sulfasdil ' '. 1

Ferrous sulfate

T-80.0; ■ \

T-8G0NH3R-350-P-4G0

Sulfur

T-SOO and. sulfur

T-800NH3 and sulfur

gmo/pot

none

' Zol V ,:2 ol'; :

2.1 '

2 0 1

2 . 1

2 : 6 1 ' • , 2 .1 ." •

; 2*1:;'/: 2 , 1

m

1.65

I. 85

2.012 'ol2 ‘ >

2.17 '

3.19

3. 36

: 3.73

» Total s copper

jjtg./pot

122.22225.00

236.11

255,55

250.00

250.00

341.67

422.22

422.22

]Ag»/pot

15.00

13.90

17.78

/ 17,78"

17.22

22.78

32.22

40.00

41.11

&Average of three replicates of identical treatment.

PLA

NT

MA

TE

RIA

L

(DRY

W

EIG

HT

)-g

m.

CONTROL SULFA- Fe(S04) T - 8 0 0 T - 8 0 0 R - 3 5 0 SULFUR T - 8 0 0 T - 8 0 0SOIL - NH3 P- 4 0 0 SULFUR NH3 *

SULFURFigure 5. The dry weight of Kafir sorghum tops grown in Gila fine sandy loam so il m aterial receiving

various reacted mine tailing products, sulfur, iron sulfate, and Sulfasoil.

03CO

Cu

PER

PO

T-

g4 0

3 0

20

SULFA- CONTROL T - 8 0 0 T - 8 0 0 Fe(S04) R -3 5 0 SULFUR T - 8 0 0 T - 8 0 0SOIL NH P - 4 0 0 SULFUR NH3

SULFUR

Figure 6. Total uptalce of copper found in Kafir sorghum tops grown in Gila fine sandy loam so ilm aterial receiving reacted mine tailing products, sulfur, iron sulfate, and Sulfas oil*. COto

Fe PE

R P

OT

-/^

g

5 0 0

400

300

200

mo I Y77A V/A V/A V/A V/A V/A Y/A Y/A V/ACONTROL SULFA- Fe(S04) T - 8 0 0 R - 3 5 0 T - 8 0 0 SULFUR T - 8 0 0 T - 8 0 0

SOIL NH3 P- 4 0 0 SULFUR NH3SULFUR

Figure 7. Total uptake of iron found in Kafir sorghum tops grown in Gila fine sandy loam soil materialreceiving reacted mine tailing products, sulfur, iron sulfate, and Sulfasoil.

§

41

Table 5. Analysis of variance between treatments as indicated by Duncan0s Multiple Range Test of copper and iron uptake into Kafir sorghum plant tops, *

Materials : ' : Oven V dry Weight

/» ' 8 e Iron

o ( . ;■6 Copper8

Control ' ■ A v '^ , ' A .: . ; , ■ - .a ■. ■' ; ; '

Sulfasoil Ar \ B A

Ferrous sulfate a , B • • A

T-800 \ A B ' i- B A

T-800MH3 ■ A 3 : B , A

R-350”B-400 A B B A B

sulfur ■■ B : G; ' \ .. ; B C :

T“800 sulfur ' • ' : , G : ' c ■;-x’ 1 ' : c

T«800m3 Sulfur G c c

* Five percent level of significants was used.

. ;■ : ' • . 42 ' ;

than Bj and B is less significant than Co For example8 in the dry weight

comparisons9 sulfur is significantly different than the control* Sulfa-

soil* and ferrous sulfate* but not significantly different from Tr800, /

T—BQONHg 9 R-35O-P-40O 9 T—800 plus sulfur* and T=800NHg plus sulfur© How™

ever 9 T-800 plus sulfur is significantly different from R-350™P™400*

T-SOONHgs, and T-800„

The results of the greenhouse test indicate also that atmnoniatioh

of reacted tailings treated with 8 0 0 pounds of sulfuric acid increases .

plant growth and also increases the uptake, of iron and copper into the

plant© There seems to be no correlation between the amount of water-

soluble iron in the reacted tailings and the total iron found in the

plantSo Ferrous sulfate is wholly water-soluble* Sulfasoil; 5V6 percent* '

T-800: 2ol percent8 and T-8 OONH0 ; 1®5 percent water-solublee This would

indicate that9 in the case of sulfur and sulfur plus reacted failings*

the sulfur has some unknown effect on the availability of the micronutrients

of the soil for plant absorption © . However * it did not appear that the pH

value was affected by the sulfur since there was no difference in soil

paste pH values between the sulfur and nonsulfur treated soil© Table 6

shows that the pH values of the treated soils remained the same or changed

very little from the pretest pH value of 7o60 Therefore9 one can only

asSume that the sulfur reacted with the tailings or the iron and copper

in the soil in small micells or pockets to make iron and copper more avail­

able to the plants© These small pockets ate so small compared with the

soil mass that a paste pH value nullifies such' isolated condition®

43

Table 6a The p# v&lims @ soluble salts^ nitrate nitrogen9 availablephosphate $ and soluble sulfur found in Gila sandy loam soil material receiving various sulfur bearing soil amendments

, and cropped once to Kafir sorghunu

. ■ ' ' pH Value Materials of

. ; r . . Paste

; h 2°-v Soluble .} Salts*

t69 ■;

. 9

h2o-Soluble N03-N* ■

9 ,cv ; >■e Soluble ,»•■ poa -p*. »

, H2°“: ; , Solubleso4-s*

ppm ppm ppm ppm

Mbhe y " 7,6 ' \ 1960 y. 215-' ' - / ' 75 . 80

S u l f u r :: - . Va4 , ■ .2940 . 140 92 2638

Ferrous■ -sulfate ,,: % ■■'.,■■7*6,.' : ;.,;.:;3360^'': 290 . 82 . ' V :,„. ' 1565

Sulfaspil ; ■ 7a 4.- ; 2240 190 ' \ ■ -82\- 183

R-35Q-P-4QQ 7 a 4 2368 200 86 362

T-800 7a5 2380 ' 225 '76 y 348

T-8P0 4 S 7a6 ' 2823 120 86 ' 3292

T-80GNHg 4 S ,1-704 v--2«5.7:> 160 88 3350

The average of three repliGates of idehti‘cai; treatments s

44

The Iron of the pyrite concentrate (R-SSO^B^OG) was absorbed

by the plants better in the asnal greenhouse pots test than in the

Stanford=BeMent seedling test0 No explanation car be found for this

lack of agreement• : . . . ,

Plate 1 shows the difference in amount of plant material and

width of the individual blades between the two treatments— -T-800 and

. sulfur® The T-800 appears to be somewhat ehlorotie compared to the

luslh green growth of the sulfur, treatments The beneficial effect of

the sulfur in the relief of chlorosis and improvement of plant growth

when added to the reacted tailings compared with the tailings without

addition of sulfur can be seen in Plate 2 o. Plate 3 shows the comparison

between the no treatment and the reacted tailings with and without

ammonration and sulfur addition0 ■ Again $ sulfur appears to provide

better plant growth than the other materials* Plate 4 shows the differ­

ences between ferrous sulfate and that of tailings and sulfur applications

This contrast would tend to indicate that a water-soluble iron treatment

is not the whole answer to iron chlorosis in this soil since iron sulfate

supported poorer growth than sulfur® Nitrogen also was not a limiting

factor for accelerated, growth in this soil® In plate 5 9 Sulfasoil is

compared with sulfur and sulfur plus tailings® The Sulfasoil which has

both a much higher total iron content as well as water-soluble iron per­

centage is not as effective as elemental sulfur in correcting chlorosis

and increasing plant-growth® \ ; \

45

Plate 1

Growth of Kafir sorghum in Gila fine sandy loam (soil material) receiv­ing:

A— T-800, 1 T/A B— Sulfur, 1 T/A

Plate 2

Growth of Kafir sorghum in Gila fine sandy loam (soil material) receiv­ing:

C— T-800, 1 T/AD— T-800, 1 T/A

sulfur— 1 T/A

46

Plate 3

Growth of Kafir sorghum in Gila fine sandy loam (soil material) receiving:

A— Control (none) B-T-800, 1 T/AC— T-800, 1 T/A

and sulfur, 1 T/A D— T-800NH3, 1 T/A

and sulfur, 1 T/A E— T-800NH3, 1 T/A

Plate 4

Growth of Kafir sorghum in Gila fine sandy loam (soil material) receiving:

A— Control (none) B-T-800, 1 T/AC— Sulfur, 1 T/A D— T-800, 1 T/A

and sulfur, 1 T/A E— Ferrous sulfate,

1 T/A

4 7

Plate 5

Growth of Kafir sorghum in Gila fine sandy loam (soil material) receiving:

A— Control (none)B— Sulfasoil, 1 T/A C— Sulfur, 1 T/A D— T-800, 1 T/A

and sulfur, 1 T/A

Greenhouse Test to Evaluate Sulfur and Rates of

"Its'Application

This experiment was designed to evaluate the effect of sulfur at

different rates and to find the minimum effective rate of application,

A random design was used in this experiment, and statistical analyses

were made on the results of the iron, copper, and sulfur chemical anal­

ysis. The statistical method used was the same as in the previous experi- .

meats. There were no significant differences in the dry weight of plant

material nor in the iron and copper analyses in Table 7. However, sig­

nificant differences were found in the sulfur analysis. The results of

the Duncan test is shown in Table 8. A determination of the pH value of

soil pastes from the variously treated pots showed that the elemental

sulfur did not decrease the pH value of the soil mass as a whole. This

would support McGeorge8s (23) findings that one ton or less of elemental .

Sulfur oxidised very rapidly and has little or no effect on the permanent

soil pH values. The conclusions reached from the results of this experiment

were that, with this particular soil, sulfur at the rate of one ton per ,

acre is insufficient to neutralize the carbonates and overcome the buffer

capacity of the soil. The calcium carbonate equivalent of the plowed layet

in Gila fine sandy loam in Arizona generally ranges from 2.0 to 10 percent

or more, depending on the depth at which the sample is taken. In a major­

ity Of field crops, the greatest concentration of -roots occur in the first

two feet of the soil profile. This depth represents about 8 million pounds

of soil per acre. If 3.5 percent calcium carbonate equivalent is used as

the amount in a soil, then this means that there are 280,000 pounds of V

49

Table 7* A summary of the dry weight of the iroa, copper's, and sulfur’ content of Kafir sorghum grown under greenhouse conditions in Gila fine sandy loam soil material treated with sulfur and

- . ' : SUlfateSo : ' : " . : '

Materialsapplied

~!l ..... tr Rat© ' 9, 8 Application

DryWeight*

» .—• Iron*8

r ' V, Copper* c Sulfur*

gm0/pot gm./pot jig./pot ; pig./pot mg./pot

Control . none 2.01 258 ; '17 28Ferrous

sulfate ' • 2,1 . .. 2.63 301 21 33Sulfur 2 a0 . , 2.41 253 17 33

Sulfur 1.6 2.57 264 , 21 39Sulftir 0.8 2.47 275 21 37

Sulfur 0.4 2.41 288 15 36Sulfur 0.1 2.50 278 14 ’ 37 •

Potassium. sulfate ' 0.15 iO • o

..;s

■:

242 / 20 : 32

Manganoussulfate 0.13 2.65 . 248 19 30

A . . ■ , - .Average of three replicates of identical treatmentse

Table 8* Analysis of variance between treatiuetits as indicated by ■ Duncan’s Multiple Rbnge Test of sulfur uptake into Kafir sorghum plant topSo * , '

Materials 6 Effect bn sulfur on sulfur uptake\ ■ . * ■ . . ■ ,: o : ' , '

C o n t r o l ; A

Manganous sulfate . ' A

Potassium sulfate A B

2.0 gms of sulfur - A B

Ferrous sulfate . ' ', ' A.'' B

0.4 gm. of sulfur B €

0.8 gm. of sulfur B G

0.1 gm. of sulfur B C

1.6 gmo of sulfur C

*Fivb percent level of significants was used.

caleium: carbonate: in an acre two feet deep. If it requires 98 pounds of

sulfuric acid to neutralize 100 pounds of calcium carbonate* then 274*400

pounds of sulfuric acid af^ needed to react completely with the 280,000

pounds of calcium carbonate* This would mean that 44»8 tons of elemental

sulfur would be required to neutralize a soil with .3*5 percent calcium

carbonate equivalent. This* also, is not taking into account the buffer

capacity of the soil. Therefore, it cannot be expected that the pH values

of the soil in the pot test would decrease measurably with a sulfur appli­

cation of only one ton per acre® As in the previous experiment, any small

micella or pockets of lowered pH values would be destroyed in a paste mixture.

The results from the analysis on the uptake of sulfur into the

plants are in no logical sequence. This suggests that sulfur ftself appar­

ently is not a deficiency in the plants and that elemental sulfur does not

function to enhance plant growth by merely providing available sulfur.

The results of the second long-term test to evaluate the effect

are found in Table 9 and Figures 8, 9* 10, and 11, This experiment was

designed to serve as a check on the first experiment, A random design was

used and statistical analysis carried out in the same manner as previously

indicated. There were statistically significant differences in oven dry

weight of plant material and the iron, copper, and sulfur uptake into the

plants. The results are shown in Table 10, A was significantly lower

than B*, B lower than G* G lower than 0, and D was lower than E„

Apparently only iron Sulfate was found to significantly increase

yields over that of the control or the other materials. However, wherever

more than one-fourth ton of sulfur x»as applied, yields were better than

Table'9® A summary, of the -iron, copper,, and sulfur content in the: fops of Kafir sorghum grown under green­house conditions in Gila fine sandy loam soil material with various sulfur and sulfate treatments«

Materialtested

«

»Amountapplied

. ' ; : ; gnu/pot

Gontrbl none -

Manganoussulfate 0e13

Ferrous sulfate 2*1

Potassium .sulfate 0al5

Sulfur da 1

Sulfur 0o4

Sulfur da 8

Sulfur lo 6

Sulfur 2,0

Rate. applied

girto /pot

none

do 13 2 o l ...

da 15

do 1

d»4

d„8

la 6

2 a d

: Oven dry weight of

sorghum tbps Iron

gnu/pot

: . 2,28.

■ 2a77

3 a 35

; 2 a 55

2*27

2*36

2*59

2*71

2*45

jUga/pOt

267;::

244

350

322

261

328

472

461

289

Copper

^ g 9/pot

-V: ' 23

23

' 25/

' 22 2?

22

2135

25

Sulfur

mgm*/pot

11

1112

10

: • : 1114

10

10

Average of three replicates of identical treatmentEOlto

53

Table 10. Analysis of variance between treatments as Indicated by Duncan9s Multiple Range Test of copper, iron, and sulfur uptake into Kafir sorghum plant top's. *

Materials96 Oven dry - weight 8 '' IronD

9 ' ' 08 Copper 69 - ' ; e Sulfur - -

Control A , - / a b - ' v b , ; ■ a ,:

Manganous sulfate. B A B" ■ A

Potassium sulfate - .m- : ABGD ; ’ - A

0.1 gm. of sulfur A ■ AB B ' A

0.4 gm. of sulfur ; AB" - ' ; BCD.'' : : B A

0.8 gm. of sulfur AB .v 'e : . A ; ■./ C

1.6 gm. of sulfur E ', v ; D A

2.0 gm. of sulfur AB ABC c A '

Ferrous sulfate ; c CD : B

* Five percent level of significants was used.

PLA

NT

M

AT

ER

IAL

(D

RY

WE

IGH

T)-

gm

. 4

3

2

0. .Ig.ofS CONTROL .4g. of S 2.0 g.of S K2SO4 .8g.ofS 1.6g.of S Mn504 Fe (S04)

Figure 8. The dry weight of Kafir sorghum tops grown in Gila fine sandy loam so il material receiving K,Fe, and Mn sulfate and various rates of sulfur.

01■p

5 0 0

400

CL 300

LU

LL200

100M n SO 4 . I g . o f s CONTROL 2.0g.ofS K2 SO4 A g . o f S Fe(S04) I.Gg.ofS .S g .o fS

Figure 9. Total uptake of iron found in Kafir sorghum tops grown in Gila fine sandy loam soil materialreceiving K, Fe, and Mn sulfate and various rates of sulfur.

Cu

PER

PO

T-^

g40

3 0

20 - F

10

0 — c—C...X J V-S. .S.../A----------------------/I / /—CJ --------- /.—C-—<L_a-----VjL— fc- A —I---L c — — ------- / _ C_ / — ------------------ / A.

. S g .o fS K2 S 0 4 .Ig .o fS . 4 g . o f S CONTROL MnS0 4 2 .0 g .o fS Fe(S04) I.Gg.ofS

Figure 10. Total uptake of copper found in Kafir sorghum tops grown in Gila fine sandy loam soilmaterial receiving K, Fe, and Mn sulfate and various rates of sulfur. ino>

SUL

FUR

PE

R PO

T m

g 15

10

5

0Ig. of S 1.6 g. of S 2.0 g. ofS K2 SO4 CONTROL .4g.of S Mn 5 0 4 Fe(S0 4 ) .Qg.ofS

Figure 11. Total uptake of sulfur found in Kafir sorghum tops grown in Gila fine sandy loam soil materialreceiving K, Fe, Mn sulfate and various rates of sulfur.

58

where no sulfur was added® Iron sulfate applications caused increases ■

in iron and copper uptake®. There was a trend towards an increase in

iron and edpper when sulfur was applied^ hut this was not progressive

and was somewhat erratic® The possible explanation for these hetero­

geneous results is that, small- pockets of sulfur reduce the pH values

around this element as it oxidized® The plant root hairs could conceiv­

ably be in: contact With such small pockets where the surface contact

would be a factor in' producing a favorable acidity to make the iron and

copper9 as well as certain other elementss more available to plants as

indicated by the data® , ■.

SUMMARY.

Mine tailings 9 which contained iron and other sulfides, were

subjected to high tempemttires and treated .with sulfuric acid in an

attempt to partially oxidize them to polysulfides and sulfates $ which

makes the plant nutrient elements more available to plants. These

reacted tailings were evaluated b y ■the Stanford-DeMeht seedling tech­

nique and the usual greenhouse pot test to determine their ability to

supply iron and-copper for the;plant,

, In the most highly oxidized reacted tailing— T-800— =42ep .per­

cent of the total iron was: water-soluble, ."However, the total amount of

iron per unit weight was about 5 to 6 percent0 This is a very low content

of iron when compared with other iron correctives now on the market. The

mine tailings provided only small amounts of iron to plants. It appears

that rather large amounts of these materials would be required to correct

the incidence of chlorosis in,agricultural crops.

Elemental sulfur was found to be very effective in correcting

iron chlorosis and. increasing plant growth in one of the experiments, ■

Experimental pot tests were set up to evaluate the effect of sulfur on

plant growth and on the uptake of iron and copper by sorghum, plants.

Various rates of sulfur were used up to one ton per acre-six inches.

Elemental sulfur mixed into the soil at the rate of one ton per

acre did not lower the pH value of calcareous soil pastes. In one of the

■ - ' ■ ' 59 ■■■■;■ :

60

experimeats, iron and copper intake by plants appeared to be increased

from the reacted mine tailings as well as from the soil by an associa­

tion with elemental sulfur,. The uptake was not progressively greater

with increasing amounts of sulfur® The data did not give conclusive

evidence that sulfur was correlated with iron and copper uptake„

There were indications that nitrogen increases the uptake of

iron and copper in sorghum plants$ according to the experimental data®

Whether this was due to the nitrogen itself or because of its encourage­

ment of plant growth" cannot be determined from the data0

LITERATURE. CITED

1® Atitipov-Karataevg I«, Ny7 The Movement of Copper in • Soils. Pedology (UoSeSeRo ); ppo 652=9 $ 1947e= (CeA0 42$6972d0 1948).

2® Bambergs$.K0 Trace-Element Levels in Plants and Means to Increase the Effectiveness of Trace-Element Fertilizers e Otdel® Biolag Riga9 67-80s 1955. (C.A. 53;106241. 1959).

3« . . and Balode9 A. Absorption of Mn$ Zn$ and Cu in Soil.Latvyas PSR. Zinatu Akad Vestis No. 8, 45-56 $ '1957*(C.A* 52 %4079h* 1958)* "

4® Bearg F* E* (editor)* Chemistry of the Soil. Reinhold Publishing Corporation $ New Yorkg 19609 p. 238®

5* (editor)* Chemistry of the Soil* Reinhold Publishing: Corporationg New York, 1960, p* 247® '

6* Boischof s P* 8 DurrouXg, M. 9 and Sylvestres G. The Fixation of Ironand Manganese in Calcareous Soils* Ann* Inst* Natl* Recherche Agron* § Ser* A* Ann* Agron* 1, 307-15, 1950* .(C*A® 45i6331c®

■ . " 1951)* . ' . ; (;■_

7* Btargessg Pe S® and Pohlman$ G® G* Citrus Chlorosis as Affected by . Irrigation and Fertilizer TreatinentSo Arizona Agr* Expt*

Sta®, Bull.. 124= 1928® : •

8* Burstrom, H* and Boratynski, K* Copper and Manganese Absorptionby Wheat at Different pH Values* Polish Agr* Forest Ann* 38$ 147-699 1937* (C.A® 31:70891* ' 1937).

•9* Brown, J® C® and Holmes, R* S* Irong The Limiting Element in, Chlorosis* I® Availability and Utilization of Iron Dependentupon Nutrition and Plant Species* Plant Physiol. 30:451-7,

■ - 1955° .

10® ; : : a ' • - ' . * ahd Spechts A* W. Ibid*, II. Copper-Phosphorous Induced Chiorpsis Dependent upon Plant Species

. and Varieties® Plant Physiol. 30:457-62, 1955.

11. Cheng, K® L* and Bray, R* H* Determination of Copper in Soils and . Plant Material* Anal® Chem® 25$655-59« 1953*

61

62

.12® Duncan$ D® B« Multiple Range and Multiple F Test Biometrics II»' • ' ■ 1-42s: 1955® ' ' '■ . '

13® Earleys E® B® Oxidation of Plant Material with a Mixture of Nitric Acidj, Waters and Perchloric Acid® Univ® of 1 1 1 ® ? Dept® of Agron® 9 Mimeo® AG 14761950®

14® Giesekingg J® Ea>- Sniderj, H® J® s and Getag C® A® Destruction of Organic Matter in Plant Material by the .Use of Nitric and

. Perchloric Acids® Ind® and Eng® Chem® $ Anal® Ed® 7:185-6,' : , 1935® " : ■ . :■ . ; ■ \

15® Haas, A® R® C® The pH of Soils at Dow Moisture Content® Soil Sci®■ ■ -. 17 ®:39., 1941® : •. . . '• : , -

16® Harper, W® G® Soil Series Description® Soil Conservation Services U®S® D® A® 1945 (Revised, 1956)® ' . ■

17® Hoagland, D® R® and Arnong D® I® The Water-Culture Method for. Growing Plants without Soil® Calif® Agr® Expt® Sta® Circ®

347 (Revised) $ 1950® , r . . , .■

18® Jackson9 M® L® Soil Chemical Analysis, Prentioe-Hall,' Inc®, Englewood Cliffs, N® Jes 1953s, p®389®

19® Kiiman® S® The Importance of Ferrous Iron in Plants and Soils®, Soil Sci® Soco Amer® Proc® 2:385-392s, 1937®

20® Maier, R® H® Oxidation^of Plant- Material with a Mixture of Nitric ■■"'■"Acid, Water, and Perchloric Acid® Univ® of Ariz® , Dept®

of Agr® Chem® and Soils, Mimeo-Revised9, 1959® (unpub®)

. 21® . . ■■ 0 Modified Procedure for the Determination of Iron®• ... Univ®" of Ariz® 9 Dept® of Agr® Chem® and Soils® (unpub® )

22® Maume, E® and Bouatj, A®, Influences of the Variety and the Medium ." on the Absorption of Sulfur by Wheat® Compt® Rend® Acad®

Agr® France 23 , 426-30, 1937® (C®A® 31;50154® 1937)®

23® McGeorge, W® T® Sulfur, A Soil Corrective and Soil Builder, Univ®, of Ariz® Agr® Expt® Sta® Bull® 2 0 1 , 1945®

24® , ® Nutrient Interrelations in Lime-induced Chlorosisas Revealed by Seedling Test and Field Experiments® Ariz® Agf® Expt® Sta® Tech® Bull® No® 116, 1948®

25® . ■■, ' . . ® Lime-induced Chlorosis in Western Crops® Better■;. Crops with Plant Food 35,:l7-20 9 1951®

63

26. » Abbott, J„ lio»vatid Breazeale, E, L, Some Prop­erties of a Soil Ha.vi.ng a.High Percentage of ReplaceablePotassium: field"and Laboratory Studies on ComparativeValue of Soil Cottditionerso Ariz, Agr, Expt. Sta.Rpt,

' ; > ; ' ; No, -I 32, "1956, ■ :

27. and Bfeazeale, E, L, The Value of Byrite andByrrhotite as Soil Conditioners, Ariz, Agr, Expt, Sta,Rpt, No. 124, 1955,

28. ~ : - ■ and Green, R. A. Oxidation of Sulfur in ArizonaSoils and Its Effect on Soil Properties, Ariz. Agr. E%pt. Sta, Tech, Bull. 59, 1935,

29. Olson, R, V, Iron Solubility in Soils as Affected by pH and FreeIron Oxide Content, Soil Sci Soc, Am. Proc, 12:153-7,

’’ V ' ' ; 1947, . • ■ - ' . V, ; : ■ '30. ' ■ ' ■ ' -- . Effect of Acidification,, Iron Oxide Addition, and

Other Soil Treatments on Sorghum Chlorosis and Iron Absorp­tion. Soil Scii Soe, Am. Proc. 15:97-101, 1950,

31. •Rediske, J. H. and Biddulph, 0. The Absorption and Translocationof Iron. Plant physiol, 28:576^593, 1953.

32. Shaw, W, M,, Indirect Flame Photometric Determination of TotalSulfur in Biological Material. J. of Agr. and Food Ghem. .

. 9:18-21, 1961.

33. Shkol'nik, M, Y. and Makafoua, N. A, Antagonism of Iron and Copper.Doklady Akad, Nauk. (U.S.S.R.) 70:121-24, 1950 (C.A. 45:

: 47881, 1951). . ■ -.y./;,.. .34. Smith, H. V. The Effect on Plant Growth of Treating Soils with

Copper-bearing Pyrite. Jour, Am. Soc. Agron. 22:903-915,' • ' 1930. ' , ' . "■ . " ; .. / , _ ■ ;

35. Sommers, I. I. and Shive, J, M. The Iron-Hanganese Relation inPlant MetaboTism, Plaht. Physiol, 17:582-602, 1942.

36. Stanford, G. and DeMent, J. D. A Method for Measuring Short-termNutrient Absorption by Plants, Soil Sci. Soe. Am. Proc.21:612-617, 1951. .

37. Thofne; D. W. Facotrs Influencing the Solubility of Iron and Phos-phorous in Chlorotie and Nonchlorotic Areas of Hyrum Clay

• Loam. Iowa State Col. Jour.,’.. Sci. 15:433-445, 1941.

64-

38a , ■ and Wallace a A0 Some Faetors Affecting Chlorosison High-lime Soils'. I. Ferrous and Ferric iron. • Soil Sei« 57;299-312$ 1944.

39® Truog9 E 0 Soil Reaction Influence oil Ayailability of Plant Nutri­ents® Soil Sci® Soc® Am® Proe® 11:305-8® 1946®

40® Wilsonj, £.« D® Arizona Zinc and head Depositss Arizona Bureau of , Winesg Bull® 156; (Creasey9 pp® 112 =■ ISOJs, 1950®