Porównanie metod oznaczania całkowitej zawartości miedzi, manganu, cynku i molibdenu w glebach

R O C Z N IK I G L E B O Z N A W C Z E T. X X V , D O D A T E K , W A R S Z A W A 1974

K A Z IM IE R Z B O R A T Y Ń S K I, E L IG IU S Z R O S Z Y K , S T E F A N IA R O S Z Y K , M A R IA Z IĘ T E C K A

C O M P A R IS O N OF D E T E R M IN A T IO N M E T H O D S O F T O T A L C O PPE R M A N G A N E S E , Z IN C A N D M O L Y B D E N U M C O N T E N T S IN SO ILS

Institute of Soil Science and Agricu ltu ral Chemistry- A gricu ltu ral U niversity in W rocław

It is often purposeful to know the potential reserves of macro- and microelements irrespective of determinations of these elements in soil. For this purpose either chemical [5,

8

The aim o f the investigations carried out by the authors was to compare several chemical and spectrographic methods of determining total contents of copper, manganese, zinc and molybdenum in soils.

S O IL M A T E R IA L A N D D E T E R M IN A T IO N M E TH O D IC S

The investigations w ere carried out on 30 soil samples different with regard to mechanical composition, organic carbon content and reaction (Table 1). They w ere taken from the upper soil layer in the fields of several countries of the W rocław province.

T a b l e 1

Number o f sample3 examined in the in te rv a ls of clayey p a r t ic le s , c o llo id a l c la y , organic С and pH

j Cleyeу particles Colloidal cley Organic С pH

1 j vais п’лгЛэег of samples inter­ v a ls number of samples inter­ vals number of samples in te r­ v a ls number o f samples j <r 10 7 ^ 5 7 ^ 1.00 11 ^ 5 o 5 11 11-35 13 6-10 12 1.01-1.50 15 5.6-6.5 15 > 5 6 10 > 1 1 11 > 1.51 4 > 6.6 *

In the investigations the following methods w ere applied : — digestion of soil with hydrofluoric acid [

11

— fusion of soil with sodium carbonate [4],

— spectrographic method applied at our Institute and described pre­

viously by one of the authors [

10

— etching of soil with aqua regia after N e r n e s et al. [

8

W ith application of the last method the contents of copper and man­ ganese w ere determined not only in extract, but also by the spectro­ graphic method in the residue of undigested soil.

A ll the above methods w ere applied for manganese and copper de­ terminations, w hile zinc and molybdenum were determined only by some of them (Talbles

2

The sole analytical determination of microelements passed into solution was carried out by colorimetric methods, namely: Cu— b y the method with P b (D D T C

)2

6

1

2

IN V E S T IG A T IO N R E S U LTS

Although in some cases considerable differences occurred, the quan­ tities of the microelements determined by the fusion and hydrofluoric method were, on the whole, similar (Tables 2, 3).

W ith the spectrographic method used for copper and manganese by about

10

2

The zinc content in soils, determined in the extract by aqua regia after Nemes et ah, w as slightly low er as compared with that determined by the fusion or hydrofluoric method {Table 3).

The copper and manganese contents determined by the method of Nemes et al. were much lower, by about 30% and

20

2

Aqua regia did not pass into solution the total amount of the micro­

elements investigated. This was proved by considerable quantities of these elements found in the residue of undigested soil after extraction with aqua regia, determined b y spectrographic method.

The sum of manganese content in solution and soil residue was compatible with the M n amounts passed into solution by the fusion or hydrofluoric method (Table 2).

Despitete some differences in the amounts of the elements determined by respective methods, a close relationship between their amounts passed into solution b y hydrofluoric and other methods, as w ell as those

de-Com parison of determination methods.., ₆₉

T a b l e

2

Copper Manganese

J spec­ И ernes spec­ Hemes

HF fusion tro ­ graph Nemas extract + residue HF fusio n tr o ­ graph Names extract + residue 6,2 6.0 8 2.6 7.6 180 152 160 130 200 7.2 6.5 10 3.6 8.6 230 240 310 254 304 8.2 8.4 12 5.2 13.2 270 235 230 240 330 8.5 9.2 14 6.5 15.5 285 268 295 ' 254 334 9.6 9.2 15 5.7 13.7 295 280 325 257 377 1 1 .2 10.0 12 8.2 16.2 310 280 290 268 338 11.3 10.0 14 6.0 15.0 330 316 320 188 ЗОЗ 1 1.8 13.2 12 7.7 15.7 335 388 470 365 480 12.5 12.0 16 10.4 16.4 370 380 450 383 453 12.5 12.0 11 5.4 11.4 375 408 400 328 39Ô 12.6 12.4 11 7.2 13.2 405 440 45О 336 426 13.2 12.4 11 5.7 13.7 405 420 425 255 385 16.0 17.5 19 14.0 22.0 415 400 j 390 288 388 16.5 15.6 17 7.4 17.4 420 430 j1 390 j 240 З45 17*2 18.4 18 10.4 18.4 43О 460 ! 605 398 563 17.8 17.5 25 10.5 23.5 435 400 390 220 300 18.2 19.2 24 14.0 25.0 440 476 550 410 500 18.6 17.8 23 11.7 24.7 440 436 470 324 434 18.7 20.4 28 lo. 6 24.6 455 428 480 340 440 18.9 20.4 24 13.2 21.2 455 420 500 414 554 19.5 21.2 24 13.2 20.2 480 520 470 316 466 21.5 19.2 19 10.4 21.4 49О 440 400 З45 440 21.5 20.0 25 14.8 26.8 5OO 500 I 675 566 636 22.8 24.4 22 14.0 21.0 510 488 535 380 485 24.0 22.4 25 20.2 27.2 540 588 525 456 576 24.6 23.2 26 20.4 28.4 550 520 650 400 530 26.2 23.0 32 21.7 33.7 550 428 525 333 433 27.8 26.4 31 22.7 30.7 605 580 795 484 494 33.6 36.4 34 28.0 39.0 620 608 710 400 625 72.6 70.0 76 61.6 61.8 1440 1363 1515 1060 1250 Lean 13.7 18.6 21 13.3 22.2 452 443 492 354 460 Fluctua­ I52--1368

tions 6.2-72*6 6.0-70.0 8-76 2.6-61.8 7.6-81.8 180-1440 160-1515 I3O-IO6O 2OO-I25O

tei mined by spectrographic method (Table 4) were found. The some relationship (r > 0,9) w as found also (between all random pairs of methods of determining respective microelements.

C O N C L U S IO N S

On the basis of the investigations on comparison of several chemical methods and spectrographic method of determining total contents of Cu, Mn, Zn and Mo in soils the following can b e stated :

T a b l e 3 Total zinc and molybdenum content in soils determined by different methods, in ppm

Zinc Molybdenum

EF fusion Nemes HF fusion

22 25 23 0,50 0.45 25' 26 28 0.70 0.95 28 30 24 0.75 0.65 33 28 3° 0.75 0.65 54 38 3° 0.85 0.95 35 38 30 0.90 0.90 36 34 32 0.95 1.10 33 34 30 1.10 1.20 38 42 36 1.20 1.10 40 43 34 1.45 I.30 43 43 46 1.50 1.25 45 52 40 1.60 1.55 45 49 44 1.85 2.00 45 47 50 1.90 I.90 45 40 39 1.95 2.25 47 50 40 2.00 I.90 48 50 50 2.20 2*00 49 45 41 2.30 2.55 50 54 47 2.40 2.45 4*2 52 49 2.50 2.65 54 54 56 2.55 2.20 55 50 46 2.75 2.35 62 58 56 2.75 2.80 64 72 68 2.75 2.55 70 65 69 2.80 2.70 72 72 64 3ol5 5.45 74 70 68 3.30 3ol5 78 70 6/; 3.35 3.00 95 104 102 3.35 3*55 •26 100 112 4.90 5.25 lie an 51 51 48 2.03 2.02 l\luctu£- 22-55 r:oi:s 25-100 23-112 O.50-4.90 0.45-5.25

1

2

3. Aqua regia (after Nemes et al.) did not pass into solution the total contents o f copper and manganese.

4. A close relationship was found between the amounts of respective microelements determined by the methods used.

It was possible to carry out the present work owing to a financial support of the Committee for Soil Science and Agricultural Chemistry, Polish Academy of Sciences.

Com parison of determination methods.. 71

T a b l e 4 Linear correlation coefficients and regression

lines equation for the microelements amounts /in ppm/ determined by different methods

X _У r y = ax + b

Copper

Etching of soil with HF

Fusion of soil with sodium Spectrographic method Method of Nemes et al.

Method of Nemes et.al., filtrate + re sidue 0.985 0.975 0.981 0.982 y = 0.98 z + 0.57 y = 1.01 z + 2.59 у = О. SO x - 3 . W у = 1.03 X + 1.95 ISanganese Etching of soil with HP

Fusion of soil with sodium Spectrographic method Method of Nemes et al.

Method of Names et al., filtrate + residue 0.985 0.953 0.916 0.931 у = 0о94 у- + 17.72 у = 1.06 X + 11.2 3 у = 0.69 з: + 42.07 у ■_ 0.78 X V 104*90 Zinc Etching of soil with HP

Fusion of soil with sodium Method of Nemes et al.

0.97-3 0.962 у = 0.99 X + 1.С7 у = 1.07 а: - 6.07 Molybdenum Etching of soil

with. HF Fusion of soil with sodium 0.982 у = 1.01 z - 0.03

j

n = 20

j

1

R EFERENCES

[1] B o r a t y ń s k i K., R o s z y k o w a S., Z i ę t e c k a М.: O metodach chem icz­ nych (kolorym etrycznych) oznaczania zasobności gleb w mangan przysw ajalny dla roślin. Rocz. glebozn. 15, 1965, 1, 167-190.

[2] B o r a t y ń s k i K., R o s z y k o w a S., Z i ę t e c k a M.: Badania nad przysto­ sowaniem do oznaczeń seryjnych m etody G rigga służącej do określania w g le ­ bie przysw ajalnego molibdenu. Rocz. glebozn. 16, 1966, 2, 301-326.

[3] G l i ń s k i J.: Fizyczne m etody oznaczania ogólnej zawartości m ikroelem entów w7 glebach. M ateriały z Konw ersatorium poświęconego badaniom m ikroskład- ników w glebach i roślinach. K om itet G leboznawstwa i Chem ii R olnej P A N , s. 75-85, Lublin 1967.

[4] J а с к s o n М. L.: Soil chemical analysis. P ren tice-H a ll 1958.

[51 K a b a t a A.: Przegląd fotom etrycznych metod oznaczania m ikroelem entów (Cu, Co, Zn, Mo, B) w roślinach i glebach. Pam. puł. Prace IU N G 3, 1961, 81-91.

[6] K a r d a s z T., R u z i e w i c z J.: Przystosow anie do analiz seryjnych m etody Scharrera i Schaum löffela oznaczania m iedzi w w yciągach glebowych. Rocz. glebozn. 16, 1966, 2, 449-457.

[7] K o c i a ł k o w s k i Z.: Chemiczne m etody oznaczania ogólnej ilości m ik ro ele­ mentów w glebach. M ateriały z konwersatorium poświęconego badaniom m i- kroskładników w glebach i roślinach. K om itet G leboznawstwa i Chem ii R o l­ nej P A N , s. 55-73, Lublin 1967.

[8] N e m e s N., D u c a, B i l a n s C., S t a n e s c u D.: L a méthode de determ ination des m icroélém ents du sol et quelques leur contenu dans le sols de la T ra n ­ sylvanie (R. P. Roumaine). Rocz. glebozn. 10, 1961, 279-286.

[9] R i n k i s G. J.: M ietody kolorim etriczeskogo opriedielenija riada m ikroele- m ientow w poczwach, rastienijach i tkaniach żiwotnych. M icroelem ienty w siel- skom chaziajstwie i miedicinie. K ijó w 1963, 351-355.

[10] R o s z y k E.: Zawartość wanadu, chromu, manganu, kobaltu, niklu i m iedzi w niektórych glebach Dolnego Śląska w ytw orzonych z glin pylastych i u tw o­ rów pyłowych. Cz. I. Ogólna zawartość m ikroskładników. Rocz. glebozn. 19, 1969, 2, 223-247.

[11] A grochim iczeskije m ietody issledowanija poczw. Izd. Nauka, M oskwa 1965.

К. Б О Р А Т Ы Н Ь С К И , Э. Р О Ш И К , С. Р О Ш И К , М. З Е Н Т Е Ц К А С Р А В Н Е Н И Е М Е ТО Д О В О П Р Е Д Е Л Е Н И Я О Б Щ Е ГО С О Д Е Р Ж А Н И Я М ЕДИ, М А Р Г А Н Ц А , Ц И Н К А И М О Л И Б Д Е Н А В П О Ч В А Х И нститут почвоведения и агрохимии Сельскохозяйственной академии в г. Вроцлаве Р е з юм е На дифференцированном почвенном материале (30 образцов) проводились исследования по сравнению трех химических методов (фтороводородного, сплава и травления царской водой) со спектрографическим методом определения об­ щего содержания Cu, Mn, Zn и M o в почвах. Исследования показали следую щ ее: 1. количества Cu, Mn, Zn и M o проведенные в раствор с помощью ф торо­ водородного метода и метода сплава бы ли согласными, 2. количества Си и Мп определенные спектрографическим методом бы ли выше определенных обоими предыдущ ими методами, 3. царская вода (метод Немеса и сотр.) не проводила в раствор п олн ы х к о­ личеств меди и марганца, 4. 'между количествами отдельны х микроэлементов определенны х приня­ тыми методами сущ ествует тесная взаимосвязь. К. B O R A T Y Ń S K I, Е. R O S Z Y K , S. R O S Z Y K , М. Z IĘ T E C K A C O M P A R A IS O N DES M E TH O D ES DE L A D E T E R M IN A T IO N DE C U IVR E , M A N G A N È S E , Z IN C E T M O L Y B D È N E D A N S LE S SO LS

Institut de Pédologie et de Chim ie Agricole, U n iversité Agronom ique de W rocław

R é s u m é

Sur le m atériel varié de sol (30 échantillons) on a fa it des études sur la comparaison de 3 méthodes chimiques: fluorohydrogénique, d’alliage et celle de

Com parison of determination methods... ₇₃

rongeurem ent avec l ’eau royale et la m éthode spectrographique de la déterm ination du contenu de Cu, Mn, Zn et M o dans les sols.

On a constaté que:

1. Les quantités de Cu, Mn, Zn et M o introduites dans la solution à l ’aide de la méthode fluorohydrogénique et celle d’alliage ont été conformes.

2. Les quantités de Cu et M n designées à l ’aide de la m éthode spectrogra­ phique ont été plus hautes que celles obtenues à l ’aide des deux méthodes p ré ­ cédentes.

3. L ’eau royale (méthode de Nemes et collab.) ne laissait passer les quantités complètes de cuivre et de manganese à la solution.

4. On a constaté une dependence stricte entre les quantités des m icroélem ents particuliers désignés et les méthodes appliquées.

K. B O R A T Y Ń S K I, E. R O S Z Y K , S. R O S Z Y K , M. Z IĘ T E C K A

U N T E R S U C H U N G E N Ü B E R VE R SC H IE D E N E B E S T IM M U N G S M E T H O D E N DES G E S A M T G E H A L T E S A N K U P F E R , M A N G A N , Z IN K U N D M O L IB D Ä N

IM BO D EN

Institut fü r Bodenkunde und Agrikulturchem ie der Landw irtschaftlichen U niversität in W rocław

Z u s a m m e n f a s s u n g

Es wurden Untersuchungen durchgeführt, w elche den V ergleich von v ie r v e r ­ schiedenen Bestimmungsmethoden des Gesamtgehaltes an Cu, Mn, Zn und M o im Boden bezweckten. A ls chemische M ethoden w urde die Flussäure- die Soda­ schmelz- sowie die Königswasserauszugsmethode nach Nem es und Duca angewandt. Ausserdem w urde die spektrographische Bestimmungsmethode dieser Elemente hinzugezogen. Die Untersuchungen wurden anhand von 30 unterschiedlichen B o­ denproben durchgeführt.

A u f Grund der Untersuchungen w urde folgendes festgestellt:

1. D ie Flussäure- sowie die Schm elzm ethode führten übereinstimmende M en ­ gen an Cu, Mn, Zn und M o in Lösung über.

2. Die Königswasserm ethode dagegen führte nicht die ganze M enge an K u p fer und Mangan in Lösung über.

3. Die Cu- and M n-M engen, w elche m it H ilfe der spektrographischen M ethode erm ittelt wurden, waren höher als bei der Flussäure- und Schmelzmethode.

4. Es besteht eine signifikante K orrelation zwischen den m it H ilfe der ange­ wandten Methoden festgestellten Mengen der einzelnen M ikroelem ente.

K. B O R A T Y Ń S K I, E. R O S Z Y K , S. R O S Z Y K , M. Z IĘ T E C K A

P O R Ó W N A N IE M E TO D O Z N A C Z A N IA C A Ł K O W IT E J Z A W A R T O Ś C I M IE D Z I, M A N G A N U , C Y N K U I M O L IB D E N U W G L E B A C H

Instytut G leboznawstwa i Chem ii Rolnej A k ad em ii Rolniczej w e W rocław iu

S t r e s z c z e n i e

N a zróżnicowanym m ateriale glebow ym (30 próbek) przeprowadzono badania nad porównaniem trzech metod chemicznych (fluorow odorow a, stopu, traw ienia w

o-dą królewską) i m etody spektograficznej oznaczania całkow itej zawartości Cu, Mn, Zn i Mo w glebach.

W badaniach stwierdzono co następuje:

1. Ilości Cu, Mn, Zn, M o przeprowadzone do roztw oru metodą fluorow odorow ą i metodą stopu były zgodne;

2. Ilości Cu i Mn oznaczone metodą spektrograficzną były w yższe od uzyska­ nych obu poprzednim i m etodam i;

3. W oda królewska (metoda Nemesa i współ.) nie przeprowadzała do roztworu całkowitych ilości m iedzi i manganu;

4. Stw ierdzono ścisłą współzależność m iędzy ilościam i poszczególnych m ik ro­ elem entów oznaczonych stosowanymi metodami.

P r o f . d r K a z im ie r z B o r a ty ń s k i In s ty t u t G le b o z n a w s t w a i C h e m ii R o ln e j A . R . W r o c ła w , ul. G r u n w a ld z k a 53