DETERMINATION OF TRACE ELEMENTS IN ARSENIC AND …

-Geologica Macedonica Vol 17 p 73-82 (2003) GEOME2 ISSN 0352 - 1206 Manuscrip t received Decem ber 152002 UDC 553497 543422 Acc epted March 20 2003

Original scientific paper

DETERMINATION OF TRACE ELEMENTS IN ARSENIC AND ANTIMONY MINERALS BY ATOMIC ABSORPTION SPECTROMETRY WITH PREVIOUS MATRIX

MODIFICATION

Nikola Angelov Trajce Stafilov

Institut e of Chemistry Faculty ofNatural Sciences and Mathematics Sts Cyril and Methodius University PO Box 162 MK-1001 Skopje Republic of Macedonia

A b s t r a ct Th e applica tion of direct electrotherma l atomic absorption spec trometry (ETAAS) in the analysis of arsenic (rea lgar and orpiment) and antimo ny (stibnite) minerals is limited due to strong matri x interferences on the atomiza tion of trace analytes Therefore the trace elements determination is poss ible only after matrix separation Methods based on matrix separation by reduction or preci pitation of arsen ic and antimony as a matrix element is sugshyges ted In the present paper matrix separation by precipitation is studied in order to propo se optima l methods for the determinat ion of Cd Co Cu Cr Fe Mn Ni Pb and Zn in realgar orp iment and stibnite T he removing of arse nic and antiniony can be successfully performed by its reduction with sodium tetrahyd ridoborate(lII ) (NaBH4) in the presence of HCI or HN03 T he conditions for this method (mass of NaBH4 conce ntration of acids temperature) were optimized Dur ing this procedure inves tiga te elements are not reduced and can be determined from the solut ion by ETAAS or by flame atomic absorption spec trometry (for Fe Mn and Zn) Applying this me thod the investigated elements were determined in realgar orpime nt and stibn ite minerals from Allchar mine Macedonia

Key words T race elemen ts realga r orpimen t stibnite determination atomic abso rption spec trometry

INTRODUCTION

The mos t occurred minerals in Allchar locashy termination in geo logical samples (Stafilov 2000) tion Republi c of Macedonia are arsenic minerals However the application of flame (FAAS) and realgar (AS4S4) and orpiment (AS2S3) and antimony electrothermal atomic absorption spectrometry miner al stibnite (Sb2S3) It is very important to folshy (ETAAS) in trace elements analysis of minerals is low the content of lead in these minerals because limited becau se of matrix inte rferences especially of using them as monitors for determining the conshy because of high content of main constituent eleshytribution of background reactions which or iginate ments in the mine rals Therefore determin ation of from natural radio activity on condition that they trace elements is easier after their separation from are genetically formed at the same peri od as the the matrix There are a numb er of paper concer shylorandite (Freedman et al 1976) The examinashy ning of trace elements determinations in geological tions on the other element contents will help for samples by ETAAS (Stafilov 2002) In some of obtaining important knowledge for geoc hemistry presented pape rs (Sedykh et al 1980a Sedykh et on the mine and expl anation on the background al 1980b Tominaga and Umezaki 1982 Zeshyradiatio n of the location (Palme et al 1988) This lentsova and Yudelevich 1983 Kuroda et al is very important in the investigation in the 1986 Stafilov et al 1990a Lazaru and Stafilov LOREX Project which used the mineral lorandite 1993 1994 2000 ) direct determination was sugshy(TIAsS2) present in this dep osit as solar neutrino gested In our previou s investigations we have detector measuring the content of 205Pb isotope showed that in ETAAS determinations arsenic produced by the nuclear reaction between solar (Stafilov et al 1990a 1990c Lazaru and Stafilov neutrino and 205Tl accumulated in lorandite 1993 1994 2000) and antimony (Stafilov et al (Freedman et al 1976 Pavicevic 1994) 1990c) decrease the absorbance of some of the inshy

Atomi c absorption spectrometry (AAS) is one vestigated elem ents Similar results were obtained by Zelentsova and Yud elevi ch (1983) of the most used technique for trace elements deshy

XIII_1233

74 N Angeov T Stafiov

To overcome interferences it was suggested this paper the method of separation of different on addition of different matri x modifier (Komarek trace elements (Cd Co Cu Cr Pb Ni Fe Mn and et al 1980 Kuroda et al 1986) In the case of Zn) from arsenic (realgar AS4S4 and orpiment arsenic matrices different methods for trace eleshy AS2S 3) and antimony (stibnite Sb 2S3) minerals is ments separation were applied extraction (Stafilov suggested The elimination of arseni c and antishyand Todorovski 1987 1988 1990 Stafilov et al mony from the matri x solution is performed by 1994 Lazaru and Stafilov 2000) precipitation their reduction by sodium tetrahydridoborate(III) (Stafilov et al 1990c) or evaporation of arsenic in (NaBH4) in the presence of HCl or HN03 to eleshythe form of sesquioxide (Shelpakova 1991) Conshy mentary form and elimination as a precipitate Inshytinuing our work on trace elements determination vestig ated elements don t precipitate and stay in in arsenic and antimony mine rals (Stafilov and Toshy the solution and can be analyze applying FAAS or dorovski 1987 1990 Lazaru and Stafilov 1993 ETAAS Optimization of important parameters 1994 1998 2000 Stafilov et al 1988 1990a which influence on this proce ss (mass of NaBH4

1990b 1990c 1993 1994 1995 Lazaru et al concentration of acid s temp erature) were detershy1999 2002 Zendelovska and Stafilov 2001) in mined

EXPERIMENTAL

Instrumentation PSD-I00 Autosampler and Varian SpectrAA 220 atomic absorption spectrophotometer was used for

A Varian SpectrAA 640Z Zeeman atomic abshy FAAS The instrumental parameters for FAAS and sorption spectrophotometer equipped with a Vari an ETAAS determination are given in Tables 1 and 2

T able 1 Instrumental parameters for determination by FAAS

Parameter As Sb Cd Co Cr Cu Fe Mn Ni Pb Zn

Wavelength nm 1937 2176 228 8 2407 3575 3248 248 3 2795 2320 2833 2139 Spectral slit nm 05 02 03 02 07 07 02 07 02 07 07 Lamp current mA 10 10 20 30 25 15 30 20 4 10 15 Gas mixture Acetyleneair

T able 2 Instrumental parameters for trace elements determination by ETAAS

Parameter Co Cd Ni Cu Cr Pb Wavelength nm 2425 2288 2320 3274 3579 2833 Spectral slit nm 02 05 02 05 02 05 Lamp current mA 70 40 40 40 70 50 Calibration mode Absorbance peak height

_~~ ~g l() 1 ~ 9~ () ~~~lt ~ i () t __ __ _ Zeeman DRY

-~ middot middotTemiddotmmiddotp~middot~atmiddot~~e~middot middot middotomiddotCmiddot middot middot middot-~--middot- middot middot - middot---middot - - middot middot-middotmiddot --i middoti6 middot middot middot _ middot middot middot _middot middot middot middot middot_ middotmiddotmiddotmiddotmiddotmiddotmiddot 120 _____ _yen__-__- __ 120 120 120

Ramp time s 45 45 45 45 45 Hold time s 10 10 10 10 10 PYROLYSIS TernperatureX 750 250 800 800 1000 400 Ramp time s 5 5 5 5 5 5 lj()19tiJ1e s _ _ __3 3 3 3 3 3 ATOMIZATION Temp-~ai~e middotoC--- - ----- middot-- -middot-2300--middot_ middot--1806----- ---24middot00---- - - -2305-middot--middot- middotmiddot--- -middot26-60---- -- --2-100middot-middot Ramp time s 1 1 1 1 I I H CI~_ t~~_~ _ __ ~_ _ __ _ _~_ ___ _ _~_ ____1 ~____ L _ _ CLAENING

--Tmiddotemp~~~w~e--oC -_middot-----_----middot--246o- - ----1 906--- middotmiddot---middotmiddot--2560---middot---middot--2-400------ - middotmiddotmiddot2600- --- middot--middot2-10-0- --shyRamp time s 1 I 1 I 1 1 Hold time s 2 2 2 2 2 2 Gas Argon

Geologica Macedonica 17 73-82 (2003)

Deten llination ofrace elements in arsenic and antimony minerals by atomic absorption spectrometry with previous mstrix modification 75

Reagents and samples

All reagents and standards were of analytical grade Stock solutions of all investigated elements were prepared by dissolving of high-purity salts or metals The mass concentrations of elements in these solutions were 1000 mg-T from which all diluted solutions were prepared The solution of sodium tetrahydridoborate(III) was prepared by dissolving 125 g NaBf4 in volumetric flask of 25 ml in the mixture of 3 ml 25 NH40H and 10-15 ml redistilled water After dissolution flask was filled up to mark

Mineral specimens of realgar orpiment and stibnite were taken from the Allchar mine Crven Dol locality adit No 21 (Jankovic 1988 Boev et al 1993a) Mineral specimens were carefully seshylected from ore samples using microscope and then grinned to powder

Procedures

Realgar and orpiment In the glass beaker of 100 rnl 01 g of powdered samples of realgar or orpiment were dissolved in 10 ml concentrated

RN03 and 1 ml of HzOz (30 ) The solution was evaporated almost to dryness The residue was disshysolved in 2 ml concentrated HCI with a minimum of boiling and 13 ml of redistilled water were added The reduction of As was performed by addshying of 18 ml (slowly by dropping) of sodium tetshyrahydridoborate (NaBH4 ) solution (126 mg of NaBH4 for 1 mg As(V)) and HCI so the solution have concentration of 1 mol-T HCl The precipishytate of elemental form of arsenic was filtered and the solution was transferred into a volumetric flask of 25 ml From this solution determination of inshyvestigated trace element was performed Iron manganese and zinc were analyzed by flame atomic absorption spectrometry (FAAS) and the other elements by ETAAS

Stibnite In the glass beaker of 100 ml 01 g of powdered sample was dissolved in 10 crrr of cone HCI 1 crrr of cone HN03 and 1 crrr of HzOz The solution was evaporated almost to dryshyness and the residue was then dissolved in 2 crrr concentrated HCI with a minimum of boiling and 13 ml of redistilled water were added The following procedure is the same as for realgar and orpiment

RESULTS AND DISCUSSION

Investigation ofarsenic and antimony interferences on trace elements absorbance

As it was mentioned in the Introduction the major problem which must be confronted in AAS mostly in ETAAS besides the choice of appropri shyate instrumental parameters regards the study and control of the matrix effects The interference of matrix element of the mineral studied (As and Sb) on the Fe Mn and Zn determination by FAAS and on the Cd Co Cr Cu Ni Pb determination by ETAAS was investigated Series of solutions with the same concentration of these elements and difshyferent concentration of interfering elements were prepared so that the concentrations of these eleshyments were similar to the concentrations in the sample solutions Results show that the interfering element tends to decrease the absorbance of invesshytigated elements in ETAAS measurements (Figs 1 and 2) As it can be seen during direct determinashytion of investigated trace elements arsenic and anshytimony decrease their absorbance To eliminate these interferences it is necessary to separate trace

Geologica Macedonica 1773-82 (2003)

elements from arsenic and antimony matrix In this study elimination of As and Sb was performed by reduction in elemental state precipitation and filshytration Reduction of As and Sb from the mineral solutions was performed by sodium tetrahydridoshyborate(III)

A

025

005 o 50 100 150 200

3m(As) m(M) 10shy

Fig 1 Influence of arsenic on Ihe absorbance of Co () Ni (e) Pb (A) and Cd (_) in ETAAS determination

------------------76

02

N Angelov T Stafilov

~5 L -_ - --=

~ middot middot ----f- -f-- middot ---~--0 15

o 10 0 200 30 0 400

m(Sb ) m(M) 10- 3

Fig 2 Influence of antimony on the absorbance of Cd (+) Co ()Cr () Cu ( ) Ni (0) Pb (A)

in ETAAS determination

Optimization of the condition f or arsenic and antim ony reduction and elimination by sodium

tetrahydridoborateiIII)

In this work the elimination of arsen ic and anshytimony was performed by their precipitation into elemental As and Sb using NaBH4

NaBH4 + 3H20 + HCI =NaCI + HJBOJ + 4H 2

2As J+ + 3H2 =2As + 6W

Table 3

2AsS + + 5H2 =2As + 10H+

2Sb3++ 3H2 =2Sb + 6H+

2Sbs + + 5H2 =2Sb + 10H+

As it can be seen from the reactions the reshyducti on of As and Sb has two phases obtaining of hydrogen and the reduction of As and Sb from tree or five-o xidant state into elemental As or Sb From these reactions it can be seen also that the stoichiometric ratio of As(Ill) or Sb(III ) and NaBH4

is 23 and for As(V) or Sb(V) this ratio is 25 The optimal mass of NaB H4 was es tablished by measshyuring the redu ction grade of As and Sb by changshying the mass of NaBH 4bull Experiments were pershyformed both for As(III) and Sb(III) and for As(V) and Sb(V) on room temp erature and on temperashyture of wate r bath (about 70 QC) Mass of NaBH4

which was taken du ring these experiments was 09 1 12 16 and 2 times higher than calcu lated soichiometric ratio For tree-oxidant state forms nishytric acid was taken and for five valent form hydroshychloric acid The obtained recoveries for As Sb and the investigated elements are given in Tables 3 and 4

Dependence of recovery (R ) ofAs Co Cd Cr Cu Fe Mn tlaquo Pb and Znfrom mass of NaBH4

in the presence of As

m(NaBH4)1mNaBH4) calculated As Co Cd Cr Cu Fe Mn Ni Pb Zn

As(III)

Room temperature bullbull bull _ bull bull bull bull bullbullbull bull bull bull bull bull bull bull bull bull bull bull bull bull bull bull ~ _ _ bullbullbull ___bull bull bull bullbullbull_ bullbullbull_ bullbullbullbullbull bullbullbullbullM bull bull _ bull bull _ _ _ bullbullbullbullbullbullbull~ ~ ~_ ~ _ _ _ ~middot

09 354 980 981 100 795 929 9560 980 980 100 10 190 980 961 100 846 917 9560 981 980 100 12 68 100 961 100 935 918 9560 100 977 100 16 14 965 953 956 92 1 875 9250 982 95 0 965 20 14 898 910 810 890 851 8990 938 943 896

_ ___ H _ _ _ _bull w bull bull bull bull bull bull bullbull bull bull bull __bullbull _ _ __ww__ _~ W

_~___ _ _ _ _ _ Te ITJE~ r~_t~~~f~0 0lt=_ ____ _--- -- -________________-_09 367 966 950 100 861 936 100 100 100 100 10 245 943 945 100 854 926 9800 100 100 100 12 95 960 945 955 830 875 972 1 100 100 955 16 37 910 middot 901 955 729 875 94 15 950 961 955 20 14 854 877 947 700 851 9012 938 902 911

As(V)

____~ - _______- _---- _ ______ __ _~~lt~ ~~~_E r~~ ~~ wmiddotmiddotmiddotmiddotmiddotmiddot____ _-__shy09 349 694 948 100 101 929 1000 985 986 100 10 148 1000 948 100 101 918 936 976 986 100 12 87 1000 919 100 69 935 954 903 815 100 15 18 1000 897 100 60 930 954 873 815 100 20 I7 767 793 959 45 800 913 756 710 935

_~___ __ --- ____-------_ ___--__--__ ___ ____________----_ __- _____---- ---________-shy________________ ____ _________ _____~~~pera~~~~ ltJf ~_~ ______ _________ _ _

~

__ ____ _ _-~ ~--

09 415 747 982 100 983 938 1000 100 100 100 10 227 1000 963 100 934 928 955 976 100 100 12 108 1000 974 100 915 899 972 954 100 100 15 98 1000 959 100 797 750 972 942 100 100 20 46 1000 942 100 684 881 936 942 100 9694

Geologica Macedonica 1773- 82 (2003)

Determination oftrace elements in arsenic and antimony minerals by atomic absorption spectrometry with previous matrix modification 77

Table 4

Dependence oJrecovery (R ) ofSb Co Cd Cr Cu Fe Mn Ni Pband Zn from mass oJNaBH4 in the presence ojSb

m(NaBH4) Sb Co Cd Cr Cu Fe Mn Ni Pb Zn

mNaBH4) c lculated

Sb(Ill)

Room temperature

09 38 100 100 100 413 100 930 100 900 100

10 19 100 986 100 360 100 950 100 100 945

12 15 100 986 960 346 100 940 100 100 891

15 ll 100 100 920 253 100 970 966 700 835

20 07 100 100 920 253 100 940 933 900 702

Temperature of 70degC

09 54 100 986 920 706 933 920 933 100 872

10 46 100 986 920 720 933 930 906 900 860

12 42 960 986 920 680 965 930 906 900 830

15 39 960 980 920 626 977 930 906 800 783

20 31 940 980 920 __--______-__--shy _--__

624 888 _ ___-_

910 906 780 bull bullbull _ __ H bullbull __bullbullbullbullbullbull

765

_- _ _ Sb(V)

- _-_ _- shy ---___ bullbullbullbullbull __-_ __ bull __-_

Room temperature _- _shy__ bullbullbullbullbullbull____- _____ --_

09 380 100 100 100 922 892 974 100 100 100

10 jj9 100 960 100 897 846 974 100 100 970

12 300 100 100 100 823 975 974 100 100 970

15 277 100 100 958 603 901 987 970 100 960

20 203 100 946 958 603 843 987 970 100 910 ____---__--- _ __ __- __ _ _ __ _____ --_ ___- _ _ ___---_---- _-_____ _____

~-__--_ _~-

Temperature of 70degC __-_-_- ---_- _____ _____________w__w____--____- _~ _____-_ _____

09 400 941 790 100 867 872 974 970 950 940

10 379 941 835 100 882 896 974 940 950 940

12 347 941 100 100 882 897 974 940 100 920

IS 290 882 980 970 867 775 935 870 100 920

20 263 765 833 970 725 615 883 860 950 910

As it can be seen from the results given in Tables 3 and 4 better results on the reduction of As and Sb are obtained on room temperature The reduction rate for As is from 6464 (09 from stoichiometric ratio with NaBH4) up to 9866 (2 times higher than stoichiometric ratio) As optimal mass of NaBH 4 for the reduction of As was taken 12 times higher mass than calculated It can be also seen that except Cu the other investigated elements dont precipitate with NaBH 4and stay in the solution and can be directly analyzed In the case of copper by the increasing of mass of NaBH4 the recovery of copper decreases because in the presence of HCI copper precipitates by NaBH 4

Geologica Macedonica 1773-82 (2003)

NaBH4 + 3H20 + HCl =NaCl + H3B03 + 4H2

CuCh + H2 =Cu + 2HCI

Keeping mass of NaBH4 constant and changshying the concentration of acids optimal concentrashytions of HCI (for As(III) and Sb(III) and Sb(V) and HN03 (for As(V) were determined The concentrashytion range for HCl and RN03 for As was from 025 to 20 mol-T and for Sb from 15 to 35 rnol-l The results are given in Tables 5 and 6 Experishyments were performed both on room temperature and on water bath temperature For optimal conshycentration for arsenic was taken 2 mol-l of HCI and HN03 and 3 mol-T of HCl for Sb

78 N Angelov T Stafilov

T able 5 Dependence of recovery (R ) ofAs Co Cd Cr cu Fe Mn Ni Pb and Zn

from the conc entration ofHCl in the presence ofAs

c(HCI)mol I- 1 As Co Cd Cr Cu Fe Mn Ni Pb Zn

As(III)

Room temperature

025 436 424 224 353 301 207 266 162 407 100

05 372 100 829 100 285 831 827 756 100 100

10 175 100 921 100 275 883 911 821 100 100

15 62 100 971 100 254 1000 9 19 854 100 100

20 28 100 941 100 218 1000 953 910 100 442

middotmiddotmiddotmiddot__ ___middotmiddot _M_ _ _~_ __ __ _ __ ww_ middotmiddot_ _middot__ Temperature of 70 DC

w M _ bull bull__ bullbull _ middot __middot_middotmiddot middot middot ________-_shy -___ ___ -___ bull_ 05 436 490 209 401 481 2 10 266 153 423 100

10 299 100 829 100 397 831 908 691 100 100

12 143 100 917 100 306 903 945 728 100 966

15 138 100 927 100 278 100 961 854 100 983

20 136 100 9 17 100 245 100 891 888 100 980

As(V )

___-shy - - -- shyRoom temperature

_--__ shy _shy_ _- -shy____---- _bull bull

025 420 918 601 851 900 666 875 1000 982 1000

05 335 856 897 978 923 833 9 17 980 951 1000

10 180 930 948 1000 945 918 935 976 935 1000

15 65 936 948 929 945 958 917 955 902 932

20 40 856 948 877 950 458 933 942 902 954

__-_ -__-__-_bullbull___-shy _ ___shy _-Temperature of 70 DC

_ bull~ ___ _-__shy 025 429 950 658 934 920 9 16 875 1000 982 1000

05 210 968 970 1000 935 918 966 999 962 1000

10 110 980 973 1000 960 918 970 1000 955 1000

15 95 952 982 963 968 958 966 987 968 988

20 87 952 979 942 975 958 958 993 937 988

Table 6 Dependence of recovery (R ) of Sb Co Cd Cr claquo Fe Mn st Pb and Zn

f rom the concentration of HCl f or Sb(lIl)

c(HCl)molT Sb Co Cd Cr Cu Fe Mn Ni Pb Zn

Room temperat ure ~-_ __-_-~ ___ __~ _____-_ - -_- __-_ _ _________- ____-_ _____- _ ____---- __-- -_

~--~ ~

15 26 1000 100 960 586 1000 930 900 900 986

20 35 1000 986 960 506 1000 930 935 1000 986

25 54 1000 980 960 613 1000 940 986 1000 100

30 50 1000 970 960 643 1000 930 966 900 993

35 66 1000 960 920 680 1000 910 966 900 956 ______-- ---__ __--_ __-__-- - -- - - _ __-______~-~ _--_ _ -__ ___~- ___--__--_- __--- -- __- - _ __shy

Temperature of 70 DC ~ ~__ _ _- ____--_ _ _ _______--__ __--_ ___ __- ---_____~~ _~ _~ _ _____-__

~ ~

15 54 1000 980 840 760 1000 920 966 900 871

20 54 1000 980 840 786 1000 920 966 1000 860

25 62 1000 980 840 906 1000 920 930 1000 837

30 66 1000 957 840 786 1000 890 930 1000 756

35 70 1000 957 820 880 1000 880 930 1000 763

Geologica Macedonica 1773-82 (2003)

Determination of trace elements in arsenic and antimony minerals by atomic absorption spectrometry with previous matrix modification 79

To verify the method some samples of realshy No mM(added) l1v1(calculated) R gar and orpiment minerals with standard addition ~g ~g g-I

of Cd Co Cr Ni and Pb were prepared and Orpiment treated by using the proposed procedure The reshy 1 119 sults given in Table 7 show that satisfactory recovshy

2 50 169 165 976 ery results were obtained (from 926 to 995) Beshy

3 100 219 218 995 cause of higher content of Fe Mn and Zn these Stibniteelements were determined by FAAS directly from

the obtained solutions (Table 8) I 395

2 50 445 434 975

3 100 495 470 944 R~_~ ~ _ _ __ __ ___ _____ __--- -- -- - ----- __

Table 7 Pb

Content of Co Cd Cr Ni and Pb in realgar orpishy Realgar

ment and stibnite determined by standard addition I 114

meth od 2 50 164 163 988

3 100 214 209 961 R ugg

YM(calculated) Orpiment

Co I 021

Realgar 2 50 07 1 067 947

I 008 3 100 121 119 988

2 100 108 100 926 Stibnite

3 200 208 196 942 I 065

Orpiment 2 50 115 107 930

I 005 3 100 165 152 921

2 100 105 098 938 Ni

3 200 205 198 936 Realgar

Stibnite I 130

I 500 2 50 180 174 967

2 50 642 594 925 3 100 230 220 956

3 100 694 645 929 Orpiment ___ __ middotmiddotmiddotmiddotmiddot _~middotmiddot _____middotP_-_bull__ __ __ - -- - - _ _____ _

Cd I 073

Realgar 2 50 103 099 961

I 154 3 100 153 146 954

2 50 204 199 975 Stibnite

3 100 254 250 984 I 821

Orpiment 2 50 87 1 826 948

I 045 3 100 921 863 937

2 50 095 089 936

3 100 145 138 952

Stibnite Table 8

I 294 Content of Fe Mn and Zn in realgar orpiment and2 50 344 323 939

stibnite mineral samples (in jlg g-l)3 100 394 366 929

Cr Mineral Fe Mn Zn Realgar

Realgar 14058 1780 925 I 160

Orpiment 2267 318 549 2 50 21 201 958

Stibnite 925 115 8863 100 26 257 990

Geologica Macedonica 17 73-82 (2003)

80 N Angeiov T Stafilov ------------------- ---_

Using these methods investigated elements neutron activation analysis Palme et al 1988 were determined in various samples of the realgar Frantz et al 1994 Lazaru et al 2002) mass specshyorpiment and stibnite from Allchar mine (Table 9) trometry (Todth 1988 Boev et al 1993b Frantz The obtained values for their content are in agreeshy et al 1994) or AAS (Lazaru and Stafilov 1993 ment with those obtained for the same mineral s 2000 Stafilov et al 1990 ) (Table 9) by us and by the others authors using

Table 9

Measured content levels f or Co Cd Cr Ni Pb Fe Mn and Zn in realgar orpiment and stibnite from All char mine (given in Jlgg-I )

Element Realgar Orpiment Stibnite

Co lt00 8 (Palme et al 1988) lt I (Boev et aI 1993) lt40 (Frantz et aI 1994) 010-080 (Lazaru and Stafilov 2000) 139plusmn056 (Lazaru et al 2002) 008

lt04 1 (Palme et al 1988) lt7 (Frantz et al 1994) 0086-11 6 (Lazaru and Stafilov 2000) OlOOplusmnOO17 (Lazaru et al 2002) 005

lt 10 (Boev et aI 1993) 590

Cd lt100 (Lazaru et al 2002) )54

lt lOO(Lazaru et al 2002) 045

294

Cr lt20 (Palrne et al 1988) lt1 (Lazaru and StafiJ ov 1993) 698 (Frantz et aI 1994) 264plusmn014 (Lazaru et aI 2002) 160

lt lOO (Palme et aI 1988) lt1- 326 ( ~azaru and Stafilov 1993) 042plusmn004 (Lazaru et aI 2002) 119

lt10 (Boev et aI 1993) 4 (Lazaru and Stafilov 1993) 395

Ni lt 10 (Palme et al 1988) lt1-4 10 (Lazaru and Stafilov 1993) 075-176 (Lazaru and Stafilov 2000) 130

lt 30 (Palme et al 1988) lt1-74 (Lazaru and Stafilov 1993) 129-486 (Lazaru and Stafilov 2000) 073

lt200 (Boev et ai 1993) 96 (Laza ru and Stafilov 1993) 821

Pb 038 (Todt 1988) 08 (Boev et al 1993)

001-08 (Frantz et al 1994) 5 (Ljubicic et aI 1988) 029-3 16 (Lazaru and Stafilov 2000) 114

116 (Todt 1988) 2 (Boev et al 1993) 007-116 (Frantz et al 1994) 165-373 (Lazaru and Stafilov 2000 ) 021

lt lO (Boev et al 1993) 038-247 (Stafilov et aI 1990) 065

Fe lt20 (Palme et aI 1988) 365- 14 lO (Lazaru and Stafilov 1993) 57500plusmn2300 (Lazaru et aI 2002) 14058

lt200 (Palme et al 1988) lt800 (Boev et aI 1993) 96-620 (Lazaru and Stafilov 1993) 169plusmn12 (Lazaru et aI 2002) 2267

gt1000 (Boev et aI 1993) 925

Mn lt90 (Boev et al 1993)

704-955 (Lazaru and Stafilov 1993)

lt4 (Frantz et aI 1994)

100 (Palme et ai 1988)

lt20 (Boev et aI 1993)

50-283 (Lazaru and Stafi lov 1993)

lt50 (Boev et aI 1993)

115

1780 lt8 (Frantz et aI 1994)

318

Zn lt30 (Frantz et aI 1994)

665plusmn27 (Lazaru et al 2002)

925

28 (Palme et al 1988)

lt07 (Lazaru et al 2002)

549

lt30 (Boev et aI 1993)

886

This work

GeologicaMacedonica 17 73-82 (2003)

Determinetion oftrace clements in arsenic and antimony minerals by atomic absorption spectrometry with previous matrix modification 81

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Jankovic S 1988 The Allchar Tl-As-Sb deposit Yugoslavia and its specific metallogenic features NucJ Instr Phys Res A271 286

Komarek J Kolcava D Sommer L 1980 Atomic absorpshytion spectrometry of cobalt in the presence of chelating agent Collect Czech Chem Commun 45 3313-9

Kuroda R Nakano T Miura Y Oguma K 1986 Detershymination of trace amounts of nickel and cobalt in silicate rocks by graphite furna ce atomic absorption spectrometry elimination of matrix effects with an ammonium fluoride modifier J Anal At Spectrom 1429

Lazaru A Stafilov T 1993 Determination of Fe Mn Cu Cr and N i in sulfide min erals from Alshar by atomic abshysorption spectrometry Geologica Macedonica 7 73-80

Lazaru A Stafilov T 1994 Determination of cobalt and zinc in some minerals from Alshar mine by atomic absorpshytion spectrometry Proceedings on XXVI October Confershyence of Miners and M etallurgists Donji Milanovac pp 427-31

Lazaru A Stafilov T 1998 Determination of copper in sulfide minerals by Zeeman electrothermal atomic absorpshytion spectrometry Fresenius J A na Chem 360 726-8

Lazaru A Stafilov T 2000 Determination of Co Ni and Pb in arsenic minerals by Zeeman electrothermal atomic ab shysorption spectrometry Bull Chem Technol Macedonia 19 21-6

Lazaru A me R Skvarc J Kristof E S Stafilov T 1999 Neutron induced autorad iography of some minerals from Allchar min es Radiation Measurements 31 677shy682

Lazaru A Jacirnovic R Ilic R Mihajlovic D Stafilov T 2002 Determination of major and trace elements in some minerals by ko-NAA J Radioanal Nucl Chem 253 427-4

Palme H Pavicevic M K Spettel B 1988 Major and trace elements in some min erals and ore from Crven Dol Allchar NucJ Inst Meth Phys Res A271 314-9

Pavicevic M K 1994 The LO REX - Project solar neushytrino detection with the mineral lorandite N Jb Miner AM 167205-245

Sedykh E M Bel yaev Yu I Sorokina E V 1980 Matrix effect during electrothermal atomic absorption determinashytion of silver tellurium lead cobalt nickel in minerals of complex composition Zh Anal Khim 35 2162-9

Sedykh E M Belyaev Yu I Sorokina E V 1980b Elimination of matrix effects in electrothermal atomic abshysorption determination of silver lead cobalt nickel and

tellurium in samples of complicated composition Zh Ana Khim 35 2348-52

Shelpakova 1 R Rossin A E Chhanisheva T A Shchershybakova O 1 1991 Atomic-absorption determination of impurities in high-purity arsenic with preliminary matrix removal by volatization in the form of its sesquioxide Vishysokochist veshchestva 5 170-5

Stafilov T Todorovski T 1987 Determination of gold in arsenic-antimony ore by flameless atomic absorption specshytrometry At Spectrosc 8 12-4

Stafilov T Todorovski T Grozdanova B Spandzeva Lj 1988 Determination of thallium in ore from All char by atomic absorption spectrometry Nuc Instr Meth Phys Res A271 321-3

Stafilov T Todorovski T 1990 Determination of molibdeshynum in arsenic-antimony ore by flame less atomic absorpshytion spectrometry AI Spectrosc 11202-4

Stafilov T Jordanovska V Aleksovska S 1990 a Matrix interferences in the determination of lead in As-Sb-Tl ores by electrothermal atomic absorption spectrometry Bull Chem Techno Macedonia 8 93- 8

Stafilov T Jordanovska V Aleksovska S 1990b Detershymination of lead in arsenic minerals from Alshar by atomic absorption spectrometry Bull Chem Techno Macedonia 9 159-66

Stafilov T Jordanovska V Aleksovska S 1990c Detershymin ation of lead in antimonite by electrothermal atom ic absorption spectrometry Vest Slov Kem Drust 37 141-8

Stafil ov T Lazaru A Pernicka E 1993 Determin ation of thallium in sulfide minerals by Zeeman electrothermal atomic absorption spectrometry Acts Chim Slo 41 37shy46

Stafilov T Aleksovska S Jo rdanovska V 1994 Determishynation of lead in lorandite and marcasite by electrothermal atomic absorpt ion spectrometry N lb Miner Abh 167 401-8

Stafilov T Lazaru A Pernicka E 1995 Determination of silver in sulfide minerals by electrothermal atomic absorpshytion spectrometry At Spectrosc 16 158-61

Stafilov T 2000 Determination of trace elements in min erals by electrothermal atomic absorption spectrometry Specshytrochim Acta Part B 55 893-906

Todt W 1988 Isotope dilution mea surements of Pb U and Tb concentration in lorandite from Allchar Nucl Instr Meth Phys Res A271 251-2

Tominaga M Umezaki Y 1983 Ev aluation of interference suppressors in electrothermal atomic absorption specshytrometry Anal Chim Acts 148 285-91

Zelentsova L V Yudelevich 1 G 1983 Atomic absorption analysis of high purity arsenic Zh Anal Khim 38 1404 -7

Zendelovska D Stafilov T 200 I Extraction separation and ele ctrothermal atomic absorption spectrometric det erminashytion of thallium in some sulfide minerals Anal Sci 17 425-8

Geologica Macedonica 1773-82 (2003)

Determination ot trs cc clem ents I iI arsenic and antim ony minerals by atomic absorption spectrometry with previous matrix modification 81

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Komarek J Kolcava D Sommer L 1980 Atomi c absorp shytion spectrome try of cobalt in the pre sence of chelating agent Collect Czech Chern Commun 45 3313-9

Kuroda R Nakano T Miura Y Oguma K 1986 Detershymination of trace amount s of nickel and cobalt in silicate rocks by graphite furna ce atomic absorption spectrometry elimination of mat rix effects with an am monium fluoride modifier J Anal At Spectrom 1429

Lazaru A Stafilov T 1993 Determination of Fe Mn Cu Cr and Ni in sulfide minerals from Alshar by atomi c abshysorption spectrometry Geologica Mscedonice 7 73-80

Lazaru A Stafil ov T 1994 Determina tion of cobalt and zinc in so me minerals from Alshar mine by atomic absorpshytion spectrometry Proceedings on X XVI October Confershyence of Miners and M etallurgists Donji Milanovac pp 427-3 I

Laza ru A Stafilov T 1998 Determination of copper in sulfide minerals by Zeeman elect rothe rmal atomic absorpshytion spectrometry Fresenius J A na Chem 360 726-8

Laza ru A Stafilov T 200 0 Determ ination of Co Ni and Pb in arsenic mine rals by Zeeman e lectrotherma l atomic abshysorp tion spectrometry B ull Chem Technol Macedonia 19 21- 6

Lazaru A Ilic R Skvarc J Kristof E S Stafilo v T 1999 Neutron induce d autoradiog raphy of som e minerals from Alichar mines R adiation M easurements 31 677shy682

Lazaru A Jacimovic R Ilic R Mihajlovic D Stafilov T 2002 Determination of major and trace elements in some minerals by ko-NAA J Radioanal Nuc1 Cbem 253 427--4

Palme H Pavicevic M K Spettel B 1988 Major and trace elements in some minerals and ore from Crven Dol Allchar N uc1 Inst Meth Phy s Rcs A271 3 14-9

Pavicevic M K 1994 Th e LOREX - Project solar neu shytrino detection with the mineral lorandite N Jb Miner A M 167205-245

Sedykh E M Bel yaev Yu I Sorok ina E V 1980 Matrix effect during electrothermal atomic absorption determinashytion of silver tellurium lead cobalt nickel in minerals of complex composition Zh Ana Khim 35 2162-9

Sedykh E M Belyaev Yu I Sorok ina E V 1980b Elimination of matrix effects in elec trothermal atomic abshysorpt ion determination of silver lead cobal t nickel and

Geologica Macedonica 1773- 82 (2003)

tellurium in samp les of complicated composition Zh Anal Kbirn 35 234 8-52

Shelp akov a I R Rossin A E Chhanisheva T A Shchershybakova O L 1991 Atomic-absorpt ion determination of impurities in high-purity arsenic with preliminary matrix removal by volatization in the form of its sesquioxide Vishysokochist veshchestva 5 170-5

Stafilov T Todoro vski T 1987 Determination of gold in arsenic-antimony ore by flameless ato mic absorption spec shytrometry At Spectrosc 81 2--4

Stafilo v T Todorovski T Grozdanova B Spandzeva Lj 1988 Determ ination of thallium in ore from Allchar by atomic absorption spectrometry N ucl Ins tr Meth Phys Res A271 321-3

Stafilov T Todorovski T 1990 Deter mination of molibdeshynum in arsenic-antimony ore by flameless atomic absorpshytion spectrometry At Spectrosc 11202--4

Stafilov T Jordanovska V Aleksovska S 1990a Matrix interferences in the dete rmination of lead in As-Sb-T l ores by electrothermal atom ic absorption spec trome try Bull Chern Techno Macedonia 8 93-8

Stafilov T Jordanovska V Aleksovska S 1990b Detershymination of lead in arsenic mine rals from Alshar by atomic absorption spec trometry Bull Chern Technol Ma cedonia 9 159-66

Stafi lov T Jordanovska V Aleksovska S 1990c Detershymination of lead in antimonite by electrothermal atomic absorption spectrometry Vest Sio v Kern Dtust 37 141-8

Stafilov T Lazaru A Pernick a E 1993 Dete rmin ation of thall ium in sulfide minerals by Zeem an electrothermal atomic absorp tion spec trometry Acta CIJJin Slo 41 37shy46

Stafilov T Aleksovska S Jordanovska V 1994 Determishynation of lead in lorand ite and marcasite by electrothermal atomic absorption spectrometry N Jb Miner Abb 167 401-8

Stafi lov T Lazaru A Pemicka E 1995 Dete rmination of silver in sulfide minerals by electrotherm al atomic absorpshytion spectrometry At Spectrosc 16 158-6 I

Stafilov T 2000 Determination of trace elements in minerals by electrothermal atomic absorpt ion spectrometry Specshytrochim Acta Part B 55 893- 906

Todt W 1988 Isotope dilution measurements of Pb U and Th concentration in lorandite from Allchar Nucl Instr M eth Phys Res A271 25 1-2

To minaga M Umezaki Y 1983 Evaluation of interference suppressors in electrothermal atomic absorption specshytrometry Anal Chim Acta 148 285-9 1

Zelentsova L V Yudelevich I G 1983 Atom ic absorption analysis of high purity arsen ic Zh Anal Kbim 38 1404 -7

Zendelovska D Stafilov T 2001 Extr action separation and e lectrothermal atomic absorption spectrometric determinashytion of tha llium in some sulfide minerals Anal Sci 17 425~8