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Three trace-element geological materials certified as a result of a co-operative investigation
Talanta. Vol 22, pp 1048-1050
Pergamon
Press
1975 Pnnted m Great Bntam
ANALYTICAL DATA THREE TRACE-ELEMENT GEOLOGICAL MATERIALS CERTIFIED AS A RESULT OF A CO-OPERATIVE INVESTIGATION OLAV
H J CHRISTIE
Umversrty of Oslo, Laboratory of Mass Spectrometry, P b 1048 Bhndern, Oslo 3, Norway (Received 19 December 1974 Accepted 13 January 1975) Since 1968 twenty-two chemtcal analysts from Nordtc countrtes have partrcrpated m a co-operattve work for mtercahbratron of trace-element analytical techniques Three geological materials were selected as working samples ASK-l, Larurkrce, from the Tvedalen quarry SW of the town Larvrk, Vestfold country, South Norway Thts 1s a type locality of the hghtcoloured variety of larvrktte, described by Barth 1 ASK-2, Schzst, from the Upper Tremadoc Ceratopyge schist [3b of the Oslo region Aremgan (Lower Ordovraurn)] m the underground of St Olavs plass, Oslo 1, Norway,‘described by BJ0rlykke ’ ASK-3. Sulohlde ore. from the zmc-lead ore-body at Bleikvash mines, Nordland county, North Norway,. described by Vokes ’ Preparation of samples
Each sample was mrttally washed m pure water and cut m pieces with a hydrauhc rock cutter After the first crushmg m a Jaw crusher the sample was spht mto two parts Equal amounts of the two parts were powdered m a steel rmg eccentric ml11 (Labor-Scheibschwmgmuhle, Srebteckmk, Germany) The finely crushed sample was spht mto two parts, and the parts again mrxed together m a heavy cardboard contamer with a 40-kg Turbula mixer (Wtlly
Bachofen, Basel, Switzerland) The cardboard container showed no signs of wear after the homogemzatron The homogenerty of the sample materials was checked thus ten independently collected samples of each matertal were pressed, without bmdmg matenal and wrth a backing of polyjvmyl chlortde), to form drscs of 25 mm diameter smtable for X-ray fluorescence analyses Counts of the K line of rron of 64sec duratton were recorded five times for each sample The estimated relatrve standard deviation of the number of counts per recordmg of the total number of samples was 0 6”/, whereas 14 recordings of one of the samples over the whole period of analysts gave an estimate of relattve standard devratton of 0 4%, mdicattve of absence of mstrumental drift The 95% confidence interval was Y(l f. 00017) for the whole set of observations and Jz(1 k 00021) for the drift-check parallels Participants and chozce of recommended values
Laboratories and analysts who have supplied concentration data are listed m Table 1 The recommended values m Tables 2 and 3 have been selected m a series of round-table meetmgs of the partrcrpatmg analysts These values are given as means of values supplied by partrctpants The means are based upon two or more values m good agreement and reported by at least two analysts from
Table 1 Analysts 1 2 3 4 5
L-H B T A-L K 0 H J
Andersson Anderassen Arnfelt BJerlykke Bolhngberg
6 A 0 Brunfelt 7 B Bruun 8 0 H J Christie 9 L Damelsson 10 G C Faye 11 S Fregerslev 12 F J Langmyhr 13 14 15 16
W Lund S Melsom P E Paus A R Selmer-Olsen
17 A Srmonsen 18 E Stemnes 19 G Sundkvtst 20 I Serrensen 21 C U Wetlesen 22 H Zachartasen
FOA, S-104-05 Stockholm 80, Sweden Geologrcal Survey of Norway, P b 3006, N-7001 Trondhemr, Norway A B Atomenergr Studsvrk, S-611 01 Nykopmg 1, Sweden Instttute of Geology, University of Oslo, P b 1047 Bhndern, Oslo 3, Norway Umverstty of Copenhagen, Mmeralogrcal Museum, Bstervoldgade 10, DK-1350 Kerbenhavn, Denmark Umversrty of Oslo, Mmeralogtcal-Geologrcal Museum, Sars gate 1, Oslo 5, Norway University of Oslo, Mmeralogrcal Geologrcal Museum, Sars gate 1, Oslo 5, Norway Umversrty of Oslo, Laboratory of Mass Spectrometry, P b 1048 Blmdern, Oslo 3, Norway Swedish Institute of Metal Research, Drottnmg Krlstmas vag 48, S-l 14 28 Stockholm, Sweden Geological Survey of Norway, P b 3006, N-7001 Trondheun, Norway Umverslty of Aarhus, Department of Geology, DK-8000 Arhus C, Denmark (Some data m collaboration with analyst no 15) Umverstty of Oslo, Institute of Chemrstry, P b 1033, Bhndern, Oslo 3, Norway Umversttv of Oslo. Instrtute of Chemtstrv. P b 1033, Bhndern, Oslo 3, Norway Institute of Industrral Research, Forskmngsveren 1, Blmdern, Oslo 3, Norway Instrtute of Industrial Research, Forskmngsveren 1, Blmdern, Oslo 3, Norway Norwegian Agriculture Umversrty, Laboratory of Chemical Analysis, 1432 Vollebekk, Norway Technical Umversrty of Denmark, Instrtute of Mineralogy, Bld 204, 2800 Lyngby, Denmark Instrtute of Atomic Energy, 2007 KJeller, Norway Bohden AB Ronnskarsverken, Centrallaboratorlet, Skeleftehamn, Sweden The Geological Survey of Greenland, Bstervoldgade 10, DK 1350, Ksbenhavn K, Denmark Central Institute of Industrial Research, Forsknmgsveren 1, Blmdern, Oslo 3, Norway Falconbrrdge Nrkkelverk A/S, 4600 Krrstransand S, Norway 1048
ANALYTICAL
Table 2 Uncertified concentration
SlO*
TIO~ Al203 Total Fe as Fe,Op MnO MgO CaO Na,O K@ Fe cu Pb Zn S C
ASK-l Larvlklte
ASK-2 Schist
ASK-3 Sulphlde ore
59 5 11 186 46 013 11 32 65 42
542 092 188 69 003 20 07.5 08 53
74 trace 03
Au As B Ba Be Bl Cd Cl Co Cr cs cu Ga Hg In Ll Mn MO NI Rb SC Sr Tl V Zn Zr
005 1130 4
85
-
mean because there has been general agreement on the superiority of given methods or experience of some of the participants Some of the participants have found this type of work so encouraging that it ~111be continued with other materials Samples of the present three reference materials are available m 75-g lots, together with a list contammg all reported concentration values and covering 41 trace elements Further mformatlon 1s obtainable from the author
values (ppm) and analytical methods used
ASK-2
ASK-3
04 153
19 006 630 35
4
100 6 40 15 7 29 -
14 27 90 11 120 25 -
18 1020 110 85 7 680 main element 49 105 400
30 280 60 148 175 100 mam element 220 166 168
aa atonuc-absorption methods ch wet chemical methods, mainly tltrlmetrlc ‘3s spark-source mass-spectrometry OS optical spectrography xr X-ray fluorescence analysis naa neutron-activation analysis TAL 22/12-H
004 008 005 0018 0 070 35 6 014 21 92 4150
-
Table 3 Recommended trace concentration
Ag
1049
values (%) of major and some mmor constrtuents
different laboratorles and usmg different methods, each analyst havmg a thorough knowledge of his own method The methods applied are anodlc strlppmg voltammetry, atomic-absorption spectrometry, electrolysis, flame emlsslon methods, gravlmetrlc methods, spectrophotometry, tltrlmetrlc methods and X-ray fluorescence The evaluation of the results has benefited considerably from the extensive methodological dlscusslons m which most of the partlclpants have taken part In several cases the recommended values are different from the arithmetic
ASK-l
DATA
33 340 7 88 25 1450 6 76 177 260 45 37
33 main element
Methods used aa, ms, naa, OS naa ms, OS, xr OS OS OS aa, ms, xr aa, ms, naa, 0% XT ch, naa aa, naa, os, xr aa, ms, naa, OS, xr naa aa, ch, naa, OS, xr ms, naa, os, xr aa, OS aa, naa aa, OS aa, ms, naa, os, xr ms, naa, os, XT aa, ms, OS, xr aa, naa, os, xr naa naa, OS, xr aa, ch, OS ch, ms, OS aa, naa, OS, xr OS, xr
1050
ANALYTICAL
Acknowledgements-Among the partclpants, L -H AndersF J Langmyhr and E Stemnes m particular have offered valuable suggesttons for the tmprovement of the text Part of this work has been supported by Nansenfondet, Oslo son,
DATA
REFERENCES
1 T F W Barth, Skrrfter Norske Videnskaps-Akad Oslo,
1. Mat -Natur Klasse. 1944. No 9, 1 2 K 0 BJerlykke, Sedrmentology, 1974, 21, 251 3 J M Vokes, Norges Geol Undersokelse, 1963, No 222. 1
Summary-The results of a Nordic analytlcal trace-element study of three geologzal samples are given Recommended concentration values for 27 trace elements and 14 mam elements have been arrived at by the analysts m the course of several round-table conferences The samples are now available as reference materials, for other analytical laboratories
Pergamon
Press
1975 Pnnted m Great Bntam
ANALYTICAL DATA THREE TRACE-ELEMENT GEOLOGICAL MATERIALS CERTIFIED AS A RESULT OF A CO-OPERATIVE INVESTIGATION OLAV
H J CHRISTIE
Umversrty of Oslo, Laboratory of Mass Spectrometry, P b 1048 Bhndern, Oslo 3, Norway (Received 19 December 1974 Accepted 13 January 1975) Since 1968 twenty-two chemtcal analysts from Nordtc countrtes have partrcrpated m a co-operattve work for mtercahbratron of trace-element analytical techniques Three geological materials were selected as working samples ASK-l, Larurkrce, from the Tvedalen quarry SW of the town Larvrk, Vestfold country, South Norway Thts 1s a type locality of the hghtcoloured variety of larvrktte, described by Barth 1 ASK-2, Schzst, from the Upper Tremadoc Ceratopyge schist [3b of the Oslo region Aremgan (Lower Ordovraurn)] m the underground of St Olavs plass, Oslo 1, Norway,‘described by BJ0rlykke ’ ASK-3. Sulohlde ore. from the zmc-lead ore-body at Bleikvash mines, Nordland county, North Norway,. described by Vokes ’ Preparation of samples
Each sample was mrttally washed m pure water and cut m pieces with a hydrauhc rock cutter After the first crushmg m a Jaw crusher the sample was spht mto two parts Equal amounts of the two parts were powdered m a steel rmg eccentric ml11 (Labor-Scheibschwmgmuhle, Srebteckmk, Germany) The finely crushed sample was spht mto two parts, and the parts again mrxed together m a heavy cardboard contamer with a 40-kg Turbula mixer (Wtlly
Bachofen, Basel, Switzerland) The cardboard container showed no signs of wear after the homogemzatron The homogenerty of the sample materials was checked thus ten independently collected samples of each matertal were pressed, without bmdmg matenal and wrth a backing of polyjvmyl chlortde), to form drscs of 25 mm diameter smtable for X-ray fluorescence analyses Counts of the K line of rron of 64sec duratton were recorded five times for each sample The estimated relatrve standard deviation of the number of counts per recordmg of the total number of samples was 0 6”/, whereas 14 recordings of one of the samples over the whole period of analysts gave an estimate of relattve standard devratton of 0 4%, mdicattve of absence of mstrumental drift The 95% confidence interval was Y(l f. 00017) for the whole set of observations and Jz(1 k 00021) for the drift-check parallels Participants and chozce of recommended values
Laboratories and analysts who have supplied concentration data are listed m Table 1 The recommended values m Tables 2 and 3 have been selected m a series of round-table meetmgs of the partrcrpatmg analysts These values are given as means of values supplied by partrctpants The means are based upon two or more values m good agreement and reported by at least two analysts from
Table 1 Analysts 1 2 3 4 5
L-H B T A-L K 0 H J
Andersson Anderassen Arnfelt BJerlykke Bolhngberg
6 A 0 Brunfelt 7 B Bruun 8 0 H J Christie 9 L Damelsson 10 G C Faye 11 S Fregerslev 12 F J Langmyhr 13 14 15 16
W Lund S Melsom P E Paus A R Selmer-Olsen
17 A Srmonsen 18 E Stemnes 19 G Sundkvtst 20 I Serrensen 21 C U Wetlesen 22 H Zachartasen
FOA, S-104-05 Stockholm 80, Sweden Geologrcal Survey of Norway, P b 3006, N-7001 Trondhemr, Norway A B Atomenergr Studsvrk, S-611 01 Nykopmg 1, Sweden Instttute of Geology, University of Oslo, P b 1047 Bhndern, Oslo 3, Norway Umverstty of Copenhagen, Mmeralogrcal Museum, Bstervoldgade 10, DK-1350 Kerbenhavn, Denmark Umversrty of Oslo, Mmeralogtcal-Geologrcal Museum, Sars gate 1, Oslo 5, Norway University of Oslo, Mmeralogrcal Geologrcal Museum, Sars gate 1, Oslo 5, Norway Umversrty of Oslo, Laboratory of Mass Spectrometry, P b 1048 Blmdern, Oslo 3, Norway Swedish Institute of Metal Research, Drottnmg Krlstmas vag 48, S-l 14 28 Stockholm, Sweden Geological Survey of Norway, P b 3006, N-7001 Trondheun, Norway Umverslty of Aarhus, Department of Geology, DK-8000 Arhus C, Denmark (Some data m collaboration with analyst no 15) Umverstty of Oslo, Institute of Chemrstry, P b 1033, Bhndern, Oslo 3, Norway Umversttv of Oslo. Instrtute of Chemtstrv. P b 1033, Bhndern, Oslo 3, Norway Institute of Industrral Research, Forskmngsveren 1, Blmdern, Oslo 3, Norway Instrtute of Industrial Research, Forskmngsveren 1, Blmdern, Oslo 3, Norway Norwegian Agriculture Umversrty, Laboratory of Chemical Analysis, 1432 Vollebekk, Norway Technical Umversrty of Denmark, Instrtute of Mineralogy, Bld 204, 2800 Lyngby, Denmark Instrtute of Atomic Energy, 2007 KJeller, Norway Bohden AB Ronnskarsverken, Centrallaboratorlet, Skeleftehamn, Sweden The Geological Survey of Greenland, Bstervoldgade 10, DK 1350, Ksbenhavn K, Denmark Central Institute of Industrial Research, Forsknmgsveren 1, Blmdern, Oslo 3, Norway Falconbrrdge Nrkkelverk A/S, 4600 Krrstransand S, Norway 1048
ANALYTICAL
Table 2 Uncertified concentration
SlO*
TIO~ Al203 Total Fe as Fe,Op MnO MgO CaO Na,O K@ Fe cu Pb Zn S C
ASK-l Larvlklte
ASK-2 Schist
ASK-3 Sulphlde ore
59 5 11 186 46 013 11 32 65 42
542 092 188 69 003 20 07.5 08 53
74 trace 03
Au As B Ba Be Bl Cd Cl Co Cr cs cu Ga Hg In Ll Mn MO NI Rb SC Sr Tl V Zn Zr
005 1130 4
85
-
mean because there has been general agreement on the superiority of given methods or experience of some of the participants Some of the participants have found this type of work so encouraging that it ~111be continued with other materials Samples of the present three reference materials are available m 75-g lots, together with a list contammg all reported concentration values and covering 41 trace elements Further mformatlon 1s obtainable from the author
values (ppm) and analytical methods used
ASK-2
ASK-3
04 153
19 006 630 35
4
100 6 40 15 7 29 -
14 27 90 11 120 25 -
18 1020 110 85 7 680 main element 49 105 400
30 280 60 148 175 100 mam element 220 166 168
aa atonuc-absorption methods ch wet chemical methods, mainly tltrlmetrlc ‘3s spark-source mass-spectrometry OS optical spectrography xr X-ray fluorescence analysis naa neutron-activation analysis TAL 22/12-H
004 008 005 0018 0 070 35 6 014 21 92 4150
-
Table 3 Recommended trace concentration
Ag
1049
values (%) of major and some mmor constrtuents
different laboratorles and usmg different methods, each analyst havmg a thorough knowledge of his own method The methods applied are anodlc strlppmg voltammetry, atomic-absorption spectrometry, electrolysis, flame emlsslon methods, gravlmetrlc methods, spectrophotometry, tltrlmetrlc methods and X-ray fluorescence The evaluation of the results has benefited considerably from the extensive methodological dlscusslons m which most of the partlclpants have taken part In several cases the recommended values are different from the arithmetic
ASK-l
DATA
33 340 7 88 25 1450 6 76 177 260 45 37
33 main element
Methods used aa, ms, naa, OS naa ms, OS, xr OS OS OS aa, ms, xr aa, ms, naa, 0% XT ch, naa aa, naa, os, xr aa, ms, naa, OS, xr naa aa, ch, naa, OS, xr ms, naa, os, xr aa, OS aa, naa aa, OS aa, ms, naa, os, xr ms, naa, os, XT aa, ms, OS, xr aa, naa, os, xr naa naa, OS, xr aa, ch, OS ch, ms, OS aa, naa, OS, xr OS, xr
1050
ANALYTICAL
Acknowledgements-Among the partclpants, L -H AndersF J Langmyhr and E Stemnes m particular have offered valuable suggesttons for the tmprovement of the text Part of this work has been supported by Nansenfondet, Oslo son,
DATA
REFERENCES
1 T F W Barth, Skrrfter Norske Videnskaps-Akad Oslo,
1. Mat -Natur Klasse. 1944. No 9, 1 2 K 0 BJerlykke, Sedrmentology, 1974, 21, 251 3 J M Vokes, Norges Geol Undersokelse, 1963, No 222. 1
Summary-The results of a Nordic analytlcal trace-element study of three geologzal samples are given Recommended concentration values for 27 trace elements and 14 mam elements have been arrived at by the analysts m the course of several round-table conferences The samples are now available as reference materials, for other analytical laboratories