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U.S. Geological Survey silicate rock standards
Ckochimicaet Cosmochhica Acta, 1967,Vol. 31, pp.289 to 308.
Pergamon Preen Ltd.Printed InNorthern Ireland
U.S. Geological Survey silicate rock standards* FRANCIS J. FLANAUAN U.S. Geological Survey, Washington,
D.C.
(Received 19 Augwrt 1966) Am&The U.S. Geological Survey has processed six silicate rocks to provide new referenoe samples to supplement G-l and W-l. Complete conventional, rapid rock, and speotrochemical analyses by the U.S. Geological Survey are reported for a granite (replacement for G-l), a granodiorite, an andmite, a peridotite, a. dun&e, and a b&t. Analyses of variance for nickel, chromium, copper, and zirconium in each rock sample showed that for these elements, the rocks can be oonsidered homogeneous. Spectrochemicd estimates are given for the nickel, chromium, oopper, and ziroonium contents of the samples. The petrography of five of the six rooks ia described and CIPW norms are presented.
INTRODUCTION THE U.S. Geological Survey and other organizations that perform similar research have lacked the reliable reference materials necessary for the standardization of instrumental analytical techniques. The favorable response of the scientific community to the introduction of the granite G-l and the diabase W-l (FAIRBURN and others, 1951) was both immediate and continuing but the supply of G-l has been exhausted for some time. Other laboratories have prepared standard rocks (TAYLOR and KOLBE, 1964, Table 3) but there is still a need for other reference materials to cover a wider variety of rock types and elemental concentrations. To fill this void the U.S. Geological Survey has processed a series of rooks to be issued as analyzed samples in the same manner as G-l and W-l. It is hoped that these samples can be used as primary reference materials for the determination of major, minor and trace constituents in rocks. Two of the samples reported herein should present challenges to the analyst because of their high nickel and chromium contents. The amounts of each sample processed range from 200 to 300 lb. The results so far obtained by the U.S. Geological Survey laboratories are being published to stimulate early use of the samples as reference materials and to encourage other laboratories to report or publish their data so that the compositions of the samples may be established. Samples are available from the author to those laboratories that wish to participate in the analysis. The petrography of five of the six rocks is described and CIPW norms presented in the section by Himmelberg. The U.S. Geological Survey had no hand specimens of G-2 and a petrographic analysis was not possible. However, CHAYES and SUZUKI (1963) report that G-2 is somewhat coarser than the fine blue granite once quarried at Westerly but the difference is not great. The essential minerals of G-2 are indistinguishable from those of G-l (see CHAYES, in FAIRBAIRN and others, 1951) but G-2 is appreciably poorer in quartz and microcline and richer in plagioolase and biotite.
* Publioation authorized by the Director, U.S. Geological Survey. 1
289
290
~RANOIS
J.
~LAiYAGAN
The author is indebted to the geologists who oollected the samples and to the analysts who participated in the program. He is especially grateful for the continued support and encouragement provided by F. S. GRIMALDIand for the discussion of the statistical problems with W. J. YOUDEN, George Washington University. SAMPLES The samples for which data are reported herein 8re: Westerly Grtanite, from Sullivan qularry, Bradford, Rhode Islthnd, collected by Felix Chsyes, Geophysio81 L8boratory, Carnegie Institution of W~~~gton, 8s & replacement for G-l (@AYES and SUZUKI, 1983). Ssmple colbeted in the SWf4 of SW/P of C8rolina (RX) 76min. quladr8ngle about 3 miles east of the site where G-l ~8s collected. GSP- 1 Grcbnodiorite, collected by Leonwlrd B. Riley, U.S. Geologic81 Survey, from the Silver Plume Quctrry on Highway U.S. 6, about 1500 ft west of Silver Plume, Colorado. AGV-I Andesite, collected by George W. Walker, U.S. Geologic81 Survey, from sec. 12, T. 41 S, R. 27 E, east wall of Guano Valley, Lake County, Oregon. PCC- 1 Peridotite, oollected by E. H. Bailey 8nd M. C. Blske, U.S. Geolagiaal Survey, 8s stream boulders from the Cazadero ultr8mafio mass, East Austin Creek, NE/4 of NW/B, Caztzadero76min qu8dr8ngle, Sonom8 County, California. DTS-1 Dunite, collected by Dwight F. Crowder, U.S. ~ol~i~l Survey, from the south‘ border of sec. 3, T. 36 N, R. 7 E, Twin Sisters 8re8, Hamilton (Washington) 15minute qusdr8ngle. BCR-1 Basalt, Columbia River Group (Yakima type), collected by Asron 6. W8ters, U.S. Geologic81 Survey, from the Bridal Veil Flow Quarry, NW/4 of SWI4, sec. 14, T.l N, R.8 E, Bridal Veil quadrangle (WasNngtonOregon). G-2
SAMPLEPKocKsswa The processing of the samples includes the following steps: (1) examine pieces 8nd clean if necessary; 12) break pieces with 8 sledge; (3) pass through j&w crusher {steel); (4) pass through rolls crusher (steel); (5) mill in a bell mill (high density porcelain liner and balls) until at least 80% passes a ZOO-mesh screen (remove hslf-pint sample from mill for sieve tests and disc8rd sieved materisl); (6) mix in a st8inless steel blender; (7) remove a sample of about three pints from the blender, pour over the surface of 8 stainless steel cone into thirtytwo bottles under the periphery of the base of the cone; the eamples 8re identified by the number of the split and the position around the cone; rotate blender end repeat (7) until the sample is exhsusted; (8) randomly seleot samples for tests for size distribution and homogeneity from around the midpoints of the first, middle, 8nd last thirds of the betch of bottled samples; random norm81 deviates were used to select samples within thirty bottles on either side of the midpoint; the latter ~8s included in the sampling as 8 zero deviate; (9) using rsndom numbers, store the remaining s8mplea in boxes so that the last sample to be placed in the box will be the first sample that would have been chosen randomly for distribution.
291
U.S. ceologi4 survey r4ilhh rook SbM
The randomized normal deviates used in (8) and the random numbers used in (9) were extracted from tables prepared by the RAND CORPORATION (1966). It seemed desirable to prepare the samples fine enough so that at least 80% of each would pass a 200-mesh screen. This is in contrast to G-1 and W-l which were prepared coarser. Four bottles containing a total of approximately 100 g were randomly selected near the midpoints of each third of the lot and the contents were combined and screened. The averages of the resulting size distributions of each of the six rocks are shown in Table 1 from which it is evident that the particle size more than meets the objective. Table 1. Particle size distribution (o/,) Rock
sample
Number of sieve tests
G-2
GSP-I
AGV-I
PCC-1
DTS-1
BCR-1
2
3
3
3
3
3
tr tr 0.6 0.4 99.1
tr tr 1.6 m 92.8
0.1 0.1 I.6 4.0 94.3
tr tr 0.1 0.6 99.3
Mesh size -100 - 120 -170 -200
+100 +120 +170 +200
o-1 0.1 0.4 0.9 98.5
CONTAMINATION While planning the program it was decided not to remove tramp iron and steel that might be introduced from the action of the sledge, jaws and rolls because the magnetic removal of tramp iron would also remove magnetite, if present. There are two other sources of possible contamination, the high density porcelain balls and liner of the ball mill, and the stainless steel of the blender and sampling cone. There is a possibility, however slight, that contamination might occur from the blender because all the bulk samples were rotated in the blender about 3000 times before the sampling and bottling procedure was completed. A small experimental design to test for homogeneity and for contamination from the stainless steel was arranged and samples were randomly selected under step (8) of the procedure above. Each of the three spectrographic laboratories of the U.S. Geological Survey was furnished one bottle from each of the three thirds of the entire batch of bottles. It was assumed that contamination from the stainless steel might be detected from an increase in the Ni and Cr contents of the samples from the first to the last thirds. There is an inferred estimate of the contamination introduced from the high density porcelain balls of the ball mill. One step in the milling process was to wash the balls and liner of the mill after completing each sample and to weigh the batch of balls when dry. The initial weight of the balls was 367 lb and after milling some 2400 lb of rock the weight was 364i lb. This weight loss of 2+ lb, including at least one ball (-_it lb) lost and not recovered, amounts to a possible contamination of about O*lo/o, of which three quarters is alumina. This estimate of possible contamination is made under the assumption that all rocks are of equal hardness and cause equal wear on the balls. No attempt was made to estimate the weight loss of the liner of the mill.
FRANCIS J. FLANAQ~
292
ANALYTICALDATA Since the initial distribution of the samples to those laboratories that expressed a willingness to help establish the compositions, one laboratory has reported both rapid rock analyses and the quantitative spectrographic determinations of major, minor, and trace elements; another, the spectrographic determination of traces; a third, conventional rock analyses; two others, gamma ray spectrometric determinations of U, Th and K in four samples; a sixth, the determination of U, Th, Re, OS and Hg by neutron activation analysis; another, the spectrographic determination of traces in G-2 and GSP-1. The laboratories of the U.S. Geological Survey have made rapid and conventional rock analyses and spectrographir determinations of minor constituents. The data obtained so far by our laboratories are given in Tables 2-13. The Table Type of analysis: Split/Position: SiO,
2. Chemical analyses of granite G-2 Conventional 20/16 69.20 15.42 1.01 1.49 0.76 1.98 4.05 4.46 0.47 0.18 0.47 0.13 0.04 0.08 0.01 0.13 0.01
*w, Fe,O, Fe0 MgO cao Nf%,O K,O H,O+ H,OTiO, P&S MnO
co2 Cl F S
Cc203
-
NiO
BaO
lOl/lS 69.22 15.42 1.03 1.46 0.76 1.95 4.14 4.45 0.45 0.18 0.48 0.13 0.04 0.08 0.01 0.14 0.01 -
0.22
0.17
Subtotal Less 0
100~11 0.06
100.11 0.07
Total Analysts
100.05 E. L. Munson
100.04 v. c. Smith
:
(%)
Rapid 2115 69.1 15.6 1.2 1.4 0.73 1.9 3.8 4.6 0.69 0.16 0.48 0.16 0.08 0.10
__-
100
61/l 69.2 15.7 1.2 1.4 0.74 1.8 4.0 4.5 0.66 0.17 0.49 0.16 0.04 <0.05
100/13 69.0 15.6 1.1 1.4 0.68 2.0 4.1 4.5 0,77 0.14 0.48 0.14 0.08 0.05
-~
100 100 1’. Elmore, S. Botts, G. Chloe and L. Artis
chemical analyses were made by the conventional methods described by PNK (1964) and by the rapid methods described by S~apruo and BRANNOCK(1962) and these analyses are so designated in the tables. The conventional data are single analyses whereas the rapid rock data are the average of two analyses. The spectrographic data were obtained by the method of BASTZONand others (1980) and these data for several elements will be used to test for homogeneity and
293
U.S. Geologioal Survey ailioaterook standards Table 3. Quantitative speotroohemioald&e rminationa of trace constituentsin granite G-2 (ppm)*
Split/ Position: B& Be Cl3 co Cr cu Ga La Li Ml-l MO Nb Ni Pb Pr Rb SC Sn Sr Ti V Y Yb Zr
Denver
Menlo Park
Laboratory:
Washington 100127 21/11
20/19
61/9
lOl/lO
21112
60/31
1400 1700 3 3 <400 <400 0 3 7 7 12 12 16 I6 110 100 55 66 340 400
1400 1400 3 3 <400 <400 6 6 7 7 12 14 14 19 100 120 65 76 360 340
1700 2100 3 -
1700 2000 -
200 -
210 -
200 -
<2 <20 20 <7 3 30 30 -
<2 <20 20 <7 4 30 30 -
<2 <20 20 <7 2 40 30 -
560
560
200 -
210 -
200 -
<2 <2 <20 400 400 2800 2800 38 40 <20 <20 <2 <2 280 280
<2 <2 <20 340 550 2400 2800 32 40 <20 t20 <2 <2 260 280
2000 2000 3 3 <400 <400 5 5 8 6 11 12 16 14 90 120 56 66 320 380
<7 6 <6 400 700 2600 -
<7 4 <5 500 76o 2700 50 37 <20 12 <4
<7 4 <5 500 660 2800 50 42 <20 14 <4
* Noneign&ant
40 42 t20 15 <4 1 260 360
-
zeros are &own in small= type; -
2
1800 2100 -
3
1900 2100 2 2 <400 <400 6 6 12 8 12 12 20 20 120 130 38 36 280 270 <2 <2 20 lo 2 2 60
40 t80 t80 180 180 4 4 <20 440 440 3100 2600 40 30 <20 <20 2 1 340 340
= not looked for.
60/21
101113
2000 1900 2 3 <400 <400 5 5 11 11 9 9 20 20 100 100 34 32 300 270 <2 <2 20 20 3 3
2100 2100 2 2 <400 <400 4 5 7 8 13 11 20
60
40 <80 <80 150 160
4 4 <20 410 440 2800 2800 30 30 <20 <20 1 2 270 270
IO
90 120 34 33 260 260 <2 <2 lo IO
2 2 40 40 <80 <80 160 190 4 4 <20 440 440 2200 2900 30 30 <20 t20 1 1 310 340
FRANCIS J. FLANAGAN
294
Table 4. Chemical analyses of grandoiorite GSP-1 Type of analysis:
Conventional
split/ position
70117
SiO,
67.22 15.35 164 2.34 0.99 2.07 2.79 5.60 0.69 0.10 066 0.28 0.05 0.10 0.03 0.39 0.03 -
&Al Fe,% Fe0 MS0 C&O %G K2O
H,O+ H,OTiO, PAI MllO co2 cl F S %GfJ NiO BaO Subtotal Less 0 Total Analysts
:
s9/19 67.31 15.26 166 2.36 0.97 2.06 2.82 5.51 0.54 0.10 0.66 O-28 0.04 0.11 0.04 0.38 0.03 -
0.14
0.12
100.27 0.19
100.23 0.19
100.08 E. L. Munson
100.04 v. c. Smith
__-__
Rapid
14/0
4212
67-l 16.5 2.0 2.1 0.96 2.0 2.8 6.6 0.72 0.11 0.68 0.31 0.05 0.06
67.3 15.5 2.0 2.2 0.92 2.0 2.7 5.5 0.63 0.10 0.66 0.32 0.04 <0.05
-ii%
(%)
69/14 67.2 16.5 2.0 2.2 0.90 1.9 2.8 5.5 0.72 0.10 0.65 0.32 0.05 0.06
100 100 P. Elmore, S. Botts, G. Chloe and L. Artis
contamination. Nonsignificant zeros in the spectrographic dats are indicated by smaller type. There are insufficient chemical datfe to perform the statistical analysis for which m experimental design has been arranged. The spectrographic data were determined by R. E. Mays in the Menlo Park laboratory, A. L. Sutton, Jr., H. G. Neiman, and J. Haffty in the Denver laboratory, and S. Berman in the Washington laboratory. The upper sets of data by the Denver laboratory were determined by Sutton and the lower sets by Neiman and Haffty. The determinations in the ultraviolet were obtained by the aroing of duplicate portions of a prepared sample mixture. Separate determinations were made for the alkalis in the visible region. The useful concentration ranges for the quantitative spectroohemical estimation of minor and trace elements in rooks are given in Table 1 of BASTRONand others (1960). The limits of quantitative estimation in this table are averages and may vary with analysts, plates, and instruments. Such variations in the lower limits are reflected in the results reported. These lower limits indicate the maximum amount of an element if it is present in a sample. Other elements looked for but not deteoted and their lower limits ~bsppm,
U.S. Geologioal
296
Surveydioate rook standards
Table 6. Quantitative qeohohemioal dehrminations of trace oonatituentain granodioriteGSP-1 (ppm)* L&OlMO~: Split/ Position: Ba Be Ctl co Cr CU Ga La Li Mn MO Nb Ni Pb
Rb SC Sn Sr Ti V Y Yb Zr
Wa&ington
14113
41132
09128
14112
41122
70114
13120
42110
70111
1000 1000 <2 <2 800 8 7 11 9 65 16 16 200 200 44 60 420 420
1000 1000 <2 <2 800 -
1000 1000 <2 42 800 -
1100 1200 -
1200 1200 -
1100 1400 -
<2 -
<2 -
<2 -
8 8 10 10 48
8 8 10 10 60
260 -
270 -
260 -
<2 20 30 9 8 60 60 340 8 8 10 200 430 3800 -
<2 20 30 9 6 60 60 -
<2 30 30 9 6 60 60 340 -
1200 1600 <2 <2 600 600 6 6 16 16 43 43 10 20 360 340 37 31 310 370 <2 <2 30 30 6 6 60 70 80 80 260 260 10 16 <20 220 270 4100 3600 30 40 40 40 3 3 780 630
1400 1500 <2 <2 600 600 6 7 14 18 38 44 10 20 240 400 31 30 290 290 <2 <2 30 30 4 5 60 70 80 80 220 260 10 15 <20 220 220 3600 3400 40 60 40 60 3 3 740 660
1600 1600 <2 <2 400 600 7 6 I6 17 60 44 20 20 170 180 32 28 440 470 <2 <2 30 30 7 7 90 90 80 80 230 230 10 6 <20 240 240 4100 4000 60 40 30 30 3 3 640 640
60
Pr
Denver
Menlo Park
-
16 16 220 240 44 50 460 460 cl0
-
16 16 220 200 44 60 600 460 Cl0
70 68 30 28 t4 1 630 660
-
330
9 9 9 300 310 3800 -
8 10 10 300 340 3600 -
70 64 30 34 t4 2 630
60 62 30 29 <4 2 630 640
640
* Nonaignifhnt zeros are shown in smaller type; -
= not looked for.
FEMW~S J. FLANAGAN
296
where noted, are: Ag (2); As ~2~0); Au (40); 3 (20); Bi (20); Cd (loo) cs (60); @ (lo); Hf (loo); Hg (1 per cent); In (20); Ir (loo); OS (loo); Pd (6) Pt (80); Re (20); Rh (6); Ru (20); Sb (200); Ta (400); Te (2-000); Th (looo} Tl (loo); U (1000); W (400); Zn (600). except
Table 6. Chemical analyses of an&site AGV-1 (%) Type of analysis: Split/ position: SiO, AJO, =202 Fe0 i%G cao Na,O %?O H,O* !%)pa026 ;?uLnO CO, Cl F S CrsGa NiO BaO
~onvontion&l 55130
55124
59.00 17.10 4.35 2.07 1.50 4.89 4.23 2.87 069
58-99
17.18 4.38 2.05 150 4.92 4.24 2.85 062 1.49 1.05 0.49 0.10 0.01 0.02 0.04 0.00 0.14
Subtotal Less 0
1.05 1.46 0.49 @IO O-01 o+n? 0.04 0.00 0.13 -II_ 100~00 0.02
Total Analysts:
99.98 E. L.
100*05 V. C.
Munson
Smith
_l-_l-1sps 59.1 17.3 4.7 1.9 l-6 4.8 4.2 23 0.70 1.2 l*U 052 0.11 0.05
Rapid 56/l
92124
59.2 17.3 4.6 2.0 1.5 4.8 4.2 2.8 0.80 1.2 1.0 053 0.10
59.1 17.4 46 2.0 1.4 4.7 4.2 2.8 0.80 1.2 1.1 0.53 0.11 <0,05
-100.07 0.02
SP~C~OURAP~C
100
100 100 P. Elmore, S. Botts, G. CWoe and L. Artis
DATA AWD ~~MO~E~E~Y
A two-way analysis of variance with replicate determinations was used to test for homogeneity and contamination using spectroohemical date for several elements in each rock stcmple. The laboratories and the samples selected from the three thirds were used tls the two variables of classification in the experimental design that was elected to isola;te and estimate the variation in the data attributable to these two c~&s~~c&tions. Because of missing data and those reported as ‘less than’, there are no trace elements for which a complete set of data for the six stbmples was available. Nickel, chromium, oopper and zirconium vrsfues were reported more campletely
297
U.S. Geologio&lsurvey sili&e rock &Gaal* Table 7. Qmntihtive s~~~e~~ de&&tions andmite AGV- 1 (ppm) + Labor&my: split/ Position: B8 Be ce CO
cr
cu
Cl3 La Li Mn MO
Nb
Ni Pb
Menlo Park
Rb SC Sri Sr Ti V Y Yb zr
Washington
D0lW0r
H/32
55121
93124
1818
56/Q
93/21
19/l
55/31
9310
1800 1800 <2 <2 t400 t400 16 16 16 16 55 70 18 10 <60 <60 15 20 800 900
1800 1400 <2 <2 <400 <4oo 15 17 20 18 70 70 14 16 <60 <6o 10 15 800 900
1800 1400 <2 <2 t400 <4oo 14 18 18 18 70 75 16 16 <00 <60 12 12 900 900
1200 1200 -
1200 1200 -
1100 1200 -
<4 -
<4 -
<4 -
13 13 12 9 63 96 21 25 <40 <90 10 -
14 16 11 10 62 04 22 27 <40 <90 9 -
13 15 I1 8 58 66 22 26 <40
670 -
650 -
650 -
<9 <20 20 14 15 30 40 -
<9 20 20 15 7 30 40 -
<9 <20 20 15 12 30 40 70 -
1500 1600 <2 <2 <400 <400 11 10 17 17 72 100 20 20 <40 <40 14 9 740 740 4 4 30 30 12 13 50 60 <80
1500 1500 <2 <2 <400 <4oO 10 11 9 9 65 60 20 lo <40 <40 8 11 670 700 4 4 20 20 9 10 50 40 <80
1500 1600 <2 <2 <400 <400 11 12 9 6 62 60 lo lo <40 <40 11 11 670 770 4 4 20 20 11 12 40 50 <80
40
Pr
of trace constituentsof
-
70
-
80
14 12 t20 700 730 6100 -
x2 16 <20 700 650 6000 -
13 15 <20 700 670 5600 -
150 140 20 22 <4 2 220 200
140 140 20 28 <4 2 220 230
150 140 20 26 <4 2 220 240
zeroa we shown in smaller type: -
= not looked for.
298
FRANCIS J. FLANAGAN Table 8. Chemioal analyses of peridotite PCC-1 (%) --Type of analysis : Split/ Position:
Conventional
-
SiO, A’,% F%O, Fe0 M@ CaO Na,O IV H,O+ H,OTiO, PA
MnO CO2 Cl F S ~%@?I NiO BaO
14126
14116
1515
41.92 0.77 2.72 4.93 43.35 o-40 0.00 0301 4*54 0.67 0.01 0.00 0.12 0.18 0.01 o-00 0.00 0.42 0.30 0.01
41.89 0.74 2.73 4.88 43.28 0.44 0.02 0.00 4.59 0.63 0.01 0.01 0.12 0.18 0.01 0.00 0.00 0.42 0.31 0.01
42.4 0.69 2.9 4.8 43.2 0.47 <0.06 <0*05 4.8 0.64 0.00 0.06 0.12 0.06
Subtotal Less 0
100.36 0.00
Total Analysts
100.36 E. L. Munson
:
Rapid ___~__.
-
100.27 0.00
-
100.27
v. c. Smith
100
.~_ __..._~__
43/l
69/13
42.4 0.65 2.8 4.9 43.0 0.46 <0*06 <0.05 4.8 0.63 o*oo 0.04 0.12 0.10
42,4 0.69 2.8 4.9 43.0 0.48
100 100 P. Elmore, S. Botts, G. Chloe and L. Artis
and samples for which these d8tta are available are indicated below Ni Cr CU Zr X X G-2 X X X X GSP-1 X AGV-1 X X X PCC-1
DTS-1 BCR-1
X
X
X
X X
X
X
X
To simplify cslcul&ions, the spectrographic date were coded, where neoess8ry, by removing nonsignificant zeros. The data which are then in the form of the nickel dsta shown for GSP-1 in Table 14 correspond to an array for 8 two-way analysis of veriance with duplicate determinetions, and after performing the calcul8tions for this design shown by DIXON and Masay (1961, p. 135), the conclusions drawn are summarized in Table 16. This table shows that the means of thirds for the four elements determined in the six rocks do not contribute significantly to the total variation end, therefore, each of the six rook samples can be considered homogeneous for niokel, chromium, copper and ziraonium. Estimates are msde of the ei%ots of pos&le oonfoPPinetion
299
U.S. Gwlogioal Survey &hate rook atandaxh apeotroahamios deter&nations of trace wmstituente in peridot&e PCE-1 (ppm)*
Table 9. ~ti~ti~e
split/ Position: Ba Be Ce co Cr CU
Ga
la/l9
4319
<4 <4 <2 <2
<4 c4 <2 <2
L&X
40 <60
Li Mn MO
m
Ni Pb Pr Rb SO Sn Sr Ti V Y Yb Zr
<2 <2 300 900
400 <400 I00
110 2700 16 16 Cl0
Wa&ington
Denver
Mimlo Park
Laboratory:
70/10 <4 t4 t2 - <2 c400 (400 80 100 3400 13 10
t2 <2 800 1100 40 Cl0
<20 t20 2300 2200 <20 t20
15112
42131
69127
IS/l1
<4 <4 -
-
<4 <4
<4 <4 -
<4 -
<4 -
<4 -
100
110 100 2600 3100 8 10 <4 <4 <40 (90
<20 t20 <2 t2 <4oo <400 71 79 1600 3000 7 9
<4 t20 <20 2600 2800 <20 <20 -
<4 <20 <20 2600 2400 <20 <20 -
t4 <20 <20 2300 2300 <20 <20 -
flo I10 2800 3200 9 6 <4 <4 <40
8 II <9
t4 50 -
30 32 (20 <9 <4 4
<20 <20
120
2600 3600 10 8 <4 <4 C40
<20
<20
zeroaare shown in smaller type; -
10 9
42121 <20 <20 <2 <2 c400 <400 93 97 2400 2200 8 10
t40 <40 t2 <2 86o 830 t2 <2
30 30 <20 <20 1 2 40
t20
t2o
t20
40
<80
~80 t20 <20 10 10 (20 <2 <2 40
= not looked for.
<20 <20 <2 <2 <400 c4oo 81 68 1200 2400 7 13
1800 <20 <20 <80 <80 t20. <20 9 9 t20 <2 <2 40 40 20 30 (20 <20 1 2
40
t20 <20 9 9 <20 <2 t2 lo 60 20 30 <20 t20 1 2 t20 <20
70/13
50
FRANCIS J. FJXNACAN
300
in the three thirds for each element. These effects, expressed as the deviations of the means of each third from the grand mean of all determinations of an element in the rock samples, were calculated and are shown below. Deviation
of means of thirds from the grand means (coded data)
_____..-.-~
Grand mean
Thirds ---.---
Element
1
2
Ni Cr cu Zr Av. dev.
0.5 0.7 0.7 0.5 0.6
-0.5 0.25 -0.2 -0.25 -0.2
3
,Y
0 -0.95 -05 -0.25 -0.4
15.6 12.3 24.6 29.7
The average effects range from a positive deviation for the means of the first third to increasing negative values for the last two thirds. These effects do not support the original assumption of an increase in nickel or chromium from the Table 10. Chemical analyses of dunite DTS-1 Type of analysis :
53123
+ x HZOTiO, P2Orl MnO co2
Cl F S Cr203 NiO BaO
Total Analysts
__
40.55 0.31 0.98 6.93 49.85 0.03 0.05 0.01 0.32 0.11 0.00 0.00 0.12 0.07 0.00 6.00 0.00 0.65 0.30 0.02
SiO, Al203 Fe203 Fe0 MgO CaO Na20
Subtotal Less 0
:
Rapid
Conventional
Split/ Position:
100.30 0.00
100.30 E. L. Munson
(%)
32114
10/31
3312
40.65 0.25 1.01 6.84 49.80 0.00 0.04 0.00 0.41 0.08 0.01 0.00 0.12 0.07 0.01 0.00 0.00 0.64 0.31 0.02
41.3 0.28 I.3 6.5 49.4 0.10 <0.05 <0*05 0.58 0.07 0.00 0.04 0.12 0.11
41.3 0.28 1.0 6.9 49.6 0.06 < 0.05 <0.05 059 0.08 0.00 0.04 0.13 0.11
53/18 41.3 0.28 1.2 66 49.6 0.07
100.26 0.00
____
100.26 v. c. Smith
100
100 100 P. Elmore, S. Botts, G. Chloe and L. Artis
301
U.S. Geological Survey eilicate rock sttmdards Table 11. Q;uantitativespcetrochemiceldeterminationsof trace constituents of dunite DTS-I (ppm)*
split/ Position: BE% Be Ce CO cr ccc GLL L& Li N-I X0 Mb Ni Pb PF Rb SC Sn Sr Ti V Y Yb zr
11/e
32115
53132
<4 <4 <2 <2 <400 <400 120 130 4000 8 8
<4 <4 <2 <2 <400 <400 85 100 4000 0 8 Cl0 cl0 <60 t60 <2 <2 900 900
t4 t4 <2 <2 <400 t400 110 120 4000 -
* Nonsi@f&mt
We&i@On
Denver
Menlo Perk
Laboratory:
7 9
r1/5
3215
54118
<4 <4 -
<4 <4 -
<4 -
<4 -
130 130 4000 4600 8 6 <4 <4 <40 <90 <3. 880 -
220 130 3600 4800 6 4 <4
<4 120 120 4200 4000 6 3 <4 <4 (40
840 -
840 -
t4 <20 <20 2400 2400 <20 <20 -
<4 <20 <20 2300 2600 <20 <20 -
<4 <20 <20 2500 2000 <20 <20 -
<7 5 <9
a7 4 t9
<20 13 <20 <9 t4 <2 t20 <20
(20 11 <20 <9 t4 <2 <20 <20
<7 5 <9
zeros are shown in smaller type; -
10113 t20 t20 t2 t2 <400 t4oo 120 110 4300 3100 4 3
= not looked for.
32125 <20 <20 t2 <2 <400
1700 2000 <20 <20
64/M <20 <20 <2 <2 <400
FRANCISJ. FLANAQAN
302
Table 12. Chemical analyses of basalt BCR-1 (76) Type of snalysis: Split/ Position: SiO, AleO, Fe,O, Fe0 MS0 CaO N%O g TiZO, P,O, MnO CO, Cl F S C%O, NO BaO
Conventional
Rapid _-
39125
13116
13/N
4012
06/Z
54.10 13.70 3.24 9.07 3.47 6.91 3.26 1.69 0.60 1.24 2.26 0.35 0.19 0.02 0.01 0.05 0.04 -
54.15 1363 3.17 9.09 3.60 6.92 3.32 1.69 0.62 1.21 2.26 0.36 0.19 0.02 0.01 0.06 0.04 -
54.2 14.0 3.6 8.8 3.6 6.8 3.1 1.6 0.20 1.3 2.2 0.46 0.19
64.2 14.0 3.6 8.8 3.6 6.8 3.2 1.6 0.20 1.3 2.2 0.45 0.19 <0.05
64.1 14.0 3.6 8.8 3.6 6.8 3.2 1.6 0.30 1.3 2.2 0.47 0.19 <0.05
0.06
0.07
Subtotal Less 0
100.16 0.04
Total Analysts:
100~11 E. L.
100.29 0.04 ~. 100.26 v. c. Smith
100
100 100 P. Elmore, S. Botts, G. Chloe and L. Artis
tit to the last thirds, and possible contamination from the stainless steel may, therefore, be considered insignificant. The conclusions in Table 16 also show that the laboratory means are t)significant source of variation in more than two thirds of the tests made and laboratory bias therefore exists. However, the between-laboratory components of varianoe generally seem quite reasonable. For this prelimin&ry report we shall table only the laboratory means and standard deviations with 16 degrees of freedom derived after pooling the sums of squares and degrees of freedom for the thirds, the interaction, and the within-groups vkstion from the analysis of variance. These estimates are shown in Table 16. Because of the few complete sets of data presented here, analysis of the other trace element data, recommended values, and further discussion will be deferred until more data become available.
U.S. Geologieel Survey, Menlo Park, Californie WRAPHY of five of the silicate referenoesamples and CiPW norms are presentedbelow. Model anslyses for the eoamer wined samples were detwmiwd fram thin wetions U&IS a
303
U.S. Geologid Survey silieat0 rook stars Table 13. Quwtitative speotrochemi~ detwminations of tzaoe uonstitueds of b&t BCR-1 (ppm)*
Split] Position: B& Be Ge CO
Gr Cki
GE& La Li Mn MO
Nb
Ni Pb Pr Rb SC StI Sr Ti V Y Yb zr
13122 400 600 <2 <2
+ Nonsi@Eant
39122
6712
12130
40110
650
480
660
MO
620 720 -
620 780 -
<4 -
<4
<2 <2 t400 t400 30 34 13 13 24 24 20 20 ~60 <60 19 18 1800 2000
<2 t2 <400 <400
29 37 14 14 20 30 23 32 <40
I10 120 46 50 <20 400 340 -
30 32 11 12 23 22 18 16 <60
380 400
300 380
60
60
490 410 40 68 4 6 190
<20
60 Ii 6 180 180 !zIeros
W~u
Dtmver
Menlo Park
Laborstory:
60 6 8
170 1sO
-
33 40 lb 27 21 33 22 31 <40 t90 13 1300 <9 <20 30 12 10 <20
20 -
50
30 48 (20 300 420 12000 -
are shown ill fznlaller
670
780 <4 31 30 14 14 19 31 24 28 <40
50 -
-
220
M/31
-
39132
860 900 t2 <2 <4?00 <400 32 32 17 17 24 29 20 20 <40 <4o 14 16 1300 1300 9 7 50 40 8 9 30 40
780 920 <2 <2
60
32 53 <20 300 380 12000 -
33 44
480 420 40 51 4 5 206 200
500 390
type; -
13123
40
44 6 6 200 190
= not
33 33 <2o 410 370 12000 13000 250 270 60 50 6
6 160 140
looked for.
<4OO
c.400 30 29 12 12 36 35 20 20 t40 t40 20 22 1600 1600 6 6 60 50
6 7 40 40 <80 t8o 70 80
36 36 <20 310 370 12000 12000 170 210 60 60 4 6
66/M 880 880
t2 <2 <400 <&O
26 23 14 9 32 31 20 20 <4o <40 14 27 1700 1700 6 6 40 30 9 8 30 30
160
ISO
160
160
394
FRANCIS
J. BLDNAN
Table 14. Nickel determinstiona in sample GSP-1. (ppm) --~.-._
Laboratory
-
Totals
%3nlo Park
Denver
Washington
for thirds
1
5 II
9 8
Subtotal
19
-i?-
5 5 IO
46
2
8 10
9 5
4 5
Thirds
Subtotal 3
18
T-4
41
9 7 7
Subtotal
10 12 F$
-E
Ip
Laboratory totals
59
4c,
33
9 9
61 CT 2 I38
count of 1000 points. Indices of refiaotion were measured usiug a spindle stage, and optical augles were determined by direct measurement to two optio axes using the universal stage. The CIPW noxms (Table 17) were oalaulated using a U.S. Geological Survey computer program of the norms for the for the Burroughs B-5600 computer at Stanfoxd ~n~ve~ity. In collation classical analyses, SO,, Cl, F, S, NiO and BaO were omitted and the remaining oxides were recaitmlated to XOOo/o so that a more reeliitic comparison could be made with the norms of the rapid rock analyses. GRANDIO~TE GSP-1 A medium grained h~~~o~~~~-~~ular rook consisting essentially of quartz (277;), plagioclase (2S”/0),microcline (30%), biotite (90/e),and muscovite (5%) with minor iron oxide (2%), apatite, fluorite, zircon, pyrite, and epidote. Secondary minerals in&de serioite, calcite and hematite. Plagioolase, An& = 1548 & 0.002), shows polysynthetic twinning and minor alteration to sericite and e&rite. Microcline has well-developed grid twinning and is slightly microperthitic. Myrmekite is present but not common. Quartz is strained and uommonly contains small, randomly oriented, unidentified needles. IIematite occurs ss xhns around pyrite. Petrographically the rook is an adamellite. AN~ES~TE AGV-I Aphanitic, finely porphyritic, with a trachytic texture. Phenoarysts ( < 1%) c3onsistof plagioclaee (sodic labradorite), augite, and an unidentified reddish brown, trausluoent, nonpleoohroic, birefringent miner& Groundmass consists of subparallel plagioclase microlites (approximately An,,_,,, WALKER G. W., oral commmrieation), altered pyroxene, iron oxides, are aommonly yellow-brown glass, and shreds of a mioaceous mineral. Plagioclase phen~a zoned and some contain included ~0~~~ materid. According to the chemioal election of R~FN (1952) this rock is a trachymndesite. PERIDOT~TEPCC-1 Primary granular olivine (58%) snd orthopyroxene (9%) are partially replaoed by mesh structure serpentine (32%). Other minerals present include p&nary disseminated ohromite, secondary magnetite, and a traoe of talc and aarbonate miner& 0li.e exhibits undulose extirmtion and deformation btmds. Some orthopyroxene shows bending of oleavage traces. Oiivine is colorless; Q = 1~651 Ifr:0602, /I = 1,670 f 0*002, y = 1889 4 O+&? (for&e&e 92-90); 2V, = 80”. Ortbop~ox~~ uolorless, y = I.678 f 0*004 (akin 90); 2V; = 85-88”. Discontinuous exsolution lame&e of dinopyroxene are commonly present in orthopyroxene. The serpentine minerals consist of lizardlte plus minor olinoohrysotile (X-ray identification). Tale appears to be associated primarily with orthopyroxene.
U.S. Geological Snrvey silicate rook standarda
308
Table 15. Conoluaionstirn the enalyws of vtiame for four elemcmtsin all rock sampI@
Sample G-2
Source of variation
Elem0nt Ni
Cu
Zr
NS S
NS*
NS
-
NS*
NS
-
Third8 Labs
Cr
GSP.1
ThirdE Labs
NS
NS
-
NS
AGV-1
Thirds Labs,
NS
NS* S*
NS NS
NS NS
-
NS
-
Pee-1 DTS.1
BCR-I
ss S
NS
Thii
-s
Lab0
s-s
Thirds Labs
NS
-
NS
Thirda
NS S
NS NS
NS S
Labs
-
s-s
-
-
* Teeted 8kgainh a signifiaant intera&ion. s = ant {F*es)* NS = ~o~~~t
NS
S
(F.,&
Table 16. Laboratory meaw and &mdard deviations (ppm)* Laboratory
All Labs
Sample
Menlo Park
Denver
Niokel
GSP-1 AGV-L PCC- 1 DTS-1 BCR-1
9.8 18.2 2180 2020 23-2
7.7 13.0 2480 2470 x0*0
5.6 11.2 1750 1860 7.8
7.7 14.1 2140 2110 13-7
1.54 2.33 185 161 2.30
~~~
G-2 GSP- f. AGV-1 BCR-I
7.0 10.0 17*7 14.1
8.0 14.3 10-l 16.3
9.6 16.1 11.1 13.5
8.2 13.6 13.0 14.6
1.25 1.68 2.72 4.21
Copper
G-2 AGV- 1 PCC-1 DTS-I BCR-1
12.1 68.3 12-5 8.1 23.1
9.7 68.1 8.3 6.3 25.7
11.0 70.8 9.0
10.9 69.1 9.9 6.4 26.6
l-22 12.4 2.26 1.74 4.40
Zimonium
G-2 GSP-I AGV-1 BCR-1
Element
273 373 207 183
290 538 221 200
Wa&in@on
311 613 198 158
* Nonsigniscant zeros are shown in smaller type.
Mean
291 508 209 180
Std Dev.
33.4 67.9 17.3 11.6
FRANCIS
306
J.
I?LANAGAX
Table 17. CIPW Norms
--._
Granite G-2 Splitposition
I~~
20/16
101/16
2115
61/l
100/13
23.5 0.8 26.6 34-6 8*5 1.9 1.2 1.5 O-9 0.3 O-2
23.1 0.8 26.5 35.3 8‘4 I.9 1-I l-5 O-9 0.3 0.2
24.7 1.5 27.4 32-4 7.8 I.8 0.9 1.8 0.9 0.4 0.2
24.1 1.5 26.8 34.x 7.6 1.9 0.9 1.8 0.9 0.4 0.1
22.9 O-8 26.8 3.w 8.8 1.7 1.0 1.6 0.9 0.3 0.1
Gmnodiorite GSP-I Sp~tlFosi~ion
70117
69119
1416
42/2
6Qfl4
c1 c
“4.5 2.0 32.8 23.8 7.9 2‘5 2.0 2-4 1.3 0.7 0.2
24.4 1.9 32.8 24.1 7.8 2.4 2.0 2.4 1.3 0.7 0.3
24-4 2.1 33.4 23.9 7.6 2.4 l-2 2.9 1.3 0.7 0.1
25.6 2.4 32.8 23.0 7.6 2.3 1.4 2*Q l-3 0.8 0.1
25.1 2.4 32.8 23.9 7.0 2.3 1.4 2.9 1.2 O-8 0.1
Of
ab an en & mt il aP CC
Andesite AGV - 1 Splitt~~iti~~
65/30
55124
18/26
5611
92f24
q c
12.8 17.4 36”7 19.7 0.8
12.7 17.2 36.7 19-Q 0.7
13.1 16.9 36.2 20.5 -
51sn
-3-a
-3.8
-4.1
13‘4 16.9 36.2 20.4 ..“.... -3.8
13.7 0.3 16.9 36.3 19.9 -3.6
EL il aP ce
4.0 I.7 2.0 1.2 -
4.0 1.7 2.0 1.2 -
3.6 2.3 I.9 1.3 0.1
4.0 I*9 I.9 1.3 0.1
2.2 3.7 2.1 1.3 0.1
Ol?
ab an wo
U.S. Gislogio%l Survey %ilieat%rook %iand%rd%
307
Table 17. CIPW Norms, continued Peridot& PC&l Splitlpoeition 0 Or
ab an wo en f% fo fs mt om il %P co
X4/26 0.6 0.1 0*9 25.9 1.6 61‘6 4.2 4.2 0.7 -
la/l6
0.2 1.0 26.6 1.6 61.8 4.1 4.2 0.7 -
1616
43/l
69113
-
-
-
0.3 0.4 1.6 -
0.3 0.4 1.5
0.3 0.4 1.6 -
26.4 l-6 61.8 4.2 4.4
26*9 1.7 61.2 4.3 4.3
-
-
0.1 0.1
0.1 0.2
26.8 l-7 61.2 4.3 4.3 0.1 0.2
0.4
Dunite DTS-1 Split/l?o%ition c OF
sb en f% fo b mt om il %P co mg
53123
32114
10/31
3312
63118
0.2 0.1 0.4 1.6 0.1 86.3 8.9 1.4 1.0 -
0.2 0.3 2.4 0.2 86.6 8.7 1.6 0.9 -
0‘1 0.3 0.4 4.8 o-4 83.4 8.3 1.9
O-1 0.3 0.4 3.7 0.4 84.2 9.1 1.6 0.1 -
0.1 0.3 0.4 4.1 0.4 84-O 8.6 1.8 -
0.1 0.1
0.1
o-2
0.1 0.1 0.1
Bwalt BCR-1 Split/l?o%itiori
g Or
ab an wo ;: mt B aP co
39125
13116
13116
4012
6612
8.1 10.2 28.1 l&l 6.0 8.8 10.8 4.8 4.3 O-8 -
7.8 10.2 28.6 17.6 6.2 8.9 10.9 4-7 4.4 O-8 -
9.6 9.6 26.6 19.9 4.6 9.1 10.1 6.2 4.2 l-1 0.1
9.1 9.6 27.6 19.4 4.8 8.8 x0.1 6.2 4.2 1.1 0.1
9.6 27.6 19.4 4.8 9.1 10.1 6.2 4.2 l-1 0.1
8.9
308
FRUVCIS J. FLANAGAN
DUNITE DTS-1 Medium grained, primary olivine (99%), orthopyroxene and olinopyroxene occur in an allotriomorphio-granular texture with euhedral to subhedral disseminated ohromite and a trace of light green amphibole. Serpentine occurs along narrow, continuous fractures in olivine. Olivine shows abundant deformation bands. Olivine is colorless; for&e&e 91.5% (determined by the X-ray method of HOTZ and JACKSON, 1963); a = 1.650 f 0*002, p = 1.667 & 0,002, y = 1685 i 0.002; 2V, = 84-87”. The amphibole has indices of refraction OL= l-634 f 0*002, /‘I= 1.645 + 0.002, y = 1.658 + 0*002; 2’c’;. = 80-87”; ZVG w 20”. BASALT BCR- I
An aphanitio, hypocrystalline, basalt with an intersertal texture consisting of randomly oriented plagioolase laths with interstitial augite, brown glass, and iron oxides. The plagioolase is slightly zoned with an approximate composition of An,, (/3= 1560 + 0.002). Augite is brown with 2 V’y variable from 3 l-44”. Individual grains of pyroxene may show zoning from augite to sub-oaloio augite. The glass is partially devittied and commonly contains abundant iron oxides. Using R~MANN’S (1952) chemical classification of volcanic rocks this sample is an andesine traohybasalt. REFERENCES BA~TRON H., BARNEIZTP. R. and MURATA K. J. (1960) Method for the quantitative speotrochemical analysis of rocks, minerals, ores, and other materials by a powder d.o. arc technique. U.S. Gwl. Suru. BeJE.I004+, 165-182. &AYES F. and Suzcnu, Y. (1963) A replacement for reference sample G-l. Cm In&i&tio~ of Washington Yeur Book 62, Annual report of the Director of the Geophysioal Laboratory, pp. 155-156. DIXON W. J. and MASSEY F. J. JR. (1961) Introductiora to S6atisticcslAndy&. McGraw-Hill. FAIRBAIRN H. W. et cd. (1961) A cooperative investigation of pm&ion and acouraoy in ohemioal, spectrochemioal, and modal analysis of silicate rocks. U.S. Geol. &VU. Bulk 980, 71 p. HOTZ P. E. and JACKSONE. D. (1963) X-ray determination curve for olivines of composition Fo,,, from stratiform and alpine-type peridotites. U.S. Geol. &TV. Prof. Paper #E, 101-102. PEOK L. C. (1964) Systematic analysis of silicates. U.S. Geol. Surv. BwU. 1170, 89 p. RAND CORPORATION(1955) A Milliola Random Digits with 100,000 Nowmd Deviatea. The Free Press, Glencoe, Illinois. Rm A. (1962) Nomenclature of volcanic rooks. Bull. Volcunoe. Serie II XII, 76-102. SJU.P~~ L. and BRANNOOKW. W. (1962) Rapid analysis of silioate, carbonate and phosphate rocks. U.S. GeoZ.Surv. BUW. ll44-A, 56 p. TAYLOR S. R. and KOLBE P. (1964) Geochemioal standards. Gemhim. Coamochim. Acta 28, 447-454.
Pergamon Preen Ltd.Printed InNorthern Ireland
U.S. Geological Survey silicate rock standards* FRANCIS J. FLANAUAN U.S. Geological Survey, Washington,
D.C.
(Received 19 Augwrt 1966) Am&The U.S. Geological Survey has processed six silicate rocks to provide new referenoe samples to supplement G-l and W-l. Complete conventional, rapid rock, and speotrochemical analyses by the U.S. Geological Survey are reported for a granite (replacement for G-l), a granodiorite, an andmite, a peridotite, a. dun&e, and a b&t. Analyses of variance for nickel, chromium, copper, and zirconium in each rock sample showed that for these elements, the rocks can be oonsidered homogeneous. Spectrochemicd estimates are given for the nickel, chromium, oopper, and ziroonium contents of the samples. The petrography of five of the six rooks ia described and CIPW norms are presented.
INTRODUCTION THE U.S. Geological Survey and other organizations that perform similar research have lacked the reliable reference materials necessary for the standardization of instrumental analytical techniques. The favorable response of the scientific community to the introduction of the granite G-l and the diabase W-l (FAIRBURN and others, 1951) was both immediate and continuing but the supply of G-l has been exhausted for some time. Other laboratories have prepared standard rocks (TAYLOR and KOLBE, 1964, Table 3) but there is still a need for other reference materials to cover a wider variety of rock types and elemental concentrations. To fill this void the U.S. Geological Survey has processed a series of rooks to be issued as analyzed samples in the same manner as G-l and W-l. It is hoped that these samples can be used as primary reference materials for the determination of major, minor and trace constituents in rocks. Two of the samples reported herein should present challenges to the analyst because of their high nickel and chromium contents. The amounts of each sample processed range from 200 to 300 lb. The results so far obtained by the U.S. Geological Survey laboratories are being published to stimulate early use of the samples as reference materials and to encourage other laboratories to report or publish their data so that the compositions of the samples may be established. Samples are available from the author to those laboratories that wish to participate in the analysis. The petrography of five of the six rocks is described and CIPW norms presented in the section by Himmelberg. The U.S. Geological Survey had no hand specimens of G-2 and a petrographic analysis was not possible. However, CHAYES and SUZUKI (1963) report that G-2 is somewhat coarser than the fine blue granite once quarried at Westerly but the difference is not great. The essential minerals of G-2 are indistinguishable from those of G-l (see CHAYES, in FAIRBAIRN and others, 1951) but G-2 is appreciably poorer in quartz and microcline and richer in plagioolase and biotite.
* Publioation authorized by the Director, U.S. Geological Survey. 1
289
290
~RANOIS
J.
~LAiYAGAN
The author is indebted to the geologists who oollected the samples and to the analysts who participated in the program. He is especially grateful for the continued support and encouragement provided by F. S. GRIMALDIand for the discussion of the statistical problems with W. J. YOUDEN, George Washington University. SAMPLES The samples for which data are reported herein 8re: Westerly Grtanite, from Sullivan qularry, Bradford, Rhode Islthnd, collected by Felix Chsyes, Geophysio81 L8boratory, Carnegie Institution of W~~~gton, 8s & replacement for G-l (@AYES and SUZUKI, 1983). Ssmple colbeted in the SWf4 of SW/P of C8rolina (RX) 76min. quladr8ngle about 3 miles east of the site where G-l ~8s collected. GSP- 1 Grcbnodiorite, collected by Leonwlrd B. Riley, U.S. Geologic81 Survey, from the Silver Plume Quctrry on Highway U.S. 6, about 1500 ft west of Silver Plume, Colorado. AGV-I Andesite, collected by George W. Walker, U.S. Geologic81 Survey, from sec. 12, T. 41 S, R. 27 E, east wall of Guano Valley, Lake County, Oregon. PCC- 1 Peridotite, oollected by E. H. Bailey 8nd M. C. Blske, U.S. Geolagiaal Survey, 8s stream boulders from the Cazadero ultr8mafio mass, East Austin Creek, NE/4 of NW/B, Caztzadero76min qu8dr8ngle, Sonom8 County, California. DTS-1 Dunite, collected by Dwight F. Crowder, U.S. ~ol~i~l Survey, from the south‘ border of sec. 3, T. 36 N, R. 7 E, Twin Sisters 8re8, Hamilton (Washington) 15minute qusdr8ngle. BCR-1 Basalt, Columbia River Group (Yakima type), collected by Asron 6. W8ters, U.S. Geologic81 Survey, from the Bridal Veil Flow Quarry, NW/4 of SWI4, sec. 14, T.l N, R.8 E, Bridal Veil quadrangle (WasNngtonOregon). G-2
SAMPLEPKocKsswa The processing of the samples includes the following steps: (1) examine pieces 8nd clean if necessary; 12) break pieces with 8 sledge; (3) pass through j&w crusher {steel); (4) pass through rolls crusher (steel); (5) mill in a bell mill (high density porcelain liner and balls) until at least 80% passes a ZOO-mesh screen (remove hslf-pint sample from mill for sieve tests and disc8rd sieved materisl); (6) mix in a st8inless steel blender; (7) remove a sample of about three pints from the blender, pour over the surface of 8 stainless steel cone into thirtytwo bottles under the periphery of the base of the cone; the eamples 8re identified by the number of the split and the position around the cone; rotate blender end repeat (7) until the sample is exhsusted; (8) randomly seleot samples for tests for size distribution and homogeneity from around the midpoints of the first, middle, 8nd last thirds of the betch of bottled samples; random norm81 deviates were used to select samples within thirty bottles on either side of the midpoint; the latter ~8s included in the sampling as 8 zero deviate; (9) using rsndom numbers, store the remaining s8mplea in boxes so that the last sample to be placed in the box will be the first sample that would have been chosen randomly for distribution.
291
U.S. ceologi4 survey r4ilhh rook SbM
The randomized normal deviates used in (8) and the random numbers used in (9) were extracted from tables prepared by the RAND CORPORATION (1966). It seemed desirable to prepare the samples fine enough so that at least 80% of each would pass a 200-mesh screen. This is in contrast to G-1 and W-l which were prepared coarser. Four bottles containing a total of approximately 100 g were randomly selected near the midpoints of each third of the lot and the contents were combined and screened. The averages of the resulting size distributions of each of the six rocks are shown in Table 1 from which it is evident that the particle size more than meets the objective. Table 1. Particle size distribution (o/,) Rock
sample
Number of sieve tests
G-2
GSP-I
AGV-I
PCC-1
DTS-1
BCR-1
2
3
3
3
3
3
tr tr 0.6 0.4 99.1
tr tr 1.6 m 92.8
0.1 0.1 I.6 4.0 94.3
tr tr 0.1 0.6 99.3
Mesh size -100 - 120 -170 -200
+100 +120 +170 +200
o-1 0.1 0.4 0.9 98.5
CONTAMINATION While planning the program it was decided not to remove tramp iron and steel that might be introduced from the action of the sledge, jaws and rolls because the magnetic removal of tramp iron would also remove magnetite, if present. There are two other sources of possible contamination, the high density porcelain balls and liner of the ball mill, and the stainless steel of the blender and sampling cone. There is a possibility, however slight, that contamination might occur from the blender because all the bulk samples were rotated in the blender about 3000 times before the sampling and bottling procedure was completed. A small experimental design to test for homogeneity and for contamination from the stainless steel was arranged and samples were randomly selected under step (8) of the procedure above. Each of the three spectrographic laboratories of the U.S. Geological Survey was furnished one bottle from each of the three thirds of the entire batch of bottles. It was assumed that contamination from the stainless steel might be detected from an increase in the Ni and Cr contents of the samples from the first to the last thirds. There is an inferred estimate of the contamination introduced from the high density porcelain balls of the ball mill. One step in the milling process was to wash the balls and liner of the mill after completing each sample and to weigh the batch of balls when dry. The initial weight of the balls was 367 lb and after milling some 2400 lb of rock the weight was 364i lb. This weight loss of 2+ lb, including at least one ball (-_it lb) lost and not recovered, amounts to a possible contamination of about O*lo/o, of which three quarters is alumina. This estimate of possible contamination is made under the assumption that all rocks are of equal hardness and cause equal wear on the balls. No attempt was made to estimate the weight loss of the liner of the mill.
FRANCIS J. FLANAQ~
292
ANALYTICALDATA Since the initial distribution of the samples to those laboratories that expressed a willingness to help establish the compositions, one laboratory has reported both rapid rock analyses and the quantitative spectrographic determinations of major, minor, and trace elements; another, the spectrographic determination of traces; a third, conventional rock analyses; two others, gamma ray spectrometric determinations of U, Th and K in four samples; a sixth, the determination of U, Th, Re, OS and Hg by neutron activation analysis; another, the spectrographic determination of traces in G-2 and GSP-1. The laboratories of the U.S. Geological Survey have made rapid and conventional rock analyses and spectrographir determinations of minor constituents. The data obtained so far by our laboratories are given in Tables 2-13. The Table Type of analysis: Split/Position: SiO,
2. Chemical analyses of granite G-2 Conventional 20/16 69.20 15.42 1.01 1.49 0.76 1.98 4.05 4.46 0.47 0.18 0.47 0.13 0.04 0.08 0.01 0.13 0.01
*w, Fe,O, Fe0 MgO cao Nf%,O K,O H,O+ H,OTiO, P&S MnO
co2 Cl F S
Cc203
-
NiO
BaO
lOl/lS 69.22 15.42 1.03 1.46 0.76 1.95 4.14 4.45 0.45 0.18 0.48 0.13 0.04 0.08 0.01 0.14 0.01 -
0.22
0.17
Subtotal Less 0
100~11 0.06
100.11 0.07
Total Analysts
100.05 E. L. Munson
100.04 v. c. Smith
:
(%)
Rapid 2115 69.1 15.6 1.2 1.4 0.73 1.9 3.8 4.6 0.69 0.16 0.48 0.16 0.08 0.10
__-
100
61/l 69.2 15.7 1.2 1.4 0.74 1.8 4.0 4.5 0.66 0.17 0.49 0.16 0.04 <0.05
100/13 69.0 15.6 1.1 1.4 0.68 2.0 4.1 4.5 0,77 0.14 0.48 0.14 0.08 0.05
-~
100 100 1’. Elmore, S. Botts, G. Chloe and L. Artis
chemical analyses were made by the conventional methods described by PNK (1964) and by the rapid methods described by S~apruo and BRANNOCK(1962) and these analyses are so designated in the tables. The conventional data are single analyses whereas the rapid rock data are the average of two analyses. The spectrographic data were obtained by the method of BASTZONand others (1980) and these data for several elements will be used to test for homogeneity and
293
U.S. Geologioal Survey ailioaterook standards Table 3. Quantitative speotroohemioald&e rminationa of trace constituentsin granite G-2 (ppm)*
Split/ Position: B& Be Cl3 co Cr cu Ga La Li Ml-l MO Nb Ni Pb Pr Rb SC Sn Sr Ti V Y Yb Zr
Denver
Menlo Park
Laboratory:
Washington 100127 21/11
20/19
61/9
lOl/lO
21112
60/31
1400 1700 3 3 <400 <400 0 3 7 7 12 12 16 I6 110 100 55 66 340 400
1400 1400 3 3 <400 <400 6 6 7 7 12 14 14 19 100 120 65 76 360 340
1700 2100 3 -
1700 2000 -
200 -
210 -
200 -
<2 <20 20 <7 3 30 30 -
<2 <20 20 <7 4 30 30 -
<2 <20 20 <7 2 40 30 -
560
560
200 -
210 -
200 -
<2 <2 <20 400 400 2800 2800 38 40 <20 <20 <2 <2 280 280
<2 <2 <20 340 550 2400 2800 32 40 <20 t20 <2 <2 260 280
2000 2000 3 3 <400 <400 5 5 8 6 11 12 16 14 90 120 56 66 320 380
<7 6 <6 400 700 2600 -
<7 4 <5 500 76o 2700 50 37 <20 12 <4
<7 4 <5 500 660 2800 50 42 <20 14 <4
* Noneign&ant
40 42 t20 15 <4 1 260 360
-
zeros are &own in small= type; -
2
1800 2100 -
3
1900 2100 2 2 <400 <400 6 6 12 8 12 12 20 20 120 130 38 36 280 270 <2 <2 20 lo 2 2 60
40 t80 t80 180 180 4 4 <20 440 440 3100 2600 40 30 <20 <20 2 1 340 340
= not looked for.
60/21
101113
2000 1900 2 3 <400 <400 5 5 11 11 9 9 20 20 100 100 34 32 300 270 <2 <2 20 20 3 3
2100 2100 2 2 <400 <400 4 5 7 8 13 11 20
60
40 <80 <80 150 160
4 4 <20 410 440 2800 2800 30 30 <20 <20 1 2 270 270
IO
90 120 34 33 260 260 <2 <2 lo IO
2 2 40 40 <80 <80 160 190 4 4 <20 440 440 2200 2900 30 30 <20 t20 1 1 310 340
FRANCIS J. FLANAGAN
294
Table 4. Chemical analyses of grandoiorite GSP-1 Type of analysis:
Conventional
split/ position
70117
SiO,
67.22 15.35 164 2.34 0.99 2.07 2.79 5.60 0.69 0.10 066 0.28 0.05 0.10 0.03 0.39 0.03 -
&Al Fe,% Fe0 MS0 C&O %G K2O
H,O+ H,OTiO, PAI MllO co2 cl F S %GfJ NiO BaO Subtotal Less 0 Total Analysts
:
s9/19 67.31 15.26 166 2.36 0.97 2.06 2.82 5.51 0.54 0.10 0.66 O-28 0.04 0.11 0.04 0.38 0.03 -
0.14
0.12
100.27 0.19
100.23 0.19
100.08 E. L. Munson
100.04 v. c. Smith
__-__
Rapid
14/0
4212
67-l 16.5 2.0 2.1 0.96 2.0 2.8 6.6 0.72 0.11 0.68 0.31 0.05 0.06
67.3 15.5 2.0 2.2 0.92 2.0 2.7 5.5 0.63 0.10 0.66 0.32 0.04 <0.05
-ii%
(%)
69/14 67.2 16.5 2.0 2.2 0.90 1.9 2.8 5.5 0.72 0.10 0.65 0.32 0.05 0.06
100 100 P. Elmore, S. Botts, G. Chloe and L. Artis
contamination. Nonsignificant zeros in the spectrographic dats are indicated by smaller type. There are insufficient chemical datfe to perform the statistical analysis for which m experimental design has been arranged. The spectrographic data were determined by R. E. Mays in the Menlo Park laboratory, A. L. Sutton, Jr., H. G. Neiman, and J. Haffty in the Denver laboratory, and S. Berman in the Washington laboratory. The upper sets of data by the Denver laboratory were determined by Sutton and the lower sets by Neiman and Haffty. The determinations in the ultraviolet were obtained by the aroing of duplicate portions of a prepared sample mixture. Separate determinations were made for the alkalis in the visible region. The useful concentration ranges for the quantitative spectroohemical estimation of minor and trace elements in rooks are given in Table 1 of BASTRONand others (1960). The limits of quantitative estimation in this table are averages and may vary with analysts, plates, and instruments. Such variations in the lower limits are reflected in the results reported. These lower limits indicate the maximum amount of an element if it is present in a sample. Other elements looked for but not deteoted and their lower limits ~bsppm,
U.S. Geologioal
296
Surveydioate rook standards
Table 6. Quantitative qeohohemioal dehrminations of trace oonatituentain granodioriteGSP-1 (ppm)* L&OlMO~: Split/ Position: Ba Be Ctl co Cr CU Ga La Li Mn MO Nb Ni Pb
Rb SC Sn Sr Ti V Y Yb Zr
Wa&ington
14113
41132
09128
14112
41122
70114
13120
42110
70111
1000 1000 <2 <2 800 8 7 11 9 65 16 16 200 200 44 60 420 420
1000 1000 <2 <2 800 -
1000 1000 <2 42 800 -
1100 1200 -
1200 1200 -
1100 1400 -
<2 -
<2 -
<2 -
8 8 10 10 48
8 8 10 10 60
260 -
270 -
260 -
<2 20 30 9 8 60 60 340 8 8 10 200 430 3800 -
<2 20 30 9 6 60 60 -
<2 30 30 9 6 60 60 340 -
1200 1600 <2 <2 600 600 6 6 16 16 43 43 10 20 360 340 37 31 310 370 <2 <2 30 30 6 6 60 70 80 80 260 260 10 16 <20 220 270 4100 3600 30 40 40 40 3 3 780 630
1400 1500 <2 <2 600 600 6 7 14 18 38 44 10 20 240 400 31 30 290 290 <2 <2 30 30 4 5 60 70 80 80 220 260 10 15 <20 220 220 3600 3400 40 60 40 60 3 3 740 660
1600 1600 <2 <2 400 600 7 6 I6 17 60 44 20 20 170 180 32 28 440 470 <2 <2 30 30 7 7 90 90 80 80 230 230 10 6 <20 240 240 4100 4000 60 40 30 30 3 3 640 640
60
Pr
Denver
Menlo Park
-
16 16 220 240 44 50 460 460 cl0
-
16 16 220 200 44 60 600 460 Cl0
70 68 30 28 t4 1 630 660
-
330
9 9 9 300 310 3800 -
8 10 10 300 340 3600 -
70 64 30 34 t4 2 630
60 62 30 29 <4 2 630 640
640
* Nonaignifhnt zeros are shown in smaller type; -
= not looked for.
FEMW~S J. FLANAGAN
296
where noted, are: Ag (2); As ~2~0); Au (40); 3 (20); Bi (20); Cd (loo) cs (60); @ (lo); Hf (loo); Hg (1 per cent); In (20); Ir (loo); OS (loo); Pd (6) Pt (80); Re (20); Rh (6); Ru (20); Sb (200); Ta (400); Te (2-000); Th (looo} Tl (loo); U (1000); W (400); Zn (600). except
Table 6. Chemical analyses of an&site AGV-1 (%) Type of analysis: Split/ position: SiO, AJO, =202 Fe0 i%G cao Na,O %?O H,O* !%)pa026 ;?uLnO CO, Cl F S CrsGa NiO BaO
~onvontion&l 55130
55124
59.00 17.10 4.35 2.07 1.50 4.89 4.23 2.87 069
58-99
17.18 4.38 2.05 150 4.92 4.24 2.85 062 1.49 1.05 0.49 0.10 0.01 0.02 0.04 0.00 0.14
Subtotal Less 0
1.05 1.46 0.49 @IO O-01 o+n? 0.04 0.00 0.13 -II_ 100~00 0.02
Total Analysts:
99.98 E. L.
100*05 V. C.
Munson
Smith
_l-_l-1sps 59.1 17.3 4.7 1.9 l-6 4.8 4.2 23 0.70 1.2 l*U 052 0.11 0.05
Rapid 56/l
92124
59.2 17.3 4.6 2.0 1.5 4.8 4.2 2.8 0.80 1.2 1.0 053 0.10
59.1 17.4 46 2.0 1.4 4.7 4.2 2.8 0.80 1.2 1.1 0.53 0.11 <0,05
-100.07 0.02
SP~C~OURAP~C
100
100 100 P. Elmore, S. Botts, G. CWoe and L. Artis
DATA AWD ~~MO~E~E~Y
A two-way analysis of variance with replicate determinations was used to test for homogeneity and contamination using spectroohemical date for several elements in each rock stcmple. The laboratories and the samples selected from the three thirds were used tls the two variables of classification in the experimental design that was elected to isola;te and estimate the variation in the data attributable to these two c~&s~~c&tions. Because of missing data and those reported as ‘less than’, there are no trace elements for which a complete set of data for the six stbmples was available. Nickel, chromium, oopper and zirconium vrsfues were reported more campletely
297
U.S. Geologio&lsurvey sili&e rock &Gaal* Table 7. Qmntihtive s~~~e~~ de&&tions andmite AGV- 1 (ppm) + Labor&my: split/ Position: B8 Be ce CO
cr
cu
Cl3 La Li Mn MO
Nb
Ni Pb
Menlo Park
Rb SC Sri Sr Ti V Y Yb zr
Washington
D0lW0r
H/32
55121
93124
1818
56/Q
93/21
19/l
55/31
9310
1800 1800 <2 <2 t400 t400 16 16 16 16 55 70 18 10 <60 <60 15 20 800 900
1800 1400 <2 <2 <400 <4oo 15 17 20 18 70 70 14 16 <60 <6o 10 15 800 900
1800 1400 <2 <2 t400 <4oo 14 18 18 18 70 75 16 16 <00 <60 12 12 900 900
1200 1200 -
1200 1200 -
1100 1200 -
<4 -
<4 -
<4 -
13 13 12 9 63 96 21 25 <40 <90 10 -
14 16 11 10 62 04 22 27 <40 <90 9 -
13 15 I1 8 58 66 22 26 <40
670 -
650 -
650 -
<9 <20 20 14 15 30 40 -
<9 20 20 15 7 30 40 -
<9 <20 20 15 12 30 40 70 -
1500 1600 <2 <2 <400 <400 11 10 17 17 72 100 20 20 <40 <40 14 9 740 740 4 4 30 30 12 13 50 60 <80
1500 1500 <2 <2 <400 <4oO 10 11 9 9 65 60 20 lo <40 <40 8 11 670 700 4 4 20 20 9 10 50 40 <80
1500 1600 <2 <2 <400 <400 11 12 9 6 62 60 lo lo <40 <40 11 11 670 770 4 4 20 20 11 12 40 50 <80
40
Pr
of trace constituentsof
-
70
-
80
14 12 t20 700 730 6100 -
x2 16 <20 700 650 6000 -
13 15 <20 700 670 5600 -
150 140 20 22 <4 2 220 200
140 140 20 28 <4 2 220 230
150 140 20 26 <4 2 220 240
zeroa we shown in smaller type: -
= not looked for.
298
FRANCIS J. FLANAGAN Table 8. Chemioal analyses of peridotite PCC-1 (%) --Type of analysis : Split/ Position:
Conventional
-
SiO, A’,% F%O, Fe0 M@ CaO Na,O IV H,O+ H,OTiO, PA
MnO CO2 Cl F S ~%@?I NiO BaO
14126
14116
1515
41.92 0.77 2.72 4.93 43.35 o-40 0.00 0301 4*54 0.67 0.01 0.00 0.12 0.18 0.01 o-00 0.00 0.42 0.30 0.01
41.89 0.74 2.73 4.88 43.28 0.44 0.02 0.00 4.59 0.63 0.01 0.01 0.12 0.18 0.01 0.00 0.00 0.42 0.31 0.01
42.4 0.69 2.9 4.8 43.2 0.47 <0.06 <0*05 4.8 0.64 0.00 0.06 0.12 0.06
Subtotal Less 0
100.36 0.00
Total Analysts
100.36 E. L. Munson
:
Rapid ___~__.
-
100.27 0.00
-
100.27
v. c. Smith
100
.~_ __..._~__
43/l
69/13
42.4 0.65 2.8 4.9 43.0 0.46 <0*06 <0.05 4.8 0.63 o*oo 0.04 0.12 0.10
42,4 0.69 2.8 4.9 43.0 0.48
100 100 P. Elmore, S. Botts, G. Chloe and L. Artis
and samples for which these d8tta are available are indicated below Ni Cr CU Zr X X G-2 X X X X GSP-1 X AGV-1 X X X PCC-1
DTS-1 BCR-1
X
X
X
X X
X
X
X
To simplify cslcul&ions, the spectrographic date were coded, where neoess8ry, by removing nonsignificant zeros. The data which are then in the form of the nickel dsta shown for GSP-1 in Table 14 correspond to an array for 8 two-way analysis of veriance with duplicate determinetions, and after performing the calcul8tions for this design shown by DIXON and Masay (1961, p. 135), the conclusions drawn are summarized in Table 16. This table shows that the means of thirds for the four elements determined in the six rocks do not contribute significantly to the total variation end, therefore, each of the six rook samples can be considered homogeneous for niokel, chromium, copper and ziraonium. Estimates are msde of the ei%ots of pos&le oonfoPPinetion
299
U.S. Gwlogioal Survey &hate rook atandaxh apeotroahamios deter&nations of trace wmstituente in peridot&e PCE-1 (ppm)*
Table 9. ~ti~ti~e
split/ Position: Ba Be Ce co Cr CU
Ga
la/l9
4319
<4 <4 <2 <2
<4 c4 <2 <2
L&X
40 <60
Li Mn MO
m
Ni Pb Pr Rb SO Sn Sr Ti V Y Yb Zr
<2 <2 300 900
400 <400 I00
110 2700 16 16 Cl0
Wa&ington
Denver
Mimlo Park
Laboratory:
70/10 <4 t4 t2 - <2 c400 (400 80 100 3400 13 10
t2 <2 800 1100 40 Cl0
<20 t20 2300 2200 <20 t20
15112
42131
69127
IS/l1
<4 <4 -
-
<4 <4
<4 <4 -
<4 -
<4 -
<4 -
100
110 100 2600 3100 8 10 <4 <4 <40 (90
<20 t20 <2 t2 <4oo <400 71 79 1600 3000 7 9
<4 t20 <20 2600 2800 <20 <20 -
<4 <20 <20 2600 2400 <20 <20 -
t4 <20 <20 2300 2300 <20 <20 -
flo I10 2800 3200 9 6 <4 <4 <40
8 II <9
t4 50 -
30 32 (20 <9 <4 4
<20 <20
120
2600 3600 10 8 <4 <4 C40
<20
<20
zeroaare shown in smaller type; -
10 9
42121 <20 <20 <2 <2 c400 <400 93 97 2400 2200 8 10
t40 <40 t2 <2 86o 830 t2 <2
30 30 <20 <20 1 2 40
t20
t2o
t20
40
<80
~80 t20 <20 10 10 (20 <2 <2 40
= not looked for.
<20 <20 <2 <2 <400 c4oo 81 68 1200 2400 7 13
1800 <20 <20 <80 <80 t20. <20 9 9 t20 <2 <2 40 40 20 30 (20 <20 1 2
40
t20 <20 9 9 <20 <2 t2 lo 60 20 30 <20 t20 1 2 t20 <20
70/13
50
FRANCIS J. FJXNACAN
300
in the three thirds for each element. These effects, expressed as the deviations of the means of each third from the grand mean of all determinations of an element in the rock samples, were calculated and are shown below. Deviation
of means of thirds from the grand means (coded data)
_____..-.-~
Grand mean
Thirds ---.---
Element
1
2
Ni Cr cu Zr Av. dev.
0.5 0.7 0.7 0.5 0.6
-0.5 0.25 -0.2 -0.25 -0.2
3
,Y
0 -0.95 -05 -0.25 -0.4
15.6 12.3 24.6 29.7
The average effects range from a positive deviation for the means of the first third to increasing negative values for the last two thirds. These effects do not support the original assumption of an increase in nickel or chromium from the Table 10. Chemical analyses of dunite DTS-1 Type of analysis :
53123
+ x HZOTiO, P2Orl MnO co2
Cl F S Cr203 NiO BaO
Total Analysts
__
40.55 0.31 0.98 6.93 49.85 0.03 0.05 0.01 0.32 0.11 0.00 0.00 0.12 0.07 0.00 6.00 0.00 0.65 0.30 0.02
SiO, Al203 Fe203 Fe0 MgO CaO Na20
Subtotal Less 0
:
Rapid
Conventional
Split/ Position:
100.30 0.00
100.30 E. L. Munson
(%)
32114
10/31
3312
40.65 0.25 1.01 6.84 49.80 0.00 0.04 0.00 0.41 0.08 0.01 0.00 0.12 0.07 0.01 0.00 0.00 0.64 0.31 0.02
41.3 0.28 I.3 6.5 49.4 0.10 <0.05 <0*05 0.58 0.07 0.00 0.04 0.12 0.11
41.3 0.28 1.0 6.9 49.6 0.06 < 0.05 <0.05 059 0.08 0.00 0.04 0.13 0.11
53/18 41.3 0.28 1.2 66 49.6 0.07
100.26 0.00
____
100.26 v. c. Smith
100
100 100 P. Elmore, S. Botts, G. Chloe and L. Artis
301
U.S. Geological Survey eilicate rock sttmdards Table 11. Q;uantitativespcetrochemiceldeterminationsof trace constituents of dunite DTS-I (ppm)*
split/ Position: BE% Be Ce CO cr ccc GLL L& Li N-I X0 Mb Ni Pb PF Rb SC Sn Sr Ti V Y Yb zr
11/e
32115
53132
<4 <4 <2 <2 <400 <400 120 130 4000 8 8
<4 <4 <2 <2 <400 <400 85 100 4000 0 8 Cl0 cl0 <60 t60 <2 <2 900 900
t4 t4 <2 <2 <400 t400 110 120 4000 -
* Nonsi@f&mt
We&i@On
Denver
Menlo Perk
Laboratory:
7 9
r1/5
3215
54118
<4 <4 -
<4 <4 -
<4 -
<4 -
130 130 4000 4600 8 6 <4 <4 <40 <90 <3. 880 -
220 130 3600 4800 6 4 <4
<4 120 120 4200 4000 6 3 <4 <4 (40
840 -
840 -
t4 <20 <20 2400 2400 <20 <20 -
<4 <20 <20 2300 2600 <20 <20 -
<4 <20 <20 2500 2000 <20 <20 -
<7 5 <9
a7 4 t9
<20 13 <20 <9 t4 <2 t20 <20
(20 11 <20 <9 t4 <2 <20 <20
<7 5 <9
zeros are shown in smaller type; -
10113 t20 t20 t2 t2 <400 t4oo 120 110 4300 3100 4 3
= not looked for.
32125 <20 <20 t2 <2 <400
1700 2000 <20 <20
64/M <20 <20 <2 <2 <400
FRANCISJ. FLANAQAN
302
Table 12. Chemical analyses of basalt BCR-1 (76) Type of snalysis: Split/ Position: SiO, AleO, Fe,O, Fe0 MS0 CaO N%O g TiZO, P,O, MnO CO, Cl F S C%O, NO BaO
Conventional
Rapid _-
39125
13116
13/N
4012
06/Z
54.10 13.70 3.24 9.07 3.47 6.91 3.26 1.69 0.60 1.24 2.26 0.35 0.19 0.02 0.01 0.05 0.04 -
54.15 1363 3.17 9.09 3.60 6.92 3.32 1.69 0.62 1.21 2.26 0.36 0.19 0.02 0.01 0.06 0.04 -
54.2 14.0 3.6 8.8 3.6 6.8 3.1 1.6 0.20 1.3 2.2 0.46 0.19
64.2 14.0 3.6 8.8 3.6 6.8 3.2 1.6 0.20 1.3 2.2 0.45 0.19 <0.05
64.1 14.0 3.6 8.8 3.6 6.8 3.2 1.6 0.30 1.3 2.2 0.47 0.19 <0.05
0.06
0.07
Subtotal Less 0
100.16 0.04
Total Analysts:
100~11 E. L.
100.29 0.04 ~. 100.26 v. c. Smith
100
100 100 P. Elmore, S. Botts, G. Chloe and L. Artis
tit to the last thirds, and possible contamination from the stainless steel may, therefore, be considered insignificant. The conclusions in Table 16 also show that the laboratory means are t)significant source of variation in more than two thirds of the tests made and laboratory bias therefore exists. However, the between-laboratory components of varianoe generally seem quite reasonable. For this prelimin&ry report we shall table only the laboratory means and standard deviations with 16 degrees of freedom derived after pooling the sums of squares and degrees of freedom for the thirds, the interaction, and the within-groups vkstion from the analysis of variance. These estimates are shown in Table 16. Because of the few complete sets of data presented here, analysis of the other trace element data, recommended values, and further discussion will be deferred until more data become available.
U.S. Geologieel Survey, Menlo Park, Californie WRAPHY of five of the silicate referenoesamples and CiPW norms are presentedbelow. Model anslyses for the eoamer wined samples were detwmiwd fram thin wetions U&IS a
303
U.S. Geologid Survey silieat0 rook stars Table 13. Quwtitative speotrochemi~ detwminations of tzaoe uonstitueds of b&t BCR-1 (ppm)*
Split] Position: B& Be Ge CO
Gr Cki
GE& La Li Mn MO
Nb
Ni Pb Pr Rb SC StI Sr Ti V Y Yb zr
13122 400 600 <2 <2
+ Nonsi@Eant
39122
6712
12130
40110
650
480
660
MO
620 720 -
620 780 -
<4 -
<4
<2 <2 t400 t400 30 34 13 13 24 24 20 20 ~60 <60 19 18 1800 2000
<2 t2 <400 <400
29 37 14 14 20 30 23 32 <40
I10 120 46 50 <20 400 340 -
30 32 11 12 23 22 18 16 <60
380 400
300 380
60
60
490 410 40 68 4 6 190
<20
60 Ii 6 180 180 !zIeros
W~u
Dtmver
Menlo Park
Laborstory:
60 6 8
170 1sO
-
33 40 lb 27 21 33 22 31 <40 t90 13 1300 <9 <20 30 12 10 <20
20 -
50
30 48 (20 300 420 12000 -
are shown ill fznlaller
670
780 <4 31 30 14 14 19 31 24 28 <40
50 -
-
220
M/31
-
39132
860 900 t2 <2 <4?00 <400 32 32 17 17 24 29 20 20 <40 <4o 14 16 1300 1300 9 7 50 40 8 9 30 40
780 920 <2 <2
60
32 53 <20 300 380 12000 -
33 44
480 420 40 51 4 5 206 200
500 390
type; -
13123
40
44 6 6 200 190
= not
33 33 <2o 410 370 12000 13000 250 270 60 50 6
6 160 140
looked for.
<4OO
c.400 30 29 12 12 36 35 20 20 t40 t40 20 22 1600 1600 6 6 60 50
6 7 40 40 <80 t8o 70 80
36 36 <20 310 370 12000 12000 170 210 60 60 4 6
66/M 880 880
t2 <2 <400 <&O
26 23 14 9 32 31 20 20 <4o <40 14 27 1700 1700 6 6 40 30 9 8 30 30
160
ISO
160
160
394
FRANCIS
J. BLDNAN
Table 14. Nickel determinstiona in sample GSP-1. (ppm) --~.-._
Laboratory
-
Totals
%3nlo Park
Denver
Washington
for thirds
1
5 II
9 8
Subtotal
19
-i?-
5 5 IO
46
2
8 10
9 5
4 5
Thirds
Subtotal 3
18
T-4
41
9 7 7
Subtotal
10 12 F$
-E
Ip
Laboratory totals
59
4c,
33
9 9
61 CT 2 I38
count of 1000 points. Indices of refiaotion were measured usiug a spindle stage, and optical augles were determined by direct measurement to two optio axes using the universal stage. The CIPW noxms (Table 17) were oalaulated using a U.S. Geological Survey computer program of the norms for the for the Burroughs B-5600 computer at Stanfoxd ~n~ve~ity. In collation classical analyses, SO,, Cl, F, S, NiO and BaO were omitted and the remaining oxides were recaitmlated to XOOo/o so that a more reeliitic comparison could be made with the norms of the rapid rock analyses. GRANDIO~TE GSP-1 A medium grained h~~~o~~~~-~~ular rook consisting essentially of quartz (277;), plagioclase (2S”/0),microcline (30%), biotite (90/e),and muscovite (5%) with minor iron oxide (2%), apatite, fluorite, zircon, pyrite, and epidote. Secondary minerals in&de serioite, calcite and hematite. Plagioolase, An& = 1548 & 0.002), shows polysynthetic twinning and minor alteration to sericite and e&rite. Microcline has well-developed grid twinning and is slightly microperthitic. Myrmekite is present but not common. Quartz is strained and uommonly contains small, randomly oriented, unidentified needles. IIematite occurs ss xhns around pyrite. Petrographically the rook is an adamellite. AN~ES~TE AGV-I Aphanitic, finely porphyritic, with a trachytic texture. Phenoarysts ( < 1%) c3onsistof plagioclaee (sodic labradorite), augite, and an unidentified reddish brown, trausluoent, nonpleoohroic, birefringent miner& Groundmass consists of subparallel plagioclase microlites (approximately An,,_,,, WALKER G. W., oral commmrieation), altered pyroxene, iron oxides, are aommonly yellow-brown glass, and shreds of a mioaceous mineral. Plagioclase phen~a zoned and some contain included ~0~~~ materid. According to the chemioal election of R~FN (1952) this rock is a trachymndesite. PERIDOT~TEPCC-1 Primary granular olivine (58%) snd orthopyroxene (9%) are partially replaoed by mesh structure serpentine (32%). Other minerals present include p&nary disseminated ohromite, secondary magnetite, and a traoe of talc and aarbonate miner& 0li.e exhibits undulose extirmtion and deformation btmds. Some orthopyroxene shows bending of oleavage traces. Oiivine is colorless; Q = 1~651 Ifr:0602, /I = 1,670 f 0*002, y = 1889 4 O+&? (for&e&e 92-90); 2V, = 80”. Ortbop~ox~~ uolorless, y = I.678 f 0*004 (akin 90); 2V; = 85-88”. Discontinuous exsolution lame&e of dinopyroxene are commonly present in orthopyroxene. The serpentine minerals consist of lizardlte plus minor olinoohrysotile (X-ray identification). Tale appears to be associated primarily with orthopyroxene.
U.S. Geological Snrvey silicate rook standarda
308
Table 15. Conoluaionstirn the enalyws of vtiame for four elemcmtsin all rock sampI@
Sample G-2
Source of variation
Elem0nt Ni
Cu
Zr
NS S
NS*
NS
-
NS*
NS
-
Third8 Labs
Cr
GSP.1
ThirdE Labs
NS
NS
-
NS
AGV-1
Thirds Labs,
NS
NS* S*
NS NS
NS NS
-
NS
-
Pee-1 DTS.1
BCR-I
ss S
NS
Thii
-s
Lab0
s-s
Thirds Labs
NS
-
NS
Thirda
NS S
NS NS
NS S
Labs
-
s-s
-
-
* Teeted 8kgainh a signifiaant intera&ion. s = ant {F*es)* NS = ~o~~~t
NS
S
(F.,&
Table 16. Laboratory meaw and &mdard deviations (ppm)* Laboratory
All Labs
Sample
Menlo Park
Denver
Niokel
GSP-1 AGV-L PCC- 1 DTS-1 BCR-1
9.8 18.2 2180 2020 23-2
7.7 13.0 2480 2470 x0*0
5.6 11.2 1750 1860 7.8
7.7 14.1 2140 2110 13-7
1.54 2.33 185 161 2.30
~~~
G-2 GSP- f. AGV-1 BCR-I
7.0 10.0 17*7 14.1
8.0 14.3 10-l 16.3
9.6 16.1 11.1 13.5
8.2 13.6 13.0 14.6
1.25 1.68 2.72 4.21
Copper
G-2 AGV- 1 PCC-1 DTS-I BCR-1
12.1 68.3 12-5 8.1 23.1
9.7 68.1 8.3 6.3 25.7
11.0 70.8 9.0
10.9 69.1 9.9 6.4 26.6
l-22 12.4 2.26 1.74 4.40
Zimonium
G-2 GSP-I AGV-1 BCR-1
Element
273 373 207 183
290 538 221 200
Wa&in@on
311 613 198 158
* Nonsigniscant zeros are shown in smaller type.
Mean
291 508 209 180
Std Dev.
33.4 67.9 17.3 11.6
FRANCIS
306
J.
I?LANAGAX
Table 17. CIPW Norms
--._
Granite G-2 Splitposition
I~~
20/16
101/16
2115
61/l
100/13
23.5 0.8 26.6 34-6 8*5 1.9 1.2 1.5 O-9 0.3 O-2
23.1 0.8 26.5 35.3 8‘4 I.9 1-I l-5 O-9 0.3 0.2
24.7 1.5 27.4 32-4 7.8 I.8 0.9 1.8 0.9 0.4 0.2
24.1 1.5 26.8 34.x 7.6 1.9 0.9 1.8 0.9 0.4 0.1
22.9 O-8 26.8 3.w 8.8 1.7 1.0 1.6 0.9 0.3 0.1
Gmnodiorite GSP-I Sp~tlFosi~ion
70117
69119
1416
42/2
6Qfl4
c1 c
“4.5 2.0 32.8 23.8 7.9 2‘5 2.0 2-4 1.3 0.7 0.2
24.4 1.9 32.8 24.1 7.8 2.4 2.0 2.4 1.3 0.7 0.3
24-4 2.1 33.4 23.9 7.6 2.4 l-2 2.9 1.3 0.7 0.1
25.6 2.4 32.8 23.0 7.6 2.3 1.4 2*Q l-3 0.8 0.1
25.1 2.4 32.8 23.9 7.0 2.3 1.4 2.9 1.2 O-8 0.1
Of
ab an en & mt il aP CC
Andesite AGV - 1 Splitt~~iti~~
65/30
55124
18/26
5611
92f24
q c
12.8 17.4 36”7 19.7 0.8
12.7 17.2 36.7 19-Q 0.7
13.1 16.9 36.2 20.5 -
51sn
-3-a
-3.8
-4.1
13‘4 16.9 36.2 20.4 ..“.... -3.8
13.7 0.3 16.9 36.3 19.9 -3.6
EL il aP ce
4.0 I.7 2.0 1.2 -
4.0 1.7 2.0 1.2 -
3.6 2.3 I.9 1.3 0.1
4.0 I*9 I.9 1.3 0.1
2.2 3.7 2.1 1.3 0.1
Ol?
ab an wo
U.S. Gislogio%l Survey %ilieat%rook %iand%rd%
307
Table 17. CIPW Norms, continued Peridot& PC&l Splitlpoeition 0 Or
ab an wo en f% fo fs mt om il %P co
X4/26 0.6 0.1 0*9 25.9 1.6 61‘6 4.2 4.2 0.7 -
la/l6
0.2 1.0 26.6 1.6 61.8 4.1 4.2 0.7 -
1616
43/l
69113
-
-
-
0.3 0.4 1.6 -
0.3 0.4 1.5
0.3 0.4 1.6 -
26.4 l-6 61.8 4.2 4.4
26*9 1.7 61.2 4.3 4.3
-
-
0.1 0.1
0.1 0.2
26.8 l-7 61.2 4.3 4.3 0.1 0.2
0.4
Dunite DTS-1 Split/l?o%ition c OF
sb en f% fo b mt om il %P co mg
53123
32114
10/31
3312
63118
0.2 0.1 0.4 1.6 0.1 86.3 8.9 1.4 1.0 -
0.2 0.3 2.4 0.2 86.6 8.7 1.6 0.9 -
0‘1 0.3 0.4 4.8 o-4 83.4 8.3 1.9
O-1 0.3 0.4 3.7 0.4 84.2 9.1 1.6 0.1 -
0.1 0.3 0.4 4.1 0.4 84-O 8.6 1.8 -
0.1 0.1
0.1
o-2
0.1 0.1 0.1
Bwalt BCR-1 Split/l?o%itiori
g Or
ab an wo ;: mt B aP co
39125
13116
13116
4012
6612
8.1 10.2 28.1 l&l 6.0 8.8 10.8 4.8 4.3 O-8 -
7.8 10.2 28.6 17.6 6.2 8.9 10.9 4-7 4.4 O-8 -
9.6 9.6 26.6 19.9 4.6 9.1 10.1 6.2 4.2 l-1 0.1
9.1 9.6 27.6 19.4 4.8 8.8 x0.1 6.2 4.2 1.1 0.1
9.6 27.6 19.4 4.8 9.1 10.1 6.2 4.2 l-1 0.1
8.9
308
FRUVCIS J. FLANAGAN
DUNITE DTS-1 Medium grained, primary olivine (99%), orthopyroxene and olinopyroxene occur in an allotriomorphio-granular texture with euhedral to subhedral disseminated ohromite and a trace of light green amphibole. Serpentine occurs along narrow, continuous fractures in olivine. Olivine shows abundant deformation bands. Olivine is colorless; for&e&e 91.5% (determined by the X-ray method of HOTZ and JACKSON, 1963); a = 1.650 f 0*002, p = 1.667 & 0,002, y = 1685 i 0.002; 2V, = 84-87”. The amphibole has indices of refraction OL= l-634 f 0*002, /‘I= 1.645 + 0.002, y = 1.658 + 0*002; 2’c’;. = 80-87”; ZVG w 20”. BASALT BCR- I
An aphanitio, hypocrystalline, basalt with an intersertal texture consisting of randomly oriented plagioolase laths with interstitial augite, brown glass, and iron oxides. The plagioolase is slightly zoned with an approximate composition of An,, (/3= 1560 + 0.002). Augite is brown with 2 V’y variable from 3 l-44”. Individual grains of pyroxene may show zoning from augite to sub-oaloio augite. The glass is partially devittied and commonly contains abundant iron oxides. Using R~MANN’S (1952) chemical classification of volcanic rocks this sample is an andesine traohybasalt. REFERENCES BA~TRON H., BARNEIZTP. R. and MURATA K. J. (1960) Method for the quantitative speotrochemical analysis of rocks, minerals, ores, and other materials by a powder d.o. arc technique. U.S. Gwl. Suru. BeJE.I004+, 165-182. &AYES F. and Suzcnu, Y. (1963) A replacement for reference sample G-l. Cm In&i&tio~ of Washington Yeur Book 62, Annual report of the Director of the Geophysioal Laboratory, pp. 155-156. DIXON W. J. and MASSEY F. J. JR. (1961) Introductiora to S6atisticcslAndy&. McGraw-Hill. FAIRBAIRN H. W. et cd. (1961) A cooperative investigation of pm&ion and acouraoy in ohemioal, spectrochemioal, and modal analysis of silicate rocks. U.S. Geol. &VU. Bulk 980, 71 p. HOTZ P. E. and JACKSONE. D. (1963) X-ray determination curve for olivines of composition Fo,,, from stratiform and alpine-type peridotites. U.S. Geol. &TV. Prof. Paper #E, 101-102. PEOK L. C. (1964) Systematic analysis of silicates. U.S. Geol. Surv. BwU. 1170, 89 p. RAND CORPORATION(1955) A Milliola Random Digits with 100,000 Nowmd Deviatea. The Free Press, Glencoe, Illinois. Rm A. (1962) Nomenclature of volcanic rooks. Bull. Volcunoe. Serie II XII, 76-102. SJU.P~~ L. and BRANNOOKW. W. (1962) Rapid analysis of silioate, carbonate and phosphate rocks. U.S. GeoZ.Surv. BUW. ll44-A, 56 p. TAYLOR S. R. and KOLBE P. (1964) Geochemioal standards. Gemhim. Coamochim. Acta 28, 447-454.