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DISTRIBUTION OF HEAVY ELEMENTS HAZARD- 

— OUS TO HEALTH, SALINAS VALLEY REGION, 

CA. By: Hasmukhrai H. Majmundar. ' 







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M ^m mm 



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PHYSICAL Sa, lit 



PHYSICAL 
SCIENCES 
UBRARIf 



DISTRIBUTION OF HEAVY ELEMENTS 
HAZARDOUS TO HEALTH, 

ALINAS VALLEY REGION, CALIFORNIA 



1980 



.IFORNIA DIVISION OF MINES AND GEOLOGY 



CIAL REPORT 138 





P % 



rA** 





STATE OF CALIFORNIA 

EDMUND G. BROWN JR. 
GOVERNOR 

THE RESOURCES AGENCY 

HUEY D. JOHNSON 
SECRETARY FOR RESOURCES 

DEPARTMENT OF CONSERVATION 

PRISCILLA C. GREW 
DIRECTOR 



DIVISION OF MINES AND GEOLOGY 

JAMES F. DAVIS 
STA TE GEOLOGIST 



Special Report 138 



DISTRIBUTION OF 

HEAVY ELEMENTS HAZARDOUS TO HEALTH, 

SALINAS VALLEY REGION, CALIFORNIA 



By 

Hasmukhrai H. Majmundar 

Geochemist 

1980 



CALIFORNIA DIVISION OF MINES AND GEOLOGY 

1416 Ninth Street, Room 1341 

Sacramento, CA 95814 



CONTENTS 

Page 
ABSTRACT v 

INTRODUCTION 1 

GEOLOGY 2 

DEVELOPMENT OF SAMPLING AND ANALYTICAL PROCEDURES 4 

Sampling techniques 4 

Sample preparation 4 

Digestion 4 

Stream sediment samples 4 

Bedrock samples 4 

Analytical techniques 4 

Mercury 4 

Arsenic 7 

Cadmium, copper, lead, and zinc 7 

Phosphorus 7 

RESULTS OF ANALYSES 8 

Mercury 8 

Arsenic 8 

Cadmium 8 

Lead 8 

Copper and zinc 9 

Phosphorus 9 

CORRELATION 9 

CONCLUSIONS 29 

RECOMMENDATION 31 

ACKNOWLEDGMENTS 31 

REFERENCES 31 

APPENDIX A. Locations of stream sediment samples 32 

APPENDIX B. Locations of bedrock samples 33 

APPENDIX C. Computer programs 35 

APPENDIX D. Digestion procedures 37 

APPENDIX E. Analytical techniques 39 

APPENDIX F. Chemical analyses of stream sediments 47 

APPENDIX G. Chemical analyses of bedrocks 48 

APPENDIX H. Precision and accuracy of the analytical techniques 50 

APPENDIX I. Statistical treatment of data 51 

iii 



ILLUSTRATIONS 



Figures 



Page 



Figure 1. Index map of drainage basins in Salinas Valley 3 

Figure 2. Index nnap of locations of stream sediment samples, Sali- 
nas Valley 5 

Figure 3. Index map of locations of bedrock and some stream 

sediment samples from Salinas Valley 6 

Figure 4. Technique for collecting composite stream sediment sam- 
ples 7 

Figure 5. Arsenic in stream sediments 10 

Figure 6. Arsenic in bedrocks and some stream sediments 1 1 

Figure 7. Cadmium in stream sediments 12 

Figure 8. Cadmium in bedrocks and some stream sediments .... 13 

Figure 9. Copper in stream sediments 14 

Figure 10. Copper in bedrocks and some stream sediments 15 

Figure 11. Lead in stream sediments 16 

Figure 12. Lead in bedrocks and some stream sediments 17 

Figure 13. Mercury in stream sediments 18 

Figure 14. Mercury in bedrocks and some stream sediments 19 

Figure 15. Phosphorus in bedrocks and some stream sediments.. 20 

Figure 16. Zinc in stream sediments 21 

Figure 17. Zinc in bedrocks and some stream sediments 22 

Figure 18. Correlation between arsenic and cadmium in stream sedi- 
ments 23 

Figure 19. Correlation between arsenic and copper in stream sedi- 
ments 23 

Figure 20. Correlation between arsenic and zinc in stream sediments 

24 

Figure 21. Correlation between cadmium and copper in stream sedi- 
ments 24 

Figure 22. Correlation between cadmium and zinc in stream sedi- 
ments 25 

Figure 23. Correlation between copper and zinc in stream sediments 

25 

Figure 24. Correlation between cadmium and copper in bedrocks 26 
Figure 25. Correlation between cadmium and phosphorus in bedrocks 

26 

Figure 26. Correlation between cadmium and zinc in bedrocks .. 27 
Figure 27. Correlation between phosphorus and copper in bedrocks 

27 

Figure 28. Correlation between copper and zinc in bedrocks 28 

Figure 29. Correlation between phosphorus and zinc in bedrocks 28 

Figure 30. Digestion apparatus for volatile elements 37 

Figure 31. Non-flame mercury device 39 

Figure 32. Working curve for mercury 41 

Figure 33. Arsine generation apparatus 41 

Figure 34. V/orking curve for arsenic 43 

Figure 35. Working curve for P^Oj (high phosphate) 45 

Figure 36. Working curve for P2O5 (low phosphate) 45 

Figure 37. Cumulative frequency distribution for arsenic in stream 

sediments 52 

Figure 38. Cumulative frequency distribution for arsenic in bedrocks 
52 



Figure 39. Cumulative frequency distribution for cadmium ii 
sediments 

Figure 40. Cumulative frequency distribution for cadmiun 
drocks 

Figure 41. Cumulative frequency distribution for copper ii 
sediments 

Figure 42. Cumulative frequency distribution for copper in I 

Figure 43. Cumulative frequency distribution for lead in stre 
ments 

Figure 44. Cumulative frequency distribution for lead in be( 

Figure 45. Cumulative frequency distribution for mercury ii 
sediments 

Figure 46. Cumulative frequency distribution for mercury in I 

Figure 47. Cumulative frequency distribution for phosphori 
drocks 

Figure 48. Cumulative frequency distribution for zinc in stre 
ments , 

Figure 49. Cumulative frequency distribution for zinc in bei 

Figure 50. Histogram for arsenic in stream sediments .... 

Figure 51. Histogram for arsenic in bedrocks 

Figure 52. Histogram for cadmium in stream sediments 

Figure 53. Histogram for cadmium in bedrocks 

Figure 54. Histogram for copper in stream sediments .... 

Figure 55. Histogram for copper in bedrocks 

Figure 56. Histogram for lead in stream sediments 

Figure 57. Histogram for lead in bedrocks 

Figure 58. Histogram for mercury in stream sediments .. 

Figure 59. Histogram for mercury in bedrocks 

Figure 60. Histogram for phosphorus in bedrocks 

Figure 61. Histogram for zinc in stream sediments 

Figure 62. Histogram for zinc in bedrocks 



Tables 



Table 1. Effects of anomalous levels of cadmium 

Table 2. Predicted concentration of cadmium 

Table 3. Correlation matrix (stream sediments) 

Table 4. Correlation matrix (bedrocks) 

Table 5. Correlation of geology and stream sediment che 
Table 6. Phosphorus and cadmium determinations in samp 

other ports of the United States 

Table 7. Correlation of geology and bedrock chemistry 

Table 8. Comparison of various digestion techniques 

Table 9. Precision tests for ten replications of samples 

167/73, and N.B.S.120a 

Table 10. Accuracy of arsenic, copper, lead, mercury, ( 

analyses 

Table 1 1. Various parameters calculated on the basis of cu 

frequency curves 



ABSTRACT 

Samples of stream sediment and bedrock from the Salinas Valley region were analyzed 
to determine the distribution and the amounts of potentially health-hazardous heavy ele- 
ments (arsenic, cadmium, copper, lead, mercury, and zinc). Cadmium was found to be 
anomalously high in the stream sediments and soils in the King City-Son Ardo area in the 
extreme southeast corner of the project area. The California Department of Agriculture 
obtained similar high-cadmium values in samples of agricultural soils from the some area. 
The stream sediments appear to be derived from Middle Miocene marine strata exposed 
in the drainage basin. The source of the anomalous cadmium in these stream sediments in 
the King City-San Ardo area was traced to relatively thin beds of phosphotic rocks. 
Cadmium might exist in the phosphotic rocks elsewhere in the United States, and, because 
of the potential health hazard from cadmium, these other phosphotic rocks should be 
evaluated for possible cadmium contamination. 



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in 2012 with funding from 

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DISTRIBUTION OF 

HEAVY ELEMENTS HAZARDOUS TO HEALTH, 

SALINAS VALLEY REGION, CALIFORNIA 



By Hasmukhrai H. Majmundar' 



INTRODUCTION 

n July 1971, Governor Ronald Reagan mandated an intera- 
«|Cy public health project to determine the sources and distri- 
(ion of certain health-affecting elements in the Salinas Valley, 
'ticipating in the study were a number of organizations repre- 
iting State, local, and federal agencies and also the private 
3:or. The project was coordinated by the Project Committee of 
■ Monterey Basin Pilot Monitoring Project, composed of rep- 
smtatives of each of the participating State and local agencies. 
"; project objective was to design an efficient and effective 
initoring program for tracing the source, movement and fate 
tmvironmentally harmful substances, and to determine the 
>int to which such a program could be planned and imple- 
nted by a multitude of agencies with separate interests and 

jonsibilities with regard to environmental quality. 

'he report presents the results of the California Division of 
'lies and Geology participation in the project. The Division's 
a in the project included ( 1 ) the development of accurate 
imiques for sampling the stream sediments of the project area; 
I the development of analytical procedures for detecting very 
rill concentrations of arsenic, cadmium, and mercury; and (3) 
h preparation of maps showing the distribution of arsenic, 
amium, copper, lead, mercury, and zinc in the sediments of 
inas Valley. These elements were selected for study because 
their health-hazard characteristics. 

'ertain compounds of arsenic are poisonous when eaten in 
i^e than trace amounts, but little is known about their other 
hracteristics, including their carcinogenic potential. Neverthe- 
::, arsenic is generally well known to be an undesirable element 
:m a health standpoint. Throughout the world arsenic is most 
tndant in areas in which sulfide deposit occurs. 

admium is a known cause of high blood pressure and has 
ei identified as an extremely carcinogenic element (as has 
i.el). In its primary occurrence in nature, cadmium generally 
i isociated as a trace impurity with lead-zinc sulfide mineral 
s mblages, and it can be expected to abound in areas contain- 
1 such minerals. The phosphatic sediments in the Middle Mio- 
e; unit of the project area are known to contain zmc; and, as 
xected, the presence of cadmium in these phosphatic sedi- 
1 Its was later confirmed by Project data. 



ijomia Division of Mines and Geology, San Francisco, CA 



Cadmium may be introduced into the environment by such 
industrial discharges as mine wastewater, smelter or refining 
exhausts, or electroplating wastes. It is also introduced when 
fertilizers containing phosphate rock are added to agricultural 
soils; such phosphate fertilizers contain 9 to 36 ppm Cd, which 
is absorbed in some grains and vegetables to the extent of 1 to 
4 milligrams per hundred grams (mg/lOOg) (Furst and Haro, 
1969). Superphosphate, another form of commercial fertilizer, 
can also be a source of cadmium in certain vegetables (Schroeder 
and Balassa, 1963). 

Although the uptake of cadmium in plants is species depend- 
ent and certain crops can accumulate it much more readily than 
others, in general cadmium is retained in plants at concentra- 
tions ten times greater than those in animals. Older animals, 
however, because of the longer duration of their exposure, can 
have higher levels of concentration than plants. Strangely 
enough, children retain higher concentrations than adults. 

The Monterey Basin Pilot Monitoring Project discovered that, 
in certain sections of the project area, elevated levels of cadmium 
are present in aquatic life as well as in terrestrial soils, plants, and 
animals. Filter-feeding organisms and scavengers living in the 
sediments were found to have the highest cadmium values. 

Human beings can be exposed to cadmium via food, water, 
and air. Of these, however, exposure through food is by far the 
most significant. In uncontaminated areas, most foodstuffs con- 
tain less than 0.05 jug Cd/g wet weight, and the average daily • 
intake probably is about 50 jag. Liver and kidney probably have 
concentrations larger than 0.05 jag/g. When foodstuff is con- 
taminated by cadmium in soil and water, the cadmium concen- 
trations may increase considerably. In water, the normal 
concentration of cadmium is less than 1 ng/g. If the cadmium 
concentration in drinking water exceeds 5 ng/g, it contributes a 
significant amount in daily uptake of cadmium. The normal 
concentration of cadmium in air is about 0.001 jag/m'. In areas 
where cadmium-emitting factories are situated, average cad- 
mium concentrations of 0.1 to 0.5 jug/m' have been recorded, 
which may result in the inhalation of 2 to 10 ju.g cadmium per 
day. Smoking also contributes to daily intake. Smoking one pack 
of cigarettes contributes 2 to 4 jag/d intake. (Friberg and others, 
1971; Sandstead and others, 1974) 

Table I gives the effects of anomalous levels of cadmium on 
animals and plants. Environmental cadmium poisoning has been 



CALIFORNIA DIVISION OF MINES AND GEOLOGY 



SR 



Table 1. Effects of anomalous levels of cadmium. * 



Emironmental 
Le\cl 


EfTecis on Plants 


EfTects on Animals 
Other than Man 


Effects on Man 


Established 


Conjectured 


Established 


Conjectured 


Established 


Conjectur 




Absorbed 












Low 


through 

plant 

roots 


- 


- 


- 


— 


- 


High 


- 


Toxic 


Acute: 

Testicular 

hemorrhage, 


Interferes 

with 

utililzalion 


- 


Hypertensio 
Competes w 
Zn at 








male 
sterility. 
Chronic; 
hypertension. 
Little 
transfer to 
cow's milk 
from oral 
dose 


of Zn, Fe, 
and Cu. 
(Se prevents 
Cd-induoed 
pregnancy 
toxemia.) 




metallothior 
binding site 
kidney. Regi 
differences i 
human kidn 
(Japan and 
United State 
have higher 
levels). 



♦After Hopps, H.C. (1974). 



established as the cause of an estimated 100 human deaths in 
Japan by itai-itai disease. Table 2 gives the predicted concentra- 
tions of cadmium in soils, municipal drinking water, and vegeta- 
bles. The median values probably represent ordinary, adequate 
levels of cadmium in water, soils, and foods (Sandstead and 
others, 1974). 

Table 2. Predicted concentration of cadmium. 





Median 


Range 


Soils, ppm 


0.06 


0.01 - 0.7 


Finished Municipal 


->1.0 


< 1.0- 10 


Water, ppb 






Forge Grasses, ppm 


0.37 


0.03 - 2.4 


Forge Legumes, ppm 


0.04 


0.04 - 0.05 


Vegetables and 


0.10 


0.01 - 0.96 


Fruits, ppm 







'Credited to Helen L. Cannon 
By Hopps, HC, 1974. 



Copper and zinc, when ingested in the presence of each other, 
can be toxic in varying degrees to fish and to humans. 

The high toxicity of lead has long been known. The hazard 
from naturally occurring lead is small compared to that of man- 
created lead contamination, mostly from tetraethyl lead gaso- 
line. 

Mercury is highly toxic and has been identified as a carcinogen 
(Furst and Haro, 1969). It concentrates m body tissues with age 
and has been the source of area-wide health problems. Mercury 
tends to concentrate in the internal body organs of animals 
(liver, kidneys), and in plants. The U.S. Geological Survey in- 
vestigated mercury in air, water, soil, and rock, and its effect on 
man (Fleishcher, and others, 1970). Most of the earth's crust 
contains little mercury (80 ppb Hg), but large amounts of mer- 



cury are generally present in areas in which any type of si 
deposit occurs. Mercury enters the atmosphere througl 
natural disintegration and decomposition of mercury-be 
minerals. Mercury is removed from the atmosphere by ra 
and by absorption in particulate matter. The particulate tr 
may be temporarily suspended in streams or lakes, but it 
to settle to the bottom eventually. 

The Division's study provides background data on the na 
distribution of these six elements in the project area and c 
used as a base level against which other participants in the 
project can monitor air, water, particulate matter suspend 
air and water, agricultural soils, vegetables, milk, hospital 
and industrial discharges in Monterey County. 

The California Department of Water Resources include 
ron among the elements tested in their analyses of stream ' 
samples during the project. However, Boron could m 
analyzed for lack of a sensitive analytical procedure to me 
its presence in stream sediment samples. 

As indicated by analyses of the stream sediments, a higl 
portion of cadmium is present in sediments and soils near 
City and San Ardo. An effort was made to trace the souijj 
this cadmium by collecting bedrock samples from this area ' 
bedrock samples also were analyzed for arsenic, cadmium 
per, lead, mercury, and zinc. The proportion of cadmiun 
found to be high in some of the phosphatic beds. Therefo! 
the bedrock samples containing more than 10 ppm Cd also 
analyzed for phosphorus in order to determine the correi 
between the two. It was established that there is a very 
correlation between these two elements; when one eleim 
higher, the other seems to be higher. 



GEOLOGY 



i 



The geological framework of the project area is describ( 
Hart (1966) and Durham (1964, 1966, and 1970) and s' 
on open-file maps by Dibblee (1967, 1968, 1969, 1971 and! 
and the Geologic Map of California (Jennings and Strand, 
Jennings, 1958). The Salinas River drainage area extends; 



[iO 



DISTRIBUTION OF HAZARDOUS HEAVY ELEMENTS 



Kmiles southeast of this project area (Figure 1), but the main 
c nations in the project area are pre-Cretaceous metamorphic 
cks, Upper Cretaceous granitic intrusive rocks, and Tertiary 
o'leistocene marine and nonmarine sedimentary rocks. 

he pre-Cretaceous rocks are known as the Sur Series and 
csist of crystalhne limestone and dolomite, quartzite, schist, 
riss, and various contact metamorphic rocks. They are the 
li:st rocks of the project area and are located on the segment 
fie west flank of the Salinas Valley that lies roughly between 
cdad and Salinas. 

Ipper Cretaceous granitic rocks are predominant in the Gabi- 
irRange on the northeast flank of the Salinas Valley, extending 
D'hly from King City past Salinas. 



The Tertiary and Plio-Pleistocene units occupy the southern 
two-thirds of the project area on both flanks of the Salinas 
Valley and the San Antonio and Nacimiento River drainage 
basins. The predominant Tertiary unit is the Miocene Monterey 
Formation, consisting mainly of siliceous and clayey shale and 
sandstone beds. In the Monterey Formation, phosphatic beds 
and petroliferous clay shale occur separately in various localities. 
The Monterey rocks and minor Plio-Pleistocene Paso Robles 
continental sandstone, conglomerate, and clay occur mainly in 
the southwest part of the project area — on the west flank of the 
SaUnas Valley and in the basins of the San Antonio and Naci- 
miento Rivers. The principal Pliocene unit is the marine Pancho 
Rico Formation, consisting mainly of diatomaceous mudstone 
and siltstone. The Pancho Rico and the Paso Robles Formations 
are exposed along the east flank of the Salinas Valley from about 
the latitude of Greenfield to the south edge of the project area. 

The phosphatic beds of the Monterey and the Pancho Rico 
Formations are the sources of the anomalous cadmium concen- 
trations in the project area. 

The Carmel River drainage basin is dominated by rocks of the 
pre-Cretaceous Sur Series, upper Cretaceous granitic intrusive 
rocks, and Miocene Monterey Formation. 




u»»!l. Index map of drainage basins in Salinas Valley 



CALIFORNIA DIVISION OF MINES AND GEOLOGY 



SR 



DEVELOPMENT OF SAMPLING AND 
ANALYTICAL PROCEDURES 



Sampling Techniques 

Sampling for the first part of the project was restricted to 
stream sediments of the drainage basins of the Sahnas and Car- 
mel Rivers. Samples were collected from most of the streams in 
the area (Figure 2). A few samples were taken from ephemeral 
streambeds in canyons which are dry in the summer. The soil 
and sediment in several of the canyons have been disturbed 
during cultivation of barley for cattle feed, making it difficult to 
obtain reliable, undisturbed samples. Streams generally were 
found to be excellent in terms of convenience and reliability for 
collecting samples. A total of 201 samples of stream sediment 
were collected. Locations of these samples are given in Appendix 
A and shown on Figure 2. Locations of samples 572-576 and 593 
are included on Figure 3, as they were collected south of the 
project area, near San Miguel and Bradley. 

Sites for stream sediment sampling were spaced evenly over 
the project area and were selected as representative of the tribu- 
tary streams. Composite samples were taken at each locality to 
represent the upstream drainage area. Figure 4 illustrates the 
pattern used: a tablespoon of the surficial sediment was collected 
at each of the sample points, spaced about 12'/, feet apart by 
pacing, and put in a sample bag. Large pebbles and organic 
debris were discarded immediately. 

Usually, 650-800 grams of sediment, representing 100 to 150 
individual sample points, were collected; resulting composite 
sample was treated as a unit. 

The size of the area sampled in this manner depended upon 
the local width of the stream beds, which ranged from about 20 
feet to hundreds of feet. This method was devised to decrease the 
geochemical variability that might otherwise occur in a sample 
collected from a single point. The samples generally were collect- 
ed from the active channel between the stream's terraces in both 
the wet and seasonally dry parts of the channel. Where this was 
not possible — for instance, in the deep water channels of the 
Salinas and Carmel Rivers — samples were collected from the 
stream deposits adjacent to the deep water. In areas under culti- 
vation, the courses of intermittent streams could be traced by the 
fresh green color of the barley or grass and sampled accordingly. 
The sediment or, where necessary, the surface soil was collected 
along the trace of the stream path, and a composite sample was 
made. 

A similar composite sampling technique was applied in col- 
lecting bedrock samples. From each rock formation, at each 
location, rock chips were collected at intervals of one to two feet 
over the entire exposure. A composite sample was made by 
crushing all of the chips. Thus, each composite sample provided 
a representative sample of the exposed portion of each forma- 
tion. A total of 259 composite bedrock samples were collected. 
(Figure 3 and Appendix B). At some locations, samples were 
collected from a depth as great as two feet, as well as from the 
surface, in order to check the vertical variability. 

Computer programs (Appendix I) were used for preparation 
of the sample identification list, tables of chemical analyses, and 
for storage and retrieval t)f chemical analyses. 



Sample Preparation 

The organic contents of each stream sediment sample, su 
dried leaves, grass, bark, rootlets, and other foreign objects, 
removed by handpicking, using a magnifying lens. Wet sai 
were dried under infrared heat lamps; all other samples 
air-dried. After the samples were sieved and all material 1 
than 18-mesh was discarded, the minus 18-mesh fractiot 
split (using a Jones splitter) until a representative portii 
120-130 grams was obtained. This was pulverized (usi 
Braun pulverizer) and used for chemical analysis. 

Bedrock samples were similarly crushed, pulverized, and 
for chemical analysis. 



Digestion 

STREAM SEDIMENT SAMPLES 

Two separate digestion techniques were employed for st: 
sediment samples: one for arsenic, cadmium, copper, lead, 
cury and zinc; the other especially for cadmium. Samples 
taining less than 2.5 ppm Cd could not be determined \ 
digested by the total digestion technique which requires a 
tion factor of 25, while the detection limit for Cd is 0.1 pp 
solution. This would make it impossible to detect the verj 
concentrations of cadmium present in some of the sam 
Therefore, a special digestion technique was used on the po! 
of the split to be analyzed for cadmium. Both techniques 
described in detail in Appendix D. 

For the minimum concentrations of element that can ben 
ured, see footnotes under Appendices F and G. 

BEDROCK SAMPLES 

Bedrock samples with a high concentration of phospho 
created a special problem when digested by the total diges 
technique. A white complex compound was produced w 
adhered to the glass walls of the apparatus and could no 
removed easily, particularly from the inaccessible, thin, and 
row closed tube of the modified soxhlet extractor. The com'' 
compound would sublime when heated but would condens 
the same wall when cooled. Because of this contamination p 
lem the extractor could not be reused, so another digestion! 
nique was developed (see Appendix D). Also, there was* 
doubt as to whether or not the cadmium salts from the bedij 
samples were completely dissolved by use of the cold acidexl 
tion technique, which worked so satisfactorily for the 5tr 
sediments. Thus, various techniques were developed and M' 
to digest bedrock samples. Details of these techniques ait 
given in Appendix D. 



I . 



Analytical Techniques 



MERCURY 



For purposes of pollution control or toxicity monilOf 
many analytical techniques are used to analyze for mefClir 
various types of samples. Atomic absorption spectrophotOW 
is excellent for use in trace element determination, but th«l' 
nique lacks the sensitivity to measure mercury in the partH 
billion range. The fiameless technique of atomic absorption 
used here, which gave a detection limit of 0.1 ppb Hg, 



DISTRIBUTION OF HAZARDOUS HEAVY ELEMENTS 






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263. '— - 

i26i >: 



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249. .i^P ■ 
• •251 247 
.m •248* 



24 9« 



•244 



680, 

603^« ^ 
604 



HUWTERllSGETyiHrLITARYfiCSERVATION ' ' » *" i-Ll , - ' ^^*, 







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; Index map of locations of stream sediment samples, Salinas Volley. 



CALIFORNIA DIVISION OF MINES AND GEOLOGY 



SR J 



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EXPLANATION 
SYMBOLS 
Bedrock samples 
Stream sedimeni samples 



^ - j""'e 






\ !». 



-r A^ - "-.^ -X. =^,-^ 

- . --our; ■ .5-« .J ', ^V' 'aos-r;;^- -• >. V-" .^ ' < 













Figure 3. Index map of locations of bedrock and some stream sediment samples from Salinas Valley. 



f80 



DISTRIBUTION OF HAZARDOUS HEAVY ELEMENTS 



SAMPLE SPACING 
APPROXIMATELY 12'/2ft. 




Approximate scale 



Figure 4. Technique for collecting composite stream sediments samples. 



he mercury salts in digested samples were reduced to cle- 
at tal mercury by the addition of stannous chloride to the 
aiple solution in a reaction vessel equipped with a magnetic 
tier. The mercury vapor thus released was transported by 
e;tion through a drying column to an absorption cell. The 
bl'rption cell replaced the conventional burner in the optical 
a of the atomic absorption spectrophotometer. The absorp- 
was measured at the 2537 A Hg wavelength and plotted on 
- cart recorder. Mercury standards were measured and record- 
djimilarly. The concentration of mercury in the samples was 
eirmined by relating the peak heights of those of the standards. 
Jeiils of this technique are described in Appendix E. 

\tiENIC 

.rsenic presents certain analytical problems which make its 

2"mination difficult. The commonly used air-acetylene flame 
ot be used because arsenic reasonance lines lie in the far 
hi-violet region, where flame absorption is a problem. With 
lame, which creates a high background, there is a strong 
absorption and the available energy striking and photomul- 
P-:r is reduced. If an argon-hydrogen flame is used instead of 
leiir-acetyline flame, these problems are considerably re- 
U(d. A danger of the argon-hydrogen flame is that it is color- 
•ssand an operator may touch the burner when the unit is in 
pfition. 

I the technique used, arsine gas was produced by reduction 
tt^hydrogen generated by the addition of zinc to hydrochloric 



acid. This arsine gas was collected in a rubber balloon, along 
with excess hydrogen and hydrogen sulfide gas if sulfide miner- 
als were present in the sample. The arsine gas was carried away 
and introduced into the flame by means of an argon carrier gas. 
This technique gave very good sensitivity, allowing the detection 
of arsenic at submicrogram levels. By releasing the original sam- 
ple matrix, interelemental interferences in the fiame also were 
minimized 

The sample digests which were used for mercury determina- 
tion also were used for arsenic determination after removing the 
suspended particles by filtering. The only difficulty with these 
digests is that they contain a considerable amount of nitric acid, 
which prevents the production of arsine. Nitric acid was, there- 
fore, completely removed from these sample digests by slowly 
heating them with concentrated sulfuric acid. 

Details of the adopted procedure are given in Appendix E. 

CADMIUM, COPPER, LEAD, AND ZINC 

Cadmium, copper, lead and zinc were determined by routine 
atomic absorption analytical procedures by direct aspiration of 
the sample digests. 

PHOSPHORUS 

Phosphorus was determined with the x-ray spectrometer by 
mixing one gram of 230-mesh sample with one gram of What- 



CALIFORNIA DIVISION OF MINES AND GEOLOGY 



SR 



man CF-1 1 cellulose powder, making pellets in Spex caps, and 
analyzing with an EDDT crystal and Cr target x-ray tube (Ap- 
pendix E). All phosphorus results are corrected for the presence 
of high calcium. 



RESULTS OF ANALYSES 



Mercury 

The general level of mercury in both stream sediments and 
bedrocks is lower than Taylor (1964) reports in the earth's crust 
(80 parts per billion); in bedrock samples, however, its level is 
about the same as in soils. 

Only six stream sediment samples contained anomalous 
amounts ( > 65 ppb Hg) of mercury. The largest mercury con- 
centration was 512 ppb Hg in Thompson Canyon, apparently 
from middle Miocene Monterey rocks. Five other samples con- 
tained 75-88 ppb Hg; three from streams draining an area of 
Pleistocene nonmarine sediments, and two from San Lorenzo 
Creek, which drains an area of Middle and/or Lower Pliocene 
marine sedimentary rocks and Holocene alluvium. 

The threshold level — the transition point between normal 
(lognormal, here) and anomalous concentration — of mercury is 
64.5 ppb Hg in stream sediment samples and 50 ppb Hg in 
bedrock samples. The cumulative frequency distribution for 
mercury for stream sediments is lognormal, while the bedrock 
samples show the presence of two separate populations with the 
anomalous population being 35 percent of the total analyzed 
samples. 

Arsenic 

Arsenic in the stream sediments seems to be at levels generally 
found in the earth's crust (Taylor, 1964), but lower than levels 
generally found in soils (Vinogradov, 1959). Arsenic appears to 
be present in the bedrocks at considerably higher levels than 
generally found in crustal rocks, but at approximately the same 
levels generally found in soils. The threshold levels of arsenic in 
the stream sediments is 9.25 ppm, and only three samples (1.5 
percent of total collected samples) exceed this upper limit. From 
their locations near the south end of the project area, these three 
samples seem to have been derived from the rocks of the Middle 
Miocene marine Monterey Formation. In general, the samples 
collected from the southeast portion of the project area (the 
source apparently being the same rocks) show higher concentra- 
tions of arsenic than the samples collected from other parts of 
the area. 

The threshold levels of arsenic in bedrocks is 38 ppm, and only 
eight samples (three percent of total collected samples) appear 
to exceed this upper limit. The distribution seems to be lognor- 
mal in both stream sediments and bedrocks. Samples of clay 
seams have unusually high amounts of arsenic. 

In the project area, arsenic compounds are used as a chicken 
feed supplement to increase their growth rate, and chicken drop- 
pings are widely used as a fertilizer. No connection was estab- 
lished in this study between this possible source of arsenic and 
the anomalous arsenic \alues. Overall, arsenic is not abundant 
enough to be a health hazard in the project area. 



Cadmium 

In Monterey County, some stream sediment samples s 
higher concentrations of cadmium than the general world-' 
concentration in the crust (0.2 ppm; Taylor, 1964) or in the 
(0.5 ppm; Vinogradov, 1959). In general, the stream sedir 
samples collected from southwest and southeast of King 
and San Ardo contain anomalously large amounts (1.5 ppr 
cadmium. Stream sediment samples from that same area are 
high in arsenic and zinc. The source of these sediments appai 
ly is the Middle Miocene marine rocks. 

The California Department of Agriculture and the Unive 
of California at Davis, Department of Environmental Toxic ■ 
gy ran a special sampling program in the Greenfield-King C 
San Ardo area to determine the cadmium contents of agr 
tural soils and the plants growing on them. Their results, i 
140 collected samples, show that Lockwood Loam soil, as 
as the vegetation associated with it, contains greater amoun 
cadmium than other soils and their associated vegetation. S 
ach and other leafy vegetables appear to carry higher cadn: 
contents than citrus fruits; grapes, in particular, contained r 
mal amounts of cadmium. Lockwood Loam soil has been for 
from older alluvial fans derived from the same general vie 
in the southeast part of the project area in which sediments 
high concentrations of cadmium. The results of the study 
ducted by California Division of Mines and Geology persoi 
therefore, correlate positively with results of studies mad 
personnel of the California Department of Agriculture am 
University of California at Davis Department of Environm( 
Toxicology. In addition to surface samples, the Departmei 
Environmental Toxicology took several cores of agriculi 
soils from this area to depths of six feet, and found that cadn 
concentration is generally high and uniform throughout the 
foot depth. This indicates that cadmium's presence is not di 
the addition of fertilizer to the surface soils. 



The background calculated for a perfect frequency disti 
tion curve corresponds to the mode and median values and i 
geometric mean of the results (Lepeltier, 1969). This geom 
mean is a more significant value than the arithmetic mean, 
also a more stable statistic, and less subject to change witf 
addition of new data and less affected by high values. The re 
for cadmium in bedrocks illustrate this. A high concentrati( 
cadmium in some of the bedrock samples produces the aritl 
tic mean of 27.2 ppm Cd, which is higher than the threshold 
of 1 5 ppm Cd. The geometric mean, however, which is 5.2 
Cd, is not affected by the very high cadmium content of < 
of the samples. The concentrations of cadmium in bedrock ; 
pies is higher than crustal or soil abundances (Taylor, 1 
Vinogradov, 1959). A total of sixty-three samples (24 pei 
of all samples collected) exceed the threshold level. The cun 
tive frequency distribution for cadmium shows the preseni 
two distinct populations, one normal and the other pos 
anomalous. It also shows a positive skew in the direction of 
values. 

Lead 

The geometric mean of lead content of all stream sedii d 
samples is 7.9 ppm, which is less than the values reportcij, 
Taylor(1964) for crustal abundance (12.5 ppm), or by ^ 
gradov ( 1959) for its abundance in soil (10.0 ppm). Leadl 
seem to be higher in bedrock samples than generally four 
crust or soil. The threshold levels of lead in stream sediment! 
bedrocks are 29.0 ppm and 33.0 ppm Pb, respectively, and 



I 



180 



DISTRIBUTION OF HAZARDOUS HEAVY ELEMENTS 



i'ms to be distributed at random throughout the project area, 
/sediment sample from the Salinas River near San Ardo con- 
Ined 102 ppm Pb, and five other stream sediment samples, 
J:>stly from Elkhorn Slough drainage, contained anomalous 
cunts of lead ranging from 38 to 53 ppm. The cumulative 
quency distribution for lead in bedrock samples is primarily 
al, with only one percent of the population being anoma- 



Copper and Zinc 

llfhe combined total of these elements in the sediments 
lyzed was lower than the world-wide average in the crust (Cu 
i Zn 70.0 ppm; Taylor, 1964), or in the soil (Cu 20.0, Zn 50.0 
n; Vinogradov, 1959). The King City-San Ardo area shows 
h levels of arsenic and cadmium as well as high levels of 
iper and zinc. 

he general levels of copper and zinc in bedrock samples seem 
»e lower than those in most crustal rocks, but about the same 
n soils. 

"he threshold level for copper is 13.0 ppm in stream sediments 
40.0 ppm in bedrocks. For zinc, the threshold level is 74.0 
1 in stream sediments and 250.0 ppm in bedrocks. Thirty- 
;e stream sediment samples contained more copper than the 
shold level; nine samples contained more zinc. The source of 
ment for most of these samples was the Middle Miocene 
ine Formation. 






he cumulative frequency distribution for copper in both 
.m sediments and bedrocks shows the presence of two popu- 
ms, one normal, the other anomalous. The cumulative fre- 
ficy distribution for zinc in both stream sediments and 
rocks shows lognormal distribution. 

Phosphorus 

nly the bedrock samples having more than 10 ppm Cd were 
yzed for phosphorus. The level of phosphorus seems to be 
iderably higher than soil and crustal abundances reported 
Taylor (1964) and Vinogradov (1959) respectively. The 
shold level is 1 .0% P. The cumulative frequency distribution 
)hosphorus shows the presence of two separate populations; 
III! ercent of the total analyzed samples constitute the anoma- 
population. 



no 



■cm this analytical data, single element distribution maps for 
stream sediments and bedrocks were prepared for each 
yMent (Figures 5 through 17). 



CORRELATION 

sresultsof the analyses of the stream sediment and bedrock 
were processed by means of a stepwise regression corn- 
program devised by Health Sciences Computing Facility 
^.L.A. Comparisons between concentrations of all elements 
were made in pairs, using regression analysis, in an effort 
irn which elements tend to be associated in the materials 



labular summary of the correlation matrices, arranged in 
^6f elements used in the computation, is presented in Tables 



3 and 4. Any correlation higher than 0.5000 is higher than 50:50 
average; correlation higher than 0.7000 are considered meaning- 
ful in the present study. For the stream sediment samples, six 
pairs of elements (As-Cd, As-Cu, As-Zn, Cd-Cu, Cd-Zn, and 
Cu-Zn) show significant correlations (Figures 18 through 23): 
if one element in a pair is high in a sample, the other tends also 
to be high; however, it is not possible to predict the quantity of 
the other element by analyzing only one element in each pair. 



Table 3. 


Correlation matrix (stream sediments). 




As 


Cd 


Cu 


Ph Hg Zn 


As 


1.000 


0.8724 


0.7732 


0.1859 0.2892 0.7875 




1.0000 


0.7558 


0.0527 0.2414 0.8326 


Cd 






1.0000 


0.3692 0.4425 0.8816 

1.0000 0.1994 0.2219 

1.0000 0.4088 

1.0000 


Cu 
Pb 
Hg 
Zn 



Table 4. 


Correlation 


matrix (bedrocks). 






As 


Cd 


Cu 


Pb Hg P 


Zn 


As 


1.0000 


0.4129 


0.4698 


0.4502 0.1931 0.."(224 


0.5278 




1 0000 


0.7548 


02699 02532 0.9492 


0.9123 


Cd 






1.0000 


0.3189 0.1615 0.8409 


0,9020 


Cu 








1.0000 0.1059 0.2199 


0,3803 


Pb 








1.0000 0.3710 


0.2060 


Hg 








l.OOOO 


0.9478 
1 (KK1 


P 
Zn 



An attempt was made to correlate the analytical results of 
stream sediment chemistry with the geology of the area to deter- 
mine which bedrock units were parents of the anomalously high 
values of each tested element. This correlation of stream sedi- 
ment chemistry with the geology of the area was inferential at 
best, because some of the samples had accumulated from a num- 
ber of possible parent rocks, and at that stage no analyses had 
been made to determine which bedrock formations have concen- 
trations of one or more of the elements tested. A transparent 
copy of the stream sediment sample locations map was posi- 
tioned over the geological map of Monterey County (Hart, 
1966), and the possible sources of each sediment then were 
determined in terms of geological formations exposed in the 
drainage basins. Wherever there was doubt, the two most likely 
sources were considered. The stream sediment samples collected 
from the Salinas and Carmel Rivers and from the Arroyo Seco 
were not used in this correlation, because they were transported 
from long distances and represent a heterogeneous mixture of 
sediments received from many geological formations. The scope 
of this first stage of the project did not include the testing of 
individual geological units. 

Table 5 lists the range and average amounts of the six elements 
in stream sediment samples derived from the various geological 
formations in the project area. 

Among the bedrock samples, six pairs of elements (Cd-Cu, 
Cd-P, Cd-Zn, Cu-Zn, P-Cu, and P-Zn) show significant as- 
sociations (Figure 24 through 29). Samples belonging to phos- 
phatic beds appeared to have high-cadmium contents. In fact. 
almost all phosphatic rocks in the area have high cadmium 
contents except eleven samples which have high cadmium but 
low phosphorus. Four samples have free-sulfur encrustations 
that probably resulted from sublimation of sulfide solutions All 



10 



CALIFORNIA DIVISION OF MINES AND GEOLOGY 



SR 1 



EXPLANATION 



High 

Intermediate high 
Intermediate low 
Low 



(ppm As) 

31-40 

21-30 

11-20 

6-10 




Figure 5. Map showing arsenic in stream sediments. 



Iii80 



DISTRIBUTION OF HAZARDOUS HEAVY ELEMENTS 



11 




< - 


\ 1 




■^ 






\r 


^ k 






-r-^._/-; ~ 



\ 



^>v,-^.:. }"' 






<- I. 



/ 'T3^* V 



i^ \ 



^^ 



•iA 






-< -^^^ ^ 






'^^ V:, i^^f^i-'^^ 




ARSENIC 
'NTENT OF SAMPLES 

(ppm As) 
» ;igh 51-75 

> 'termediate high 26-50 

I termediate low 16-25 

3 ow 11-15 

ig(5 6. Maps showing arsenic in bedrocks and some stream sediments. \ '*' 






': /M/dfc,«./.Y., 



\t^ 



12 



CALIFORNIA DIVISION OF MINES AND GEOLOGY 



SR 



EXPLANATION 



• High 

O Intermediate high 
Intermediate low 



15.1-26.0 

10.1-15.0 

3.1-10.0 

0.5- 3.0 




Figure 7. Map showing cadmium in stream sediments 



DISTRIBUTION OF HAZARDOUS HEAVY ELEMENTS 



13 



'^^. 



V^' 



> \ y 



■ ^'J , 



- '' :^">;- .\. - 



^ ■ 



V 






V 















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-A. 



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y 






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c^ 



A 









y 





















N^ ■^. 



g 



3 ^ . 14 



'"^ '>7 ^i';; 



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I 












n^ 















> 



> / 
















DD 



• r 



"-r - 



V 



^ 



V A_ / N 



q 












CADMIUM 
(MTENT OF SAMPLES J 

(ppm Cd) . ■" ,"'*■' 

^ 'iry high 301-700 "\ 

Ugh 101-300 

^l':ermediate high 51-100 

■ kermediate low 26-50 

3 l,w &-25 

'gi- 8. Maps showing cadmium in bedrocks and some stream sediments. 



,\ 



■" .'-1,'-^ 



/A, -O^ 



♦S^ ^ - _ 









V 
_ -tv,-- 



^,^ 












^ 















°f 






14 



CALIFORNIA DIVISION OF MINES AND GEOLOGY 



SR 1 




EXPLANATION 



o 



High 

Intermediate tiigh 
Intermediate low 
Low 



'^ ^ 







(ppm Cu) 
31-40 
21-30 
11-20 

6-10 



V 















•%>,.' 



HtP 



Figure 9. Map showing copper in stream sediments. 



980 



DISTRIBUTION OF HAZARDOUS HEAVY ELEMENTS 



15 



, , . ^^-*.;| 




1 \ 






■..; ■) 



/ 



w 






^' L 












^, :4 _ ^'^^^ ^. • K ^. "^ ''■ 



I . 



/v-^v;;... 



-<; 



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:.\^ 






t-r'' 9 ^ ! ^ ' \ ^\^- '• 




K -^^ ^' :^>^ rf "--V , : 



•U 
/? 




V(J> 









3 r.^^v. 









. ^ ■ — " 






/ 















I' ) 



I 



I 



I 



-^^-y- v/C- ,.^- ,;,,^^0 



^>-. 



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V 



N 



, "13^* V - ^ 



\' 



\ 



r 



■\ —> 



\ 






- - / i r- 






■^■.^\&>v '^-i;^, /^f^t^z --J-.0,. .. . 






.V^/ 0-i-' '^ 



/ 






- vfc,. 



<«« 



rs^^ - 






,'^~~i 



^ 1i / 



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^ ^ ' f . 



. 1-^ 


^'- 


-•'■■> - 


p"- 


. - ■ ^ A ■ ^^ ^ 


.■^'T." 
















COPPER 
ffiNTENT OF SAMPLES 





(ppm Cu 


•:igh 


151-200 


3'termediate high 


101-150 


■ termediate low 


51-100 


3)w 


31-50 



iflB 10. Maps showing copper in bedrocks and some stream sediments. 



8 



16 



CALIFORNIA DIVISION OF MINES AND GEOLOGY 



SR i; 



', -'^ „ '. - 



. y '' ^ ' 'tyx 



EXPLANATION 



• High 

O Intermediate high 
ntermediate low 
D Low 



(ppm Pb) 
41-55 
26-40 
16-25 
10-15 






^'v^ . 




^b" 


a 


-^ 


\ 


■ l 


JCf 


1 ' 1 ' 


/ '^ 
^ ^ 
// 

t 


1 "^ ' 



Figure 11. Map showing lead in stream sediments. 



i?80 



DISTRIBUTION OF HAZARDOUS HEAVY ELEMENTS 



17 






II' -J- 



■-4 



l<^^^.- 





%^ ^,x ^ ^, '"':; ^'.^^ 

<^ ^ -^ '^ .V^ / 






\ 






t- " 




q 






r 


P 
cP 




/ 1 ' 




D 


cP SdB 


> ^:^ ^ 






^ ° 



V V 



V 



^■^.; 









e 



' ^ V 







LEAD 
:(NTENT OF SAMPLES 



' '' /.. ,. "■•• 



<^ 





(ppm Pb) 


Ugh 


56-70 


)l':ermediate high 


41-55 


I lermediate low 


31-40 


]lw 


21-30 



r- 



gu 12. Maps showing lead in bedrocks and some stream sediments. 



^ 



18 



CALIFORNIA DIVISION OF MINES AND GEOLOGY 




Figure 13. Map showing mercury in steann sediments 



1*80 



DISTRIBUTION OF HAZARDOUS HEAVY ELEMENTS 



19 



'irjr 



, ■ > \ y ^ • \ 












i' 









k / ,A/.,' > c 



' An 



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>- 



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X .,n 



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^ ^i^ 



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f 



MERCURY 
NTENT OF SAMPLES J 

(ppb Hg) 
gh 251-560 \ 

Jftermediate high 101-250 

■ termediate low 51-100 

3 iw 25-50 

gu 14. Maps showing mercury in bedrocks end some streom sediments. 






'Vi.M'^''''* _ 






' '■"■kl 



^' A^ ^ \ ^ ; X X _ L ^ 



■ii;. ^\ ^ 



r. n 






20 



CALIFORNIA DIVISION OF MINES AND GEOLOGY 



SR 1 











\( 






x-< 



V, 






-"^v , ,- .^ *- ^ --f i.^ " V ) ^ "'"'. ' V JIv ^ 












/• '- 









' ■%< 



,1 



or- '^C 

/ .J, 



'/ 



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'' ■ (■ 



■ \ 



< \ 



V, 



■/": 



'ii 






i* V 



>< 



r--^-, 



r . 



\' 




PHOSPHORUS 
CONTENT OF SAMPLES 

% P) 

• High 10.1-18.0 

O Intermediate high 3.1-10.0 

■ Intermediate low 1.1-3.0 

D Low 0.5-1.0 

Figure 15. Maps showing phosphorus in bedrocks and some stream sediments. 



980 



DISTRIBUTION OF HAZARDOUS HEAVY ELEMENTS 



21 




EXPLANATION 



• High 

O Intermediate high 

■ Intermediate low 

D Low 










(ppm Zn) 
76-100 
51- 75 
36- 50 
25- 35 



% 



a ■- 



^d ' 



\ 






a 



(■^ 16. Map showing zinc in stream sediment 



22 



CALIFORNIA DIVISION OF MINES AND GEOLOGY 



SR 1 



' ''■'// 



\ A 



>>s- 



,..rTr,«..rA V 



,,I,ih y 



M> 



V 







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'V. 



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^ 



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^- // 



/ <^ 



/,•/ 



/^ 



<> 



^ 






-f 






QK 



-;". 






V 









ZINC 
CONTENT OF SAMPLES 






^ 



V- 












• High 

O Intermediate high 
■ Intermediate low 
O Low 



(ppm Zn) 

251-500 

151-250 

101-150 

51-100 



■■■i D 



> ^- <* 









' '•■''■MS 



iv./ 



Figure 17. Maps showing zinc in bedrocks and some stream sediments. 






980 



DISTRIBUTION OF HAZARDOUS HEAVY ELEMENTS 



23 

















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24 



CALIFORNIA DIVISION OF MINES AND GEOLOGY 



SR 





(U 




a. 




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ujdd's>7 



980 



DISTRIBUTION OF HAZARDOUS HEAVY ELEMENTS 



25 





V 




Q. 




E 




o 




in 




a> 




c 


<l> 


O 


Ql 


c 


i- 


o 


o 


JZ 


C/5 


■^ 




0) 


a> 


^ 


c 


o 


O 


^ 


• 


+ 





-o 


If) 


c 


(^ 


o 


m 


^ 


S 


^ 




a 




o 


in 




OJ 


c 


C\J 


0) 


in 


* 








01 




M 






f^ 


c 













o 


o 


41 










in 





r- 


U 



Ludd'n^ 





a> 




Q. 




E 




o 




If) 




a> 




c 


0) 


O 


Q. 


c 


E 


o 


o 

CO 


^ 




(U 


<u 


k- 


c 


o 


O 


2 


* 


■ 



oidd 'uz 



26 



CALIFORNIA DIVISION OF MINES AND GEOLOGY 



SR i: 



100 



90 - 



80 - 



70 



60 



50 



40 



30 



20 



10 



• • 



• • • • » • 

.tA'?.rff>k:'>A^*:..s.. . . 



One Sample 

More than One Sample 



.»^.t« tAf 



-I 1 1 r 



10 20 30 40 50 60 70 80 

Cu, ppm 

Figure 24. Correlotion between cadmium and copper in bedrocks and some stream sediments. 



90 100 110 120 130 



17.5 



14 - 



10.5 



oT 



3.5 



++++++ 



• One Sample 

- More than One Sample I 



_i I I I I I I I I I I I I I I — I — I — i- 



32.5 97.5 162.5 2275 292 5 357.5 422.5 487 5 552.5 617 

65 130 195 260 325 390 455 520 585 

Cd, ppm 

Figure 25. Correlation between cadmium and phosphorus in bedrocks and some stream sediments. 



1:980 



DISTRIBUTION OF HAZARDOUS HEAVY ELEMENTS 



27 



100 



90 



80 



70 



60 - 



E 

Q. 

^ 50 

•a 

o 



40 



30 



20 



10 



.• ..V •• • 



•••••• . 

• • 

*.«.. .v.* 

• •• 
•• • 






• One Sample 

* More than One Sample 



20 40 60 



80 



100 120 140 

Zn.ppm 
Figure 26. Correlation between cadmium and zinc In bedrocks and some stream sediments. 



160 180 200 220 240 



10 












• 


90 












• 
• 


80 












• 


70 








9 






60 






• 








L 


• 










• 


40 




• 




• 


• 




30 






• 






• 
• 




• 




• 


• 




• 


20 






, • 




• 






• One Sample 


1 


• • 
• •• 


• • 

• 


• 






* More than One Sample 







10 20 30 40 50 60 70 80 90 100 110 120 130 140 150 

Cu.ppm 
Figure 27. Correlation between phosphorus and copper in bedrocks and stream sediments. 



28 



CALIFORNIA DIVISION OF MINES AND GEOLOGY 



".5 



••.."».' 



20 40 60 80 100 l20 140 160 180 200 220 240 250 

Zn.ppm 
Figure 28. Correlation between copper and zinc in bedrocks and some stream sediments. 



100 



90 



80 



70 



60 

E 

Q. 

<=^ 50 

o 
40 



30 



20 



10 






. .. J. .J. 

• ,••••••»•, •• • • • 






• One Sample 

» More than One Sample 



20 40 



60 



140 160 180 200 



Figure 29. 



80 100 120 

Zn.ppm 

Correlation between phosphorus and zinc in bedrocks and some stream sediments. 



I 



)80 



DISTRIBUTION OF HAZARDOUS HEAVY ELEMENTS 



29 



ible 5. Correlation of geology ' and stream sediment chemistry. 



Geological Formations 



As(ppm) 
Range Average 



Cd{ppm) 
Range Average 



Cu(ppni) 
Range Average 



Pb(ppm) 
Range Average 



Hg(ppb) 
Range Average 



Zn(ppm) 
Range Average 



lluvium (8) 



Qal 



Qal/Pml 
nuvium/Middle or Lower Pliocene 
^arine (10) 

i Qt 

iiver Terrace & Fan Deposits (27) 

! Qt/Gr 

liver Terrace & Fan Deposits/ 

esozoic Granitic Rocks (9) 

Qc 
leistocene Nonmarine (19) 

Qp 
iHo-Pleistocene Nonmarine (8) 

Qp/Pml 
lio-Pleistocene Nonmarine/Middle 
- lower Pliocene Marine (10) 

Mu 
)per Miocene Marine (7) 

Mm 
iddle Miocene Marine (24) 

Gr 
!$ozoic Granitic Rocks (21) 

m-Ls 
e-Cretaceous Metamorphic 
■cks (11) 



0.57-2.85 1.7 



1.80-4.76 3.4 



0.10-6.83 1, 



0-0.42 0.2 



0.1- 0.4 
0.64 



-28 14 



0-20 



10-23 



0-40 17 



0.12-l.i 



1.0 



0.70-7.55 2.3 



0.65-5.95 2.3 



1.30-6.13 3.2 



0.50-2.85 



0.18-11.40 4.0 



0.30-4.25 



0.10-1.93 0.8 



0-13.2 



0-0.5 



0-0.45 0.1 



0.04- 0.5 
2.13 



0.1-1.2 O.i 



0.14- 1.0 
4.23 

0.18-24 7.5 



0-0.4 0.1 



0-0.1 



0-20 



0-10 4 



3-28 10 



0-5 



5-15 11 



0-15 



3-23 



3-13 5 



3-15 



0-25 10 



0-13 



5-53 U 



0-28 8 



5-20 9 



21-S 



0-61 



44 



24 



0-46 20 



0-88 



0-25 



0-20 10 



0-15 7 



0-15 5 



0-53 



13-48 30 



0-48 



0-512* 25 



0-41 23 



0-75 24 



10-35 22 

30-700* 43 

5-82 26 

6-34 18 

5-180* 25 

7-25 18 

10-57 35 

7-50 22 

14-100* 50 

11-57 24 

10-55 27 



NOTES: 



1 



Refer to Hart, E.W., 1965 for detailed geology of the project area. 

The number in brackets for each geological formation denotes the number of samples taken into 
consideration for calculating the average values. Also, only units represented by 8 or more 
samples, were considered in the geology-chemistry correlation. 

Anomalously higher values not considered for average. 



ehigh cadmium contents. High cadmium contents also were 
Old in three samples collected from the crushed rocks in the 
I conada fault zone and in four stream sediment samples from 
h Hames Valley. According to Burau (Richard G. Burau, 
J versity of California at Davis, personal communication, 

-r), the soils in Hames Valley also are high in cadmium. 

1 view of the demonstrated relationships between phospho- 
uand cadmium, a decision was made to analyse phosphatic 
a pies available from areas outside the study area. In general, 
ihphatic rocks from other parts of the United States do not 
ie;ssarily have high cadmium contents (Table 6). Some sam- 
il , however, had enough cadmium, (i.e., 1 10 ppm Cd in phos- 
)he from Idaho) to warrant concern about the possibility of 
0<i pockets of contaminated phosphatic rocks in other United 
ities or world localities. It is therefore recommended, that the 
J Geological Survey or a similar institution undertake an 
n stigation of cadmium contamination in phosphatic rocks in 
>'aous locations. 

erard Bond (personal commmunication, 1974) of the Uni- 
■ eity of California at Davis has found that samples of phos- 
■)hic rock which is exported from Vernal, Utah, to Canada for 
iSis a rock phosphate fertilizer, have a Cd content of 10 ppm. 



Some phosphatic rock quarries in Wyoming have 30 to 1 50 ppm 
Cd, depending on sample location. Rock from these quarries is 
used as a rock phosphate fertilizer in the United States and is 
definitely contaminating agricultural soil and, in turn, the crops 
which grow on them. These observations support the necessity 
for further studies of cadmium in phosphatic rocks. 

The geology of the study area was correlated with the chemis- 
try of the area (Table 7). Unusually high amounts of cadmium 
occur in the phosphatic beds of the Monterey and Pancho Rico 
Formations, in stream sediments of Hames Valley, and in sam- 
ples from the Rinconada fault zone. These samples are also high 
in arsenic, copper, lead, and zinc. Perhaps cadmium contamina- 
tion in the phosphatic rocks is the result of Miocene volcanic 
activities. 



CONCLUSIONS 

• Six pairs of elements (As-Cd, As-Cu, As-Zn, Cd-Cu, Cd- 
Zn, Cu-Zn) in the stream sediments and six pairs of elements 
(Cd-Cu, Cd-P, Cd-Zn, Cu-Zn, P-Cu, P-Zn) m the bedrock 
show significant associations. 



L 



30 



CALIFORNIA DIVISION OF MINES AND GEOLOGY 



SR 



Table 6. Phosphorus and cadmium determination in 


samples from other parts of the United States. 








Lab. Numbers 


P 

(%) 


Cd 
ppm 


Locations 


Source | 


ibS/li 


16.42 




11.8 


National Bureau of Standard 1 20a, Florida 


National Bureau of Standards, Washington, D.C. 




366/73 


9.84 




30 


Pamlico River, North Carolina 




Fred Kelley, Cal. Div. Mines & Geol., S.F., CA. 




367/73 


2.53 




1.6 


Magadalena Bay, Baja California 




Fred Kelley, Cal. Div. Mines & Geol., S.F., CA. 




372/73 


12.81 




11.2 


Clay Canyon, Utah 




J.H. Madsen, Jr., University of Utah, Salt Lake City, I 


373/73 


14.21 




110 


Idaho 




L.S. Praler, Bureau of Mines & Geology, 


Moscow, 


Idai 


377/73 


11.96 




60 


Pine Mountain, CA 




Fred Kelley, Cal. Div. Mines & Geol., S.F., CA. 




378/73 


8.51 




30 


Pine Mountain, CA 




Fred Kelley, Cal. Div Mines & Geol., S.F., CA. 


' 


379/73 


13.35 




11.3 


San Juan Capistrano, CA 




Edmund Kiessling, Cal. Div. Mines & Geol., L.A., 


CA 


380/73 


7.94 




2.2 


Dredge Sample, off so. CA Coast 




Jack Veder, U.S.G.S., Menlo Park, CA. 






381/73 


3.45 




13.6 


Dos Pueblos Creek, Naples Section, CA. 




H. Gower, U.S.G.S., Menlo Park, CA. 






382/73 


111 




21 


Trench, Chico Martinez Section, CA. 




H. Gower, U.S.G.S., Menlo Park, CA. 




■| 


383/73 


5.13 




50 


Trench, Chico Martinez Section, CA. 




H. Gower, U.S.G.S., Menlo Park, CA. 






384/73 


4.43 




31 


Trench, Chico Martinez Section, CA. 




H. Gower, U.S.G.S., Menlo Park, CA. 




i 


385/73 


0.61 




4.4 


Trench, Chico Martinez Section, CA. 




H. Gower, U.S.G.S., Menlo Park, CA. 




1 


386/73 


0.20 




3.4 


Trench, Chico Martinez Section, CA. 




H. Gower, U.S.G.S., Menlo Park, CA. 




J 


387/73 


0.50 




1.6 


Trench, Chico Martinez Section, CA. 




H. Gower, U.S.G.S., Menlo Park, CA. 






388/73 


0.52 




3 


Trench, Chico Martinez Section, CA. 




H. Gower, U.S.G.S., Menlo Park, CA. 






389/73 


1.28 




2.2 


Trench, Chico Martinez Section, CA. 




H. Gower, U.S.G.S., Menlo Park, CA. 






390/73 


0.21 




2 


Trench, Chico Martinez Section, CA. 




H. Gower, U.S.G.S., Menlo Park, CA. 






391/73 


15.32 




1.6 


Florida 




D.A. Graetz, University of Florida, Gainsville, Florida || 


392/73 


2.40 




3.8 


Lopez Mountain, CA 




Earl Hart, Cal. Div. Mines & Geology, S.F., CA. 




393/73 


2.80 




5 


Lopez Mountain, CA 




Earl Hart, Cal. Div. Mines & Geology, S.F., CA. 




394/73 


2.90 




5 


Lopez Mountain, CA 




Earl Hart, Cal. Div. Mines & Geology, S.F., CA. 




395/73 


11.50 




2 


Santa Margarita, CA 




Earl Hart, Cal. Div. Mines & Geology, S.F., CA. 




396/73 


4.90 




89 


Lopez Mountain, CA 




Earl Hart, Cal. Div. Mines & Geology, S.F., CA. 




460/73 


1.5 




7.5 


Lopez Mountain, CA 




Earl Hart, Cal. Div. Mines & Geology, S.F., CA. 




461/73 


29.0 




22.5 


Wheeler Springs, CA 




Earl Hart, Cal. Div. Mines & Geology, S.F., CA. 




462/73 


0.11 




2.0 


Lopez Mountain, CA 




Earl Hart, Cal. Div. Mines & Geology, S.F., CA. 




463/73 


3.08 




71.5 


Santa Margarita, CA 




Earl Hart, Cal. Div. Mines & Geology, S.F., CA. 




464/73 


1.46 




7.2 


Lopez Mountain, CA 




Eari Hart, Cal. Div. Mines & Geology, S.F., CA. 




466/73 


14.05 




2.6 


Dredge Sample, off So. CA Coast 




Jack Veder, U.S.G.S., Menlo Park, CA. 






467/73 


9.25 




1.9 


Dredge Sample, off So. CA Coast 




Jack Veder, U.S.G.S., Menlo Park, CA. 






468/73 


9.82 







Dredge Sample, off So. CA Coast 




Jack Veder, U.S.G.S., Menlo Park, CA. 






469/73 


9.03 




1.2 


Dredge Sample, off So. CA Coast 




Jack Veder, U.S.G.S., Menlo Park, CA. 






Table 7. Correlation c 


f geology ' 


and bedrock chemistry. 








5TRATIGRAPHIC CLASSIFICATION 
OF SAMPLES 


MAP 
SYMBOL 


NO. OF 
SAMPLES 


ARSENIC (ppm) 


CADMIUM (ppm) 


COPPER (ppm) 


LEAD (ppm) 


MERCURY (ppb) 


PHOSPHORUS {%) 


ZINC 


(ppm , 


Range 


Average 


Range 


Average 


Range 


Average 


Range 


Average 


Range 


Average 


Range 


Average 


Range 


Aver 


Stream sediments 









8 


4-13 


9 


3-28 


11 


10-25 


20 


10-30 


20 


0-40 


17 


0.06-0.16 


0.09(4)2 


28-114 


6f, 


Rinconada fault zone . . . 




--- 




3 


10-14 


12 


17-22 


19 


25-38 


30 


18-27 


22 


0-43 


19 


0.17-0.36 


0.28 


53-72 


6C] 


PALEOZOIC 




mSci/ 
































tletasedinientary rocks. . . 




2 




1 







19-24 


21 


12-19 


16 









n.d. 


26-31 


2: 


MESOZOIC 




gr.grd 


































Granitic rocks 


• • 


gqd,gb 




5 


0-2 


1 







12-33 


19 


15-21 


18 


0-11 


5 




n.d. 


15-34 


r 


UPPER CRETACEOUS AND PALEOCE 


NE 




































Unnamed units (marine) . . 




KTg 




3 


1-3 


2 







9-13 


12 


16-20 


18 









n.d. 


20-25 


i. 


EOCEfJE 






































The Rocks Sandstone. . . . 




Tr 




1 




3 









8 




17 




15 




n.d. 




i 


OLIOGENE 




































1 


Uerry Formation 




Tbe 




2 


0-4 


2 







8-30 


19 


18-19 


19 


0-5 


3 




n.d. 


10-26 


li' 


Church Creek Formation . . 




Tee 




2 




2 







8-15 


12 


19-23 


21 


435- 
560 


498 




n.d. 


23-33 


21; 


OLIGOCENE-MIOCEtJE 


















2.5- 


















1 


Vaqueros Sandstone (marine) 




Tvq 

Tvt 




3 

1 


1-3 


2 
0.5 








12.5 


6.0 
13.8 


15-20 


17 

18 


0-5 


4 
2 




n.d. 
n.d. 


9-21 


i: 

2:1 






Tvc 




5 


1-3 


2 







1.5- 
31.3 


9.7 


14-18 


16 


0-220 


74 




n.d. 


8-14 


1; 


MIDDLE MIOCENE 






































Monterey Formation .... 




Tmc 




6 


1-18 


9 


0-6 


1 


18-45 


32 


18-23 


20 


0-238 


55 




n.d. 


28-64 


41 






Tml 




15 


1-17 


6 


0-6 


2 


10-38 


21 


14-30 


22 


0-78 


8 




n.d. 


10-52 


2: 






Tm 




54 


2-72 


10 


0-23 


4 


3-45 


22 


11-48 


19 


0-160 


18 


0.06-0.10 


0.08(9) 


3-81 


3: 






'hosphat 
beds3 


ic 






































70 


3-69 


20 


3-626 


93 


7-195 


63 


15-63 


26 


0-268 


25 


0.13-17.11 


3.5 


20-468 


14 


PLIOCENE 






































Santa Margarita Formation. 




Tsm 




1 









0.2 




5 




16 









n.d 




< 


Pancho Rico Formation (man 


ne) 


Tpd 




2 


3-13 


8 


3-5 


2 


8-10 


9 




16 


0-92 


46 




n.d 


25-32 


2! 






Tps 




4 


2-13 


8 


0-1 


1 


5-13 


9 


17-25 


21 


0-50 


14 




n.d 


18-24 


21 






Tpi 




4 


9-17 


14 


2-5 


3 


8-23 


16 


20-33 


24 


158- 

300 

0-63 


216 


0.09-0.12 


0.11(2) 


21-76 


41 






Tpo 




38 


2-21 


8 


0-4 




8-38 


15 


12-30 


21 


21 




n.d 


16-64 


2i 






Phosphatic 




































beds 3 




5 


1-32 


12 


7-100 


29 


6-132 


41 


18-25 


21 


8-175 


52 


0.17-4.65 


1.12 


43-238 


8! 


Unnamed unit (marine). . . . 




Tus 




11 


2-14 


6 


0-7 


2 


3-30 


11 


14-24 


19 


0-48 


11 




0.11(1) 


9-37 


2: 


PLEISTOCENE 






































Paso Robles Formation. . . 




QTc 
QTt 




1 

1 




4 
3 




"1 






20 
5 




28 
15 




70 





n.d. 
n.d. 




3/ 
1< 






OTp 




13 


0-15 


6 


0-: 


1 


8-38 


19 


15-25 


20 


0-63 


11 




0.11(1) 


14-58 


2< 


'uurham, 1964a, 1964b, 1966 


19,'0; Dibblec 


, 1971, 1972. 








Number in parentheses deno 


tes number of samples analyzed for phosphorus. 








Phosphatic beds in Montcre 


y and Pancho Rico Formations are not separately mapped. 








Abbreviations as used in H 


art, E.i;., 1966 


, Mines and mineral resources of Monterey County. 








n.d. = not determined. 






































ii 



)80 



DISTRIBUTION OF HAZARDOUS HEAVY ELEMENTS 



31 



Cadmium is present in anomalously high proportions in the 
Hing City-San Ardo area, especially in the sediments derived 
Dm the Middle Miocene marine Monterey Formation. Cad- 
mium is also unusually high in the phosphatic beds; these beds 
e the main source of cadmium contamination in the stream 
diments and agricultural soils (Lockwood Loam Soil) of the 
!ing City-San Ardo area. 

Cadmium is the only hazardous element present in quantities 
at would threaten public health. 

RECOMMENDATION 

Because similar pockets of cadmium-contaminated phosphate 
Ids may occur elsewhere, such phosphatic materials should be 
i-evaluated before they are used as raw material for fertilizers. 



ACKNOWLEDGMENTS 

I thank Glenn A. Borchardt, Edward E. Welday, and Richard 
M. Stewart for many valuable suggestions and discussions, and 
for reading the manuscript. Dr. Borchardt assisted me in phos- 
phorus analysis and in computing the data. Duane A. McClure, 
Thomas H. Rogers, Lydia Lofgren, Charles B. Smith, Earle W. 
Deneau, and Dorothy L. Hamilton helped with field work, labo- 
ratory work, and typing. I also thank Earl W. Hart, Frederic R. 
Kelley, and Edmund W. Kiessling of the California Division of 
Mines and Geology; H. Gower, and Jack Veder of the U.S. 
Geological Survey; J.H. Madsen, Jr. of the University of Utah; 
L.S. Praler of the Idaho Bureau of Mines and Geology; and DA. 
Graetz of the University of Florida, Gainsville,for providing me 
with the samples mentioned in Table 6. 



REFERENCES 



nit) 

[)blee, T.W., Jr., 1967-1968, Geological map of the San Ardo quadrangle, 
California: U.S. Geological Survey open— file map. 

[jiblee, T.W., Jr., 1967-1969, Geological map of the King City quadrangle, 
California-. U.S. Geological Survey open— file mop. 

Dblee, T.W., 1971, Geological map of the Bradley quadrangle, California: 
U.S. Geological Survey open-file map. 

Cblee, T.W., 1971, Geological map of the Bryson quadrangle, California: 
U.S. Geological Survey open-file map. 

—Dblee, T.W., 1971, Geologic map of the Junipero Serra quadrangle, Cali- 
fornia: U.S. Geological Survey open— file mop. 

ubiee, T.W., 1972, Geologic map of the Greenfield quadrangle, Califor- 
nio: U.S. Geological Survey open— file map. 

I^biee, T.W., 1972, Geologic map of the Soledad quadrangle, California: 
U.S. Geological Survey open-file map. 

Dham, D.L., 1964a, Geology of the Reliz Canyon, Thompson Canyon, and 
San Lucas quadrangles, Monterey County, California: U.S. Geological 
Survey Bulletin 1141-Q. 

Dham, D.L., 1964b, Geology of the Cosio Knob and Espinosa Canyon 
_- quadrangles, Monterey County, California: U.S. Geological Survey Bulle- 
tin 1161-H. 

Ohom, D.L., 1966, Geology of the Homes Valley, Winpost and Valleton 
quadrangles, Monterey County, California: U.S. Geological Survey Bulle- 
tin 1221-B. 

iJiam, D.L., 1970 Geology of the Sycamore Flat and Poroiso Springs 
quadrangles, Monterey County, California: U.S. Geological Survey Bulle- 
' tin 1285. 

•i, B.P., 1971, Rapid x-roy fluorescence determination of phosphorus in 
>logic samples: Applied Spectroscopy, v. 25, no. 1, p. 41-43. 

lagan, F.J., 1973, 1972 values for internationol geochemicol reference 
samples: Geochimica et Cosmochimica Acta, v. 37, p. 1189-1200. 



fier, M., and others, 1970, Summary of the literature on inorganic 
Bochemistry of Mercury, in Mercury in the environment: U.S. Geological 
iorvey Professional Paper 713, 67 p. 

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chimica et Cosmochimica Acta, v. 29, p. 229-248. 



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'I 980 



DISTRIBUTION OF HAZARDOUS HEAVY ELEMENTS 



35 



APPENDIX C 
Computer Programs 



PROGRAM NO. J. 

1ST OF SAMPLE IDENTIFICA TION INFORMA TION 

This program provides a table containing the lab number, 
ame of material, field number, location, county name, latitude, 
)ngitude, and formation (or other reference) for each sample. 

Card 

Vb. Type 

Job card 

System control cards 

a) //STEPA EXEC FORTGCLG 

b) //FORT. SYSIN DD * 

"LIST OF SAMPLE IDENTIFICATION INFOR- 
MATION- 
FORTRAN IV source deck 

System control cards 

a) //G<\>. FT06F001 DD SYScf>UT = A 

b) //G<it). FT05F001 DD * 

List of counties (12 cards) 



Columns Format 



Entry 



Description 



1-80 



5 (4A4) 



Al (K) Twelve cards each with 5 
counties in alphabetical 
order 5A16 format (Ex: 
"Alameda," etc.) 



(' Option card 



^olumns Format 



Entry 



Description 



1-2 12 KFM Number of personal ref- 

erence cards to be read 
(Ex: "26" formations). If 
"O" none will be read. 

3 ^ 12 LIST If LIST = O no more list 

follow, IF LIST ^ O an- 
other list will follow this. 

Personal reference cards (optional) If KFM ^ O, KFM 

cards are included. 



oJumns 



Format 
Entry 



Description 



1-20 



5A4 First 20 columns of KFM cards 

contain name formation etc., to 
appear in table. 



Sample Identification Cards 

These are the sample I.D. cards used by the DMG Geo- 

chemical Section for each sample submitted for analysis. 



Columns 



Format Entry 



Description 



1-7 A4,A3 X(l), Lab number 

X(2) 

8-22 3A4,A3 X(3)- Name of material 

(6) 

23-30 2A4 X(7), Field number 

X(8) 

31^7 4A4, Al X(9)- Location (nearest geo- 

X(13) graphical feature) 



54-55 


12 


LAT Degrees of latitude 


56-59 


F4.2 


FLAT Minutes of latitude to 
nearest one-hundreth 


60-61 


12 


L Degrees of longitude with 
the 100 understood (i.e. 
"121" degrees is repre- 
sented by "21"). 



62-65 F4.2 FL<|)N Minutes of longitude to 

nearest one-hundredth 

69-70 12 ICO County number (see al- 

phabetical list of 58 coun- 
ties) 
59 = "OUT OF 

STATE" 
= blank 

79-80 12 IFM Personal reference num- 

ber (Ex: number of for- 
mation from list of 
formations to be read in) 



9. End Card 

9's in all columns 

10. Repeat cards 6 - 9 if LIST ^ O 

1 1 . System control card 

/* 



36 



CALIFORNIA DIVISION OF MINES AND GEOLOGY 



SR li 



STORAGE AND RETRIEVAL OF CHEMICAL ANALYSES* 

The format for entering chemical data on computer cards is 
the periodic table. Data for the first ten elements can be entered 
on the first card. The format for entering these ten elements is: 
(10 (Al, F6.2), 2A4, IX, II). Hydrogen (atomic no. 1) would 
be entered in columns 2 to 7. Helium (Z = 2) would be entered 
in columns 9 to 14. Oxygen would be entered in columns 51-56. 
These are the 6 columns prior to and including column 56 
(atomic no. 8 times 7 columns per element). Columns 1, 8, and 
50 can be used to indicate whether the data is in ppm ( ) , ppb 
(*), or percent (%). Since oxygen is included as one of the 
elements, all other data is reported in the elemental form. Lab 
numbers are right adjusted in columns 72-78. 

Cards for the remaining elements in the periodic table are 
prepared in the same way. Column 80 is used to indicate the 
decade of the atomic number. For example, data for cadmium 
(Z = 48), would be in columns 51-56 of a card with the number 
4 in column 80. Data for tin (Z = 50) would be in row 10 of 
the same card since Z = 50 (4 x 10 + 10). 

Only numbers and decimal points can be used in the data 
columns. The only exceptions are columns 1, 8, 15, 22, 29, 36, 
43, 50, 57, and 64 used to indicate data in other than ppm 
concentrations. 

The advantages of this method of data entry are: 

1 . Subsequent analyses of additional elements can be added 
to the data set without repunching the old data. 

2. The systematic order of the elements remains unchanged 
with the addition of new analyses. 

3. New users of the system could probably locate data for the 
elements simply by knowing that it was "based upon the 
periodic table." 

A disadvantage of the system is the large number of cards 
needed to represent an analysis. All ten cards representing the 
periodic table need not be included unless the analysis happens 
to have elements from each decade of the periodic table. 

•This format is only used to punch the computer cards. 



4. System control cards 

a) //STEPA EXEC FORTGCLG 

b) //FORT. SYSIN DD* 

5. Data card A (column 80 = 1) 



Column 



Format 



Entry 



Description 



30-35 



F6.2 Phosphorus (%) 



6. Data card B (column 80 =2) 



58-63 
65-70 



F6.2 
F6.2 



CU 

Zn 



Copper (ppm) 
Zinc (ppm) 



Arsenic (ppm) 



Cadmium (ppni 



Mercury (ppb) 



7. Data card E (column 80 = 3) 

16-21 F6.2 As 

8. Data card D 1 (column 80 = 4) 

51-56 F6.2 CD 

9. Data card E (column 80 ( = 7) 

65-70 F6.2 HG 

10. Data card F (column 80 = 8) 

9-14 F6.2 PB Lead (ppm) 

72-78 2A4 AN ^,Z Lab number 

Repeat cards 5 through 10 for each sample. 

1 1 . End card 

9's in all columns 



Repeat card 1 1 five more times. (The number of end cai 
is equal to the number of data cards representing a siiU 
sample, 6 in this case.) 



PROGRAM NO. 2. 

TABLE OF CHEMICAL ANAL YSES 

This program provides a table containing chemical analyses. 
The cards for the input are prepared as explained above in 
"Storage and retrieval of chemical analyses." 

Card 

No. Typ^ 

1. Job card 

2. System control cards 

1) //STEPA EXEC FORTGCLG 
b) //FORT. SYSIN DD* 

3. "TABLE OF CHEMICAL ANALYSES" 
FORTRAN IV source deck 



12. System control card 

/* 

This program can be adapted to other elements as the ne 
arises. 



PROGRAM NO. 3. 
STEPWISE REGRESSION ANAL YSES 

This program computes a multiple linear regression equal 
in a stepwise manner, giving correlation matrix and plotting 
correlation curves for various elements. This program was w 
ten by the Health Sciences Computing Facility of Universit; 
California, Los Angeles; refer to its program # BMDP2R 
details. 



)80 



DISTRIBUTION OF HAZARDOUS HEAVY ELEMENTS 

APPENDIX D 
Digestion Procedures 



37 



^)TAL DIGESTION TECHNIQUE 
aOSED DIGESTION SYSTEM) 

)rdinary digestion techniques could not be employed on sam- 
) 5 to be tested for mercury and other volatile elements, because 
ii);he danger of losing them due to their volatility. Therefore, 
in heating of the digest in a closed system was required during 
nple preparation. Wet digestion of the samples was achieved 
vh a 1:1 mixture of concentrated nitric and sulfuric acids, with 
\ apparatus (Figure 30) in a reflux position. 

^^iparatus 

he apparatus mainly used for digesting samples for mercury 
u lysis consisted of a digestion flask, a modified soxhlet extrac- 
t-:0 a dropping funnel, and a Friedrichs condenser. 

he digestion apparatus (Figure 30) is a modified version of 
ht used by the Association of Official Analytical Chemists 
^'ijrwitz, 1970) to digest fruit pulps and other vegetables for 
"ucury determinations. All units of apparatus are made from 
)};x glass. Unit 3 is a modified soxhlet extractor, 5 centimeters 
nutside diameter, with a 250 millimeter capacity, a facility to 
ivrflow, and without an inner siphon tube but equipped with 
lOpcock on the tube leading to the digestion fiask, unit 1. With 
r hstopcock open, the apparatus is in the reflux position, when 
led, this unit serves as the trap for condensed steam and acid 
ues. The top of the unit is attached to a 34-cm-long Frie- 
Irhs condenser, unit 4. The bottom of unit 3 is attached 
hiiugh the center neck of a two-neck, round bottom, 500 ml 
li stion flask, unit 1 . The two necks of this flask are 3 cm apart 

rovide working clearance. The ofl"set neck is used to attach 
>-ml dropping funnel, unit 2. 

ecause mercury compounds tend to absorb the glassware 
u ices, this apparatus and the separators were rinsed with a 

1 te HNOj and then with deionized distilled water. Also, dur- 
a, he course of digestion of a series of samples, blanks were run 
n checked for possible contamination at least twice a week. 
1 usual workload was eight samples a day. 

*ejents 



Concentrated HNO, (Baker Special, suitable for mercury 
determination); 

HNO, - H,SO, mixture (1:1); and 

Urea - 40 percent (W/V) 

nedure 

Thoroughly mix the pulverized sample on a plastic sheet 
and spread it flat. Weigh 10 gm of the sample by taking 
increments from all sides, corners and grids in order to get 
a representative sample from the pulverized bulk powder. 
Drop this powder in the digestion flask and dampen it 
with a few ml of (1:20) HNO,. Let it stand overnight; or 



F=a» 




UNIT 4 



UNIT 3 — * 




UNIT 2 



UNIT 



UNIT I. DIGESTION FLASK 

UNIT 2. DROPPING FUNNEL 

UNIT 3. MODIFIED SOXHLET EXTRACTOR 

UNIT 4. FRIEDRICH CONDENSER 

Figure 30. Digestion apparatus for volatile elements. 

2. Heat gently on a heating mantle by setting rheostat at 30 
volts for 20 to 30 minutes. The stopcock should be kept 
in a reflux position while heating. 

3. Add, dropwise, 30 ml HNO3 - H^ SO4 (1:1) mixture. 
Change the rheostat to 60 volts. Heat until dense white 
H2SO4 fumes cease with stopcock in the reflux position. 

Note: Because nitrous oxide fumes rise into the reflux con- 
denser, it is necessary to rinse the apparatus from the top with 
a minimum amount of deionized distilled water. While rinsing, 
care should always be taken not to increase the volume signifi- 
cantly. 

4. Boil for one hour. Count the time after the first bubble 
starts. 



38 



CALIFORNIA DIVISION OF MINES AND GEOLOGY 



SR 



5. After boiling for one hour, add 10 ml concentrated HNOj. 
Heat for 15 minutes more. 

6. Rinse the apparatus with water. 

7. Add 10 ml of 40 percent urea. Close the stopcock. Heat 
and collect the solution in the soxhlet extractor, Figure 
30, unit 3, for 15 to 20 minutes. 

8. Shut down, cool and pour all the contents of the flask, 
including the fine suspended particles, into a 250-ml volu- 
metric flask. Cool, make to volume with distilled water 
and transfer to a polyethylene bottle. 

9. Prepare blank solutions in the same way and check for 
possible contamination. 

Important Note: Do Not Filter. When taking an aliquot for 
mercury determination, agitate the bottle and include the sus- 
pended particles in the aliquot. If filtered, the mercury deter- 
mined is always less than the amount present in the sample. For 
the determination of other elements, filter and then take the 
aliquot. For arsenic determination, it is necessary to use a special 
treatment to remove the nitric acid present in the digest because 
it hinders the arsenic determination. Nitric acid was completely 
removed from sample digests by slowly heating with concentrat- 
ed sulfuric acid until brown fumes of nitrous oxide were no 
longer visible and white, dense fumes of sulfuric acid evolved. 

TOTAL DIGESTION TECHNIQUE 
(OPEN DIGESTION SYSTEM) 

Because of the contamination problem, discussed earlier in the 
test, various digestion technqiues were developed and tested to 
digest the bedrock samples. The following is the account of these 
techniques: 

Method A - Mechanically agitate 10 gm of sample for one hour 
with 20 ml of 2N HNO,. After agitation, decant 
the solution for analysis. 

Method B - Heat 5 gm of sample for two hours with 40 ml of 
2N HNO,; cool and dilute to 100 ml volume with 
deionized water. 

Method C - This is the total digestion technique used in diges- 
tion of stream sediments. Heat 10 gm of sample in 
a special closed digestion apparatus with a mixture 
of 40 ml HNOj and H^ SO, (1:) and 10 ml of 40 
percent urea; cool and dilute to 250 ml volume 
with deionized water. 



Method D - This may be called an open version of the l al 
digestion technique described in C. Heat 10 gi i 
sample with a mixture of 40 ml HNO, and H2 ). 
(1:) and 10 ml of 40 percent urea in sand batl m 
a hot plate. 

Method E - This technique is used mainly in rapid siH te 
analysis and is known as the B solution met <i 
(Riley, 1958). Heat 0.5 gm of sample in te n 
crucibles on water bath, with 10 ml perchloric d 
1 5 ml hydrofluoric acids; cool and dilute the c ir 
digest to 500 ml with deionized water. 

Table 8 shows the results of analyses of 1 5 samples digests ly 
using all the above techniques. It is clear that methods B ai E 
bring out most of the cadmium in solution. Method E reqi 3 
a long digestion time and is not desirable for samples having « 
cadmium contents as there is a dilution factor of 1000 in vol i 
Therefore, the remaining samples were digested by method I ir 
cadmium determination. 

An attempt was made to use hydrochloric acid instea i 
nitric acid in methods A and B. However, this produced very lei 
white precipitates which interfered with the analysis by ate ic 
absorption spectrophotometer, so nitric acid was used throi 1 
out. 

Past experience with marine and stream sediments showec le 
necessity of using the closed digestion technique for mercury d 
other volatile elements. As the phosphatic samples seeme 
raise a special problem, it was decided to compare the resul 1 
digests obtained by methods C (closed digestion) and D (( n 
digestion) for arsenic, copper, lead, mercury, and zinc. No y 
preciable differences were found in the resulting analyses. 

All the samples were digested by method D for all anal ^ 
except cadmium. This was contrary to prior experience a 
probably can be explained by the lack of methyl mercury ir ; 
bedrock samples, thus allowing the use of an open diges n 
system. 

ACID EXTRACTION TECHNIQUE 

The detection limit in samples digested by the total diges n 
technique was too low to measure cadmium in the low con 
trations in which it occurs in some of the stream sediment s 
pies. Therefore, an acid extraction method was utililzed 1 
which 20 g of the pulverized sample in a bottle with 40 ml of I 
(two molar) HCI was shaken for one hour on a mechar I 
shaker. After one hour, the suspension was filtered and used f 
cadmium determination. 



Table 8. Comparison of various digestion techniques. 















Values considered 


SAMPLE # 


METHOD A 


METHOD B 


METHOD C 


METHOD D 


METHOD E 


for report are 
calculations. 


101/73 


36.5 <2» 


89.5 '=" 


28.0 


59.5 


90.0 


90.0 


111/73 


19.5"'> 


22.6 


15.0 


18.8 


20.0 


22.6 


112/73 


15.0<«> 


19.4 


14.0 


16.3 


20.0 


20.0 


115/73 


75.5<*> 


96.0 


64.6<2> 


66.3 


70.0 


96.0 


116/73 


41.5<»> 


47.2 


39.0 


41.0 


50.0 


50.0 


121/73 


19.8<^' 


38.5 (i^* 


16.0 


17.5 


30.0 


38.5 


155/73 


32.0<''> 


32.8 


20.0 


27.3 


30.0 


32.8 


159/73 


72.5<«» 


166.0 


21.0 


43.8 


150.0 


166.0 


160/73 


57.5"" 


121.0 <2> 


22.0 


35.5 


120.0 


121.0 


162/73 


22.0<''» 


27.6 


24.5<3' 


23.0 


27.0 


27.6 


167/73 


225.0<2> 


348.0 


68.0 


92.5 


300.0 


348.0 


168/73 


175.0<« 


348.0 


53.0 


75.0 


330.0 


348.0 


171/73 


46.5 '2> 


52.0 


42.7<''> 


32.3 


50.0 


52.0 


206/73 


29.5«' 


32.2 


23.2 


26.3 


20.0 


32.2 


277/73 


43.4«" 


99.0 


25 


48.5 


100.0 


100.0 



Note: The figure in parentheses is the number of times the sample was digested, and the value given is the average of this number. 



DISTRIBUTION OF HAZARDOUS HEAVY ELEMENTS 



39 



APPENDIX E 
Analytical Techniques 



i|>; MERCURY 

Apparatus 

1. Atomic Absorption Spectrophotometer: Perkin Elm- 
er, Model 403, equipped with concentration read out, 
deuterium baciiground corrector, mercury hollow 
cathode lamp and a chart recorder, model 165. 

2. Laboratory kit for flameless mercury determination: 
Refer to Figure 3 1 . This device was assembled in the 
Division laboratory as follows: 

a) Needle valve: Lab-Crest threaded, glass needle 
valve, with angle design; 

b) Flowmeter: Monostat air-flowmeter; 

c) Reaction vessel: prepared by cutting a 1000 ml 
plain hydrometer pyrex cylinder in half; 



d) Absorption cell: made up of clear, transparent, 
plastic tube, 2.5 cm o.d. and 10 cm length, with 
quartz end windows. 

Additionally there are moisture traps, a dehydration 
trap, and a trap to remove mercury from the incom- 
ing air, if any is present. The whole system is an open 
system. 

Reagents 

1. Stannous Choride solution: 10 percent weight/vol- 
ume prepared in 20 percent HCL. Prepared fresh 
every 2 to 3 months. 

2. Anhydrone (magnesium perchlorate) : commercial- 
ly available. 

3. Mercury standards: stock solution of 1000 ppm Hg, 
purchased from Harleco, was used to prepare the 
working standards. Serially dilute to 0.1, 0.5, 1,5, 10, 




I. NEEDLE VALVE 
2.AIR-FL0WMETER 
3.ACTIVATED CHARCOAL TRAP 

4. TWO-WAY STOPCOCK 

5. REACTION VESSEL 



6.MAGNETIC STIRRER 
7.M0ISTURE TRAP 
8.DEHYDRATI0N COLUMN 
9.ABS0RPTI0N CELL WITH 
QUARTZ WINDOWS 



Figure 31. Non-flame mercury device. 



40 



CALIFORNIA DIVISION OF MINES AND GEOLOGY 



SR 13 



and 25 ppb Hg, using 10 percent HCl. Because of the 
acid diluting medium for the standards, the mercury 
values remained reasonably uniform and were used 
for a period of one week before fresh working stand- 
ards had to be prepared. The standard blank was 
prepared in the same way, and each blank was tested 
for any possible contamination. One of the standards 
was run as an unknown between each batch of sam- 
ples to check reproducibihty. 

4. Activated charcoal and glass wool. 
Procedure for Flameless Mercury Measurement 



1. Set up the atomic absorption (AA) unit with the Hg 
hollow cathode lamp and with flow-through absorp- 
tion cell in place of burner, keeping the following 
settings: 

Wavelength - 253.7 A 

Sht setting - 5 (3 mm, 20 A 

Lamp current - 10 milhamps (mA) 

Air flow rate - 835 ml/min at 1 atmosphere and 

70° F. This can be adjusted by keeping the stainless 

steel ball in the air-flowmeter at 8. 
Concentration mode - 1-80 (approx.) 

Adjust wavelength for maximum energy; align ab- 
sorption cell for minimum absorbance. 

2. Turn on the deuterium background corrector and let 
it warm for 10 to 15 minutes. 

3. Turn on the chart recorder keeping the following 
settings: 

Input switches - float and negative 

Chart speed - 5 mm/min 

Power Knob - "Amp" for warm-up and then to 

"Servo." 

4. Keep the clean reaction vessel with a two-way stop- 
cock in the by-pass position. Keep the magnetic 
stirrer in an off position, and adjust the air flow at 
the rate of 835 ml/min. Zero the instrument with the 
blank mercury-free air. 

5. Change the activated charcoal, anhydrone and glass 
wool daily. 

6. Take 100 ml deionized HjO in a reaction vessel and 
pi pet 10 ml of the standard or agitated and unfiltered 
sample solution. If standards are used, start with the 
lowest concentration. The standards which were 
used for the present analysis contained 1, 5, 10, and 
25 ppb Hg, respectively. 

7. Turn the knob of the chart-recorder from "Servo" 
to "Chart." Before starting the actual analysis, ad- 
just and 100 percent concentration using the 
ZERO and GAIN controls of the recorder. Use 
blank (100 ml H^O + 2 ml 10 percent SnCl^) for 
adjusting percent and 25 ppb Hg standard for 
adjusting 100 percent. 



8. Add 2 ml of 10 percent SnClz, using a 2 ml tip-i!| 
pipette. Close the reaction vessel immediately. 

9. Start the magnetic stirrer and activate aeration b' 
turning on the two-way stopcock. Numerical rea<; 
out of the instrument and the readout on the nj 
corder will be recorded simultaneously. Write tl| 
identifying sample or standard number on chart p 
per. 

10. When the intensity in ppb reaches zero on the reai 
out of the instrument, turn off the magnetic stirrf 
switch aeration to bypass position, and remove tl 
stopper from the reaction flask. At the same tiiE 
change recorder from "Chart" to "Servo." 

11. Rinse down the fritted aeration tube with YiW. 
(1:20) and then with distilled water. About oncei 
week, or more often if necessary, this fritted aeratiii 
tube is cleaned in an ultrasonic bath, because t 
digest contains suspended particles that fill the poi 
in the fritted portion of the aeration tube. 

Figure 32 represents the working curve drawn from the pea 
obtained on AA recorder by running various standards. TI 
curve was used for all samples to convert observed peak heigl 
into corresponding concentrations. 



(b) ARSENIC 

Apparatus 

All arsenic determinations were carried out on a Perki 
Elmer 403 atomic absorption spectrophotomet 
equipped with a three-slot burner head, model 1 65 cha 
recorder, and a deuterium background corrector. The |. 
used for arsine generation (Figure 33) is a laborat( 
assembled device consisting of a reaction flask, dos 
column, collection balloon, and a four-way stopcock 



i 



Reagents 

1. Concentrated hydrochloric acid. 

2. Potassium iodide solution (15 percent) 

3. Stannous chloride solution - 20 percent in 8N H 

4. Zinc - granular, 20 mesh, analytical reagent gra 

5. Arsenic standard - stock solution of 1000 ppm s 
was prepared as follows: 

a) Weigh exactly 1 .320 gm As^O, ( A.R. grade) i 
dissolve in 25 ml of 20 percent potassium • 
droxide. 

b) When the powder is dissolved completely, r i- 
tralize this solution to a phenolphthalein d 
point with 20 percent HjSO,. 

c) Dilute to one liter with 1 percent HjSO,. 

From this stock solution, working standards of 5,5' 
25, 35, and 50 ppb As were prepared fresh d:y 



980 



DISTRIBUTION OF HAZARDOUS HEAVY ELEMENTS 



41 



70 



60 



50 



40 



C 
^30 

V 

L 



20 



10 



0^. ir 



I 



10 



25 

Concentration in ppb 



50 



lure 32. Working curve for mercury. 



VACUUM 
ADAPTER 



COLLECTION 
BALLOON 




i3 — 



ARGON 
INPUT 



FOUR -WAY 
STOPCOCK 



^ 



ARSINE GENERATION FLASK 

Figure 33. Arsine generation apparatus. 



TO ATOMIC ABSORPTION 

SPECTROPHOTOMETER 

BURNER 



42 



CALIFORNIA DIVISION OF MINES AND GEOLOGY 



SR 1 



Other reagent solutions were prepared fresh for each 
batch of samples. 

Procedure 

1. Set up the A. A. unit with the As hollow cathode 
lamp; start the deuterium background corrector and 
a chart recorder and let them warm for 15 to 20 
minutes. Keep the following settings: 

Wavelength - 193.7 A 

Slit setting - 4 

Lamp current - 20 mA 

Fuel (H,) Flow - 20 

Oxidant (Ar) Flow - 30 

Concentration Mode - 0-10 

Recorder Response - 2 or 3 

Recorder Chart Speed - 20 mm/min. 

2. Make the required connections for hydrogen as the 
other fuel and argon as the other oxidant in the 
burner control chamber. Connect the auxilliary ar- 
gon (from the back of the burner control) to the 
four-way stopcock (refer to Figure 33) and connect 
the other side of the four-way stopcock from where 
the arsine and hydrogen gas is driven off to the 
auxilliary oxidant position in the burner-nebulizer 
assembly. The other two sides of the four-way stop- 
cock are connected to the generation flask for intro- 
ducing the carrier argon gas and to carry the arsine 
and hydrogen produced to the burner nebulizer as- 
sembly. This can be done by changing the stopcock 
to the purge position. Argon in the bypass position 
is used to zero the instrument. Push the zero button 
when the flame is on. 

3. Pipette 20 ml of standard or sample digest in the 
generation flask. If the sample has a higher concen- 
tration of arsenic, take less aliquot. 

4. Add hydrochloric acid in such a quantity that the 
solution becomes 4 normal (N) when diluted to 40 
ml with distilled water. 

5. Add 1 ml of 15 percent potassium iodide solution 
with a tip-up pipette or micro-pipette. Mix well. 

6. Add 1 ml of 20 percent stannous chloride solution, 
mix well and allow the solution to stand 3 to 4 
minutes. 

7. Completely wipe off the inside of the generation 
flask where additions are made. Connect the genera- 
tion flask to the assembly with four-way stopcock in 
a bypass position. 

8. Add 1.5 g of zinc metal to the generation flask 
through the side-dosing column and immediately 
close the dosing funnel stopcock. Wait 4 to 5 min- 
utes until reaction between zinc and hydrochloric 
acid is complete and all the arsenic present in the 
solution has turned to arsine gas. 

9. After 4 to 5 minutes, activate the recorder chart, 
light the flame and, keeping argon in bypass posi- 
tion, zero the instrument. 



10. When zero is recorded on the chart, change ; 
four-way stopcock 90° to purge position, allow ; 
the auxiliary argon to flow through the flask i \ 
carry the collected arsine into the burner. Rect I 
the peak, and when the recorder-pen comes to z i 
position, return the four-way stopcock to byp , 
position and turn off the flame. By turning off : 
flame at this stage, considerable argon and hydro, i 
gas can be saved. 

Standard and sediment-digest blanks were run « ■ 
eral times, and the average value obtained was s - 
tracted from the corresponding values of stands |s 
and samples. 

The only danger in using this devise is that, due to moist ;, 
zinc particles stick to the surface of the stopcock of the reac n 
vessel or dosing column. This might permit leakage of arsine >, 
which might be inhaled by an operator. To avoid this, dry e 
neck of the dosing column and generation flask complete!} y 
wiping with a Kimwipe. As a further precaution, a port e 
fume-hood was built over this device and connected to the 1: )■ 
ratory exhaust hood system. 

Figure 34 represents the working curve drawn from the pi cs 
obtained by running various standards. This curve was use o 
calculate the concentration of all samples. Various stand is 
were run between the analyses to check the reproducibi y, 
which was found to be very good (see Appendix H). ) 



(c) CADMIUM, COPPER, LEAD, AND ZINC 



I 



Cadmium, copper, lead, and zinc were determined by d ci 
aspiration of respective standards and setting the working ci es 
on the AA instrument. The filtered digests of the samples re 
then aspirated, and concentrations were read directly or he 
digital readout screen. The deuterium background correctoi as 
used for the analyses of cadmium, lead and zinc. , 

Because the total digestion technique was not sufficiently -n- 
sitive to analyze the low quantities of cadmium present in ise 
sediments, the acid extraction technique was used. The v |ies 
from each of the digestion methods were quite comparabl {in- 
dicating that practically all of the cadmium had gone into iu- 
tion with the acid extraction technique. 

I 

The acid extractions of most of the stream sediment sar le 
were analyzed for copper, lead, and zinc. The values obt. ic 
were compared with those obtained from the totally dig e 
samples, and it was found that the samples digested by the :i 
extraction technique showed lower concentrations than sai 
digested by the total digestion technique; therefore, the l 
digestion technique was used for copper, lead, and zinc. 

(d) PHOSPHORUS 

Phosphorus was determined with the x-ray spectrometi b' 
using one gram of 230-mesh sample, mixing it with one grr 
Whatman CF-1 1 celluose powder, making pellets in Spex p^ 
and analysing with an EDDT crystal and Cr target x-ray bi 
All the phosphorus results are corrected for the presence of ig 
calcium. 

The procedure for phosphorus determination is a mode 
technique after Fabbi (1971). The clayey nature of the -^ 



»80 



DISTRIBUTION OF HAZARDOUS HEAVY ELEMENTS 



43 



I35r 



i30- 



ISi I' 



25 



r 

( 

10 



0"^- 



15 



25 
Concentration in ppb 



35 



50 



tcwRre 34. Working curve for arsenic. 



liyzed precluded extensive pulverizing sieving to 400 mesh as 
sigested by Fabbi. 

1. Grind the sample for two minutes in Model #3800 
Pitchford Pica Blender Mill, using stainless steel 
cylinders, stainless steel end buttons, two 15-mm 
stainless steel balls, and two aluminum end caps 
with four rubber '0' rings. Fill each vial approxi- 
mately '/j full ( — 10 gm of less than #10-sieve 
material). 

2. Split about '/, of this sample for hand grinding to 
230 mesh with agate mortar and pestle. 

3. Dry the sample in the oven at 110° C. 



Mix 1.0 gm of sample with 1.0 gm of Whatman 
CF-11 cellulose powder in a capped vial in a pica 
mill. 

5. Prepare pellets, in duplicate, by filling Spex caps 
about half full of poly vinyl alcohol and other half 
with mixture of sample and cellulose, using a pres- 
sure of 16 tons per square inch. 



The samples were then analyzed with a Cr Target x-ray tube, 
EDDT analyzing crystal, and a flow proportional counter at 
1620 volts used in conjunction with a Phillips-Norelco vacuum 
spectrometer. X-radiation was generated at kV and 37.5 mA on 
the target tube. A baseline setting of 8.5 volts and a window- 
setting of 9 volts was used to discriminate against most of the 
CaK interference. The remainder of this interference was sub- 
tracted in the following estimation: 

1 . Each sample was analyzed four times for at least 20 
seconds and up to 100 seconds (for very low P 
samples) for counts between 8.5 volts and 17.5 
volts. This would include all P and about 3 percent 
of the Ca counts due to a sample. 

2. Each sample was analyzed four times for 10 to 20 
seconds for counts beyond 8.5 volts. This includes 
essentially all P and ail Ca counts. 

3. About 3 percent of the Ca counts occur in the 
interval between 8.5 and 17.5 volts. This was deter- 
mined from average data on a sample of powdered 
CaCOj and Cf-11 (1:1) run at the beginning and 
end of each day. The correction factor (RCa) was 



44 



CALIFORNIA DIVISION OF MINES AND GEOLOGY 



SR ! 



calculated using the following formula: 



R 



Ca 



8.5- 



•17.5 
CR 



■0.0 
CR 



17.5 
CR 



8.5- 



Where: 



8.5 



17.5 

CR = counts per second between 8.5 and 17.5 volts 
for CaCOj 

-0.0 

CR = counts per second greater than 8.5 volts for 
CaCO, 

4. The following was used to obtain Ca- corrected 
values for P: 



CR, 



Where: 



17.5 
CR - 



8.5 



/ ^0.0 /17.5 

Rca / CR- / CR 

V8.5^ 8.5^ 



CRt 



corrected count rate for phosphorus 



17.5 
CR 



counts per second between 8.5 and 17.5 
volts for the unknown or standard rock 
sample (PHA on "diff) 



R(22 = correction factor for Ca (see above) 

-0.0 

CR = counts per second beyond 8.5 volts for the 
8.5 ^ unknown or standard rock sample (PHA on 

"integral") 

5. A standard high-phosphate sample was counted before 
and after each set of unknown samples. A fixed position 
(no. 2) was used to eliminate orientation variability 
between runs. Standard rocks were run in the second 
fixed position (no. 4). Instrumental drift was eliminat- 
ed from the data by using the ratio method. Count rates 
of unknown samples were first corrected for Ca inter- 
ference, then divided by the corrected count rate for the 
high-phosphate standard. This standard was corrected 
in two ways: (a) the regular Ca interference was sub- 
tracted, and (b) interpolations of data at the beginning 
and end of each run were used as divisors to get ratio 
comparisons. (For example, if the Ca-corrected count 
rate for the standard was 2800 cps at the beginning of 
a run, and 2600 cps at the end, the count rates for the 
three unknowns would be divided by 2750, 2700, and 
2650 cps, respectively.) 

PREPARATION OF THE HIGH PHOSPHATE STANDARD 

The high-phosphate standard was prepared by mixing Florida 
phosphate (National Bureau of Standards Sample 120a) and Cf 
- 1 1 cellulose powder and comparisons were made. During ap- 



proximately two weeks of continuous use, this standard ga i 
about 40 percent in x-ray intensity. Apparently, the cellule s 
partially destroyed by the x-ray beam. Similar change also s 
observed on another specimen which increased the inter y 
about 15 percent in 3 days. The cellulose destruction prob y 
depends on the number of hours of exposure; the chang n 
intensity is not gradual, so a correction for this change could ii 
be made. ■! 

A new standard ("A) was prepared by mixing 1.0 gr if 
Florida Phosphate (National Bureau of Standards Sample V. ] 
with 1.0 gm of a clayey sediment (1 1/73). The clayey mat al 
acted as an excellent binder, and no destruction or chan} n 
intensity was observed in 4 weeks of continuous usage. A d i- 
cate sample ("B), which had received very little x-radia n, 
gave identical results before and after this period. 

PREPARATION OF THE STANDARD WORKING CUR\ 

A. Standards with to 0.5% PzOs 

Standard rocks G-2, GSP-1, AGV-1, BCR-1, SY-1, T-1, ' e 
mixed with CF-1 1 cellulose powder (1:1). These were comp d 
to the high-phosphate standard "A" to obtain a curve in le 
range to 0.5% P2O5. 

B. Standards with 5 to 35 % P^^ 

Florida phosphate (National Bureau of Steandards 120a as 
mixed with reagent grade CACO, in various proportions, ne 
gram of each of these was then mixed with CF-11 cell se 
powder (1:1) to prepare a pellet. The standards were la sd 
P-10 (50% 120a + 50% CF-11), P-8 (40% 120a -h % 
CaCO, + 50% CF-11), P-6, (30% 120a + 20% CaC( + 
50% CF-11), P-4 (20% 120a + 30% CaCO, + 50% CF ), 
P-2 (10% 120a + 40% CaCO, + 50% CF-11), and « 
(50% CaCO, + 50% CF-1 1 ) . These were then compared I he 
high-phosphate standard "A", as were all other samples. 

Samples with unknown PjOs concentrations were then ^ 
pared to these two curves. For unknown samples with 0. 
values between 0.5 and 5%, a curve was prepared by inter la- 
tion of data from the two standard curves. 

CALCULA TOR PROGRAMS FOR XRF ANAL YSIS 

The Commodore programming calculator was used to i -u 
late the data. It takes about 2 hours to calculate data gene'ed 
in 6 hours of x-ray operation. The five programs are as fo *t 

7. Calculate the average count rate. 

Enter counting time, CR,, CR,, CR„ CR4; record answer in| 
Avg." Column of XRF data sheet. Program Code: 

MMMM,N, 0.4, IV, 2 y„ W, AC, 42. 6. 26. 26. 26. -f ' 
7393. 437., R, AC, 20, 1, 2, 3, 4 Ans. 

2. Calculate Rq^ from "diff" and "integral" data foiw 
pie P—O run at beginning and end of the day's 



T7.5, 
CR 



0.0, record 
CR 



Enter 

/ CR 

s.sy 8.5 

^Ca ^"'^ average the two values. Program Code: 



no 



DISTRIBUTION OF HAZARDOUS HEAVY ELEMENTS 



45 



5,, W. AC, 42. 6. 23. 4363. 493. 63 + 7., R, AC, 50, 2000, 

Ans.: 0.02564 



3 Calcium correction. 



tfe Rca' ^n'^'' 



17.5 ^0.0, and record "cor- 

CR / CR reeled cps" 



8.5- 



^gram Code: 

Ra, IV, 2 % W, AC, . 6. 23. 4383. 72362. + 3.423. 637., 
3(0, 5000, Ans.: 2936 






=!, 5 - 



• 2 



t 



20 
P-6 



30 
P-8 P-IO 



VoPaOs 

35. Working curve for P2O5 (high phosphate). 



4. Drift correction. 

Enter "corrected cps" for first or last analysis of an individual 
run, whichever is highest. Record first value under "cps drift" 
for first unknown if the first "B" corrected " cps" value was 
larger than the last. Record the first value under the third un - 
known if drift resulted in an increase in "corrected cps" of the 
"B" standard. Program Code: 

4, IV, Oy,, W, AC, 42. 3. 426. 393. 7362. 3.+ 423. 636. 3. 636. 
3. 637., R, AC, 280, 260, Ans.: 275, 270, 265 

5. Calculation of sample to standard ratio. 

For each unknown, enter the "corrected cps" and then it's adja- 
cent "cps drift." Record the sample to standard ratio under 
"sam/std." Plot on 0-0.5% or 0.5 to 35% P^Os graphs. 
Program Code: 



5 %, W, AC, 96.37., R, AC, 2, 3, 



Ans.:0.66667 




Figure 36. Working curve for PjO, (low phosphate). 



46 



CALIFORNIA DIVISION OF MINES AND GEOLOGY 



NOTES FOR APPENDICES F AND C 

1. Detection limit in sample digests is as follows: 

As - 1.0 ppb; Cd - 0.01 ppm; Cd (acid digest) - 0.01 

ppm; 

Cu - 0.1 ppm; Pb - 0.1 ppm; Hg - 0.1 ppb; Zn - 0.1 

ppm. 

2. Detection limit in samples is as follows: 

As - 25.0 ppb; Cd - 0.25 ppm; Cd (acid digest) - 0.02 

ppm; 

Cu - 2.5 ppm; Pb - 2.5 ppm; Hg - 2.5 ppb; Zn - 2.5 

ppm. 

3. '0.0' means either the element is not detected or it is 
present in quantity less than the specified limit of detec- 
tion. 

4. 'N.D.' means not determined. 

5. * Not used in statistical calculations. 

6. (For Appendix G only). Detection limit for P is 0.01%. 



iO 



DISTRIBUTION OF HAZARDOUS HEAVY ELEMENTS 



47 



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48 



CALIFORNIA DIVISION OF MINES AND GEOLOGY 



APPENDIX G 

Chemical Analyses of Bedrocks 

and Some Stream Sediments 



LAH. 


as 


CO 


cu 


PB 


HG 


P 


ZN 


NO. 




. . . (PPMl 




(PPb) 


(«) 


(PPM) 




....... 








"9J/73 




o.s 


30.0 


*22!3' 


*42!5* 


N.n. 


*26!o* 


:*4/n 


"♦.O 


^.0 


17.5 


19.0 


0.0 


N.n. 


62,0 


'V-D/n 


1 1.5 


H.i. 


27.5 


IH.H 


15.0 


N.n. 


46,0 


'ih/Ti 


I'^.S 


?H, (J 


25.0 


22. S 


30.0 


0.16 


1 14.0 


>J7/73 


1'..0 


-?! .S 


37.5 


20.9 


15,0 


0.36 


72.0 


9h/73 


I'l.O 


17.? 


27.5 


27.0 


0.0 


0.31 


53.0 


9^/73 


1/^.5 


1 7.S 


25.0 


17.5 


42.5 


0.17 


56. 


10(;/73 


! 1 .5 


3.6 


20.0 


20.0 


7.5 


N.O. 


34.0 


lOJ/73 


^y.o 


90. n 


110.0 


27.5 


7.5 


4.42 


214.0 


10^/73 


'.0 


9.6 


20.0 


24.8 


8.8 


0.54 


41.0 


10:V73 


M.S 


'.6 


17.5 


23. « 


0.0 


N.O. 


47.0 


104/73 


6.n 


I.'* 


27.5 


21 .0 


22.5 


N.O. 


23.0 


IQS/ZS 


-i.1 


1 .0 


1 7.5 


19. "i 


15.0 


N.O. 


14.0 


1'-'^/ 73 


:i.o 


■*. 


22.5 


17.5 


0.0 


N.O. 


26.0 


10 7/ 73 


3.S 


11.1 


25.0 


22.5 


5.0 


0.11 


5'*.0 


10?/73 


?.? 


1 .-? 


22.5 


24.5 


30.0 


N.O. 


22.0 




^^.3 


9.6 


20.0 


18.5 


7.5 


0.18 


43.0 


' 10/73 


^.e 


' .0 


15.0 


15.0 


7.5 


N.O. 


17.0 


Ml/73 


:*H.5 


^?.6 


47.5 


2fi.O 


7.5 


0.52 


100.0 


ll>'/73 


<r"^.H 


20.0 


25.0 


IP.** 


0.0 


0.58 


85,0 


1 ! V73 


1 \ .5 


1 .-^ 


22.5 


19. "< 


8.8 


N.O. 


26,0 


11^/^3 


] 7.d 


3.'' 


30.0 


21.0 


0.0 


N.O. 


25,0 


?. '.'3/73 


^9.q 


9'-.0 


130.0 


26.5 


27.5 


4.55 


235.0 


11^/73 


3^.S 


50.0 


57.5 


2n.fl 


7.5 


1.98 


154.0 


117/73 


1^.5 


6.0 


20.0 


17. « 


0.0 


N.O, 


36.0 


llH/73 


'..S 


is.o 


15.0 


19.3 


0.0 


0.3S 


50.0 


119/73 


9.S 


1.4 


25.0 


in.fl 


0.0 


N.O. 


24.0 


Un/73 


(S.O 


3.6 


25.0 


21.3 


0.0 


N.O. 


?4.n 


l?l/73 


U4 


3B.S 


7.5 


27.8 


0.0 


1.48 


107.0 


\?.?/17. 


6.S 


1 .? 


22.5 


18.8 


0.0 


N,0. 


19.0 


1?3/7J 


c'O.R 


3.6 


17.5 


19.8 


60.0 


N.O. 


32.0 


l<''./73 


S.l 


s.n 


10.0 


19.3 


72.5 


N.O. 


24.0 


1^5/73 


1 I.'. 


s.o 


22.5 


20.0 


72.5 


N.O. 


52.0 


\Zf^/ti 


7.2 


0.4 


17.5 


28.3 


0.0 


N.O. 


10.0 


wu ty 


S.l 


1.0 


30.0 


19.5 


20.0 


N.O, 


21.0 



LAH. 


AS 


CO 


CM 


PR 


HG 


P 


ZN 


Nl). 




. . . (PPMl . 




(PP8) 


(«) 


(PPM) 










*'!!.. 


*12H/73 


15.0 


12!o 


22.5 


*22!5' 


0.0 


'o!l3 


74.0 


129/73 


20.0 


20.0 


21.3 


21.3 


12.5 


0.57 


90.0 


130/73 


9.5 


19.4 


15.0 


29.3 


0.0 


N.n. 


58.0 


131/73 


72.0 


4.0 


27.5 


47.8 


160,0 


N.O. 


48.0 


132/73 


5.1 


1.0 


20.0 


21.8 


0,0 


N.O, 


26.0 


133/73 


4.8 


3.8 


27.5 


25.0 


5,0 


N,n, 


28.0 


134/73 


5.3 


2.4 


30.0 


23.3 


0,0 


N,0, 


31,0 


135/73 


11.8 


3.0 


45.0 


21,8 


5.0 


N.O. 


54.0 


136/73 


10.0 


6.0 


32.5 


21,8 


5.0 


N.O. 


64.0 


137/73 


3.2 


0.2 


12.5 


20.0 


5.0 


N.n. 


10.0 


138/73 


0.4 


0.0 


30.0 


18.3 


5.0 


N.O. 


10.0 


139/73 


2.5 


0.0 


7.5 


16.8 


15.0 


N.O, 


8.0 


140/73 


5.7 


?.2 


15.0 


19.3 


15,0 


N,0. 


30.0 


141/73 


2.3 


0.3 


17.5 


16.0 


10,0 


N.O. 


16.0 


142/73 


1.1 


17.0 


5.8 


20.0 


25.0 


0.30 


58.0 


143/73 


7.0 


6.4 


17.3 


30.0 


0.0 


N.O. 


48.0 


144/73 


2.1 


1.0 


10.0 


16.3 


10,0 


N.O. 


32.0 


145/73 


9.0 


1.8 


12,5 


17.3 


0,0 


0.28 


20.0 


146/73 


4.3 


5.0 


25.0 


19.5 


0,0 


N.O, 


33.0 


147/73 


6.3 


8.0 


7.5 


28.5 


0.0 


0,21 


42.0 


146/73 


17.5 


0.9 


22.5 


18.0 


5.0 


N,0. 


25.0 


149/73 


17.0 


14.0 


37.5 


22.5 


5.0 


0.08 


58.0 


150/73 


16.0 


3.6 


17,5 


19.3 


0.0 


N.n. 


38.0 


151/73 


5.3 


6.0 


25.0 


17.0 


0.0 


N.O. 


39.0 


1S2/73 


14.3 


10.0 


30.0 


24.5 


57.5 


N.O. 


77.0 


153/73 


5.1 


8.0 


20.0 


19.8 


5.0 


0.26 


44.0 


154/73 


9.0 


1 .0 


12.5 


16.5 


50.0 


N.O. 


19.0 


155/73 


19.3 


32.8 


32.5 


25.3 


5.0 


1.22 


118.0 


156/73 


10.0 


15.4 


25.0 


18.8 


0.0 


0.14 


55.0 


157/73 


14.3 


10.0 


25.0 


16.0 


5.0 


0.07 


62.0 


15H/73 


8.5 


5.7 


23.0 


15.0 


0.0 


N.O. 


37.0 


159/73 


14.8 


166.0 


150.0 


26.3 


11.3 


7.72 


275.0 


160/73 


18.5 


121.0 


132.5 


25.0 


17.5 


7.29 


245.0 


161/73 


0.5 


n.8 


12.5 


17.0 


5.0 


N.O. 


21.0 


162/73 


27.5 


27.6 


57.5 


24.5 


0.0 


0.33 


103.0 



LAB. 


AS 


CD 


CU 


P8 


HG 


P ^ 


NO. 




. • . (PPMl . . . . 




(PP8) 


(») (B' 








^^ 


. , . . 


'l63/73 


"igli* 


8!o 


'3715* 


2o!o 


**o!o* 


0.32'V, 


164/73 


9.8 


2.9 


15.0 


18.8 


45,0 


N.O. 3 


165/73 


1 7.5 


0.6 


35.0 


22.5 


0,0 


N.O. 3 


166/73 


5.3 


0.6 


20.0 


16.5 


2,5 


N.n. 1 ) 


167/73 


19.5 


348.0 


122.5 


24.0 


17.5 


11.54 35) 


16ri/73 


31.5 


348.0 


162.5 


27.0 


140.0 


15.01 33) 


169/73 


22.0 


3.8 


37.5 


18.8 


0.0 


N.O. 3') 


170/73 


12.5 


11.0 


32.5 


16.8 


0.0 


0.24 51 


171/73 


18,8 


52.0 


74.0 


27.0 


0.0 


1.94 14) 


172/73 


1.5 


5.0 


12.5 


23.0 


5.0 


N.O. 31 


173/73 


10.5 


6.5 


25.0 


22.0 


0.0 


0.31 k-i 


174/73 


0.8 


0.1 


32.8 


20.8 


11.3 


N.O. iJ 


175/73 


9.0 


5.3 


20.0 


18.3 


0.0 


N.O. « 


176/73 


0.0 


0.2 


5.0 


15.5 


0.0 


N.O. 


177/73 


27.0 


150. -0 


124,5 


22.5 


0.0 


9,21 2J0 


178/73 


5.8 


18,6 


15,0 


18.0 


0.0 


0.57 {\ 


179/73 


17.0 


10,0 


22,5 


18.0 


5.0 


0.51 ?'l) 


180/73 


2.6 


0,8 


3,0 


12.8 


5.0 


N.O. 


181/73 


65.0 


14,0 


47,5 


35.0 


31.3 


0.57 fO 


182/73 


5.8 


9.0 


22.5 


18.5 


0,0 


0.60 M) 


183/73 


4.8 


1.8 


10.0 


23.0 


5.0 


N.O. ;o 


184/73 


7.0 


6.0 


45.0 


18.8 


0.0 


N.O. «o 


185/73 


4.8 


1.0 


25.0 


15.8 


0.0 


N.O, ;'o 


186/73 


14.8 


0.8 


20.0 


24.3 


2.5 


N,0, 10 


187/73 


2.1 


0.2 


7.5 


18.0 


0.0 


N.O, '0 


188/73 


14.H 


10.0 


30.0 


18.0 


45.0 


0.17 ( 


189/73 


4.8 


1.0 


27.5 


13.8 


5.0 


N.n. ,0 


190/73 


4.8 


1.0 


26.3 


20.0 


77.5 


N.n. 


191/73 


1.4 


0,1 


23.0 


28.0 


0.0 


N.O. :'o 


192/73 


17.5 


1,1 


45.0 


20.0 


21.3 


N.O. ■ 


193/73 


3.2 


0,3 


5.0 


15.0 


0,0 


N.n. :o 


194/73 


4.8 


0,6 


2,5 


13.8 


0,0 


N.O. 


195/73 


8.0 


0,6 


25,0 


11.3 


0,0 


N.n. 


196/73 


20.0 


3.0 


24.0 


22.5 


77.5 


N.O. '0 


197/73 


3.0 


2.4 


7.5 


15.0 


0.0 


N.O. ;l 



LA«. 


AS 


CO 


CU 


PB 


HG 


P 


NO. 




, . , (PPMl . 




(PPB) 


(%) ( 














'l98/n" 


8.5 


*'3!I' 


22.0 


10.0 


0.0 


N.O, 


199/73 


5.3 


3.0 


10.0 


15.0 


0,0 


N.O. 


200/73 


10.5 


10,0 


15.0 


18.8 


5.0 


0.06 


201/73 


6.3 


7.3 


25.0 


15.5 


2.5 


0.07 


202/73 


7.0 


7.6 


12.5 


15.0 


0.0 


0.07 


203/73 


12. >< 


10.0 


22.5 


21.8 


40.0 


0.07 


204/73 


1.0 


0.5 


12.5 


14.0 


138.0 


N.n. 


205/73 


13.3 


16. »^ 


22.5 


22.5 


40.0 


0.07 


206/73 


6.3 


32.2 


33.3 


17.5 


0.0 


0.99 


207/73 


3.5 


0.5 


7.5 


15.8 


0.0 


N.O. 


208/73 


4.3 


0.5 


20.0 


27.8 


70.0 


N.O. 


209/73 


2.3 


0.8 


7.5 


20.0 


47.5 


N.n. 


210/73 


3.2 


5.0 


7.5 


16.3 


0.0 


N.n. 


211/73 


8.0 


3.0 


17.5 


18.0 


62.5 


N.O. 


212/73 


9.8 


13.1 


20.3 


20.0 


40.0 


0.07 


213/73 


7.0 


4.0 


10.0 


16.5 


47.5 


N.O. 


214/73 


7.5 


0.5 


10,0 


16.3 


0.0 


N.O. 


215/73 


3.0 


7.2 


2,5 


14.5 


0.0 


0.31 


216/73 


12.8 


2.8 


10,0 


15.0 


92.5 


N.n, 


217/73 


9.8 


2.3 


37,5 


30.0 


0.0 


N.n. 


218/73 


12.3 


2.0 


15.0 


18.8 


0.0 


N.n. 


219/73 


10.0 


10.6 


20.0 


15.0 


0.0 


0.37 


220/73 


9.8 


0.1 


7.5 


23.0 


0.0 


N.O. 


221/73 


4.3 


0.8 


18.5 


21.5 


7.5 


N.O. 


222/73 


12.8 


1.2 


9.3 


22.0 


0.0 


N.O. 


223/73 


6.3 


0.2 


13.8 


21.0 


0.0 


N.n, 


224/73 


14.3 


1.0 


10.0 


20.8 


0.0 


N,0. 


225/73 


8.5 


0.3 


7.5 


18.8 


0.0 


N.Dt 


226/73 


12.3 


0.3 


7.0 


16.8 


30.0 


N.O. 


227/73 


7.0 


0,0 


12.8 


20.0 


55.0 


N.O. 


228/73 


3.0 


0.1 


9.8 


20.0 


0.0 


N.n, 


229/73 


19.3 


0.0 


15.5 


22.0 


55.0 


N.O. 


230/73 


4.8 


0.2 


11.8 


19.3 


62.5 


N.O. 


231/73 


2.6 


0.2 


8.0 


19.0 


0.0 


N.O. 


232/73 


2.6 


0.4 


7.5 


17.0 


40.0 


N.O. 



DISTRIBUTION OF HAZARDOUS HEAVY ELEMENTS 



49 



APPENDIX G (continued) 

Chemical Analyses of Bedrocks 

and Some Stream Sediments 



L3. 


AS 


CO 


cu 


PR 


HG 


P 


^N 


;. 




. . . (►^p 


^) . .. . 


.... 


(PP8) 


(*) 


(PPM) 








'23/73 


10.5' 


o!2 


'l7.5 


20.5 


"o!o* 


N,0, 


24!o* 


i»/73 


3.5 


0.0 


• 11.0 


19.3 


25.0 


N,D. 


24,0 


?j/73 


18.8 


1.0 


13.8 


24.5 


30.0 


N,0, 


34,0 


2h/n 


9.0 


1.8 


13.3 


25.3 


7.5 


N.O. 


49,0 


2^/73 


3.5 


1.0 


10,0 


18.8 


7.5 


N,D, 


14,0 


2)/73 


2.6 


1.0 


8.3 


20.0 


0.0 


N,D, 


23,0 


2)/73 


<*.% 


0.5 


13.0 


25. S 


0.0 


N,D, 


31.0 


2)/73 


8.5 


7.2 


16,1 


22.5 


7.5 


0,28 


46,0 


2/73 


6.3 


0.6 


37.5 


15.3 


62.5 


N,0, 


20,0 


2!/73 


4.0 


0.8 


11.5 


23,8 


0,0 


N,0, 


25,0 


21/73 


2.6 


0.1 


14.8 


23,5 


7,5 


N,0, 


44,0 


2v/73 


20.0 


O.fl 


25.8 


30,3 


25.0 


N,0. 


23,0 


21/73 


21.0 


0.1 


14.8 


25.0 


25.0 


N,0. 


20,0 


2./73 


4.8 


0.0 


15.5 


25.5 


15.0 


N.n. 


25.0 


2'/73 


7.0 


2.5 


22.5 


11.8 


55.0 


N.D. 


26.0 




7.0 


1.5 


16.0 


22.5 


25.0 


N.D. 


33.0 


2V73 


7.0 


0.1 


18.8 


25.8 


15,0 


N.D, 


21.0 


2/73 


7.0 


0.1 


13.8 


26.0 


15,0 


N,0. 


27.0 


2 /73 


9.0 


0.5 


20.0 


19.3 


7,5 


N,D, 


28.0 


2 /n 


5,3 


0.1 


9.0 


18.5 


0.0 


N,0, 


13.0 


2/73 


3.0 


0.8 


IS. 8 


24.8 


7.5 


N.n. 


28.0 


2/73 


4.3 


19.4 


20.5 


22,5 


0.0 


N.O. 


64.0 


2/73 


4. J 


2.0 


17.3 


22.5 


15.0 


N.O. 


36.0 


2 /73 


1.5 


1.0 


16,8 


26.0 


7.5 


N.O, 


33,0 


2/73 


7.0 


0.5 


9.S 


25.0 


7.5 


N,0, 


23,0 


2'/73 


4.8 


0.1 


12.8 


20.3 


15.0 


N.O, 


21.0 


2'/73 


14.8 


0.6 


9.5 


21.3 


15.0 


N,0, 


27.0 


2'/73 


12.5 


23.3 


32.5 


20.0 


0.0 


0,08 


81.0 


2i/73 


10.5 


0.6 


30.3 


24.3 


0.0 


N,0, 


30.0 


2./73 


3.5 


0.0 


7.5 


18.8 


0.0 


N,0, 


26.0 


2(773 


3.0 


0.0 


5.0 


17.3 


15.0 


N,0, 


12.0 


2t/73 


0.4 


0.0 


12.0 


15.0 


0.0 


N,0. 


23.0 


21/73 


1.2 


0.0 


23.0 


16.8 


0.0 


N,0, 


27.0 


2</73 


1.5 


0.8 


11.8 


23.5 


15.0 


N.O, 


30.0 


?»/73 


9.0 


0.1 


12.5 


25.0 


55.0 


N.D, 


25.0 



LAH. 


AS 


CI) 


CU 


P8 


HG 


P 


ZN 


NO. 




1 . . . (PPM) . . . • 




(PPB) 


(») 


( PPM) 










!*!!.. 




*303/73 


"5!3' 


"'\)'X 


17,5 


'i7!8' 


'6o!o' 


N.O, 


"28!o' 


304/73 


1.0 


1.0 


23.3 


17.5 


2J7.5 


N.O. 


42.0 


305/73 


2.4 


0.8 


13.3 


17.5 


0.0 


N.O. 


30.0 


306/73 


Z.2 


0.0 


14.3 


15.8 


3.8 


N.O. 


34.0 


307/?3 


6.2 


8.3 


22.0 


16.8 


0.0 


0.30 


46.0 


308/73 


12.9 


16.1 


25.5 


20.0 


0.0 


N.O. 


51.0 


309/73 


1,2 


8,0 


29,8 


21.0 


20.0 


0.21 


61.0 


310/73 


s.e 


2.4 


20,5 


15.3 


3.8 


N.O, 


52.0 


311/73 


66.0 


603.2 


127,5 


25.0 


230.0 


17,11 


437.0 


312/73 


69.0 


62S.6 


133.0 


25.0 


267.5 


17.11 


468.0 


313/73 


19,0 


56.0 


55.6 


25.0 


147.5 


2.97 


129.0 


314/73 


4.0 


512.0 


111.5 


30.0 


3.8 


15.32 


385.0 


31S/73 


10.0 


600.0 


160.0 


30.0 


75.0 


16.85 


455.0 


316/73 


26.5 


324.8 


155.0 


27.5 


15.0 


14.27 


285.0 


317/73 


10.0 


321 .6 


145.0 


32.5 


180.0 


14.36 


278.0 


318/73 


13.0 


260.0 


114.3 


30.0 


7,5 


12.00 


253.0 


319/73 


14.3 


21.5 


40.6 


25.0 


0,0 


0.22 


72.0 


320/73 


13.0 


35.0 


50,0 


20.0 


3.8 


0,20 


94.0 


321/73 


14.5 


2.6 


36,0 


35.0 


3.8 


0.22 


60.0 


322/73 


6.0 


3.0 


35.8 


35.0 


20.0 


0,28 


49.0 


323/ ?3 


H.O 


2.0 


26,8 


20.0 


0.0 


0,10 


29.0 


324/73 


12.0 


154.0 


195,0 


20.0 


3.8 


7,11 


265.0 


325/73 


4.3 


130.9 


150,0 


20.0 


3.8 


6,63 


255.0 


326/73 


57.0 


25.0 


36,8 


32.5 


0,0 


0,55 


105.0 


327/73 


64.0 


21.0 


34,8 


32.5 


0.0 


0,38 


99.0 


328/73 


19.0 


12,0 


20,8 


25.0 


3.8 


0.20 


80.0 


329/73 


24.0 


18.2 


28,3 


20.0 


0.0 


0.35 


96.0 


330/73 


36.0 


60.0 


97,5 


27.5 


60.0 


2.73 


173.0 


331/73 


54.0 


60.0 


95,0 


20.0 


7.5 


2,92 


147,0 


332/73 


7.0 


0.6 


8,8 


15.0 


0,0 


0,06 


7,0 


333/73 


16.0 


16.6 


17,0 


20.0 


0,0 


0,27 


65,0 


334/73 


26.0 


73.9 


87.5 


32.5 


0,0 


3.70 


165.0 


335/73 


23.5 


53.5 


28,8 


35.0 


0,0 


1.94 


129,0 


336/73 


12.0 


34.3 


7.3 


62.5 


5.0 


0.99 


88,0 


337/73 


14.5 


35,7 


6.5 


32.5 


5.0 


1,45 


89,0 



k. 


AS 


CD 


CU 


PB 


HG 


P 


ZN 


U, 




. , , (PPM) . • . . 




(PPB) 


(*) 


(PPM) 










**!*.. 




J6'73** 


"lig' 


**o!i' 


17.5 


*22!o' 


*4o!o* 


N.O. 


24.0 


26,' 7 3 


0,2 


0,0 


14.8 


19.3 


7.5 


N.O. 


15.0 


27i'73 


2.3 


0,2 


5.3 


19.0 


0.0 


N.O. 


18,0 


?7;'73 


3.6 


0,4 


8.3 


20.3 


7.5 


N.O. 


31,0 


27|73 


2.9 


0,1 


15.8 


26.3 


15,0 


N.O. 


24.0 


?7'73 


5.6 


0.2 


16.8 


26,5 


20.0 


N.D, 


26,0 


?7'73 


5.1 


2.3 


11.0 


14.0 


0.0 


N,D, 


17.0 


?7'73 


3.1 


4.0 


25.0 


30.0 


0.0 


N,D, 


30.0 


?7 73 


3.1 


14.6 


30,0 


20.0 


3.8 


0,21 


78.0 


?773 


31.8 


100.0 


132,0 


25.0 


175.0 


4,65 


238.0 


^773 


3.3 


0.5 


24.3 


19,5 


0.0 


N,D, 


30.0 


7 73 


2.5 


1.8 


20.0 


13.0 


0.0 


N,0, 


18.0 


8 73 


U.7 


0.0 


9.3 


17.} 


0.0 


N,D, 


20.0 


8 73 


1,9 


0.0 


13.3 


20.3 


0.0 


N,D, 


23.0 


8 73 


2,5 


0.0 


13.3 


16.3 


0.0 


N,0, 


25.0 


-8 73 


3,1 


0.3 


31,8 


15.5 


0.0 


N,0. 


25.0 


2I|73 


6,6 


0.4 


10.8 


14.3 


0.0 


N,0. 


14.0 


?8i73 


9.5 


16,4 


45.3 


19.0 


0,0 


0,61 


55.0 


8 73 


1.1 


0.0 


24,0 


19.3 


0,0 


N,0, 


31.0 


8 73 


2.3 


0,0 


3,0 


18.3 


0,0 


N,0, 


13.0 


8 73 


3.1 


0,1 


3,8 


16.5 


0,0 


N,0, 


12.0 


?»|73 


0.9 


0,0 


31,3 


15.8 


220,0 


N,0, 


14.0 


9 73 


1.9 


0,0 


15,0 


23.0 


560,0 


N.O, 


33,0 


9 •'3 


2.1 


0,0 


7,5 


18.5 


435,0 


N.O. 


23,0 


^ 73 


0.7 


0.0 


18.5 


11.8 


0,0 


N.O. 


26,0 


9:73 


2.7 


0.5 


8.0 


14.3 


60,0 


N.O. 


21.0 


?9';73 


1.4 


0.0 


3.0 


14.8 


0,0 


N.O. 


21.0 


?»;73 


4,0 


17.7 


27.3 


20.0 


0,0 


0.81 


62.0 


29|73 


13.3 


0.6 


28.8 


15.5 


0,0 


N.O. 


28.0 


?»1,73 


12.5 


2.7 


38.3 


21.8 


0,0 


N.O. 


58.0 


?9<73 


17.3 


0.1 


17.5 


17.8 


0,0 


N.O. 


26.0 


?9'73 


2.0 


1 .5 


15.3 


17.3 


0.0 


N.O. 


43.0 


30^73 


1.0 


0.1 


1.5 


14.3 


75.0 


N.O, 


8.0 


30i73 


0.5 


0.1 


13.8 


1«.0 


3.8 


N.n. 


22.0 


30;'73 


2.5 


'J.l 


2.5 


16,5 


0.0 


N.O. 


9.0 



LAB. 


AS 


CO 


CU 


PB 


HG 


P 


ZN 


NO. 




... (PPM) . . . . 




(PPB) 


(%) 


(PPM) 














338/73 


26.0 


67,5 


49.5 


20.0 


5.0 


3,25 


157.0 


339/73 


17.0 


2,0 


22.0 


20.0 


300.0 


0,12 


21.0 


340/73 


12.5 


2.6 


22.8 


20.0 


247.5 


0.21 


26.0 


341/73 


8.5 


5.0 


7.5 


22.5 


157.5 


0.09 


36.0 


342/73 


17.0 


11.0 


9.8 


32.5 


157.5 


0.15 


76.0 


343/73 


8.5 


23.0 


21.3 


25.0 


5.0 


0.74 


70.0 


344/73 


8.5 


20.2 


12.3 


32.5 


5.0 


0.64 


60.0 


345/73 


17.0 


4.0 


?5.5 


30.0 


90.0 


0-Oa 


35.0 


3^6/73 


23.5 


s-^.o 


110.0 


27.5 


20.0 


2.54 


15<*.0 


347/73 


21.0 


59.0 


97.5 


20.0 


25.0 


2.49 


164.0 


3'-8/73 


4.5 


24, C 


26.8 


25.0 


20.0 


0.7*. 


83.0 


3^9/73 


16.0 


151.2 


135.0 


30.0 


82. S 


9. "2 


255.0 


350/73 


1*'.5 


154.7 


165. C 


■"} . 


62.5 


10.43 


262.0 


351/7? 


2^.0 


J4,ft 


65.0 


4" . 


97.5 


l.-^A 


1?'>.0 



50 



CALIFORNIA DIVISION OF MINES AND GEOLOGY 



SR J 



APPENDIX H 

Precision and Accuracy 

of the 
Analytical Techniques 



The precision of the analytical techniques developed in this 
project was tested to determine the aggregate errors resulting 
from sample splitting, digesting, diluting, and analyzing by ana- 
lytical instruments. Ten replications of samples 607/72 and 167/ 
73 were digested and run as unknowns at various times during 
analyses. Similarly, N.B.S. 120a was digested in ten replications 
and run for phosphorous. The results of this precision test and 
the standard deviations are given in Table 9. 

To check the accuracy of the method of analyses, U.S. Geolog- 
ical Survey standard rock samples G-2 and GSP-1 were digested 



four times, and Canadian Association of Applied Spectrosco] s 
standard rock sample Sulphide Ore was digested two times d 
analyzed several times as the unknown with the other sami ;. 
Unfortunately, these rock standards did not cover the accu y 
of cadmium determination. However, cadmium was anal; d 
two times from two separate digests for each sample. The re ts 
seem to be in good agreement with each other, and the repn i- 
cibility seems to be very good. As a whole, the precisic is 
sufficient for these samples, and the accuracy of the technii s 
is very good. 



Table 9. Precision tests for ten replications of samples 607/72, 167/73, and N.B.S. 120a. 



Element 



#607/72 
(Stream Sediment] 



#167/73 
(Phosphatic Pellets) 



N.B.S. 120 a 
(Phosphatic Limestone 



Mean Standard Deviation 
X s 



Mean Standard Deviation 
X s 



Mean Standard Deviati 
X s 



As 
Cd 
Cu 
Pb 

Hg 

P 
Zn 



10 
10 
10 
10 
10 
10 
10 



3.8 ppm 

2.5 ppm 

10.0 ppm 

23.0 ppm 

19.0 ppb 



3.6 ppm 
1 . 2 ppm 

3.7 ppm 
2.4 ppm 

10.8 ppb 



19.5 ppm 

348.0 ppm 

122.5 ppm 

24.0 ppm 

17.5 ppb 



3.2 ppm 
1 .0 ppm 
2.7 ppm 
1 .5 ppm 
8.5 ppb 



16.42% 



0.12°^ 



40.0 ppm 2.1 ppm 



11.5 ppm 2.0 ppm 



Table 10. Accuracy of arsenic, capper, lead, mercury, and zinc analyses. 



Standard 
Rocks 



Reference 



As (ppm 



^ean 



ange 



Cu (ppm 



■lean 



ange 



Pb (ppm) 



Mean 



Range 



Hq (ppb) 



Mean Range 



Zn (ppm) _ 



Mean Rarn 



U.S.G.S. 
G-2 



Majmundar 



Flanagan 



2/ 



1.2(8)-^ 



0.98(4) 



0.9-1.5 



0.8-1.2 



13(8) 



11(241 



10-15 



2-17 



27(8) 



24-33 



29(18) 15-43 



46(8) 46-47 



47(5) 29-50 



80(8) 74- 
83(15) 42- 



U.S.G.S. 
GSP-1 



Majmundar 



Flanagan 



1.35(6) 1.0-1.75 



1.20(41 



1.1-1.4 



32(8) 



34(251 



28-36 



15-54 



48(8) 



51(191 



42-58 



14-80 



17(8) 16-17 



17(5) 15-41 



110(8) 96- 



114(16) 54. 



J 



C.A.A.S. 

Sulphide 

Ore 



Majmundar 
Webber-'' 



300(4) 
424(8) 



275-350 
250-500 



8273(6) 8180-8360 
8291(16) 4000-12000 



256(13) 236-274 
248(11) 200-310 



NO DATA 
NO DATA 



221(13) 20 : 
298(8) 160 



Motes : 1. Number in parentheses represents number of readings. Four separate digestions were made 
for USGS G-2 and GSP-1, and two separate digestions were made for C.A.A.S. Sulphide Ore. 

2. Flanagan, F.J. (1973). 

3. Webber, G.R. (1965). 



^ 



liO 



DISTRIBUTION OF HAZARDOUS HEAVY ELEMENTS 



51 



APPENDIX I 
Statistical Treatment of Data 



'he results of chemical analyses of arsenic, cadmium, copper, 
lei, mercury, phosphorous, and zinc are recorded in Appen- 
ds F and G. The very highly anomalous values, which are 
irrked with an asterisk (*) in the tables, were considered to be 
rfdom and were not considered in statistical calculations. All 
tl calculations are based on the 201 stream sediment and 259 
Ivrock samples. The results of analyses of cadmium and phos- 
pirous in samples from localities other than those in the area 
uler investigation is given in Table 6. 

hese data were plotted on the maps at the respective sample 
toitions by plotting one element on each map (Figures 5 
tbmgh 17). 

listograms clearly illustrate the effect of the detection limit 
ofhe analytical method. However, histograms can be mislead- 
in because they are strongly affected by slight changes in class 
mrvals. Histograms and cumulative frequency curves, drawn 
frn the same data, can be compared easily. Cumulative fre- 
qincy distribution curves were drawn for all the elements 
arlysed in the present study by the graphical methods described 
byxpeltier (1969). Frequencies were calculated from lowest to 
""est values, plotted against concentration on log-probability 
(Figures 37 through 49), and then used to calculate statis- 
-lu parameters (Table 11). Histograms were constructed (Fig- 
ui. 50 through 62) plotting the percentage of frequencies 
agnst element concentration on 2- or 3-cycle, semi-log paper. 
Stistical parameters were compared with crustal and soil abun- 

here are two reasons for drawing the cumulative frequency 
cue: to check whether it fits a lognormal distribution and, if 
it'ies, to estimate the basic parameters, background (b), coeffi- 
jtts of deviation (s', s) and threshold level (t). The back- 
er ind gives the average concentration levels of the elements in 
a j/en setting. A single straight line shows a single population, 
.iO}ormally distributed. In such a case, the background concen- 
non is indicated by the intersection of the straight line with 
ih 50 percent ordinate, illustrated in Figure 48 for zinc in 
stnm sediment samples. In the case of a perfect frequency 
diiibution curve, the background, calculated in this way, corre- 
pids to the mode and median values and is the geometric mean 
of le results. 

y projecting the intersection of the 84 percent ordinate with 
ihstraight line, a value is obtained which is divided by the 
■*netric mean value to get the geometric deviation (s'). The 
lOjrithm of this value is the coefficient of deviation (s). Coeffi- 
citt of deviation expresses the scatter of the values around (b) 
an corresponds to the spread of the values and their range, from 
'ihlowest to the highest. 

fter obtaining the background and coefficients of deviation 
h third important parameter, the threshold level (t), can be 
.dilated by the following formula: 



l0|: = (log b) + 2 s. 



Where t is threshold level; b, 
the background, and s, the coef- 
ficient of deviation. 



The threshold level represents an upper limit, above which the 
values are considered anomalous. This can be read directly from 
the graph as the abscissa of the intersection of the distribution 
line with the 97.5 percent ordinate. Values greater than this were 
considered anomalous. 

The procedure for calculating the statistical parameters can be 
illustrated easily by taking the example of zinc in stream sedi- 
ment samples. In this study, zinc represents the perfect lognor- 
mal distribution. The background calculated in this case 
corresponds to the mode and median values and is the geometric 
mean of the results. This geometric mean is considered to be 
more significant and a more stable statistic than the arithmetic 
mean. It is less subject to change with the addition of new data 
and less affected by high values. For example, the geometric 
mean of cadmium in bedrocks is 5.2, and the arithmetic mean 
is 27.2, which is greater than the threshold level. In the case of 
zinc, the geometric mean, calculated by the intersection of the 
straight line with the 50 percent ordinate, was 21.5 ppm Zn. 

If (b) is the median value and (s) the standard deviation, then 
68 percent of the population will fall between b-s and b-|-s; and 
97.5 percent of the population will fall between b-2s and b + 2s. 
As 68 percent of the population falls between b-s and b + s, 32 
percent of the population falls outsides this limit (i.e. 16 percent 
of the values fall above b + s and 16 percent below b-s). In 
Figure 48, the values b-s and b + s were obtained by projecting 
the intersection of straight line with the ordinate 16 percent and 
84 percent on the abscissa. As all the frequency curves were 
drawn in logarithmic scale, the ratios were taken into considera- 
tion rather than the absolute values. Thus, points P (at 84 per- 
cent ordinate) and A were determined. OA is the geometrical 
expression of the deviation and is known as geometric deviation 
(s'), which is a factor obtained by dividing the value read at A 
by the value at (1.86 in the case of zinc). Then dividing or 
multiplying the background value (21.5) by the geometric devia- 
tion (1.86), the upper and lower hmits respectively of a range 
that encompasses 68 percent of the population were calculated 
as 11.5 to 40 ppm Zn. Further, dividing or multiplying by the 
squares of the geometric deviation provides a range encompass- 
ing 97.5 percent of the population and extending from 6.2 to 74 
ppm Zn. 

The coefficient of deviation (s) is 0.27, obtained by reading 
the logarithmic of geometric deviation (s'), 1.86 for zinc. The 
third important parameter, threshold level, is the function of (b) 
and (s). In case of symetrical distribution (normal or log nor- 
mal), 97.5 percent of the population falls between b + 2s and 
b-2s. Thus, this upper limit was read directly from the cumula- 
tive frequency curve as the abscissa of the intersection of the 
distribution line with 97.5 percent ordinate and was calculated 
by using the preceeding formula. The threshold level for zinc was 
found to be 74 ppm Zn, taken from the curve as well as calculat- 
ed from the formula. 

In cases where a complex population was sampled (Figures 39 
through 42, 46, and 47), there were two distinct straight lines 
with different slopes, one representing the lognormal population, 
the other the probable anomalous population. The thresholds 



52 



CALIFORNIA DIVISION OF MINES AND GEOLOGY 



SR 



levels in such cases were taken at the break in slope. For exam- 
ple, in the case of Cd (in both, stream sediment and bedrock 
samples), the data show a positive skew in the direction of the 
high values, and the data for Cu (in stream sediment samples) 
show a negative skew in the direction of the low values. In such 
statistical studies the coefficients of deviation are very important. 
It is possible for two populations to have the same background, 
but they will have different threshold levels if their coefficients 
of deviation are different. 



In the case of Cd and Cu, the cumulative frequency distr ■ 
tion curves show two breaks, and the histograms give doi e 
peaks. This dual distribution suggests the presence of two - 
tinct populations. These curves also could be interpreted ^ 
splitting the data at a value taken around the place where |e 
break occurred, separating the total population into two pj 
and drawing two separate curves. In such a procedure, the co I 
cients of deviation and threshold levels may be calculated s* li 
rately for both populations. 



IT) 



999 

998 

995 

99 

96 

95 

90 

^80 

a. 

E70 

60 

°50 

0)40 
u 

1 30 

^20 
o 

iio 



I 

05 

02 
01 
005 



./ 



/• 



/• 



/ 



./ 



/' 



""'01 5 10 2 5,0 l< 

As.ppm 
Figure 37. Cumulative frequency distribution for orsenic in stream sedi ■ 
ments (N= 189). 



999 
998 

995 
990 
980 

950 
900 

800 

^700 

g6Q0 

(^500 

'o 400 

£300 
o 

(^20.0 

<D 

i- lao 

i 5.0 
o 

20 
10 
05 

02 
01 
05 

001 




•Threshold Level 



oQ>T- 



05 10 5 

Cd, ppm 

Figure 39. Cumulative frequency distribution for cadmium in stream sed- 
iments (N= 156). 



99.99 






99.95 






9990 






99.80 




•/, 


99.50 




/ 


99.00 




A 


98.00 


/ 


/ 


95 00 

« 90.00 

a. 


: ./ 

/ 




1 «° °° 


/ 




- 7000 


/ 




% 6000 


/ 




8 5000 


/ 


\\ 


(£ 40.00 
> 3000 


/ 


i 


•5 20.00 


^ 


JmA 


E 

d 10.00 


•^r 




5.00 


/ 




2 00 






100 






0.50 


■ 




020 


■ 




010 


1 1 1 1 1 — 1 — U_l-J 1 1 , — L. 





9990 
9980 
99 50 
99 00 
9800 

9500 
J 9000 

I eooo 

* 70 00 
■£ 6000 
S 5000 
(S 4000 
> 3000 
B 2000 
E 
<J 1000 

500 

2 00 
100 
50 
20 
010 



10 
As.ppm 



Figure 38. Cumlulative frequency distribution for arsenic in bedrock: N 
= 258). 




PosslbU 

Anomaloui 

Populdllon 



Threshold Level 



Figure 40. Cumulative frequency distribution for cadmium in bedroi 
= 235). 



DISTRIBUTION OF HAZARDOUS HEAVY ELEMENTS 



53 



,95 

9 

8 

5 




D 

'h 



n } 

h 



01 



/ 



Possible Anomalous / • 

Low Values / '' 



Threshold Level 




10 10 

Cu.ppm 
Fi(e 41. Cumulative frequency distribution for copper in stream sedi ■ 
rnes (N= 189). 



99 99 
99 95 






. 


99 90 








99 60 
99 50 






/ 
/ 


99 00 
9800 






fx 


9500 






/^^ 'Possible 


J 9000 






/^* Anomalous 
^' Population 


1 






./ ^Threshold Level 


- 7000 






/ 


■£ 6000 
S 5000 
£ 4000 




4/' 


/ 


S MOO 




# 




•2 2000 

E 

(J 10 00 

500 


/ 


/ 




2 00 


. /' 






100 


/ 






50 


/ 






20 








10 









Figure 42. Cumulative frequency distribution for copper in bedrocks (N 
= 259). 



* 



99 



•id 

a 


h 



/• 



/ 



/ 

/■ 



I 10 100 

Pb.ppm 

'8; 43. Cumulative frequency distribution for lead in stream sediments 
!N 167). 



9999 

9995 
99.90 
99.80 

99.50 
99.00 
98.00 



« 9000 

Q. 

I 8000 

^ 7000 
o 

■£ 6000- 

o 50 00 

a. 4000 

> 3000 

•| 2000 

E 

O 10 00 

5 00 

2 00 
I 00 
050 

020 

010 



/ 

o / 
Q. / . 

(Si / 



Possible 

Anomalous 

Populotion 



/ 



^. 



Threshold Level 




I 10 too 

Pb, ppm 

Figure 44. Cumulative frequency distribution for lead in bedrocks (N = 
259). 



54 



CALIFORNIA DIVISION OF MINES AND GEOLOGY 



SR 



999 

99 8 

99 5 
990 
980 

950 

900 

-3? 800 ■ 

a. 

§ TOO 

en 

- 600 

o 

^ 500 

<D 

400 
a> 

a 30.0 

2 2Q0 
_o 

1 100 

^ 50 [ 

20 
I 
05 

02 
01 
005 



/ 



/ 



/ 



/ 



/ 



I 10 100 

Hq.ppb 
Figure 45. Cumulative frequency distribution for mercury in stream sedi 
ments (N= 153). 



99 99 

99 95 
99 90 
99 80 

99 50 
99 00 
98 OO 

9500 

g 9000 

i 8000 

w 

^ 70O0 
c 6000 
if 5000 

a. 4000 

> 30O0 

■f 2000 
E 
3 10 00 

5 00 

2 00 
1.00 
50 

20 

10 



Possible > 

Anomolous / 
Population- 



Threshold el 




I 10 100 

Hg.ppb 
Figure 46. Cumulative frequency distribution for mercury in bedrock N 
= 135). 



99 90 
99 80 

99 50 
99 00 
9800 

95 00 



8000 
7000 
6000 
50 00 
4000 
3000 
20 00 

10 00 

5 00 

2 00 
1.00 
0.50 

020 

10 ■ 




Possible 

Anomalous 

Population 




P,% 

Figure 47. Cumulative frequency distribution for phosphorus in bedrocks 
(N = 97). 



b-2s lOb-s b 

Zn, ppm 

Figure 48. Cumulative frequency distribution for zinc in stream sediinl 
(N= 198). 



I'O 



DISTRIBUTION OF HAZARDOUS HEAVY ELEMENTS 



55 



99 99 
99 90 




99 90 




9950 
9900 


/ 


98 00 


y 


9500 


/ 




/ 


» 9000 

Jeooo 




% rooo 


./ 


J 8000 


,/ 


S 50O0 


,/ 


a 4000 


,/ 


5 3000 


/ 


1 2000 




E 


/ 


O 1000 


/ 


500 


/ 


200 


/ 


100 


y' 


O50 


./ 


020 


/ 


0.10 
nni 





Figure 49. Cumulative frequency distribution for zinc in bedrocks (N= 259). 



As. ppm 



^ rh-TTT 


— 



14 2 29 39 65 78 



15 21 50 42 60 



(2 16 5 23 36 46 64 90 



Hgs 50. Histogram for arsenic in stream sediments. 



Figure 51. Histogram for arsenic in bedrocks. 



Cd, ppm 
^•8! 52. Histogram for cadmium in stream sediments. 



I 



Oi 16 25 04 06 



22 35 54 8 13 2C 3i 50 78 l20 190 300 470 740 

Cd, DpiTi 



Figure 53. Histogram for cadmium in bedrocks. 



56 



CALIFORNIA DIVISION OF MINES AND GEOLOGY 



SR i 



Cu, ppm 

Figure 54. Histogram for copper in stream sediments. 



Pb. ppm 

Figure 56. Histogram for lead in stream sediments. 



I 14 2 2 8 4 5 6 8 II 16 22 31 44 60 

Cu, ppm 
Figure 55. Histogram for copper in bedrocks. 



10 II25I25 14 1575 175 1975 22 25 28 315 35 395 44 495 

Pb, ppm 



Figure 57. Histogram for lead in bedrocks. 



n 



Hq, ppb 
Figure 58. Histogram for mercury in stream sediments. 



Lin 



20 






































IS 
















6 








1 
i 


^ <« 










Q. 












fc 12 














) 


o "^ 
















r- 


Z 8 

e 




, 












— 


1— 1 




Z 6 




















[— 












4 










































— 
















1 





195 25 34 39 39 64 77 92 12 15 I9 24 30 37 47 69 




Hg, ppb 


Figure 59. 


Histogram for mercury in bedrocks. 

1 
1 






































1 



I 



DISTRIBUTION OF HAZARDOUS HEAVY ELEMENTS 



57 



01 016 02« 038 05 095 15 23 36 59 9 H 22 35 55 



14 22 34 



Figure 60. Histogram for phosphorus in bedroclcs. 



I r 



Zn,ppm 

igui61. Histogram for zinc in stream sediments. 



E 

a 15 



j=n 



14 Z 2S 



22 31 44 60 66 120 170 240 340 480 



Zn.ppm 
Figure 62. Histogram for zinc in bedrocks. 



abi 


7 /. Various parameters calculated 


on the basis of cumulati 


ve frequency curves. 










jrameters 


As 
(ppm) 


Cd 
(ppm) 


Cu 

(ppm) 


Pb 

(ppm) 


Hg 
(PPb) 


P* 


Zn 

(ppm) 




Id Level (t) 
ic Mean ( 3) 
Mc Mean 


Stream 
Sediments 

9.25 

1.4 

2.4 

0-11.40 


Bedrocks 

38.0 

7.0 

10.3 

0-72 


Stream 
Sediments 

1.5 

0.2 

1.4 

0-25.6 


Bedrocks 

15.0 

5.2 

27.2 

0-625 


Stream 
Sediments 

13.0 

5.1 

7.6 

0-3S 


Bedrocks 

40.0 

19.0 

30.7 

3-195 


Stream 
Sediments 

29.0 

/.9 

9.7 

0-54 


Bedrocks 
33.0 

20.0 
21.0 
10-63 


Stream 
Sediments 

64.5 

23.4 

21.3 

0-88 


Bedrocks 
50.0 
12.5 
27.2 

. 560 


Bedrocks 
1.00 
0.52 
2.56 

0.06-17,11 


Sedimenls 
74.0 
21.5 
2:^.6 
0-97 


Bedrocks 

250.0 
40.0 
46.0 

3-46T 


}u 

6« 


■ibundanre 
r, 1964) 

ince in Soils 
>grdclor, 1959) 


i.a 

5.0 


0.2 
0.5 


55.0 
20.0 


12.5 
10.0 


30.0 
10.0 


0.105 
0.080 


70.0 
50.0 




bsed on ai-..ilys 


es of only 


97 samples 

























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