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The Characterization of the Chesapeake Bay
A Svctc;aatic Analysis of Toxic Trace Elerr.e-nts
(U.S.) National Bureau of Standards
Washington, DC
PB82-265265
Prepared for
Environmental Protection Agency
Annapolis, MD
Region ill Library
Environmental Protection Agency
Sep 82
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EPA Report Collection
Information Resource Center
US EPA Region 3
Philadelphia, PA 19107
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I I'.\ ()()()/3-82-08S
September 198:
?D8 2-26 526 r>
THE CHARACTERIZATION OF THE CHESAPEAKE BAY:
A SYSTEMATIC ANALYSIS OF TOXIC TRACE ELEMENTS
Howard M. Kingston, Robert R. Greenberg,
Ellyn S. Hc-ary, Billy R. riardas,
John R. Moony, Theodore C. Rains
Center for Analytical Chemistry
arid
Walter S. Liqgett
Center for Applied Mathematics
National Bureau of Standards
Washington, DC 20234
Grant No. EPA-79-D-X-0717
Project Officers
Ernest L. Garner and Howard M. Kingston
Center for Analytical Chemistry
National Bureau of Standards
Washington, DC 20234
NATIONAL TECHNICAL
INFORMATION SERVICE
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TECHNICAL REPORT DATA
n-jns 01 the rci\-r;c uiivr
1. RfcPC'l ' NO.
2.
3. RECIPIENT'S ACCCSSIOf*NO.
26
4. TITLt -«Q SUBTITLE
Systcr.UiCic Ar. ilyj.is of To:-:ic Trace Ulemc'ics
5. NEPORT DATE
4. PERFORMING ORGANIZATION CODE
C300
7. AUTMOHiil
Howard M. Kingston, Robert R. Greenber,;, F.llyn S. Bear,
Billy K. H.irdas. .Ichn R.. Moody, Theodore C. Rains, I.
8. HERtQHMING OHGANIMATION HEPOMT NO.
9. Pfc. /COMING OHGANUATICN NAMt AND ADDRESS
Conner for Applied >'athenuittcs
National Bureau of SlnndarJs
U'a;;iiinr;t.on, 0. C. 2023'*
§_ Li"!'C>tt
1O. PHCGHAM tLEVENT NO.
_ __
11. CONTHACT/GHANT NO.
79-0-X-0717
12. SPONSORING AGENCY NAME Af*O AOOHESS
Chesapeake Bay Pro.^ra;.:
2083 '..'etit St. , S'lite 3C
Annapolis, Maryland 21401
13. TYPE Of REPORT AND PERIOD
Tcchtiiral
14. SPONSORING AGENCY COC"
EPA
15-SUPf LEMENTARY NOTES
16, AaST HACT
As p.)ft of » inbit.dis-tip'.iarv Muciy ol th=j Che^iDedko Bay. (he Ha'.'vnyt Bureau of Siandards JNBS) was asked to develop the technique-, and
procedures. ne:ei>Sdrv to measure (he ifdce ar,J toxic eier cnt concentralions Wlt^ m the water column throughout the length of the Cries .jcake
B_, Sc. Sn, Th. U and Znj, including some elements at concentrations consijiertly below one picoyrf in per
.nil'il'ie- (part per tn'iion! Th0 cnaroctenzanon of the C'lesapertke Bay can bf- «-v,<2£-d into dvu ma.or phases The f rst tn< ludeci the develjp'nefit
a^d corsu ction o' a m-nphng system lor tile trace meitsMic e'oments dissolved 11 water, ard a filtration system for collecting ihe pariirul ite
p'&mer*ai coT'^onent
The = fcond ohase cons sted of sampling, chemical stabilization by acid.ficjtion and stor ige of the samples in ihe fie d
The third piase of activity consisted of the chemical separation and preparation of samples for the analytical i-istrurr enul methods Thfttc-
chemical sepjrafons had been developed prior to in,*, application
The fourth major pf.ase consisred o* tne nstrumentd) analysis of the s?-nples fc the trace elements
The fifth major phase involved data reduction and evaluation of the statisucal significance of tne blank
KEY WORDS AND DOCUMENT ANALYSIS
DESCRIPTORS
. O I i T ^ I b ij T ' Q N S 7 A T r. V E N 7
Si'e attached.
b.lDENTlFIERS/OPEN ENDED TERMS
13. SECURITY CLASS , 7/irj Kepor ;
Unclassified
20 SECURITY CLAS5 jT.'lij pnxe
Unclassified
c. COSATI ' 'Cltl/Group
l. NO. OF
112. PRICE
EPA Form 2220-t (9-73)
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/,
DISCLAIMER
Certain commercial equipment, instruments, or materials are identified
in this paper in order to adequately specify the experimental procedure.
Such identification does not inply reconrnendation or endorsement by th<3
National Bureau of Standards, nor does it imply that the materials or equip-
ment identified are necessarily the best availab e for the purpose.
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iijtuum
FOREWORD
I
I
This status report is submitted in partial fulfillment of the require-
ment and conditions of Grant Number EPA-79-D-X-0717, "The Characterization of
the Chesapeake Bay: A Systematic Analyses of Toxic Trace Elements". The
period covered by this report extends from April 1979 to the end of September
1931.
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BRIEF
As part of a nultidisciplinary study of the Chesapeake Bay, the National
Bureau of Standards (NBS) was asked to develop the techniques and procedures
necessary to Pleasure the trace and toxic element concentrations within the
water column throughout the length of the Chesapeake Bay, The Inorganic
Analytical Research Division of the Center for Analytical Chemistry at NBS
has completed the analysis for selected elements (Cd, Cc, Co, Cr, Cu, Fe, MM,
Mo, Ni, Pb, Sc, Sn, Th, U, and Zn), including some elements at concentrations
consistently below one picogram per milliliter (part per trillion). The
characterization of the Chesapeake Bay can be divided into five major phases.
The first included the development and construction of a sampling system for
the trace metallic elements dissolved in water, and a filtration system for
collecting the particulate elemental component. This sample collection
system consisted of an all plastic system, using a magnetically driven
plactic pump with conventional polyethylene tubing, and included conventional
polyethylene storage drums of high purity water used in flushing of the
system. The apparatus was designed and constructed at MBS.
The second phase consisted of sampling, chemical stabilization by
acidification and storage of the samples in the field. This was accomplished
aboard the R/V Retriever, with the cooperation of both the Maryland Geologi-
cal Survey and Virginia Institute of Marine Sciences, for sample logistics
ai,d acquisition. The total complement of 102 samples was obtained, filtered,
acidified and stabilized. There were also 51 replicate bottom samples
obtained and frozen for archival use. A series of over 30 blanks were also
prepared and integrated with the 102 water samples to be analyzed. The
stabilization and storage of the water samples used some of the methodology
and experience gained on SRM 1643a, Trace Elements in Water, and stability
studies of a quantity of Chesapeake Bay water which has been under study for
several years.
The third major phase of activity consisted of the chemical separation
and preparation of samples for the analytical instrumental methods. These
chemical separations had been developed prior to this application. A few
post separation matrix alterations were made for specific instrumental
efficiency optima. The chemical manipulation involved the preparation of
samples for analysis using two major instrumental efforts, neutron activation
analysis (flAA) ana graphite furnace atomic absorption (GI'AA). A major
porticn of this effort also involved quality assurance. This was partially
accomplished by utilizing standards preoaration and NBS Standard Reference
Materials (SRM's), specifically Trace Elements in K'ater, 1643a; interspersion
of these materials was utilized in the chemical and instrumental phases of
the work. The chemical separation/sample preparation stage of this work has
been described in the literature for both instrumental techniques [1,2].
i v
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I
The fourth major phase consisted of the instrumental analysis of the
samples for the trace elements. This ph^se places most of the burden for
analysis on NAA and GFAA with isotope dilution mass spectrometry (IDMS)
contributing isotopic and concentration daca for uranium. The total number
of elemental concentrations resulting from the analyses of the contracted
elements exceeded 3,000 and involved several thousand more unreported analyses
totaling over 5,000 separate determinations.
The fifth major phase involved data reduction and evaluation of the
statistical significance ~>f the blank. The blanks were statistically modeled
for each element, and the blank and uncertainty of the blanks were applied to
the data. The concentrations were adjusted uniformly tu at least the 95"
confidence 1imit.
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INTRODUCTION AND HISTORY
This report describes the National Bureau of Standards (NBS) efforts in
c\ multidisciplinary study of the Chesapeake Bay coordinated by the Chesapeake
Cay Program Office of the U. S. Environmental Protection Agency. The NBS
used the best available technology to determine the trace and toxic element
concentrations in the water column. As part of this program, the NES has
collected and analyzed both the dissolved and suspended particulate fractions
of 102 water Simples covering the entire length of the Chesapeake Bay. The
elements of interest include Cd, Ce, Co, Cr, Cu, Fe, Mn, Mo, Ni, Pb, Sc, Sn,
Th, U, and Zn. These analyses were accomplished using specific chemical
preconcentration, separations and manipulations to prepare the samples for
analysis by Neutron Activation Analysis (NAA) and Graphite Furnace Atomic
Absorption Spectrometry (GFAAS).
The literature of marine water analysis reflects the considerable
difficulty in establishing an accurate and precise method of analysis for
trace metals. A seawater matrix defies a simplified approach. For example,
specific sampling techniques, container contamination, suspended particulate
matter, and analytical techniques have to be considered. The solving of the
analytical problem is of little value unless a representative sample can be
obtained free of contamination and properly stored until analysis.
In recent years, methods have been developed to determine trace elements
in seawater by X-ray fluorescence [4], neutron activation [5,6], spectro-
Dhotometry [7], anodic stripping voltanroetry [8], and atomic absorption
spectrometry [9-11]. However, each of these analytical techniques requires a
jreliminary separation. Fabricand, et al. [12], reported the direct
determination of Cu, Fe, Mn, Ni, and Zn in seawater by atomic absorption
Spectrometry (AAS) using an air-acetylene flame, but other workers have
reported difficulties using their technique because of light scattering and
burner clogging.
Except for neutron activation analysis and anodic stripping voltammetry,
no analytical techniques are currently available for the untreaced sample
determination of trace elements in seawater at concentrations below 5 ug L'1.
Jsually it is necessary to preconcentrate the trace elements from a large
volume and separate the transition elements from the alkali and alkaline
earth elements. In such sample preparations, the efficiency of concentration,
completeness of separation, and total analytical blank become critical to the
final instrumental method [13].
Preconcentration techniques which have been used include coprecipitation
[14], chelation and extraction [15], and chelating ion-exchange resin [13,16].
1
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Most of these separation and concentration methods require large volumes of
chemical; which can lead to high blanks unless the reagents have been
carefu'ily purified.
Of the presently used preconcentration techniques, Chelex 100 chelating
resin has been shown to be efficient and yields low analytical blanks [17].
Applications of Chelex 100 resin for trace metal preconcentration from
seawater have been reviewed by Riley and Skirrow [13]. Chelex 100 is a
strong chelator and removes metal ions from most known naturally occurring
chela-tors in seawater [17-19]. The resin will not, however, remove metals
held in organic and inorganic colloids which can be present even after
ultrafiltration. Precautions must be taken to destroy such colloids prior to
collection of the ions by the resin. Florence and Batley have reported
destroying interfering organic colloids by the addition of 0.16 M nitric acid
and heat and also by using ultraviolet irradiation of the sample prior to
collection on the resin [18,19]. While excellent recovery and low analytical
blanks are achieved, relatively high concentration of Na, K, Ca, and Mg are
retained with the trace metals. The concentrations cf these interfering
alkali and alkaline earth salts in the final sample are in milligram
quantities, as compared to the microgram and submicrogram quantities of
concentrated trace metals. The alkali and alkaline earth ions occupy the
resin sites not occupied by the transition metals and are co-eluted with the
metals when using acids [16].
A more recent separation procedure utilizing Chelex resin produced a
sample devoid of alkali, alkaline earth, and halogen elements, and left a
dilute nitric acid/ammonium nitrate matrix containing only the trace elements
of the seawater sample (Kingston and Rains, et al. [1]). This procedure was
used in conjunction with GFAA to analyze Chesapeake Bay estuarine and Gulf of
Alaska seawater samples [1'j. The method was also modified and the resin was
irradiated directly without elution, in conjunction with a NAA technique
utilizing these same samples and MBS SRM 1643a, a trace element water
standard [2]. The technique has also been applied to x-ray fluorescence
(XRF), utilizing the same Chesapeake Bay water sample and NBS SRM's 1648 and
1632, environmental samples, urban particulate and trace elements in coal
[3].
With the graphite furnace it is possible to determine 10~3 to 10~12 g of
many of the trace elements in seawater. However, the high salt content (35
g/kg) in marine water makes it difficult to effectively volatilize the matrix
without loss of analyte. The major component in seawater is sodium chloride
which has a relatively high volatilization temperature. Also, the trece
metals in seawater are present as chlorides, which have a lower volatiliza-
tion temperature. Therefore, it is difficult to volatilize the sodium
chloride during the ashing step without losses of the analyte. Calcium and
magnesium chloride are also present in seawater in "large quantities, and a
temperature greater than 2000 °C is required to volatilize these elements.
Thus, even if the sodium chloride were removed during the ashing step using
matrix modification [20], residual calcium and magnesium chlorides remain to
interfere with the analyte during atomization. These factors make separation
prior to GFAA analysis necessary.
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While the Chelex resin procedure produces a highly desirable and
appropriate aqueous matrix for most spectroscopic methods of analysis, a
solid satr.ple would be more appropriate for other instrumental techniques [3]
such as XRF or UAA [2]. In addition, the above separation procedure also
makes it difficult or impossible to analyze several elements which are held
strongly by the resin but cannot be quantitatively eluted. Chromium and
vanadium exhibit this type of behavior, and attempts to reproducibly elute
these elenents from Chelex 100 have not been totally successful.
NAA has the inherent sensitivity and accuracy to determine a number of
important trace elements in seawater at their naturally occurring levels.
Unfortunately, a salt water matrix is not well suited for activation analysis.
The use of liquid samples limits both the amount of material and the length
of irradiation available in most reactor facilities. The high levels of Na,
Cl, and Br produce an extremely high background level of radiation that
totally obscures the signals of most elements whose neutron activation
products have comparable half-lives.
Greenberg and Kingston [2] described a method of preparation for solid
samples from 100 ml of estuarine or seawater, using Chelex 100 resin,
followed by the determination of 12 trace elements by NAA. Using this
procedure, typical reduction factors of ^107 for Na, >105 for Cl, and >103
for Br are observed. This procedure has been used to analyze NBS SRM ",6423,
as well as high salinity water sample:; collected near the mouth of the
Chesapeake Bay.
Although one of the major advantages usually associated with NAA is the
possibility of post-irradiation chemistry thus eliminating the problems
associated with reagent blank and other types of contamination, the u<->e of
pre-irradiation chemistry for high-salinity waters has significant advantages.
The removal of Na, Cl, and Br greatly reduces the background level of radia-
tion during short and intermediate counts, and allows the determination of
elements not otherwise possible without some type of separation. The removal
of the matrix elements also greatly reduces the radiation dose received by
jersonnel, especially if radiochemistry is used. The preconcentration of 100
100 ml of liquid to a sample of less than 0.5 gram increases the sensitivities
for most elements and allows rare samples to be irradiated within a single
Babbit. Although other non-chemical concentration steps, such as lyophiliza-
tion, could be employed prior to irradiation; they are relatively difficult
to use with high salinity water, they leave the salts with the elements of
interest, and can also increase the blank from the equipment used. Finally,
".he use of Chelex 100 pr;or to irradiation produces a solid sample which
eliminates the problems of storage, irradiation, and handling liquid samples
for NAA.
Even without pre-chenistry, the number of sample manipulation steps
required before the irradiation of a high salinity water sample is consider-
able, including: collection; filtration; stabilization (usually by
acidification); storage and encapsulation for irradiation. Extreme care
during all these steps is necessary to prevent contamination of the samples.
Extending the pre-irradiation treatment to include the Chelex 100 concentra-
tion/separation step produces significant benefits for the additional effort
required.
3
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EXPERIMENTAL
REAGENTS
High purity water, nilric and glacial acetic acids were prepared using
subboilinj distillation at NBS [21]. All reagents used in the separation
process were preoaied in this manner and stored in clean FEP Teflon bottles
unless otnerwise stated.
Ammonium hydroxide solution was prepared by bubbling filtered ammonia
gas through high purity water until room temperature saturation was achieved.
A 1.0 M ammonium acetate solution was prepared by mixing 60 g of puri-
fied glacial acetic acid and o2 g of saturated NHUOH and diluting to 1 L in
a pre-cleaned polypropylene volumetric flask. The acidity was adjusted to a
pH range of 5.1 to 5.4 by dropwise addition of acetic acid and/or NH..OH.
All reagent and sample preparations were done in a class 100 clean air
laboratory [22].
Cheiex 100 chelating resin, 200-400 mesh size, was purchased from Bio-Rad
Laboratories.
SAMPLES
The 102 water samples were obtained from June 12, 1979, to July 6, 1979,
and tne sampling area extended from the mouth of the Chesapeake Bay or
coastal Atlantic Ocean water to the mouth of the Susquehanna River. A map
showing these approximate sample locations can be seen in Figure 1, The
sampling locations, the time sampled, and the sample patterns were coordinated
by Maryland Geological Survey and Virginia Institute of Marine Science. The
Maryland Geological Survey station reference numbers, the date, time, depth,
number of filters used, density and sample number for the samples is compiled
in Appendix 1.
SAMPLING EQUIPMENT AND PLACEMENT
The sampling equipment was designed for cleanliness and the ability to
take a sample with a minimum of elemental perturbation and contamination.
Simplicity was also a consideration, since the field operation of the system
could be under extremes in weather and physical conditions.
The system used a magnetically-driven, glass-filled, epoxy-resin pump
(using ceramic bushings). The pump assembly was dismantled and subjected to
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Fiqure 1.
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XRF analysis and found to contain only trace quantities of one element being
investigated. Only iron at the yg level was detected using the full depth
of the energv dispersive x-v-ay system.
The tubing used was conventional polyethylene (CPE) of 1 inch (2.5 cm)
in diameter. It was connected to the pump and storage by polyvinvl-
chloride (PVC) valves, tubing connectors or T's. The lowering mechanism was
a manually operated wooden drum sealed with polyurethane. The tubing was
placed through a polyethylene sling on a ship's davit and extended approxi-
mately 1 meter T'rom the ship for bottom sampling. The depth was marked on
the tubing with plastic tape at 5-f't. (1.52 rn) intervals. The bottom sampler
consisted of a 200-ft. (61 in) coil of tubing joined using one PVC connector.
The bottom of the tubing was coiled with the opening pointing up. A concrete
weight inside a 1/8-inch (0.32 cm) PVC plastic was coated with paraffin and
suspended 1 meter from the tubing opening using polypropylene cord. The
polyethylene tubing, being less dense than water, would float if the weight
actually touched bottom. However, the depth of the sampling site was
monitored using the ship's depth sensing equipment, and the lowering of the
equipment stopped above bottom, using the known depth and the length of the
tubing lowered. The bottom sample war, taken nominally 1 meter from the
bottom although in a few cases this distance was greater due to current
affect. The surface samples were taken in two ways, with two different
techniques, depending on the current.
In minimal or no current (only 5 of the surface samples), a specially
constructed float was placed on a 50-ft. (15 r;) piece of 1 inch (2.5 cm)
CPE tubing and held 7 n from the side of the ship, with the tubing 1 meter
down pointing at a 303 angle away from the ship. The float was constructed
of a 3-inch (7.6 cm) block of styrofoam, sandwiched between two sheets of
olexiglass sealed using silicon sealant, with a plexiglass <"'jbe to guide the
CPE sample tube and plexiglass hook. To the hook was attached a 24-ft.
(7.3 n) stainless steel rod all totally encased in 1/8 inch (0.32 cm) of CPE
had been heat sealed.
The majority of surface samples (95 ' of the samples) was taken with the
CPE tube taped 2 meters above the polyethylene encased hook previously
described. The hook was inserted into the water holding 1 meter of the CPE
tube below the water surface from the bow of the ship into the current.
The pumping equipment was a sealed system, and only the bottom sampler
and surface sampler were exchanged using a PVC disconnect. No glue was used;
the system was held together entirely by pressure-fitting tubing over PVC
connectors and then clamping using stainless steel hose clamps externally.
Once assembled, no pieces of equipment were replaced. A diagram of the
sampling system can be seen in Figure 2.
The filtering and stabilization of the samples were accomplished in a
small laboratory module on the stern of the ship, equipped with a class 100
clean bench. The work surface was covered with a plastic adhesive-backed
paper used in the NBS clean laboratory for a bench covering to sea'i the
'working surface.
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The filtering was accomplished utilizing Ami con and Millipnre
0.45 micrometer filters, each from a single lot. The filter holders were
Bio-Rad Laboratories polypropylene filter holders modified with a Teflon tube
on the exit. This tube fit through a hollow polyethylene stopper in a large
bell jar, and the sample bottle was placed in the bell jar under th3 filter
apparatus.
The acid was added from a quartz repipet constructed to deliver precisely
32 ml repeatedly 1,0 all sample bottles.
The sample bottles were all polyethylene CPE froa a single lot of
plastic. They were cleaned in 1:4 MCI and 1:4 UNO-, acid, alternately, for
two weeks in each acid, then rinsed and filled with high purity water [23].
Their variance in volume was investigated prior to use.
A discussion of the cleaning and suitability of the plastics and
materials used for construction and storage in trace chemical analysis is
given by Moody and Lindstrom [23].
These bottles were given a number, using the 11,000 series. Teflon FEP
bottles for long-term storage were numbered in the 10,000 series. These
numbers were inscribed onto the surfaces of the bottles.
SAMPLING PROCEDURE
T/.'o primary considerations were the prevention of contamination during
collection of the samples, and the stabilization of the two components prior
to analysis.
The bottom sample was collected by lowering the CPE tubing to the pre-
scribed depth, purging the syslem with estuarine water and allowing the same
water sample to flow through tne system for 30 minutes. The Pow rate was a
liter every 2 seconds, or 900 liters in the 30 minutes prior to collection.
A 2-liter CPE bott.e was rinsed three times with tlie sample, and then the
sample was collected and capped. It took four seconds to fill the collection
bottle. The collection bottle was cleaned and rotated between samples, being
used once every 4-5 days. It was cleaned between uses with 1:4 reagent grade
H:i03 and high purity water [23,24].
The filtration of the bottom sample was started while the upper water
column sample was being obtained. The variety of loadings required the use
of one, two, or three filters depending on the solids content of each liter
filtered. The sample bottle with the 32 mL of NBS high purity HN03 was
placed under the filter apparatus and filled to the bottle rim. Each bottle
contained 1062.5 mL, with 0.29 relative uncertainty (2s) between 12 bottles.
This was done in duplicate to provide a separate participate filter for both
GFAA and NAA. The second bottle of filtered sample was unacidified and used
to determine density, using a close range hydro.i.eter and thermometer, and
then discarded. The two sets of filters were placed in plastic filter
holders and labeled. The acidified bottle containing the aqueous sample was
placed in a CPE polyethylene bag sealed and stored in a wooden chest for
transport.
8
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While the sample was being filtered, another member of the team retracted
the bottom sampler, and the surface sampler was attached, as described, using
the PVC disconnect. The sampler was lowered to approximately 1 ± 0.3 meters,
as described, and the sample was pumped for 10 minutes at a rate of 1 liter/
2 seconds, until 300 liters of sample had passed through the system. Two
liters of the surface sample were collected using the same technique
discussed for the bottom sample. The same filtration procedure was applied
immediately upon collection. Prior to shutting down the sampling system, the
system was backflushed with UBS deionized-distilled water to flush the pump
and valves and then closed off by the valves.
An outline of the sampling procedure is shown in Figure 3, and an
overview of the sample division is shown in Figure 4.
COLUMN SEPARATION APPARATUS
The Isolab QS-Q polypropylene column with porous polyethylene resin
support was used with the QS-S 25-mL conventional polyethylene extension
funnel attached to the column to act as a reservoir for the samples.
QUALITY ASSURANCE
UBS SRM 1643a was used as a quality assurance check on the chemistry
separation preconcentration and on the instrumental methods. This material
is a synthetic water standard designed to approximate a filtered and
acidified fresh water sample. The concentrations of 17 elements have been
certified by MBS, using 'wo c more independent analytical techniques or a
reference method of known accuracy [25,26]. The ciemical preparation of
these standards were identical to the Chesapeake Bay samples and they were
dispersed among tne analyses of the dissolved samples.
COLUMN PREPARATION AND PURIFICATION PROCEDURE
The polypropylene chromatographic columns, used to hold the Chelex 100
resin, were soaked for one week in 4 M HN03 and one week in 3 M HC1 before
use. After rinsing with water, a slurry corresponding to 3.2-3.4 mL of
hydrated resin in the sodium form (about 400 rug dry weight) was loaded into
each column. Thr- resin was washed with three 5-mL portions of 2.5 M HN03 to
elute any t;ace metal contamination. Excess acid wos removed by washing the
resin with two 5-mL volumes of high purity water. The resin was transformed
to the NHU+ form by the addition of two 5-r,iL volumes of 2.0 M NH^OH. The pH
of the last few drops eluted was checked using pH paper. If they were not
basic, additional tiH^OH was added until basicity was achieved. Residual
NHUOH was removed from the resin with two 5-mL water washes.
SEPARATION PROCEDURE
The seawdter samples, which had been filtered and preserved with HNOo,
were adjusted to a pH range of 5.2-5.7 by dropwise addition of NH4OH. A few
drops of 8 M ammonium acetate was then added to aid in buffering the system.
A small amount of the sample was added to the column to allow the resin to
undergo its normal shrinkage as it changes in pH and ionic form. The 25-mL
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Water Sampling Procedure Outlined
Lower tubing to depth minus one meter
Purge sampler of air using Bay water
Sample pumped continuously for 30 minutes at 1 Hter/2 sec
2 liter sample collected in clean thrice purged polyethylene
Sample commenced filtration within minutes
Surface sasnpler connected in place of bottom sampler
Surface water pumped for 10 minutes at 1 liter/2 sec
2 liter sample collected in clean thrice purged polyethylene
Sample commenced filtration within minutes
Sampler back flushed with high purity water prior to shutdown
Figure 3.
10
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!e Distribution
Water Sample
Filter for
Graphite
Furnace
Atomic
Absorption
(GFAAS) of
Particulate
2L Sample
1 Liter of Filtered Water
Acidified with High Purity
HNO3 to 0.5N
100 ml Portions Taken by
Weight for Chemical Separation
and Preconcentration
tf
K
Water Sample
for
GFAAS
Water Sample
for
NAA
Filter from 1 Liter Filter from 1 Liter
Filter for
Neutron
Activation
Analysis (NAA)
of Particulate
1 Liter of Filtered Water
Used for Density and Temperature
Taken at Time of Collection
Figure 4.
polyethylene reservoir atop the column was then filled, and the sample passed
through the resin at a flow rate of about 0.8 mL/min. After the sample had
passed through the resin, the resin was washed twice with 5 ml of water, and
four 10-mL volumes of 1.0 M ammonium acetate were added to selectively elute
the alkali and the alkaline earth metals. Residual ammonium acetate was
removed with two 5-mL water washes.
At this point, the preparation of the aqueous samples diverged. For NAA,
the resin was air dried in the column under a class 100 clean air facility and
transferred to an acid-washed, 0.025-mru (1 mil) linear polyethylene (LPE) bag.
This bag was heat seeled and sealed within a second bag made of 0.10-mm
(4 mil) CPE, to prevent contamination during handling and irradiation. LPE
was used for the inner bags, due to its lower blank levels (compared to CPE),
11
-------
while the outer bags were iiade of CrE, due to the greater flexibility of this
material after neutron irradiation. Although LPE is, in general, stronger
than CPE, it becomes brittle after long irradiations and h?s a tendency to
crack. For GFAA, the transition metals were eluted using 7 mL of 2.5 M HN03
and collected into clean, preweiqhed 10-inL conventional polyethylene bottles.
The bottles were capped with clean polyethylene-lined caps and reweighed to
determine the weight of the effluent accurately.
STANDARDS
Two types of mlcielemental standards for NAA were used. The first type
was prepared by pipetting known amounts of milltielemental solutions onto
5.5-cm Whatman 41 filters. The filters were air-dried, pelletized, and
doubly sealed in polyethylene bags [27]. The second type was prepared by
pipetting standard solutions directly into LPE bags containing approximately
400 mg of dry Chelex 100 resin in the ammonium form, which had been prepared
using the column preparation procedure previously described. The resin was
allowed to dry at room temperature under class 100 conditions, after which
the bags were sealed and placed within second CPE bags. Molybdenum and
uranium were in separate standards, since significant amount1; of "Mo are
produced from uranium fission.
IRRADIATION AND COUNTING PARAMETERS FOR NAA OF DISSOLVED SAMPLES
The sealed samples (10-12) were packaged for irradiation with standards
and blanks, and occupied tv/o levels within the polyethylene irradiation
container (rabbit). Fach rabbit was irradiated for 4 hours in the RT-3
pneumatic tuba facility of the NBS reactor. This facility has a thermal
neutron flux of 5-101 °n-cuffs'1 [28]. Midway through the irradiation the
rabbit was removed from tiie reactor, flipped end-over-end, and reinserted
into the reactor to compensate for the linear neutron flux drop-off. After
appropriate decay intervals the samples were counted with Ge(Li) and Ge(HP)
detectors having active volumes of 60-90 cm3. A Nuclear Data ND6620
computer-based analyzer system was used for data collection and reduction.
A more detailed description of this analytical method can be found in
Appendix 2.
[RRADIATION AND COUNTING PARAMETERS FOR NAA OF PARTICULATE SAMPLES
The samples, consisting of one, two, or three filters, were folded and
sealed in two cleaned, 0.025-mm (1 mil) LPE bags. The samples and standards
(solutions pipetted onto Whatman 41 filters) were irradiated at the University
of Missouri reactor for 2-3 hours at a thermal neutron flux of 5.9 x 1013
n-cm"2^"1. After decaying for several days, the samples were shipped back
to NBS, where the outer bags were removed and the samples were counted 4 cm
from the detector. A Gamma-X detector, coupled to 8192 channels of computer
memory, was required to neasure Zn, due to the proximity of the Zn peak at
1115 keV and the much larger Sc peak at 1120 keV. The Nuclear Data ND6620
was used for data collection and reduction. Each standard, as well as some
of the samples, was counted twice to check the reproducibility of ccunting
position and the decay corrections calculated by the computer.
12
-------
DETERMINATION OF DISSOLVED FRACTION BY &FAA
The estuarine samples from tt.e Chesapeake Bby were preconcentrated using
the method described by Kingston and Rains, et al. [1]. The eluate from this
separation (contained in 2.5 M HNO-0 was analyzed directly for the Cd, Cu,
Mn, Ni and Pb by GFAA, us^ng the L'vov platform. To check for chemical
interferences, the single standard addition method was used [29]. The
instrumental conditions for aach element are given in Table 1. A more
detailed description of these methods can be found in Appendices 3 and 4.
DETERMINATION OF PARTICIPATE FRACTION BY GFAA
The solids which were collected or- 0.45 pm filters were prepared by
transferring each filter to a Teflon beaker. Then, 5 ml of HMO^ and 1 ml of
HF were added and solution warmed. After the paper had decomposed, 5 ml of
HC10,, was added and sample solution evaporated to near d'-yness. The solids
were then dissolved in 1 ml of HMO? and 5 ml of water and then transferred to
10 ml volumetric flask. The analytes were determined by GFAA, using the
instrumental conditions described in Table 1. The recovery of each analytf
was checked by the single addition method [29]. A more detailed description
of these parameters can be found in Appendix 4 and reference [1].
PROCEDURAL BLANK PREPARATION
A total of 3C sets of blanks were prepared on the ship during the
processing of the samples. Each set consisted of a dissolved fraction, and
a particulate fraction (filter). They were prepared using bottles from the
same lot which were cleaned at the same tine and contained subboiled distilled
NBS high-purity water. The blanks were opened for 20 seconds on the deck,
prior to manipulation, to simulate os closely as possible the actual samples.
This water was passed through the same lot number of Ami con and Mi Hi pore
filters, either one, two, or three filters in the same apparatus, using the
same conditions and done in between actual samples. The blanks acidified
from the same container of NBS acid was stored under the same conditions as
the samples. They were carried through all operations as if they were actual
samples and analyzed with the samples to determine the total analytical
blank.
We were unable to evaluate any blank contribution from the pumping
system, since a single sampling blank would require approximately 1000 liters
of high-purity water (^SlOO per liter) to follow the same procedure which was
used for the samples. However, in view of the non-contaminating components
of this system (all plastic), the large volume of water used to flush the
system prior to sample collection, and the rapid flow rate through the
system during sample collection any blank contribution should be negligible.
ANALYTICAL BLANK CORRECTION AND DATA ADJUSTMENT
Each element of each type of sample particulate and dissolved was
modeled for blank correction. Each element blank set was modeled, and the
resulting model was used for the blank correction. The concentration is
given as a point estimate and as an interval estimate. The interval estimates
13
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are approximately at the 95C, confidence level. The raw data were computerized,
and a set of conditions and blank influences for each element of each sample
type was submitted to the Chesapeake Bay EPA computer for adjustment into
final form. Both blank influence and statistical uncertainty were adjusted
by the computer through this series of individual elemental models.
The statistical considerations for each element are set forth in
Appendix 5 [30J.
15
-------
RESULTS AND DISCUSSION
The purpose of this report is to present the elemental concentration
data and describe the methodology used in its acquisition. These results
will be used in combination with other studies to assess the current state of
the Chesapeake Bay. The efforts utilized can be described as the best
available technology with modifications (within fiscal scope) to achieve the
maximum information available for each sample. Each concentration determina-
tion was done by the analyst having only numbered samples with no reference
as to the location or relationship of one sample to another. In all, 15
elements were analyzed (Ce only in particulates) in 102 samples (plus blanks
and standards) of dissolved and participate estuarine samples from the
Chesapeake Bay. The physical site and sample characteristics are described
in Appendix 1. The range of concentrations covered between four and five
orders of magnitude for some elements.
As one means of quality control, trace elements in water (NBS Standard
Reference Material 1643a) was treated as a sample and analyzed in conjunction
with the dissolved water samples. The results of these analyses are presented
in Tables 2 and 3. Additionally, both NAA and GFAAS techniques analyzed
certain elements in common, such as Ni.
TABLE 2. TRACE ELEMENTS IN WATER - SRM 1643a
ANALYZED USING C'iELATION AND NAA
Concentration -- ng/g
Element This Work3 Certified
Cd
Co
Cr
Cu
Fe
Mn
Mo
Ni
V
Zn
10.1
19
16
19.1
88
30.9
97
55
52
68
± 0.5
± 1
± 2
± 0.6
±16
± 0.6
± 6
± 8
t 1
± 5
10
19
17
18
88
31
95
55
53
72
± 1
± 2
± 2
± 2
± 4
± 2
± 6
± 3
± 3
± 4
Uncertainties are 2s.
16
-------
TABLE 3. TRACE ELEMENTS IN WATER - SRM 1643a
ANALYZED USING CHELATION AND GFAA
Sample Pb Hi Cu Cd
'nl
TWS -1 33 -- 16, 19 12
17, 18
17, 19
-2 26 -- -- 11
28
-3 27 -- 14 10
-4 27 56 13 13
26
27
-5 27 13 11
31
27
-6 27 49 14
29 53 16
48
Average =28 52 16 11
2s = 4 7 4 2
Certified
Values = 27 i 1 55 ± 3 18 ± 3 10 ± 1
The extremely low trace concentrations in these estuarine waters caused
the procedural blank to be of paramount importance. The integrity of the
sample can be compromised by just a brief exposure to normal laboratory air
or less than exhaustively cleaned container materials, etc. In addition, the
extremely high concentrations of alkali, alkaline earth, and halogen elements
in the marine water matrix make direct analysis difficult or impossible for
most analytical techniques.
To circumvent these problems, special chemical and instrumental proce-
dures were developed and chemical separation/preconcentration procedures
basea on the chelating resin Chelex-100 were applied prior to HAA and GFAAS
analysis [1,2]. The elimination of the matrix elements allowed the determina-
tion of i'3ny elements which could not otherwise be analyzed and enhanced
the sensitivity of other elements of interest. The control of the blank in
this procedure hi; enabled its contribution to be sufficiently low that it
did not limit the measurement of most elements in pristine samples.
17
-------
While many elements appeared to be free of any blank contribution, other
elements have a blank contribution, whicn was found to be significant. The
participate blank for zinc and chromium was contributed largely by both types
of filters used, Ann con and Mi 11ipore (0.4S micrometer). The chromium was
found to be significantly different between the two brands of filters, whilo
the zinc was indistinguishable betv.'een brands (see f'gures 1 and 2 of
Appendix 5). Attempts to preclean the filters proved ineffectual. Some
apparatus, as exemplified by the filters, is unavoidably the limiting factor
in the blank; available technology is in some cases the limiting factor due
to the level of the analytical blank for specific elements. It is necessary
to develop more specialized methodologies to achieve the lower levels of
other elements frequently belo1-; detectable limits. Analysis or most of the
elements were achievable with the available technology. Analytical procedures
extensively utilized included clean laboratory chemistry, high sensitivity
instrumental methodologies and rigorous statistical analysis of the determin-
able blank. Certain advances and refinements in techniques were achieved in
preparation for and during this study. Rather than reiterate the more
thorough discussions of each analytical technique used in the analysis of
these samples, the specifics of these techniques have been placed in the
appendices where they are described in detail (Appendices 2, 3, 4, and 5).
The concentration data are presented in tables collected in Appendix 6.
The data for both the dissolved and particulate elemental concentrations are
presented in Tables 1 through 29.
To ensure sample integrity and accurate analytical blank determinations,
thirty dissolved and particulate blanks were prepared during the sample
collection. The blanks were then carried through all manipulations and
analyses as additional samples interspersed throughout the analyses, with a
minimum of three per set. These blanks have been included TI Tables 30
through 58 of Appendix 6. They have undergone rigorous statistical scrutiny
and their influence on the concentration measurements is discussed specif-
ically in Appendix 5. Two components which it was not possible to determine
in the blank are the sampling blank and the high-purity water used to make up
the blanks.
We were unable to evaluate any blank contribution from the pumping
system, since a single sampling blank would require approximately 1000 liters
of high-purity water (^$100 per liter, if that much of this reagent could be
obtained) to follow the same procedure which was used for the samples.
However, in view of the non-contaminating components of this system (specific
plastics), the large volume of sample water used to flush the system prior
to sample collection, and the rapid flow rate through the system during
sample collection this blank contribution should be negligible. Thus it is
possible for a sampling system component to the blank to exist for one or
more elements underlying the other sources of blank.
A second contribution to the blank which ;ould not be determined was
that of the high-purity water used to make the blanks. The water is, for
the elements of interest, lower in these elements than the levels being
analyzed [21]. Since the high-purity water is not part of tlie actual samples
any contribution from the high-purity water used would raise the observed
18
-------
blank higher than it actually exists in the real samples. This then can
only contribute to an over estimation of the real blank.
Although several blanks are undetectable others have been, .in many cases,
traced to the filters or specific processes as described in Appendix 5. The
uncertainty in the concentration data take into account t-he uncertainty in
the blank as well as the instrumental uncenainties.
Some understanding of the dissolved elemental concentrations can be
gained by comparing tne concentrations to normal seawater values (Appendi . 2).
Most marine organisms can be expected to tolerate the naturally occurring
levels of toxic elements reasonably well. However, concentration data does
not give an indication of the origins of each element or its chemical inter-
actions. Even the extent of the influence of the ocean versus fresh water in
each sample can not be evaluated by studying the elemental concentrations
alone. It is only with a coordinated comparison of elemental concentration
with density and other characteristic elemental concentrations that contribu-
tions and origins can be understood and logical hypotheses be verified.
These evaluations are possible using computer assisted statistical
comparisons with data of known statistical reliability. The anrlysis, blank
contribution, corrections and mathematical manipulation of the cata in this
report have resulted in 58 data sets which are of known statistical reli-
ability. These data sets contain the sample numbers arranged in a numerical
sequence approximating the geological arrangement of the Chesapeake Bay, from
the Susquehanna River to and including the Atlantic Ocean. The concentrations
are given as a best value, and a maximum and minimum value which represents
at least the 95.' confidence limit of the concentration. The significant
figures of each concentration are determined by the range of the maximum and
minimum value.
The potential information in the particulate elemental concentration
data is even mo>~e difficult to understand. The concentrations obtained were
in elemental mass (ng) per unit volume (ml) of water. The total amount of
particulate mass suspended at the time of sample collection strongly affects
the results. Variations in current, tide, temperature, biota, v.ind conditions,
etc. can greatly influence the total amount of particulate material suspended
in the water column. The total mass collected is not a direct indication of
the amount of suspended inorganic particulate matter. The total ->ass is most
profoundly affected by the amount of salt remaining on the filter and the
amount of organic matter frequently in the form of plankton or algae residing
with it. In most cases the concentration of the elements of interest would
be much nigher in the bottom sediments than in the biological material.
Although, the oarticulate data may appear initially to br~ uncertain in
interpretive value, a tecnnique long used in the study of atmospheric
particulate material is applicable [30,31]. The comparison of elemental
ratios for di/ferent samples instead of the absolute concentration is infor-
mative. By normalizing the concentration of each element to a crustal
element, such, as Sc, problems caused by differing amounts of bottom sediment
suspended in water (loading effects) are eliminated.
19
-------
Scandium was chosen for this purpose because it has relatively few
anthropogenic uses. Since it is not used in a refined form in industry and
is refractory in nature, it is not expected to be introduced into the environ-
ment in an enriched state or in significant quantities. When these ratios
are divided by ratios of average crustal Material, a crustal enrichment
factor (EF) results. This is done for convenience and also to allow a crude
comparison with naturally occuring material. For example the elemental
concentration in proposed N8S SRM 164G, an estuarine sediment collected in
the Chesapeake Bay were transformed into EFs in Table 5.
TABLE 5. ELEMENTAL CONCENTRATIONS AND CRUSTAL
ENRICHMENT FACTORS FOR PROPOSED
ESTUARINE SEDIMENT SRM 1646
Li
Na
K
Rb
Cs
Mg
Ca
Al
Si
Sc
V
Cr
Hn
Fe
Co
Ni
Cu
Zn
Cd
Sb
Ce
Eu
Th
Hq
Pb
Concentration
in ug/g or ?;
49
2.cr.;
1.4;:
85
3.6
1.09',
0.83~;
6.25
3V
10.7
38
76
375
3.35',
10.1
32
18
138
0.36
0.43
79
1.5
9.9
0.063
28.2
Enrichment Factors
2.03
1.04
0.63
0.90
1.70
1.00
0.37
1.02
1.29
1.00
1.18
1.38
0.69
1.20
1.07
0.93
G. 76
2f (Soils = 0.47*
274 (Sed. Rock = l.i;
1.34
1.36
1.15
2.67
2.39
c
Enrichment factors relative to average soils
and sedimentary rocks [33].
20
-------
In these data the concentrations from Wpdepohls1 compilation" [32] for
crystal elements has been used. Similar though not identical results could
be obtained using other compilations. Additionally the computation of EFs
relative to average soils and average sedimentary rocks would be of value to
see how the suspended sediments of the Chesapeake Bay differ from these
natural materials. The cadmium enrichment factors relative to average
sedimentary rock and average soils [33] are given as examples in Table 5.
Enrichment factors can also be usea to identify significant inputs of
material to the hay. The t'F of an element being added to the Bay in
significant quantity from a refined source should be higher near the source
and decrease with distance.
Ideally th? CFs for each element will remain constant if the sources
contributing to the suspended sediir.ent rerr.ain the same. Although the
concentration of the various elerents may fluctuate several orders of magni-
tude from sampling to sampling, the IPs should be constant if the sources arc-
constant as they are not effected by '-ass loading.
As an example of this theory, the comparison of Sc with another rela-
tively nonanthropogenic element, Ce, is instructive. The concentration
ranges of Ce and Sc are between tv.o and three orders of magnitude. The range
of the enrichment factors, however, was just 45'J of the mean value and the
relative standard deviation was on'iy 10 . No additional variability over the
analytical uncertainties were observed. Not only were the analytical uncer-
tainties contained within these limits but the total natural inhomogeneity of
the environmental ratios for the entire estuary was also contained within
cnis range. It is instructive to recall that this study geographically
included samples of river waters from the Susquehanna, through its range of
mixing, to the Atlantic Ocean beyond the confines of the Chesapeake Bay with
both the fop and bottom of the water column sampled at each of the 51 lora-
tions. Before an interpretive value can be hypothesized for the enrichment
factors calculated from the participate data, control of the system must be
demonstrated. While this example is not an exhaustive establishment of
control it is extremely significant from an analytical measurement and
systems behavior perspective. This type of correlation reliability is rare
in environmental data.
Uses of these EFs to produce an interpretive model for evaluating and
concluding elemental relationship and origins can be postulated. However,
actual conclusions cannot be drawn until a rigorous scrutiny of the statis-
tical significance of the individual sets of enrichment factors has been
completed. Because this technique has not been used for water particulates
previously, many cross references between elements and geological positioning,
as well as within set limits, must be evaluated.
In this report the enrichment factors normalized to the Wedepohl crustal
numbers have been given without interpretation to at least the 90" confidence
limit. These values for the particulates are presented in Tables 59 through
72 of Appendix 6.
21
-------
These data are of sufficiently well known reliability that statistical
comparison can be perferred resulting in s'.ynificant trends of known
reliability. This wcrk has not been included in this report and is of a
sufficiently complex nature to comprise d separate effort. This effort has
been recently initiated.
22
-------
LITERATURE CITED
[1] Kingston, H. M., Barnes, I. L., Brady, T. J., Rains, T. C., Champ, M. A.
ej'k . 1978» 50. 2
[2] Greenberg, R. R. , Kingston, H. M. vh_ Rad^Jhern^, 1981, in press (see
Appendix 2).
[3] Kingston, H. M. , Pella, P. A. Anal. Che.m., 1981, 53_, 223.
[4] Leyden, D. E., Patterson, T. A., Alberts, J. J. Anal. Chem., 1975, 47,
733.
[5] Goldbert, E. D. "Marine Pollution Monitoring: Strategies for a Nationfil
Program", NOAA, Washington, DC, 1972.
[fi] Lee, C., Kim, N. B., Lee, T. C., Chung, K. S. Talanta, 1977, 24_, 241.
[7] Stephens, B. G. , Felkel, Jr., H. L., Spinelli, W. M. Anal . Chem. , 1974,
£6_, 592.
[8] Zirino, A., Lieberman, S. H., Chapter in "Analytical Methods in Ocean-
ography", T.R.P. Gibbs, Jr., Ed., Adv. Chem. Ser., 1975, 147.
[9] Sperling, K. R. At. Absorpt. Neivsl., 1976, 1_5, 1.
[10] Paus, P. E. Fresenius. Z. Anal. Chem., 1973, 264, 118.
'"11] Segar, D. A., Gonzalez, J. G. Anal . Chim. Acta, 1972, 58, 7.
[12] Fabricand, B. P., Sawyer, R. P,. , Ungar, S. G., Adler, S. Geochim.
Cosmochim. Acta, 1962, 26_, 1023.
[13] Riley, J. P., Skirrow, G. "Chemical Oceanography", Vol. Ill, Academic
Press, New York, 1975.
[14] Burell, D. C. Anal. Chim. Acta, 1967, 3J3, 447.
[15] Kremling, K. , Peterson, H. Anal. Chi in. Acta, 1974, 70_, 35.
[16] Riley, J. P., Taylor, D. Aj]^1_,._CJ)jm,^Acta_, 1968, 40_, 479.
[17] Davev, E. W. , Soper, A. E., Chapter in "Analytical Methods in Oceanog-
raphy", T.R.P. Gibbs, Jr., Ed., Adv. Chem. Ser., 1975, 147.
23
-------
[18] Florence, T. H. , Batley, G. E., Ta]_anta, 1976, 23, 179.
[19] Florence, T. M., Batley, G. E., Talanta_, 1977, 24, 151.
[20] Ediger, R. D., Peterson, G. E., Kerber, J. D. Al^bsor^^Jjewsl^, 1974,
13, 61 .
[21] Keuhner, E. C. , Alvarez, R., Paulsen, P. J., Murphy, T. J. Anal. Cheni. ,
1972, 44_, 2050.
[22] Federal Standard 209b, Government Services Administration, Boston,
Massachusetts, 1973.
[23] Moody, J. R., Lindstrom, R. M. Aral. Chem., 1977, 49, 2264.
[24] Maienthal, E. J., Becker, D. A. Na + 1. Bur. Stand. (U.S.) Tech. Note, 1976,
929.
[25] Moody, J. R., Rook, H. 1., Paulsen, P. J., Rains, T. C., Barnes, I. L.,
Epstein, M. S. flatl . Bur. Stand. (U.S.) Spec. Pub!., 1977, 464, W. A.
Kirchhoff, Ed.
[26] Natl. Bur. Stand. (U.S.) Certificate of Analysis, SRM 1643a, 1980.
[?7] Greenberg, R. R. Anal. Chem., 1979, 51, 2004.
[28] Becker, D. A., LaFlour, P. D. J^Jlactioanal ,._Clhein._, 1974, T9_, 149.
[29] Dean, J. A., Rains, T. C., eds., "Flair.e Emission and Atomic Absorption
Spectroi-etry" , Vol. 3, Marcel Dekker, Fiew York, 1975.
[30] Gordon, G. E., Zoller, W. H., Proceedings 1st Annual NSF Trace Contami-
nants Conference, Oak Ridge, Tennesssee, pp. 314-325, August 1973.
[31] Gordon, G. E., Zoller, W. H., Gladney, E. S., Proceedings 7th Annual
Conference on Trace Substances in Environmental Health, Colurbia,
Missouri, pp. 167-174, June 1973.
[32] Wedepohl , K. H., in Origin and Distribution _of the Elemejits, L. H. Ahrens,
ed., Pergamon Press, London, 1968, pp. 999-1016.
[33] Viru.gradov, A. P., The Geochemistry of Rare and Dispersed Chemical
Elements in Soils, The English translation, Consultants Bur., New York,
2nd~edition, 1959.
24
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APPENDIX 1
25
-------
APPENDIX 1
SITE AND SAMPLE CHARACTERISTICS
Station fio .
NBS
11102
11101
moo
11099
11098
11097
11096
11095
11094
11093
11092
11091
11C90
11039
11088
11087
11086
11085
11084
11083
11082
11031
11080
11079
11078
11077
11076
11075
11074
11073
11072
11071
11070
11069
11068
11067
11066
11065
11064
11063
11062
1106i
11060
11059
11058
11057
11056
11055
11054
11053
11052
11051
MGS
0
0
1
1
53
53
51
51
2
2
6
6
3
3
54
54
55
55
56
56
13
13
14
14
IE.
IE
57
57
5£
5£
55
5S
61
61
60
60
62
62
63
63
64
64
25
25
24
24
23
23
21
21
65
65
Location
Longitude
76 18 34
76 18 34
76 4 28
76 4 28
76 0 17
76 0 17
75 59 18
75 59 18
76 2 38
76 2 33
76 23 39
76 23 39
76 19 2
76 19 2
76 27 41
76 27 41
76 23 38
76 23 38
76 21 22
76 21 22
76 29 34
76 29 34
76 25 45
76 25 45
76 18 48
76 18 48
76 24 17
76 24 17
76 21 25
76 21 25
76 19 39
76 19 39
76 16 56
76 16 56
76 19 38
76 19 38
76 13 41
76 13 41
76 8 14
76 8 14
76 57 53
75 57 53
76 7 35
76 7 35
7C 12 44
76 12 44
76 17 25
76 17 25
75 58 18
75 58 18
75 55 36
75 55 36
Latitude
39 15 24
39 15 24
39 32 60
39 32 60
39 27 25
39 27 25
39 30 17
39 30 17
39 24 49
39 24 49
39 9 1
39 9 1
39 5 54
39 5 54
38 49 5
38 49 5
38 48 50
38 48 50
38 49 0
38 49 0
38 39 5
38 39 5
38 39 16
38 39 16
38 39 21
38 39 21
38 25 44
38 25 44
38 25 50
38 25 50
38 25 57
38 25 57
38 11 13
38 11 13
38 11 19
38 11 19
38 11 15
38 11 15
38 11 40
38 11 40
38 12 18
38 12 18
38 59 27
38 5C) 27
33 0 0
:j o o
38 G 0
38 0 0
38 4 55
38 4 55
37 58 18
37 58 18
Time
Time
17:45
17:45
13:30
13:30
*
*
12:00
12:00
8:45
8:45
15:30
15:30
9:00
9:00
15:30
15:30
12:00
12:00
7:45
7:45
6:30
6:30
15:15
15:15
0:15
0:15
8:00
8:00
;
:
:
:
:
;
:
:
8:30
8:30
10:00
10:00
6:00
6:00
18:30
18:30
12:00
12:00
9:00
9:00
of Sampl ing
Month/Day/Year
July
July
July
July
July
July
July
July
July
July
July
July
July
July
July
July
July
July
July
July
July
July
June
June
June
June
June
June
June
June
June
June
June
June
June
June
June
June
June
June
June
June
June
June
June
June
June
June
June
June
June
June
6
6
5
5
5
5
4
4
4
4
3
3
3
3
2
2
2
2
2
2
1
1
30
30
30
30
30
29
29
29
29
29
29
29
29
29
29
28
28
28
28
28
27
27
27
27
26
26
26
26
26
26
1979
1979
1979
1979
1979
1979
1979
1979
1979
1979
1979
1979
1979
1979
1979
1979
1979
1979
1979
1979
1979
1979
1979
1979
1979
1979
1979
1979
1979
1979
1979
1979
1979
1979
1979
1979
1979
1979
1979
1979
1979
1979
1979
1979
1979
1979
1979
1979
1979
1979
1979
1979
Depth
in
Feet
T
018
T
025
T
022
T
on
T
010
T
019
T
023
T
100
T
105
T
048
T
025
T
041
T
020
T
037
T
081
T
022
T
042
T
033
T
097
T
023
T
024
T
025
T
044
T
B
T
030
T
088
Dens_rtya
0.9995
0.9994
0.9978
0.9984
0.9978
0.9977
0.9980
0.9983
0.9979
0.9978
1.0014
1 .0015
1.0012
1.0013
1.0027
1.0031
1.0028
1.0067
1.0033
1.0026
1.0035
1.0034
1.0036
1 .0034
1.0032
1.0035
1.0G46
1.0051
1.0042
1.0088
1.0042
1.0038
1.0043
1.0066
1.0043
1 .0053
1.0051
1.0103
1.0050
1.0049
1.0042
1 .0047
1.0042
1.0052
1.0033
1.0065
1.0031
1.0051
1.0047
1.0053
1.0056
1 .0060
Filter
No. &
Salinity" JType
3.21
3.08
0.95
1.75
0.95
0.82
1.22
1.62
1.08
0.95
5.74
5.88
5.48
5.61
7.48
8.01
7.61
12.80
8.27
7.34
8.54
8.41
8.67
8.41
8.14
8.54
10.01
10.67
9.47
15.60
9.47
8.94
9.61
12.67
9.61
10.94
10.67
17.60
10.54
10.41
9.47
10.14
9.47
10.81
8.27
12.54
8.01
10.67
10.14
10.94
11 .34
11 .87
3 M
3 M
1 M
1 K
2 M
2 M
3 M
3 M
2 M
2 M
3 M
3 M
2 M
2 M
2 M
2 M
2 M
2 M
2 M
2 M
3 M
2 M
2 A
2 A
3 A
2 A
2 A
2 A
2 A
2 A
2 A
2 A
2 A
2 A
2 A
2 A
2 A
2 A
2 A
2 A
3 A
2 A
2 A
2 A
2 A
2 A
2 A
2 A
2 A
2 A
2 A
2 A
26
-------
Appendix 1, Site and Sample Characteristics continued
Station No. Location
Jii.s__ ^S LGJllitud_e
Depth
Time of Sampling in
Time Month/Day/Year Feet
Filter
No. &
JZEL_
11050
11049
11048
11047
1104Q
11045
llOnl
11043
11042
11041
11040
11039
11033
11037
11036
11035
11034
11033
11032
11031
11030
11029
11028
11027
11026
11025
11024
11023
11022
11021
11020
11019
11018
11017
11016
11015
11014
11013
11012
11011
11010
11009
11008
11007
11006
11005
11004
11003
11002
11001
76
76
73
78
80
80
81
81
85
85
84
84
77
77
79
79
82
82
83
83
87
87
36
86
88
88
89
89
90
90
93
93
92
92
94
94
91
91
97
97
96
96
100
100
98
98
99
99
95
95
75
75
75
75
75
75
75
75
76
76
76
76
76
76
76
76
76
76
76
76
76
76
75
75
76
76
76
76
76
76
76
76
76
76
76
76
76
76
76
76
76
76
75
75
76
76
75
76
76
76
57 3
57 3
55 33
55 33
58 5
58 5
51 41
51 41
4 27
4 27
7 56
7 56
7 5P,
7 58
10 46
10 46
11 29
11 29
13 17
13 17
10 38
10 38
55 0
55 0
7 52
7 52
1 3
1 3
10 26
10 26
10 56
10 56
21 34
21 34
6 11
6 11
1 6
1 6
3 54
3 54
7 9
7 9
54 53
54 53
03 06
03 06
13 58
13 58
16 38
16 38
37
37
37
37
37
37
37
37
37
37
37
37
37
37
37
37
37
37
37
37
37
37
37
37
37
37
37
37
37
37
37
37
37
37
37
37
37
37
37
37
37
37
36
36
37
37
37
37
37
37
53 50
53 50
50 55
50 55
46 53
46 53
45 36
45 36
41 1
41 1
40 20
40 20
52 1
52 1
49 31
49 31
45 8
45 8
41 35
41 35
31 23
31 23
38 44
38 44
25 39
25 39
24 13
24 13
22 7
22 7
18 50
18 50
20 26
20 26
19 3
19 3
21 31
21 31
14 19
14 19
10 49
10 49
55 46
55 .46
01 15
01 15
0 32
0 32
12 £6
12 46
.
:
:
13^15
13:15
9:30
9:30
6:30
6:30
17:30
17:30
14:00
14:00
10:45
10:45
8:30
8:30
14:30
14:30
10:30
10:30
7:15
7:15
13:00
13:00
:
9:30
9:30
:
10:30
10:30
7:05
7:05
13:30
13:30
9:30
9:30
7:00
7:00
14:00
14:00
8:30
8:30
16:00
16:00
0:01
0:01
June
June
June
June
June
June
June
June
June
June
June
June
June
June
June
June
June
June
June
June
June
June
Jure
June
June
June
June
June
June
June
June
June
June
June
June
June
June
June
June
June
June
June
June
June
June
June
June
June
June
June
24
24
24
24
23
23
23
23
23
23
22
22
22
22
22
22
22
22
21
21
21
21
21
21
20
20
20
20
20
20
19
19
19
19
15
15
14
14
14
14
14
14
13
13
13
13
12
12
12
12
1979
1979
1979
1979
1979
1979
1979
1979
1979
1979
" 1979
1 579
1979
1979
1979
1979
1979
1979
1979
1979
1979
1979
1979
1979
1979
1979
1979
1979
1979
1979
1979
1979
1979
1979
1979
1979
1979
1979
1979
1979
1979
1979
1979
1979
1979
1979
1979
1979
1979
1979
T
095
T
078
T
060
T
B
T
033
T
042
T
057
T
055
T
075
T
041
T
030
T
055
T
034
T
046
T
024
T
040
T
014
T
053
T
B
T
no
T
024
T
065
T
060
T
055
T
035
1.0053
1.0053
1.0067
1 .0068
1.0053
1.U077
1.0069
1.0067
1.0064
1 .0089
1.0052
1 .0096
1.0044
1.0084
1.0051
1.0091
1.0057
1 .0100
1.0052
1.0080
1.0064
1.0099
1.0044
1.0050
1.0080
1 .0126
1.0107
1.0091
1.0079
1.0090
1.0071
1 .0090
1.0085
1.0085
1.0085
1.0132
1.0108
1 .0110
1.0123
1 .0139
1.0110
1.0118
1.0156
1 .0194
1.0035
1.0064
1.0082
1 . 01 03
1.0099
1 .0091
10.94
10.94
12.80
12.94
10.94
14.13
13.07
12.80
12.40
15.73
10.81
16.67
9.74
15.07
10.67
16.00
11.47
17.20
10.81
14.53
12.40
17.06
9.74
10.54
14.53
20.66
18.13
16.00
14.40
15.87
13.34
15.87
15.20
15.20
15.20
21.46
18.26
18.53
20.26
22.39
18.35
19.60
24.66
29.72
8.54
12.40
14.80
17.60
17.06
16.00
2 A
2 A
2 A
3 A
3 A
3 A
2 A
3 A
2 A
2 A
2 A
2 A
2 A
2 A
2 A
2 A
2 A
2 A
3 A
2 A
2 A
2 A
2 A
3 A
2 A
2 A
2 A
2 A
2 A
2 A
3 A
3 A
3 A
3 A
2 A
2 A
1 A
2 A
2 A
2 A
2 A
2 A
1 A
1 A
2 A
3 A
3 A
3 A
2 A
2 A
NOTE: T Depth = top sample (riesrrili&r! in experimental section); NBS = National Bureau
cf Standard^ sample ni/mber; MGS = Marylar.'i Geological Survey site number;
Density = 25 CC; Filler = 1, 2, or 3 - the PUT,ber of filters used for a 1 liter
sample, A or V. - Amicon or Millipore C.45 micrometer filters were used.
t-V
Uncertainty ±0.0002
"Calculated from density; supplied by EPA
27
-------
APPENDIX 2
G^eenberg and Kingston (1981), in press
28
-------
SIMULTANEOUS DETERMINATION OF Ti.'ELVE TRACE ELEMENTS IN ESTUARINE AND
SEAVJATER USING PRE-IRRAOIATION CHROMATOGRAPHY
R. R. Greenberg and H. M. Kingston
Center for Analytical Chemistry
National Bureau of Standards
Washington, D. C. 20234
I
( Introduction
The considerable difficulty of trace element analysis in a high salt
matrix such as seavater, estuarine water, or brine is clearly reflected in
the literature. The extre,:'?ly high concentrations of the alkali metal'.,
the alkaline earth metals, and the h.ilogens, combined with the extrer.ely
low levels of the transition metals and other elements of interest, make
direct analysis by most analytical techniques difficiJt or impossible.
Typical elemental concentrations in seawater [1] are listed ir Table 1.
The use of a separation and/or preconcentration procedure prior to
analysis is usually required. Riley and Skirrow have revicv/ed many of the
alternative separation and preconcentration techniques employed to elimi-
nate the matrix and/or concentrate the trace cli ,,.ents from a high-salinity
material [1]. One of the prominent methods of seawater preconcentration
*
uses the chelating resin Chelex-100 . Early Chelex-100 procedures,
*
Certain commercial equipment, instruments, or materials are identified in
this paper in order to adequately specify the experimental r^vu^'ire.
Such identification does not imply rccoraendation or endorsement by ti,?
National Bureau of Standards, nor does it i.nply that the materials or
equipment identified arc necessarily the best available for the purpose.
29
-------
however, only partially separated the alkali and alkaline earth metals
prior to the analysis of the eluted elements of i Merest [2-5].
A no re recent separation procedure utilizing the Chelt-x resin pro-
duced a sample devoid of alkali, alkaline earth, and halogen elements, and
left a dilute nitric acid/ammonium nitrate matrix containing only the trace
elements of the seawater sample [6]. V.'hile this procedure produces a
highly desirable and appropriate matrix for most spectroscopic methods of
analysis, a solid sample v/ould be ir.ore appropriate for other instrumental
techniques [7] such as x-ray fluorescence (XRF) o~ neutron activation
analysis (NAA). In addition, the above separation procedure also makes
it difficult or impossible to analyze several elements which are held
strongly by the resin but cannot be quantitatively eluted. Chromium and
vanadium exhibit this type of behavior, and attempts to reproducible elute
these elements from Chelex-100 have not been successful.
Neutron activation analysis has the inherfnl. sensitivity and accuracy
to determine a number of important trace elements in seawater at their
naturally occurring levels. Unfortunately, a salt weter matrix is not
well suited for activation analysis. The use of liquid samples limits
both th? amount of material and the length of irradiation available in
most reactor facilities. The high levels of Ma, Cl, and Br produce an
extremely high background level of radiation that totally tbscures the i
signals of most elements whose neutron activation products have cor.para- I
ble half-lives.
This paper will describe a method to prepare solid samples from J
100 i;;L or csluarine or seai-.ater, using Chelex-100 resin, followed by the '
determination of 12 trace elements by NAA. Using this procedure, typical I
-------
decontamination factors of £10 for Na, £10 -for Cl, and £10 for Br are
observed. This procedure has been used to analyze NBS Standard Reference
Material 16<13a (Trace Elements in Hater) as well as high salinity water
sampler, collected near the mouth of the Chesapeake Bay.
Although one of the major advantages usually associated with fJAA is
the possibility of post-irradiation chemistry thus eliminating the problems
associated with reagent blank and other types of contamination, the use
of pre-irradiation chemistry for high-salinity waters has significant
advanlages The removal of Na, Cl, and Br greatly reduces the background
level of radiation during short and intermediate counts, and allows the
determination of elements not otherwise possible without sonic type of
separation. The removal of the matrix elements also greaMy reduces the
radiation dose received by personnel, especially if radiochemistiy is used.
The preconcentration of 100 ml of liquid to a sample of less than 0.5 gra.r
increases the sensitivities for most elements and allows r.ore samples to be
irradiated within a single rabbit. Although other, non-che.nical , concen-
tration steps, such as lyophilization, could be employed prior to
irradiation, they are relatively difficult to use with high salinity water,
they leave the salts with the elements of interest, and they can also
increase' the blank from the equipment used, as well as from the material
used to contain the sample. Finally, the use of Chelex-100 prior to
irradiation produces a solid sample which eliminates the problems of
storage, irradiation, and handling liquid samples.
Even without pre-chemistry, the number of sample manipulation steps
rrqiiirfil before the irradiation of a high salinity water sample is con-
siderable including: collection; filtration; stabilization (usually by
31
-------
acidification); storage and encapsulation for irradiation. Extreme care
during all these steps is necessary to prevent contamination of the samples.
Extending the pre-irradiation treatment to include the Chelex-100 concen-
tration/separation step produces significant benefits for the small
additional effort required.
Experimental
Reagents. High purity water, nitric and glacial acetic acids were
prepared using subboiling distillation at the National Bureau of Standards
(NBS) [8]. All reagents used in the separation process v;ere precrred in
this manner ?r.d stored in clean FEP Teflon bottles unless otherwise stated.
Ammonium hydroxide was prepared by bubbling filtered e-r.onia gas
through high purity water until room temperature saturation was achieved.
A l.Oi-i an.conijrn acetate solution VMS prepared by mixing 60 g of
purified glacial acetic acid and 62 g of saturated NrLOIl and diluting to
1 L. in a polypropylene volumetric flask. The acidity was adjusted to a
pH range of C.I to 5.4 by dropwis? addition of acetic acid and/or tiM.OH.
All reagent and sample preparations v;ere done in a class 100 clean air
laboratory [9].
Chelex-100 rhelating resin, 200-400 mesh size, was purchased from
Bio-Rad Laboratories.
Column Separation Apparatus. The Isolab QS-Q polypropylene colu~n
v/ith porou~ i-oly^tliylene resin support was used with the QS-S 25-rnL
conventional polyethyl"i.? extension funnel attached to the colunn to act
as a reservoir for the samples.
.32
-------
ScntipT_cs_. Approximately 160 liters of high-salinity, estuarine water
were obtained during high tide at the Virginia Institute of Marine Science
(V1KS), Gloucester Point, Va., located ne~r the mouth of the Chesapeake Bay.
The sample was collected with a sul^'iersible pump and plastic tubing
permanently submerged approximately 100 m offshore from the Institute [6].
The seawater v/as pumped directly into a conventional polyethylene drum
which had been cleaned first with hydrochloric and then with nitric acid
and purified water prior tc use [10]. After filtration through a 0.45-pm
millipore filter using an all polypropylene filter apparatus, the seawater
v/as collected in a polyethylene carboy and acidified (to 0.6M in UNO,)
with high purity hNO^ to prevent bacterial growth [6], to stabilize the
trace element concentrations [11,12], and to strip any trace elements
bound by colloidal particles [4,5].
Aliquots of this stabilized sample have been previously analyzed by
graphite furnace atomic absorption spectrometry (GFAAS) [G], x-ray fluores-
cence spectronetry (XRF) [7], a/id isotope dilution inass spectro-nr.try (IKIS)
[13]. Hach of these analytical techniques employed a separation/concen-
tration step prior to analysis.
National Bureau of Standards-Standard Reference Material 1643a (Trace
Elements in V.'ater) was used to represent a low salinity water sa;,iple.
This material is a synthetic water standard designed to approximate a
filtered and acidified fresh water sample. The concentrations of seven-
teen elements have been certified by NBS using two or more independent
analytical techniques, or a reference method of l;r.ov;n accuracy [12,14].
-------
Separation iVcK.ediirc;. The polypropylene chro,,H to'iivphu columns,
used to hold the Chele/.-lOO resin v;ore allowed to soak for on? week in
4H lliiO-, and one week in 3H HC1 before use. After rinsing with water, a
slurry corresponding to 3.2-3.4 ml of hydrated rosin ir. the so:liun form
(about AGO r.Kj dry weight), was loaded into each coUir.n. The resin was
washed with tiir^e 5 nL portions of 2.M HliCk to eluLe tal
contamination. Ixr.ess acid v-^s removed by v;ashiii'j tlr? resin ,;ith 1',;:, r> nl
volumes of v;at':r. The resin \:as transfor.ned to the M!!, lorp. hy the
fi
addition of tuo 5 ml. volumes of 2. OX !i;i,n;i. The pi I of 1 ho l?st fev/ drops
elute>! v;.is checked using pii paper. If tiiey v:.?re not l;:.ic., :.'Jditior!.'\l
NILOH was adc'.o'! until basicitv \:os achieved. ;',:,iiin ! '..':',C'.l '.n.r. r'^./v, '
'l ' ri
from the resin \n1h v.:o 'j i:il '..'-.iltr \;ai,ii':-s. fiu1 sor/MU'- SiV.r/les, v/nic.h
!wvo been filtered and prese. -od v.'ith MM'),, \.rorr odjuv.'.ec! to / p!l vaiifje
\J
of 5.2 - 5.7 by dropwise addition 01 i'.'.l^O'.l. /".' fc./ drops o' !'' inr-'ioniiiiis
acetate was then added to aid in bufferinj i.i." system. A s". 11 onouu'. of
the sair.plc was added to the colur.a to allou the resin to uncLrcjO it1-.
normal shritik-iyo us it changes in p;-l and ioiiic form. The 2r., ;.-.!. poly-
ethylene reservoir atop the col inn was then filled and the s,-.~.ple passed
through the resin at a flow rate of about 0.8 i.il./niiii. After the sar.iplc-
had passed through the resin, the resin was washed twice with 5 ml. of water,
and four 10 ml volumes of 1.0!', en.nionii.un acetate were cycled to selectively
elute the alkali and the aTrflinc earth ratals. Residual r.^r,onii;r;i acetate
was reiaoved with two 5 nil. water >;OSI.L". The resin was then air dried in
the column under a class 100 clean air facility and transferred to an
acid-washed, 0.025 \»:\\ (~\ mil) linear polyethylene (l.?l'. hag. This bag
was heat staled, and sealed within a second hvj tv.ade of O.O/'/ nia (3 oil)
34
-------
conventional polyethylene- (Cf'L), to prevent contain nation during handling
and irradiation. Linear polyethylene was used for the inner bags due to
its lower blank levels (compared to CPE), while the outer bags were made
or CPE due to the greater flexibility of this material after neutron
irradiation. Although LPE is in general stronger than CPE, it becomes
brittle after long irradiations and has a tendency to crack.
Sta_iu!ard_s_. Two types of multieleir.ental standards were used. T'no
first type was prepared uy pipetting known amounts of multielemental
solutions onto 5.5 cm l.'hatrcan 41 filters. The filters were air dried,
pelletixed and doubly sealed in polyethylene bags [15]. The second type
was prepared by pipetting standard solutions directly into LPE bags
containing approximately 4CO uig of dry C'nelex-100 resin in t!ie amwotmn
form, which had been prepared using the coliriiti preparation procedure
previo'isly described. The resin v/as allo'.-ed to dry at roc;;i temperature
m.der Class-100 conditions after which the bags wore sealed and placed
within second CPE bags. Molybdenum and uranium were in separate standards
on
since significant amounts of Ho are produced frcT. uranium fission.
Irradiation and Countina Parameters. Two irradiations and five
counts, after appropriate decay intervals, were used to determine the
twelve elements. The samples were irradiated in the RT-3 pneumatic tube
facility of the f!3S Research Reactor (t.BSR). In this position the thermal.
13 2-1
neutron flux is 5 x 10 n-cn s and the Cu/Cd ratio is approximately 70.
Radial fljx variations v;ithin the rabbit are ^2 percent [16]. The samples
wre ccjnted with Ge(Li) and Ge(HP) detectors having active volumes of
>
60 90 ci..'. A liuclcar Data i:D G620 co:;puter-bssed analyzer system was used
for data collccti'm and reduction.
-------
Vanadium and manganese were determined after a 2-minute irradiation.
The samples, standards, and blanks were individually packaged, and each
was held rigidly in place within the rabbit wi th poly-foam to ensure a
reproducible irradiation geometry. Vanadium was determined from a
5-minute count beginning about 2 minutes after irradiation, and manganese
was determined from a 10-nn'nute count approximately 2 hours after
irradiation.
The samples v/ere then repackaged for the long irradiation. Ten to
12 samples, standards arid blanks were placed within a single rabbit, and
occupied two levels. The rabbits were irradiated for 2 hours, removed
from the reactor, flipped end-over--ond, and reinserted in the reactor for
\
an additional 2 hours in order to compensate for the linear neutron flux ;
i
drop-off within this facility. The CPE bags were removed, and Cu IMS 1
i
determined in the samples with a 30-miriute to 2-hour count, ""-2 days after
j
irradiation. The 511 keV -\-ray produced by the annihilation of positrons \
1
emitted b> Cu (t, ,? = 12.7 hours) was used. An investigation of
potential 511 keV -(-ray emitters (discussed below) indicated that the only
significant contributor to the ' Cu 511 peak (^0.1») was 'tia, which
produces 511 keY y-rays by positron annihilation following pair-production
events, and occurs mainly in the Pb shielding surrounding the detector.
This effect was minimized by counting the samples with an unshielded
detector. The Ha present in the sample was due almost entirely to the
LPE bay used to contain the samples. No difference was ubsfwcd between
24
the Na levels in the seawater samples and the blanks. The " 'Na contriLj-
tion to the 511 peak was determined by irradiating some NaCl and counting
in the same geometry used for the samples. The observed ratio of 511 to
56
-------
A
?4
1368 keV y-rays (0.020) was used to subtract the Na contribution from
the 511 peak of the samples.
239 239
Molybdenum and uranium .(using the lip daughter of U) were
determined by counting the scruples 4 cm from the detector, at least 48
hours after irradiation. This decay period was necessary to establish
the equilibrium between Mo and its Tc daughter. The Mo concentration
235
in the water must be corrected for the apparent Ko produced by U
fission. The apparent Mo/ll ratio was determined from the Mo and U stan-
dards irradiated with the samples. In the RT-3 facility of the N3SR,
this ratio is 2.0, or 2 ug of Mo appear to be present for every 1 i;g of
U in the sample. This ratio would of course be different at different
facilities since the epithennal to thermal cross section fcr Mo activation
is i.i'ich greater than for '" ~'U fission.
1'- 0 140
Scandium, Cr, fe, Co, Mi, Zn, Th, and li (using the " Ba, La, and
Ku fission products from ~~JU) were determined by counting the samples
six weeks after irradiation for 24-48 hours directly against the detector.
235 238
Since uranium is determined independently fro.n the U and U isotopes,
the natural isotopic abundance can be checked. The only standards used
for this co.iiit were those pipetted directly on the Chelex-100 resin, since
co iting geometry differences between sairjales and standards can produce
large errors when counting so close to the detector.
CO
Nickel was detcnr.inec! using the 811 keV -y of Co produced by an
(n,p) rcuctit.ii <~>n °fji. This line was not always visible due to its
proximity to the 81G ;,:'. '' La -,-, and to the relatively '.n'gh background,
due in port to La. Much bet',--,- statistics for Ni could be obtained
by recounting the sftr.ples about 3 months after irradiation.
-------
_. The recovery and behavior of each element during
the preconcentration and separation procedure was investigated using
radioactive tracers. The tracers v/ere added to 100 ml of seawater prior
f
i to pH adjustment, allowed to equilibrate, and were processed in an
' identical manner to the one previously described for the samples.
The eluted seawater and buffer solutions were collected in polyethyl-
ene dottles, adjusted to the same volume (height) and counted. The resin
I samples v/ere transferred to similar polyethylene bottles, and nitric acid
v;as added to strip the tracers fro:n the resin. After volume adjustment,
these samples were also counted. The three types of samples were compared
against each ether, and against a standard (unprocessed) spike in the
same geometry.
Results and Discussion
0-I'J^°l5xtl"'-'- The results of the tracer studies are shov:n
in Table 2. Vanadium, Mn, Co, Hi, Cu, Zn, and U were quantitatively
retained by the resin. The rcprooucibility of the elements not quantita-
tively retained, Sc, Cr, Fe, Mo, and Th, was sufficient to allow retention
corrections to be nade for these elements in the samples. Additional
retention studies were undertaken from distilled water, and identical
results, within statistical limits, were obtained for all elements with the
exception of Sc, whose retention on the resin increased to 100 percent.
This inc'-o^so nay be due to the total absence of Cl ion to complex with
the- Sc ° ion.
The small quantities of \.h? tracers in the ammonium acei'ate buffer are
probably due to residual column dead volume from the effluent. Chromium,
Mo, and Th, however, appear to have lost significant quantities in the
-------
' buffer elution. This is the first evidence of any removal cf elements
chelated on the resin by the buffer [6,17]. This could be due to changes
in the ionic form or oxidation states of these elements. Certain elemental
i
species can be reduced by ionic exchange resins on the column. In addition, [
the capability to form certain anionic species could influence this
phenomenon.
Pesin Characteristics. This resin was found to be extremely weli
suited for the described procedure. L'hen dried in the colur.n, the resin
takes on rathei unique physical characteristics. L'hen most ion-exchange
resins dry, they are crumbly and tend to crack and fall api-rt. The 200-400 j
mesh Chelex-100, when air dried in the column, shrinks to about one quarter
of its hydrated size, and forms a relatively hard rod that pulls cleanly
av/ay fror, the walls of the polypropylene col i. Tin. The resin was transfer-
red relatively easily to the polyethylene bag, and only rr.rely were small
pieces not directly transferred, requiring SOTIO additional manipulation.
Separation fro:" f'atrix Elements. The observed separation of t-'ic
elements of interest from the alkali r.etals and alkaline earth metals was
excellent. The concentrations observed in the processed seawater samples
were identical to those in the blanks, where these elt-rnents were present
within the polyethylene bags. necontonina.tion factors of >10 for Ka and
o
£10 for Cs were observed. Separation frc;n Cl also was excellent. Again
the samples and blanks appeared identical, with the Cl originating in the
5
bags. Tno observed decontamination factor for Cl was ^10 .
The separation fro.n Er was good. At least 99.9 percent ot ih? T.r
5
(decontar-i nation factor >1G ) was renoved. The regaining Br (<0.1
percent), however, still produced u relatively high level of background
-------
radiation, and elevated dead time, during the intermediate counts. The
determination of Cu, Mo, and U, however, was not seriously affected.
Attempts to further reduce the Br levels by additional water washes,
and by heating wit.i an IR lamp have not been successful.
l»se of 511 keV y-ray for Copper Determination. A number of nuclides,
64
other than Cu, can emit 511 kcV y-rays by positron emission, by direct
emission of 511 keV y-rays, or from positron annihilation resulting from
pair-production events. Host positron emitters produced by neutron
activation ere insignificant, compared to Cu, when counted 1-2 days
after irradiation, due to their half-live; (either too long or too short),
neutron cross sections, isotopic abundances, branching ratios, or a
con.bination of these factors. The most common positron emitter in
natural materials, other than Cu, is Zn. A simple comparison of
nuclear parameters [13,19] indicates that for the irradiation of equal
e.,f
masses of Cu and Zn, the 511 kcV activity of TCu would be approximately
10,000 times greater than that of Zn 24 hours after irradiation, and
approximately 3000 times greater 48 hours after irradiation. In practice,
Zn can easily be detected by the presence of its 1115 keV y-ray since
65
Zn emits approximately seventeen 1115 keV y-rays for each 511 keV y-ray
[18,19]. Using a typical germanium detector approximately nine 1115
keV y-rays are seen for each 511 keV y-ray emitted by Zn, due to the
i difference in detector efficiencies. The Zn contribution to the 511
.
5 peak could easily be detected, and subtracted ('.f significant) using the
1115 keV peak. The presence of Zn was not detected while counting
the sai..pl(.:. for Cu, and any possible interference was
-------
counts 48 hours after irradiation and typically seen 1-2 days \
64 I
after irradiation, other than thos? fro? Cu, result from positron anni- ]
i
hilation follov.'ing pair-production especially in the Pb shield surrounding
the detector. This can be greatly reduced by coon Ling the samples with an
unshielded detector. Eliminating the shield reduces this type of 511 by
greatly increasing the distance fro;n the detector to regions where pair-
production/annihi lation .events can occur, .such as the walls of the room,
floor, ceiling, etc. In addition, removing the Pb shield greatly reduces
the atomic number (Z) of the stopping material. Since the probability of
2
pair-production increases as Z of the stopping material, while that for
Coaipton scattering increases as Z L'^]; fewer pair-production events
occur, further reducing the number of 511 keV ,-rays.
41
-------
Since relatively high energy v-rays are required for pair-production,
their presence can be easily detected. One t° two days after irradiation,
the major producer of pair-production events is the 2754 keV y-ray of
Na. This interference can be easily determined, as previously described,
and subtracted from the samples. The observed ratio of the 511 to 1363
keV y-rays of Na for the detector, counting geometry and room used was
?4
0.020, and the rertil ting correction for the lia contribution to the 511
keV peak in the-samples ranqed from 0.1-1 percent.
A final check of the Cu detet./n'nations was made by counting SO.T.O of
the samples twice, with at least 24 hours L?tween counts. The observed
decay of the 511 peak matched the half-life of fCu within a few percent,
which can be attributed to the counting statistics.
Blp_Q_ks_. The concentration of the blanks is an important part of any
trace element analysis. Despite the careful handling of samples, and the
precautions taken, the blank levels for so,,:e elements were significant
compared to the levels of trace elements in the samples analyzed, and to
typical seawater (Table 1). The blank concentrations observed are listed
in Table 3. These blanks represent a "total process blank" and were
prepared using NBS high purity water [21]. This water was treated in a
manner identical to that of the samples, including: filtration in the
field, acidification, storage and chem'cal manipulation. There was no
correction for the elemental concentrations in the water itself, since
this cannot be measured for most of the elements of interest. Some
cie-'ents were not normally distributed among the blanks. This would be
extremely important when single (unique) samples are analyzed.
42
-------
The relatively high Cr blank is duo almost entirely to the LPC bag
used to contain the samples. If this presents a problem, another type of
polyethylene could be used, or else the samples could be carefully trans-
ferred before the Cr count. The relatively high Kn and V blank values
v/ere due primarily to the outer CPC bag which was not removed after the
short irradiation, in order to minimise the possibility of contamination.
The blank levels for these el erne,its could be significantly reduced by
transferring the samples to new outer bags after the short irradiation.
JJI££? JUpJ^l^in^'ater^^R^MMSa. National Bureau of Standards-
Standard Reference Material 1643a VMS used to check the analytical
procedures, and to test U-.P applicability of this procedure to a low-
salinity water sample. This synthetic water standard prepared at [IBS
v/as designed to approximate a filtered and acidified fresh water sample
[14]. The sample sixes used for analysis were varied frc;n 8-50 grams.
The results obtained are listed in Table 4, and agree well ,;ith the
certified values. Concentrations for Sc, Th, and U are not reported
since these elements were not added to this SRil. The relatively large
variability observed for Fe v/as due partially to the counting statistics,
but was also significantly affected by the variability of the blanks
(especially important for the smaller samples), as sho'..n in Table 3.
Sea wator Sainplcs. The results obtained for the replicate analysis
of seawator are listed in Table 5. The previous results obtained by
GFAAS, XRF, and IDMS for this material are also listed in Table 5. The
concentrations of Cu, Fe, Mn, Hi, U, and Zn determined by i,,".". uc/-ee with
the values determined by the other analytical techniques within the
stated uncertainties.
43
-------
The agreement between the concentration-; determined by f!AA and GFAAS
is not only significant from an analytical vie*-;, but also from a sample
stability view. The first step in the analysis of any water sample is its
collection and stabilization for the particular parameters of interest.
Since approximately 3 years had elapsed between the analysis by GFAAS and
that by MAA, the sample had indeed been stabilized by the addition of
nitric acid, at least for Cu, Fn, f'n, Ni, and Zn. This stability gives
added confidence in the integrity of other natural water samples pre-
served in a similar manner.
The concentrations of Co, Fe, Sc, and 7n found in this water sample
are essentially the sr.me as those reported by Riley and Skirrow [1] and
listed in Table 1. The slightly lower concentrations of Mo, Ni , U, and
V in this Sc.ir.ple IP ay reflect a slight dilution of the seawater with fresh
water fror. the Chesapeake Bay. The concentrations of Cr, Cu, and Mn are
slightly elevated al-^ve the scatter values, possibly due to a localixcd
or general source in the Bay itself. The Th concentration observed was
nuch lower than the previously reported value for seawater [1]. Since
approximately 4 years had elapsed between collection and analysis, and no
long-term study of Tli stability has been re-ported, the stability of this
element is uncertain under these conditions. However, a large number of
additional water samples have been collected throughout the Chesapeake
Bay and processed within 1-3 months. The dissolved Th concentrations
were typiv-cV'v ^_n.O'J02 ng/mL near the nouth of the Ray, and about
0.001-0.002 ng/mL nejr L^ top of the Cay.
44
-------
A
Conclusion
The application of the Chclex-100 resin separation and preconcentra-
tion, with the direct use of the resin itself as the final sample for
analysis, is an extremely useful technique. The elements demonstrated to
be analytically deterriinable from 100 ml samples of high salinity waters
are: Co, Cr, Cu, Fe, Hn, f'o, Ni, Sc, Th, U, V, and Zn. The deternination
of Cr, and V by this technique offers significant advantage; over methods
requiring aqueous final forms, in view of their poor elution reprodi-cibil-
ity. The renoval of ?!a, Cl, and Br allows the determination of elements
with short and intermediate half-lives without radiocheniistry and greatly
reduces the radiation dose received by personnel. This procedure has
been successfully applied in a study of more than one hundred samples
collected throughout the entire length of the Chesapeake Bay. The
salinity of these sarrples varied from that of fresh water to that of
Atlantic Ocean water.
45
-------
References
1. J. P. RILEY, G. SKIPJVJ'.,', Chernica 1 Oceano9raphy. Vols. I and III,
Academic Press, New York, 1975.
2. J. P. RILEY, D. TAYLOR, Anal. Chin. Acta, 40 (1968) A79.
3. E. W. DAVEY, A. E. SOPER, Chapter in Analytical Methods i_n
Oceanography. T. R. P. Gibbs Jr., Ed., Adv. Cheni. Ser., 1"7, 1975.
4. T. H. FLORENCE, G. E. BATLLY, Jala/it a_, 23 (197G) 179; ?4 (1977) 151.
5. C. LEE, N. B. KIM, I. C. LEE, K. S. CHUNG, Talanta. 24 (1977) 2*1.
6.. H. M. KII1GSTON, I. L. BARNES, T. J. BRADY, T. C. RAINS, M. A. CHAMP,
Anal. Chen. , 50 (1978) 2054.
7. II. KINGSTON, P. A. PELLA, Anal. Chen., 53 (1981) 223.
8. E. C. KUEK.'IER, R. ALVAREZ, P. J. PAULSEI!, T. J. MURPHY, Anal . Che-".,
44 (1972) 2050.
9. J. W. USELLER, MASASP-5074, Office of Technology Utilization, NASA,
Waslii."olon, D.C. , 1959.
10. J. R. rIOODY, R. M., R. M. LII.'DSTROM, Anal. Chcrn. , 49 (1977) 2254.
11. E. J. MMEHTHAL, D. A. BECKER, !iatl. Bur. Stand. (U.S.), Tech
Note, 926, 1976.
12. J. R. MOODY, H. L. ROOK, P. J. PAULSEi!, T. C. RAIMS, I. L. BARNES,
M. S. EPSTEIfi, Nat'l. Bur. Stand. (U.S.) Spec. Pub!., 454, W. A.
Kirchhoff, Ed., 1977.
13. W. R. KELLY, Personnel Communication 1981.
14. tiatl. Bur. Stand. (U.S.), Certificate of Analysis.. SRM 1643a, 19SO.
15. R. R. GRLEnDt.y., Anal. Chen., 51 (1979) 2004.
16. I). A. BECKER, P. D. '. Qr'EUR, J. RadioanaT. Chcm., 19 (1974) 149.
-J6
-------
17. H, H. KltlGSTO'l, "Quantitative Ultratrace Metal Analysis of High
Salinity Uater Utilizing Chelating Resin Separation," Interagency
Energy-Environmental Research and Development Program Report,
EPA/f'.BS, EPA-GOO/7-79-174 (1979).
18. C. H. LEDERER, V. S. SHIRLEY, Eds., Table of Isotopes, Seventh Ed.,
John Hi Icy and Sons, New York, 1973.
19. 1. M. H. PAGDEt!, G. J. PE/ToON, J. \\. BEl.'CRS, i^_RadJ p2naK_CheR L ,
8 (1971) 127; 8 (1971) 373; 9 (1971) 101.
20. R. D. EVANS, Th£_ j^tcmic J!ucJL?_ul McGraw-Hill, flew York, 1955.
21. T. J. MURPHY, t.'atl . Bur. Stand. (U.S.), Spec. Publ . 4??, P. 0.
LaFleur, Ed. (1976).
47
-------
/ Abstract
A procedure is described for the preconccntration of 100 ir.L of
i
/ estuarine and seawater into a solid sample using Chelex-100 resin. This
solid sample weighs less than half a gram and contains the transition
metals and many other elements of interest, but is essentially free
from the alkali metals, the alkaline earth metals, and the haloqens.
The concentrations of Co, Cr, Cu, Fe, Mn, Mo, fli, Sc, Th, U, V, and
Zn have been determined in seawater when thir. procedure v.^s coupled to
neutron activation analysis.
48
-------
Table 1. Elemental Correntrations in Scav/ater.
Concentration - na/nL
Major Elements
Fron rof. 1.
Minor Elements
-4
f!a
K
!!g
Ca
Sr
S
Cl
Br
7
1.03 x 10'
c.
3.8 x NT
1.3 x 106
i;
4.1 x 10°
A
8 x itr
r
9 x 10J
7
1.9 x 10
A
6.7 x in1
Sc
V
Cr
Mn
Te
Co
Ni
Cu
Zn
Mo
Th
U
6 x 10'
2.5
0.3
0.2
2
0.05
1.7
0.5
4.9
10
0.01
3.2
49
-------
Table 2. Recovery and Characterisation of Selected Trace
Elements frc:n Seawater
Percent Retention3
Sectwater Anoni
Element
Cob
Cr
Cuh
Feb
(.;nb
Mo
Nib
.Sc
Th
U
V
Zn"
Isotope
60
51
64
59
54
99
65
46
230
235
48
65
Co
Cr
Cu
Fc
Mn
Mo
Hi
Sc
Th
U
V
Zn
Effluent
0.30
4.16
0.026
6.3
<(
1.00
0.09
14.58
12.74
<(
2.36
0.04
:'. 0.
i 0.
.< 0.
A 1.
).05
A 0.
A 0.
A 0.
A 0.
).2
A 0.
A 0.
04
26
002
9
17
01
18
42
34
01
irn Acetate
Chelex-100
Buffer
<0
0.90
-------
Table 3. Blank Concentrations -- ng/gc
Co
Cr
Cu
Fe
Hnfc
Mo
0.012 ± 0.009
1.55 i 0.10
0.17 i 0.04
1.3 i 0.6
0.17 + 0.18
<0.01
Ni
Sc
Th
U
Vb
Zn
Uncertainties arc Is for at least 5 blanks
"'includes outer bag
<0.2
O.OOC12 ± O.OC004
o.ooos ± n.oon?
<0.01
0.1? i 0.03
0.6 ± 0.2
51
-------
Table 4. Trace Elements in Hater - SR" 1 543a
Concentration - ng/g
a
Element
Co
Cr
Cu
Fe
I'm
l-'o
Mi
V
Zn
This V,
19 ±
16 ±
19.1 ±
88 ±
30.9 ±
97 i
56 ±
52 ±
68 ±
fork
1
2
0.6
16
0.6
6
8
1
5
(..Kl L 1 1 1
19 ±
I/ i
18 t
88 i
31 ±
95 i
55 ±
53 ±
72 i
t:'J
2
2
2
4
2
G
3
3
4
al)ncertainties arc 2s
Uncertainties are 95?- confidence limit
52
-------
Table 5. Trace Elements in One Seuv/atcr Sample
Concentration - nq/mlc
Eleinsnt
Co
Cr
Cu
Fe
Mn
Mo
Hi
Sc
Th
U
V
Zn
NAAU GFAAS XRF IDMSC
0.043 ±
3.3 ±
2.01 *
2.1 ±
1.89 i
5.3 »
1.2 ±
0.00096 ±
-------
APPENDIX 3
54
-------
i m:\N.\l.\'I U'.\l.t'UKMI.VI'H\. I ),-nm!«r i'Cs. |>|i -''H.I ju'ii. U ihc An,, nun Chi-nm il ><»
Separation of Eight Transition Elements from Alkali and
Alkaline Earth Elements in Estuarine and Seawater with
Chelating Resin and Their Determination by Graphite Furnace
Atomic Absorption Spectrometry
H. M. Kingston.' I. L. Barnes, T. J. Biady, and T. C. Rains
National Measurement Laboratory, Center lor Analytical Chemistry. Inorganic Analytical Research Division. National Bureau of Standards,
Wasti'ngton. D C .'0234
M A. Champ
The American University. Washington. D C 200 IE
A method is described for determining Cd, Co, Cu, Fe, fv'.n.
Hi, PI), nnd Zn in seawater using Chetex 100 resin and graphrte
furnace atomic absorption spectrometry. The pH of the
seavvater is adjusted to 5.0 to 5.5 and then passed through
a Chelex 100 resin column. Alkali and alkaline earth metals
are eluted from the resin with ammonium acetate and then
the trace elements are eluted with two 5-mL aliquots of 2.5
M HN03. The difficulties previously encountered with resin
swelling and contracting have been overcome. By careful
selection of the instrumental conditions, it is possible to de-
termine subnanogram levels of these trace elements by
graphite furnace atomic absorption spectrometry. The pro-
posed method has been shown to separate quantitatively the
elements desired from the alkali and alkaline earth metals and
has been applied in the analysis of trace elements in estuarine
water from the Chesapeake Cay and seawater from the Gulf
of Alaska.
The lik'rat'ire of marine water analvsis reflects the <
siderable difiiui'ty in establishing an accurate and pn-t >
method of aiirfksK lor trace metals A seawater matrix tU'.
a simplified approach. For example, .specific sampli
techniques, conta.ner contamination, suspended partu'u.'.
mailer, and analytical technique-- ha\e to he con-idcrtd.
is hi'vond the scope of this paper in discuss all ol the-e p
ran etcrs; howcvtr. the solving oi the analvtica! pn>!>'-
free c/f foiitr-mination and propirK stored until aiial'.M-
In recent vear-. method-. ha\i. been di'\eloped to -lettrsiv
traie elements in seav. ater hv X-r,i\ tluoresceiHe (I >. neutr
ac'ivation (-', (), j-pectrnphotonietrv (/), anodic stripping
\oltainnietr\ ( 51. and atomic .ihsorption spectrometry (6 N
However. ea«.h of these analytical techniques requires a
prelinun.ir. Mr-paratiou. Kahruand et al. (.'*! rejKirted the direct
delernnii.ition of t\i. Ke, Mn. Ni, and 7,n in seavvater hv atomic
absorption spectrometry (AAS) usm;; an air acet\lene flame.
hut other workers have reported difficulties vising their
technique because of lijiht 'catterms; and burner clogging.
Except for neutron activation analysis and anodic stripping
M>!tammeUN. uci analytical techniijiies are currently available
for the direct dcttrmination of trace elements in seavvater at
concentrations below ."> ^g i, '. Usually it is necessary to
precoiuentrate the trace elements from a large volume and
separate the transition elements from the alkali and alkaline
earth elements. In such sample preparations, the efficiency
ot cc ncetUr.ition. completeness of separation, and total
an.iKtical blank become critical to the final instrumental
method I/O).
I'recnrKentration techniques which have been used are
coprec ipitaiion (//>. dictation and extraction (12). and
cbelalin;, i->n-exch.in«e lesin (III, /.il Most of these isolation
method-, require large volumes oi chemical^ vvhuh can lead
to high bi.mk^ unk'" tiic- reagents have Ix-eii carefullv puriil'd.
OI the presently used preconcentralion technic|iies, Chelev
l(«t (lu'latmg resui has been --howi'i to be ttlicienl and yields
lo.v anahtual blanks (//). Applications otThelex HH) resin
for trace metal preconcentration from seavvater have been
re\ le'ved !>\ Ui!c.\ and Skirrovv ( K'n Chelev. 1(1(1 is a stropg
c hviator and 11 movers metal ion^ trom most known n;>Uirnl!v
occ.iniij; ihcl.itor- in seaw.Uer (/ / Kit. The resin will t ol.
however, rtmovc metaU held in organic and inorganic colloids
whuh can be piesent CASH alter ullr.ifiltiation. Precautions
SS
-------
ANALYTICAL CHEMISTRY, VOL. 5C>, NO 14, DECEMBER 1978 2065
Table 1.
amental Parameters
wavelength,
t nm
228 8
240.7
32-1.7
218 3
279 5
232 0
2,Vi a
213 9
icxle. Normal mod
^T & !:
SBW,
nm
0.7
0.2
0 7
0 2
0 7
0."
0.7
07
e. c Note
(503
sral
e drying,
expansion T-sec1
1
2
1
o
^1
r>
3
0.5
. r -
100 30
100 30
!0n <0
100-30
100-'50
iot/-r,o
100- iO
10030
temperature.
HGA
' chaning
7'-sec
200-20
500-30
700 30
600 30
300-30
1000-30
-100-3'1
500-20
-2100
a omi/ation
7'-wc
2100-7
i'700-7
2.100-6
2700-7
2700-7
2700-6
2200-7
2000-7
ttas
Ar"
Ar"
Ar"
Ar"
Ar"
Ar"
Ar1-
Ar6
e'e merit
Cil
Co
Cu
Fe
M-i
Ni
rt
Zn
must he t,iI.on to destroy such coll.mis prior to (dilution of
the ions In ihe resin. Florence artl liath-v have destioved
interfering organic colloids. In the addition of o.lfi M mine
acid and heat .md also by using i-itraviolel irradiation ol the
sample prior to collection by the r sin (/>, /*>). \Yhileexcellent
recovery and low analytiial blar.V-. are achieved, a relatively
high i'onci-ntration ul Ka, K, ('.-, and \!« are retained with
the trace metals The coiK?ntr:u;';n ot the-.- interfering alkali
and alkaline earth salts ,\\ the- f :ml sample are in milligram
quantities, i'-. compared to ''ie inuogram and siibmiirogram
quantities ot concentrated Iran- metals. Tlie alkali and al-
kaline earth ions occupy the rt.-in sites n< t occupied In the
transition inetaK and are co-eluted with the met.iK when using
acids (I'll
T!ie complete separation of the alkali and alkaline "arth
metal.s from the trace metals in seawater has not been pre-
viously accomplished Using Chelex 100, whi< h ha- restrict'd
its u-e. While the salts remaining alter prce one einrot ion do
not interfere with instru.ncnlai techniques .such as (lame
atomic alMirption ijo1) or polarography (/.> /"), thiy do inhibit
instrument.il techniques wlm ]i ;ire more susceptible to matrix
intereletnent effects Mich a-, Homeless atomic absorption (/.S).
neutron activation analysis !/°), optical emission sp« trometry
Using inductively cempled plusnia or eiectr'Kle plasma ule arc)
('20), and spark source mass r-pectrornetry (21)
With the development ot the graphite furnace for AAS, it
is now po.-sible to determine K) ' to 10 ' g of many of the trace
elements in sea.cater. However, the hi^h salt c'ontcnt (l?.i R/kf!>
in marine water makes it trature
atur.itni' was achieved.
A 1 0 M .jrinionunn ad tate solution was prep.'tre-d by mixing
(10 K (it purilnd gluial actt'.c actd and 62g ol saturated \H,OH
and diluting to 1 I, in a |«ilvpronvlene volumetric flask Th.°
aciditv was ac.jdsted to pH ,"i 0 In uropwise addition of UNO,
and 'or NH.OH. All r< agent -md sample1 preparations were done
in a das- UK) clea.. air laboratory [2!>.
CheltA 1(X> f helatmg ic-sin, 200 400 mesh size, was cure-based
from Bio-Kad Laboratories.
The radioactive trace's Ve, ''Mn, and r"/n m ().") K HO v.ere
puntied reagents obtained trorn the Chemical and Rudioisotope
Division of It'N The "Co. and the ^hort lived isotoi>c-s,''Cu and
' 'Ni, svere made ,jy the Neutron Activation Analysis Group at
NHS fruio 'Tive-ll s" pure mt-lals Dnci di-M>Kecl in nitric acid. The
''"Cd and -'"Ph were obtained bv the Activation Analysis droup
from other .-.ources and anri!\/ed u-ing pul.se height analysis for
ladii (he'iucal puntv hetor-. use
All stanclard stod- s'iKitions for .\.-\S were prepared from high
puritv nieta'i or salts in siiblh.:ini<; di-tilkd NHS aucK as descnlx'd
by Dean and Rams (_'">!. U'lirknid solutions wire prepared as
needed
Counting Apparaius. 'ihe vrav counting ol the ekmental
tracers was done utili/inL' a 7.(1 cm X 7.6 cm Xall'i'll crystal and
a-siK'iated electronics.
Seawater. The seawnter was obtained d'armg high tide at the
Virginia Institute of Matir.e Seience (VIMS), (llotitester Point,
\ a , ori the Chesapeake Bay The sample was collected with a
submersible pump and piaspe tubing peimanentlv submerged
appro\;inatelv 1(K) ni otishore froni the Institute. The seawater
was pumped directlv mto a ceuiventional p< Ivethylene drum which
had bee n cleaned fir-t with hvciroc hloiic and then with nitric acid
and purified water prior to u-e (26>. After filtration through a
0.4.i-nm milli|«, /'>).
AAS Apparatus. 'I he instrumental svstem used in this study
(.insists of a i'erkin-Klme- Model 003 atomic absorption spec-
trometer with HGA-2HK) gr.-phile lurnace tC.FAAS) The 2.V/iL
iliemot ot sample was introduced into the furnace with the AS-1
autosimpler The instrumental parameters aie given in Table
1.
Column Separation Apparatus. The Isolab QS-Q polj-
[>rop>'lene column with porous p'dv^thvlene resin support v^as
used lor 100-in I, and 1-L sample volumes Although the same
eolumn was used for both s;imple vohim(1s, the amount ot resin
and reservoir systems were entirely different. For the 100-mI,
sample,, the QS-S 2.'i-ml. conventional pol\, thvlene exlension
funnel was attached to the column to act as a tescrvoir lor the
sample.
Kcu a 1-1. sample the r«'-ervoir wa' :< 1-1. Teflon (FKl'l bottle
mvr rted and modified with a rn.u < :i.ed Tello'i (TFK) closure
insert contatii'ng a nnen;))ore venung tuoe and 0111 let tube The
cutlet was connected to a v.ilve CI FK.I by l..'i;i-mm ('',, in ) i d
Te lion (FKl'l tubing lonnei lor and In.keel to the re servoir with
a speuallv mac hmed mount ('I FKi whie h sealed the1 column into
the elosed system '1 he mount contained a vent (sealed with nvlon
56
-------
2066 ANALYTICAL CHEMISTRY. VOL. 50, NO 14, DECEMBER 1978
Reservoir BotH« * -
Vtodrfwd Closure*
Microbor* Tubing f\tr Vsnt* Jjj
1 59 mm I J Tubing *
Nyton Screw
Vdnt -^_
Modifxd Clamp
Palypropylana Column
Porous Polyethylene Plat*
ft to B 2.0 cm
0 to C 4 5 cm
A to C 6 5 cm
S5 mm id B 135 mm id.
2 mm Radius Step
C 8 5 mm i d
Figure 1. Apparatus used for hokjmg and delivering large volumes of
seawalor a! a controlled rate to Cheiex 100 resin The apparatus
(excluding the column and clamp) was fabricated from Teflon FEP (')
or Tefloi TFE (T) which has desirable nonwetting and noncontaminating
properties
screw, allowing the removal ml. of 2 0 M NIL.OH was added in
5-mL volumes. After checking thi. pH of the effluent to ensure
basicity, the column was then rinsed with 10 to 1 5 ml. ot water
to rerrove the exrc ss NH.OH
Column [Jre was weighed into a 1-L Teflon (FEP)
bottle and the pH adjusted in the same manner as previously
described The bottle became the reservoir and vvas fitted with
a modified closure (see Figure 1) The bottle was inverted and
the air purged Irom the system by means of the vent on the
column mount. The flow rate was -uljusted using the valve and
the height of the reservoir. The flow rate was kept to less than
0.2 inL/min until the shrinkage of the resin was complete. Then
the flow rate was increased to 1.0 nil, 'mill and left overnight to
flow through the column After passing the sample through the
column, the valve and tubing uere removed at the tonnector above
the column mount and replaced with a smaller reservoir containing
70 mL of 1.0 M ammonium acetate. '1 he flow rale was adjusted
to 0.5 ml,'mm until the reagent was exhausted. The resii, was
then w ished with 10 ml, of water. The transition metals were
eluted with two 5-mL portions of 2.5 M HNO., into preweighed
polyethylene bottles as previously described
RESULTS AND DISCUSSION
Effect of Direct Injection of Seawater into Elec-
trothermal Device. From the detection limits published in
the literature for GFAAS, it could be assumed that several
of the heavy metals in seawater could be determined by direct
injection of the sample into the electrotheima! device.
However, in reality this has not been proved to be true unless
the samples are taken Irom heavily polluted areas. A sample
from the Chesapeake Bay was analv/ed for Cd, Co, Cu, Mn,
Ni, Pb, and Zn by direct injection into the graphite furnace
by AAS Only lead and nickel produced absorption signals
of any analytical value. The other elements could not be
detected. This is due in part to the highly depressing effect
of the matrix on the analyte signal which can vary by a factor
of 2 to 10 depending upon the analyte. AKo, when the sample
is evaporated, a small amount ol solution may be trapped in
the salt crystal lattice which could result in losses due to
splattering during the atomr/ation cycle
The absorbances obtained for lead and nickel were very
erratic due to the smoke produced during atorni/ation. Ediger
et al. (22) used matrix modification with ammonium nitrate
to assist in the removal of sodium chloride; however, the
method of standard addition was necessary to correct for
interferences. In applying their method of matrix nicMlification
to the Chesapeake Bay sample, Cd, Co, Cu, Fe, Mn, a'id 7,n
were still not detected
Separation of Calcium and Magnesium from Analytes
on Chelex 100. To effect a separation of calcium and
magnesium from the trace elements on the Chelex 100 resin
column, it is necessary to (house a separating agent that can
be purified to produce a low analytical blank AKo, the
separating agent should not produce any adverse effects on
the itnalyles in the {JFAAS analysis. The ammonium ion
reacts similarly to the alkali elements, and ammonium nitrate
or acetate can be produced from high purity reag"nts
\\hile both ammonium nitrate and ammonium acetate
remove sodium and potassium .'it identical rates, ammonium
nitrate produced tailing of the c \lcmm and magnesium which
57
-------
ANALYTICAL CHEMISTRY, VOL. 50, NO. 14, DECE.MBER 1978 2087
Table II. Concentration of Alkali and Alkaline Earth
M'.-tak in Seawater before and after Separation or.
Crielex 100 Resin Column
pH 3.O
ug/mL
sample
original
wash6
H,O
NH.NO,
NH4COOCH,
Na K Ca
6200 267 283
after separation"
320
0.3
1 0
10 350
0.7 83
2.0 0.25
MR
742
03.
1.3
<0.05
" 100 mL of seawater prcconcuntratc into 7 mL of 2.5
M HNO,. b Column washed with 50 mL of a given
fluent
!:if;ure 2. Comparison of ammon'urn acetate vs ammonium nitraie
for" the separator! of calvjm from a Chelex 100 resin column v*hich
has prev ous'/ chelatea 100 mL of seawater
Wt appreciable quantities of tber-e alkaline eaiths in the linal
UNO, effluent (Figure 2) (Table II). However, ammonium
i.cetate elutc-d calcium and magnesium trom the column with
failing of only 1 to 2 bed volumes (Figure 2). Manganf.^e.
which has the smallest selectivity toeflicient of the transition
metals of inter^t, was not fluted at pH 5.0 by ammonium
acetate or ammonium ivtrate. A relatively high concentration
of ammonium acetate in the 2 5 M HNO, effluent produced
a suppression of several of the analvtes by GFAAS, however,
the problem was alleviated bv washing with 5 to Jo mL of
water prior to the stripping of the column with the 2.5 M
HNO, (Figure 2).
There is a contribution to the removal ot calcium and
magnesium from the resin by the acetate anion which does
not appear with the nitrate ion. Sodium and potassium are
replaced bv the ammonium ion. but this cation is onlv partially
responsible 'or the complete separation of chelatcd calcium
and magnesium Using ammonium acet.Ue.
Effect of pH on the Separation. A studv of the pH of
the separating agent il V. ammonium acetate) showed that
a minimum pH of 5.0 v as required to retain the transition
metal ions on the C'helcx 1'!') rt'sin while removing the alkali
and alkaline earth ions. Below pH 5 (I, it was found that the
transition metals were eluted b> the 1 M ammonium acetate.
From pi 1 5.D to ."> .">. the transition metals Ccl, Co, Cn, Fe. Mr.
Ni, I'lj, and V'n were re'iimui bv tin- resin while llu- Na. K.
C.i, and Ms; were ciu.intitateiv eluted (see Figure :il.
The c hei.itinj; elti< leiuv of Chelex 1(111 increases for the
transition nr. ta!-, from pH I to "> and r( ai he.-i an optimum at
Figure 3. Comparison of ammonium ac°tate elution of Ca, Mg. and
Mn in the pH range of 3 0 to 5 0 The c/aph depicts percent of the
total column content ot an element eluteo wi'.h volume
approximately pH .YO. For most ot the transition elements,
this optimum efficiency remains for an inertace of several pH
units. However, the chf'latiiif1, efficiency oi Chelex 100 for Co
and Cu has been shown to decrease above pH GO (29-32).
The chela'ion efliciencv of Chelc\ 1'H) tor (,'a and M>; has
ht-en reported to be -imilar to those ot the transition metals
increasing with pH to a maximum at pH 5 in low ionic
strength solutions (,'td. 331. Ho-,ever, in high ionic strength
solutions of sodium chloride, there exists a minimum in the
thelation of Chelex 100 lor both Ca and \\K from pH 5.0 to
5.8. Above pH 5.8 the chelating efficiency for Ca and Mg
increases sharply (33}.
From our experimental results and the literature, a working
range of pH 5.0 to 5 5 was established lor both the precon-
centralum of the transition elements from the seawater and
the elution of the alk.ai and alkaline earth elements from the
lesin vising the ammonium acetate.
Separation Parameters for (?oth 100-mL and 1-L
Seawater Samples. The separation parameters, as described
in the Procedure sect'on, \re represented graphic illv for a
lO'i-mlj sea water sample IP Figure !. and for a 1-L sample
in Figure 5. The ditlereiuc between the two systenis is
approximately double the amount ot resin lor the 1-L sample.
The larger amount of resin wr.s found to be necessary for
quantitative retention ol this L.rger volume, but is still rather
sin ill considering a 10-fold \t\ rease in the total ionic content
ot the larger sample An increased volume of ammonium
acetate v.as required lor the removal of the greater quant it v
ol s.ilis occupving more residua! sites. Also, a laiger volume
of water is required to wash the residual ammonium acetate
from the column prior to transition metal clut -m with mtiic
,u',d. '1 lie elimination H'aimviimiuni aiel.ile was found to be
necessary to prevent both bu 'lenng of the acid wash rind a
suppression of the C.FAAS sigi al caused In tne acetate in the
subsequent analysis Thv acid traction did not undergo tailing
58
-------
2068 ANALYTICAL CHEMISTRY. VOL. 5C. NO- 14. DECEMBER 1978
I
- 2 SM HNOj
J
Figure 4. Represents the separation obtained using 1.0 M ammonium
acetate at pH 5 0 to 5 & for the transr>.on meais from Na, K, Ca. and
Mg chelated m a cokjrm of Chetex 100 from a ;CO-rrs- stawater sample
F'gure 5. Represents the separate obtained './sing 1.0 M ammonium
acetate at pH 5 0 to 5 5 for the transition meats from Na. K. Ca. and
rv'g chelated on a column of Chetex 100 from a 1-L seawater sample
from the transition metals a'; seen by atomic absorption or
by radio trr.cer studies. The Chelex KM resin in the presence
of 2.5 M HNO, does not chelate the tran-ition metals and thev
are eluttd simultaneou-ly into a single -Tiall volume of ac id.
Chelex UK) re-in is a dynamic rtsin. and h> ihe nmnionitiin
form at a pH of 7 to I!, the resin shrinks to approximately
', , of its original volume when subjected to the seavvater
sample at pH .").() to "> :>. The particle .-'.je and -ul>-equi'nt flow
r.ite were also reduced and the use of trip «>i'jtnn apparatus
for 1-L samples became necessary to imrea-e ihe pressure uf
the sample to obtain if realistic flow ran- tor o.ith the sample
and amnr mum acetate. The flow rate ot 1 ml, nun was
attained in adjusting the Teflon valve and n-crvoir height
simultaneously to control the pressure. 1 lie residual volume
which would retain any sample in the iritirt- apparatus was
(Climated at less th.in (I 10 ml, Th; u-.- of all Tellon
e impont :it.- in contac t with the sample .-tturfi- the noiiwetting
tharacteri-tii- and noneontaniin.itir.i; nature of this fluoro-
< .irbon which cau be .scrupulously c'.eaned in ,u id (_W>
Another important benefit of tin- appjratL- i-. lh.it during
the preeiiruen'ration onto the Chvlex Inn, the sample and
column are protected from Contamm ition iroin the envi-
r mnii-nt. the nnlv entrance into the s\ -;< rn is rnic roUire tube
v> Inch can in- fitted wMri a InU-r ;.i i-\. !;:'ie 'nriii nl.ite cnn-
t.mun Jtu 'ii The-e ch.ir.K ten.-.tu-. make- the fiumn apparcitus
very attra-live for fi*-ld ur -hi[>b"ar(l u-t- to prevent con-
i iminntiiin.
59
Itadiochcrnic^l Study. Kadiochemical tracers were used
to gain specific information about the behavior of each ion
during preconcentration and separation using the Chelex 100.
The tiacers were added to the -eawater as one radioi^otope
per sample prior to the pH adjustment. The column pro-
cedure was identical in all respects to the preparation of the
analytical samples previously described. However, all effluent
from the column was collected, including the seawater. The
seawater, ammonium acetate buffer, acid effluent, and column
resin were collected in polyethvlene Imttles. The 1-L samples
were collected in iVI-mL lx>ttles and the 100-mL sampler were
collected in 125-mL Ixittles. Distilled water was added to the
bottles prior to measurement to make all liquid levels the same
to give constant counting geometry.
The samples were counted for l()-min periods for y radiation
only (Table III). The counting statistics for each element were
optimized by energy discrimination. The concentration of
tracers used gave from 10" 10' count,-, in a 10-min |jeriud while
background wa^ kept to 10' Hi1 counts during the same
period. The statistical error wa.-, obtained using the following
equation (31, .V.5).
Qr = 100 x ---- V';V. + A',,
where (^c = percent experimental error corrected for back-
ground, k = number of standard deviations, .V = cpm = counts
per minute or period unit time, s = sample including back-
ground, and b = background.
This technique enabled the use of MCu and &>Ni short-lived
isotopes as well as VjFe and MMn intermediately-lived isotopes
since counting of all fractions could be completed in -SO min.
The error caused by the decay of the-* isotopes over the course
of the experiment was eliminated; nickel which has a hall life
of only 2.G h. decayed l>evond u.-efulne-*s o\er the I-day period
of the 1-L experiment.
The counting technique was checked for total recovery using
"'/n. The tracer wa> r.dcled to J.">() mL of the seawater vunple
and counted prior to manipulation This volume vva* then
dddi'd to 750 ml, of seawater and trs-ated as a 1-L '"'7.n .-piked
seawati r sample. The final acid volume was then counted at
the end of Ihe separation .'.s prev iou-ly described. The total
quantitv obtained agreed for both the acid fraction and total
recover-, 99 O'J ± 0 12 and 100.1 ± u.12, respectively. Thus,
the counting ( r all effluent fractions and the column itself
allows the specific identification of all losses, as well as the
tot'il recovery of the element of inteie^t in the acid fraction.
The Ammonium acetate separation did not remove a de-
tectable amount of any trace mual whh the possible exception
of Fe which could haw been in the residual volume from the
seawater effluent. Thus, the separation docs not affect the
maximum efficiency of the cone put rit ion alone, and the Na,
K, (\t. and Mg can be eliminated v.ith the same efficiency as
the traditional concentration alone
The majority of any minute los-es i'h l.-lc/c, Co O.HTr. and
Fe fi.S'/r is due to incomplete removal of Ihe transition metal
ions from the seawater. The chela'ion etficiency of both '"Co
and '''Fe was studied b\ Callah.m et al (-'(2). They found that
the two oxidation .states of cobalt and iron reacted sir.nlarlv
and that 10(>7r retention of cobalt ai.d iron could oiilv be
achieved bv reduiti-.,-, of Cofllli toCotllt and Fe(Ill) to Fcdli
using sodium dithfinue (Na;S (),l at |>H 50 to .").;i. In natural
seawaler the approximate concentration of Co(ll) was found
to be %7i of the total cobil*. Tlu-v obtained 9l> to 99VC
retention lor cobalt and l.l.r>9i .'or iron without an\ attempt
to reduce the tnv.iltnt ions, which is in agreement with our
finding'-.
The ladioctu inii ,il trae cr t xpei imcnts for Cd. Cu. ! t. Xi.
and /n were repeated sevcr.il times and all values fell within
Ihe calculated error limits with the exieption ol those for iron.
-------
ANALYTICAL CHEMISTR.'. VOL. 50, NO. 14. DECEMBER 1978 2069
O r-l
O O
j CO IN C)
, c o oi
c
0
5
O f~i
o o
i « u -
i / --- O o
« aj
O O
O O
o q f> o
o o ° o
., r. ° .,
O «-« T' £*t
o b o" cJ
O C^i
do g
O '3 CO O -
o o o o 2 i
d o o o' a
V v >
O
o
U
c
I S
il
i c-i
3 Op
£ do
g v .'
~* fs. CO O
t- cr- ^ x co
O O O O CC
. ? CO !M
O O ;
O O c-l
CO '
CO O O
"o o
o
O -T *
O O O O O C) ~ C-J
o o o o o o o o
V V V V v'
CO O CO *' " ^
pOOOTCOCO
O O O O 1-1 3 !3 -
Table IV. Trace Elements in Chesapeake Bay
concentration, ng/mL"
element blank
Cd
Co
Cu
Fe
Mn
Ni
Pb
Zn
{ephtjte
<001
<0.1 <
^0.1
0.2 t 0 1
<0. 1
--01
-0.1
:005
anaiv six of four samples.
sea water
005
:0.1
2.0
2 1
2.0
1.2 :
0.3 j
-1 8
- 0.01
0 1
0.5
0 1
0.1
0.2
0.3
60
Iron exhiUited a 27c \%iri.ition arounci the average value (Table
III). This could be due toallered ratHfe of Feill) and Fe(IlI)
between samples tested.
GFAAS Determination of Trace Elements in Scawater
from the Chesapeake Bay. The reliability of the proposed
separatum and preconoentrutiori method \\o.-> tested !).>' making
replicate aiui!y.-.es on a sample of teawater. These samples
were processed as described in the Separation and I'reum-
tentraticn Procedure. Then the S lit mL i>f 2.5 N HN'O.T
effluent toiletud uas analv/ed for the trace elements by
C.FAAS. The instrumental conditions tor c!r\ing, charring,
and atomizing (Table 1) for each analyte were optimized to
obtain the maximum sensitKity and precision with the
minimum of interferences. The samples (25 ^L) were in-
trodiued into the graphite furnace with the AS-1 which
imprmed t!ie precision of the anahsis with the minimum
amount of contamination. It was necessary to preclean each
sample cup in m the AS-1 with 207c HNO, to remo\e trace
contaminants. IJ>ro!ytic and nonpyrolytic coated Kraj)hite
tulx's were used in this study. The life o! the pyrolytic coattd
tube was extended In a factor of three o\er the nonp\rolytic
(oated tube in the presence of 2.."> M HNO,. Background
correction with the deuterium arc lamp was used for each
analyte
For t"K h anal\~i.s the hollow cathode lamp was turned on
and allowed to stabiii/e (15 to (>0 min>. Working standard
solutions oi each anaKte were prepared in 2."> M HNO;. and
then a three to the point calibration curve was established
ming the optimum instrumental conditions. After the cal-
ibration curve wa- established, the unknowns were determined
u->mg a sample brirketing technu]iip. .\s a check for chemical
interferences, ejth sample vva.- tested b> the single standard
addition method (.#>') and no chemical interferences were
encountered. The results are given in Table IV. Cobalt was
no* detected using a liK)-mL sample To obtain an analytical
value for cobalt in the Chesapeake Bay Water, a 1-L sample
would IK- required to l>e separated and prec-oncentrated Some
difficulty \s.\s encounU-d in the ilFAAS determination .)f iron.
Iron is known to form carbides in the graphite furnace which
produce erratic results Also, a high reagent blank war, ob-
tained (see Table IV) whereas the reagent blanks for the other
elements were ' low our detection limits The lead values
are clo^e to the detection limit iisinij a I(H)-mL sample With
a I)..')- to 1-1. -jrnple. the pre< ision of the lead analysis could
be improved.
Recovery of! rqce Klcmcnts Added to Chesapeake Bay
Seavvater. Sincv thtre are no samples of seavvater with
accurate anakliial v.ilue-. for the trace elements under .study.
the .'KCuriKV of the CJ'AAS technniui- was checked by adding
O.'i to 2(1 111;; 1,1 i, of the trace elements to six samples of
seawater and processed as previoiislv described Recoveries
of 90 'o 1 \~',r were obtained t I able ''I The high recovery
salue (or vine w,i> clue to the low c'onci'iiiralion added to the
sample-. S,nu /me i-s(> sensitive by <'rFAAS. a 1-to 10-fold
dilution of the 1 "> M HNO, efil'ient had to be made. Since
-------
2070 ANALYTICAL CHEMISTS, VOL. 50, NO 14, DECEMBER 1978
Table V. Recovery of Trace Elements Added to
Samples of Seawater by GKAAS
concentration, n^/mL"
cle-
ment
Cd
Co
Cu
Ke
Mn
Ni
PL.
Zn
present
0 05
<0 1
2 0
2 1
2 1
1.2
0.3
4 h
added
0.5
1.0
1.0
2.0
20
20
1 0
0 5
found
0 5-1 0.02
1.07 0.02
2 '! 0 07
3.7 0.4
4.2 -001
32-01
1.4 : 0.07
6.2 .* 0.09
av.
rcco\--'ry.
0
CM
107
97
90
9o
100
1 (if>
111
" Replicate analysis of six samples.
a dilution was required fc r OFAAS. the original spikes added
to the s*av.attT were t(H)
m. These samples were treated in the same 'tiuiiiier and no
alteration in the separation technique v as neces-ars. The
trace metal concentrations from Ala-kan -eav-ater v.ere lound
to be generally lower in concentration over those of 'lie
Chesapeake Bay. The value- i«r I'b ami Mn were found to
be consistently 1 to 2 orders of magnitude l>e!ow tho-e rc|x>rted
here fur the.-e -aine elemental concentrations in the Chesa-
peake Hav.
CO.NCLl SION
The application of Chelex UK! resin and CiKAA.s vised in
this investigation lias been shown to provide a new w,iy ol
detL-rmn in:,' Cd. Co. Cu, Ke. Mn. Ni. I'b, and /.it in -tawnier.
Chelex li'O re-sin is known to be an ellicient ineitis ot sep-
arating many of the trace elements from the .ilk ill metals.
however. bv U-HIK an amrm.njum acetate wash, (.ilcmm and
magnesium are also removed. Calcium and magnesium se-
verely suppre-s many analytc-s in C.KAAS and. with tlieir
removal, the detection limit- of rnanv trace cements by
GFAAS can be extended to -ubnar,o|;ram per r.iimht'.T. In
our radiotra.-er study, the recovt-rv ol Cd, Cu. Mn. Ni. and
Zn was jcrtatcr than 999'/< while t.V' recoverv of Co. 1'h. and
Ke was 9'rf ?>. ~-'^-1. and 9H i'« . respect i\el\ The pre< ision of
the technique wa> limited by the (1KAAS measurements which
varied with the element and comeutration present. Not only
has the propo-e'l technique been
the Cht-apc-ake Hay but the rr-
detprmin..tion of C'd. Mn. Ni, n' '
seavvater from the Gulf of AlasKH.
ACKNOWLEDGMENT
The authors express their gratitude to ]. H Moo:i\. K.
Hu^e It, and \V A Hov man 111 lor their help IP the prep-
lied to siM'.satt-r Irom
v.as applied to the
. the ii", nil- level in
aration of materials and seawater collection.
LITERATURE CITED
(1) D. r leyden, T A Patterson, and J J Alberts. Anal Own . 47. 733
(1976)
(2) E D GoWbert. Marine Pollution Monf.ytn^: Strategies fc a National
Proyam . NOAA, Washington, D C , 1972
(3) C Lee. N B Kim. I C teo, and K S C'^ng. Tabnta. 24. 241 (1977)
(4) B G Stephens, ri L Felkel. Jr. and W M Spmelli. Ana! Chem , 46,
692 (19 "4)
(51 A Zinno and S H Liebermcm. Chapter in "Analytical MeiTOds m
Ocoanoyraphy ', T R l> QBDb. Jf , Ed . A-' Chem Ser . 147. 1975
(6) K H Sperling, At Absorpl Ne»sl 15, 1 (1976)
(7) P E PdU', tresenius 2 Anal Chem , 264, 113(1973)
(81 D A Segar and J G Gon2alez. Ansl Chim Ada. 58, 7 (197?'
(9) B P Fabricand. R R Sawyer. S G Ungar, and S Aaior, Ceochu >
Cos-n.-x.him Ada, 2F. 1023(1962)
(10) J f HueyandG Skirrow. Chemical Gcud'Kigrapny . Vol III. AcarJemc
Press. New York, 1975
(11) DC Bu;o|l. An?l Chim Ada. 38 447(1967)
(1?) K Krc-mling and H Pe'erson. Ami Chun Acln. 70. 35 ('974)
(13) J P Biley and D Taylor, Anal Chim Acts. 40, 479 (1SCB)
(14) b W Davey and A E Soper, Criapler in Analytical Mettxws in
Oceanography ' T R P Gibbs. Jr . Ed . fdv Chem Ser . 147. i975
(15) T M Florence and G F Batle,-. Talanta.tt, 179(1976)
(16) T M Florence and G F. Bai:e, 7a/anra,24. 151(19/7)
(17, T M Florence and G t Bailey, Talanta. 22, iOI (1975)
(18) A G C'OtigLis and A Y Crinbilo Chapte* in ' Ana'/tica! Me'hods in
Oceanography'. T R PfC»bbs Jr Ed, Adv Ct'om Set , 147. 1975
(19) f> Forbug and S Sundqreen. Aral Chem . 23. 1202(1960)
120) P VV J M Ooumans and F J Delic*. Speclroctam Act,-!. Part B. 31,
355 11976)
(21) P J Pauhen. pnvale communication
(22) R D Eoiger, G E Pelerion and J D Kerber. At Absorpl Newsl. 13,
61 11974)
(23) E C Keuhnsr R Alvarez. P J Paulsen. and T J Muphy, Anal Chem.
44. 2050 (1972)
(24) J W Useiler, NASASP-5074 O(f,ce cl Technology Utilization, NASA,
Washington. D C . 1969.
(25) J A Uean and T C Pains. Ed , Flame Em-ssion and A'ornic Absorption
Spectrometry', Vol 2, Components and Techniques, Marcel Dekker, New
York, 1971
(26) J H Moody and R M Lindstrom Ami Chem . 49. 2264 (1977)
(27) E J Maenttial and D A Beci.ef, Neil. Bin Sana (US ), Tec1) Wore.
929. 1976
128) J R Moody H L Rook P J and Pau en. T C Rains, I L Barnes.
and M S Epstein'. Nn'.l 6V Stand iU S ) Spec Putil . 464, '/' A
Kirchhofl. Ed , 1977
(29) B holymaka. R[jioch?m R.-il.oj'ul le.T , 17, 313 (1974)
(30) D E Leyden and A L Un*"wood J Pny Chem . 68 2093(1964)
(31) M G Lai and H A G-jya, U S Ninal Radiological De'er.se LabOfa'.ory.
Dept of Convnerce. f-iational Tecr-tfiical Intornviiion Service, AD-6J85185.
1966
(32) C M CniWwn. J M Pascual and M G Lai, U S Naujl Radiological
Defense La'ooralcfv Dopt jf Con^x^ce Natioisii Technical Ir'Ofmalton
Service AD-647661, I960
(33) G H Luttie! Jr "C More, and C T Ksnner, Anal Civm , 43 1370(1971).
(34) A C Ka>SPf. J Slam trfoc 36. 128(lB59i
(35) R E Lapp and H L VAndrews Nuclear Radiation Physics", Prer,t»ce-Halt.
F.nylpwood Cli'fi. N J . 1959
(36) J A Dean ,ind T C Rains Ed Flame Emission and Atomic Absorntion
SpectrorTKj'jv , Vol 3 Elements and Matrices Marcel Dekker. New York.
197S
Rn n\; I) for review .luly 31. 197S. Accejiled September '2Ci,
1978. '] his paper was taken in part from the dissertation
written b\ H M K. and accepted by the <;i dilate school. The
Amt'ncan University, in partial lullillment of the requirement.s
for the degree ot Doctor of I'h:lo-:iohv in ChemKtry. Inord'.r
to iif.ii '|U itflv describe materials and cxperime; tal ptoc'edures,
it was occasionally iuyessar\ to identify ,-ommercial products
b\ manufacturer's njitne or label In no instance does such
identification im|ilv endorsement b\ the National Bureau of
Standards nor does it imj !v that the particular products
-------
-s
APPENDIX 4
62
-------
U.S. DEPARTMENT OF COMMERCE
NATIONAL BUREAU OF STANDARDS
WASHINGTON. D.C. TZZJ*
June 17, 1981
REPORT OF ANALYSIS
To: H. H. Kingston
Subject: Determination of Cadmium, Copper, Lead, Manganese, and Nickel in
Aqueous and Solid Samples from the Chesapeake Bay
Method: Atomic Absorption Spectrometry
Atomic absorption spectrometry (AAS) is a unique analytical technique for
the determination of metallic elements. At the present state-of-the-art
the method is widely used to determine seme 60 elements. For some elements
concentrations as low as Id"11* g can be detected [Ij.
The basic conponents of AAS are the (1) primary source of radiation,
(2) production of atonic vapor (flame or electrothermal), (3) wavelength
isolator, (4) radiation detector, and (5) readout.
A number of radiation sources are availablp but the hollow cathode lamp
(HCL), in general, Vj satisfactory for post AAS .vork. For a few elements
which err.it radiation in the far ultraviolet region of the spectrum such as
arsenic and selenium, electrodeless discharge lamps (EDL) are recommended.
EDL's are typically more intense sources of radiation and in a few
cases give improved sensitivity over the KCL.
Historically a flame was the original means of oroducing atomic vapor for
AAS. The flame is still the basic source for the vast majority of the AAS
measurements [2], and it will probably remain ^o for the forseeable future.
The major advantages of the flameras a means of production of atomic vapor
are: (a) simplicity of the technique, (b) soeed with which a determination
can be made, and (c) relative little maintenance of system. The major
disadvantages are (a) a relative large quantity of sample is required for a
determination, (b) a hostile environment is created for the production of
ground state atoms, (c) large quantities of oxidant and fuel gases are
requirec , and (d) sensitivity is limited for many el?ments.
In general the concentration of most the trace elements in seawater are
below the detection limit of flame atomizaticn systems. Therefore, nonflame
or electrothermal atomization (ETA) is generally used. The first furnace
device proposed for AAS was that described by L'vov [3]. In his early work,
a solution was placed on the end of the electrode and evaporated to dryness.
The sample was then vaporized by a dc arc into a carbon furnace. This
device produced impressive detection limits but was limited because of power
requirements and poor precision.
63
-------
Massmann [4] constructed a sornev.'hat simpler graphite furnace which is
basically being used by all manufacturers today. Interierences encountered
v/ith electrothermal atomizaticn devices are more pronounced than in most
flame systems, and the analyst has to rely upon the standard addition
technique or closely matching of 'standards with unknown to correct for the
interferences. Recent improvements in electrothermal atomization-AAS have
greatly reduced analytical interferences. Graphite used in the absorption
cell is a porous material which is easily penetrated by liquids and gases.
Atomic vapor can freely pass through a 1-mm thick wall of hot graphite.
.Coating the graphite tubes with a thin layer of pyrolytic graphite has been
found to greatly reduce the effects of the porosity of the graphite and
increase the sensitivity of some elements. By the inserting of a L'vov
platform in the graphite absorotion cell, it is possible to atomize the
sample at more nearly constant temperature conditions [5]. This reduces
analytical interferences by volatilizing the sample into a gas which is
hotter than the surface from which the sample is volatilized.
The L'vov platform is available from two of the major AAS instrument
manufacturers (Perkin-Elmer Corporation, and Instrumentation Laboratories).
While these platforms can be obtained commercially, they can be prepared in
the analyst laboratory with a minimum of cost. For the P&E-HGA system,
the platforms are constructed by cutting the two ends of a graphite tube
into six (three from each end) 7-mm x 5-mm grooved, curved sections. These
cuts are made using a small stainless steel saw. After the sections are
cut the sides of each section ore filed so that the platform will fit the
inside contour of the graphite tube.
The graphite tube is positioned in the furnace head. The right window
is temporarily removed and the platform inserted. The platform is then
centered directly beneath the sample pert using a metal rod. Adjustments
of the automatic injector tip is made to insure that it does not corr.e into
contact with the platform surface.
An essential part of any AAS unit is the monochromator. The monochromator
must isolate the analytical line from the various other lines emitted by
the source. Failure to resolve the analytical line from all spectral
irradiation will result in a loss of sensitivity and nonlinear calibration
curve. Another important component of an optical system is the slits to
the monochromator. It is desirable that the slit widths be variable as
they control the resolution of the monochrcmator. Normally the analyst
operates at a slit width which gives the desired resolution from any
adjacent lines. For some analytes the minimum slit width fails to give
the desired resolution of the analytical line and, in that case, a tradeoff
is made between spectral resolution and sensitivity of the analyte.
The multiplier phototube is widely used as the radiation detector. A list
of the most commonly used multiplier phototubes is given by Rains [6].
For readout devices, meters and recorders are popular. Digital readout
devices are gaining in popularity and may be considered essential for highly
precise work. Advantages are that operator bias in madng readings is
eliminated, and since the digital device employs a decinal-to-binary or
BCD converter on the output, the signal can be fed to a printer or tape
punched for subsequent computation on a computer.
64
-------
ETA-AAS is being widely used for the determination of trace metals in
seawater because of its low detection limits and its relative ease of
operation [7]. Hov/ever, concentrations of most trace metals in seawater
are often faelcw the detection limit of even the ETA-AAS method. Also, the
dissolved solids (3.5 g/L) in seav/ater may cause serious interference in
the determination of many trace elements. Matrix modification is often
used to help alleviate the interference associated with high solids;
however, this technique was found to be effective only in a few cases. If
the trace metal is below the detection limit of ETA-AAS, some form of
prpconcentration is required. Many studies [2,8-10] have been reported
to serve this purpose.
Evaporation is a widely used procedure. It is simple but slow and chemical
treatment of the sample is minimized. Only rarely do problems of volability
of components or losses on container walls prevent the use of evaporation.
However, if the total dissolved solids are high, then preconcentration by
evaporation may result in a solution with unacceptably high total solids.
Chelation and solvent extraction is a very common method of concentrating
trace metals. One advantage is that unwanted bulk matrix components such
as the major salts in sea water are often not extrurted. Extraction is
rapid and concentration factors of 20-50 can be achieved. For successful
extraction the aim is to form a stable complex ,vhich has low solubility in
the aqueous phase but has high solubility in the organic phase. The organic
phase should have limited solubility in water. Problerrs are encountered
with chelation and solvent extraction because the distribution of the complex
between the two phase is affected by the pH, the concentration of the organic
reagent, the solubility of.the complex in the two phases and the ionic
strength of the aqueous phase.
Co-precipitation techniques are frequently used to preconcentrate trace
elemental concentrations. In this technique ths analytes are collected by
precipitation on a "carrier-precipitate'1, which is dissolved in a small
quantity of solution. The co-precipitation technique has a number of
disadvantages such as lengthy and tedious procedure, and the final solution
may contain large quantities of dissolved solids.
Ion-exchange methods, although very time-consuming, can be used to concentrate
many metal ions. Col urn.is can be mad.e in any desired size, from a few cubic
millimeters up to columns of many cubic meters. The diameter of the
column depends on the amount of material to be treated; the length depends
on the difficulty of th<> separation to be accomplished. Ion-exchange
resins are porous insoluble 3-dimensicnal polymeric compounds, usually in
the form of powder or small beads. They include firmly bonded organic
functional groups. Associated with thesa functional groups are ions,
either cation or anions, which can be exchanged for ions in solution.
A description of the various anion and cation exchange resins is given by
Dean [11]. Kingrton et.al. , [12] used Chelex 100 resin and ETA-AAS to
determine Cd, Co, Cu, Fe, Mn, Hi, Pb, and Zn in estuarine water from the
Chesapeake Bay end seawater from th? Gulf of Alaska.
65
-------
Procedure
A. Aqueous
A test portion of the estuarine sample from the Chesapeake Bay was precon-
centrated by H. M. Kingston and E. S. Seary using the method described by
Kingston et al., [12]. The cluate from'this separation which is 2.5 M HN03
was analyzed directly for the analytes by ETA-AAS using the L'vov olatform.
To check for chenical interferences, the single standard addition method
was used [2]. The instrumental conditions for each element are given in
Table 1.
B'. Solids
The solids which were collected on 0.45 urn filter paper were prepared by
transferring the filter paper to a Teflon beaker. Then, five ml of H!I03
and one ml of Hf were added and solution warmed. After the paper had
decomposed, five ml of HCIO^ was added and sample solution evaporated to
near dryness. The solids were then dissolved in one ml of HfI03 and five ml
of water and then transferred to 10 ml volumetric flask. The analytes were
determined by ETA-AAS using the instrumental conditions described in Table 1.
The recovery of each analyte was checked by the single addition method [2].
References
[1] L'vov, B. V. Atomic Absorption Spectrochenical Analysis, Adam Hilger,
London; 1970.
[2] Dean, J. A. and Rains, T. C., eds., Flame Emission and Atomic Absorption
Spectrometry, Vol. 3. Marcel Dekker, New York; 1975.
[3] L'vov, 8. V. Inzhenerno-Fizicheskii Zhurnal, 2_, 44-52 (1959).
[4] Massmann, H. Spectrochimica Acta, 233, 215-226 (1968).
[5] Slavin, W. and Manning, r>. C., Anal. Chem., 5T_, 261-261 (1979).
[6] Rains, T. C., Special Technical Publication 443, American Society
for Testing and Materials, 1969.
[7] Horlick, G., Anal. Chem., 52_, 290R-305R (1980).
[8] Riley, J. P. and Taylor, D., Anal. Chim. Acta, 40, 479 (1968).
[9] Muzzarelli, R. A. A. and Rocchetti, R., Anal. Chim. Acta, 6J3, 35 (1974).
[10] fiix, J., Goodwin, T., At. Absorp. Mewsl ., 9_, 119 (1970).
[11] Dean, J. A., Chemical Separation Methods, Van Nostrand Reinhold,
New York, 1969.
-------
[12] Kingston, H. M. , Parries, I. U, Brady, T. 0., Rains, T. C., Anal
Cht-i., 50, 2064 (197S).
-V <,-
T. C. Rains, Research Chemist
T. A. Rush, Chemist
< /; >' -r : .
-------
CD
O
CM
CM
1
t 1 1 . 1 ' 1
O O O O O
O CD O O O
n ^o r^- r^ ^*
CM CM CM CM CM
o
en
C 0
i QJ
S- > 1
i- »
000 00
«3~ ^3" *3" - co oo oo
o o o o o
^j~ *d~ «^r «3~ «}
III II
to in ir> in tr>
CM CM CM CM CM
O t i r i r-
to
4J
CO
f- 01
« ro
*- o
CO
O-
o.
o s
t- f- >-> O 1- i.
' U-
J_
,-
«o
4-*
C
CJ
E ro
3 o
vo
^~*
"> UJ
c
-< »a
Q-
*
^~
C
O
i in
>V5 C
(J f3
c/> d
X
UJ
CM CM CM in ro
~sr
oo E
c/i c
t>-- r r^ r t^
. .
o o o o o
*~~ en
c
ill
E
CD
r^.
UJ
.O XI
~O ~ C »r- Xt
o o E: 2: a.
C
o
f
+-> 10
«O "O
o c:
T- 0
i-
fO i-
E <*-
E
S- C i-
O i- O
(j_ n_
4-> X)
ra cu -o
r 10 CO
o. ri oo
=
o O cu
> Q- -0
z o
_J CM E
_C *~^. Q.
M rn H
r- Z ro
3 ct:
-------
Table 2. Control Samples.
Sample Pb Ni Cu Cd
TWS -1
-2
-3
-4
-5
-6
Average =
Std. Dev. =
Rel . Std. Dev. % =
Control, SRM 1643a,
Certified Values 27 ± 1 55 ± 3 18 ± 2 10 ± 1
33
26
28
27
27
26
27
27
31
27
27
29
28
2.1
7.6
16, 19 12
17, 18
17, 19
11
14 10
56 13 13
13 11
49 14
53 16
48
52 16 11
3.4 2.2 0.8
6.5 14 7.4
69
-------
APPENDIX 5
70
-------
APPENDIX 5
BLANK UNCERTAINTIES AND CORRECTIONS
Correction for the analytical blank must be made along with two other
corrections, one for chemical retention anrt the other for the volume change
upon sample acidification. The correction for the analytical blank is the
correction for any contamination picked up during sample handling and
analysis. This correction is the most complicated of the three because the
contamination is modeled as random. For each element and each sample type,
the distribution of the measurements on the blank is obtained. This distri-
bution is used to predict the contamination in the Bay samples and thus to
correct for it. Because the prediction of a random variable is involved,
this correction increases the uncertainty, sometimes considerably. The other
two corrections involve only scaling the results.
Eacn measurement is presented in two ways, as a point estimate of the
quantity and as an interval estimate that is approximately at the 95% confi-
dence level. Note that this summary of the Bay measurements may not be
adequate for all purposes. The Bay measurements will be used in various ways
to draw conclusions: two measurements will be compared, two ratios of
measurements will be compared, the maximum measurement will be compared to
the others, and the average of the measurements from some region will be
compared with measurements from another region. In each of these cases,
whether the difference observed could be caused by measurement error must be
investigated. The proper answer to this question involves, among other things,
the measurement-to-measurement dependence of the measurement error. However,
the point-estimate, interval-estimate summary is useful. It provides a basis
for conclusions when the differences observed are much larger than the
measurement error.
Correction for the blank involves three steps. First, the blank
measurements are modeled. This consists of exploratory analysis, estimation
of a transformation to normality, determination of any dependence on the
batch in the case of the dissolved samples, and determination of any
dependence on the number of filters in the case of tho particulate samples.
Second, the model For the blank measurements is used to find a point estimate
and a one-sided or two-sided prediction interval for tne blank contribution
to the Bay samples. This is done ignoring the uncertainty due to estimation
of the transformation from the data. Third, these predictions are combined
with the uncorrected measurements each of which is accompanied by the stan-
dard deviation of its measurement error. This combination is done in various
ways depending on whether the blank measurements are normal or not, depending
on whether the prediction interval is one-sided or two-sided, and depending
71
-------
or how many of the blank measurements are below the detectable limit. When
the blank measurements are not normal, the Bcnferroni inequality is used.
When most of the blank measurements are below detectable linits, the
procedures are somewhat ad hoc and depend on the magnitude of the detection
limits compared to the concentrations observed.
THE BLANKS
Organization
The measurements that are included in this work conclude the accumulation
of concentration data obtained from samples collected during the 1979 cruise
sampling the Chesapeake Bay. Each elemental blank of each type sample,
particulate and dissolved, was modeled and adjusted using the following
procedures. The data base for the numbers was the raw data uncorrected from
the instruments. Due to the complex nature of the blaiK and sample relation-
ship the computerized blank corrections were rigorous and required an
individual treatment by element. These blank influences are unique for each
element and for each type cf sample of each element (particulate or
dissolved), and occasionally are influenced by the group or batch in which
they were chemically manipulated in the separation and concentration proce-
dures. These factors and other considerations contributed to an individual
statistical model for each elemental blank of the two sample types. This
procedure was necessary for a complete and adequate assessment of the blank
contribution of the concentrations analyzed.
The blank values with uncertainties also appear as discrete data and are
themselves important and are input and maintained with the data for future
reference.
Each element was treated individually ard the statistical evaluation and
mathematical manipulation necessary to correct the average value for the
blank and uncertainty was addressed. In some cases the blank was relatively
insignificant in relation to the levels of the element of interest. In other
instances the level of the blank was below detectable limits and was
evaluated with the understanding that the limit of detection was an upper
limit below which the concentration of thf: blank exists unknown.
72
-------
The total data base for the entire project is organized as follows:
TABLE I. ORGANIZATION OF DATA
Elements Determined
in the Participate
Elements Determined
in the Dissolved
Portion of the Sample Portion of the Sample
Instrumental
Method of
Determination
Data Subset A
Ce
Co
Cr
Fe
Mo
Sc
Sn
Th
U
Zn
Data Subset C
Cd
Cu
Mn
Ni
Pb
Data Subset B
Co
Cr
Fe
Mo
Sc
Sn
Th
U
Zn
Data Subset D
Cd
Cu
Mn
Ni
Pb
Neutron
Activation
Analysis
(NAA)
Graphite Furnace
Atomic Absorption
Spectrometry
(GFAAS)
Corrections
There are several reasons for the need of a more refined method of
handling blank contribution than are traditionally utilized. The blanks are
significant for several elements. The en gin of the blank concentration
dictate the statistical treatment of the blank. There are several sources of
blank contribution and also more than a single statistical relationship for
the concentration range of the blanks. Therefore, it is necessary to
establish a statistical model for each elemental blank to arrive at a statis-
tically accurate mean value and uncertainty range that is known within the
desired confidence limit and which produces, after subtraction, a corrected
concentration with uncertainties that are at least at the 95 percent
confidence limit.
Each element of the sample type (dissolved and particulate) is discussed
separately. Each blank model is presented and the subsequent mathematical
manipulation documented. A detailed mathematical procedure follows
describing the statistical form of correction, its magnitude and some
explanations, where relevant, to specify the blank procedure used in each
case.
73
-------
Cobalt; Dissolved (Data Subset B)
The model of the blank was log normal with a 0.0045 ng/mL shift,
log(Xi .-0.0045)-vrJ(.,a2). This should be read: the logarithm of the blank
values X.. minus 0.0045 ng/mL was normally distributed N with mean \i and
variance a2. This model suggested two sources of Co, one at 0.0045 ng
(possibly from the irradiation film or the resin) underlying the other
contributing source distributed log normally.
The point prediction P was 0.0091 ng/mL with a lower limit L=0.0049 ng/mL
and upper limit 11=0.0659 ng/mL.
Since subtraction of a blank was required, adjustment of the uncer-
tainties was made to the 97.5 percent confidence limit to produce an after
manipulation of at least the 95 percent confidence limit. The adjustment of
the confidence limit from one sigma to 97.5 percent was accomplished by
equation 1.
C-2.24a, C, C+2.24a (1)
where C was the uncorrected concentration and a represented the uncertainty
given to C. To produce the blank correction and adjust the confidence limits
in one step, equation 2 was used with the upper limit (U) subtracted from
C-2.24a, the point prediction (P) was subtracted from C and the lower limit
(L) was subtracted from O2.24a:
[(C-2.24a)-U], (C-P), [(C+2.24a)-L] (2)
If the minimum value thus obtained is less than zero, the situation in which
the observed concentration could not be distinguished from contamination at
the 2.5 percent level occurs. In this case, the minimum value was replaced
by zero. Also, any other values that were less than zero were replaced by
zero.
Iron, Dissolved (Data Subset B)
The iron blank was modeled by log(X. -0.4)^N(;i ,02). The point prediction
was P=1.12 ng/mL with lower limit L=0.56 ng/mL and upper limit U=3.68 ng/mL.
Equation 2 produced a corrected value with limits at least at the 95 percent
confidence limit.
Lead; Dissolved (Data Subset B)
The blanks were modeled by a log normal distribution log(X. . KN(U ,o2)
with a point prediction of 0.133 ng/mL and a lower limit of 0.0563 ng/mL and
an upper limit of 0.316 ng/mL. Utilizing equation 2 produced corrected
values with limits at least at the 95 percent level.
74
-------
Thorium; Dissolved (Data Subset B)
The thorium blank values were distributed log normally log(X. .) <-N(M ,a2)
and hjd a point prediction P of 0.0004 ng/mL and a lower limit L=6.GOOO ng/mL
with an upper limit of 11=0.0044 ig/mL. Due to the non-computation of the
lower limit L, a modification to that side of the equation 2 was made which
resulted in eliminating the need to have a 2.5 percent uncertainty reserve
for computational purposes. Thus the equation used for the adjustment of
thorium was as follows:
[(C-2.24a)-U], (C-P), [(C+1.96o)-L] (3)
The values adjusted in this manner resulted in blank corrected data v;ith an
uncertainty of at least the 95 percent confidence limit.
Copper; Dissolved (Subset D)
The copper blank data was modeled in a log normal manner.
Log(X, .HN(u.a2) with a point prediction of 0.06 ng/mL and lower limit
L=0.00 with an upper limit 11=0.84 ng/mL. The handling of these blanks was
similar to that of the dissolved thorium. The use of equation 3 was
implemented.
Chromium; Dissolved (Data Subset B)
The model for the chromium blank was normally distributed, X. .^N{y ,o?).
> J
The point prediction P was 1.55 ng/mL with a standard deviation o. of
0.10 ng/mL. In this case the concentration uncertainties and the blank
values were both modeled normally. Thus, another form for the correction
procedure resulted.
Correction for the chromium blank was accomplished by subtracting P from
C, C-P. The correction of the uncertainties to at least the 95 percent
confidence limit was accomplished by substituting a (the reported analytical
uncertainty) in the following equation for each concentration uncertainty. A
return to the symmetrical normal form was possible for chromium, see equation
4.
(C-P) ± 1.96/T^7" (4)
This was a result of the majority of the chromium being contributed by the
LPE irradiation film in which the sample was sealed, and thus it wac logical
to have obtained a normal distribution.
Scandium; Dissolved (Data Subset B)
The blanks were normally distr
with point prediction P=0.00012 ng/mL. The standard deviation a was 0.00004
The blanks were normally distributed for scandium following X. .'vN(-i ,o?)
t., .. ,,.f,}.-ri.
-------
ng/mL and was treated in a similar manner as the chromium. Equation 4 was
utilized in the adjustment of the concentration data to at least the
95 percent confidence limit.
Bgtch Preparation Blank_Dep_endenc_e
In the preparation of the dissolved samples for both NAA and GFAAS
analyses the chemical manipulation was complex and time consuming. The time
required co prepare each sample necessitated a batch organization The
batches were usually organized in numerical order. At this time the batch
blanks, standards and corresponding blank filter numbers corresponding to the
samples being prepared were also prepared. In the statistical analyses of
the blanks and samples the bacch dependence of this preparation was also
checked statistically. It was found to be significant in a few cases and in
these cases a within batch point prediction P, lower limit L, and an upper
limit U were calculated. For both aata base set B and D the sample numbers
were coded to include their batch run number for example 11,001 1, Blank 9 1
and 11,0018 1, were all prepared in batch r_n number 1. The last d-igit
coming after the space for both data set B ond D indicated the batch in which
it was prepared. There were 8 batches and where a run dependence was
statistically significant the element had a set of P, L, and U values for
that batch.
Nickel; Dissolved (Data Subset D)
There was observed a statistically significant batch preparation blank
component for nickel. The blank values for nickel werft log normally distribu-
ted log(X. .) ,'<(ii. ,a?). The P, L and (J values are given in Table II.
\J vJ
TABLE II. THE P, L, AND U VALUES hOR THE DISSOLVED NICKEL
BLANK CORRECTIONS
_______ Concentration in ng/mL -------
Batch Number Point Prediction r Lower Limit L Upper Limit U
1
2
3
4
5
6
7
8
O.C5
0.04
0.23
0.18
0.06
0.06
0.23
0.10
0.02 0.18
0.01 0.12
0.07 0.77
0.05 0.62
0.02 O.?0
0.02 0.21
0.07 0.78
0.03 0.32
These P, L, and U values were treated as other blank <, ; -rections with a
mathematical operation following equation 2. The only difference was the use
of the P, L, and U corresponding to the same batch number rather than using a
sirgle point and limits for all batches.
76
-------
Zinc; Dissolved (Data Subset B)
The zinc blanks were modeled using 3 log normal distribution with a
starter component log(X. .-H .Oh-N(|i. ,T ). The batch component dependent point
' J J
predictions and limits appear in Table III.
TABLE III. THE P, L, OR U VALUES FOR THE DISSOLVED ZINC
BLANK CORRECTIONS
Batch Number
1
2
3
4
5
6
7
8
Point Prediction P Lower
0.56
0.83
0.80
1.21
1.09
1.57
1.73
3.05
in ng/mL
Limit L
0.00
0.00
0.00
0.11
0.05
0.29
0.37
1.02
Upper L'imit U
2.12
2.76
2.60
3.42
3.18
4.14
4.45
7.08
The treatment of these blank corrections and adjustments of the uncertainty
on the concentration was as described previously. Batches 1 through 8 were
adjusted using equation 2.
Manganese; Dissolved (Data Subset D)
The manganese blanks were modeled using a normal distribution and
demonstrated a batch dependency X . .^N(y - ,c?). The P, L, and U values are
presented in Table IV. ^
TABLE IV. THE P, L, AND U VALUES FOR THE DISSOLVED MANGANESE
BLANU CORRECTIONS
.
Batch Number
1
2
3
4
5
6
7
8
_ Pnnr
Point Prediction P
0.56
0.73
0.00
0.36
0.18
0.00
0.69
0.00
entration in ng/m
Lower Limit L
0.20
0.37
0.00
0.00
0.00
0.00
0.25
O.CO
[____-_--
Upper Limit U
0.93
1.10
0.008
0.72
0.56
0.003
1.13
0.008
77
-------
The treatment of these blank corrections and adjustment of the uncertainty on
the c6ncentration was as described previously. Batches 1 through 8 were
adjusted using equation 2.
Concentrations Needjng No Blank Correction
Molybdenum, Tin, and Uranium; Dissolved (Data Subset B)
Cadmium; Dissolved (Data Subset 0)
Manganese; Particulate (Data Subset C)
For each of these elements the blank contribution to the measurement was
undetectable in almost all blank samples. Jt was therefore statistically
impossible to provide even the most minute correction resulting from a blank
component in the qiven concentrations It was also not possible to project
the probability increase in the limits of the concentrations given.
However, this was not significant for uranium, molybdenum, or manganese
where a consistent measurement two to three orders of magnitude above the
limit of detection was uniformly measured for the samples. Any blank correc-
tion given these conditions was insignificant. Therefore supposing the louer
limit of detection to be its maximum upper level, no blank correction was
necessary.
For cadmium and tin the majority of the samples were below the detection
limits. There were no tin volues for any blanks and statistically no
i. evaluation could be made. The observation that the blanks for tin were a1!
below the lower limit of detection gdve confidence that the measured concen-
trations for the sables were significant levels cf tin and were tea!
observations, not artifacts of a variable blank.
There were four cadmium blanks observed just above the detection limit.
The data were not strong enough tc support a consistent blank at or above the
detection limit of the instrument and no blank correction could be attempted
for cadmium.
Although no blank correction was needed it was necessary to adjust the
upper and lower limits of the data to at least the 95 percent confidence
limit. To accomplish this equation 5 was used.
C-1.S6;;, C, J + 1.96.- (5)
Copper; Particulate (Data Subset C)
This statistical treatment was applied to copper and a dependence on the
number of filters used in the sample collection was found to be a significant
contributing factor to the blank concentration. As in previous work of this
type the P, L, and U were dependent upon the number of filters for that
* soirple. The number of filters for each sample is given in Appendix 1. It
was found that there was no significant dependence related to the type of
filters, therefore only the nur.bers of filters used to collect the sample was
significant. Table V provides the P, L, and U used for the blank correction.
73
-------
To correct the concentrations for blank and obtain the uncertainties to
at least the 95 percent confidence liimt equation 2 was used.
TABLE V. THE P, L, AMD U VALUES FOR THE PARTICULATE COPPER
3LANK CORRECTION
Number of
Filters
]
2
3
Point Prediction
0.23
0.46
0.68
P Lower Limit L
0.08
0.23
0.39
Upper Limit U
0.45
0.76
1.06
Lead; Particulate (Data Subset C)
Since only a few blank levels were marginally above the lowest limit of
detection the blank values were influencing only a small number of the
concentrations obtained. Although a blank correction was not warranted for
the concentrations, an uncertainty of a magnitude comparable with the blank
influence was included. This was accomplished by increasing only the lower
uncertainty. Using an upper lir.iit U = 0.04 ng/mL and adjusting the data to
at least the 95 percent confidence limit using equation 6 produced a
conservative treatment for the data.
[(C-2.24a)-U], C, C + 1.960
Nickel; Particulate (Data Subset C)
(6)
Reasoning similar to that for the lead particulate data led to a similar
treatment where U = 0.09 ng/mL. Applying this in equation 6 yielded a confi-
dence limit of at least the 95 percent confidence limit.
Zinc; Particulate (Data Subset A)
The blanks for zinc consisted of 1, 2 or 3 filters. Since the data
showed clearly that the amount of contamination depended on the number of
filters, a model for the dependence of the contamination on the number of
filters was needed. Contamination might have increased with the number of
filters because the filters themselves introduce contamination and because
more handling is needed for more filters. Thus, the contamination might have
been modeled as the sum of 1, 2 or 3 independent random variables depending
on ,iow nany filters are in the blanks. With this model, the mean and the
var'anc ; of the contamination were both proportional to the number of filters.
Thai the variance was proportional to the mean suggested the use of the
square root transformation to obtain data for which the variance did not
depend on the number of filters. In figure 1, the square root of the con-
tamination was plotted versus the square root of the number of filters. A
linear relation between the two square roots was plausible but the data were
79
-------
1.5-1
Square Root of Zinc Concentration
for Blanks
x
X. V rnil'ipore
+, -L Amicon
V,JL Less than'values
1.0-
c
o
c
o
o
0.5-
0.0-J
i
0
1
Number of Floors
Figure 1.
x
i
3
80
-------
insufficient to provide any support for the hypothesis of constant variance.
Note that two different filters, FP Hi pore and Ami con, were represented but
could not be distinguished.
Let Z be the amount of contamination and N tie number of filters. The
model
/Z =
+ e (7)
was fit by ordinary least squares giving the fo lowing predictions for the
amount of contamination in the real samples.
TABLE VI. THE P, L, ANSJ U VALUES FOR THE PARTICULATE ZINC
BLANK CORRECTION
Number of
Fil ters
1
2
3
Point Prediction P
0.20
0.41
0.61
98.75" Confidence Limits
L
0
0
0
U
1.30
1.30
2.27
To obtain limits for the zinc measurements that were at least at the 95'i
confidence ievel, the original values denoted by C ± c were used to obtain
96.257, confidence limits for the concentrations uncorrected for the blanks
C - 2.24c, C, C + 1.96a (8)
Then, subtraction of the upper lim^t (U) on the blank from C - 2.24a, the
point prediction (P) from C, and t.ie lower limit (L) on the blank from
C + 1.96a as indicated in equation 8 yielded equation 3.
[(C-2.24a)-U], (C-P), [(C+l.96o)-L] (3)
The values for F1, L, and U corresponded to the number of filters used for the
sample being operated upon. If the minimum value thus obtained was less than
zero, the situation existed in v;hich the observed concentration could not be
distinguished 1rom contamination at the 2.5. level. In this case, we
replaced the minimum value by zero. Also, any other values that were less
than zero were replaced by zero.
Chromium; Particulate (Data Subset A)
Our analysis for chromium was the same as that for zinc (Data Subset A)
with two exceptions. First, the polyethylene bag that contained the filters
contributed 0.07 ng to the concentration as seen from the measurements on the
bag alone. Thus, subtraction of 0.07 ng before taking the square root was
81
-------
necessary. The result which is plotted in figure 2 shows clearly that the
Millipore filters contained less chromium than the Amicon filters, suggesting
that the filters and not the handling contributed the chromium. This idea
was supported by the values for the filters that were not subject to handling.
For this reason, separate relations for each filter type were fitted. Figure
2 shows that the variance for the Amicon filters was larger (the F-test is
significant at the 0.01 level). Nevertheless, the sums of squares were pooled
to estimate the variances. This pooling was based on the assumption that each
set of filters had the same uniformity and was subject to the same contamina-
tion mechanisms.
To correct the concentrations for blanks and obtain the uncertainties to
at least the 95/i confidence limit, equation 2 was used.
[(C-2.24a)-U], (C-P), [(C+2.24a)-L]
TABLE VII. THE P, L, AND U VALUES FOR THE PARTICIPATE CHROMIUM
BLANK CORRECTION
(2)
Concentration in ng/mL
MILLIPORE
Point Prediction
P
0.18
0.35
0.53
97.5% Confidence Limits
I
0.12
0.21
0.33
U
0.46
0.72
0.97
AMICON
1
2
3
0.71
1.43
2.14
0.48
1.04
1.62
1.17
2.04
2.89
Iron; Particulate (Data Subset A)
For iron the square root of the iron measurement was normally distributed
with mean 1.04 ng/mL and standard deviation of 0.4 ng/mL we conclude
that the contamination might be as high as 3.7 ng/mL (at the 97.5:; limit).
Because the data on the contamination is so sketchy (due to 'less than'
values predominating), the measurements and their upper limit are not adjusted
for contamination. The lov.'er limit was reduced by 3.7 ng/mL to account for
the possibility of contamination. The upper limit, point prediction, and
lower limit were calculated as follows:
[(C-2.24a)-3.7], C, C+1.96o
(ID
This ga,"? at least a 9573 confidence limit. Any minimum value less than zero
after adjustment v/as adjusted to zero as a negative was not possible.
82
-------
Square Root of Chromium Concentration -0.07
for Blanks
_J
E
o
o
o
c:
o
o
1.5-
1.0-
0.5-
0.0
X millipore filter
§ Amicon Filter
O Unprocessed Filter
0
1
I
2
Numbor of Filiars == M
Figure 2.
\
-------
Scandium; Particulate (Data Subset A)
... we conjecture that the square root of scandium measurements might
be modeled as normal with mean 1.14 x 10~2 and standard deviation 1.14 x 10~2.
This suggests that the contamination might be as high as 0.0013 ng/mL as with
ircn this value could be subtracted from the lower limit on the values for the
real samples. The highest observed blank value was half this amount. The
samples were adjusted to yield a final 95/> confidence- limit overall.
C-1.96.J, C, C + 1.96a (12)
Fortunately, most measurements on the real samples were well above the
observed contamination values.
Uranium; Particulate (Data Subset A)
For uranium, the blanks are all reported as 'less than1 values. These
values, which are quite variable, reflect primarily the background levels
rather than the uranium levels. All that can be said is that the contamina-
tion observed in the blanks does not exceed 0.02 and that the contamination
may be orders of magnitude less than 0.02. Unfortunately, the uranium values
for several real samples are less than 0.02. For these samples, the
possibility that the observed levels are due to contamination cannot be
objectively ruled out. A user of the uranium values should be warned of this
problem, but no correction of the uranium values for the contamination was
applied.
To adjust the upper limit and lower limit to yield a final confidence
limit of 95'i, the samples were adjusted as follows:
C - 1.96o, C, C + 1.96a (13)
This was appropriate because no blank adjustment was necessary.
Cerium, Cobalt, Thorium and Molybdenum; Particulate (Data Subset A)
For cerium, cobalt, thorium and Tiolybdenum, we can do little but observe
that the blank values observed are certainly less than 0.038 for Ce, 0.017
for Co, and 0.003 for Th. Correction for the blank was suggested since the
data are too limited to allow any model of the contamination to be surmised.
Fortunately, most measurements on the real samples are well above the
observed blank values.
To adjust the upper limit and lower limit to yield a final confidence
limit of 95", the samples were adjusted as follows:
C - 1.96o, C, C + 1.96a (5)
Thi<: was appropriate because no blank adjustment was necessary.
84
-------
The Correction for Chemical Retention of the Pissolved Concentrations
As published in the 1978 article by Kingston, et al., the retention of
the elements was either quantitative or had a reproducible recovery. These
recoveries which have been documented in the 1978 Analytical Chemistry
article including Cd, Co, Cu, Fa, Mn, Ni, Pb, and Zn as applicable to sea,
estuarine, and fresh water utilizing GFAAS as the analyzing instrument (1).
The other elements of interest Cu, Mo, Sc, Sn, Th, and U were tested for
their recoveries to calibrate the technique for these elements. The
retentions applicable to these analyses are given collectively in Table VIII.
TABLE VIII. THE RETENTION OF SELECTED TRACE ELEMENTS DONE BY
NAA OR GFAAS AS DIRECTLY APPLICABLE TO THESE
SAMPLES (UNCERTAINTIES AT THE ONE SIGMA LEVEL)
Element
Percent Retention (R)
Cd
Co
Cr
Cu
Fe
Mn
Mo
Ni
Pb
Sc
Sn
Th
U
Zn
99.99 ±
99.5 ±
94.94 ±
99.97 ±
93.1 ±
99.99 ±
98.38 ±
99.91 ±
98.4 ±
84.84 ±
83.85 ±
82.83 ±
98.8 ±
99.96 ±
0.071
0.3
0.33
0.03
2.2
0.11
0.19
0.083
0.48
0.22
0.16
0.34
0.2
0.097
The percent retentions in Table VIII were used to correct the concentrations
of the dissolved samples of data subsets B and D, after the blank values had
been subtracted. They were, however, not applicable to the particulate
samples in data subsets A and C and were not applied to these data subsets.
The statistical uncertainty of these corrections for each element was
evaluated and shown to be insignificant when compared to the instrumental
uncertainties, the blank contribution and the conservative arithmetic
handling of the data. Application of the uncertainties at this time could
result in a rounding error more significant in most cases than the uncer-
tainty of these retentions.
The correction was made for each best value and its lowest and Mgnost
estimate using the form x = £ where x was the final concentration adjusted for
85
-------
retention, blank, and which was at least at the 95 percent confidence limit;
R was the fractional retention in decimal form; and y was the concentration
after blank correction and 95 percent adjustment.
There were certain elements in the dissolved data subsets B and D for
which the correction was unnecessary due to the completeness of the retention.
These elements were: Cd, Co, Cu, Mi, f-'n, U, and In. Therefore the retention
corrections were made on Cr, Fe, Mo, Pb, Sc, Sn, and Th only.
These corrections were carried out in such a way as to make use of the
computer memory storage of additional significant figures from previous
operations. The rounding error was minimized by only rounding after the last
computation had been completed, only then returning to the original number of
significant figures. Example:
x - _ -1111 x - - i? 02 x - _ - 13 2P
0.8283 ""> x 0.8283 '^U£> x 0.8283
This was the last adjustment step for the dissolved data subset D and these
concentrations were rounded to ths original number of significant figures.
Following the example each concentration had two significant figures and was
returned to two significant figures i.e., 11, 12, and 13 ng/mL, respectively.
Adjustment for Volume
There remained an adjustment that was applied to the particulate subset
A and dissolved subset B concentrations only. This factor was applied to
sample concentrations and range but net to any less than upper limit values
or blank values. This correction arose from a volume change due to the acid
added for stabilization of the samoles.
The ratio to be multiplied was
. ,.0285
This correction was made on data sets C and D during the analysis by GFAAS.'
The Final Form
These aforementioned manipulations adjusted the concentration data to at
least the 95 percent confidence limit, compensated for blank and retention
were applied where necessary, producing a data set in final form.
Two types of data information were left uncorrected after these manipula-
tions, the blanks themselves and the less than numbers. Both of these groups
were preserved in their original form, i.e., the blanks and less than numbers
did not have blank correction manipulations operated upon them. The blanks
.vcre Maintained in separate data files by element and sample type with their
uncertainties. The less than values were also maintained but with the other
concentration data indexed by sample number. They did not, however, lose
their identity as less than numbers and, when retrieved, were retrieved as a
less th-^n with no discrete mean value or uncertainties.
._or. i-rV - u n ' !i, A
-------
LITERATURE CITED
(1) E^senhart, Churchill, "Expression of the Uncertainties of Final Results'
NBS Special Publication 300, Vol. 1, page 69-1201 (1969).
(2) Currie, Lloyd A. "Limits for Qualitative Detection and Quantitative
Determination, Application to Radiochemistry" Anal. Chem., 1968, 40_
(enclosed).
87
-------
APPENDIX 6
88
-------
Table 1
1HE CONC^nTRATJOr* OF .US-S^VED
C 1 f« N A.r.'OGk A f S/MIL LILITEP)
IHF PANGt
THE 95%
RfciPPrSENTS
AT L
Li'-'ITS
M IM M Ij
BEST VALUE
MAXI.'-'U'-'
11102
11101
11100
11099
1 \09»
11097
1 i09o
11095
11094
11093
11092
11091
11090
1 1 Q8 9
1 1 0 b r>
110*7
1 1 Od6
11085
110*4
110H3
1 1 0 1 2
110*1
llObO
11079
11078
11077
11076
11075
11074
11073
11072
11071
11070
11069
1106ft
11057
1 i 0 o 6
11065
1 1 0 o 4
1 1 0 b 3
11062
11061
11060
11 0 < 9
1105B
1 1057
11056
11055
1 1054
11053
11052
8
8
8
8
8
fe
Q
7
7
7
7
7
7
7
7
7
7
7
7
7
7
7
6
b
6
6
6
6
o
6
6
b
6
6
6
5
5
5
5
5
5
5
5
5
5
5
5
5
c.
5
4
0
0
u
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
(.'
0
0
0
0
0
0
.oyi
.050
.020
.077
.034
.06^
.048
.014
.068
.035
.043
,0b7
.035
.030
.059
.069
.068
.067
.050
. 0 3 £
.026
.053
.025
. 0 2 4
.043
.035
.029
.010
.025
.020
. r 4 4
0.007
0.101
0.062
0.024
0,095
0.042
0 . G 0 7
O.C'>7
0 . < 0 7
0.007
0,087
0.060
0.018
0 . 0 b 6
O.C-45
0.053
0.083
0 .045
0.007
0 . r, r 1 7
0.007
0.' 33
0.071
0.007
o . c -r/
0 . 0 « 4
0.083
0.062
0.016
0.032
0.041
0.007
0.007
0.031
0.010
0.055
0.007
0.01?
0.045
0.007
o . c n
0 . r> 2 3
u . o n
0.007
0 . 0 2 i
0.007
0.007
0.00?
0.007
0 .007
O.C56
0
0
0
0
c
0
0
0
0
0
0
0
o
0
0
0
0
0
0
0
0
0
0
0
0
0
0
o
0
r
0
.121
.074
.02P
.113
.050
.105
.072
.022
.104
.055
.063
.009
.055
.046
. 0 8 7
. 1 ''5
.100
. 09°
.C74
.05b
.038
, 049
.037
.036
.Ot-,7
.055
.041
.027
.037
. 0 < ;
. (>* y
X
'«$ Vr-^V^f'filiinl
-------
T?ble 1 continued
1HK CO''C<- r.'THA riCr.' LK DISSOLVED CAD" 11!"
( 1% NAvO'.'HAvS/viLLiLjTf.-p)
Tne. kASG«-~ Ff^KS^MS AT J,fAE7
Trif-" 4 < 0.0)7
11U4 S 4 o.Oll 0.0iS 0 . 0 I o
110^44 < 0.0 o 7
11^434 0.024 0.03n 0.0 31-
110 4 2 J < 0.0 0 7
1 1'' » 1 4 < 0 . 0 0 7
U 0 4 0 4 < 0 . 0 o 7
H03V 4 0.04s 0 . 0 h rt 0 . 0 7 2
Ho3e 3 0.019 0.0? J 0.027
11037 3 U.0 ? 4 0.0^0 0.03o
1103ft 3 < 0.0)7
1103b 3 < O.f'07
H034 3 < y.007
M ' - 3 3 3 < 0 . 0 0 7
11032 3 < 0.007
1l0313 < o.on7
IK'JO 3 < 0.007
1 ! 0 2 * 3 < 0 . 0 0 7
lK>2?i3 < 0.007
110?7 3 < 0.007
11026 3 < C.007
1 1 0 2 S 3 < 0 . 0 0 7
11024 2 < O.C07
HU232 < 0 . 0 n 7
H022 ? < O.OO/
11021 ? O.ru U.U1S 0.019
11020 2 0.028 0.034 0.040
11 C 1 9 2 0.032 0.010 0 . 0 ft u
HOlfa 2 r>.oob O.C07 0.004
11017 ? O.jOS 0.007 O.r.O'V
HCIfc 2 0.0)2 0.01* 0.020
11015 2 < 0.007
11014 2 < O.C'07
110132 < o.0 0 7
110122 < 0.0 I 7
110112 < 0.0 o 7
1 ICi 1 '" 1 < 0 . 007
11C09 1 < 0.007
1 1 0 0 b 1 < 0 . f") 7
110r'7 t < O.C 07
1 i '' C c 1 < 0 . 0 0 7
1 1 -J 0 5 1 < o . 0 0 7
110041 < 0.C n 7
110031 < (, .007
11002 1 < 0.007
11001 1 go < 0.007
-------
Table 2
'IHK C'Jf.Ctf.TRATlu'.' OF DISSOL/^D
( !< -iA.-.CGPA'-S/ -H.LIL1T--H)
Tnl. K
THE:
;K KKPPKS'-NTS AT I^'AJ
CO'^F lOKNCtC LIMITS
?-.PLL
"I N I'-'UM
11102
1 1 1 o 1
11100
11099
1 1 U u »<
1 1"<*7
11 1. '-< *
1 1 n r-i 5
i 1 U S -*
11043
1109 J
11091
11000
110*9
1 lu*-h
1 1 o b 7
1 1 0 f c
1 1 0 s. b
1 1 0 V 4
1 10 i- 3
1 1 0 f 2
1 lOc-1
1 H/j-'G
11 07 9
1 1 o 7 (
11077
1107o
1107b
1 1074
11073
11072
11071
11070
11069
11 0 6 b
1 1 0 o 7
11066
11065
1 1 0 b 4
11 Ob3
11 0 e 2
11061
11060
110S9
1 1 Ob?
11 (iS 7
1 1 0 b b
1 lObb
1105 -1
1 1 0 b 3
110b2
fe
B
8
H
h
h
(4
7
7
7
7
7
7
7
7
7
7
7
7
7
7
7
6
6
b
6
6
b
b
6
6
6
6
6
6
b
5
5
5
b
b
5
b
5
5
b
b
5
b
C,
4
0.000
0 . 0 '1 0
0.077
0.000
0 .000
o.ooo
0 . OOH
o.ooo
0.07 '.)
O.Olb
o.ooo
0.000
0.00 0
o.ooo
0.000
0.000
o.ooo
0.429
0. 000
0 . 0 0 0
o . n o n
O.Oof,
O.C 00
0.00 S
0. JOG
o.ooo
0.000
0 .038
0 . 0 0 0
0.128
0.000
0.000
0,000
0.00?
0 . 0 0 0
o . 1 OS
0.000
0.031
o.ooo
0 . (1 b 8
0 . 0 0 0
o . o o o
0 . 0 0 0
0 . 0 0 0
0 ,OOQ
0.003
0 . 0 0 U
0.00 0
o. ooo
0 . 0 0 u
0 .000
0.049
0.041
0.1-54
0 . 0 h d
0 . o f, b
o. o s o
0 . o 7 b
OS7
ISh
0*2
044
0.026
0.025
0.041
0.063
0.04*
0 .049
('.020
0 . 0 ? 6
0.031
0 . 1 6 S
0 . " 2 7
0.0 7h
O.Obft
O.Obl
0 . 0 -1 U
0.1 10
o r o i ^
0.210
O.o2i
0.023
0.073
0.070
0 . 0 S 5
0.189
G . 0 S
-------
Table 2 continued
Ihr
ff AT JC'< OF DlSoPLV^D
C IN
'ME KAf.GL
JTS AT LF.AST
CONFinrs'Cf
11051
llObO
110*4
3 1 ( 4 H
ll&O
1 1 0 < t-
11045
11044
1 1 ( ; 4 3
11042
110-ii
11 0 4 C
1 1 0 j <.
11 OJS
11037
11036
11 0 3 5
11034
i io.n
11032
11031
11030
11(29
1)02«
1 1 u 2 7
11026
1 1025
1 1 0 2 4
11023
1102?
11021
1 1 u 2 0
13019
1 lOli,
11017
1 i 0 1 1>
11015
1 U. 1 £
1)013
11012
1 1 .'; 1 J
1 1 0 1 r-
1 J 0 (. o
1 1 CO 3
1 10 f 7
1 1 f o '>
1 ! 0 0 b
1 1 0 0 «
1 1 r>;>3
1 1 0 0 t
11001
4
4
4
44
4
4
4
4
4
4
f
1
4
3
3
3
3
3
3
3
3
3
3
3
3
3
3
2
2
2
2
2
2
2
2
y.
2
?
2
?
1
1
X
1
1
1
1
1
!
1
1
0.000
0 . 'iQO
O..I07
0.000
0.013
0.014
0 . 0 a 0
0.000
"."13
0. O0'>
0.^20
0 . 0 f) 1
0.021
o.ooo
0 . 0 ^ J
o.ooo
0.02^
0. i; oft
O.i 27
0.000
0 . u o H
0 . v 2 *
0 . C b 7
0 . 0 0 0
0 . 0 0 0
o.oo o
0 . o l n
0 . 0 0 0
fl . C 0 0
') . v.' V 0
0.0"
0 . 0 ; r.
c.o- i
0 i_. " :",
0 . G 0 0
0.00 0
0 . 0 0 0
0 . 0 : o
0 .000
0 . (J 0 0
0.017
u . 0 n 0
0 . 0 n r,
0 . OV.HJ
o.-'~:>
: ..',.-,,>
0 . 0 ''0
0. nt'O
0 . ^ 0 0
> . y 0 <->
<> . 0 1 o
0.0^3
0.r-64
0 . n 7 s
0 . 0 b Q
U . 0 3 3
0 . T *? 1
O.OJ7
0.0 H
0 . Ti 3
0.<>24
0 . 0 Q 0
0 . ,} 2 n
0 . 0 -H
0.021
G. 1-5&
0.014
0 . n 9 >
0 . 0 t J
U . 0 Q 7
0.06')
0 . 0 7 n
0 . n <) fi
0. 144
O.O-.M
0.061
O.OS1)
0.07*
0.036
0.045
0.057
0 . 0 7 -j
0 . 0 J *
0 .072
0 . 0 S 3
0 . 0 -J 0
0.016
0.061
C . 0 5 Q
0 . 0 2 S
0.04^
0.0rf7
O.T4 »
o . ) i b
0. ')42
r'.
-------
Table 3
OF DI
»», ,'fc.D
THF, K
1HF
MM VH,"
f--r'?PK.S«::.'Ti>
Cn'JFIDE'iCk.
BEST VAf,ilL"
AT LF.AM
LIMITS
MA/I"!J'-'
11102
11 101
1 1 1 0 0
11099
1 109«
11007
1109&
11095
11094
11093
110r-2
11 0 V 1
11090
1 1 0 & 9
1 1 Ofc H
1 1 0 P 7
1 1 0 ft t
1 1 0 b b
MGf-4
1 1 0 t- 3
1 1 0 H 2
1 1 0 M
HOi-0
1107V
1 1 C 7 b
11077
11076
1107b
11074
11073
11072
11 J71
11070
110b9
11 ObH
11 0 fc 7
U 0 6 b
110f.5
11084
1 1 0 6 3
1106/
llObl
1 1 0 fc 0
1 1 Ob9
11 0 b P
1 1 0 b 7
1 1 0 b o
1 1055
1 1 0 b i
1 1 0 b 3
11C52
8
8
M
%
8
b
P
7
7
7
7
7
7
7
7
7
7
7
7
7
/
7
t>
6
6
6
6
6
t>
b
6
6
b
o
6
5
i
b
S
b
b
t;
b
5
S
b
b
b
b
v
4
0.00
0.10
0.11
0.00
0 . 0 0
0.02
O.CO
0 . 0 )
0 . u 0
0.00
0.00
0 . G 0
O.'JH
G . o o
0.00
1.20
o . o o
'i.OO
0 . 0 0
0. 00
0 . C>>
0 . 0 2
0.00
0 . 0 0
0.00
0.00
o . o o
0.04
0.42
u . 0 0
0.07
0 . 0 0
0.1')
O.I 7
0 . 0 ( i
0.00
0 . O9
0 . 0 0
o.oo
0.00
o . o o
0 . 0 0
o.oo
'i.OO
0 . 0 C'
0.00
o.oo
0 . 0 0
o.OO
0 . 0 0
0.00
0
0
0
0
0
0 .
0.
0.
0.
0.
0.
0.
0.
0.
0.
1 9
40
41
21
24
} 2
17
3i
10
16
2*
14
37
11
14
o . 1 q
0.10
0.27
0.1 1
0.03
P . 3 0
0.17
0.03
0.26
0.17
O.Ob
0.32
0.71
0.0?
0.36
O.OS
0.17
0.47
0.00
o.ot
C.39
0.09
0.10
0.02
0.00
O.ll
0.12
0.2b
0.1 4
0.1?
0.00
O.C2
0.00
0.19
0.02
0.47
0.70
0.71
0.49
0.52
n . fr 3
0.45
u.60
o . 4 R
0.4S
O.b?
0.41
0 . f b
0 . 3 H
0.41
2.1b
0 . 4 P
0,37
0 . S f.
0.40
0.30
0 . S 9
0.46
0.30
0 . 5 b
0.4*
0.33
0.61
i.os
o . 3 b
O.h4
0.33
0.4^
0.77
0.2S
o.?s
0.6^
0.36
0.37
0.2^
0.75
0.3H
0.3^
O.S3
0 . 4 1
0.3'.
o.?6
0.2t»
0.17
0 . -1 P
0.29
-------
I
j Table 3 continued
THK Cn.iCfuTKAriOV OF OISSCijVRD
THE RVCt. H':P«s:.srJTS AT LEAST
TrtF 95* CONFIDF'.CE LIMITS
!IM"
3
3
3
3
3
3
3
3
3
j
3
3
3
2
2
2
2
2
2
2
2
2
2
2
?
2
2
1
1
t
1
1
1
1
1
1
1
0.00
0.00
0 . u ',;
0.00
0.00
n.OO
u. t 1
0 . n o
o.oo
0.00
0.00
o.oo
0.00
0.00
0 . 0 o
0.00
0.00
0.00
O.bl
o.oo
C . 0 0
".00
v . 0 0
o.oo
n.OO
o.oo
0.02
0.00
n.OO
o. on
0 . 0 0
o.oo
0 . 0 0
0.00
o.on
o.oo
0.00
O.oo
0.00
o.oo
0. in
0.00
0.00
0.00
0.1 <*
0.00
O.b2
0 . 0 0
0.00
0 . 0 0
u.oo
0.04 0.32
0.03 0.30
0.0" 0.32
0.00 0.22
0.11 0.38
0.09 0.36
0.41 0.71
0.00 0.29
0.17 0.46
0. J 1 0.28
0.04 0.32
0.16 0.4b
0.2* 0.57
0.14 0.41
''.00 o.ll
0.11 0.38
0.01 0.2*
0 . 0 < 0.35
n.o4 I.JP
0.12 0.39
0.00 0 . 1 S
0 . 0 4 o . J 2
0.1-5 0.47
C' . 1 4 0.41
0.00 o,26
0.08 0 . 3 S
0.37 O.h3
0.01 o.2 b
0.00 0.14
O.Ob 0.33
0.03 0.30
n.03 0.35
<">. C 1 0 . 2 8
P.0 6 0.34
0.00 0.24
0.00 0.27
O.ll 0.38
0.11 0.3 H
0.00 0.00
0.00 0.11
0.40 0.70
0.21 0.49
0.00 0.2 7
0.1J 0.43
0.1 * 0.7 4
0.11 0.^3
0.°? ].?2
0 . Cn 0.11
0 . 0 0 0.23
0.00 0.27
0.01 0.2*
-------
Table 4
rr.'CK'.'Ti;> 41 ];»' IF- DISSDLVFO
(r>; :.'Ar.OGF A vs/ x T LLIL I
THfc. hA'.KK f-KPpc-Sfc-'ifS AT LKART
CC\TIDF /cf-: LIMITS
MJrf«t> WIMMIJH PEST VAL'JE ''AXI'-'ljv
11102
lllol
* 1 i \J *J
1 I 0 ^ V
1 1 0 9 1
110 c, 7
1 1 0 '-i 6
1 1 0 ', 5
1 1 0 9 4
1 1 0
11087
llfihb
1 1 0 b 5
1 1 U H 4
1 1 0 h 3
1 1 Oe2
1 1 o <; l
110« fi
1 1 0 7 S»
1 1 0 7 e
11077
11076
11075
1 1074
1 1 (1 7 3
11072
11071
1107 0
1 1 0 ^ ^
1 3 0 ^ ^
11067
1 1 0 6 fe
11065
1 1 0 6 4
110t>3
110*2
11061
11060
11059
11057
1 1056
11055
11054
1 1 0 5 3
B
8
8
%
e
P
p
7
7
7
7
7
7
7
7
7
7
7
7
7
7
7
6
b
6
6
6
6
6
b
6
6
6
6
fc
5
5
5
5
5
5
5
5
5
5
5
5
5
5
0.3*
u.36
0.52
0.20
C. 32
0.22
0.00
0 . 0 0
0 . 0 0
0 . 0 0
0.00
0.00
0 . 0 n
0.00
0,00
0. '0
0 . 0 )
0 . 0 ',
0.00
o.oo
0.00
0.00
o.oo
0.00
o.oo
0.00
0.00
O.C'O
u.OO
o.oo
n . o o
O.on
0.00
0 . 0 o
0.00
0 .no
1.50
1.4«
1 .64
1 . ? 3S
o'.bl
o OH
.
.^2
-------
Table 4 continued
THf CU.-JCrf/fhfillP', OF UISS&LVFO COPPi-F<
( ! '.' Nt'jnGHA^s/y ILLI LI TF'-?)
THh HAKGt RF f f^^'lTS AT LEAST
IHt 95'i CO-F TDKNCE LIMITS
SA"PIF NU'-cFP M IM I y ;j >.< DKST VALlit «AXiyii''
11 0 b 1
11'JbO
11049
1 1 0 4 fc
110-n
1 1 0 4 b
1 ! 0 4 5
11^44
1 1 0 '4 3
11042
11041
11040
11039
1103*
11037
1103 r.
11035
1 1034
1 1 0 3, 3
11032
11031
11030
11029
1102*
11027
1102c
11025
11024
11023
11022
11021
11020
1 1019
1 1 0 1 &
1 1 u 1 7
HOlb
1 107
1 H' fj h
1 1 0 ! i 5
1 inc. 4
11003
11002
3. 1 C 0 1
4
4
4
4
4
4
4
-i
4
4
4
4
4
3
3
3
3
3
3
3
3
3
3
3
3
3
3
2
2
o
2
2
2
2
2
2
2
2
2
2
2
1
1
1
I
1
1
1
1
1
1
0.00
0.00
0.00
0.00
0 . 0 '.'
o.oo
0.00
c.oo
0.00
0 . 0 0
0.00
0.00
'>.!<*
o.oo
0 . 0 0
o.oo
0 . b 7
0.00
0.14
0.00
0.00
0.00
0.00
0.00
0.00
0 . 0 0
0 . < > 0
0.00
0.00
0.00
(i . 0 0
o.oo
0.00
0.00
o.oo
J . 0 0
0.00
0 . ? 2
0 . 1 -t
"'.03
0 . 0 0
o . 0 0
o.oo
< 0 . 0 rt
< 0.08
< 0.08
< 0 . 0 4
< 0.03
< 0.0%
< 0.0 a
O.IQ
0.18
0.29
0.19
0.3)
O.I'D
0.32
0.1 1
0.3b
0.08
0. J9
0.31
1.14
0.35
0.4-1
0.2^
1.80
0.22
1.14
0.29
0.27
0.20
0. 19
0.30
0.34
0. 1 7
0.21
0. J3
0.29
0.27
0.26
0.25
0.33
0.32
< 0.0,4
0.47
0.17
0.23
1 . 4 'i
1.14
1 .(H
O.bR
0.25
0.23
0.31
0.2P
0.4 3
0.28
0.47
0.2?
0.4*
0.21
0.49
0.1*
O.b5
0.45
1.40
0.4^
0.60
0.37
2.75
0 . .3 4
1 .40
0.43
0.39
0.32
0.31
0.44
0.4^
0.27
0.33
0.47
0.43
0.3°
0.3P
0.37
0.47
0.63
0.27
0.35
1.79
1.40
!.?<«
0.7f>
0.37
0.3'j
-------
Table 5
Ihf Cfi!/rK,' 3
4 . 40 5.7'-
o.Ol C.95
0.42 1.S3
3. ? . -: Q
2.30 3.41
0.53 1.40
0.09 1.20
0.53 I.o4
4.^4 6.20
7.52 3.hj
2 . 9 h 4.0"
0.75 1 . b 2
33.01 38.53
0.7b 1.62
1.63 2 . 7 b
i.o^ 1.Q5
2.8b 3.«6
0.97 l.M
2. OH 3.10
3.29 4,h5
2.9.oo
25.23
0.00
0.00
O.OO
0.00
0.00
0.00
0.00
0.00
O.i' 0
0 . 0 0
0.00
0 . 0 o
0.00
0.00
O.Ou
o.on
0.00
0 . 0 ')
0 . U 0
0.00
2.04
-------
Table 5 continued
CONCKf»rhATJL.'J
(I'J :*4
OK
IRON
. ILTTKfO
THt PA'iGt
ThK 95*
FH PUFSEKTS
CO:iFrDK"<'Ct
BFST VALUF
AT LEAST
LIMTS
11051
11050
11049
1104h
11047
11046
U045
1 1 u 4 4
11043
1 104?
11041
1 1040
11039
1103*
110)7
11036
1 J03b
11034
11033
11032
11031
1103 0
1 1029
11028
11027
11026
11025
11024
11023
1 1022
11021
11020
DOIQ
1 1 0 1 et
11017
11016
11015
11014
1 J 0 1 3
11012
1 101 1
1 i o i o
11009
1100*
11007
13006
11 V 0 b
1100 4
1 1 U 0 3
11002
11001
4
4
4
4
4
4
4
\
4
4
4
4
4
3
3
3
3
3
3
3
~i
3
3
3
3
3
3
2
2
2
?
2
2
2
2
2
2
2
2
2
2
1
1
1
1
1
1
1
1
1
1
0 . 0 0
0.00
0.3ft
0.00
0.00
0.00
0.00
0.00
0.00
o.oo
0.00
0.00
0.00
0.00
0.00
0.00
11. 19
0.00
1 . Ih
o.oo
0.0(;
o.oo
0.00
0.00
O.oo
o.oo
0.00
0.00
0.94
0 . 0 0
10.00
0.00
0 . 0 0
0.83
0.00
o.oo
u.OO
0.00
O.oO
0 . 0 0
0 . 0 0
o.oo
0 . 0 0
2.15
0 . 0 u
0.00
0.00
0.00
0.83
o . <;o
0.00
1,
2,
3,
2,
1,
2.
1 .
1 .
2.
0.
2.
0.
* «
0.
3.
o.
16.
2.
4.
1 .
2.
I.
3.
1.
0.
0.
1.
0.
4.
0.
14.
0.
U.
4.
0.
0.
o.
0.
o.
o.
i.
2
3
5
1
1
2
1 ,
4,
1
86
«5
95
74
"6
52
30
P6
63
^7
5?
64
,41
,42
,19
,31
,00
,08
73
19
OR
52
Ifi
52
97
53
Ofl
09
51
53
56
P6
97
40
09
20
97
64
CM
4?
30
52
29
7?
0 3
19
9b
1 a
40
30
2.97
5.32
3.85
2.97
3.63
2.42
2.72
74
09
63
51
1.97
3
2
3
1
3.52
1.29
4.30
1.1»
1 8 . 5 (J
3.J9
3.19
2.64
4.30
2.64
1 ,&4
1 .64
1.^5
1.20
5.b7
1 .tO
16.91
1.96
2.09
5.76
1.20
1.31
2.01,
1 .75
1 .20
1.53
2.17
7 . 0 p
2.20
2.3J
4.07
2.31
b.7f-
2.J?
3. OR
-------
*»*«-
Table 6
THE CONCENT RATION
(IN
OF DISSOLVED MANGANESE
SAVPLb.
THfc. RANGE. REPRESENTS AT LEAST
THC 95% CONFIDENCE LIMITS
M I \ I M ij y
BEST VALUE
M A X I P U *
* V
11102
11101
11100
11C9V
11098
1109"*
11096
1 1 0 y 5
11094
11093
11092
11091
11090
11069
1108X
11047
11086
1 1 0 3 5
110*4
1 1 Oo 3
HUb2
11031
llOeO
11079
1 1 0 7 a
11077
11076
11075
11074
11073
11072
11071
11U70
11069
11068
11067
1 lObb
llOfab
1)064
11063
1106.2
11061
HOirO
11059
1 1 0 5 &
11057
11 0 5 *
Il»b5
110b4
1105 j
11052
8
ft
d
3
8
B
8
7
7
7
7
7
7
7
7
7
7
7
7
7
7
7
6
6
6
6
6
6
6
6
6
6
6
6
6
5
5
b
b
5
5
5
5
5
5
5
5
5
b
5
4
1.24
I.b4
6.62
5.65
2.80
2.22
4.95
2.17
6.00
3.73
0.00
0.00
0.00
0.00
0.00
2.07
0.12
320.67
0.00
2.27
2.65
5.40
0.69
1.82
2.12
2.62
7.^5
86.19
0.51
109.59
0.52
1.01
0.45
33.29
1.54
150.64
0.24
31.02
1 .67
5.07
1.77
2.P4
0.04
4.10
0 . 0 0
2, .06
0.16
1 .67
1 .29
2.34
2.78
1.70
2.10
8.20
7.00
3.70
2.90
6.30
3.51
6.01
5.51
0.61
0.71
0.51
0.41
0.71
3.41
1.01
388.31
O.bt
3.61
4.21
7.41
0.90
2.50
2.80
3.30
10.10
97.40
0.67
131.00
0.6S
1.2;
0.59
49.50
2.UO
195. P-2
0.62
3d. 12
2.72
7.02
2.^2
4.12
0.60
5.32
0.3S
26. P2
0.74
7.72
2.12
3.62
4.01
2.15
2.55
9.77
8.34
4.60
3.^7
7.b4
4.fc5
10.02
7.29
1.27
1.60
1.17
1.07
1 .60
4.75
1.90
455. °b
1.70
4.95
5.77
9.42
1.10
3.17
3.47
3.97
12.34
108.60
O.P3
153.40
O.R«
1.46
0.72
60.70
2.45
240.80
1 .20
45.02
3.^7
H.77
3.67
5.20
U . 9 6
7.34
O.b"
31.4?,
1.12
3.57
2.75
4.70
5.30
-------
r
Table 6 continued
TriS CO.'iCK.JTRJTlON OF DISSOLVFD
!L RANGf: REF-RESF-JTS
THE 95% CO'i
I M M M ".
bt'ST VALUf
AT LrA.ST
''AX If
11051
11050
11049
1104P
1 1047
1 1 0 4 o
11 (Kb
11044
11043
11042
11041
1104 0
11039
11038
11037
1103d
1 1 0 3 b
1)03-4
11033
' 1032
11031
11030
1 1029
1 1 0 2 f
11027
1 1 02t>
11025
1 Iu24
1 1 C 2 3
11022
11021
11020
11019
1 1 Old
1101 7
11016
1 1015
11014
11013
11012
11011
1 1 0 1 i)
11004
1 1 0 0 H
H U 0 7
11006
11005
lluo*
1 1 0 c: 3
110t!2
11001
4
4
4
4
4
4
4
4
4
4
4
4
4
3
3
3
3
3
3
3
3
3
3
3
3
3
3
2
2
2
2
2.
2
2
2
2
2
2
2
2
2
1
1
1
\
}
1
1
1
1
J
2.6B
2.3b
4.21
3.46
11 .29
lh .60
0.00
0.23
3.06
0.00
12 . b 2
0.23
10.69
0.70
33.27
0,50
12.60
0.52
12.40
0.42
9.55
0.68
58.23
0.49
6.30
2.^0
6 , Ib
0 . 0 0
2.5*
9.46
1.03
7 .06
1 .60
0.55
0.00
2.20
2.00
2.10
3.96
2.3?
2.77
0 . 6 2
1.12
0.90
1.90
1.30
1 . 22
1 . 0 2
9.33
3.91
3.64
6.14
4.94
14.34
21.41
0.22
1.04
4.L 4
0.27
IS. 24
O.oi
13.74
40
0
1 b
00
56
3 0
0.68
15.10
0.56
67.20
0.63
B. 10
3.70
8.50
0.57
3.67
4.07
12.07
2.07
9.67
1.37
0.00
3. 17
,27
,37
67
64
04
45
°4
94
?4
2.01
11.94
5.20
4.90
P. 07
6.42
17.39
2 b. y B
0.71
1 .Sb
6.02
0.76
19.96
1.39
Ih.7P
1.11
4 b . 7 2
O.H2
17.()9
O.S4
17.79
0.69
1 4. li4
1.09
76.16
0.7H
9.P9
4.60
10.52
1.3P
5.1b
5.55
14.67
3.10
12.27
4.13
2.1«
0.32
4.73
4.53
4.63
3.50
7.37
4 . <-' 0
5.30
2.25
2.75
2.97
3.97
3.H7
2.P5
2.1-S
14.54
-------
B**'* *
Table 7
THF CONCENTRATION Of DISSOLVED N'OLYBDEUJM
(I 'I N a NOGP A ;''S/.'" 1- LL I L IT EH )
NUMBER
THE
THf
'[MMUM
95%
FF'PRKSFvFS AT LF-A5T
CONFJittMCF LIMITS
PEST VALUE
MAX IP UK
Illu2
11101
11100
11099
1 1 u 9 a
11097
11096
1 1 0 '_' b
11094
11093
11092
11091
11090
11089
1 1 0 P 8
11087
11066
11085
110K4
1 1083
1 1 f i- 2
110*1
1 1 0 b 0
1 1070
11078
11077
'1076
.1075
1 1074
11073
1107^
11071
11070
11169
1 1 o 6 e
110b7
1 1 066
1 10o5
11064
1 10*3
] lOt>2
1 1 (- 6 1
11060
11 0 b 9
1 1 0 5 ^
11057
11056
11 0 b b
1 1 0
b
6
6
6
6
b
6
6
6
6
6
5
b
5
b
b
5
b
5
5
b
b
K
_-
5
5
s
4
0.87
0.7?
0.69
0.75
0.59
O.feO
O.b4
0.80
0.5R
0.64
1.50
1 .99
1.49
1.26
1.57
1.49
1.7S
3.0^
1.99
1 . 7 . 0 3
2.20
2.93
2,4}
3.03
2.61
1 .07
O.P9
0.86
0.92
0.71
0.72
0.. 67
0.96
0 . V 0
0 . 7 o
l.f-3
40
82
2
1
1.54
1 .98
2.40
2.19
3.86
2.40
2.19
2.30
5 0
30
40
2.40
2.^0
2.Q2
2.71
2.40
3.96
2.30
2.71
2.H2
3.13
2.61
3.65
2.7]
4. HO
2.92
2. hi
2.61
2,"?
2.82
-- - (- ?_
2.4C
3 ; 4 &
? . 4 0
"3 . 3 "
J.34
3.d/i
2 . < 7.
-------
Table 7 continued
1HK CH'-Ci-' .li'ATlUf. CF 0 I SGOLV t'V
THfc. KA'JGF Wr i1*- !$*. T5 5T LKAC'T
THfe
r'IM-'U,*' al SI VAt-UK
llObl
HObu
11049
11 0 4 H
11047
1 1 0 * c
lit- Ib
1 1 0 4 4
11043
11042
1 1 0 -i 1
110*1!
11C 39
1 1 0 3 >
11037
1103o
11035
110*4
1 1 L- 3 3
1 1032
1 i ') 3 1
1 1 v 3 'J
1 10 2 c.»
1 1 0 2 fc
11027
11026
11025
11024
11023
11022
uo;i
1 1 0 '^ 0
11019
1 1 0 1 d
11017
11016
1 1 <> 1 b
11C14
11013
1101?
1 1 C 1 1
1101 (
1 1 0 0 9
1 lOOtt
1 1 u C' 7
i 1 U 0 f j
1 lO'-ib
1 1 n o 4
1 loOJ
I 1 0 o ^
U U 0 1
4
4
4
4
4
4
4
4
4
4
4
4
4
3
3
3
3
3
3
3
3
3
j
3
3
3
3
2
2
/
2
2
2
2
2
2
2
2
2
2
2
I
1
1
1
\
1
I
1
1
1
1
2.h2
2.73
2.30
2.73
2.73
2. ft)
2.bl
2.b2
3.1 4
2.^2
2.9*
2.41
3. bo
2.51
3.56
?.o2
3.Q4
2.73
'.<»'
2.i 3
l.KS
2.C I
4.51
2.5?
7.94
3.s«
5.03
:;,4S
5. ho
4 ,bl
4.ol
3.^*
4.^0
4.71
4.1^
2.52
5.^7
4.0
}.5fc
4.09
b.7b
-.71
t.r.0
f>.29
7. Kb
2.41
3.5"
4.72
5.7o
S.O?
5.24
3.03 3.44
3.11 3,55
2.51 2.71
3.1; 3.55
3,14 3 . * s
3.24 3 . f '>
2.72 7.°V
2.93 UJ-i
3.55 3 . r* h
3.03 3 , * 4
3.J5 3.7f^
7 . o 2 3.73
3^97 4.Jfr
2.7? 2 . w 2
*.97 4.3*-
} . 0 3 3.44
4 . 3 Q 4 . t- r.
3.1 ; K*Sb
1.J4 -1.M!
j . c b
4 . 7 f
3.3b 3.7^
S. 1 ? b.7£
2.c-3 3.3;
3.3S 3.7h
5.29 4.70
b.27 6.?^
5.?3 b.b4
5.02 5.^3
4 . ? 9 4.70
4.
-------
Table 8
* OK MSSCLVFf)
^.S/i"* LLJ MTtJP
; A * Pi.fr; '. u »
Ink W
1HK
" I'. I w;;-
Li
"AXI'-IJ"
1 1 1C 2
111C1
11100
i 1 1': 9 4
1 1 U S n
1 1007
1 I 'j y h
1 1 r- 9 b
HOC. 4
1 1 0 V J
11 r' 9 ?
1 1UVJ
1 Iv^O
1 1 fi t 9
ll.'-p
11 CM 7
1 10f(-
1 1 0 H b
1 1 n £> -4
i 1 '>.}
110-2
1 1 <'>i j
1 I 0 n o
1 1 ' 1 f
1 1 .) 7 h
11077
1 1 0 V r,
1 1 0 7 b
1107 4
1 1073
111/72
1 1 >i 7 1
1 i 0 7 -'
i 1 0 ') 4
1 3 C> n 3
1 1 ';c 2
1 ! < t i
1 l"bO
1 i v S 9
1 1 ' ) b '-
\ 1 ' b 7
1 1 0 b ^
1 1 ' ) b b
) 1 i. b J
1 1 ' > S j
1 1 i'b2
S
"t
i
h
H
P
6
7
7
7
7
7
7
7
7
7
7
7
7
7
j
7
>
c
0
c-
*
6
t>
s
f,
fc
A
b
6
b
5
b
:>
b
b
b
b
b
t;
b
S
^
^
S
>
''' - '> 6 1 . 1 b
0 . " i 1.37
O.'-H 1.37
1.02 5 .bH
0.74 i . ^ j
I!.'?} 1.40
f>.'>'J 1.04
O.lb r,. S 1 . fc b
J . ? "3 1 . » S
n . h b 1 . " b
0.77 i ] #,
'J . - - 1 . b 7
r.77 i.eo
0 . V 5 1 . 9 b
0 . '- 2 i . V l
') . r' o 1.4s
0 . 'T ! 1.40
1 . r' 4 3 . b ?
1.03 1 . b ?
0 . - h 1 . ^ j
1 . 1 I 1 . f 0
u . b 5 1.10
O.*P 1 . V)
<-' . ~ s ! . 3 7
0.71 i.ui
') . b 7 0.9}
0.*2 1.74
0 . 7 f* 1 . l e
f; . -* 3 i.3s
0.^7 t . i -j
1.01 l . 4 J
0.->o 0.92
1 .'^ 1 .b?
0.77 1.13
0. "b 1.2^
0.^3 1.3}
1 ' . ° -5 1.35
<' . '/ r 1 . (i f,
:'.r<^ 1.3-j
<" . f s 1.01
r' . ^ t 1.27
0.7! l . ,1 7
o . * ; i . ' ^
".77 i.,-.
0 . i - _ 1 . ', J
1 . /. g
1.71
1 .71
1 ,<>«
1 .SV
1.74
1 .33
1 . io
i '} i
1.60
3.31
2. IS
2.6b
2.15
2.1b
? ! i'j
2.07
2.1*
2^21
1 . 't S
1 .7*
1 ' 1
1 *«4f.
I *^ y
1 Q C
1.41
1 .61
1.34
1 .20
1 . SS
1.4?
1 .KO
1.5"
lily
i i 91
1 . JS*
i .b7
l.f-b
1 . f-*
1.32
l.f-7
l.Sf
1.33
1.2c
1.4^
1 . 4^
105
-------
Table 8 continued
C'-,-CM.T^AT;UN OF RtSSCLVFD U
(If- f.'tr.OG
THL i^AUGr: RE.PPFSl.'iTS AT LIAST
THE 95 i COSt- IfJEMCE LI "ITS
"FSf VALUK
MAXTVI1V
1 1 0 b 5
110?. 0
no***
5 1 04 »
ilO-*7
11 0 » to
i 1<>45
! 1 U -, 4
1104?
U 0 4 'i
\ 10 '« 1
i 1 0 4 o
J 1 0 3 9
I J03h
1 1037
11036
I ) 0 > b
I 1 ( 3 4
! 1 u 3 3
i 10 jk
11031
) 1 0 3 0
11029
1102*
1 J027
I 1 0 ? b
11025
1 102««
11023
llf.22
11021
1 1020
J 1 0 i 9
1 tOici
11017
1 1 0 1 h
1 lOlb
1 i 0 1 4
t 1013
1 lu 1 2
11011
11010
1 I f; i; 9
1 1 U(IH
1 3007
i 1006
i i 0 0 b
11004
1 ] 0 0 3
? I 0 0 ?
i iUOl
4
4
4
4
4
4
4
*
4
4
1
4
4
3
3
3
3
3
3
3
3
3
3
3
3
3
3
2
2
2
2
2
2
2
?
2
2
2
2
2
2
]
1
1
1
1
1
1
1
1
1
f .2G
0 . -5 0
0.30
0.47
. '4
1.23
I. 11
o.3l
0,57
0 . b 1
o.;o
I.Ob
0.42
0.13
0 . 2 '.
O.f>2
0.^1
O.e>2
0.67
O.bb
0 . 9 b
0. H7
0.5Q
0.70
O.b3
0.57
O.b3
0.66
0.60
0.47
0.40
O.b5
0.29
0.54
0.4 1
(> . 4 b
o . o <;
".bo
o.SO
104
0.95
1.11
0.96
l.?S
0.5-1
0.56
0.96
1.40
1.10
1 .07
1.13
1.J7
1.09
1.1S
0.82
2.30
1.62
2.22
1 .99
1.1?
1.38
1.32
0.9 h-
1 .93
1. 18
O.SO
1.00
0.90
O.b9
0.90
0.97
1.15
1.25
1.17
0.67
I.00
0.81
O.B5
O.&t
0.94
0. hf>,
0.7f<
0.71
0.6ft
0.55
0.87
0 . 7 A
O.ftl
0.97
0.«9
O.Si
1 .30
1.51
1.31
1 .72
O.H9
0.85
1.31
1.17
1 .50
1 .47
1 .53
1 .57
5 .49
1.5&
1.20
?.«!
2.12
2.b3
2.49
1.55
l.fil
1.75
1.34
2.43
1.56
1.27
1.38
1.13
1.1?
1.13
1 .22
1.40
1.50
1.42
1.10
1.25
1.04
1 .OH
1.04
1.17
1.) 1
0.99
0.92
1.11
0.73
1.10
0.9 9
1 .04
1 .20
1.12
1.02
b...
-------
Table 9
THE CUf'CKNTRATlGN OF DISSOLVED LEAD
SA'-'FLF.
THE' RANGE
THc 95%
I V I) !«!
REPhESE'JTS
BEST
AT LE:AST
LIMITS
VAXJf
11102
11101
11100
11099
11098
11097
1 1 0 9 fa
11095
1 1094
11093
11092
11 091
11090
11099
llOBb
110H7
1108o
11005
11084
11 0 P. 3
1 1 0 b 2
HOrfl
11080
11079
1107«
1 1077
11076
lll/7b
11074
11073
1107?
11071
11070
11069
11066
11067
1 1 Obb
1 1 0 o 5
1 1 Ot>4
11063
11 0 ft 2
11061
11060
11059
llObfc
1 1 0 b 7
11056
110S5
11 Ob4
11053
11052
6
8
8
8
P
6
8
7
7
7
7
7
7
7
7
7
7
7
7
7
7
7
o
6
6
6
6
6
6
6
6
t
6
6
6
5
5
5
5
5
5
5
5
5
b
5
5
5
5
5
4
0.27
0.00
0.00
0.00
0.00
0.10
0.00
0.03
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0 . 0 0
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
u . o o
0.00
0.00
0.00
0 . 0 0
o.oo
0.00
0.08
0.1 1
0.00
0.00
0 . u 0
0 . n o
o . o o
0 . 0 0
0 . 0 0
0 . 0 0
0 .00
0.00
0 . 0 0
0 . 0 <">
0 . I *
0.47
0.
0,
0,
0,
0,
0.
0.
0,
0,
0,
0,
51
Qa
00
OB
16
40
10
33
16
04
02
0.00
0.00
0.00
0,
0,
0,
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0,
0.
0.
0.
0.
0.
o.
0.
0,
0.
0.
0.
0.
0,
o,
0.
0,
0,
0.
U ,
0.
0 .
00
21
00
00
00
00
00
04
00
00
11
00
01
00
00
00
00
05
03
03
24
33
43
12
21
13
1 4
1 3
10
03
15
1 3
20
1 3
1 7
52
0.63
0.12
0.20
0.31
0.60
0.22
0.52
0.3i
O.lh
0.14
0.12
O.U
0.07
0.07
0.36
0.1?
O.OP
0.11
0.11
0.10
0 . 1 f-,
0.07
0 . r< 4
0.23
0.03
0.13
O.Ob
0. 12
0 . (, 9
0.11
0.17
0.15
0. 15
0 . 4 1
0
O
0
0
0
0
0
57
f-5
?7
41
2'-
33
2f
ins
O.e3
0.22
0.20
0.3<:
0.2«
0 . 3 5
G.?fc
0.32
0.73
1.19
-------
Table 9 continued
CONChf, r RATIO', DF UISMJf,V'JD LKAD
( I'i ',A,VjG^A*S/""-IL.LJL tTER)
PHE PANG-' Fk-f-FEShJUT.S AT LF/,«'
THE 95* CONFrnKfiCt LITfS
2
1 1 0 1 9 2
11017 2
11 A 1 i- *
1 0 1 h 4
1 1 0 1 S 2
11014 2
11013 2
11 o 1 / 2
HC11 2
11010 1
'. 1 0 ' ! 0 J
1 ! '.'0 5 1
11007 1
1 1 0 0 c 1
1 1 ( M S 1
i 1 ' ' J }
1 1 0 0 4 1
1 1 00 J 1
11002 1
11001 1
0.00
0 . <) 0
0 . 0 o
0 . 0 (i
0.00
0 . u 0
0 . C 0
0 U 0
o.oo
0 . 0 0
0 . 0 u
o , o o
0.00
0 . 0 0
o.oo
0 , U 0
0 . 0 0
'-' . '! 0
0 . 0 (;
0 . I) 0
0 . 0 0
o . o o
0 . 0 0
0 . 0 0
1 1 . 0 C
0 . 0 0
0.95
0 . 0 3
'» . 0 0
0 f)!'1
^ ' V
; . J o
0 . 0 0
C . 0 0
0 . 0 0
0.00
o.oo
0.00
) . 0 0
0.00
o.ll
0.0 0
u . :/ 0
0 . 0 ^
0.0 0
0 . On
0 . 0 0
0 . 0 i
0.0 1)
u . 00
') . 0 0
0 . 0 0
106
0.00
o.oo
0.01
0,01
0.05
O.Ov
O.OIS
0.07
0 f ' 3
' » J
0.04
0,03
0. 12
0.22
1 r. u
'J r 0 S
0 . 1 3
0.0 fe
0.05
0.07
0 . 0 0
'J . 1 0
0.06
0 . 0 "
O i ir
1 . V V
0 . 0 0
0.04
01 <
1 »
1.5'*
0.33
0 . 2 0
0.14
o.n
0< r
. 1 s
0.06
0.00
'J . 0 4
0.09
0.1 5
I"! ', O
LJ . \J V
0 . 0 7
O -11
o . '« 1
/-, 4
O.I'-!
0 . 0 0
0 . n o
0.00
,-J /- »
'.'.' 0
n r, }
V . O }
0 . 0 r>
O A )
V . J /
0 . 0 'f
0.01
0.06
0. J 1
0 10
*' -1 "
0.13
0.13
0.17
0.12
0.17
0 1 ^
V * 1 ~
04 i
. 1 1?
O.lh
O.is
0.27
01 i i
. ,5q
0.17
'>. 2*-
0.20
0.17
O 1O
*~ » I V
0.12
f ' *
f| . /V
(i . ] »;
C* 44
'.11
<> . 1 (.'
0 . 0 s
c.u
0.31
2.13
<>.52
0.3-5
O.^o
i'l "' "3
" * / J
0.30
0 . 1 H
0.11
0 . 1 f.
0.21
0.25
0.2o
0 . 1 g
O.M
f; 51
V . 1 ,1
r 1 1
« 11
I'l 1 -1
V * j £
O.-r,
f - 1 1
o.ll
f 1 f
'.11
0.14
" r< *~
0 . / v
0.1 3
0.1 *
-------
Table 10
THE CONCE.JTKATIfJ'j OF DISSOLVf
(I" MAfvCGr AMS/'-'.ILULITEK)
THE RANGE
THE 9S*.
I M
REPRESENTS
CONFIDENCE
PEST VALUE
AT LEAST
LIMITS
MAXI
1 U 0 2
11101
11100
11099
110QH
11097
1 1 U<5f>
11 0 9 b
} 1 0 <, 4
1 1093
1 1092
1 1 0 1 i
1 1 0 V 0
11039
110HH
110? 7
110*0
HOH5
1 10*4
11083
1 1(. «2
I i 0 f. 1
1 1 <) f> u
I 1 0 7 <>
1107P
11077
1107s
i 107b
1 1074
1107J
11072
110/1
t 1 070
1 1 u 6 9
11068
1 1067
l 1066
11065
11064
1 1 0 o 3
1 1 Co2
1 IC61
1 1 J 6 -j
1 i 0 S ->
1 it-bS
1 1 '-J S 7
1 ! r: b b
1 1 0 b b
1 ! v 5 4
1 1 :, 5 3
8
8
6
a
8
H
9
7
7
7
7
7
7
7
7
7
7
7
7
7
7
7
5
6
0
6
6
6
6
iS
D
6
6
6
6
5
b
S
b
5
b
5
b
S
5
5
b
5
b
5
0.0005o
0 . 0 0 u 9 8
0.00073
0 . 0 0 f 6 1
0.00094
0 . ij 0 048
0 . 0 0 0 9 b
0.00090
0 . 0 0 U D 5
0 . 0 0 0 P 9
0 . 0 o 045
0.00039
0 .00055
0 . 0 0 0 3 1
0.00041
0.00070
0.00033
0.00069
0 . 0 U 0 3 7
0 . 0 0 022
0 . 0 u 0 2 1
0. 00 D 5 2
0 . 0 fi 0 ? 6
0 . 0 "! 0 2 1
0.00039
O.oOOSn
0.00 0 5 9
0. 0005*1
0 . 0 0023
0 .00041
0 . 0 0 0 2 b
0.00-J25
<} . 0 ' i 0 3 '/
0 . 0 0 0 ? 6
0 . U 0 0 2 2
0 . 0 0 o I b
0.00 0 ? j
0.0 00 20
0 . ii 0 0 -J 9
0 . 0 0044
o.o,-- o b H
0 . 0 0 0 7 u
0.000] 7
0 .">) o 2 I
J. J'lO I 2
0 . 0 0 0 2 7
0 . '» 0 0 3 I
0 . ") 0 fi 3 4
j . f ' 0 0 ; r
0 . '") v 'j 4 b
1 i
107
0.00068
0 . 0 0 I I 3
0.00086
0 . 0 y 0 7 4
0 . 0 n o « Q
0 .0005 }
0 . r> 0 I I 0
0 . U 0 1 0 5
0.00'.i79
0.00 ! 0 }
0 . 0 0 0 S B
0 . 0 0 0 5 1
0.00067
0.00063
0 .00053
0.000*1
0 . 0 0 0 4 4
0.000*2
0 . u o 0 4 «
0.00033
0 . o o n * o
0 . 0 . ; o f, i
0.0003o
0.0 OOJ 7.
0.00051
0 . 0 0 0 6 i
0.00073
0.00072
0.00034
0.00053
0.00039
0.00035
0 . 0 0 " -} -;
0.00036
0.1/0033
0 . 0 0 n ? 5
0.00" 3 1
0.00030
0.00061
C . C ')0b6
0 . 0 0 o 7 2
0 . 0 0 ft 9 0
0.00023
0 . 0 0 0 3 2
O.OH23
0 . 0 0 0 3 ?
0.00041
0 . 0 0 '/ 1 6
^.0005 .?
0 . 0 i o 'i 9
0 . r' 0 0 b 9
0 . C 0 0 R 0
0.0012f<
0 . 0 0 1 0 0
0 . 0 0 0 0. 1
0 . 0 0115
0.00171
0.00126
0.00121
O.G0092
0.001 19
O.C'0070
0.00063
0.00079
0 . 0 0 0 7 b
0.00065
0.00097
0.00054
0.0fi09b
0 .00060
0 . 0 0 n 4 3
0 . 0 G 0 4 1
0 0 o 076
0.0f>047
0.00042
0,00063
0 . 0 o f 1 8 0
0 . 0 1> Of? fc
0 . 0 0 OPS
0,00045
0.00065
0 , fifi«)49
0 . 0 0 0 4 b
0. 00060
0.00047
0 .00043
0. OHO 36
O.cyoub
o . c (. n 4 1
0.0007?
0 . 0 u 0 6 R
0 . f 1 0 0 P 5
0.00103
0 . C 0 0 3 o
0.00042
0.00034
0 . (-004 P
0 . 0 o r. 5 ;
0 . n ., o 5 a
0 . r, f j o 7 0
0 . 0 0071
0.1.0071
-------
Table 10 continued
T.HF C9NCF?."I«AT10V OF DISSOLVKD
SA-pj,F N
THE
KF.pMF.se: MS
6K5T VAL'JE
AT LEAST
L I u J 1 S
^AXI-
UObl
1 ITbO
1 1049
1 1 0 4 H
11047
11 0 4 b
1 l')4b
1 H; 4 4
110*3
11042
1 1041
1 1 0 -i 0
1 1 0 j 9
i 1 0 3 b
11037
11036
1 1 0 3 b
1 1034
11033
1 1032
11031
11031.'
J 1 o / 0
11 - 2 H
1102V
1102c
11»25
1 1 'J 2 4
11023
1 1 « i 2
1 i 0 2 1
11-120
I 1019
1 K>ld
1 1 u 1 7
11016
1 1 0 1 b
1 1U14
11013
1UH2
1 1 U 1 1
1101 >J
1100*
i 1 0 0 *
11007
1100 ">
1 i C 0 5
! 1004
11003
1 1002
i 1 0 0 ]
4
4
4
4
4
4
4
1
4
4
4
1
4
3
3
3
1
3
3
3
3
3
3
3
3
3
3
2
2
2
2
2
2
*-,
^_
2
2
2
2
2
2
2
1
1
1
1
1
1
1
1
1
1
0.00031
0.00070
O.^IK'33
O.O'V-29
0.00035
(1.000 $4
0 . 0 0 0 7 b
0.'K> j21
0.00 Ob 6
> . 0 0 0 1 7
o . o oo b o
0.00020
0 . 0 0 0 3 n
0.00032
0 . 0 0 0 1 b
o . o o o i »
0.1)021 4
O.OOOt 7
0. yOU 31
0 . U 0 <) 3 1
0.<'OM3b
0.00026
0 . o o ;> 4 b
'I. '!<,(< U
o . o o <; 1 2
0 . 0 -j 'if. 1
0 . 0 0 o 3 3
O.v'0032
O . 0 0 0 P 9
0 . 0 0 0 2 b
0. Ouu?e
0 . 0 n o 3 4
0 . 0 0 f 3 7
0.00035
0.00 0 3 1
O.i-OO?!
0. 00025
U . o 0 029
0.00012
0.Q 3
0 . 'J U 0 n H
" . 0,V.ib9
o . ", o n Q y
0 . 0 0 0 M
0.00034
0 . 0 C 0 3 7
O.COri H
0 . 0 0 CH 4
0.00 0 4 4
0 . 0 0 0 4 0
C . 0 0 0 4 7
o , o o o ; H
0 . 0 0 0 3 S
0.00032
0 . !j T 0 f) 3
O.H Of 2 3
0.000o2
o.oooj?
0 . 0 0 0 S 0
0.00 0 J 7
0.00030
O.G0023
0.00240
0 . 0 0 0 2 <
0.00096
C . 0 0 0 ', 1
0.00047
0 . r> 0 0 } b
0.00057
n . 0 0 0 4 5
0 . 0 0 0 4 4
0.00032
0.00 0 ^ 5
0 . C 0 0 4 2
0.00104
0.00039
C . 0 0 0 3 Q
0. no<»4b
0 . 0 0 0 4 n
o . o n > 5 1
0.00041
0.00032
0.00035
0.0 Ou 50
0 .00023
0.00031
0.00120
0.00047
0.00014
0.001 lo
o . o o o v o
0 . 0 0 0 .^ 1
0. OOn 7 3
0.000=2
0 . 0 0 0 b 6
0 . 0 "i 0 ' >
0 . v 0 0 4 a
0 . C 0 0 5 2
0.^0097
C . 0 0 C b 4
0.00051
0.00059
0. 0005b
0.00'i4b
b
0 . uOOt»0
-------
I Table 11
ThK CfriCK.NTtATlOr. OK niSSOLV-it n,
(I': ^MnGHA"S/* [LL1LIT=;«)
'THL -tAUGt FKPRf S-: ; TS 4T LtA.ST
1HF 9Sri CO'.F I *>:'.'<:' LIMITS
K M'.'-'HtP rlM'-'UV 'iKST VAL'JrT V AX I K1
0.43
1 . 7 h
0.74
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
I
1
1
1
1
1
1
1
1
1
1
1
I
1
!
1
1
1
1
1
1
1
1
i
1
1
I
1
1
i
1
1
1
1102
1101
1100
1099
109"j
J097
109t
1095
10^4
1093
1 0^2
1C 91
1090
1069
108R
i o % ;
10£16
<0e5
10 & 4
10? 3
lO*'/1
1 0 * 1
10* u
1 0 7 -
107ft
1077
1076
1075
1074
1U73
1072
1071
1070
1069
lOfcfc
10c7
1 05
10b4
1063
1 lit) 2
lUol
1 0 1 0
1 o c, y
105c
1 0 5 7
H/5t
1055
10 1,4
1053
1052
8
tf
8
0
8
9
a
7
7
7
7
7
7
7
7
7
7
7
7
7
7
7
6
c
6
6
6
6
o
6
6
O
6
o
0
5
5
5
5
s
5
5
5
b
5
5
5
3
5
5
.j
0 . 1 '-'
1.44
<
<
0. ^D
<
<
<
<
<
<
<
<
<
<
<
<
<
<
<
<
<
o.n
<
<
0.74
O.o?
0.57
<
<
<
<
<
<
<
<
<
<
<
<
<:
<
<
<
<
<
<
<
<
<
f
1C9
0
t
x
o
0
0
0
0
o
0
0
o
0
0
0
0
0
0
o
n
0
n
0
0
0
0
1
0
i
o
0
0
0
0
0
0
0
0
.1
0
o
n
0
(_;
0
0
0
(J
0
A
o
Q
'
.31
. f, j
.40
.10
.50
.4:)
.40
.50
.40
.40
.50
.20
.30
.30
.60
. toO
.50
.bo
. 90
.50
.50
. D'I
.37
.40
.50
.10
.97
.35
.50
. 5 0
. 4 0
.50
.40
.50
.50
.oO
.50
.50
.50
. f n
.50
.50
. 50
.50
.50
'; n
~f '
.5 )
-' '
. 50
. 5u
4 0
"
. t> i
1.4c
l.?b
-------
Table 11 continued
CO'.Cfr'ilHATlO:. OK DIPSOLVCD TI'<
( 1;» i. A %OGK A * S / » I L LI b I 'I K « )
hft'.GK F-l^nKoh: iTS AT L^A
THF: 95* CONKI^F\CH" LTVITS
SA*FLL" MJV?frk !> I'J I * U,V t 1 1 < 0 . 4 0
110
-------
Table 12
THt C'J'.C'-TNTxATiOr; OF DISSOLVE') THOKIUM
( J 'I r.'AVDGK AMS/«< I LLI L I ?KH )
'' I f I y 'J v
THfc HAf.Gt; ^PK^FTCS AT l^AST
1HF-: 95% CQ'«KIOK%O; LIMITS
B KS r VALUE
VAXI"U'<
1 11''2
1 U 0 1
11100
1 1 0 <* y
1 t 0 '-; -e
1 1 0 w 7
IK of,
1 U' * b
1 1 J44
1 1 04 3
i 1 u 9 2
11 0^1
1 1 0 & 0
110^4
1 1 0 ft n
11 Of- 7
1 1 0 r 6
1 H. 6 b
1 1 6 ?
1 1 0 * 1
1 1 C b 0
11059
1 1 0 b *-
1 1 0 S ?
e
t)
8
f
i.
3
e
7
7
7
7
7
7
7
7
7
7
7
7
7
7
7
b
O
6
6
6
6
o
6
fc
6
6
6
6
5
b
b
b
5
'}
5
b
b
5
b
5
S
s
S
4
0.00000
o.ooooo
0.00000
0. 00() 00
t'.uoono
o.uoooo
o.ooooo
0.0000 0
0.000 u 0
o.ooooo
0.0 0 0 0 0
0.00 Ono
0. 00 000
0 . fiO(n)0
0 . n 0 0 0 u
t,'.".'»0(,f!
0. 00 COG
G.OuOyO
O.OOOC"
0 . 0 0 0 0 0
0.00137
0 . 0 0 S 7 I
0 . 0 o 1 9 9
0.00124
0,0^1 37
< 0 . f1 1 1 1 i) 0
0 . 0 0 1 1 2
0 . ( 1 0 ) 7 b'
0.0"0'.H
0 . 0 'J A '»
0.001 ,
0. on<. r/
0 . 0 0 o 2 S
'J . 0 0 0 3 7
< 0.00200
< 0.00 ?>{!
< o. co i'»o
< 0 . 0 0 v 0 0
< 0.0 oi 00
< 0.0 "> >f-.r,
>" . 0 '"» » ) S 0
0 . 0 ;' o a 7
< n . n , , , , a -i
< O.i.'O 00
< O.OO'i^O
0 . 0 '1 1 n 1
0 . 0 0 1 n !
0 . 0 0 2 -» a
< 0.0rn40
< 0.0o'""50
< O.dOO'i^
< O.OOOOO
< 0.000^0
< 0.0i>i- =i;
< C.OOOQD
0 . 0 o i i ?
0.00112
< 0 . 0 0 i 0 0
< 0.0^)00
< 0.0 OK! 0
< 0.0 0 i C: 0
< 0 . 0 0 i o 'i
< 0 . C 0 1 0 o
< 0 . 0 . > 1 0 (i
< 0 . 0 "M 0 -.
< O.OOi
< 0.00;
< O.OOi i ' i
< 0 . 0 ',' 0 9 ri
< 0.0 0 fi Q -)
< 0 . 0 3 7 0
0.00259
0.00694
0.00346
O.T0223
0 . 0 0 2 .i b
0 . 0 0 2 1 f
0.00222
0.0 n 2 if-
i " -* .
*
- s f
0.0^136
U.OC123
O.f.OU*
O.fH'172
0 . 0 0 1 » 5
0.002^0
0.00260
0.00347
0.0025'-'
0.002^4
111
-------
Table 12 continued
PHIL COiCFVnJATICN OF D15 SOL /cJO THORIUM
SA^PLh
IMF RANGE REPRFG
THt 95% CO.FI'
MI'. I Mil'-' PFST V 4
' r s
&T LEAS'
LIMITS
"AX
llObl
11050
11049
1 1 0 4 c
11047
11046
1 1 04 b
110^*4
11043
11042
1 1041
1 1040
11039
1 1 0 3 H
11037
1103o
11035
11034
11033
11032
11031
11030
1 1 u 2 h
1 id2L
11027
1 1 0 ? b
1 1 0 2 b
51024
1 Iu2 3
11022
11021
1 1 0 2 0
11019
1101 V
11017
11016
1 1 01 b
11014
11013
11012
31011
11010
1 1 0 0 9
11 0 0 'f
11007
1 1 0 d o
1 lOOb
! lGi'4
1 1 Oi.3
11002
11001
1
4
4
4
4
4
4
4
4
4
4
4
4
3
3
3
3
3
3
3
3
3
3
3
3
3
3
2
2
2
2
2
2
2
2
2
2
2
2
2
2
1
1
1
1
1
1
1
1
1
I
0.00000
o.ooooo
0.00000
0 .'.0000
0.00000
0.00000
o.ooooo
0.0000 0
0.0(iOOO
0.0000 0
0.0000 0
0.00000
0 . U 0 0 0 0
0.0000 0
0 .00000
0 . u 0 0 0 u
0 . 0 0 0 0 0
0. 00 f '00
" . 0 0 0 0 0
<
<
<
<
<
<
<
<
<
<
<
<
<
<
<
<
<
<
<
<
<
<
<
<
<
<
<
<
<
<
<
<
0.00037
0.00075
0.00090
0.00070
0 . 0 0 o 8 0
0.00040
0 . 0 0 * b 0
0.00037
0 . 0 0 0 Q 0
0.00 )70
0 . 0 0 0 s 0
0.00 0 7 0
0 . 0 0 0 h 0
0 . 0 0 "i a o
O.OOOxo
0.00174
0 . 0 0 3 H 5
O.OOlhl
0.002H
0.00211
0.00 I 37
0.000*0
0 . C 0 0 2 4
0.00 ,'' 7 0
0 . 00^ c, ,
0.000^ !
0.000 -IP.
0 . C 0 I 0 0
0.001 1 2
o . u o i i'i r>
C.0010Q
0.00''7S
O.OOIOQ
0.00100
0 . 0 0 0 2 S
0 . 0 0 0 7 b
0.00070
0 . " 0 ') 7 0
0.00050
0 . 0 o r> f, o
O.OOo SO
0 . 0 0 0 2 S
0.00 0 0 0
0.0010 0
0.00100
0.00 0 7 0
0 . ( 0 0 Q 0
0.00070
0 . 0 0 n t 1
0. Oo. TO 6
0 . OOOS,)
C. 00 136
0.00197
0 . 0 0 1 4
-------
Table 13
THK CIKCKNTRATIOM UF OISSOLVL'i) URAUIU"
( JN NAMOGRA^.S/^ JLLILITKP)
SAVPLK fvU.'-
Trie: KA.'JGE
THi-j 9b%
REPP£S;-:fJTS AT LFA5T
CONFJOKf.'O: LIMJTS
PEST VAMJi-;
MAXP'U"
13 102
1110J
11100
11099
1 1 0 9 fe
11097
11096
11095
11094
110*3
1 1 ft 9 2
11091
1 1 0 w 0
110B9
1 1 0 8 H
HOP?
11086
1 lOfeb
110*4
110J-3
1 1 r.'f>2
1 1 0 b 1
1 1 0 6 0
11079
11078
11077
1107b
11075
11074
11073
11072
11071
11070
11069
1 1 U b fc
11067
11066
11065
11064
11063
11062
HObl
11060
1 1059
11058
11057
11036
11055
11054
11053
11052
' 8
b
8
8
ft
e
8
7
7
7
7
7
;
7
7
7
7
7
7
7
7
7
6
6
6
6
6
6
6
6
6
6
6
6
6
5
5
5
5
5
5
5
5
5
b
5
5
5
5
5
4
0.124
0.117
0.175
0. 146
0. 190
0.161
0.161
0.154
0.163
0 . 1 5 R
0.253
0.330
0.237
0.237
0.464
0 . 4 b 4
0.464
0 . 9 2 R
0.474
0.443
0. 5?t>
0.515
0. 53h
0.515
0.454
0.495
0.670
0.711
0.577
1.103
0.557
0 . 5 o g
0.639
0 . * 7 6
0.639
0.742
0.64-5
1.247
0 . V 9 4
0.773
0.577
0.650
C . ft 7 u
0.814
0.599
0 . « 8 o
0.546
0.763
0.691
0.732
0.8? 4
0.139
0.130
0.105
0.153
0.210
0.179
0.179
0.170
0.136
0.176
0.27?
0.37')
0.257
0.257
0.501
0.525
0.504
1.028
0.535
0.433
0.59^
0 . 5 7 b
0.507
0.576
0 . 5 I 4
0.545
0.751
0.792
0.638
1.224
0.617
0.^99
0.977
0.72-1
0.710
1 , 3 q q
0 . P 7 4
0.^54
0.63s
0.730
0.751
0.9^5
0.65?
1.0^0
0 . 6 0 ;
0.771
o. 3 n
0.90-5
0.152
0.142
0.216
179
230
197
197
186
204
194
29&
411
277
277
544
5P5
544
129
0.595
0.5/4
0.647
0.636
0.657
,636
,575
,GOf>
,«31
,P73
69R
345
679
719
760
07R
801
903
770
530
955
934
699
611
631
975
0 . 7 1 P
0.667
0.924
0 . H 5 ?.
-------
Table 13 continued
THE aXJCFMPATlCP! 'Jf DISSOLVED
( I N 'J At.TJGR A!-'S/u JLLILITrP)
f-UVHKK
TKc. RC^.GF.
THE 95%
HRST VAf.UF.
AT LAAST
v A x i v u »
U C b 1
1 10bO
11049
1104*5
11047
11046
11045
11044
11043
11042
1 10^1
1104U
1C 39
1 0 3 &
1037
1036
1035
1034
11033
1 1 0 3 /
1 1 0 .5 1
1103 0
1 1 0 2 9
110??
11027
11 02 fa
11025
11024
11023
11022
11021
1 1 0 7 G
1 1 0 1 «
1 1 0 1 o
11017
1 1 Olb
11015
11014
1 1013
11012
11011
11010
11009
1 1 0 0 h
1 1007
11006
11 u v b
11004
11003
1 1 0 ',
11001
4
4
4
4
4
4
4
4
4
4
4
4
4
3
3
3
3
3
3
3
"j
J
3
3
3
3
3
3
2
2
2
2
2
2
2
2
2
2
2
2
2
2
1
1
1
1
1
1
1
1
1
1
0.938
0.939
0.814
1.010
Q.QhP
1.000
0.742
0 . 6 0 b
1.052
O.S66
1.371
0.917
1.443
0.691
1.165
0.814
1.217
O.M5
1.237
0 . * 5 ft
1.144
O.HS7
1.412
O.frbO
O.«01
1.185
1.515
1 .371
1 . \ H 4
1 .1 34
1.154
1.00 0
1.154
1.154
1.072
0.757
1 . 4 0 2
1 .505
0 .bdP
1 .253
1.^5?
1 . 2 S R
1 . 5 ? b
1.773
2.370
0 . 5 G 7
0 .9r9
1 . 1 96
1 .464
1 .256
1.350
1
1
0
1
1
1
034
090
095
111
090
100
0 . o 6 9
1.17,2
0.967
1.512
1 .019
1.601
0.771
1 . 7 t) 6
0 . fi -} 5
1.3S«
0 . 9 4 «S
0 . 3H 7
1 .-574
U. 74)
30 o
676
512
b 1 6
255
275
100
275
114
1 .275
1.153
9.333
1.5*3
1 . h 6 6
0 . 6 * 9
1.3"'
2 . 1 o 0
1 .975
2.571
0.627
1 .07')
1.316
1
1
0
1
1
1
0
0
1
1
1
1
1
0
1
0
1
1
1
1.
1.
1
1 ,
o,
0,
1,
1,
1.
1,
1,
1,
1.
1.
1,
1.
0.
1,
1.
o,
1.
2.
,140
, 1^1
975
,212
,1"!
,201
903
,729
,293
06 fl
653
119
7 6 6
fl52
407
499
047
519
057
386
r,fi,«
735
427
S3R
653
396
201
3<56
3Q6
314
Q14
725
729
540
361
1.540
1.»1P
2.17f
2. IT"
0.6R8
1.17"
1.437
1.7^-6
1 . 5 4 0
1.632
-------
Table 14
THL CONCENTKATIO'i PF DISSOLVED '?, I'v'C
C 1 >; N ANCGH A-S/M I LL 1 L I r»rj )
N'G-: Hf-:ps^su -
1.92 3.7*
2.44 4 j
0.00 1.47
O.b9 2.3/
?.b\- - 4.50
2.64 4.50
G.3R i.'il
1.10 27 3
0.01 0 . -1 7
0.00 1.42
' } f> O r <
v « 5."» - / » v i
1 . b 2 j . h I-
0.2S 1.77
0.0" 1.06
1 . f> -i 2.61
O.o5 2.1 2
11081
11080
11079
1 lU7b
11077
1 1 0 7 b
1 10 7 b
j 1074
11073
11072
11071
11070
11069
11068
1 1 0 e 7
11066
1 1 Ob5
lido 4
1 10^3
1 1 0 n 2
1 1 0 o 1
11 0 f. 0
1)059
11 Ob*
110 il
1 1 o b' 6
1 10 b b
1 1 f > i; ,4
1 1053
1 I 0 b 2
6
8
8
H
F
8
H
7
7
7
7
7
7
7
7
7
7
7
7
7
7
7
6
6
6
6
6
6
6
6
6
6
6
r^
6
5
b
5
5
5
b
5
5
5
5
5
5
5
5
b
4
0.00
o.oo
o.oc
0.00
0 . 0 0
0.00
0.00
0.00
4.14
1 .60
0.00
o.oo
0.00
n .00
0.00
0. ou
0.00
0.00
0.00
o.oo
o.oo
o. <">o
0.00
0 . 0 0
0 . 0 0
0 . 0 0
0.19
0 . 0 0
o . o o
.) . 0 0
o . n o
0 . 0 0
0 . 0 0
0.0<".
(.'.00
0 . 0 0
0 . 0 ')
0.00
2.31
0 .no
') . Ou
i ' . 0 0
l.(-9
0.00
0.00
0 . 0 u
0.00
d.OO
1.3"
0 . 0 0
o . o o
-------
Table 14 continued
THE CfnO-'JTWMltn C+ DT <-;Sir, V"u ZT'C
( I -i '. fi -;'5vJf( A v.i/ v ILL 11. 1 T-.'n )
THF: -m CQ-.FDF\CI::
11051
11050
1104W
1 10. r
11027
11026
1 K'2b
11024
IK' 2 3
11022
11021
1102 0
\ lul 9
11014
11017
11016
1 1 o : b
1K>14
11013
1 1 & 1 2
1 1 0 1 I
1 '. 0 1 '}
1 1 u 0 9
1 1 0 0 n
11007
1 1 0 0 b
1 ! 0 '.i 5
1 ! 'H. 4
1 1 v<;3
1 lOi.'?
i ; o o i
4
4
4
4
4
4
4
4
4
4
4
4
4
3
3
3
3
3
3
3
3
3
}
1
3
3
3
2
2
2
2
2
2
2
2
?
.^
2
?
2
2
1
!
1
1
1
1
)
I
:
i
0 . 0 0
2. w*
J . 'Ju
0.00
0.00
0.00
0 . 0 0
0 . 0 0
0 . U 0
O.'iu
0 . 0 0
o.oo
0 . 0 o
0.0 0
0 . 0 0
0 . '-in
0 . f. 0
7 . f 7
O."0
5.3^
o . o n
O.u 0
o . <> o
O.I' '.'
0 . <) 0
O.^b
0 . 0 0
0. ^
0 . 0 0
0 . 0 0
0 . 0 0
0 . f i 0
0 . I' U
o . o o
0 . } 0
0.00
0 . 0 0
0 . 0 0
0. HO
0 . n o
0 . 0 0
0 . 'i 0
o . n o
o.oo
0.00
o.'^e
0 . 0 0
o . ; 7
o . o n
? . -1 3
0.00
0.00
6.06
o.OO
0.13
0.00
0.31
0.00
1.9;
O.?r.
<>.u->
U . C ->
0.21
1.02
O.-l
0.14
3 . 1 V
0.4?
11.11
0.7^
*.13
0 . 0 0
0.43
1 . 0 >
(I. ^T
a. 9 7
2.37
0.37
1 ,2b
o . 0 1
Or 7S
0.6-4
1.3*
1.1S
2.? 4
^.53
0 . f) 0
O.OO
0 . 4 3
o.co
0 . 0 0
r>.?2
0 . S 0
0 . 2 i
0.31
0.14
1.33
1.3^
2.30
0.^2
7.V6
r . 4 i
0. 79
6.11
t .27
1.43
1 . f> 1
1 .b?
1.10
3.<>4
1 . 4 «
0 . Q 1
1 .IV
l.b-'
4.47
l.Jfr
13.31
0.^7
1 .3'-
2.1?
2.01
2. on
3.f«.
1 .33
?. '
-------
Table 15
Hi-
S A
L r' f. U *
IMF RA sG r
1' H h a b :
AT LrAST
LIMITS
11102
11101
t 1 1 0 0
11017
1 1C 9*)
1 1 0 V £
110P4
11L-V3
ll'*92
1 1 J91
11090
1 1089
1 1 0 b *
1 1 0 P 7
1 1:.' b 6
11035
11 OH 4
110,3
11 u n 2
1 i r, H i
i n«'.
1 1 0 7 *
1 1 0 7 H
1107 7
11076
11075
11074
11073
11072
110?)
11070
1 1 0 c> 8
11066
HCob
1 10M
i 1 " b 3
11062
1106!
1 1 0 fc 0
1 1 059
1 I'"' S b
1 ICb/
1 iobb
110*5
1 i (.' 5 4
1 1 u b 3
lios?
o . o i .,
0.07b
0.00?
o.on
0 . i"i $ 0
'> . . 0 i }
<5.<:>i*
e .015
o.'Hl
0 . J 1 1
''.012
0 . 0 M
o . " o j
o.OO 2
0 .006
0 . -j 0 o
0 .031
0 . 0 P 1
o . :. } *
0 . 0 0 2
0 . 0
-------
Table 15 continued
-;: C'r.'Cfc'.'J THAT ION OF PASlICULflTe CADMIUM
( T \' :J A 'tQGR ft'-'f /^ 11 L ILI PER )
5 A M P L t f. U M B E R
THK
AT LEAST
THE 95% CONFIDKVCF LIMITS
bPST
11051
11050
11049
11048
11047
11046
1 1045
11044
11043
11042
11041
11040
11^39
11 0 .* S
11037
11036
11035
H034
11033
11032
11031
1)030
11029
11028
11027
1 10 2 o
11025
11024
11023
11022
11021
11020
11019
1 1 0 1 b
11017
1 1 Olb
11015
11014
11013
1 1012
11011
1 1 0 1 0
11009
11008
1 1 0 0 7
1 1
-------
Table 16
THE CONCENTRATION OF PA»TICULATR CERIUM
(I'-.' NANUCRA^S/VILLILITKP)
SAMPLE
THE RAMGK ^tCPPFSr.NTS f.T LF.AST
THE 95% COMFIOK'JCE LIV.TTS
REST V\I,JK
« A X1 ?' U ^
11102
11101
11100
11099
11098
11097
11096
1 109b
11094
11093
11092
110*1
11090
1 108°
11 0 B B
110fr7
110b6
11085
1 1 0 H 4
110 fe 3
llOb?
1 1 0 « 1
11 u 8 o
11079
11078
11077
11076
11 0 7 b
11074
11073
11072
1 1071
11070
11069
MObfe
11067
1 1066
11065
11064
1 5 0 b 3
11062
11061
11060
1 1 r. 5 9
11058
1 1 0 b 7
1 1 0 b 6
1 1 0 b b
1 1 0 b 4
1 10b3
11052
3.
3.
1.
1.
2,
2.
3.
3.
4.
4.
1.
2,
0.
0,
0.
1.
0.
0,
u.
0.
0,
0.
0.
0.
0.
0.
0.
0.
0.
0,
0.
0,
0.
0.
0.
0.
0.
0.
0.
0.
1.
0.
').
o.
0.
0.
0.
0.
0.
0.
0.
814
165
227
370
682
S14
711
431
32H
402
b7b
7b3
H04
474
031
042
127
127
144
072
lb'7
057
057
299
309
123
142
065
114
186
278
061
137
1 54
4 (j 2
04-'
1 5b
227
fal 4
814
630
033
037
03«
175
"81
237
39?
680
01 1
217
2H6
368
571
085
217
114
334
731
563
777
864
8^4
535
152
102
141
141
119
4
4
1
1
2
3
4
4
4
4
1
2
0
0
0
1
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
2
0
0
0
0
0
0
0
U . 4 3 2
0 . 7 f. t
0.32^
17b
063
065
339
350
137
15H
071
127
206
,170
,442
,0b7
,175
,267
,016
,761
,0*7
,043
0 ~\ 4
,195
,257
,414
,620
,407
,773
,489
b20
,517
,?37
1 34
,725
945
96 b
b95
273
112
0.155
0.155
177
08 B
193
069
073
380
390
151
175
077
139
226
318
<~>77
165
433
195
30P
739
217
S42
049
050
216
777
472
-------
Table 16 continued
The
OF PAf-TICULATF OJHTUM
C I''.
TMK
" '>'KPR*.Sf''Mr. AT I KAST
'' f 'i I v u M
v A «; I ''!
1 1 0 b 1
1 1 0 b 0
1 1 0 17
1 1016
1 1015
11014
11013
It 2
1 1 0 0 1
0.279
t!.4 t»5
C . 4 5 4
n . 2 b b
0.794
0.039
0 . Q 6 9
0.279
0 . 7 S 3
0.030
<; .938
0 . 0 4 4
'-1. 7 4 <
0 . 1 b b
i',019
«'» . 1 ri 6
0.034
r> . f- n I
0.141
0.703
>;.i? i
0 . i b 3
0.144
.453
,207
,92H
, I *9
,b7 7
,794
,70]
0.027
0.402
0.093
0.216
0.206
1.010
0 . I 0 b
0.23 7
0.155
0.747
1.629
5.66o
0 . b 2 5
0 . 5 2 t)
0.144
0 . 4 3 i
0.31 9
0.7 15
0 . S 1 4
1.2?rt
0 . * 7 4
0.043
I . 0 7 0
0.319
0 . =i 6 4
0.039
0. i.)9
0 . 0 3 i
I.039
0 . T b 2
0.359
0 . I « 5
0.073
0.2"*
0.0,0
0 . 0 '-» l
0 . 115
0 . d i *
0.1,4
o. n +
0.165
0.319
0.095
0.491
0.2-17
1 .02-?
0. 153
0.«74
0 . 7 » 2
0.039
0.442
0.113
0.2 n
0 . 2 71>
1 .1 11
0.117
120
0 . 1 7 S
0.267
1 . R 1 0
6.171
0 . 9 7 h
0.5*6
0.166
0. +7 <
0.339
0.956
0.047
1.170
0.3*9
0.945
0.043
0.319
0 . 0 3 «
1.14 0
O.CM
0.32«
,205
,027
,27*
,046
1*5
9? 4
n .104
n . 5 3 4
0.1»5
0.359
0 . 1C 5
0.534
0.787
1.12"
0.167
0,
0,
0,
0.
. r 9 fJ
,956
, ^62
,051
0.4fi3
0.133
0.757
0.746
1.217
0.124
0 . 3 1 «
0.195
0,
I ,
6,
1 ,
0,
0,
258
09?
775
026
647
1^5
0 . 5 1 J
-------
Table 17
Tht C''j'< i M < i
TI-E RAU^r REPPFSR.NT& AT Lfc'AST
ThF 95* CONFIDENCE. LIMITS
HKST VALUE ,*AXT.; - u
11079
1 1C 7 'f
13077
11076
13075
11074
110-73
11072
11071
11070
J 1 0 f- «
1 1 r» t r,
11067
HObb
llot>5
1 1 o fc 4
11063
H 0 b 2
1106}
1 1 0 C, 0
1 1 0 5 V
i 1 0 b f-,
11057
11058
1 K' b 5
1 1 0 5 ;
Il'"'L-3
3 10 S 2
1.134
1.175
0.567
0 . 6 0 H
1.051
1. 2n«
1.2 Ob
1.165
? . 1 r, .\
?.lc4
0.4V4
1.1 01
0.340
0.350
0.175
0.402
0 . 0 a M
0.0/7
0.053
0.057
0.04';
0 . 0 h ti
n . o 3 j
0.f'34
0.065
0.064
0.037
0 . (, S i
0 . 0 2 'i
0.015
0.044
O.Of.4
0.02o
0.040
0 . 0 3 6
0 . 0 Q 2
0.013
0.027
0.013
0.054
0.2P9
0.117
0.019
0.026
0.013
0.035
0.037
0.05'*
0 . G M
0.1'ic,
1.255
1.2'*&
0.627
0 . *> ») 8
l.m
1.409
1.347
1.2?f'
2 . 3 6 '3
2. ^5
O.S15
1.22-*
0 . J R 1
0.3^1
0.193
0.442
0.055
0.031
0.059
C . >T 6 3
0.044
0 . T ? 2
0.023
0.037
0.079
0.065
0.3?9
0.130
0.023
0.03)
0.022
0 . 0 J t»
0.045"
0 . 0 6 5
0.072
0.121
0.017
1.376
1.417
O.h««
0.729
1.293
1.407
^ . S 6 7
1.345
0.421
0.431
0.211
0.4^3
0 . 0 (, l
0.035
0.065
0.06°
O.fMS
i", . f, fi 4
0.03^
0.042
0.077
0 . 0 e 0
0.049
0.065
0.037
0.019
0.0 5h
0.030
0.034
o . 0 4 b
0 . 0 4 c
O.H?
0.033
n.o-17
o , 0 4 s
0.078
0.3h 9
0.142
0.027
0.034
0.026
0.043
0.053
0 .071
0 . 0 ? 0
0.133
0 . 0 5 S
fc,,.
-------
Table 17 continued
THE CO'.'CK? T»ATION OK PAKTirULATe COHAI/f
SA.'-TI.F: MJV £.?;
ThF P-V>bf: MK
MKST vit.ui-:
S AT LEAPT
LT'ITS
IK'bl
11050
11049
II C 4 fr
I 1 1; 4 7
11046
1U-45
11041
11 it 4 3
11042
11041
11040
1 1 C 3 V
1J03S?
11037
1 1 0 1 b
11M3S
11034
1 1 0 3 J
11032
1 1 U 3 1
llOjft
1 J 0 } V
I1('2f
11027
11026
1 1 U 2 b
11024
11023
11022
1 1021
11020
llOl^i
1 1 0 1 F
11017
1101 b
11 "15
11014
11013
11012
1 j 0 1 1
11010
11009
31008
11007
11006
i 1 0 0 5
1 1 C (,' 4
1 1 < 0 J
1)00?
11001
0.053
0.074
0.0*1
O.OS7
0 . 1 2 ::<
0.022
o.l 6 4
0 . ',.' f , 3
0.206
0 . 0 ^ H
0.044
0.031
0 . 1 b f»
0.0 Jo
0.043
0 . 0 2 (*
0.02"
0.019
0.040
0 . o 2 J
0 . 0 (_, 4
0.^40
0 . 11 ?
O.f'b4
0.100
0 . 0 3 b
0.043
0.0 2^
0.093
O.C47
0.1 49
O.CJ6
U.I Ob
0 . 1 6 S
O.lh3
O.D 26
0.06?
0 . o a 1
O.Obl
0.049
0.14*
0 . 0 ? 3
0.057
0.031
0.047
0 . 2 5 S
0.94^
0.1^5
0.097
0.039
0.072
122
0.059
0.0*4
0.092
0.063
0.11?
0.02b
C.li?
0.071
0 . ? 7 6
0.032
0 . 0 b 0
0.037
0.17?
0.04?
O.U49
0.040
0.035
0 . 0 ? 1
0.01-
0.02?
0 . 1 7 \
0.050
0.127
0.0 A?
0.112
0.0-11
0.051
0.131
0.107
0.057
0. 165
0.042
0.1 IS
0.1*3
0 . 1 * 1
0.034
0.072
053
057
o 5 a
165
f> ? 9
Ob 9
035
153
2 SH
-i J 9
171
1 o 9
'1 5 1
0 in
0.065
0.0<54
0.102
0.069
0.156
0.030
0.2^0
0.079
0.246
0 . 0 3 h
0 . 0 b h
0 . 0 4 J
0 . 1 » o
O.Odfl
O.OSS
0.05?
0.04J
0.073
0 . 0 S 2
0 . C 3 5
C . 0 ft 4
0.0f>0
0.141
0.070
0.124
0.047
0.121
0.0»7
0. 1"!
C.04S
0.13C
0.201
0.199
0.042
C.0«2
0.06b
0.063
0.060
0 . 1 ? 1
0.035
O.OH]
0.039
0.060
0.33r<
1 . 1 S 0
0 . 1 fc 7
0.121
0.064
O.OR8
-------
Table 18
THE OKJfK'lTJ-AIlON CF Pfcf-T ICULftTE
(IN 'JA\nGfAMS/"ILMLITEP)
PANGE RK.pfFNCf- LIMITT,
VALUE
M A X I M U '*
i U 0 2
1 1 1 ' U
1 i 1 0 0
now
1 1093
11097
11096
11095
11094
11093
11092
11091
11090
1 1 0 B 9
110*6
119*7
1 1086
11035
1 1 0 b 4
1 1 0 « 3
1 1 0 * 0
n o 7 H
1 i 0 7 R
11077
11076
11075
11074
11073
11072
11071
11070
11069
1 1 0 o 8
11067
11066
1 1065
1 1 0 h }
11063
1 I 0 6 2
1 1061
11060
11059
11057
11056
11055
U 0 S 4
HU53
1 1 ^ ', 2
3.5R
3.45
0. H2
0.»6
2.01
2.30
3.76
3.16
3.63
3.d3
1.52
2.55
0.47
0.43
u.l 7
O.R5
O.uO
0 . 0 u
0.00
0.00
O.oo
0.00
0.00
0.00
0.00
0.00
0.00
o.oo
0.00
0.00
o.oo
tt.OO
0.00
0.00
0.00
0 . 0 0
o.uo
0,00
0.00
0.00
0.48
0.00
0.00
0.00
0.00
o.oo
0.00
0.00
0.00
0,00
0.00
123
4.49
4, 60
1.77
1. 31
2.62
3.14
4.91
5.01
6 . 17
4.47
2.41
3.17
0.99
C.95
0.67
1 .44
0.14
0.13
0.x. 3
0.22
0.16
0.34
0. 0'-»
0.14
0.37
0.22
0.09
0.5Q
0. 16
0.00
0.27
0.36
0.00
0.25
0.02
0.44
0.00
0.1 1
0.15
0.44
1.71
0.00
o.oo
0.00
0.13
0.08
O.oi
0.38
0.22
O.S2
0.39
5,
S,
1,
16
49
40
1.53
,00
.74
PO
.91
5.OR
5.0(5
3.10
4.13
1.27
1.23
0.93
1.79
0.36
0.35
0.44
0.43
0.44
0.55
O.oH
0.73
1.14
1.22
0.75
0.55
O.H5
0.97
0.53
0.83
0.5P
\ .05
0.52
0.70
0.74
1.05
2.70
0.54
0.3-3
0.37
0.72
0.67
0.57
0.99
0.80
1.16
1.00
-------
Table 18 continued
THE: C
( 1 1<
IO'; OF PSPIICULATI-:
A \ 0 G P A *> S / l> I L L 1 L J T K «
THF PA\'GK PEPKKSFNTS AT LfcASf
Tir. 95'jj COrJFirtNCh LIMITS
'MM V U K
Ri-f-.T
!, A X ] '' U "
11051
11050
11049
11 0 4 d
11047
11046
1 1
0.73
0.66
O.fcO
0.46
1.00
0.15
0.71
0.34
1.11
0.35
0.25
0.43
2.45
0.19
o!l5
0.14
0.49
0.76
1 .OC
r.3^
1.64
0.91
1 . 0 0
0.02
1 .40
0.80
1.23
0.74
2.14
31
21
73
74
0.62
0.94
0.59
0.73
1.03
1.0*
0.46
1.71
0.50
0.57
2. IP
6.76
! .79
1 .45
-------
Table 19
Th£ Cnf.CKKTRATJC'. OF PARTIO'tATF
(IN
SA^PuK
THE RANG*" HKPHESENT5 AT LEAST
THE 95% C0..f IDE"»CE LIMITS
M 11,1 P U H
BEST VAli'JK
MAXIf-'Uf'
1110?
11101
1 1100
11099
1 109b
11097
11096
11095
11094
11093
1 1 C 9 2
11091
11090
11089
11088
llOti?
11086
11085
11084
1 1 0 b 3
11082
110*1
1 K- 6 0
11079
i 1 0 7 B
11077
11076
11075
11074
11073
11072
11071
11070
11069
11068
11067
1 10&D
11065
11064
11063
11062
11061
11 0 h 0
11059
1 1 0 3 &
11057
1 H) 5 6
11 0 => b
1 1 0 5 4
11053
11052
0.19
0.39
0.43
0.33
0.59
0.77
0.37
0.37
0.92
1.92
0.00
0.19
0.00
0.00
0.00
o.uo
0.00
0 . (> 0
0.00
0 . 0 0
0.00
0.00
0 . 0 o
0.00
0.00
o.oo
o.oo
0.00
o.oo
(> . 0 0
0.00
0.00
0.00
o.uo
0 . 0 '"
o.oo
0.00
0.00
o.oo
0 . 0 0
o.oo
0.00
0 . 0 0
o . o o
o.oo
0.00
0 . 0 0
0 .
-------
Table 19 continued
1HF COl.CtXTRATlON OF
PART ICULATK
1LL1LIT1>.)
CHPPFP
THfe. KANGE REPRESENTS AT LEAST
1HL 95,% CONFIDENCE LIMITS
SAMPLb.
K 1N 1M U M
Bfc.ST
''AX I HI) V
llObl
11050
11049
11048
11047
11046
11045
11044
11043
1 1 U 4 2
110*1
11040
11039
11038
11037
11036
11035
11034
11033
1103?
11031
11030
11029
1 1 0 2 fa
11027
11026
11025
11024
11023
1102?
11021
11020
11010
llOlb
1 1017
11 0 1 6
H 0 1 b
11014
11013
11012
11011
11010
11009
1 1 o o e
11007
1 1 0 0 6
11 OOb
1 1C' 0 4
11003
11002
11001
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0,00
0 .00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
o.oo
0.00
0.00
0.00
0.00
0.00
o.oo
0.00
0.00
0.00
0.00
0.00
0.00
0.00
o.oo
0.00
0.00
O.no
o.oo
0.00
0.00
0 . 0 0
o.oo
0.00
o.oo
0.2?
1.32
0.00
0.00
0.00
0.00
126
0.24
0.00
0.00
0.00
0.07
0.00
0.42
0.00
0.13
n.eo
o.oo
o.oo
0.23
o.oo
o.oo
0.00
o.oo
0.00
0.00
0.15
0 .00
0.21
0.11
0.03
0.19
0.00
0.06
0.00
0.00
0.07
0.22
0.00
0.00
0.09
0,06
0.00
0.10
0.26
0.00
0.00
0.49
0.00
0 . 0 -J
0.00
0 . 0 2
0.14
2. b ?.
0 .2')
0.00
0.00
0.0?
O.f 3
0.25
0.23
0.11
O.b4
0.70
0.93
0.27
0.00
0.29
0.34
0.33
0.6?
0.28
0.28
0.2R
0.15
0.13
0.30
0.64
0.2P
0.60
0.47
0.45
0.66
0.31
0.42
0.31
0.21
0.43
0.63
0.41
0.41
0.58
0.53
0.21
0.46
0.54
0.33
0.33
0.94
0.32
0.3h
0.17
0.24
1.1°
4.23
0 . h Q
0. Ib
0.33
0.40
-------
Table 20
THE CC'»CE'JTf ATION
(lu
OF PARTiCUL ATF I PON'
S6VPLE MJS6KP
MI < I «' i
THE, PAIvGE REPRESENTS M LFAST
THE 95% CONFIDENCE LIMITS
VALUE
M A XI M I) *'
11102
11101
11100
11099
11098
11097
11096
11095
11094
11093
11092
11091
11090
1106Q
noes
11087
11086
11085
11084
11063
11082
110*1
11 o e o
11079
11073
11077
11076
11075
11074
11073
1107?
11071
11070
11069
noes
11067
) 1066
110o5
11064
11063
1)062
11061
11060
11059
H05e
11C. b 7
1 105o
11 0 b S
11 0 i> 4
11053
11052
1529
1620
462
493
920
1113
1578
1499
1692
1681
645
12(55
382
39?
230
524
42
69
b5
64
3?
sa
22
27
120
128
60
85
22
122
6P
106
24
83
66
199
14
103
83
230
1718
1831
535
566
1039
1?55
1790
271
12
19
17
102
36
111
136
241
1 17
1903
1892
740
1450
432
442
257
597
50
82
66
7
40
103
31
35
140
148
71
101
31
142
Rl
123
30
99
79
226
23
120
103
257
782
298
19
25
23
119
44
t?9
!58
2h7
144
1879
2012
595
626
1 140
1376
1971
J P4B
2084
2074
821
1591
472
277
657
54
90
72
85
44
113
35
39
154
162
77
111
35
156
R9
136
32
109
B7
24C
27
132
117
277
662
318
21
27
?5
131
<5P
111
175
2RP
127
-------
Table 20 continued
Jht Cnfv'CF'iTRATJON
(IN
'.F PAHT I CO'I. ATE
H1NIMUV
THF:
THE
BF.ST
PA\:GE KfPHFSF'JTS AT LEAST
955 CQMKinE'JC* LIMITS
1 1051
11050
11044
11048
11047
11046
11045
11044
1 1043
1 1042
11041
11040
11039
11036
11037
1103b
Hu35
11034
11033
11032
11031
11030
11029
1102*
11027
11026
11025
11024
11023
11022
110?l
11020
11019
1101F
11017
11016
11015
1101<*
11013
11012
11011
11010
J 1 U 0 9
11003
1 1 0 C 7
1 lUOh
11005
11001
11 0 0 3
11002
11001
111
177
IBS
105
310
10
403
104
269
15
Ufi
12
454
22
142
7
84
9
92
13
57
76
382
56
1 99
64
133
39
210
95
441
6fi
269
362
331
15
173
53
101
92
45
1 18
72
1 14
747
2584
382
237
70
220
128
129
204
215
122
360
16
453
121
319
~2
160
IK
5 0 4
31
165
17
1 o r,
14
107
20
<>H
92
13 2
67
22h
77
155
47
237
1 10
51 4
81
319
411
331
24
200
64
1 1H
107
501
56
138
35
1 34
813
2911
432
270
«3
247
141
274
235
134
400
ie
493
133
359
24
177
20
544
35
IfM
24
no
16
117
22
74
102
472
73
246
fi5
171
51
257
120
575
89
359
452
421
70
130
11 7
544
62
152
93
472
297
91
2b7
-------
Table ?1 . .
THE CO'.CKUTHATION OK PA KT IC'JUTE ''6 f!
(I;, VA?-JOGRAl''S/.VILLIL:TtiK)
THE 1- A .\ G (; P E P K K .c- <; N T3. a )' L ?. A G~7
THE" 95% CCNr JOr'JCK LIMITS
N'U^bFh MIMMUM HtST VALUE ,''AX I
11102 92.5 116.0 139.5
11101 102.5 «2£.0 149.5
11100 95.5 - 119.0 '142.-5
11099 106.b 130.0 153.5
11093 130.6 156.0 .. . -- los.4
11097 152.6 .!«??. 4 -0 -2-i-;-. 4
11096 157.b 187.0 216.4
11095 154.6 184.0 213.4
11094 2 4 fi. 6 276.0 3 <" -' b . 4
110°3 311.8 349.0 386.2
11092 53.1 65.2 7P.5
11091 94.3 llb.O 130.7
11090 .35.7 44.1. "5.2.5
11089 38.3 47.3 5fc.3
HO&b 30.9 37.6 44.3
11067 60.3 73,6 r6.9
11066 21.0 26.1 31.2
11085 2.3 2.9 3.5
1 1 0 t 4 21.1 2 h , ') 31.3,
11083 24.3 30.? . _ - "36'.~i
110»2 27.1 .--3-.S' "" 40.5
11081 ?-9.4 36.7 H-i.O-
110S 0 14.6 16. 1 21.6
11079 15.8 19.5 -- 23.2
11078 15.9 19.6 23.1
11077 19.0 23.7 ---.---:--.-?»:._:._
11076 32.4 40.0 "47.6
11075 34.3 41.9 "- 49.5
11074 ^.7 12.1 14.5
11C73 O.S 1.2 1.6
11072 12.4 Ib.b IP.e
11071 17.6 ^1.3 2h.O..
11070 5.2 6..6 _...--f"~rt
11069 fl.O ' '9.% ...--'"" 11. ft
HOfeb 15.4 . }.--.*"""" 22.4
11067 30.7 _ - "" 3b.l 45.5
11066 5.0 fi . 4. 7 . R
llOr.5 72.9 28.6 - 3-1.3
11064 15.3 19.2 2 J.I
11063 23.1 29.0 31.9
11062 26,7 32.4 3 fr. 1
11 ii 61 45.3 52.9 " feC.5
11 0 6 LI 10.0 12.4 . J,-V.
11059 1 ». 9 23.4 .. : - "27.0
1105b 10.0 12..-i 14.'}
11057 10-. 0 - J i-. 4 1 4. H
11U56 1^.1 - 2^.6 2h.l
11055 18.2 22.5' 26. »3
11054 10.a 13.3 ' 1h. "
11053 13.7 16. P . 19.
110^? 1 J.8 16.9 " """- 20.'
129
-------
Table 21 continued
THE
( p
OF
ILL I LI IKK)
SAV.PLF
THF SAMGK
'I UK 9Vi
;-, r.'t'M t
Rf P HE SET
AT LKAST
LIMITS
"A/I'";"
1 1051
11050
11049
J 1 0 <5 fr
1 1017
111-46
1 1 0 4 b
11044
1 1 o 4 3
1104?
1 1 u4 1
11040
110.59
1 1 0 3 *
11037
1 "> 3 a
1 1 0 ? b
11034
11033
1 103i
110)1
1103 r>
1 1 1 7 -
1 1 0 2 r*
11027
1 1 J?^
11025
1 1024
11023
11022
1 1021
ll()2v
1 1 "1 9
1101F
1 1 0 1 7
llClf
llClb
1 1 '"' 1 4
11013
11012
lion
1 1 (. 1 0
11009
1 1 0 0 *
1 1 0 '- 1
1 10 0 b
1 1 CM 1 5
1 1 Oi it
1 10 0 3
1 1 c o :
1100)
*».
!>.
34.1
10.1
9 . *
11.6
11. "
16. b
6.3
10.0
9. *
11.7
* . 3
13. S
1^.1
12.?
1 ? . 4
15.3
29.1
11. H
7.7
Q . '"I
9.b
11.4
13.7
13. h
If .1
33.0'
29. x.
9.3
10.7
6.*
13.*
10.Q
26.')
7. i
4. 9
e.i
a.*
22.5
11)1 . 0
20.1
IV. 2
1 t> . *-
15."
1.-0
-~ ~~ -~r -- ~
22.P
24.1
27. o
2fc , 3
17. H
14.5
S4 . 9
M .9
40. «
12.1
ll.fi
14.0
14.3
19.7
7.7
12.0
11. I
14.1
10.1
16.0
I7.fi
1'l.h
14. H
1 O f
34.fi
14.?
9.3
11.0
11.5
13.1
'2 '2 . 4
16.5
21. *
39.7
3^.?
11 .3
12.9
1 0 . «
16.5
13.3
31.o
c . 'J
1 1 . f<
'- .7
10.6
2r. . ?
u ; . -I
23.P
2 2 . '}
2" . 1
1 « . f
-------
Table 22
T>£
-.fPATIO; IT P-A^TICULATF
(P. ^AVG^rA^S/'-
f- L f"
V 1 'J I
THK
(-FPPFSFNTS AT LFA.S7
.''AXJ "I,"
\ »lir2 < 0.05
; 1 1 i u i < o . o *j
i I 1 1 Of! 0.00 O.Q?
1 1 1 " f j ft r\ *- -
; * - - ^ o . r v o.o?
1 1 t r >< u
; z * " - < 0 . 0 3
: 1Ji'"7 < o.o.!
1 1 o ^ -,
: ' l ~ < 0 . 0 n
1 1 ^ Q «\ »
1 ' ' - < U . 0 7
' 11 V'..? 0.00 o.o*
! 1 ", <, 5 ..
1 ' - - - < U . 0 fi
U'JS? O.of) 0>0,
i HO^I 0.13 0.2b
llv'?u f C\ s\ &.
v U » ' *3
t 11^9 o.oi o.os
' 11"^ o.y. 0.02
nt"° < O.OQ
HC-e < 0.03
1 ! ° ' 3 < 0 . 0 3
I 1 C - 1 < r .-n
N ' < . ' J J
11 'J " j < 0 . 0 ?
i 1 ^ « : ^
1 * - * < o . o H
1 1 ' ' * t ,"' << -. ,
11- . .,.' 0<1)?
!!'""'" ^ ^ ^ -,
1 < 0 . 'i 2
1 ' J ' -* < 0 . 0 2
110r < 0.03
11 l' -' 7 < 0 . 0 3
I'07" < 0.03
1 I u' 5 < o . 0 2
H°7- < 0.03
1* ^ T *
J' 7j < 0.04
1 1 u 7 ? < 0 . o 4
11071 < 0>0,
11070 < 0>r,3
IU-09 < o.n?
1 i 'J n " < 0 . i f ,
not? < Opns
110511 < 0.05
H"r5 < n.(,,i
ni'n4 < o.-;4
I 1 < / ** 1
i i j ^ < 0 . 0 5
1 ! '". 2 O..;0 0.0?
i \ . i ,-. \ ^
* ' } l < U . f -J
Iiflr'" < 0..-2
1 ! ' > '- ' f - -,
* J - < 0 . i) }
iJ^- < o.>?
H057 < u>0.
1 1 " "- t
1 - - < 0 . 1 3
1 1 f > V -
a * ' D- < 0 . 05
n t ^ -; < ,_, _ .-, .;
1 i ', S i < ,, ^ 0 ,
ii.-b^ < -/>V(
151
--.l..T-i^ta.^Jggejgjgij%^^!^ i- -i n- t.l- ~j*«*+.Jt,l~mMasa*iuM,
o.ob
f, /^ *:
J ' ' ~
0.2-1
0.03
0.37
0 . 0 9
0.06
0 I f,
\ ' 9 U l'
0.0^
-------
Table 22 continued
THt CO«jCfc>TKATIUU CF PAf21
11023
1 1 0 2 i
1 1 " '* 1
11020
11019
1 1 U 1 «
11017
l'f| If
I 1 0 1 b
U014
11013
H'Jli
li on
11 CIO
11009
1!006
H0(l?
3 1 r"'-t
11003
0.01
<
<
<
<
f
<
<
<
<
<
<
<
<
<
<
<
<
<
<
<
<
<
<
<
<
<
<
<
<
<
<
<
<
<
<
<
<
<
<
<
<
0.06
0.20
0.20
0.09
0.10
0.05
O.HO
0.60
0.05
0.03
0.10
0.03
o.oH
o.o?
0.05
0 . 0 V
0.03
0.05
0.03
0.04
0.03
0. 40
O.OJ
0.06
0.05
C.?l
0.05
0.06
0.06
0.02
0.08
0.03
0.06
0.70
0.06
n*06
0.70
O.'M
o.'i/'s
0.06
0. ftO
0.71
0.07
0.07
0.41
o.05
O.Ob
152
-------
r
Table 23
THE coNCr-:,n'MrioN
(IN N
OF PAPTJCULATE NICKEL
THF PA'.GF.
ThK 9b%
AT
" I \ I H U M
BEST I/AM1F
11102
11101
11100
11099
11098
1 1 C 9 7
11096
11095
11094
1 1 C 9 3
11092
11091
1 1090
11069
11086
11067
11066
1 1 0 b b
11 U is 4
1 U< <- 3
1 1 0 f 7
11 0 b 1
1 1 Ob 0
1 1 0 7 V
11G78
J 1077
1107o
11075
11074
11073
1K-72
11071
1107 0
11069
1 1 U 6 h
11067
110h6
HOob
1 106-1
110fc3
11,'t?
11061
11060
1 1 0 b 9
1 1 0 b *
1 1 0 b 7
1 1 0 b 6
1 1 Obb
1 1 Cb4
1 1 0 b 3
1 1 0 b 2
1.7't
2.04
0.69
0.89
1 .36
1 .96
1 .76
1 .64
3.14
4.01
O.ob
1.16
0.46
O.bO
0.26
0.63
0.07
o.oo
o . r. 8
o.io
0,0*
0.07
0 . 0 «
0 . 0 4
0 . 1 3
0.14
0.03
0.04
O.OQ
0.00
0.17
0.2b
0.09
0.01
0.10
o.i^
0. 1?
O.Ob
0.07
0 . 2 ft
0.42
0 . 7 '->
0.03
0.04
0 . 0 b
0.11
O.Oc
0.13
0.11
0.26
f. 11
2.bO
2.PO
1.00
1.20
1 .90
2.50
2.30
2.4H
3.90
5.00
0.92
1 .70
0.73
0.77
0.4T
0.94
0.20
0.11
0.24
0.26
o.20
0.17
0.29
0.30
0.16
0.17
0. 10
0.43
0.22
0.14
0.26
0,L<7
0.2«
0,1*
0.20
0.
0,
1,
o,
0.
o.
o.
0.
/IB
r 4
10
16
17
133
,27
,24
0.29
0.27
0.46
0.27
3.09
3.39
1.20
1.40
2.29
2.89
7.69
4.49
5.7H
1 .OH
2.09
0. ?9
0.03
1.34
0.24
0.13
0 . 3 0
0.32
0.24.
0.26
O.?l
0.35
0.20
0.21
0.31
0. 12
0.43
0.51
0.26
0. 1 t-
0.32
0.44
0.34
0.22
0.24
0.7f-
1.30
0.2"
0.21
0.22
0.33
0. 3u
«.3S
0 . 3 3
0 . b 6
0.33
-------
Table 23 continued
ThK CljrJCEMPATlO.'i W PAH1ICUbATP NICKR'L
(IN NA;4UGKA"£/*-'lLLILITfc.iU
HANfiK P
THE 9b% COf.'f
V Ke'ST
AT T,FAST
LIMITS
11051
no 50
1 1049
1 1 U 4 P
11047
110*6
11045
1 1 (. i
-------
Table 24
TKK CnnCf-:;«Th'ATlO,V OF PAR f ICt'LA'I £ LEAD
THE RAN'Gc R t P R j-J ,S K',' fS *T Lf AST
TH
SAVPLE 'I'J.'luf-jR M I'» T'-'U M
1 1 102
1 1 ln 1
1110U
1 1099
11098
1 1 0 o 7
11 >'"9f
i i 0 9 b
11C93
11092
1 1091
11090
H u b 9
11088
1 1 0 b 7
110*6
1 1 o « 5
1 1 0 « 4
1 1 (' h 3
1 1 o ; 2
11 0 n 1
1 1 0 * 0
11079
1 107c
11077
] 1 0 7 c
11 0 7 S
1 1 0 7 4
11073
Hi/72
Ii071
1 1 r. 7 0
i I06y
1106"
1 1067
1 1 0 e b
' 1 uf 5
1 10 (. 4
1 1 0 h 3
1 1 0 1- 2
11061
1 I 0 M/
11059
1 1 0 S n
11057
1 lu5o
1 1 '>S5
i 1 (.' 3 4
1 1 0 1, 3
i 1 0 3 2
1,61
2.09
3.01
0 . 9 J
1.71
2,49
3.76
5. '-i?
S. 44
1.49
2.^4
0.42
0.41
0.2o
0.03
0.12
0.11
0 . i) -
0 . Ou
ij . ''i 0
0.04
0.06
O.Ob
0.03
0 . 0 0
1 . 0 1
0 . 0 1
0 . C9
o . TO
o.ci
0.00
0.22
0.12
0 . C> t>
0.24
0.4*
0.62
'' . 0 /
0 . 0 4
0.01
0.2:
O.'io
0.07
0.3 3
0. 3h
o ....
VALUE
2.10 2.49
2.'0 3.3?
I.'JO 1.S9
1.40 1.79
2.20 2.SQ
3.?0 3.79
4.70 s.48
7.30 8.4*
-'.60 4.19
<=.M 7.4*
2.2^ 2.79
4.10 5.08
O.b4 0.fcO
0 . fr 3 0.79
0.43 o.S 3
^ q 3 1 . i 3
3.06 G.0 £
0.05 0.07
0.09 0.11
0.23 0.29
0.72 o.2R
°.'^ 0.20
O.OS 0.07
0.14 o. o e
0.12 0 .
-------
Table 24 continued
THF CO*Cfcr:TRATION OF l-A»TICilLATf. LEAD
( J'f iJAi'.'PiJfiAVS/viLLIMTER)
E'MS AT LEAST
E 95^* COMf ine-.JO" MMITS
11051
11050
11049
1 104?
11047
11046
11045
i 1 044
11043
11042
1 1041
11040
1 1039
1 1 -'' j 8
11(37
1 1 U 3 h
11035
1 1034
1 1U33
11032
1 i (> i i
i t. \ J t
11 o 3 0
1 1 r: 2 9
1 1028
11027
3 1 u 2 >>
11025
1 1 u 2 4
1 1023
11022
JJ021
1 1 020
I 1 0 1 <*
1 1 0 1 8
11017
1 1 ' > 1 r
11015
1 1 '/I 4
11 u 1 3
11012
1 I O 1 1
L 1 A i
1 H> 1 0
M > o
-------
Table 2
T!'L CO.VCKMKATJQN Op PARTICULAR SCANDIUM
(IN NArv'OGRA"S/MILLILITF:R)
THE PAN'GP HEPhESE'.'To AT LKAST
THE 95% COI.FIDFMCF. LJVJT.S
SAMPLE MUMBL'R
Bf'ST VALUE
' 0 » b
U.0277
0.0472
0.1212
0.3797
0.1407
0.0061
0.0072
0 . 0 0 7 3
0.0308
0. (J 1 60
0 . o 4 4 1
o . 0 f- n i
' 0.1335
0. O^f'o
137
-------
Table 25 continued
THt: CONCR.;TPATION OF PARTICIPATE SCANDIUM
C Hi < A'JOCK A MS/".ILL I LITER)
X 11. I * U
TKt RANGfe) RFPPFSE*T.C AT LEAST
THE 95% CONFIDENCE LJMTT.S
BEST VALUF
» !
t
11U51
1 1 0 b 0
11049
11046
1 10 4 7
1 1046
11045
1 1044
11043
11042
11041
11040
11039
1 1038
11037
1103b
11035
11034
11UJ3
1 )032
110 Jl
11030
11029
11028
11027
11026
11025
1 1 0 2 4
11023
110^2
11021
11020
11019
1 1 0 1 %
11017
11016
1 1 "> 1 5
11014
11013
110)2
11011
11010
11009
1 1 0 0 fe
11007
11006
1 1 0 0 5
1 1004
1 1 0 0 3
11002
11001
0.0453
0.0742
0.0742
0.0402
0.1256
0.0053
0.1S15
0.0422
O.ltho
0.0045
0.0412
0.0042
0.1423
O.OU75
0 . 0 3 fi 1
0.0032
0.0247
0 . 0 0 2 S
0.0263
0.0^4^
0.0134
0.0216
U.ll ftt)
0.0175
0 . o 6 S 0
0.0216
0.0143
0 . 0 1 2 b
0.0639
0.0309
0.1412
0.0206
0 . 0 8 M 7
0.1 Jb5
O.lu*2
0.0059
0 . 0 5 *> 7
0.0165
0 . 0 3 0 9
0 . 0 2 P 9
0 . 1 H M
0.0140
0.0392
0.0237
0.03bl
0.25R7
0 . t> 2 4 B
0 . 1 2 7 y
0.0773
0.01 9 f,
0.0649
0.0494
0.0823
0.0823
0.0442
0.1 399
0.0059
0 . 1 6 7 f,
0.0463
0.129b
0.0051
0.0453
0.0046
0.15Q4
0.0083
0.0422
0 0 0 3 6
O.C267
0.0030
0.0298
0.0050
0.014%
0.0237
0. J 30F.
0.0195
0.0730
0.0237
0.04fi3
0.01 39
0.0699
0.0350
0.1553
0.022-5
0.0987
0.12^6
0.1193
0 . 0 0 6 5
0.0627
0.0195
0.0350
0.0329
0.1625
0.015ft
0.0432
0.0257
0.0401
0.2963
0.9256
0. M19
0.0*54
0.0216
0 . d 7 1 n
0.0534
0.0903
0.09C3
0.04»3
0.1540
0 . 00 h S
0.1833
0.0503
0.1407
0.0057
0.0493
0.0050
0.1745
0.0091
0.0462
0.0040
o.o2yfc
0.0032
0.0308
0.0054
G.01h2
0 . C 2 5 7
0.1427
0.021*
0 . 0 f> 1 1
0.0257
0.0524
0.0153
0.0760
0.0390
0.1694
0.0246
0 . ] f i f 8
0.1407
0.1304
0 . o (i 7 1
0.0688
0.0205
0.0391";
0.0369
o. neb
O.ili 72
0.0472
0.0277
0.0443
0.3152
1 . 0 2 6 4
0.1^60
0. 1/9 34
0.0236
O.U770
138
U-,.
-------
Table 26
THE CONCENTKATIO'J OF PA*TICULATt TIN
THE RANGE RF.PHF.SEM'S AT LFAST
THE 95% COPvFID^f.'CrJ LIMITS
SAMpLK MI.'-'bFR VIMMUM BEST VflLUE MAXIM'IM
11102 < 3.00
11101 < 3,00
11100 < 0.60
IK'99 < 0 . 5 0
11098 < 1.00
11097 < 2.00
11096 < 2.00
11093 < 2.00
11092 < 2*°°
11091 < 2-°°
11090 < l'QO
11069 < 0.60
11089 < °'6n
11067 < °'60
11086 < 2'°°
HOS5 < °-SO
11084 < °-7l!
HOtfl -J
11080 < °-40
11C70 < °-30
1107fr C °-:'0
.11077 < °'50
11076 < °'50
11075 < °'40
11074 < °'30
11C73 < °-
-------
Table 26 continued
THE CONCRr.'.'TfcATin?.' OF PA(-"f ICUL a TE TIN
(IN N
11048
11047
11046
11045
JlOOb
UOO'i
110C3
TH£ RAMGE REPRESENTS AT LFAST
THF 95% CQ^FIt^CF LIMITS
SAMPLE * ...,..,
VALUE.
< o'sn
11042 °'SO
1 °*» < o'L°
11040 ' 0'^
11039 < O' 0
>7°
, , .- , , <
0 *
11033
11032
11029 < o\n
11078 < °'70
31^;7 < 0.70
ur'f < i-00
no
< '-"o
o2 < 2-°°
09 < °-7°
11018 < C-VO
S 7 < LOO
no < 02-2°
11012 0"'°
11010
M009
1100.
111107
!
140
i!
-------
Table 27
THE CONCENTRATION OF PARTICULAR THORIUM
(IN *.'AMOGRA,MS/"ILLILIT!:::?)
Mjf>'BEP
ni'TMU/-'
THE PANGE REPRESENTS AT LKAST
THE 95% CONFIDENCE LIMITS
PEST VALUE
M A X IP U v
11102
11101
11100
11099
11098
11097
11096
11095
11094
1 1093
1 1092
n o 91
1 1 U 9 0
11089
11088
11C66
11 0 b 5
1 10b4
110*3
11082
1 U 11
11080
11079
1107?
11077
1 1 076
11075
11074
11073
11071
11071
11070
11069
1106S
11 01> 7
11066
11065
11064
11063
11062
1 lOol
1H60
11059
11056
11 U 5 7
1105b
11055
11054
1 1 0 5 3
0.4538
0.4S46
0.1330
0.1392
0.27«1
0.3299
0.4538
0.4431
0.494"
0.4949
0.1855
0.3094
0.09b9
0.1010
0.0587
0.1371
0.0103
0.0103
0.0155
0.0165
0.0094
0.0196
0.0066
0.0067
0.0^2
0.0443
0.0147
0.0173
0.0075
0.009S
0.0247
o.o m
0.0069
0.05 55
0.0176
0.0495
0.0021
0 . 0 1 \\
0.028V
0.0635
0.2472
0 . 0 (> 4 8
0 . 0 0 3 a
0.0051
0.0031
0.0216
0.0083
0 . 0 2 5 M
0.0505
0.0907
0.0371
0.5142
0.5451
0.1471
0.1553
0.2903
0.3702
C.5142
0.4834
0.55S4
0.5554
0.2057
0.3497
0. 1070
o. i in
0.0643
0.1512
0.0123
0.0123
0.0175
0.01 83
0.0106
0.0216
0.0074
0.0075
0.0463
0.0483
0.0164
0.0191
0.0083
0.0108
0.0267
0.0411
0.0079
0.0175
0.0216
0.0555
0.0041
0.0154
0.0329
0.0936
0.2674
0.1049
0.0014
0.0063
0.0043
0.02i7
0 . (,' 0 9 7
0.0298
0.0566
0.1 008
0.0411
0.5747
0.6056
,1612
,1714
,3184
,4106
,5747
5237
6158
6158
2258
3900
1 170
1212
0708
U53
0144
01 44
CJ95
0201
01 18
0236
0052
OC83
0503
0524
0180
0209
009i
0.01 18
141
0.0452
0.008Q
0.0195
0.0^56
0.0616
0.0061
0.0195
0.0369
0.1037
0.2876
0.1150
0.0050
0.0075
0 . C 0 5 5
0.0257
0.0111
0.0339
0.062*
0.0452
-------
Table 27 continued
THK' CUNCE'JTHATION
(I.M NANO
OF P4RTICUL A TIT.
SAMPLE MJMBfr'R
THE RA'.JGE REPRESENTS AT L^AST
Trit 95% CONFIDENCE" LIMITS
BfTST VALUE
M A X11< U !'
11051
11050
11049
11048
1104 7
1)046
1 1 0 4 b
11044
110^3
1 1C42
11041
1 1C40
1 1 o : y
11038
1)037
1103b
11035
11034
11033
11032
11031
11030
11029
1 1 0 2 P
1 1027
1 Iu2r>
1 1 0 2 b
1102',
11023
11022
11021
1 1020
1 1019
11018
11017
1 1 0 1 b
11015
11014
11 0 1 3
11012
110)1
1 1 C 1 0
11009
1 1 0 0 S
1)007
11006
M 0 0 5
1 1 0 0 4
11 003
11002
1 1001
0.0371
0.0639
0.0639
O.C340
0.1093
0.0039
0.1350
0.0371
0.1041
0.0030
0.0350
0.0030
0.1206
0.0047
0.0299
0.0186
0 . u 0 1 7
0.0227
0.0034
0.003}
0.0 If,',
0 ,oQ^9
0.0124
0.0526
0. 01=16
O.OJbO
0.0031
0.0515
0.0207
0.11Q5
0.0135
0.0691
0 . 0 P 7 6
0 . (m 5 6
0.0485
0.0145
0.0243
0.0237
O.llf.5
0.012-5
0.03^0
0.0186
0 . 0 7 6 ?
0.1711
0.6183
" . '> JO 7
0 . 0 6 0 (5
0.0145
0.0515
0.0411
0.0699
0.0720
0 . 0 3 R 1
0.1214
0.0045
0. 1491
0.0411
0.1162
0.0040
0.0391
0.0034
0.1347
0 , 0 u 6 3
0.0339
< 0.0050
0.0226
0.0023
0.0247
0.0044
0.0103
0 . 01 «5
0.1070
0.01 44
0.05P6
0.0206
0.0391
0.0101
0.0576
0.02-17
0.1 316
0.0175
0.0771
0.0977
0 . 0 9 5 6
< 0.0050
0.0545
0.0185
0 . 02P a
0.0273
0.1306
0.0144
0.0360
0.0206
0.0309
0 . 1 P, 9 2
0.67*8
0 . 1 0 0 &
0 . 0 6 6 «
0.0185
... 0.0576
0.0452
0.0760
0.0801
0.0421
0.1335
0.0051
0.1632
0.0452
0.12R3
0.0050
0.0431
0 . 0 0 3 R
0. 1 4fi»
0.0070
0.0380
0.0267
0.0029
0.0267
0 . Ci 0 5 4
0.0123
0.0205
0.1170
0.0164
0.0047
0.0226
0.0431
0.0125
0.0636
0.0287
0.1437
0.0215
0.0352
0 . 1C 7 P
0.3057
0.0606
0.0225
0 . 0 3 2 &
0.03)0
0.1427
0 .0 1 t> 4
0.0400
0.0226
0.0349
0.2074
0 . 7 3 ° 3
0.1109
0.077°
0.0225
0 . n f, 3 c,
-------
table 28
The COr-'CKMHATIUK Or" P APT IC'JLft'f E 7)'R A "I IU
(IN f J A N n GH A11S/"I r, LILIT E» )
S A « P L K f» J «
THE KA'V'MC: r-tPSF'Srf.in S AT" T FAST
THE 95% rur-!finfr.'cr LJMITS
3EST VALUE
M A X I M U.«
11 102
11101
11 100
11099
11'iOtf
11097
11096
11095
11094
11093
1109?
11091
11G90
110&9
11086
1 1087
11066
110B5
1 1044
110b3
1 i 0 1 ?
1 1 0 ft 1
110" 0
11079
1 1 0 7 S
11077
11076
1 1 0 -, '>
11074
11073
1 1072
11071
1 J 0 7 0
11HA9
i n- o P
110*7
in i-e
J l<--,5
1 i ') - 4
1 1 f. 6 3
not. 'i
11061
llOoO
11059
1 1 o L y
11057
I 1 0 t. (:
11 U 5 5
1 1 U s 4
i 1 'J 5 3
1105?
0.1144
0.1227
0.0402
0.0402
0.075?
0.0856
0.1958
0 . 1 5 5 a
0. 1 391
0.1742
0.0577
0. 1093
0.0269
0.0289
0.0114
0.0402
0.0036
0.0066
0.0044
0.0052
0,0073
0 . 0 0 7 1
0.0029
n . 0 1 2 2
O.OJ14
0 . 0 U 5 7
0 . 0 0 <) 0
0.0024
1 9 o
0.0r>91
0 . 0 2 4 »
0 . 0 0 1 4
J . !J 0 1 8
0.0020
0 . 0 0 1 7
0.0034
0.01 :) 4
0.0355
0.0737
0.0124
0.1265
0. 13*8
0.044?
0 . C 4 -i 2
0.0833
0.0956
0.139°
0 , t 7 1 a
0.1532
0.3923
0.0638
0.1214
0.03?^
0.0329
0.0154
0.0463
O.OC')2
0 . 0 0 P ",
0.0057
0 . 0 n 6 0
< 0 . 0 ! 0 "
0 . 0 0 q h
.0.00^ .
0.0039
0.01 3
0 . 0 0 - )
0.0/37
0.0771
0 . 02HH
0.0024
0.0036
0.0034
O.OOH7
0. 004^.
0 . 0 U 4
.0.0! 75
0 . 0 2 7 -i
0.01 -» 4
' "0.1386
0. 1SA9
0 . 0 4 R 3
0 . 0 4 P 3
0.0014
0 . 1 0 S 7
0.1640
. f'.,t?<7 n f, 9
0 . 0 0 6 P
0 . 0 0 « 7
0.004''
0 . 0 0 4 °
0 . 1, 1 5 0
0.0154
0-OOaa
0.0315
0.0056
0.0133
0,0105
0.0154
0.0055
').0?04
0 .011?
n . o :> 5 ^
(i. 0051
O.ni"^
o . M, M.;
0.0? 7 7
0.0852
0.
0 . 0 ] o 4
-------
Table 28 continued
( T %'
f j 0 0 K A '4 S / ' I L, 1 1 L 1 1 -. r. )
'C »EP^L5t~.'>4o
045
044
J43
1042
10-11
1
1
1
Ji
040
039
03*
1037
1
1
1
1
1
1
1
1
1
1
1
03b
035
034
033
032
031
0 3 0
029
>)2i*
027
026
1025
1
1
1
1
1
1
1
1
1
1
1
1
1
1
I
1
1
1
1
1
1
i
1
024
023
02?
021
020
019
01 R
017
01 b
015
014
013
01?
01 1
01 0
009
00 H
007
006
0 0 5
004
0 0 3
00?
0
0
0
0
0
o
0
0
0
0
0
0
0
0
0
0
0
.^
0
0
0
0
0
0
0
0
0
0
0
0
(
0
u
0
f,
,0114
.0005
.031"
. 0 1 d 9
.0011
.0011
.0004
.0073
.0018
. 0 0 b 7
.0062
.0052
.OU52
.0042
.0062
.0145
.0073
.0033
.01 14
.OC93
.0052
.0155
. 0 ? 1 7
.01 9iS
.0031
.0052
.0062
.0031
.0-15?
.0021
.0002
.1341
.OISK-.
. 0 1 o 5
.005?
<
<
<
<
<
<
<
<
<
<
<
<
<
<
<
1001 0.i>/-oQ
14-1
Mt^afttffr
0
0
0
n
0
0
0
0
(i
0
0
n
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
c
0
r-
o
0
0
0
0
J
0
0
0
0
0
o
0
0
-,
0
n
0
i";
0
0
.
m
*
*
»
*
*
,
*
-*
*
»
a
*
*
,
.
01 34
0500
0300
021*
037'*
Onvj
1000
OQ on
0329
0 0 3 t
03 CO
0031
0?05
0 U 2 0
01 34
00 3n
0 1 o c
0 Of 2
0032
0072
0072
'. 0 6 I
0 5 0 v
0 0 K 2
01 ^5
0 1 0 0
0113
0045
0)34
"113
0 S 0 0
OOQ">
0195
027%
0237
0050
0100
0051
0072
00 a 2
0 o 0 '"i
o 0 S 1
0072
0 0 4 1
0 0 ^ 2
1 0 0 0
1543
0737
02.-A
007;
0320
», ^^^
0
0
0
0
0
0
0
0
0
0
0
n
o
0
n
0
0
0
0
n
0
c
0
0
0
0
0
0
0
o
o
0
0
0
0
0
-*-»«.,
.0154
.0
*
.C
,<
337
431
3*9
051
. 0 0 5 1
,f-
* '
407
r->4
.0054
.0
. 0
.0
. o
10?
102
nq2
oc<2
.00*2
.0
.0
.0
102
2?5
153
,nr,57
.0
' *
.('
154
133
133
23*
.033*
.0
. 0
. 0
.0
. 0
'277
072
"9?
10?
072
. 0 0 ^ ?
s r.
.<
. i
. 0
^ i ,
.<'
^
(,f. i
102
744
?77
/ U-
no T
300
*w««*v>*«-.-iSS^* J
tt.rt.r1Tt»t'- -1^-^-j»..^-jt
-------
Table 29
COvCFUTHAlJf^ PF KAPTICdLATE Zl'.'C
(P. *;A/.
1>r' FA%RK PFPF-FSKM.S AT l.CAST
IHfr.
''P.I*U> . 9 3
4.77
9.2?
O.i*
1 . fc";
0 . I 0
l.f-J
o.oo
O.OQ
o.oo
0.00
0 . 0 ')
0 . C 0
f 1 . 0 A
o.oo
n.oo
0 . 0 U
0 . 0 0
o.oo
0 . 0 0
o.oo
0 . 0 0
o.oo
O.Ou
0 . U 0
0 , C 0
0 . 0 ')
0 . 0 0
f.1 . 0 0
0 . b 0
0.0,'
0 . 0 0
0.00
0 . 0 0
0.00
( . 0 0
0 . 0 n
o.oo
0 . 0 0
&.22
*. *2
?.=)R
3.39
7. ?T
8.P3
10. 49
10.3?
lb.52
13.4*
7.39
12.5-?
'.77
3.4Q
2.36
4 .00
0. tb
0.33
0.5S
0. 45
0.42
0.73
0.73
O.bO
0.87
0.74
0.60
O.S3
0.53
0.07
O.b'9
o.-n
0.21
0.22
0.56
1.06
C.?2
< 1.0 0
0.71
< 2.oo
2. 6b
0.« 2
0.3*
0.12
0.27
0.14
'.37
0 . ) o
O.bO
0 . 4 S
< 1.'-)
145
« 6S
.
9 P6
^
3.49
4.00
^ . 52
10. 2f
12.73
12.21
17. 5S
lb.«1
h.P3
14.58
3.b9
4.31
2 . 9 H
5.03
0.6»
0. PS
1.17
1 .04
1 . 1Q
1 .2"
1 . 27
1 .OS
1 .6*
1 . 3n
1.12
1.0*
1 . OP
O.bS
1.13
1.44
0. 7b
O.Q2
1.12
1.62
0.94
1 ,94
3.69
1 .74
0 .
-------
Table 29 continued
Thf C'UCF'.'TWATIOn UP PACTICI-'LATE
SAMPLE
M I M .'' 'J V
The. RAVGfC RKPRFSFNTS AT LFA?T
951= CONFIDJ-HCK LIMITS
VALUF
MAXIMUM
HObl
11050
il 0 4 9
11048
11047
1 1046
11045
11 CM
1 1043
11042
11041
11040
1 1039
1 1 0 3 P
11037
11036
11035
11034
1 1 C 3 3
11032
11031
no 30
1 105^
1 1 0 2 a
11027
1 1 u 2 5
11024
11023
110??
1 1 0 <> 1
1 1020
11011
llOlb
11017
1 1016
11015
11014
1H-13
11012
11C11
11010
: i o o 9
11006
1 1 0 0 7
1 ! C 0 6
11005
11004
110C3
11002
U 0 C 1
0.00
0.00
0.00
".00
O.OU
0.00
o.oo
0.00
o.oo
o.oo
0 . 0 0
0.00
0.00
0.00
0 . 0 0
o.oo
0 . 0 >J
0.00
o.oo
0.0"
0.00
0 . 0 r'
0 . 0 0
0.00
0 . 0 n
0 . 0 0
o.oo
0.00
o.oo
0.00
0 . n o
0 . 0 0
0.00
0 . 0 0
0 . o r>
0.00
0.57
2.24
11.35
0. &R
o.oo
0.43
0.73
0.67
0.15
1.12
0.11
2.15
0.79
1.12
0.04
0.25
0.20
1.74
0.30
0.50
< 0.60
0.00
.1.02
0. 30
0.23
< 0.50
0. U
1.41
0. 30
0.81
0. }2
0.40
0.50
< 0 . yQ
< 2.00
1.64
0. 10
1.33
1.12
1.02
< 0.40
1 .22
< 0.90
0.50
0.30
1 .ol
< 0.50
< 0.90
0.37
2. 1 b
4.^7
14 . jO
3.03
1.43
< 0.90
. 0 0
1 .01
1.37
1.31
0.7R
2.15
0.44
3.3P
1 .46
2.15
0.56
0.83
O.fR
2.56
0.92
1.11
0.53
1.61
0.9?
l.'M
0.92
1.23
1.33
1.73
2. 36
2.15
l.RS
2.05
1.13
2.46
0.70
2.77
6.?5
17.14
4.31
1 .54
146
-------
Table 30
COK'Cfc'M RM ION'S
(IN 'NA^OG
FOR DISSOLVFD
SAMPLE
THE, RAN'GK PKPRL'SHMTS THF
r)'/K SIC* ft LKVKL
,*.IM»»U« Bf-JST VALUE
3-3
B-9
e--9
B-l 1
B-b
b-7
H-ll
i*-3
B-7
h-17
P-19
P-21
B-21
B-25
«-l 1
ri-13
ti-21
B-4
B-D
0-8
ri-10
?-l ?
1
1
1
2
2
2
3
3
3
4
4
4
b
b
6
6
0
7
7
7
B
b
0.019
0.019
< 0.007
< 0.00?
< 0.007
< O.On?
< 0.007
< 0.007
< 0.007
< 0.007
< O.O'i?
< 0.007
< 0.007
0.021
< 0.007
< 0.007
< 0.007
< 0.007
< 0.007
0.013
0 .021
0.021
< 0.007
< 0.007
< O.OQ7
0.0?)
0.047
0.023
0.0?3
147
-------
Table 31
CONCM
(If!
THE:
:* i M y u
f: N F S1 ^'
PEST ',
ED CfH-ftl,T
THL
LFVKf,
VAXIMUM
b-3t
B-7B
b-9t?
t"-l 1 A
b - b f
b-7A
fa - 1 1 h
t--3t<
h-7t'
B-J 7A
fc-1 9A
R-21A
B-2H1
B - 2 5 B
F,-7b
r*-11 b
& - 1 3 :»
B-17c
H-4A
B-dA
R - 9 A
f - 1 0 A
f - 1 'i -
D-14A
1
1
1
2
2
2
3
3
3
4
4
4
b
5
b
6
6
6
7
7
7
B
b
8
0.0104
o.o '.50
n . o o b a
o.ooss
0 . 0 ft 5) 0
0 . o o b 2
o.oosu
0.0117
O.OObS
0.02*0
0.0069
0.0077
0.0074
0.0071
0.0063
0.0090
0 . 0 u 9 ">
0.0380
0.0104
0.009')
0.022^
0.0152
0 . 0 i 7 r,
0.0140
0 .0110
0.0053
0 . 0 C 7 2
0.005B
0.0051
0.0037
0.00(S3
0.0123
O.OOSS
0.0300
0.0073
0.00^1
0 . 0 0 7 H
0.0075
0.0066
0.0095
0.0100
0.0400
0.0110
0.0095
0.0240
0 . 0 l H 0
0 . 0 2 H 0
0.0147
O.Ollb
0.00^6
0.007n
0.0061
0.005ft
0.0092
0 . 0 0 h *.
o . u r; 9
0 . 0 0 r. 1
0.0320
0.0077
o . ycfiS
O.OCP2
0.0079
O.OOf}
0.0 100
Ot 0 1 05
0.0420
0.0116
0 . 0 i n n
0.0260
O.dlf*
0 . 0 2 9 0
0.0154
*^p*r *^f »»'*y"«T'
14."
-------
Table 32
SA»PLt
-'K CONC^TPATiU ,S FOK DISSOLVE
(r<; NA.'-HJGG AVS/MILLILI TEH)
M { N-1 ,'' (J X
kANGE V
orvf ,SK;
1
1
1
1
1
1
I
1
1
1
]
1
1
1
1
1
1
1
1
1
1
1
1
1
.-7
.30
.4tt
.33
.4o
.26
. n
.46
.50
.48
.49
.46
.36
.n2
.62
.4f>
.47
.4;
.40
.4o
.t>2
.5"
.4P
.5^
1.55
1.37
1.56
1.4
1.62
1.63
1 .63
1.54
1 .62
l.rO
1.75
1.64
1.75
149
-------
Table 33
BLANK COr;CENThAT10VS FOR DISSOLVED COPF'Eh
THE SANiGE REPRESENTS THE
CNt SIG'^A LEVEL
BEST VALUE
V A X J M ij v
P-9
H-ll
B-S
*-/
P-ll
r-}
A. 7
B-17
a-i'j
n-2.
f-21
B-25
b-n
(3-13
fa-21
fl-4
ci-fc
L-6
b-10
f-12
c -1 4
1
1
1
2
2
2
3
3
3
4
4
4
5
5
6
6
6
7
7
7
3
0.07
0.10
0.14
0.12
0.39
0.17
0.35
< O.Ofl
< 0.08
< 0.03
< C.OB
< O.OR
< O.OB
0.0*
0.12
0.15
0.14
< O.OH
< 0.09
0.4^
0. 19
0.30
< 0.06
< O.Cq
< O.OR
< c.o*
< 0.0"
o,
0.
0.
14
!*
16
47
21
0.43
ISO
fc'.T. .» >. ,j»<^
-------
Table 34
Bl,A\K CONCF'.TH'iTIO.'.S
(IM .N
SAMPLE !
1.13
1.74
1.93
0.70
1.40
1 .00
1.02
3.70
1.25
1.30
0.75
0.59
1.20
O.fcO
0.95
1.70
1.10
0. bri
1.50
1.10
1.53
0.90
1.10
O.b9
1.24
1.88
2.03
0.79
1 .50
1 .06
l.Ofc
3.90
1.35
1.40
O.f- j
0 . h (:
1.76
O.f-5
1 .('6
1.90
1.20
1.20
1.62
0.97
1.17
o.9e
1.3S
l.OP
2.13
o.ae
1.60
151
-------
Table 35
BLANK Oj'.Cr.MSAl IG'VS FOR DISSOLVED MANGA'.'F'SF
| THE RAf'GE w (--PRESENTS THE
[ OivK SIGMA LEVEL
SA'-IPLK MJ"3E:n "I>.l"
-------
Table 36
BLANK CONCENTRATIONS FOP DISSOLVED *PL YHDKf-.
i
II-IF RA*GE PEPRKSRN IS THt
ONK SIGMA LfVEL
I
I SA"P[,E f;UVt>F:» MI'Uv(j».- bKSi i/tL,UF MAXIMUM
I
i. P-3B 1 < 0.03
i n-7f< 1 < 0.03
b-9b 1 / < 0.10
I h-HA 2 0.13 0.14 O.J5
I H-bA 2 < 0.03
[ H-7A 2 < 0.04
I f-llri 3 < 0.03
I f--3b 3 < 0.0?
J B-7H 3 < 0.04
; P-17A 4 < 0.03
I B-19A 4 < 0.04
i B-21A 4 < 0.04
i 6-2Ib 5 < 0.04
j B-25b 5 < 0.0?
i B-7H 5 < 0.03
I b-UB 6 < 0.05
f 0-13B 6 < 0.03
S B-17B t> < 0.01
I B-4A 7 < 0.03
' B-6A 7 < 0.03
t b-ttA 7 < 0.0 3
! H - 1 o A 8 < 0 . 0 5
I a - 1 ; A & < 0 . G 3
^-14AH < 0.0 5
153
- L
-------
Table 37
HLA'IK CO'.Ch.MTHAIlOf.S FOR DISSOLVED MCKFL
(If.
-------
Table 38
BLANK CONCEI.'TRATIONS FOE DISSOLVED LEAD
F MJVbEk
THE RANGE REPRESENTS THE
ONE SIG^A LLVEL
BKST VALUE
B-3
B-9
B-9
B-l 1
B-S
B-7
R-ll
H-3
B-7
P-17
B-19
6-21
B-21
B-25
B-ll
B-13
B-21
b-4
B-6
b-&
B-m
B-12
8-14
1
1
1
2
2
2
3
3
3
4
t
4
5
5
6
6
6
7
7
7
H
6
6
0 . 2 1
0.12
0.07
0.17
0.14
0.23
0 . o y
0.08
0.12
0.11
0.08
0.11
0.19
0.17
0.16
0.12
0.05
0.1 1
0.0^
0.05
0, 15
0.10
o.oy
,23
,14
,09
,19
,16
,25
,10
.10
,14
,13
,10
,13
,21
.19
.13
.14
.07
,13
,10
,07
,17
.12
0.11
o.
0.
0.
o.
0.
0.
0.
0.
0.
0.
0.
0.
o,
0.
0,
0,
0.
0.
0.
0.
0.1Q
0.14
0.13
,25
,16
,11
.21
,lf
,27
.12
,12
i i * '
.15
.12
,15
,23
,21
.20
.16
.09
,15
,12
.09
155
-------
Table 39
SAMPLE
BLAUK CONCF.^TRATIOVS FOR DISSHLVRD SCA'JDIU/*
C I H PI ANOGR A MS/MI LLI L I TEH )
THE RA«JGE PtTPSSSSNTS THE
DNt Sid:'A LEVEL
" I V 1 M LI M
PTST VALUr:
V, A XI w I'v-
W-3B
B-7B
B-9B
B-11A
B-5A
b-7A
B-llh
P-3H
fa-7B
B-17A
B-19A
B-21A
B-21B
H-25b
B-7ti
B-11P
B-l 3n
B-17t*
b-4A
b-6 A
F-i - 8 A
B-10A
R-1?A
P-14A
1
1
1
2
2
2
1
3
3
4
4
4
5
5
5
6
6
D
7
7
7
%
P
s
0.00013
0.00011
0 . 0 0 0 1 tf
0.0001 3
0.00011
O.OOOOo
0.00007
0.00009
0 .00007
0.00004
0.00013
0.00008
0.000 i 8
0.00012
0.00006
0.00010
0.00010
1.00014
0.00014
0.0001 4
0.00009
0.00009
o . o o o o ;
0.00015
0.00014
0.00012
0.00020
0.00014
0.0001 2
0.00007
0.00005
0.00010
0.00003
0 . 0 0 0 0 5
0.00014
0.00009
0.00020
0.00013
O.OQ007
0.00011
0.00011
0.00015
0.00016
0.00015
o.oooi o
0.00010
0.00009
0.00016
0.00015
0.00013
0.00022
0.00015
0,00013
0.00008
O.OOOOO
0.00011
0.00009
0.00006
0.00015
0.00010
0.00022
0.00014
0.00008
0.00012
0.00012
0.00016
0.00019
0 . 0 0 C 1 6
0.00011
0 . 0 C 0 11
0.0001 I
0.00017
156
-------
Table 40
BLANK COrjCCNi'RAriQ'JS FOR DlSSOl.VfcJ!
THE RAMGt:
THf-,
SAMPli-
BEST VALUE
6-3B
B-7B
B-9B
b-HA
3-bA
P-7A
B-llh
B-3B
B-7B
F>-1 7 A
B-19A
F-21A
B-21B
fa-2!S&
B-7B
6-1 IB
B-l 3b
H-17b
B-4A
B-6A
d-8A
B-10A
B-12A
B-14A
1
1
1
2
2
2
3
3
3
4
4
4
5
b
5
6
fe
6
7
7
7
8
e
g
< 0.20
< 0.20
< 0.30
< 0. *0
< 0.40
< 0.30
< 0.30
< 0.30
< 0.30
< 0.40
< 0.40
< 0.40
< 0.50
< 0.30
«. 0.40
< 0.3!'
< 0.30
< 0.40
< 0.70
< 0.2"
< 0.40
< 0.60
< 0.40
-------
Table 41
fcLAf.K CnNfK'. -irtATIUNS
(in ''A'
F0« D 15
E
F'-IA
ri-lCA
3-1 2A
^ - ! } A
1
1
1
2
2
2
3
3
3
4
4
4
5
5
6
6
6
7
7
7
a
8
y
0 . 0 C 0 3 4
0.00039
0 . 0 0 <"' 3 tj
0.00024
o.ooo^o
o . ocobO
0.00410
o . o o o .; o
0 . o o 0 4 0
0.00060
0.000 JO
0.00160
0 .00030
o . o o o i o
0 . 0 0 :) 4 ?
0 . 0 > 0 17
0 . U 0 0 b ,
0.00036
0 . 0 0 0 S 0
0 . 0 0 0 J 0
O.OOMO
C. 0 0 'i S n
0 . 010 S -j
0 . C o o v-,
0.00 ^70
0.000 SO
0.00 ) S 0
0.000=0
0.00040
0.00170
0, 0 .n o ^ n
0.0006 r.
000* ()
00050
01 o h n
0.0') 1oO
0 . 0 0 0 5 0
r> t o , ti«;«.
0 . 0f. n h ?
0.00043
0 . 0 n o 6 0
(i. 0 o o 7 n
0.00-170
0.00 (.60
0 . 0 0 (t f ('
O.Ot-1 oo
0.00050
o.ooiso
O.Of-070
0 . 0 0 0 F 0
158
-------
Table 42
Cri'.CrJNTHATKl'.S FOC 0 1 SSO'.V ="D
(IN NANOGP
RANGF
^st.;,,,; is THK
^Lt '.
P-3B
h-7«
ct_9P
fr-JJA
r-bA
p -7.fi
fa - 1 1 r-
t*-3«
F-7-
n-17j -:
0.001 i
0.0020
0 . ' '"> S 3
0.03 '. n
n.0037
0.0020
0.0020
0 . 0 0 ? P
0.0030
0.0040
0.0030
o . o o ? j
0.0030
U .0010
0.0020
0 . 0 o 3 0
0.0020
0.0070
0.0017
0.0020
O.U020
d . V030
0.0020
A.00 jO
M A X J ,'' 1 ! ^
0 . 0 o i P
0.0370
0.0042
0 . 0 0 2 f
0.0054
0.0021
159
-------
table 43
HLA.'.K
c if.
Th£ HAVG? REPRESENTS THE
YAX1MJW
i'
HI
n
'4
H
p
K
o
t't
B
P
t:
h
H
rt
H
r>
P
S
r»
r,
=.
«
**
-3!'
-7r
qp
-1 1A
-'ji
-74
-1 in
-3t;
-7n
-17A
-19A
-21A
-2lft
-2bh
-7r>
-11H
-13n
-1 7H
-4 A
-6 A
o A
-10A
-12A
-14,.
I
1
1
2
2
?
3
3
3
4
4
4
r
5
b
6
6
6
7
7
7
b
P
*
0.
0.
0.
o .
1 .
1 .
».
o.
o.
1 .
1 .
(! .
1.
1 .
0.
2.
1.
1 .
0.
1 .
3.
3.
*-
3.
^6
5^
46
3o
I1?
n>3
75
76
7-J
t>4
07
Si1)
04
36
7c>
00
14
42
Hb
07
HO
30
10
iO
0 ,
0,
0;
y.
i.
i,
o,
0.
0.
1.
1.
o.
1.
1.
0.
?,
1.
1.
0.
1.
4.
3.
2,
62
34
It
82
b2
1 ^
^4
10
43
30
10
70
49
^1
13
00
50
20
3. to
0.6S
0.50
0.40
1.31
1.20
0.83
O.fi4
0.«6
1.70
1.1Q
0.99
1.16
i.50
0.84
2.?0
l.?6
1.56
0.9o
1.1^
4.20
3.70
2. 30
3.«0
160
te**WiiJ ijJ jifeii
-------
Table 44
BLANK rONCf'.rKATIOVS H'CP I'ARTICULATF CAD*
( ir; f.AN'OGRA.*'S/l-»il < O.ooi
b-« 1 0 <0.001
161
i.La.1-- ^f^^SK
-------
Table 45
BLANK
T10NS F'OH P AKT JOHj ATF CPPTUM
( IN NANT)GRAWS/;'ILLJ Lil
THE
SAMPLE
p PEPfrESFUTS THE
)VK SIGMA LEVfciL
'AfjiJR viAXJMU*
BLANK- 13
BLANK-14
bLAt.K-15
FLANK -16
PLANK-17
FLANK-1R
fa L a r. K - 2
0.0 0 b 0
0.0300
0.0040
bLANK-26
E'LAf K-5
B L A fv K - *
fcLK-1
bLK-7
LPt:
LPF
LPt:-i
LPb-2
h P* 1 0
0.0013
0,
0,
0,
0,
0,
0,
0,
0,
0,
0
0
0
0,
0,
0,
0,
0,
0.
0,.
0.0200
. C 0 8 0
,0040
.0030
.0040
.OOSO
.0060
.0070
.0320
.0050
.0020
, 0 0 » 0
.0020
.0080
.0070
.0020
.0030
. 0 0 b 0
,0014
0.0070
0.0340
0.0060
0.0015
162
irifrf «irtl»tiM*tf|-
-------
r
Table 46
HLANK CONCENTRATIONS FOR FAKTICULATE COMLT
(JU hA-jiGpftMS/f ILHL1TTR)
THt RANGE PEPKESENTS TriR
ONE SIGMA LEVF.L
Bt'ST VALUE
MAXIMUM
Ar-2
1.1 I, H (*, K - 1 3
* I., a f J K - 1 4
BLV.-K-lfs
P L A N K - 1 o
bLAr.'K-l 7
B L A pi K - 1 fe
bLAM.K-2
bLAfvK-25
BLANK. 26
BLA\'K-5
bl.ANK-8
'^Lf1-!
B L K - 7
LPK-2
.IP- 10
0.0020
0.0010
0.0042
0.0130
0 . 0 0 1 «
0.0008
0.0003
0.0020
0.0040
.0026
.0010
.0050
.0016
. 0 U b 0
.01 40
. 0 0 '/. fl
.0010
.0050
.0030
.0040
.0060
0010
.OObO
001?
0005
0030
0.0032
0.0022
0.005P
0.0150
0 . 0 0 3 P
0.0016
0.0007
0.0040
< 0.0040
1C3
-------
Table 47
'', I M v 11 y
BLANK CONCENTHft.T10NS FOP PART1CULATK CHROMIUM
(IN NAXOG
E Mjv.se.rt
THE M\GE REPRESENT? THE
ONE SIGMA LEVEL
BEST VALUE
A.v-2
B L A N K - 1 3
BLANK-14
BLANK-IS
BLAVK-11>
BLAK'K-17
BLA.vK-5 8
BLANK-2
6 L A i\ K - 2 5
HLA.\K-2b
BLAf K-8
HLK-1
BLK-7
LFE
LFt
LPfc-1
LPE-2
MP-10
0,
2.
0,
0,
0,
1,
0,
0,
1,
o,
2,
0,
0,
1,
0.
0.
0.
0.
0.
740
170
*oo
bfiO
230
260
400
270
130
440
2bO
360
710
790
064
066
Ot?6
070
220
0.450
0.780
2.290
0.630
0.720
0.240
1 .330
0.420
0.280
1 .190
0.460
2 . 3 <3 0
o.3yo
0.750
1.8 s u
0. J67
0.070
0.092
0.074
0.230
0.470
0.82"
2.410
0.660
0 . 7 6 0
0.250
1 .400
0.440
0.290
1.250
0.490
0.400
0.790
1.970
0.070
0.074
0.098
& . 0 7 8
U.240
0.49T
164
-------
Table 48
BLANK C'J^CrJVrRATIO'.S FOP P4RTICULATE COPPFP
"int~ Hir.'GF! REPRESENTS THE
OLE SIG-'A LEVFL,
SAMPLE MlvJEk WIKIVUV tFST V^LUE MAXI'MIM
B->9 0.17 0.20 0.23
B-*6 0.55 0.63 0.71
B-*22 0.49 0.55 0.61
B-«21 0.34 0.38 0.42
9-«20 0.57 0.61 0.71
b-H9 0.64 0.71 0.76
B-«12 0.57 0.64 0.71
B"«I1 0.30 0.34 0.38
^-10 0.25 0.28 o.31
Ib5
-------
Table 49
BLANK CONCENTRATIONS FOR PA.P.T 1CULATE, IRON
(IN NANOGPAMS/NILLILITFR)
SAMPLE, NUMSbH
MINIMUM
THE: PMJGE REPRESENTS THE
ONE SIG"A LEVfclL
BEST VALUE
A M - 2
iiLANK-13
BLA'JK-14
BlANK-15
bLAAK-1 7
hLSiMK-2
bLA*!K-2b
bLANK-2b
B L A N K - 5
BLANK-8
Bl'K-1
BLK-7
LPt
LPE
LP£-1
LPt-2
4P-10
yp-5+MP-9
0.90
1.40
1,43
0.30
1.90
3.30
0.40
0.30
0.70
3.00
1.10
1.55
0.80
3.00
1 .65
0.50
1
3
90
50
0.50
3.00
0.50
2.00
2.00
0.60
0.70
0.60
0.75
2.00
2.00
1.30
1.70
1.87
0.70
2.00
3."70
0.60
0.70
O.RC
166
-------
Table 50
BLANK COf'Cfff.THATinNS FOR PARTICIPATE'
(IN NAN
THf RANGt RKPRESFNTS THE
ONE SIGWA LEVEL
NUM6LP MIMVUM HcST V^LUt
H-s9 < 0.010
B-ff6 0.052 0.060 0.068
B-»22 < 0.010
H-S21 < 0.010
B-»20 < 0.010
p-*19 0.030 0.040 O.OSO
B-H12 < 0.010
P-*l1 < 0.010
B-»10 < 0.010
167
-------
Table 51
bLANK CCVJCEMKATIONS FOK PARTICIPATE vrjLYhDEMJ»'
(IN MAMOGRAMS/MILLILIPFR)
THE KANGF: REPRESENTS THE
ONE SIGl'.A LEVKL
SAMPLE NUMBER
MI ,\' 1 M U '^
BEST VALUE
BLANK-13
BLANK- 14
BLANK-lb
PLANK-16
BLANK- 17
BLANK- I*
BLA'«K-2
BLANK-25
BLANK -2 6
BLANK-5
HLANK-8
PLK-1
BLK-7
LPE
LPE-1
LPK-2
MP-10
<0
<0
<0
<0
<0
<0
<0
<0
<0
<0
<0
<0
<0
<0
<0
<0
<0
<0
<0
,006C
,0090
.0500
,0200
,OObO
,0800
,0040
,0200
.1000
.0200
,0060
.0200
.0070
. 0 0 * 0
,0002
.0070
,0200
.0100
,0040
<0.0300
168
-------
Table 52
BLANK CONCKMTKATIONS FOR PARTICIPATE NICKEL
(IN NAKOGKAMS/MILLILITER)
THE KAMGF, REPRESENTS THfc.
ONF SIG-4A LKVKL
SAMPLE NUMBER MINIMI)* B£ST VALUF!
B-(f9 < 0.02
B-«6 < 0.02
F>-*22 < 0.02
B-»21 0.06 0.07 O.Ofl
B-!>20 < 0.02
H-ffl9 0.08 0.09 0.10
R-K12 < 0.02
8-»ll < 0.0?
B-»10 < 0.02
169
-------
Table 53
bLA'.'K CONCENTRATION'S FOh PARTIC'JLATE LEAD
(IN 'J
THE (-A/JGE REPRESENTS THE
ONE SIGMfi LEVEL
SAMPLE NUMBER .'-'IMMUM BEST VALUE
B-«9 0.01 0.02 0.03
f»-c6 0.03 0.04 ' 0.05
8-»2? < 0.01
B-»21 < 0.01
H-ff20 < 0.0)
ri-#l9 < 0.01
B-*12 < O.Ol
rf-lfll 0.03 O.G4 O.Ob
B-*10 0.02 0.&3 0.0-J
170
U
-------
Table 54
BLANK CON'CK'UTKATIGNS FOR PART ICULATE SCAMDIUM
( I fJ N A iM OCR A MS /;» I LL I L IT ?. R )
THE F4MGE REPRESENTS THE
ONE SIGMA LEV,:L
SAMPLE fHIMhl H
MI til MIJ M
i3fi.ST VAMJF
MAXIMA
AV-2
BLAt;K-U
BLAhK-14
ELANK-15
BLAKK-16
BLANK- 1 7
bt,AM<-2
BLAI.K-26
BLANK-5
BLANK -6
BLK-1
BLK-7
IFF;
LPb,
LPE-l
LPE.-2
MP-10
0.00011
0,0003?
0.00049
0.00030
0 . 0 0 u b 9
0.00007
0.00003
0.00020
0.00015
< 0 . 0 0 J H 0
0.00013
0 . C- 0 0 3 4
<0.00009
< 0 . 0 0 0 2 0
0 . 0 0 0 S 3
<0.60005
0.00040
0.00076
0.00009
<0. 00040
O.OU004
<0.00020
<0.00020
<0.00005
<0.00007
00?01
00021
0 0020
<0
0
<0
0.000 IS
0,00036
0.00057
0 . 0 0 0 s o
0.00083
o.oooii
0.00005
0.00020
0.00022
0 . 0 0 0 2 5
171
-------
Table 55
BLANK CnNCE'JTKATlO'.'S FOR PflRTICULATE
ll'i
THF RAUGE HKPHKSE^TS
OVE STGMA LKVF.I
'< I M * U
A " - 2
bl,A,'.K-13
bLAM-14
B L ft ». K - 1 b
BLASK-16
^L^^K-19
r I, A N r - ?
P L A : K - 2 S
Hl-AS'K-26
!3LAN*,-«
B u K - 1
LPL
MP-10
0.30
0.20
0.20
0.20
0.30
0.20
0. 30
0.20
0.30
0.30
0.70
u. JO
C. 30
0.09
0.10
0.50
0.04
0.20
C.90
172
-------
Table 56
CCKCKf-TI'ATlQTJS FUR P« P T ICUL.ATK
(IN tiAKOGPA*5/"-'ILLJLlTr;«)
SA",PLL N'JN't'KW
I'J
Tht KA^Gt-: KEPPF5LNTS THE
0!JE SIG'A LEVKL
hJ.ANK-13
b[,Kf.K-l 4
PLANK-16
K-lb
B L A N K - 1 6
H L A N K - 7 6
f t. ft N K - o
HLK-1
M.K-7
LPE
LP£
LPF-1
l.PK-2
0.001 no
0.00020
< 0 . 0 0 7 0 0
-------
Table 57
£LAl;K Cl'^CEVrKATIONS KO^ P AF- T ICUI, ATE
(Ifv N
TH!- PAN'Gr REPRESENTS THE
ONE SI1.MA LF Vi b
WU"3KP MI'MlMUV BEST VALUE
AM-2 < 0 . 0 0 0 4 0
fl.ANK-13 <0. 00007
PL-itK-14 < 0 . 0 0 S 0 0
HLA.M<.-lb <0. 00200
bli.\«-16 <0. 00030
HLA',K-17
-------
Table 58
BLAMK CONCENTRATIONS FOh PAKTICULAT£ ZINC
(IN NJ!
THE: RANGE REPRESENTS THF
CK'E SIGMA LEVEL
sAypLr. ,\U*B(-:P Mi.«r2 0.010 0.013 0.016
t..p_10 < 0.700
"''ft1-- ,, . , __
-------
Table 59
CKUSTAL
FACTORS FOR PART ICUl Aiv CAOVIUM
KF.LATIVF. TO SCANDIU^ (WEDK:POHL)
SAVPLL MJVBErt
M I W 1 v |
THF- RANGE REPKF.^t'f.'TS AT LFAST
THF 90% CO-'^IPCNCL LIMITS
11102
1 1101
11 100
11099
11098
11097
Ii096
11095
11094
1 1093
11092
11091
11090
11069
1 108«
1 10*7
110»6
1 1095
11064
Iluh3
1 10M2
1 lObi
11080
11079
11^7-
11077
11076
111)75
11074
11073
11072
11071
11070
11069
1 106P
11067
1 lOob
11065
1 1064
11063
11062
11061
11060
!10b9
1 1058
11057
11056
1 1^55
14 / , r A
1054
1 Id53
11052
,»».. _, _._
"^^^^^^^s^mti^^fffimKS
3.496
15.113
1.676
P. 644
12. 120
ID. 740
2.992
3.937
10.124
18.4^6
6. 593
3.373
O.d98
4.330
3.083
3 . « 1 J
0.000
<
<
5.063
9.650
<
76.070
24.H39
16.277
6. llh
o.?4&
<
49.237
27.275
35.70*
2 4 . 9 7 b
0.401
0.216
0.1"5
5.599
33.522
<
<
4.715
<
C . 0 4 3
<
<
n.OOO
<
<
<
<
<
<
176
^ftja^&ajaaaidia^
5.537
20.410
3.630
12.923
16. 150
24.282
5.294
6.534
14.603
24.956
11.020
5.445
2.S36
8.391
9.723
7.090
8.007
15.707
31.414
137. SOI
5 3 . 3 « 3
37.S13
17. Jlh
1 3 . C 1 ?
105,729
49.321
74.650
50. 307
26.956
11.937
10.471
1 3 . d 1 0
72.601
10.1*3
13.069
20.942
Baaaa^Z^
7.RR9
26.P37
6.040
IP. 097
25.993
33.61?
H.159
9.P24
20.153
32.996
16.35?
7.913
S.1M
13.296
17.731
10.991
26.446
2b.OR6
SH.065
212.430
P7.qt)5
64.612
29.659
29. ssi
174.101
76.234
i?4.«e6
3 0 . 3 S b
50. 107
25.621
2 2 . -1 2 3
2 3 . S 5 0
120.003
16.524
19.137
b^.155
*~ . j
-------
Table 59 continued
CRUSTAL ENRICHMENT FACTORS FOP PAKIICHLATE CADMIUM
SELATIVF: 'iu SCANDUJV (
SA;'PLfc:
f>' I N I M U >»
THK HA«JGE RSf.PPFSENTS AT LEAST
1HH 90% CONFICF>CE LIMITS
BEST V^LUE
MAXIMUM
1 1 0 b 1
11050
11049
1104P
11047
11346
11045
11044
1 1043
11042
11041
11040
11039
1103*
11037
11036
11035
11034
11033
11032
11031
11030
1102 7
11026
11025
1 1024
11023
1102?
11021
11020
1 1019
11016
11017
11016
1015
1014
1013
1012
1011
11010
11009
1 1 0 0 fe
11007
11006
11005
11004
11 00 3
1100?
1 1 0 0 1
ka^jK^^^^^^i^^^^ 1Maiarih1ftIT
<
<
<
262.272 349.230
12.838 20.019
22.514 71.645
13.043 19.208
<
b.017 7.623
<
<
<
<
<
<
632.364 Sb?.650
<
<
<
<
<
<
<
<
<
<
<
<
33.387 54.090
0.000 6.198
6.56d 15.593
<
0.000 1.1 d4
<
<
<
<
<
0.031 1.773
<
0.119 6 . 4 « 2
<
C
<
O.H2 0.154
<
3.057 6.5bf>
<
5. 526 9.P61
177
451.432
28.810
132.079
26.686
10.771
1135. 26C
76.931
20.106
2fo.657
3.903
3.78P
14.156
0 . (» 4 2
U> . 7 9 4
15.010
"N
-------
Table 60
CfMlSTAL t:
-------
Table 60 continued
CRUSTAL KN-RICHMEMT FACTORS FOR PARTIC'ILATE CERIUM
RELATIVE TO SCANDIUM (WEDEPQHL)
THE R H
1 .44
1 SO
1.51
1.77
1 H W
1 .63
1.50
1.50
1 .61
1.55
1.79
1.57
1 .86
1.47
1.50
1.46
1.75
1.53
1 .5 '">
1.51
1.57
1,56
'..73
1.49
1.52
1.47
1.53
1 .52
1 .63
1.5-?
1.51
1.55
1.59
1.55
1.72
1.52
1.54
1 .49
1.44
] .53
1 SO
1.56
1 .76
1.4(3
-------
Table 61
CHUSTAL ENRICHMENT FACTORS FOR P APTICUr, ATE COBALT
RELATIVE TO SCAMOliJM (vEOEPOHL)
11102
11101
11100
1 1099
1109fa
11097
11096
J i095
11094
11093
11092
11091
1 1090
11089
110R8
1 10b7
1 1086
11U85
110*14
110*3
11082
1 1 0 rf 1
1 IQhO
11079
1107*
11077
1 1076
11075
1 1 C 7 4
11073
11072
1)071
11070
11069
11 0 6 *
110&7
1 1 Obb
11065
11064
J 1063
11 Ub2
1 1 < 6 1
1 lOoU
1) 0 b 9
1 1 0 5 b
11057
1 1056
11055
11054
1 lf-53
11052
2.04
1.96
3.89
3.97
3.5?
3.51
2.29
2.36
4.03
4.10
2.34
2.56
2.45
2.49
2.16
2.15
2.93
1.72
2.39
2.30
3.17
2.58
3.12
3.45
1.23
1.17
1.92
2.30
2.90
l.lb
1.44
1.45
2.64
1.83
1 .47
1.3°
1 .72
1.13
0.31
0.52
0.99
0.97
3.53
4.19
2.81
1 .33
2.71
1.5S
0.93
0.96
0.7o
RA\'G»: REPRESENTS AT LEAST
THE 90% CONFIDENCE LIMITS
NUMBER ^IMMij"! dtfST VALUE
2-41
2.83
>
4 1 4 5 . P 1
4.PO 5.pj
4.0 5.63
4-^ 5.32
2.P3 3. Si
2-92 3.62
4.83 5.Q3
4-" 6.05
2-8" 3.55
3-°9 3.71
3-°0 3.66
3-°4 3.70
2-61 3.15
2.^1 3.18
3.64 4.S1
2- 17 2.72
2.99 3.49
2.7* 3.25
3 . 3 6 4 . 7 t
3>°8 3.*67
3.PQ 4^3
4-2» 5. IP
^^ 1.H2
!.^ 1.81
2.^5 3.10
2.77 3.33
3«&2 4.50
!-44 1.78
I-"' 2.36
J-7« 2.16
3-3S 4.21
2-3l? 2.60
1.84 2.2*
1 > 6 7 2.01
3-42 5.52
1.6S ?>32
0.78 K34
°.69 0.90
1.13 1>44
LIS 1.42
4.84 6.42
5-29 6.61
3.77 4.92
LS* 1.68
3-^ 4.71
1.9B 2.2Q
1-17 ,.46
3-17 1.4?
180 1«°l 1.33
-------
Table 61 continued
TRUSTAL
rCH.MfJT FACTORS FOR PARTICULATE COBALT
RELATIVE TO SCANDIUM (WEDEPOHD
SAMPLE
THE RANiGE REPRESENTS AT LEAST
90% CONFIDENCE LIMITS
BEST VALUE
11051
11050
11049
1 1048
11047
11046
11045
1 1044
11043
11042
1 I C 4 1
11040
11039
1103t>
11037
11036
11035
1103 4
11033
1103?
11031
11 u 3 0
11029
11026
11027
1102b
11025
11024
11023
11022
11021
11020
11019
11018
11017
11016
11015
11014
11013
11012
11011
11010
11009
11 'JO 8
1 1007
1 1 f > 0 o
1 1 C 0 5
11004
n o f > 3
11002
11001
1.15
0.96
1.05
1.37
0.97
3.91
1.04
1.4o
1.71
5.65
1.05
7.65
1.04
4.61
1.09
S.17
1.17
6.90
1.5?
4.3-1
-i. 6 0
1.33
0.32
2.90
1.41
1.59
0.97
1.89
1.43
1.40
1.02
1.71
1.14
1 .37
1 .46
4.25
1.05
2.35
1.51
1.53
1.54
1.40
1.30
1.25
0.15
1 . 0 3
1.16
1.21
1.94
1.39
1.20
1.30
1 .66
1.19
5.12
1.27
1.79
2.05
7.23
1.3C
9.33
1.27
5.91
1.37
13.00
1.53
o.oS
1.17
6.67
5.^53
2.49
1 .13
3.69
1 .79
2.03
1.24
2.59
1.78
2.23
1.24
2.17
1 .40
1 .66
1.79
6.11
1.34
3.37
1.99
2.0«
1.18
2.15
1.H6
1 .56
1.21
1.32
1 .40
1 .49
2.7R
1.66
1.4H
1.60
2.00
1.45
b.60
1.54
2. 1»
.?.47
9.23
1.60
11.34
1.54
i.*70
19,05
1.94
9.47
2.28
6.77
7.33
3.26
1.39
4.64
2.23
2.54
1.57
3.45
2.21
3.28
1,49
2.73
1.72
2.02
2.19
9.34
1 .69
4.64
2.36
2.78
1.4-1
2.90
2.41
l.«2
1.92
1.53
1.63
1.71
1.83
.1 .T.°L_._.. ,,..^.!*12.
3.78
sf,
-------
Table 62
CRUSTAL E,\'RICHMEf,T FACTORS OF PANICULATE CHROMIUM
AS CO*PAKFD TO SCANDIUM (WEOEPOHL)
NUM8FR
p. i
THE HA'JGE: REPRESENTS AT LEA5T
THE 90% CO.VFIDFN'CE LIMITS
BEST VALUE
MAXIMUM
11102
11101
11100
11098
11097
11096
11095
11094
11093
11092
11091
11090
11088
110fe7
11 o a 6
11085
11054
11083
11062
110*1
110^0
11079
11078
11077
11076
11075
11074
11073
11072
11 >J 7 1
11070
11069
1 1 0 b is
11067
1 1065
11064
1 1063
11062
11061
HOfcO
11059
1105s
1 ) 0 5 7
11056
1 1055
11054
11053
11052
1.11
',99
96
.96
1.15
1 .09
,22
,35
1
1
1 .16
1.18
1.29
1.01
0.58
0.52
0.37
0.78
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0. 00
0.00
o.oo
0.00
0.00
0.00
0.25
0.00
o.oo
o.oo
0.00
o.oo
0.00
o.co
0.00
0,00
0.00
1
1
1
1
1
1
1
1
1
1
2
1
1
1
1
1
1
1 ,
1,
1 ,
2.
2,
1.
2.
1.
0.
0.
,43
,44
,64
,61
,70
65
77
53
61
26
50
33
26
55
46
65
61
91
62
46
36
82
75
33
75
75
11
00
63
52
00
09
15
25
00
3
0
1
1
0
2
0
1
0
0. S?
0.71
0.
1.
0.
0.
0.
1.
0.
0.
1.
0.
0.
1.
SO
01
00
00
00
ii 0
57
1 ;
9C
60
P5
43
1
1
2
2
2
2
2
2
2
2
3
1
1
1
2
2
4
4
4
3,
7,
4,
14,
15.
4.
3.
7.
10.
15.
8.
6.
4.
11.
7.
4.
3.
15.
5.
3.
2.
1.
0.
14.
12.
.82
.90
.15
.09
.23
.20
.34
.60
.01
.05
.17
.96
.89
.31
.37
.02
.56
.64
.06
,47
.35
,13
7*
38
59
11
31
74
65
64
12
48
33
69
17
24
09
90
7ft
OS
81
93
19
54
23.65
5.48
2. si
?.12
4.12
182
k=«^
-------
Table 62 continued
CRL'STAL ENRICHMENT FACTORS OF PAPTICULATE CHROMIUM
AS COMPAKEQ TO SCANDIUM (^EDEPOHL)
SAMPLE
I N 1 M U "
THE PA.MGE REPRESENTS AT LEAST
THF 90% CONFIDENCE. LIMITS
BEST VALUE
MAXIMUM
11051
11050
11049
11048
11047
1104b
11045
11044
1)043
11042
11041
11040
11039
11038
11037
11036
11035
11034
11033
11032
11031
11030
11029
11028
11027
11026
11025
11024
11023
11022
11021
11020
11019
11016
11017
11016
11015
13014
11013
11012
11011
11010
11009
11 0 (/ 8
11«07
1 1006
11005
11004
11003
11002
11001
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
O.H4
0.00
0.00
0.00
0.00
0.00
o.oo
0.00
0.00
0.00
0.09
o.oo
0.00
0.00
0.00
0.00
0.00
0.00
0.55
o.oo
0.00
o.oc
0.00
0 . C C
0.00
o.oo
0.00
0.00
o.oo
0.00
0.00
0.00
",oo
0.32
0.70
o.oo
0 . 0 0
o.oo
0.00
0.58
0.1S
0.52
0.00
0.26
0.00
0.00
0.00
0.46
0.00
0.00
0.00
2.16
0.00
0.00
0.00
0.00
0.00
1.21
7.35
2.22
1 .49
3. US
0.39
0.00
22
77
16
29
58
3.06
3.11
1.71
0.89
93
18
1
4
0.77
1.33
1 .46
1.90
1 .05
2.56
0.82
2.56
0.00
2.67
1.36
1.08
1.02
1. tb
0.64
1.40
0.10
1.42
5.84
0.94
,63
,91
,61
.22
.29
.45
.04
.30
.29
.10
.27
.68
,98
,19
.42
,77
,35
.06
0.21
6.30
12.85
.84
,78
,04
,69
.74
.98
.29
,25
.31
.13
.72
,13
,4R
,56
.17
,25
,15
,69
,64
,01
,76
,H5
1
1
15
1
20
3,
5,
2,
9,
1 ,
35,
5,
42,
11,
12,
2,
10.
3.
3.
4.
3.
12.
2.
2.
3.
3,
7,
4,
7.
1.
6.
6.
4.
3.
1,
1.
2.
3.
5.
3.ISO
183
-------
Table 63
CKUSTAL E,.\PICKMEMT FACTORS FO* PARTICIPATE COPPF:R
RELATIVE TO SCANDIUM (*EDEPOHL)
SAMPLk, NUMBER
MIN I M U M
THfc. RANGE REPHESEP'TS AT LFAST
THE 90% CO:
-------
Table 63 continued
CRUSTAL ENRICHMENT FACTORS FOP PARTIC'^^TK COPPER
RELATIVE 10 SCANDIUM (aeOEPUHL)
THF RA*GL RSPRF£ Et.TS AT LtAST
THF 90% CONTIDRf.'C':
BFJST VftLUK
MAXIM U y
11051
11050
11049
11048
11047
11046
11045
11044
11043
11042
11041
11040
J 1039
11038
11037
11036
11035
11034
11033
11032
11031
11030
1 *. 0 2 9
11029
110^7
11026
11025
11024
11023
11022
11021
11020
11019
11018
11017
11016
11015
11014
11013
1 1012
11011
11010
11009
11008
11007
11006
11005
11004
11(103
11002
11001
0.00
0.00
0.00
0.00
0.00
o.no
0.00
0.00
0.00
0.00
o.oo
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
o.oo
0.00
o.oo
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
u.oc
0.00
0.00
o.oo
e.oo
0.00
0.0"
0.00
C . J ?
C . 6 0
0.00
0 . 0 0
0.0"
0.00
2.26
0.00
0.00
0.00
C.23
0.00
1.17
O.r 0
r>.47
0.00
0.00
o.oo
0.6C
0.00
O.On
0.00
0.00
O.CO
C . 0 0
13.89
0.0ft
4.1 l
0.39
2.15
1.21
0.00
0.5*
0.00
0.00
C.93
0.66
D.OO
0.00
0.33
0.21
0.00
0.74
,' ,55
0.00
0.00
1.41
0.00
C.43
0.00
0.23
1.20
1.4?
0.6S
0,00
0.00
0.26
6.4r
1.57
1.44
1 .24
2.on
17.93
2.fe&
2.9?
2.40
29.7P
j.?7
36.67
2.0?
17.34
3.42
40.62
2.7«
21.35
5.22
64.56
9.74
12.(-7
1 .87
12.10
4.90
b,73
4.47
11 .67
1.53
6.55
2.08
9.21
2.14
2.33
2.33
1 9 . >> 3
3.82
15.40
5.01
5.3
3.01
1C.72
4.55
3.44
3.07
2.15
7.3'.
2.1-3
185
L-,-- _ ,'V
-------
^
Table 64
(VUSiAL I'vr-ICi^r.M FACTORS Of- P A f« T i C'J L ft i K J
Pi-.LAMVr: lu J-CA\DTbM (*bD^POHL)
THE P ?,,:;(: JUJPHFSE'.T.S AT LEAPT
Trtfr ^05, CWIDtiJCr 11'- ITS
SAMPLE N'uWBfr.fi! yiMMIJV r«KST VAL'Jfc MAXIMUM
11102 0.93 t . ! ? 1.31
11101 0.9? 1.14 1 . 3 b
11100 1.07 1.37 1.70
11099 1.09 '...it* l.t>s
11 0 91: 1.04 1.33 1 .^ ^
1 1 0 9 V 1 . 0 ^> 1.30 1,60
11090 1.01 1.27 1 .S b
11095 1.03 1.30 l.M
l'.0*4 1 . (J 7 1.33 1 . b 3
1 1 U 9 J l.Oe 1.35 i . 6 ft
11091 1.08 1.36 1.6t
ll'j'-M 1.01 1.24 1.40
! ; 0 ? 0 iJ . 9 j 1 . 1 > 1.39
1 1'; r 9 n. 9 4 1.16 1 . -5 0
1 10 ft 3 0 . 0 o 1 . 1 S 1.40
1 ! Ci £ 7 0 . 9 b 1.19 1.47
I I 0 ^ f> 0 . f" "7 1.14 1.37
HO«S l.SJ 1,97 2.3f)
] 1 0 f; 4 0 . t- b I.JO 1.31
1 1 o fc 3 0 . H h 1.14 1 . 3 <-.
11 vj6 2 0 . « b 1.19 1.46
1 1 0 f- 1 1.12 1 c 4 1 1.67
110 b 0 0.79 1.20 1.50
11079 0.91 1.3? I.ft3
110 7 b 0.77 1.00 1.23
11077 0.80 1.02 1.24
11076 1.05 1.36 1 . ft 4
11075 1.27 1.61 1.93
11074 f.7 7 1 . 1 5 1.44
11073 3.C v 3.9 S 4.R 3
1107? 0.7 'j 1.01 1.77
11071 0.81 l.<>3 1.74
11070 o.S 2 1.14 1.34
11069 1.?- l.iS 1.99
1 10 6 S ('.91 1.17 1.40
110 ft 7 1.^2 1.26 1.50
1 1 0 6 P 0 . h b 1 . 1 ^ 1 . 5 "*
llObb 1.^6 1.85 2.21
110o4 O.ft9 0.9; 1.1g
ilOt-3 0.75 0.?? l.OQ
i 1 0 c 2 0.71 0 . T 1
1 K. e 1 0.76 0.92
1 1 w hO 0.M 1.34
1 Kb -'< 1.02 1.43 1.77
1 1 f. 5 = C . '' 0 1.34 1 . ft 0
1 1 -j 5 7 1 . 10 1 . ft J 1 . '' -5
1 1 0 5 o 0 . " * 1.20 1 . -l ^
1 1'"' 5 5 0.99 1 . ? 7 1.54
110l)4 U.67 0 . ri 7 l.OS
-------
Table 64 continued
CKuSIAL £', rICH-K'.T FACTLkS OF P A f 1 T CUL
Pt-.LATIV- 10 SCAM)IJ" (*?oV. P
THK HAr.GP RFPfrKSRiTS A'l !.! AST
Thr -?0% CO'.FIDI-'.CK LI'-Tir,
^ I M < 0' fi-b'I VtLJ6: "AXIMH"
11C51 O.B2 1.03 1.2}
il 0 5 0 0.77 0.9-i 1.19
11049 '-). H 2 1.01 1. '15
I 1 0 4 b 0 . M b 1 . 0 Q 1 . 3
11046 0.f 3 1.11 1.3^
;l04b 0.67 1.07 1.2^
110«*4 O.H2 1.04 1.25
11043 0. /b 0.13 1 . 2"
11042 1.07 1.66 ?.<^o
11041 1.11 1.40 1.69
11040 0.93 1.51 1 . P 3
1103* 1.03 1.26 l.M
11038 0.97 1.46 1.33
11037 1.22 1.54 I.f7
11036 0.o 7 1.* 2 2.^1
1 i 0 3 b 1 . 1 fa 1 . 4 « 1.7*
110 34 1.0 si 1.37 2.2')
1 U) )3 1.1- 1.47 1.73
11032 !'.9r I.1)! l.r".
11031 1.3 ^ 1.H1 2 . 1n
11030 1.17 1 . 5 J 1 . « 6
11 (i 2 * 1 . 0 o 1 . ? 1 1 . S *
1 10 2 b 1.03 1.35 J.h5
11027 0.97 1.23 l.SO
1102b O.QQ 1.2M 1.S6
11025 l.oo 1.27 1.53
11024 1.01 1.35 1 . M
11023 l.Oy 1.34 1.5Q
11022 0.9 c 1.24 l.M
Ilu2l 1.^3 1.31 l.fcl
11020 1.09 1.42 1.71
11014 0 . 9 i 1 . IL' » 1.60
1101 * 1.0? 1.27 1.53
11017 1.00 1.27 1.57
1lOlo 0 . 05 1.44 1.P 6
11015 0.99 1.2o 1.53
1 M 1 4 1.02 1 . 3 fi 1 . f-. 7
11<; 13 1.02 1.34 1.67
1101? 0.-5H 1 . 2 <) 1.60
i 1 0 1 1 1.01 1.23 1 .
-------
Table 65
CHUSTAl, F'.J-JC'H'-'E.iT FACJTKS h Ow P AF f TC'I f.ATK u A WGA'JF.S;;
HKi.MIVfc TQ SCANDIUM t wfc^t'PJ-U.)
SA-'-PLL
< 1 '< 1 * U ''
THF *A\<"K RtPPFSFNTS 4T LEAST
THf 90% COf.FIDfrACE M"TTS
rjfST v;r,uc: MAXI^U"
11102
U 101
1 lluo
11099
1109F
110^7
1109&
1 1095
110^4
11093
11092
11091
11090
11 0 P 9
l 1 0 fc f-
11087
110*6
1 10 H b
5108 4
1 1 0 H 3
1 1 0 fc> 2
1 1C' b 1
1 1 0 H 0
11079
11078
11077
11076
11075
1 1074
11073
11072
11071
11070
11069
11066
1 I0b7
11065
1 1 0 6 5
11064
1 10b3
11062
11061
1 1 0 b 0
11059
1 1 0 b f
1 1057
1 1 0 b b
11055
11054
11053
i 1 ns?
2.9
3 . 0
11. 'r
12.1
7.b
7.4
5.2
5.5
8.0
10.3
4.*
4.0
4.5
1.7
6.0
5.6
22.1
^ .b
lo.7
1 7.2
37.2
19.4
26.4
27. B
5.2
6.1
29.1
26.0
17.0
1 . 1
7.0
6.9
9.3
6.4
10.8
fi.l
12.0
1 11 . ^
6.6
3.9
1.4
6.5
33.7
53.3
28.0
6.6
24.2
5 . 4
2.7
2. 1
4.n
3.9
4.0
15.7
16.2
in.4
9.7
<>.q
7.3
V.?
12.8
6.2
b.O
6.0
e. t
30. 3
3.-S
22.5
?2.9
bl. 3
25. M
36.1
37.7
7.7
H.3
39.5
34.4
23.2
1,7
9.
-------
Table 55 continued
OlU-1.-'l : HCH-'Kf.T F -CUPS
i FHAT1VK '!
IC'If. ATK
AT
fl
:,t";>L\.
'l 1
' 1 1
3 J
,' ' 1
. . t
l '
1 I
11
' 1 1
3 1
; 1 1
I . 1
I5i
, 1)
' i'
1
>
i
11
11
!i!
- -I
; K
<. 1
i'i1-
,fi i
I11
I11
! 5 1
hi
1 n
n
I n
i n
! u
"
i n
i l>
i 11
1 u
1 n
I H
U
11
11
51
1 11
! n
M t c i *!*]"
ol ; ll
0:C ' ?. 7,
. -p
cr " -:'
c,< . ..,
-I- 3};,
Jo ; *:;'
..44 . jilr-,
.43 j p;.'.;
;; . V|-./;
; n. <
r1 ; t'-
^" ' n . ,
33^ : p,..
V 3 7 , j > . >
c >< ; 4-1,5
(i 3 S ' ( ': . )
< ' i -i i b , ,^
'.i J :. ' j '1 . ^
o j :> ! . . :^
o s i i ;- ,b
03". ' V.1*
029 : ' 1J4
-2CL .- i : i . -i
'.'2'' P--L,O9
o?i, ; i iTs"-
Oli"; ' j ?'.«
J24 ; j ' .3
023 ' i :-.o
0?2 !;.7
o;?i | v.^
O C i i . i-
U 1 «* y. . V
o i b ; j . !
017 ' M . 4
03^ 2 * . n
(' i l> '1 . 5
014 , '). r
C13 : ' 5.1 .
012 ; 4 . '' '
Oil : j? . '> ,'
010 , , ; J6 . ? ,'
Co^ i : ' .' ,'3. -ti
(IDS i ; |}. i,'
v- 0 7 .' , , ' i 3 . 1 !
0!>6' ' M ;t.?;
ocs |! ! ! , ;i ,M
004 ! | j ; i ? . »
003 !n ; , 3. ^
002 ;| , , | h.f,
:-r
-------
Table 66
Cfl'SI'AL ENf-IOVtM FACTORS t O PA&7 ICUL.ATF "OLY
k^-LMIVK TO SCi.'.DIJ1- r*F-.r>KPOHL)
Hi PLf M^'bfcK ,* J '.' 1 y U " wfeST VAL'Jir.
1110 2
] 1 1 0 1
11100
1 1 U 9 9
11C9?
11091
11UV6
llOVb
11094
11093
1 1 C ^ 2
1 H' 9 1
1109Q
1 1 0 b 9
1 5 ? c k
11 0 b 7
11 ft U A
1 v * c
11 0 -5 b
n u -M
1 H '-, 5
11 1 ^- >
i 1 V ^ ^
1 1 C r 1
1 1 (.- -3 ;
11079
1 IC7-
H(i77
1 1 ( 7'f.
1 1 (' " 5
11 ('l "f J.
I t> ^ 'i
1 1 (. 3
1 1 0 ';' 2
1 1 0 > 1
1 1 0 7 0
1 1 1 ' '3 9
1 1 0 r P
1 1 0,6 7
1 1 C - £
1 1C bS
. i r 6 4
1 1 C fc 3
1 it b',
M '<6!
1106 0
1 1 ') b «
1 l'j e- >
1 ll b 7
1 ir s>,
]1 '! t* -^
1 ( , ^
1 1> b 4
1 1 ( S i
1 1 052
<
<
0.00 1.37
» . o a 1.77
<
<
<
<
0.00 2.04
<
0.00 0 . h 7
3. SO 7.47
<
0.9b 4.79
O.OC 3.33
<
<
<
<
<
f1 . o ) 10.00
<
<
<
<
<
<
<
<
<
<
<.
<
<
<
.^
,r
C
<
' . 00 0.85
1 <
<
<
<
<
<
' <
i <
<
: t
o. 17
b.^2
f*.7b
2.1H
12.19
9.44
1 0 . fc «
31.83
2.85
-------
- 1
Table 66 continued
CHiJSTAL c\f-ICH"l-'U>'CK LI"T7S
M I V U M
11027 <
11026 <
11025 <
11024 3.77 207.41 457.)?
11023 <
11U 2 2 <
11021 <
11070 <
11 o 1 y <
11 u i & <
11017 1.15 3 . 6 b 6.73
1 10) t> <
1 1015 <
11014 <
11013 <
11012 <
II Oil <
1 1 0 i 0 <
11-J09 <
11 00 d <
11007 <
llOr.5 0.00 3.11 10.33
1 1 0 U 4 <
1 1 0 >j 3 <
11 0 0 J <
-------
Table 57
CKUSTAL Ef.'PICHMKfJT FACTORS FOR PART IC'JLATK MCKt'L
F-J TO SCANDIU* (
THE HMJGF KEPRFSEfJTS AT Lt'AST
THK 90% CONFIDENCE LIMITS
SAPPLfc" MJMbtrt m.il.'.'J'-1 BKST VALUK
111"? 0.8b 1.31 1.73
11101 0.93 1.40 1.87
11100 1.28 2.06 2.7S
11099 1.5? 2.35 3,03
11093 1.24 I,Qo 2.17
11097 1.4P 2.09 2.70
11096 0.91 1.32 1.73
11095 0.91 1.49 2.10
11094 1.59 2.19 2 . R 3
11093 2.07 2.H6 3.72
11092 0.fiH 1-36 1.7 b
11091 0.73 1.17 1.58
11090 0.^0 1.5? 2.11
11069 0.97 1.63 2.17
110&B O.M7 1.69 2.27
11087 0.92 1.51 2.04
llObb l.OH 3.M 4.B6
11065 O.uO 2.11 2.76
1 10 e 4 1.03 3.23 4.39
110 b3 1.14 3.09 4.10
llOBx 1.7H 5.71 7.95
11GM 0.67 2.21 2.P4
llOf-0 2.42 6.htf 8.99
11079 0.97 5.16 7.02
11076 0.69 1.66 2.24
11077 0.71 1.66 2.21
11076 0.36 2.4.3 3.42
11075 0.42 2.19 2.94
11074 2.55 7.51 10.25
11073 0.00 2.24 2.98
11072 1.51 3.49 4.89
Ilu71 1.55 2.H9 3.74
11070 2.3B t>. M 8.79
11069 0.06 1.H 8 2.64
11068 1.14 3.00 4.10
11067 0.75 1.61 2.IS
110*6 4.59 11.55 15.61
lli,t>5 0.52 2.23 2.9*
11 014 0.44 J . * 7 1.9-1
1 i 01 3 0.73 1 . 3 ^ 1.« ?
11062 0.35 O.eO O.H1
M 0 6 i 1.7? 2.7? 3.5 4
11060 1.32 9.34 13.OH
11059 I.5 ft 8.2; 11.14
13G5e 1.97 $.57 13.47
11057 1.16 2.9« 3.91
11 " 5 b 1.65 5 .'/ 3 - 7 . 7 1
11055 0.9fc 2.30 3.08
11054 0.45 1.19 1.64
11053 0.62 1./1 1.h 2
1105? 0.59 1.5^ 2.16
192
-------
Table 67 continued
CRUSTAL
T FACTORS FOR PAH1 TCULATE
RELATIVE '10 SCANDIU" («KDEPOHL)
NUf'RF.R
i \ i " u !:
Tr>: RAn'GE RSPHFSE'JTS AT LEAST
THI-; 90% CONFIDLNCF LI "ITS
Rr.Sl VALUE
MAXIMUM
11051
11050
11049
M 0 4 fe
11047
11046
11045
1 1044
11043
1 1042
11041
11040
11039
11036
1103.'
11036
13035
11034
1 1033
1103?
11031
11030
11029
1 1 0 2 P
11027
11026
11025
1 1024
11023
11022
11021
11020
11019
1 1 0 1 (j
HOI?
1 1 0 5 b
11015
11014
11013
1101k
11011
11010
11009
HOuH
11007
1 1 U 0 6
1 1 (J v 5
HOC 4
1 1003
1100?
11001
O.H5
0.74
0.67
1.07
0.8'/
b.06
1.19
I.o9
1.07
2.50
0.97
7.61
0.96
2.97
0. 72
5.19
0.17
0.00
0.00
0.75
o.no
O.Ofc
0.49
0.00
0.75
0.31
0.03
0.00
0.13
0.10
0.72
O.b2
1.12
(1.02
0.63
0.00
0.05
fl . 00
1.70
0.30
1.71
0.0"
0.20
0.00
o.it
0.61
0.10
0 . -3 9
0 . H2
0.34
0.7 a
1
1
1
2
1
14
1
3
1
11
2
70
1
8
1
17
1
11
0
10
1
1
1
1
1
2
0
0
o
1
1
3
2
0
1
6
0
2
3
1
2
7
1
0
1
1
0
1
1
?
1
.93
,51
.43
.30
,T>9
,11
.90
.23
.83
.14
.32
.63
,69
.40
.91
.6(3
.75
, 74
,«?
,73
.93
,8n
.02
,14
,61
.15
.92
.69
.96
,55
,43
,09
.03
,47
,24
41
73
94
24
55
19
OS
22
46
90
36
75
2.52
2.01
1.92
3.00
2.17
19.29
2.51
4.78
2.45
15.37
3.15
2H.50
2.32
10. Vb
2.33
23. fl
2.43
1 7 . u 7
1.18
15.70
60
.39
.63
20
2.93
1.29
1.27
1.44
2.35
2.02
4.61
2.75
0.73
1 .67
10.77
1.51
3.H3
5.22
2,30
4.11
3.39
7.34
1.70
1 .67
1.41
0.32
2.11
2.74
3.24
2.39
-------
Table 68
CHUSTAL £;JRICH*H:NT FACTORS FOR PANICULATE LEAD
HKLATIVF. TO SCANDIUM C-"EDtPOHL)
TH^ PA.NfGE PEPPFSE MT& AT LEAST
THrZ 90% CO^FIOFf.'CK LIMITS
'' I N I'' U i-
BfSl VALUE
11102
11101
1 1 !<>u
11099
11097
11096
11095
11094
11093
11091
11090
1 Iu89
llOtifr
110&7
11066
1)0»5
1 1 0 H 4
110d3
110H2
llOtfl
1 1080
11079
1107b
11077
11076
11075
11074
11073
11072
11071
11070
11069
1 1068
11067
11065
11064
1 !Ub3
1106?
11061
11060
11059
) 1 05H
UOt. 7
1 1056
11055
1 K 54
15053
1 1 0 5 9
O.i'O
0.26
0.00
2.67
4.13
1.24
1.83
1 .13
4.1
-------
Table 68 continued
CRUSTAL
FACTORS FOK PAR1ICUL»TE LEAD
RELATIVE TO SCANOIU1^ (*EDEPOHL)
THE KA,\(JE REPRFSFNTS AT I EAST
THE. 90% CONFIDFNCb LIMITS
SAMPLE NUMBER
MIN' I '' U v
BFST VALUE
fAXI^UM
11051
11050
11049
11048
11047
11046
11045
11044
11043
11042
1 1 04 I
11040
11039
11038
11037
11036
11035
11034
11033
1 1032
11031
1 1 0 3 U
11029
11028
11027
11026
11025
11021
11023
Ilu22
11021
11020
11019
11018
11017
11016
11015
11014
11013
11012
1101)
11010
11009
11009
1 1007
HOOb
1 I 0 0 j
1 1 0 0 4
11003
11002
11001
o.OH
2.87
2.3b
3.10
2.55
7.62
2.44
6.01
3.19
4.48
3.27
24.64
2.8*
0.00
4.40
0.00
0.00
2.01
3.14
0.66
1 . ?6
6.2*
1 . tt J
0.32
0.6«
1.60
0.52
2.i?5
1 .31
4. 37
1.43
7.00
0.00
1.60
0.18
3.16
0.99
5.69
1.68
2.53
2.17
0.71
5.99
O.P5
1.73
3 . Q 5
9.45
4.86
4.03
6.12
4.27
25.47
3.90
10.OB
5.OB
16.34
5.73
48.40
4.42
1.12
6.19
2.09
1 .30
5.5?
5.00
4.78
3.»3
11.05
4.05
6.05
1.87
4.27
1 .OR
6.60
2.46
6.53
2.60
14.40
0.45
6.05
,87
,9b
1.84
,67
,81
,SQ
,20
,36
2.51
6.13
12.31
6.64
5.51
8.55
5.91
38.fi4
5.28
13.64
6.87
22.54
7.67
66.01
5.95
3.67
11.45
3.00
2.08
7.73
6.75
7.41
5.14
14.61
5.6b
9.67
2.62
6.01
1.45
9.02
3.36
8.63
3.59
22.12
0.82
9.01
2.70
8.0*.
2.54
15.26
4.99
7.H5
6.95
1.62
6.93
2.2S
3.49
6.17
195
-------
Table 69
CfcUSTAL
FACTORS FOR pAf-'TICULATK T T t!
r TO SCAoJDIU* (."EQEPQHU
SA-PLK
-If1 HIM
THE PA'NGF. t-FPPKStf.Ti. AT LKftST
IHfc. 90% CO;FIDt:NCF. IT'MTS
REST VALUif
"AXI''1M
11102
11)01
11100
11099
11098
11097
11096
Ilu9b
'1094
11093
11092
11 051
11090
1 1 0 b 9
1 1 0 v *
HO1!?
110S6
130*5
11084
1 1 0 fc 3
1 1 U n 2
11 0 "d 1
1 1 0 r. 0
11079
1107*
11077
11076
1107b
1 1 C 1 4
11073
11072
1 1. 0 7 1
1 K' 7 0
11069
11068
1 1 0 o 7
11066
IK/65
1 1 0 o i
11063
1106?
11061
HOtO
1 1 (J b
-------
Table 69 continued
CKUSTAL
T FAC'IOnS FOR PAKIICULATF TIN
KKLATIVE TO SCANDIUM ( tvE
SAMPLE
x i y u ,x
THr RANGE PKPKFSlfMS AT'LflSl
THE 90% CQ^FIDFNCh LIMPS
PEST VALUE:
11051
11050
11049
1 1 0 4 b
11047
11046
11045
11044
11043
1104?
1J041
11040
11039
11038
11037
11036
11035
11034
11033
11032
11031
11010
110/9
110/7
11026
11024
11023
11022
11021
11020
1 1 C 1 9
1101 '*
11017
11016
1 1 (J 1 5
11014
11013
11012
11011
1 1 0 i f.'
1100 >
HUMJ
11007
11006
11005
11004
11003
lion/
11001
197
-------
Table 70
CRUSTAL
T FACTORS FOP P AKTICUL ATF. THOPIU'-'
RKLATIVF. TO SCANDIU,« (X
SAMPLE
THE FAMGF F
1 1 0 ( 5
1 1 0 c 4
110o3
llOti
1 1 0 f 1
HObO
15 059
V 1 0 5 h
11057
11 C [> iS
1 1 0 b S
1 llb-i
11053
11052
0.89
0.98
0.99
0.90
1.01
1 .00
0.94
0.9*
1 .01
1.02
1.00
0.73
0.76
0.7B
0.79
0.80
0.68
0.72
0.77
0.73
O.fel
0.81
0.75
0 . 7 4
0.87
0. « 9
0.83
0. fj 3
0.83
0.80
ft . «8
0.92
0.77
0.77
n.73
0 . f- 2
0.31
0.5?
0. 7ct
0.9fl
O.S3
O.Rb
0.80
O.'JO
0.54
0.^9
0.66
0.74
O.hO
0 . >j 7
0.7H
1 .08
1 .09
1.21
1.22
1.23
1.24
1.1%
1.20
1.25
1.27
1 .21
0.96
0.92
0,94
O.QS
0.«7
0.90
0.05
0.94
O.P7
l.'H
0.95
0.93
0,91
1.06
1.07
1.01
0.99
1.00
0.97
1.07
l.U
0.97
0.94
1 .03
1 .00
0.69
0.76
( . 9 7
1 . " 7
1.00
1.04
1.03
1.21
1.05
C.R4
f ' . 9 5
J .^0
1.0D
0.06
1.29
1.34
4ft
49
51
54
4P
47
55
5R
47
17
11
13
15
19
17
J .22
1.1*
1 ."4
1.26
1.12
1.14
1.12
l.?Q
1.29
1.23
l.lh
1.21
1.13
1.31
1.33
1.21
1.15
1 .32
1.21
1.13
1.0<-
1.70
1.31
1.72
1.2*-
1.37
1.59
1 ,lh
1 .??
1.07
1.1°
1.25
1.29
5 .19
198
-------
Table 70 continued
CRUSTM t.NKIOW.T FACTORS FOB PARTIC'ILATE THORIUM
RfLATTVfc TC SCANDItjN (
THF f-ANGE REPKFSE.riTfr, AT LEAST
THfc 90% CO'.TinF'JCF LIMITS
SA»Fl.k Nb»htw t'lur'U* biST VALUE MAXIMUM
11051 O.R8 1.Do 1.27
11050 0.90 1.03 I.JO
1104V 0.90 1.11 1.37
11048 0.90 1.20 1.33
11047 0.9C 1.10 1.35
11046 0.77 0.99 1.24
11045 0.94 1.13 1.37
11044 0.9} l.M 1 . 36
11043 0.94 1.15 1.40
11042 0 . h 7 0.99 1.41
11041 0.91 1.10 1.33
11040 0.76 0.93 1.14
11030 0.98 1.0* 1.33
11038 0.6b 0.96 1.33
11037 0.
199
-------
Table 71
CKUSfAL EN^ICH^K'.T FACTCPS FO^ ^ APT ICULATE UPAMU>
Pr;[,MlVF TO SCA.-JDIU^ i < E
THF fcAVGE RKPRFSENTS AT LE.'AST
90% CUNFIDKNCf- L.I"I1K
K !
1 1090 0.66 0.^^ 1.16
11039 0.70 O.flS 1.0-?
J10?R 0.48 0.71 0.90
1 1 0 «? 7 0.74 0.94 1.18
1 1 0 3 b 0 . 7 S 1.70 1.75
1 1 r> H -i 1.46 2.04 ? . T 4
110^4 0.6a 0.96 1.V7
11 Oh 3 0.72 0.89 1.10
110^7 <
llO'-l C.«5 1.1° 1.4*S
11 0 fc 0 0 . 7 S 1.37 ? . 1 4
1 1^7P 1. HI 1 .49 2.07
1 U, 7 f 0.70 0 . 9 a 1.21
11077 0.71 O.W3 1,19
11076 1.01 1.42 1.9?
M',75 ('.00 1.93 ^.55
11074 0.33 1.S1 2.35
11073 2.7o 3.36 4. IB
11072 0.76 l.oa 1.SO
11071 0 . & 8 1.13 1.42
1 1070 0.95 1 .Se 2.36
11 (.6 9 C.OO 1.41 3.78
1 1 1) b fc 0.44 1.0 « 1 . « 2
11067 0.91 1.2? 1.58
110^6 0.5^ l.fr" 2.9S
11065 1.16 1.17 1 . >> -1
11064 0.56 0.74 0 . ° 6
1 1 0 b 3 0 . 6 S 0 . '» 5 1.10
11)^2 0.73 0.91 ] . 1 4
11 C 6 1 0.70 0.90 1.13
1 1 0
11057 0.?7 U?l 1>1
11056 O.b5 1.27 1,77
11055 0.9-1 1.54 2.04
!10 54 0.77 0.97 1.27
11053 0.71 0.92 1 . 1 H
11052 O.H2 1.06 5.35
200
-------
Table 71 continued
CHUSTAL £*:PICH«f:NT FACTCFS FO,' PARTICULATE UPAMUC
ktLATIVE TG SCAr.DIU" ( * FOF. POHL )
THE FA«GK REPRESENTS AT LEAST
THE 90% COrJFIDEr.Cr: MVTTS
SAVPU:
11051
11050
11048
11047
1104b
11045
11044
11043
11042
11U41
11040
11035
1103R
11037
1 1 0 3 fa
11035
11034
11033
11032
1 1031
11030
11027
11026
11025
11024
11023
11022
11021
11020
11019
11018
11017
11016
11015
11C14
11013
11012
11011
11010
11009
11008
lion/
1 1 0 0 b
11004
11003
1 1 0 0 2
11C01
MI («T " U f*
0.85
0.79
O.RO
0.82
0.74
0.85
0.01
0.63
1.76
7.80
O.«l
3.61
1.28
0.65
1.15
0.71
0.56
O.P7
0.60
0.95
0.85
0.57
0.02
0.60
0.61
0.53
0.67
0.73
0.44
0.30
0.56
0.52
".53
0.71
0.f-«
1.40
PEST VALUE
201
1.08
1.95
1.06
1.02
2.40
2.67
0.5?
1.27
4.00
1 1 .03
1.14
5.71
1.94
1 . O't
l.SS
1.01
0.94
1 .30
0.76
1 *y Q
1.64
0.79
0.80
1.11
0.6?
1.00
1.32
O.ft7
0.64
0.82
0.67
0.67
0.96
J .33
1 .86
<' A X J V U V
1.36
3.35
1.37
1.77
4.50
4.R3
1.15
2.04
6.77
14.73
1 .53
7.95
2.75
l.bl
1.39
1.39
1.34
0.96
1.72
1 .06
1.16
1.04
1 .74
1 .1 -3
1 .42
2.04
0.94
1 .03
l.M
O.RS
O.P7
1.77
1 . wfi
?. A 0
-------
Table 72
CRUSTAL ENRICHMENT FACTORS FOR PARTiCULATE ZINC
RELATIVE TO SCANDIUM (
SAMPLE NUMBER
M I a 1 f< U M
THE RANGE REPRESENTS AT LEAST
THE 90% CONFIDFMCL LIMJTS
REST VALUE
MAXIMUM
11102
11101
11100
11099
11098
11097
11096
11095
11094
11093
11092
11091
11090
11069
11086
11087
11086
1JOH5
11084
11C&3
11082
11081
11080
11079
11076
11077
11076
11075
11074
11073
11072
11071
11070
11069
11 Oft 8
11067
1 1066
1
1 1 0 b 4
110b3
3 106?
UOM
11060
11059
11058
1 1057
1 1 0 5 b
2.02
1.94
.76
2.35
3.30
3.47
2.96
2.96
56
14
11054
11053
11 Obi!
4,
4,
4.71
4.27
1 .26
2.27
1.72
2.02
0.00
o.oo
0.00
o.oc
0.00
o.co
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
o.oc
o.oo
0.00
0.30
0.00
0.00
0.00
0.00
0.00
0.00
O.uO
0 . 0 0
0.0 0
3.16
3.08
4.36
4.R7
5.51
5.42
4.58
4.71
6.40
5.97
7.99
6.32
4.36
5.42
6.36
4.73
2.06
4.64
5.33
3.95
7.36
5.92
16.73
11.71
3.67
3.00
6.77
5.06
11.78
1.18
4.29
4.01
4.62
2.13
4.«5
3.49
6.53
3.83
1.83
1.66
15.41
4.37
9.33
2.V5
5.92
2.33
1.6 }
1.H2
3.
3.
5.
7,
6,
,98
,98
.89
6.38
7.41
.04
,00
6.28
&.11
7.45
10.52
8.05
6.?5
7.39
8.S7
6.62
10.08
13.29
12.60
9.77
23.22
11 .27
32.37
25.75
7.74
5.90
14.07
11.09
26.23
10.1?
9.46
7.74
IP. 62
9.92
10.55
5.83
31.76
13 .54
3.40
43. 4h
25.71
31.08
7.RH
1C. . 8 6
^,36
4 . R '.;
3.31
202
-------
Ta.ble 72 continued
CRJSTAL
I[CHW>:"JT PVCTOPS'!' JP .P,iRTlCUL4TE ZINC
EL.A rrv o SCAHDH,! UEPEPOKD
Y
i !
Ml MI MUM
THF" RiM^e HI- PRESET,TS AT Ll-AfT
TH1J V0% CO.MMOFNiCT LIMT5
9F5T VALUE: I^AX JMP*
11051
11050
11046
11047
11046
11045
11044
11043
11042
11041
1 J040
11039
11038
11037
11036
1 1035
J 1 C 3 4
11033
11032
1 1031
11030
11029
11028
11027
11026
1 I 0 2 5
11024
11023
11022
11021
11019
HOlfe
11017
11016
1 1 0 1 b
11014
1 1 V 1 3
11012
1 J i> I 1
11010
11009
) 1 <"' 0 7
1 1 0 0 o
1 1005
1 1 0 0 4
1 1 0 0 3
1 1 uO/
1 1 0 U J
o.oo
0.00
0.00
o.oo
0.00
J.OO
0.00
o.oo
0.00
o.oo
0.00
0.00
O.oo
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0. 00
0.00
o.oo
0.00
0,00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
o.oo
3.00
1.66
1.01
0.00
o.oo
2.04
2.07
X.90
C.fU
1.87
4.50
2.99
3.99
2.03
1.97
1.27
9.f 5
2.56
8.35
2.79
0.00
79.66
2.42
10.49
3.25
2.55
3.56
2.faO
4.16
1.94
5.22
4.32
4.1.7
4. !>1
3 . ') c'
37. 31
5.?:
8.04
4.31
28.98
4.70
37.42
4.20
28.58
6.77
5.02
137.7?
e.03
51.08
9.62
4.44
It . 27
6.62
10,83
6 . 4b
8.47
46
14
14
03
2.01
4.55
3.36
2.11
2.3')
3.36
12.5b
3.92
3.7s
3.01
24.S6
4.40
13.93
6.20
4.31
4.06
B.43
7.-JS
6. R6
17.91
5.64
7 \ <- 6
h.82
S.53
203
------- |