NATL INST. OF STAND & TECH

A11107 3=10074

NBSIR 83-2698

The Characterization of the Chesapeake Bay:

A Systematic Analysis of Toxic Trace Elements

U.S. Department of Commerce

National Bureau of Standards

Center for Analytical Chemistry

Inorganic Analysis Research Division

Washington, D C. 20234

November 1983

Prepared for U.S. DEPARTMENT OF COMMERCE

National Bureau of Standards

Washington, D.C. 20234

WATIONAt. BUREAU

.OF STANDARDS UUHARY

NBSIR 83-2698

C» r C . O c

| DO

v THE CHARACTERIZATION OF THE CHESAPEAKE BAY:

A SYSTEMATIC ANALYSIS OF TOXIC TRACE ELEMENTS ms

c

Howard M. Kingston, Robert R. Greenberg,

Ellyn S. Beary, Billy R. Hardas,

John R. Moody, Theodore C. Rains

Center for Analytical Chemistry

and

Walter S. Liggett

Center for Applied Mathematics

National Bureau of Standards

Washington, D.C. 20234

Prepared in Cooperation with the Environmental Protection Agency

Under Grant No. EPA-79-D-X-071

7

Ernest L. Garner and Howard M. Kingston

Center for Analytical Chemistry

National Bureau of Standards

Washington, D.C. 20234

Project Officers

U.S. DEPARTMENT OF COMMERCE, Malcolm Baldrige, Secretary

NATIONAL BUREAU OF STANDARDS, Ernest Ambler, Director

TABLE OF CONTENTS

Page

Disclaimer ii

Foreword iii

Brief iv

Introduction and History 1 Experimental 4

Results and Discussion 15

Literature Cited 22

Appendix 1 - Data: Site and Sample Characteristics 24

Appendix 2 - Trace Element Analysis of Natural Water Samples by

Neutron Activation Analysis with Chelating Resin .... 26

Appendix 3 - 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 ... 32

Appendix 4 - Report of Analysis; Discussion on the Atomic

Absorption Spectrometry - Applied 39

Appendix 5 - Blank Uncertainties and Corrections 46

Appendix 6 - Data: Table 1 Through Table 72 Results 63

Appendix 7 - Data: Graphical Representation of Results 178

i
DISCLAIMER

Certain commercial equipment, instruments, or materials are identified

in this paper to specify adequately the experimental procedure. Such

identification does not imply recommendation or endorsement by the National

Bureau of Standards, nor does it imply that the materials or equipment

identified are necessarily the best available for the purpose.
FOREWORD

This status report is submitted in partial fulfillment of the requirement and conditions of Grant Number EPA-79-D-X-0717, "The Characterization

of the Chesapeake Bay: A Systematic Analysis of Toxic Trace Elements". The

period covered by this report extends from April 1979 to the end of September

1981.'

iii
BRIEF

As part of a multidisciplinary study of the Chesapeake Bay, the National

Bureau of Standards (NBS) was asked to develop the techniques and procedures

necessary to measure 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, Ce, Co, Cr, Cu, Fe, Mn,

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 trace elements in 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 plastic 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 NBS.

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 Geological Survey and Virginia Institute of Marine Science, for sample logistics and

acquisition. The total complement of 102 samples was obtained, filtered,

acidified and stabilized. 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 (NAA) and graphite furnace atomic absorption (GFAAS). A major

portion of this effort also involved quality assurance. This was partially

accomplished by utilizing standards preparation and NBS Standard Reference

Materials (SRM's), specifically Trace Elements in Water, 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].

iv
The fourth major phase consisted of the analysis of the samples for the

trace elements. This phase places most of the burden for analysis on NAA and

GFAAS with isotope dilution mass spectrometry (IDMS) contributing isotopic

and concentration data 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 quality control and calibration

analyses totaling over 5,000 separate determinations.

The fifth major phase involved data reduction and evaluation of the

statistical significance of the blank. The blanks were statistically modeled

for each element, and the blank and uncertainty of the blanks were applied to

the data. The uncertainty of the concentrations was adjusted to include at

least the 95% confidence limit.

v
I

i

!
INTRODUCTION AND HISTORY

This report describes the National Bureau of Standards (NBS) efforts in

a multidisciplinary study of the Chesapeake Bay coordinated by the Chesapeake

Bay Program Office of the U. S. Environmental Protection Agency. The NBS

used the best available technology, concomitant with funding, personel , and

time; to determine the trace and toxic element concentrations in the water

column. As part of this program, the NBS has collected and analyzed both the

dissolved and suspended particulate fractions of 102 water samples 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], spectrophotometry [7], anodic stripping voltammetry [8], and atomic absorption

spectrometry [9-11]. However, each of these analytical techniques requires a preliminary 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 untreated sample

determination of trace elements in seawater at concentrations below 5 yg L" 1. Usually 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
Most of these separation and concentration methods require large volumes of

chemicals which can lead to high blanks unless the reagents have been

carefully 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

chelators 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 mole/L 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 of 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-el uted 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 et al . [1]). This procedure was used in

conjunction with GFAAS to analyze Chesapeake Bay estuarine and Gulf of Alaska

seawater samples [1]. The method was also modified and the resin was irradiated

directly without elution, in conjunction with a NAA technique utilizing these

same samples and NBS 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"9 to 10~ 12

g of

many of the trace elements in water. 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 trace

metals in seawater are present as chlorides, which have a lower volatilization 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.

2
While the Chelex resin procedure produces a highly desirable and

appropriate aqueous matrix for most spectroscopic methods of analysis, a solid sample would be more appropriate for other instrumental techniques such

as XRF [3] or NAA [2], In addition, the above separation procedure also

makes it difficult or impossible to analyze several elements which are held

strongly by the resin and cannot be quantitatively eluted. Chromium and

vanadium exhibit this type of behavior, and attempts to elute these elements

reproducibly 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 >j07 for Na, >_10 5 for Cl, and >_10^ for Br were

observed. This procedure has been used to analyze NBS SRM 1643a, as well as high salinity water samples 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 use of

pre-irradiation chemistry for high-salinity waters has significant advantages.

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 some type of separation. The removal

of the matrix elements also greatly reduces the radiation dose received by

personnel, especially if radiochemistry is used. The preconcentration of

100 mL of liquid to a sample of less than 0.5 gram increases the sensitivities

for most elements and allows more samples to be irradiated within a single

rabbit. Although other non-chemical concentration 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 can also increase the blank from the equipment used. Finally,

the use of Chelex 100 prior to irradiation produces a solid sample which

eliminates the problems of storage, irradiation, and handling liquid samples

for NAA.

Even without pre-chemistry, the number of sample manipulation steps

required before the irradiation of a high salinity water sample is considerable,

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 concentration/separation

step produces significant benefits for the additional effort required.

3
EXPERIMENTAL

REAGENTS

High purity water, nitric and glacial acetic acids were prepared using

subboiling distillation at NBS [21]. All reagents used in the separation

process were prepared in this manner and stored in clean FEP Teflon bottles

unless otherwise stated.

Ammonium hydroxide solution was prepared by bubbling filtered ammonia

gas through high purity water until room temperature saturation was achieved.

A 1.0 mole/L ammonium acetate solution was prepared by mixing 60 g of

purified glacial acetic acid and 62 g of saturated NH4 0H 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 NH4 0H.

All reagent and sample preparations were done in a class 100 clean air

laboratory [22].

Chelex 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 the 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 to take a sample with a minimum of

contamination. REli ability 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

XRF analysis and found to contain only trace quantities of one element being

4
77D30M 77D10M 76D50M 70D3OM 76D10M 75D60M 75D30M

Figure 1. 5
investigated. Only iron at the yg level was detected using the full depth

of the energy dispersive x-ray system.

The tubing used was conventional polyethylene (CPE) of (2.5 cm) 1 inch

in diameter. It was connected to the pump and storage by polyvinyl -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 approximately 1 meter

from the ship for bottom sampling. The depth was marked on the tubing with

plastic tape at (1.52 m) 5-ft. intervals. The bottom sampler consisted of a

(61 m) 200-ft. 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 (0.32 cm) 1/8-inch 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 was 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 (15 m) 50-ft. piece of (2.5 cm) 1 inch CPE

tubing and held 7 m from the side of the ship, with the tubing 1 meter down

pointing at a 30° angle away from the ship. The float was constructed of a (7.6 cm) 3-inch block of styrofoam, sandwiched between two sheets of plexiglass sealed using silicon sealant, with a plexiglass tube to guide the CPE

sample tube and plexiglass hook. To the hook was attached a (7.3 m) 24-ft.

stainless steel rod all totally encased in (0.32 cm) 1/8 inch of CPE which

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 seal the

working surface.

6
Sampler

Pumping

System

Figure 2

7

Sample

water

outlet
The filtering was accomplished utilizing Ami con and Mi Hi pore 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 the filter

apparatus

.

The acid was added from a quartz repipet constructed to deliver precisely

32 mL repeatedly to all sample bottles.

The sample bottles were all polyethylene CPE from a single lot of plastic.

They were cleaned in 1:4 HC1 and 1:4 HN03 acid, alternately, for two weeks in

each acid, then rinsed and filled with high purity water [23]. Their volume

was determined prior to use.

A discussion of the cleaning and suitability of the plastics and

materials used for construction and storage in trace chemical analysis has

been 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

Two 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 prescribed depth, purging the system with estuarine water and allowing the same water sample to flow through the system for 30 minutes. The flow rate was a liter every 2 seconds, or 900 liters in the 30 minutes prior to collection.

A 2-liter CPE bottle was rinsed three times with the 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 filled between uses with 1:4 reagent grade

HN03 and rinsed prior to use with 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 particulate filter for both

GFAA and NAA. The second bottle of filtered sample was unacidified and used

to determine density, using a close range hydrometer and thermometer, and

then discarded. The two sets of filters were placed in plastic filter

holders and labeled. The bottle containing the acidified sample was placed

in a CPE polyethylene bag sealed and stored in a wooden chest for transport.

8
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 NBS deioni zed-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.

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 0.5 liter/s

2 liter sample collected in clean thrice purged

polyethylene

Sample filtration commenced within minutes

Surface sampler connected in place of bottom sampler

Surface water pumped for 10 minutes at 0.5 liter/s

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

9
Sample Distribution

Filter for

Graphite

Furnace

Atomic

Absorption

(GFAAS) of

Particulate

Water Sample

2L Sample

Filter for

Neutron

Activation

Analysis (NAA)

of Particulate

1 Liter of Filtered Water

Acidified with High Purity

HN03 to 0.5N

1 Liter of Filtered Water

Used for Density and Temperature

Taken at Time of Collection

4

100 mL Portions Taken by

Weight for Chemical Separation

and Preconcentration

/ \

Water Sample Water Sample

for for

GFAAS NAA

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

NBS Trace Elements in Water, 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 NBS, using two or more independent analytical

techniques or a definitive method of known accuracy [25,26]. The chemical

preparation of these standards were identical to the Chesapeake Bay samples

and they were dispersed among the analyses of the dissolved samples.

10
COLUMN PREPARATION AND PURIFICATION PROCEDURE

The polypropylene chromatographic columns, used to hold the Chelex 100

resin, were soaked for one week in 4 mol/L reagent grade HN03 and one week

in 3 mol/L reagent grade 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

mg dry weight) was loaded into each column. The resin was washed with three

5-mL portions of 2.5 mol/L high purity HN03 to elute any trace metal con- tamination. Excess acid was removed by washing the resin with two 5-mL

volumes of high purity water. The resin was transformed to the ammonium

form by the addition of two 5-mL volumes of 2.0 mol/L NH4 0H. The pH of the

last few drops eluted was checked using pH paper. If they were not basic,

additional NH4 0H was added until basicity was achieved. Residual NH4 0H was removed from the resin with two 5-mL water washes.

SEPARATION PROCEDURE

The esturine water samples, which had been filtered and preserved with

high purity HN03 , were adjusted to a pH range of 5. 2-5. 7 by dropwise addition

of concentrated NH4 0H and 2 mol/L NH4 0H. A few drops of 8 mol/L 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 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 mol/L 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-mm (1 mil) linear polyethylene (LPE) bag.

This bag was heat sealed 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),

while the outer bags were made of 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. For GFAA, the transition metals were eluted using 7 mL of 2.5 M HN03 and collected into clean, preweighed 10-mL conventional polyethylene bottles.

The bottles were capped with clean polyethylene-lined caps and reweighed to

determine the weight of the effluent.

STANDARDS

Two types of multi elemental standards for NAA were used. The first type

was prepared by pipetting known amounts of multi elemental 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

11
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 amounts 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 two levels within the polyethylene irradiation

container (rabbit). Each rabbit was irradiated for 4 hours in the RT-3

pneumatic tube facility of_the NBS reactor. This facility has a thermal

neutron flux of 5* 10 13 n*cm"2

* s”

1 [28]. Midway through the irradiation the

rabbit was removed from the 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 computerbased analyzer system was used for data collection and reduction. A more detailed description of this analytical method can be found in Appendix 2.

IRRADIATION 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 10 13

n*cm' 2 *s

_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 measure 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 counting

position and the decay corrections calculated by the computer.

DETERMINATION OF DISSOLVED FRACTION BY GFAA

The estuarine samples from the Chesapeake Bay were preconcentrated using

the method described by Kingston et al . [1]. The column eluate was analyzed

directly for Cd, Cu, Mn, Ni and Pb by GFAAS, using the L'vov platform. To

check for chemical interferences, the single standard addition method was used [29]. The instrumental conditions for each element are given in Table 1.

A more detailed description of these methods can be found in Appendices 3

and 4.

12
TABLE 1. INSTRUMENTAL PARAMETERS FOR GFAAS ANALYSIS

Perkin-Elmer 603 - HGA - 2200

a WaveElement

length

nm SBW

nm ScaleExpansion Fas

Drying

Time in s CharringTime in s Atomization

Time in s

Cd

b 228.8 0.7 2 Ar 125 - 40 800 - 40 2300 - 6

Cu ' 234.7 0.7 2 Ar 125 - 40 700 - 40 2600 - 6

Mn 279.5 0.7 2 Ar, Stop 125 - 40 800 - 40 2700 - 6

Flow

Ni 232.0 0.7 5 Ar

Ni 232.0 0.7 5 Ar 125 - 40 800 - 40 2700 - 6

pb

b 283.3 0.7 3 Ar 125 - 40 800 - 40 2400 - 6

a With L'vov Platform.

b

( NH^

) ^HPO^ used in matric modification.

c Ramp mode used for first 20 seconds.

DETERMINATION OF PARTICULATE FRACTION BY GFAAS

The solids which were collected on 0.45 ym filters were prepared by

transferring each filter to a Teflon beaker. Then, 5 mL of high purity HN03 and 1 mL of high purity HF were added and the solution warmed. After the

filter had decomposed, 5 mL of high purity HC104 was added and the sample

solution evaporated to near dryness. The solids were then dissolved in 1 mL

of high purity HN03 and 5 mL of water and then transferred to 10 mL volumetric

flask. The analytes were determined by GFAAS, using the instrumental conditions described in Table 1. The recovery of each analyte 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 30 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 that were cleaned at the same time and contained subboiled distilled

NBS high-purity water. The blanks were opened for 20 seconds on the deck,

prior to manipulation, to simulate as closely as possible the actual samples.

This water was passed through the same lot number of Ami con and Millipore

filters, either one, two, or three filters in the same apparatus, using the same conditions and done in between actual samples. The blanks were acidified

from the same reagent batch and container of NBS acid and stored under the

same conditions as the samples. They were carried through all operations as

13
if they were actual samples and analyzed with the samples to determine the

total analytical blank.

ANALYTICAL BLANK CORRECTION AND DATA ADJUSTMENT

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 are approximately at the 95%

confidence level. Both blank influence and statistical uncertainty were adjusted through a series of individual elemental models.

The statistical considerations used to adjust each element set are given in Appendix 5 [30].

14
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 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 determination 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 particulate 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 CHELATION AND NAA

Concentration -- ng/g

Element This Work3 Certified^

Cd 10.1 ± 0.5 10 ± 1 Co 19 ± 1 19 ± 2

Cr 16 ± 2 17 ± 2

Cu 19.1 ± 0.6 18 ± 2

Fe 88 ±16 +i 00 00 4

Mn 30.9 ± 0.6 31 ± 2

Mo 97 ± 6 95 ± 6

Ni 56 ± 8 55 ± 3

V 52 ± 1 53 ± 3

Zn 68 ± 5 72 ± 4

^Uncertainties are 2s.

^Uncertainties are at the 95% confidence limit.

15
TABLE 3. TRACE ELEMENTS IN WATER - SRM 1643a

ANALYZED USING CHELATION AND GFAAS

Sample Pb Ni Cu Cd

rig/ mi_

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

Certi fied

Values = 27 ± 1 55 ± 3 18 ± 3 10 ± 1 (at the 95% confidence limit)

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 procedures were developed and chemical separation/preconcentration procedures based on the chelating resin Chelex-100 were applied prior to NAA and GFAAS analysis

[1,2]. The elimination of the matrix elements allowed the determination of

many elements which could not otherwise be analyzed and enhanced the sensitivity of other elements of interest. The control of the blank in this

procedure has enabled its contribution to be sufficiently low that it did not

limit the measurement of most elements in these samples.

16
While many elements appeared to be free of any blank contribution, other

elements have a blank contribution which was found to be significant. The

particulate blank for zinc and chromium was contributed largely by both types

of filters used. Ami con and Millipore (0.45 micrometer). The chromium was found to be significantly different between the two brands of filters, while

the zinc was indistinguishable between brands (see figures 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 below detectable limits. Analysis of 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 determinable 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 in Tables 30

through 58 of Appendix 6. They have undergone rigorous statistical analysis

and their influence on the concentration measurements is discussed specifically 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 of the blank to exist for one or more elements

underlying the other sources of blank.

A second contribution to the blank which could 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 the actual samples any

contribution from the high-purity water used would raise the observed blank

17
higher than it actually exists in the real samples. This then, can only

contribute to an over estimation of the real blank.

Some blanks are undetectable others have been traced to the filters and

specific processes as described in Appendix 5. For each element the uncer- tainty in the concentration data take into account the uncertainty in the

blank as well as the instrumental uncertainties.

Some understanding of the dissolved elemental concentrations can be

gained by comparing the concentrations to normal seawater values (Appendix 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 interactions. 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 water density and other characteristic elemental concentrations that

contributions 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 analysis, blank

contribution, corrections and mathematical manipulation of the data in this

report have resulted in 58 data sets which are of known statistical reliability. These data sets contain the sample numbers arranged in a numerical

sequence approximating the geographical arrangement of the Chesapeake Bay,

from the Susquehanna River to where the Chesapeake Bay emties into the Atlantic

Ocean. The concentrations are given as a best value, and maximum and minimum

values which represent at least the 95% confidence limit of the concentration.

The significant figures of each concentration are determined by the range

between the maximum and minimum value.

The potential information in the particulate elemental concentration

data is even more 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, wind 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 mass is

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 many cases the concentration of the elements of interest would

be much higher in the bottom sediments than in the biological material.

Although the particulate data may appear initially to be uncertain in

interpretive value, a technique long used in the study of geochemistry and

atmospheric particulate material is applicable [30,31]. The comparison of

elemental ratios for different samples instead of the absolute concentration

is informative. 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.

18
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 environment

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 NBS SRM 1646, an estuarine sediment collected in the Chesapeake Bay

were transformed into EFs in Table 5.

TABLE 5. ELEMENTAL CONCENTRATIONS AND CRUSTAL ENRICHMENT

FACTORS FOR ESTUARINE SEDIMENT SRM 1646

Concentration

in yg/g or %

Enrichment Factors

Normalized to Scandium

Li 49 2.08

Na 2.0% 1.04

K 1.4% 0.63

Rb 85 0.90

Cs 3.6 1.70

Mg 1.09% 1.00

Ca 0.83% 0.37

A1 6.25 1.02

Si 31% 1.29

Sc 10.7 1.00

V 88 1.18

Cr 76 1.38

Mn 375 0.69

Fe 3.35% 1.20

Co 10.1 1.07

Ni 32 0.93

Cu 18 0.76

Zn 138 2.93

Cd 0.36 4.58

Sb 0.43 2.74

Ce 79 1.34

Eu 1.5 1.36

Th 9.9 1.15

Hg 0.063 2.67

Pb 28.2 2.39

19
In these data the concentrations from Wedepohls' compilation [32] for

crustal 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.

Enrichment factors can also be used to identify significant inputs of

material to the Bay. The EF 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 the EFs for each element will remain constant if the sources contributing to the suspended sediment remain the same. Although the concen- tration of the various elements may fluctuate several orders of magnitude

from sampling to sampling, the EFs should be constant if the sources are constant as they are not effected by mass loading.

As an example of this theory, the comparison of Sc with another relatively nonanthropogenic element, Ce, is instructive. The concentration ranges

of Ce and Sc are between two and three orders of magnitude. The range of the

enrichment factors, however, was just 45% of the mean value and the relative

standard deviation was only 10%. No additional variability over the analytical

uncertainties were observed. Not only were the analytical uncertainties

contained within these limits but the total natural inhomogeneity of the

environmental ratios for the entire estuary was also contained within this

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 top

and bottom of the water column sampled at each of the 51 locations. Before an interpretive value can be hypothesized for the enrichment factors calculated

from the particulate data, control of the system must be demonstrated. While

this example is not an exhaustive establishment of control, it is important

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 statistical 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.

20
The data have been condensed to graphical form which displays the

spacial and geographical relationships between these samples. The dissolved

concentration data, particulate concentration data, and the elemental

enrichment factors are displayed on maps of the Chesapeake Bay at the location

where the sample was collected (Appendix 7). The sample concentration or numerical magnitude is given by the area of the circle. The key for the

numberical scale represented is printed on each figure. The top sample is

represented by a 20 percent screen density and the bottom sample by a 40

percent screen density. The two samples top and bottom are superimposed and

the overl aping area is a 60 percent density. A less than is indicated by a register mark at that location. The figures use the mean values without

uncertainties, and must be interpreted using the more precise data given in

the Tables. They do, however, aid the identification of spacily significant

trends which are not easily noticed from the numerical tables.

These data are of sufficient reliability that statistical comparison

can be performed resulting in trends of known reliability. This work has

not been included in this report and is of a sufficiently complex nature to

comprise a separate effort. This effort has been recently initiated.

21
LITERATURE CITED

[1] Kingston, H. M. , Barnes, I. L., Brady, T. J., Rains, T. C., Champ, M. A.

Anal. Chem. , 1978, 50, 2064.

[2] Greenberg, R. R. , Kingston, H. M. Anal. Chem. , 1983, 55 1160 (see

Appendix 2)

[3] Kingston, H. M. , Pella, P. A. Anal. Chem. , 1981 , j33, 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 National

Program", NOAA, Washington, DC, 1972.

[6] Lee, C. , Kim, N. B. , Lee, I. C. , Chung, K. S. Talanta , 1977, 24, 241.

[7] Stephens, B. G. , Felkel, Jr., H. L. , Spinelli, W. M. Anal . Chem. , 1974,

46, 692.

[8] Zirino, A., Lieberman, S. H. , Chapter in "Analytical Methods in Oceanography", T.R.P. Gibbs, Jr., Ed., Adv. Chem. Ser. , 1975, 147 .

[9] Sperling, K. R. At. Absorpt. News!. , 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. R. , 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, 38, 447.

[15] Kremling, K. , Peterson, H. Anal. Chim. Acta , 1974, 70^, 35.

[16] Riley, J. P. , Taylor, D. Anal. Chim. Acta , 1968, 40, 479.

[17] Davey, E. W. , Soper, A. E., Chapter in "Analytical Methods in Oceanography", T.R.P. Gibbs, Jr., Ed., Adv. Chem. Ser. , 1975, 147 .

[18] Florence, T. M. , Batley, G. E., Talanta , 1976, 23^, 179.

[19] Florence, T. M. , Batley, G. E., Talanta , 1977, 24^, 151.

22
[20] Ediger, R. D. , Peterson, G. E., Kerber, J. D. At. Absorpt. News!. , 1974,

13, 61.

mi Keuhner, E. C., Alvarez, R. , Paulsen, P. J., Murphy, T. J. Anal. Chem.,

1972, 44, 2050.

[22] Federal Standard 209b, Government Services Administration, Boston,

Massachusetts, 1973.

[23] Moody, J. R. , Lindstrom, R. M. Anal. Chem. , 1977, 49^, 2264.

[24] Maienthal, E. J. , Becker, D. A. Natl. Bur. Stand. (U.S.) Tech. Note, 1976,

929.

[25] Moody, J. R. , Rook, H. L., Paulsen, P. J., Rains, T. C. , Barnes, I. L.

,

Epstein, M. S. Natl. Bur. Stand. (U.S.) Spec. Pub!

, 1977, 464 , W. A.

Kirchhoff, Ed.

[26] Natl. Bur. Stand. (U.S.) Certificate of Analysis, SRM 1643a, 1980.

[27] Greenberg, R. R. Anal. Chem. , 1979, 5T_, 2004.

[28] Becker, D. A., LaFleur, P. D. J. Radioanal. Chem. , 1974, 19, 149.

[29] Dean, J. A., Rains, T. C. , eds., "Flame Emission and Atomic Absorption

Spectrometry", Vol . 3, Marcel Dekker, New York, 1975.

[30] Gordon, G. E. , Zoller, W. H., Proceedings 1st Annual NSF Trace Contaminants 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, Columbia,

Missouri, pp. 167-174, June 1973.

[32] Wedepohl, K. H. , in Origin and Distribution of the Elements , L. H. Ahrens,

ed., Pergamon Press, London, 1968, pp. 999-1016.

[33] Vinogradov, A. P., The Geochemistry of Rare and Dispersed Chemical

Elements in Soils , The English translation. Consultants Bur., New York,

2nd edition, 1959.

23
APPENDIX 1 SITE AND SAMPLE CHARACTERISTICS

Depth

Station No

Location Time of Sampling i n NBS MGS Longitude Lati tude Time Month/Day/Year Feet Density 3 Sal inity

11102 0 76 18 34 39 15 24 17 45 July 6 1979 T 0.9995 3.21

11101 0 76 18 34 39 15 24 17 45 July 6 1979 018 0.9994 3.08

11100 1 76 4 28 3i 32 60 13 30 July 5 1979 T 0.9978 0.95

11099 1 76 4 28 39 32 60 13 30 July 5 1979 025 0.9984 1 .75

11098 53 76 0 17 39 27 25 July 5 1979 T 0.9978 0.95

11097 53 76 0 17 39 27 25 July 5 1979 022 0.9977 0.82

11096 51 75 59 18 39 30 17 12 00 July 4 1979 T 0.9980 1 .22

11095 51 75 59 18 39 30 17 12 00 July 4 1979 on 0.9983 1 .62

11094 2 76 2 38 39 24 49 8 45 July 4 1979 T 0.9979 1 .08

11093 2 76 2 38 39 24 49 8 45 July 4 1979 010 0.9978 0.95

11092 6 76 23 39 39 9 1 15 30 July 3 1979 T 1 .0014 5.74

11091 6 76 23 39 39 9 1 15 30 July 3 1979 019 1 .0015 5.88

11090 8 76 19 2 39 5 54 9 00 July 3 1979 T 1.0012 5.48

11089 8 76 19 2 39 5 54 9 00 July 3 1979 023 1 .0013 5.61

11088 54 76 27 41 38 49 5 15 30 July 2 1979 T 1.0027 7.48

11087 54 76 27 41 38 49 5 15 30 July 2 1979 100 1 .0031 8.01

11086 55 76 23 38 38 48 50 12 00 July 2 1979 T 1 .0028 7.61

11085 55 76 23 38 38 48 50 12 00 July 2 1979 105 1 .0067 12.80

11084 56 76 21 22 38 49 0 7 45 July 2 1979 T 1.0033 8.27

11083 56 76 21 22 38 49 0 7 45 July 2 1979 048 1 .0026 7.34

11082 13 76 29 34 38 39 5 6 30 July 1 1979 T 1 .0035 8.54

11081 13 76 29 34 38 39 5 6 30 July 1 1979 025 1 .0034 8.41

11080 14 76 25 45 38 39 16 15 15 June 30 1979 T 1.0036 8.67

11079 14 76 25 45 38 39 16 15 15 June 30 1979 041 1 .0034 8.41

11078 15 76 18 48 38 39 21 0 15 June 30 1979 T 1 .0032 8.14

11077 15 76 18 48 38 39 21 0 15 June 30 1979 020 1 .0035 8.54

11076 57 76 24 17 38 25 44 8 00 June 30 1979 T 1.0046 10.01

11075 57 76 24 17 38 25 44 8 00 June 29 1979 037 1 .0051 10.67

11074 58 76 21 25 38 25 50 June 29 1979 T 1.0042 9.47

11073 58 76 21 25 38 25 50 June 29 1979 081 1 .0088 15.60

11072 59 76 19 39 38 25 57 June 29 1979 T 1 .0042 9.47

11071 59 76 19 39 38 25 57 June 29 1979 022 1 .0038 8.94

11070 61 76 16 56 38 11 13 June 29 1979 T 1.0043 9.61

11069 61 76 16 56 38 11 13 June 29 1979 042 1 .0066 12.67

11068 60 76 19 38 38 11 19 June 29 1979 T 1.0043 9.61

11067 60 76 19 38 38 11 19 June 29 1979 033 1 .0053 10.94

11066 62 76 13 41 38 11 15 June 29 1979 T 1 .0051 10.67

11065 62 76 13 41 38 11 15 June 28 1979 097 1 .0103 17.60

11064 63 76 8 14 38 11 4Q June 28 1979 T 1.0050 10.54

11063 63 76 8 14 38 11 40 June 28 1979 023 1 .0049 10.41

11062 64 76 57 53 38 12 18 8 30 June 28 1979 T 1 .0042 9.47

11061 64 75 57 53 38 12 18 8 30 June 28 1979 024 1 .0047 10.14

11060 25 76 7 35 38 59 27 10 00 June 27 1979 T 1.0042 9.47

11059 25 76 7 35 38 59 27 10 00 June 27 1979 025 1 .0052 10.81

11058 24 76 12 44 38 0 0 6 00 June 27 1979 T 1.0033 8.27

11057 24 76 12 44 38 0 0 6 00 June 27 1979 044 1 .0065 12.54

11056 23 76 17 25 38 0 0 18 30 June 26 1979 T 1.0031 8.01

11055 23 76 17 25 38 0 0 18 30 June 26 1979 B 1 .0051 10.67

11054 21 75 58 18 38 4 55 12 00 June 26 1979 T 1 .0047 10.14

11053 21 75 58 18 38 4 55 12 00 June 26 1979 030 1.0053 10.94

11052 65 75 55 36 37 58 18 9 00 June 26 1979 T 1 .0056 11.34

11051 65 75 55 36 37 58 18 9 00 June 26 1979 088 1 .0060 11.87

Fil ter

No. & Type

3 M

3 M

1 M

1 M

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

24
Appendix 1, Site and Sample Characteristics continued

Depth Filter

Station No. Location Time of Sampling in No. & NBS MGS Longitude Latitude Time Month/Day/Year Feet Density Salinity Type

11050 76 75 57 3 37 53 5Q . June 24 1979 T 1 .0053 10.94 2 A

11049 76 75 57 3 37 53 50 * June 24 1979 095 1 .0053 10.94 2 A

11048 78 75 55 33 37 5Q 55 * June 24 1979 T 1.0067 12.80 2 A

11047 78 75 55 33 37 5Q 55 * June 24 1979 078 1 .0068 12.94 3 A

11046 80 75 58 5 37 46 53 13:15 June 23 1979 T 1.0053 10.94 3 A

11045 80 75 58 5 37 46 53 13:15 June 23 1979 060 1 .0077 14.13 3 A

11044 81 75 51 41 37 45 36 9:30 June 23 1979 T 1 .0069 13.07 2 A

11043 81 75 51 41 37 45 36 9:30 June 23 1979 B 1.0067 12.80 3 A

11042 85 , 76 4 27 37 41 1 6:30 June 23 1979 T 1.0064 12.40 2 A

11041 85 76 4 27 37 41 1 6:30 June 23 1979 033 1 .0089 15.73 2 A

11040 84 76 7 56 37 40 20 17:30 June 22 1979 T 1.0052 10.81 2 A

11039 84 76 7 56 37 40 20 17:30 June 22 1979 042 1 .0096 16.67 2 A

11038 77 76 7 58 37 52 1 14:00 June 22 1979 T 1 . 0044 9.74 2 A

11037 77 76 7 58 37 52 1 14:00 June 22 1979 057 1 .0084 15.07 2 A

11036 79 76 10 46 37 49 31 10:45 June 22 1979 T 1 .0051 10.67 2 A

11035 79 76 10 46 37 49 31 10:45 June 22 1979 055 1.0091 16.00 2 A

11034 82 76 11 29 37 45 8 8:30 June 22 1979 T 1.0057 11.47 2 A

11033 82 76 11 29 37 45 8 8:30 June 22 1979 075 1 .0100 17.20 2 A

11032 83 76 13 17 37 41 35 14:30 June 21 1979 T 1.0052 10.81 3 A

11031 83 76 13 17 37 41 35 14:30 June 21 1979 041 1 .0080 14.53 2 A

11030 87 76 10 38 37 31 23 10:30 June 21 1979 T 1.0064 12.40 2 A

11029 87 76 10 38 37 31 23 10:30 June 21 1979 030 1 .0099 17.06 2 A

11028 86 75 55 0 37 38 44 7:15 June 21 1979 T 1 .0044 9.74 2 A

11027 86 75 55 0 37 38 44 7:15 June 21 1979 055 1.0050 10.54 3 A

11026 88 76 7 52 37 25 39 13:00 June 20 1979 T 1 .0080 14.53 2 A

11025 88 76 7 52 37 25 39 13:00 June 20 1979 034 1 .0126 20.66 2 A

11024 89 76 1 3 37 24 13 June 20 1979 T 1 .0107 18.13 2 A

11023 89 76 1 3 37 24 13 * June 20 1979 046 1 .0091 16.00 2 A

11022 90 76 10 26 37 22 7 9:30 June 20 1979 T 1.0079 14.40 2 A

11021 90 76 10 26 37 22 7 9:30 June 20 1979 024 1 .0090 15.87 2 A

11020 93 76 10 56 37 18 50 : June 19 1979 T 1.0071 13.34 3 A

11019 93 76 IQ 56 37 18 50 1 June 19 1979 040 1 .0090 15.87 3 A

11018 92 76 21 34 37 20 26 10:30 June 19 1979 T 1.0085 15.20 3 A

11017 92 76 21 34 37 20 26 10:30 June 19 1979 014 1 .0085 15.20 3 A

11016 94 76 6 11 37 19 3 7:05 June 15 1979 T 1.0085 15.20 2 A

11015 94 76 6 11 37 19 3 7:05 June 15 1979 053 1 .0132 21 .46 2 A

11014 91 76 1 6 37 21 31 13:30 June 14 1979 T 1 .0108 18.26 1 A

11013 91 76 1 6 37 21 31 13:30 June 14 1979 B 1 .0110 18.53 2 A

11012 97 76 3 54 37 14 19 9:30 June 14 1979 T 1 .0123 20.26 2 A

11011 97 76 3 54 37 14 19 9:30 June 14 1979 110 1 .0139 22.39 2 A

11010 96 76 7 9 37 10 49 7:00 June 14 1979 T 1 .0110 18.35 2 A

11009 96 76 7 9 37 10 49 7:00 June 14 1979 024 1 .0118 19.60 2 A

11008 100 75 54 53 36 55 46 14:00 June 13 1979 T 1 .0156 24.66 1 A

11007 100 75 54 53 36 55 46 14:00 June 13 1979 065 1 .01 94 29.72 1 A

11006 98 76 03 06 37 01 15 8:30 June 13 1979 T 1.0035 8.54 2 A

11005 98 76 03 06 37 01 15 8:30 June 13 1979 060 1.0064 12.40 3 A

11004 99 76 13 58 37 0 32 16:00 June 12 1979 T 1.0082 14.80 3 A

11003 99 76 13 58 37 0 32 16:00 June 12 1979 055 1 .0103 17.60 3 A

11002 95 76 16 38 37 12 46 0:01 June 12 1979 T 1.0099 17.06 2 A

11001 95 76 16 38 37 12 46 0:01 June 12 1979 035 1 .0091 16.00 2 A

NOTE: T Depth = top sample (described in experimental section); NBS = National Bureau

of Standards sample number; MGS = Maryland Geological Survey site number;

Density = 25 °C; Filter = 1, 2, or 3 - the number of filters used for a 1 liter

sample, A or M — Amicon or Millipore 0.45 micrometer filters were used.

Uncertainty ±0.0002 ^Calculated from density; supplied by EPA

25
APPENDIX 2

Published in Analytical Chemistry, 1983, pp. 1160-1165, by the American Chemical Society

Trace Element Analysis of Natural Water Samples by Neutron

Activation Analysis with Chelating Resin

R. R. Greenberg* and H. M. Kingston

Center for Analytical Chemistry, National Bureau of Standards, Washington, D.C. 20234

Procedures are described to preconcentrate the trace ele- ments In 100, 200, or 500 mL of natural water Into a solid sample of approximately half a gram by using a chelating

resin. These procedures are applicable to both freshwater

and seawater and leave the transition metals and other ele- ments of Interest essentially free from the alkali metals, the

alkaline earth metals, and the halogens. The concentrations

of 15 elements In one seawater sample have been deter- mined by using this separation procedure coupled with the neutron activation analysis technique.

Seawater and other high-salinity natural water samples are among the most difficult materials to analyze for trace ele- ments. The extremely high concentrations of the alkali and

alkaline earth metals and the halogens make direct analysis

by most analytical techniques difficult or impossible, while

the extremely low levels of the transition metals and other

elements of interest make the analytical and sampling blanks

critical. Neutron activation analysis (NAA) has the sensitivity and

accuracy to determine a number of important trace elements

in seawater at their naturally occurring levels (7). 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 other elements whose neutron

activation products have comparable half-lives. A number of preconcentration/separation procedures have

been developed for trace elements in high-salinity water

samples by use of the chelating resin Chelex-100 (2-5). Earlier procedures, however, were only partially successful in elim- inating the alkali and alkaline earth metals, while a more

recent procedure (6) left the elements of interest in a dilute

nitric acid/ ammonium nitrate solution. While the acid-nitrate

This article not subject to U.S. Copyright. Published 1983 by the American Chemical Society

26
matrix is optimal for most spectroscopic methods of analysis, a solid sample is more desirable for NAA. In addition, the above separation procedure makes it difficult or impossible

to analyze several elements, such as chromium and vanadium,

which are held so strongly by the resin that they cannot be

quantitatively eluted. This paper describes a method to prepare solid samples

from 100, 200, and 500 mL of seawater and other natural water samples, using Chelex-100 resin, followed by trace element

determinations with NAA. With this procedure essentially

all of the alkali metals, alkaline earth metals, and chlorine are eliminated while only 0.1% or less of the bromine remains.

This procedure has been used to analyze NBS Standard

Reference Material 1643a (Trace Elements in Water), to ap- proximate a freshwater sample, as well as high-salinity water samples collected near the mouth of the Chesapeake Bay.

Although' one of the major advantages usually associated with NAA is postirradiation chemistry to eliminate the problems associated with reagent blank and other types of contamination, the use of preirradiation chemistry for highsalinity waters has significant advantages. The removal of Na, Cl, and Br greatly reduces the background level of ra- diation 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 personnel,

especially if radiochemistry is used. The preconcentration

of 100-500 mL of liquid to a sample of approximately 0.5 g

increases the sensitivities for most elements. In addition, the use of preconcentrated samples allows more samples to be

irradiated within a single rabbit. Although other, nonchemical,

concentration steps, such as lyophilization, could be employed

prior to irradiation, they are relatively difficult to use with

high salinity water, leave the salts with the elements of in- terest, and 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 results in

a solid sample which eleminates the problems of storage,

irradation, and handling liquid samples.

EXPERIMENTAL SECTION

Reagents. High-purity water and nitric and glacial acetic acids were prepared by subboiling distillation (7) at the National Bureau

of Standards (NBS). All reagents used in the separation process were prepared in this manner and stored in clean FEP Teflon

bottles unless otherwise stated. Ammonium hydroxide 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 diluting

and mixing 60 g of purified glacial acetic acid and 62 g of saturated NH4OH and diluting to 1 L in a 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 ammonium hydroxide. All reagent

and sample preparations were done in a class 100 clean air lab- oratory (8). Chelex-100 chelating resin, 200-400 mesh size, was obtained from Bio-Rad Laboratories. Samples. Approximately 160 L of high-salinity, estuarine water was obtained during high tide at the Virginia Institute of Marine

Science (VIMS), Gloucester Point, VA, located near the mouth

of the Chesapeake Bay. The density of this water was found to be 1.01354 g/mL at 23 °C corresponding to a salinity of ap- proximately 22.4 g/L. The sample was collected with a sub- mersible pump and plastic tubing permanently submerged ap- proximately 100 m offshore from the Institute (6). The seawater was pumped directly into a conventional polyethylene drum which had been cleaned first with hydrochloric acid and then with nitric acid and purified water (9). After filtration through a 0.45-jim

millipore filter with an all polypropylene filter apparatus, the seawater was collected in a polyethylene carboy and acidified to pH 0.2 with high-purity HN03 in order to prevent bacterial growth

(6), to stabilize the trace element concentrations (72, 13), and to

strip any trace elements bound by colloidal particles (4, 5). Since

this sample was taken from the bottom of the water column close to the mouth of the Chesapeake Bay and is made up mostly of Atlantic Ocean water, it will be referred to as seawater.

Aliquots of this stabilized sample have been previously analyzed

by graphite furnace atomic absorption spectrometry (GFAAS)

(6), X-ray fluorescence spectrometry (XRF) (72), and isotope

dilution mass spectrometry (IDMS) (13). Each of these analytical

techniques employed a separation/ concentration step prior to

analysis. In each of these cases the samples were eluted from the

resin and the acid fraction was analyzed.

A number of samples of “Trace Elements in Water” Standard

Reference Material 1643a (14) were processed in the same manner

as the high-salinity water samples. This synthetic water standard was prepared by NBS to represent a low-salinity freshwater sample filtered and stabilized with nitric acid. Various amounts

(8-50 mL) of SRM 1643a were diluted with high-purity water (7) and processed to test the recovery of the system on a freshwater sample of known composition.

Standards. Multielemental standards were prepared in two

ways. First, known quantities of multielemental solutions were

pipetted directly onto Chelex-100 resin in linear polyethylene

(LPE) bags (approximately 400 mg of dry Chelex-100 resin in the ammonium form). The resin used was prepared by using the same column procedure as described below. The resin was allowed to dry under clean air conditions, and the bags were sealed and placed

into second conventional polyethylene (CPE) bags. The second

type of standards was prepared by pipetting known amounts of multielemental solutions onto 5.5-cm Whatman 41 filters. The

filters were air-dried, pelletized, and sealed in two polyethylene

bags, one inside the other (75). Due to the production of "Mo

from uranium fission, the molybdenum and uranium were placed

in separate standards. Column Separation Apparatus. The chromatographic

separation systems consisted of two sets of apparatuses. The QS-Q

Isolab polypropylene column with porous polyethylene support was used in both systems. For the 100-mL and 200-mL samples

sizes, the column was fitted with the QS-S 25-mL conventional polyethylene extension reservoir. When 500-mL samples were

processed, an all-Teflon apparatus was attached to the column

by means of a machined Teflon adaptor and clamp. The adaptor was connected to a 1000-mL Teflon bottle with a modified closure by FEP Teflon tubing. This apparatus is described in ref 6. Column Preparation Procedure. The polypropylene chro- matographic columns were soaked for 1 week in 4 M HN03 and

1 week in 3 M HC1 before use. After the columns were rinsed with water, a slurry of 3.3 mL of hydrated resin (approximately 400 mg dry wt) in the sodium form was packed into the column

for use with the 100- and 200-mL sample sizes. The resin was

washed with three 5-mL portions of 2.5 M HN03 to elute any trace metal contamination. Excess acid was removed by washing the

resin with two 5-mL volumes of water. The resin was transformed

to the NH4+ form by the addition of two 5-mL volumes of 2.0 M

NH4OH. (Note the resin should not be left in the acid form for long periods.) The pH of the last few drops eluted was checked

with pH paper; if they were not basic, additional NH4OH was

added until basicity was achieved. Residual NH4OH was removed

from the resin with two 5-mL water washes. For 500-mL samples, the same procedure was followed but the resin and all reagent

volumes were increased by 50%.

Column Procedure and Dry Resin Preparation. The

seawater samples, which had been filtered and preserved with HN03, were adjusted to a pH range of 5.2-5.7 by dropwise addition of concentrated NH4OH and a solution of 2.0 M NH4OH near

the end point. A few drops of 8 M ammonium acetate were added

to aid in buffering the system in this range. Approximately 3 mL

of the pH-adjusted sample was added to the column to initiate shrinkage of the resin due to the change in pH and ionic form. At this point for the 100- and 200-mL samples, the 25-mL

polyethylene reservoir was placed on the column, and the sample was added in <25-mL increments. The flow rate did not exceed

0.8 mL/min. After the sample had passed through the resin, the

resin was washed with two column volumes of water. Four 10-mL

volumes of 1.0 M ammonium acetate were added to selectively elute the alkali, alkaline earth, and residual halogen elements.

27
1162 • ANALYTICAL CHEMISTRY. VOL. 55. NO. 7. JUNE 1983

After treatment with ammonium acetate the resins were washed

with two bed volumes of high-purity water and allowed to dry

in the columns under a clean air facility. The 500-mL samples were placed in 1-L Teflon bottles attached

to the column by machined Teflon connectors and 1.6 mm i.d. Teflon FEP tubing; this apparatus is described fully in ref 6. The

reagents were increased by approximately 50% except that 70 mL of 1.0 M ammonium acetate was used rather than 60 mL. The

flow rate was adjusted to approximately 1.0 mL/min by using the apparatus.

The samples were left to air-dry in the columns (approximately

1 week) and were each transferred to an acid-washed, 0.025 mm

(1 mil) LPE bag. This bag was heat sealed, and sealed within

a second bag made of 0.075 mm (3 mil) CPE, to prevent con- tamination 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 of conventional polyethylene 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. Irradiation and Counting Parameters. All irradiations were performed in the RT-3 pneumatic tube facility of the NBS Research Reactor (NBSR). In this position the thermal neutron flux

is 5 X 1013 n cm'2 s'

1 and radial flux variations within the rabbit

are <2% (16). The samples were counted with Ge(Li) and Ge(HP)

detectors with active volumes of 60-90 cm3

. A Nuclear Data ND

6620 computer-based analyzer system was used for data collection and reduction. The samples, standards, and blanks for the first (2-min) irra- diation were individually packaged, and each was held rigidly in place within the rabbit with Polyfoam to ensure a reproducible

irradiation geometry. Aluminum and vanadium, as well as upper

limit values for Ti, were determined from a 5-min count beginning about 2 min after irradiation. Manganese was determined from

a 10-min count approximately 2 h after irradiation. The outer CPE bags were not removed to prevent sample contamination between irradiations. The samples were then repackaged for the long irradiation. Ten

to 12 samples, standards and blanks, were placed within a single

rabbit, and occupied two levels. The rabbits were irradiated for 2 h, removed from the reactor, flipped end-over-end, and rein- serted in the reactor for an additional 2 h in order to compensate

for the linear neutron flux drop-off within this facility. The outer CPE bags were removed and discarded, and Cu was determined

in the samples with a 30-min to 2-h count, 1-2 days after irra- diation. The 511-keV y-ray produced by the annihilation of

positrons emitted by ^Cu (t X / 2 = 12-7 h) was used. The only

significant contributor to the °*Cu 511 peak (>0.1%) was ^Na,

which produces 511-keV 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 Na present in the sample was due almost entirely to the LPE bag used to contain

the samples. No difference was observed between the Na levels

in the seawater samples and the blanks. The MNa contribution

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 1368-keV y-rays (0.020) was used to subtract the

24 Na contribution (0.1-1%) from the 511 peak of the samples.

Molybdenum and uranium (using the ^Np daughter of 239U)

were determined by counting the samples 4 cm from the detector, at least 48 h after irradiation. This decay period was necessary

to establish the equilibrium between "Mo and its "Tc daughter.

The Mo concentration in the water must be corrected for the apparent Mo produced by fission. The apparent Mo/U ratio was determined (to approximately 0.5%) from the separate Mo

and U standards irradiated with the samples. In the RT-3 facility of the NBSR, this ratio is 2.0, or 2 Mg of Mo appears to be present

for every 1 Mg of U in the sample. This ratio would be different

at different facilities since the epithermal to thermal cross section

ratio for Mo activation is much greater than for fission. Upper

limit values for Cd were also obtained from the count. Cobalt, Cr, Eu, Fe, Ni, Sc, Sn, Th, U (using the 140Ba, 140La, and 103Ru fission products from ^U), and Zn were determined

by counting the samples 6 weeks after irradiation for 1-3 days

directly against the detector. Since uranium is determined inTable I. Recovery and Characterization of Selected Trace Elements from 100 mL of Seawater % retention 0

ele- ment isotope seawater

effluent

ammonium

acetate

buffer Chelex-100

resin Cd b llsmCd <0.06 <0.06 99.99 ± 0.07 Co b 60 Co 0.30 t 0.04 <0.03 99.5 ± 0.3 Cr s, Cr 4.16 ± 0.26 0.90 ± 0.07 94.94 ± 0.33 Cu b MCu 0.026 ± 0.002 <0.002 99.97 ± 0.03 Fe b "Fe 6.3 ±1.9 0.41 ± 0.01 93.1 t 2.2 Mn b MMn <0.05 <0.02 99.99 ± 0.11 Mo "Mo 1.00 ± 0.17 0.62 ± 0.03 98.38 i 0.19

Ni b 65 Ni 0.09 ± 0.01 <0.004 99.91 ± 0.08 Sc 46 Sc 14.58 ± 0.18 0.59 ± 0.05 84.84 ± 0.22 Sn 1,5 Sn 15.66 ± 0.12 0.49 ± 0.10 83.85 ± 0.16 Th 130Th 12.74 ± 0.42 4.44 t 0.50 82.83 ± 0.34 U i*u <0.2 <0.1 99.8 ± 0.2 V «y 2.36 ± 0.34 0.04 ± 0.03 97.58 ± 0.34 Zn b 65 Zn 0.04 ± 0.01 <0.02 99.97 t 0.03

0 Uncertainties are 1 standard deviation (1 s) for at least three replicate samples. b Reported previously in ref 6.

dependency from the ^U and 238U isotopes, the natural isotopic abundance can be checked. The only standards used for this count were those pipetted directly on the Chelex-100 resin, since variable counting geometries between samples and standards can produce

large errors when counting so close to the detector. Nickel was determined by using the 811-keV y-ray of “Co

produced by an (n,p) reaction on “Ni. This line was not always

visible due to its proximity to the 816-keV 140La y-ray and to the

relatively high background, due in part to 140La. Much better

statistics for Ni as well as for Eu and Sn could be obtained by

recounting the samples about 3 months after irradiation. Tracer Studies. The recovery and behavior of all elements

during the preconcentration and separation procedure, with the exception of Al, Eu, and Ti, were investigated by using of ra- dioactive tracers. The tracers were added to 100 mL of seawater

prior to pH adjustment, allowed to equilibrate for at least 24 h, and were processed in an identical manner to the one previously described for the samples.

The eluted seawater and buffer solutions were collected in polyethylene bottles, adjusted to the same volume (height), and

counted. The resin samples were transferred to similar polyethylene bottles, and nitric acid was added to strip the tracers from the resin. After volume adjustment, these samples were also counted. The three types of samples were compared against each

other and against a standard (unprocessed) spike in the same

geometry.

RESULTS AND DISCUSSION

Retention on Chelex-100. The results of the tracer studies

for the 100-mL samples are shown in Table I. Cadmium, Co, Cu, Mn, Ni, U, and Zn were quantitatively retained by the

resin. The reproducibility of the elements not quantitatively

retained, Cr, Fe, Mo, Sc, Sn, Th, and V was sufficient to allow retention corrections to be made 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%. This increase may

be due to the total absence of Cl” ion to complex with the Sc3+

ion. Other studies (17, 18) indicate that Al, Eu, and Ti are strongly retained by the resin. The small quantities of the tracers in the ammonium acetate buffer are probably due to residual column dead volume from

the effluent. Chromium, Fe, Mo, Sc, Sn, and Th, however, appear to have lost significant quantities in the buffer elution. This is the first evidence of any removal of elements chelated on the resin by the buffer (6, 19). This could be due to changes

in the ionic form or oxidation states of these elements. Certain elemental species can be reduced by ionic exchange resins on

28
ANALYTICAL CHEMISTRY, VOL. 55. NO. 7, JUNE 1983 • 1163

the column. In additions, the capability to form certain anionic species could influence this phenomenon.

Although tracer studies for 200 and 500 mL of water were

not performed, a previous study (6) of the retention of Cd,

Co, Cu, Fe, Mn, Ni, and Zn from 1000 mL of seawater used

essentially the same separation system. The published results indicated no significant differences in recovery for 100- and

1000-mL samples, with the exception of Mn, for which the recovery was only about 50% for the 1-L samples. Further

evaluation of the retention from the larger samples can be

obtained from the analytical results of the 3eawater samples

(discussed below).

It should be noted that the resin is a stronger complexing

agent than, naturally occurring organic chelators that have

been tested (3, 4). Chelex-100 will however differentiate between metal ions and colliodal particles; the colloidal

particles pass through the resin bed. Other researchers have

found acid treatment effective in making colloidally trapped

metal ions available for chelation (4). This preconcentration

and separation technique should only be used for natural

waters stabilized as described with strong acid prior to analysis or treated with acid prior to analysis.

Resin Characteristics. Chelex-100 resin was found to be

extremely well suited for the described procedure. When dried

in the column, the resin takes on rather unique physical

characteristics. When most ion-exchange resins dry, they are crumbly and tend to crack and fall apart. The 200-400 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 away from the walls of the polypropylene

column. The resin was transferred relatively easily to the

polyethylene bag by inverting the column, and only rarely were

small pieces not directly transferred. Separation from Matrix Elements. The observed sep- aration of the elements of interest from the alkali metals and

alkaline earth metals was excellent. The concentrations ob- served in the processed seawater samples were identical with

those in the blanks, where these elements were present within

the polyethylene bags. Reduction factors of >107 for Na and

>108 for Cs were observed. Separation from Cl also was

excellent. Again the samples and blanks appeared identical, with the Cl originating in the bags. The observed reduction

factor for Cl was >106. The separation from Br was good. At least 99.9% of the Br (reduction factor >103

) was removed. The remaining Br

(<0.1% ), however, still produced a 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

with an IR lamp were not successful. The ability of Chelex-100 resin to concentrate the transition metals and a number of additional elements of interest from

an alkaline earth and halogen matrix makes this resin a

valuable tool for the analysis of acid digested botanical and

biological tissue samples. Such materials have been analyzed

by X-ray fluorescence (12) and inductively coupled plasma

atomic emission spectrometry (17) after similar Chelex-100

preconcentration / separation procedures.

Use of 511-keV 7-Ray for Copper Determination. A

number of nuclides, other than “Cu, can emit 511-keV 7-rays

by positron emission, by direct emission of 511-keV 7-rays

or from positron annihilation resulting from pair-production

events. Other positron emitters produced by neutron acti- vation are insignificant, compared to “Cu, when counted 1-2 days after irradiation, due to their half-lives (either too long

or too short), neutron cross sections, isotopic, abundances,

branching ratios, or a combination of these factors.

Table II. Blank Concentrations for 100 mL of Water0 (Concentration ng/mL) b

Al c 16.9 ± 0.9 Ni <0.2

Cd <0.04 Sc 0.00014 ± 0.00002

Co 0.012 ± 0.003 Sn <0.1

Cr 1.79 ± 0.07 Th 0.0005 ± 0.0002

Cu 0.17 ± 0.04 Ti c <1

Eu 0.00012 ± 0.00003 U <0.01

Fe 1.3 ± 0.6 V c 0.12 ± 0.03 Mn c 0.17 ± 0.08 Zn 0.85 ± 0.10 Mo <0.01

a For 200 mL (500 mL) samples the blank values would

be 50% (20-30%) as large. b Uncertainties are 1 standard

deviation (Is) for at least five blanks. c Includes outer

bag; significant reduction could be achieved by removing

this bag after the first irradiation.

Of the elements retained by Chelex-100 resin, the only other positron emitter likely to be present in natural waters 24 h

after neutron irradiation is 65Zn. A simple comparison of nuclear parameters indicates that for equal amounts of Cu

and Zn, the 511-keV activity from “Cu would be approximately 104 times greater than that from 65Zn, 24 h after ir- radiation. In practice the presence of “Zn can easily be de- tected via its 1115-keV 7-ray which is observed with ap- proximately nine times greater intensity than the (“Zn)

511-keV 7-ray (using typical germanium detectors). The

presence of “Zn was not detected while counting any of the water samples for Cu, and the maximvim possible interference was found to be <0.05%. Similar investigations of other

potential 511 emitters indicated that the only significant

(>0.1%) contributors to the “Cu 511-keV peak was “Na. In

addition, some of the samples were counted several times to follow the half-life. Blanks. 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 some elements were significant, compared to the levels of

trace elements in the samples analyzed and to typical seawater. The blank concentrations observed for the 100-mL samples

are listed in Table H These blanks represent a “total process blank” and were prepared with NBS high-purity water (20). This water was treated in a manner identical with that of the

samples, including; filtration in the field, acidification, storage, and chemical manipulation. There was no correction for the elemental concentrations in the water itself, since the concentrations of most of the elements of interest were below the

limits of detection. Some elements were not normally dis- tributed among the blanks. This would be extremely important when single (unique) samples are analyzed.

The relatively high Cr blank is due almost entirely to the LPE 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 transferred before the Cr count The relatively high Mn and V blank values were due primarily

to the other CPE bag which was not removed after the short

irradiation, in order to minimize the possibility of contamination. The blank levels for these elements could be significantly reduced by transferring the samples to new outer bags

after the short irradiation. Aluminum was present in high

levels in both bags. Although better analytical results could be obtained by removing the outer bag prior to counting the sample, the remaining blank from the inner bag would still produce a high level of uncertainty for the single determination. Although no blanks were determined for the 200- and

500-mL samples, they can be calculated from the 100-mL

blanks. Since essentially all of the blank concentrations are contributed by the resin and the polyethylene bags, and not

29
1164 • ANALYTICAL CHEMISTRY, VOL. 55, NO. 7, JUNE 1983

Table III. Trace Elements in Water—SRM 1643a

(Concentration ng/g)

certified values element this work 0 (other)

A1 129 t 10 (121 ± 8) b Cd 10.1 ± 0.5 10 t 1 Co 19 ± 1 19 t 2 Cr 16 ± 2 17 ± 2 Cu 19.1 t 0.6 18 t 2 Fe 88 ± 16 88 ± 4 Mn 30.9 ± 0.6 31 ± 2 Mo 97 ± 6 95 ± 6

Ni 56 ± 8 55 ± 3 V 52 ± 1 53 ± 3 Zn 68 ± 5 72 ± 4

° Uncertainties are 2 standard deviations (2s). b Noncertified value from ref 21.

by the reagents used, the blank values for the 200-mL sample

were half those for the 100-mL samples, as the same amount

of resin and bag material was used. Approximately 50% more

resin was used for the 500-mL sample, although the bag size remained the same, and so the blank values were approximately 20-30% as large depending on whether the element was predominantly in the resin or in the bag(s). This was

determined and the appropriate blank correction made.

Trace Element in Water—SRM 1643a. National Bureau

of Standards Standard Reference Material 1643a was used

to check the analytical procedures and to test the applicability of this procedure to a low-salinity water sample. The results obtained are listed in Table III and agree well with the certified and other values (14, 21). Concentrations for Eu, Sc, Sn, Th, Ti, and U are not reported since these elements were

not added to this SRM. Since tracer studies for A1 were not performed, the agreement between the two A1 values gives

added confidence in the use of this procedure for the deter- mination of A1 in water samples. The relatively large variability observed for Fe was due partially to the counting statistics but was also significantly affected by the variability of the blanks (especially important for the smaller samples),

as shown in Table II. Seawater Samples. The results obtained for the analyses

of the different size samples of seawater are compared in Table

IV. With the exception of Mn, all values agree within the

stated uncertainties, indicating no differences in retention behavior on the resin. Approximately 10% of the Mn appears

to have broken through the resin and was lost from the 500- mL samples. This was not unexpected in view of the ~50%

loss of Mn from the 1-L tracer study.

The results obtained previously by other analytical tech- niques for this material are also listed in Table IV. The

concentrations of Cu, Fe, Mn, Ni, U, and Zn determined by

NAA agree with the values determined by the other analytical

techniques within the stated uncertainties. The agreement between the concentrations determined by

NAA and GFAAS is significant not only from an analytical

view but also from a sample stability perspective. 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 NAA, the sample has indeed been sta- bilized by the addition of nitric acid, at least for Cu, Fe, Mn,

Ni, and Zn. This stability gives added confidence in the

integrity for other natural water samples preserved in a similar manner. Only upper limit values for Cd (0.2-0.3 ng/mL) could be determined for the seawater samples. This was due largely to the high background level of radiation produced by the remaining Br (<0.1%) and by the relatively high level of U

which occurs naturally in seawater. For other samples which

are less saline, the detection limit for Cd would be greatly

improved.

The concentrations of most elements observed in this study were essentially the same, or slighlty elevated above the seawater values reported by Riley and Skirrow (1). The Th

concentration observed (0.00016 ng/mL), however, was much

lower than the previously reported value for seawater (0.01 ng/mL). Since approximately 4 years had elapsed between

collection and analysis, and no long-term study of Th stability has been reported, 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 typically <0.0002 ng/mL near the mouth

of the Bay, and about 0.001-0.002 ng/mL near the top of the Bay.

Although the uncertainties for most elements listed in Table IV do not appear significantly different for the three sample

Table IV. Concentrations of Trace Elements in a Single Seawater Sample (in ng/mL)

NAA results for

as determined

element 100-mL samples 0 200-mL samples 6 500-mL samples 0 by other techniques d

A1 <2 <2 1.1 ± 0.2 Cd <0.3 <0.3 <0.2 0.05 ± 0.01 Co 0.044 ± 0.003 0.045 ± 0.002 0.044 ± 0.002 <0.1

Cr 3.31 ± 0.14 3.20 ± 0.16 3.31 ± 0.16 Cu 2.01 ± 0.05 2.03 ± 0.05 1.97 ± 0.04 2.0 ± 0.1 Eu 0.00012 ± 0.00004 0.00016 ± 0.00003 0.00014 ± 0.00001

Fe 2.1 ± 0.2 2.0 ± 0.3 2.1 ± 0.1 2.1 ± 0.5 Mn 1.89 ± 0.03 1.86 ± 0.02 1.70 ± 0.02 ^ 2.0 ± 0.1 Mo 5.4 ± 0.1 5.4 ± 0.1 5.5 ± 0.1 Ni 1.3 ± 0.2 1.2 ± 0.2 1.2 ± 0.1 1.2 ± 0.1 Sc 0.00095 ± 0.00005 0.00094 ± 0.00005 0.00093 ± 0.00005

Sn <0.3 <0.2 0.12 ± 0.04 Th <0.0002 0.00018 ± 0.00007 0.00016 ± 0.00003

Ti <4 <4 <4

U 1.90 ± 0.04 1.88 ± 0.04 1.91 ± 0.04 1.91 ± 0.01° V 0.45 ± 0.02 0.45 ± 0.02 0.46 ± 0.01 Zn 4.9 ± 0.2 5.0 ± 0.2 4.9 ± 0.2 4.8 ± 0.3

0 Uncertainties are 1 standard deviation (Is) for at least seven samples. b Uncertainties are the analytical uncertainty (Is)

for one sample. c Uncertainties are the average deviation for two samples or the analytical uncertainty (Is), which ever is greater. d Values determined by GFAAS (6) unless indicated. e Value determined by isotope dilution mass spectrometry

(13). f Indicates Mn loss (breakthrough) of ~10%.

30
1165

sizes, the larger samples presented fewer problems and pro- vided individually more reliable data than the 100-mL samples. Not only could the larger samples be counted for shorter periods of time and still result in the same uncertainty

(counting statistics) but also the blank concentrations, which

were critical for some elements in the 100-mL samples, were

greatly reduced for the larger samples.

The detection limits for some elements were significantly

improved in the larger samples. Thorium concentrations could be determined in the 200- and 500-mL samples but not in the 100-mL samples. Aluminum and tin could only be determined

in the 500-mL samples. The main problem with A1 was the

high blank values for the polyethylene bags. One 100-mL

sample was counted for A1 after first removing both bags. A

value of 1.2 ± 0.5 ng/mL was observed, which agrees with the

value determined for the 500-mL samples (1.1 ± 0.2 ng/mL).

The relatively high analytical uncertainty for this 100-mL

sample was due in part to A1 decay during the additional time

required to remove the bags.

Although the 500-mL samples produced better analytical

results, they took considerably longer to prepare, and required

increased quantities of resin and reagents, as well as more

sophisticated equipment. The 200-mL samples, however,

required no additional effort or materials compared to the

100-mL samples. The blank influence was reduced by a factor of 2 since no additional resin or reagents was required. This

reduced blank influence, as well as the improved counting

statistics, enabled the determination of Th in the 200-mL

sample and reduced the uncertainty for several other elements. CONCLUSION

The application of the Chelex-100 resin separation preconcentration, with the direct use of the resin itself as the final sample for analysis, is an extremely useful technique for NAA.

The elements demonstrated to be analytically determinable

from samples of high salinity waters are Al, Co, Cr, Cu, Eu,

Fe, Mn, Mo, Ni, Sc, Sn, Th, U, V, and Zn. The 500-mL

samples, although involving more reagents and manipulation, gave the greatest sensitivity and accuracy, although a sig- nificant increase in time and effort was required. A sample

size of 200 mL was found to be the optimum, doubling the

sensitivity over the 100-mL samples but requiring no additional effort, however, the 500-mL sample size may be nec- essary to further reduce the blank for some elements when

analyzing open-ocean water samples. The determination of Cr and V by this technique offers significant advantages over methods requiring aqueous final forms, in view of their poor

elution reproducibility. The removal of Na, Cl, and Br prior

to irradiation allows the determination of other elements

having short and intermediate half-lives, and greatly reduces

the radiation dose received by personnel. This procedure has

been successfully applied in a study of more than 100 samples

collected throughout the entire length of the Chesapeake Bay.

The salinity of these samples varied from that of freshwater

to that of Atlantic Ocean water. Registry No. Al, 7429-90-5; Co, 7440-48-4; Cr, 7440-47-3; Cu,

7440-50-8; Eu, 7440-53-1; Fe, 7439-89-6; Mn, 7439-96-5; Mo,

7439-

98-7; Ni, 7440-02-0; Sc, 7440-20-2; Sn, 7440-31-5; Th,

7440-

29-1; U, 7440-61-1; V, 7440-62-2; Zn, 7440-66-6; Chelex-100,

11139-85-8; water, 7732-18-5. LITERATURE CITED

(1) Riley, J. P.; Sklrrow, G. ' Chemical Oceanography"; Academic Press: New York, 1975; Volumes I and III. (2) Riley, J. P.; Taylor, D. Anal. Chlm. Acta 1968, 40, 479.

(3) Davey, E. W.; Soper, A. E. In "Analytical Methods In Oceanography”;

Gibbs, T. R. P., Jr., Ed.; American Chemical Society: Washington, DC,

1975; Adv. Chem. Ser., No. 147.

(4) Florence, T. M.; Batley, G. E. Talanta 1976, 23, 179; 1977, 24, 151.

(5) Lee, C.; Kim, N. B.; Lee. I. C.; Chung, K. S. Talanta 1977, 24 , 241.

(6) Kingston, H. M.; Barnes, I. L.; Brady, T. J.; Rains, T. C.; Champ, M. A. Anal. Chem. 1976, 50, 2064.

(7) Kuehner, E. C.; Alvarez, R.; Paulsen, P. J.; Murphy, T. J. Anal. Chem.

1972, 44, 2050.

(8) Useller, J. W. NASASP-5074, Office of Technology Utilization NASA,

Washington, DC, 1969.

(9) Moody, J. R.; Undstrom, R. M. Anal. Chem. 1977, 49, 2264.

(10) Maienthal, E. J.; Becker, D. A. NBS Tech. Note (U.S.) 1976, No. 926.

(11) Moody, J. R.; Rook, H. L.; Paulsen, P. J.; Rains, T. C.; Barnes, I. L.; Epstein, M. S. NBS Spec. Publ. (U.S.) 1977, No. 464.

(12) Kingston, H. M.; Pella, P. A. Anal. Chem. 1981, S3, 223.

(13) Kelly, W. R.; Fassett, J., personal communication, 1981.

(14) National Bureau of Standards (U.S.), Certificate of Analysis, SRM

1643a, 1980.

(15) Greenberg, R. R. Anal. Chem. 1979, 51, 2004.

(16) Becker. D. A.; LaFleur, p. D. J. Radloanal. Chem. 1974, 19, 149.

(17) Jones, J. W.; Capar, S. G.; O'Haver, T. C Analyst (London) 1962, 107

,

353.

(18) Strachen, D„ personal communication, 1981.

(19) Kingston, H. M. "Quantitative Uttratrace Metal Analysis of High Salnity Water Utilizing Chelating Resin Separation", Interagency Energy-Envi- ronmental Research and Development Program, Report, EPA/NBS,

EPA-600/7-79- 174, 1979.

(20) Murphy, T. J. NBS Spec. Publ. (U.S.) 1978, No. 422.

(21) Undstrom, R. M. Internal NBS Communication, Report of Analysis 5192, 1979.

Received for review October 27, 1982. Accepted March 10, 1983. Certain commercial equipment, instruments, or materials are identified in this paper in order to adequately

specify the experimental procedure. Such identification does not imply recommendation or endorsement by the National

Bureau of Standards, nor does it imply that the materials or equipment identified are necessarily the best available for the purpose.

31
APPENDIX 3

Published in ANALYTICAL CHEMISTRY, December 1978, pp. 2064-2070, by the American Chemical Society

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. Brady, and T. C. Rains

National Measurement Laboratory, Center for Analytical Chemistry, Inorganic Analytical Research Division, National Bureau of Standards, Washington, D.C. 20234

M. A. Champ

The American University, Washington, D.C. 20016

A method is described for determining Cd, Co, Cu, Fe, Mn,

Ni, Pb, and Zn in seawater using Chelex 100 resin and graphite

furnace atomic absorption spectrometry. The pH of the seawater 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 Bay and seawater from the Gulf

of Alaska.

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. It

is beyond the scope of this paper to discuss all of these pa- rameters; however, 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 (I), neutron

activation (2, 3), spectrophotometry (4), anodic stripping

voltammetry (5), and atomic absorption spectrometry (6-8). However, each of these analytical techniques requires a

preliminary separation. Fabricand et al. (9) 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 direct determination of trace elements in seawater at concentrations below 5 *tg Lr1

. Usually 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 (10). Preconcentration techniques which have been used are coprecipitation (11), chelation and extraction (12), and

chelating ion-exchange resin (10, 13). Most of these isolation methods require large volumes of chemicals which can lead

to high blanks unless the reagents have been carefully purified.

Of the presently used preconcentration techniques, Chelex

100 chelating resin has been shown to be efficient and yields

low analytical blanks (14). Applications of Chelex 100 resin

for trace metal preconcentration from seawater have been

reviewed by Riley and Skirrow (10). Chelex 100 is a strong

chelator and removes metal ions from most known naturally

occuring chelators in seawater (14-16). The resin will not, however, remove metals held in organic and inorganic colloids which can be present even after ultrafiltration. Precautions

32
ANALYTICAL CHEMISTRY, VOL. 50, NO. 14, DECEMBER 1978 • 2065

Table I. Instrumental Parameters 'P&E 603 HGA-2100

element

wavelength, nmSBW, nm

scale expansiondrying, T-secc charring

T-sec atomizationT-sec gas Cd 228.8 0.7 1 100-30 200-20 2100-7 Ar°

Co 240.7 0.2 2 100-30 500-30 2700-7 Ar°

Cu 324.7 0.7 1 100-40 700-30 2500-6 Ar a Fe 248.3 0.2 2 100-30 600-30 2700-7 Ara Mn 279.5 0.7 2 100-30 300-30 2700-7 Ara Ni 232.0 0.7 5 100-30 1000-30 2700-6 Ara Pb 283.3 0.7 3 100-40 400-30 2200-7 Arb Zn 213.9 0.7 0.5 100-30 500-20 2000-7 Arb

a Interrupt mode. b Normal mode. c Note: T = temperature.

must be taken to destroy such colloids prior to collection of the ions by the resin. Florence and Batley have destroyed

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 by the resin (15, 16). While excellent recovery and low analytical blanks are achieved, a relatively

high concentration of Na, K, Ca, and Mg are retained with

the trace metals. The concentration of 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 al- kaline earth ions occupy the resin sites not occupied by the

transition metals and are co-eluted with the metals when using acids (13). The complete separation of the alkali and alkaline earth metals from the trace metals in seawater has not been pre- viously accomplished using Chelex 100, which has restricted

its use. While the salts remaining after preconcentration do

not interfere with instrumental techniques such as flame

atomic absorption (10) or polarography (15-17), they do inhibit instrumental techniques which are more susceptible to matrix

interelement effects such as flameless atomic absorption (18), neutron activation analysis (19), optical emission spectrometry

using inductively coupled plasma or electrode plasma (dc arc)

(20), and spark source mass spectrometry (21). With the development of the graphite furnace for AAS, it

is now possible to determine 10-9 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 trace metals in seawater

are present as chlorides, which have a lower volatilization temperature. T herefore, 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 is removed during the ashing step using

matrix modification (22), residual calcium and magnesium

chlorides remain to interfere with the analyte during

atomization.

The research presented here describes a technique for the separation and preconcentration of Cd, Co, Cu, Fe, Mn, Ni,

Pb, and Zn from Na, K, Ca, and Mg in seawater using a Chelex 100 resin column and the subsequent determination of these

trace elements by graphite furnace atomic absorption spec- trometry (GFAAS).

EXPERIMENTAL

Reagents. High purity water, nitric and glacial acetic acids were prepared using subboiling distillation at the National Bureau

of Standards (NBS) (23). All reagents used in the separation

process were prepared and stored in clean FEP Teflon bottles unless otherwise stated.

Ammonium hydroxide 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 purified glacial acetic acid and 62 g of saturated NH4OH

and diluting to 1 L in a polypropylene volumetric flask. The

acidity was adjusted to pH 5.0 by dropwise addition of HN03 and/or NH4 OH. All reagent and sample preparations were done

in a class 100 clean air laboratory (24). Chelex 100 chelating resin, 200-400 mesh size, was purchased

from Bio-Rad Laboratories. The radioactive tracers 59Fe, MMn, and “Zn in 0.5 N HC1 were

purified reagents obtained from the Chemical and Radioisotope

Division of ICN. The “Co, and the short lived isotopes, MCu and

65Ni, were made by the Neutron Activation Analysis Group at NBS from “five-9’s” pure metals and dissolved in nitric acid. The

109Cd and 210Pb were obtained by the Activation Analysis Group

from other sources and analyzed using pulse height analysis for radiochemical purity before use. All standard stock solutions for AAS were prepared from high

purity metals or salts in subboiling distilled NBS acids as described by Dean and Rains (25). Working solutions were prepared as needed. Counting Apparatus. The 7-ray counting of the elemental

tracers was done utilizing a 7.6 cm X 7.6 cm Nal(Tl) crystal and

associated electronics. Seawater. The seawater was obtained during high tide at the

Virginia Institute of Marine Science (VIMS), Gloucester Point,

Va., on the Chesapeake Bay. The sample was collected with a submersible pump and plastic tubing permanently submerged

approximately 100 m offshore from the Institute. The seawater was pumped directly into a conventional polyethylene drum which

had been cleaned first with hydrochloric and then with nitric acid and purified water prior to use (26). After filtration through a

0.

45-#im millipore filter using an all polypropylene filter apparatus, the seawater was collected in a polyethylene carboy and acidified

(to 0.6 M in HN03) with high purity HN03 to prevent bacterial growth, to stabilize the trace element concentrations (27, 28), and

to strip any trace elements bound by colloidal particles (15, 16). AAS Apparatus. The instrumental system used in this study

consists of a Perkin-Elmer Model 603 atomic absorption spec- trometer with HGA-2100 graphite furnace (GFAAS). The 25-^L

aliquot of sample was introduced into the furnace with the AS-1

autosampler. The instrumental parameters are given in Table

1. Column Separation Apparatus. The Isolab QS-Q polypropylene column with porous polyethylene resin support was

used for 100-mL and 1-L sample volumes. Although the same

column was used for both sample volumes, the amount of resin and reservoir systems were entirely different. For the 100-mL

sample, the QS-S 25-mL conventional polyethylene extension

funnel was attached to the column to act as a reservoir for the sample. For a 1-L sample the reservoir was a 1-L Teflon (FEP) bottle inverted and modified with a machined Teflon (TFE) closure

insert containing a microbore venting tube and outlet tube. The

outlet was connected to a valve (TFE) by 1.59-mm (*/ 16 in.) i.d. Teflon (FEP) tubing connector and linked to the reservoir with

a specially machined mount (TFE) which sealed the column into the closed system. The mount contained a vent (sealed with nylon

33
2066 • ANALYTICAL CHEMISTRY, VOL. 50, NO. 14, DECEMBER 1978

as it changes ionic form and pH. This shrinkage results in a resin volume of approximately one half of its original volume. After

the completion of this transformation was observed (2 to 3 min),

the remaining seawater was added to the reservoir as needed to keep it filled; the flow rate was approximately 0.8 mL/min. To

selectively elute Na, K, Ca, and Mg, and replace them with NH/,

40 mL of 1.0 M ammonium acetate was added to the column in 10-mL aliquots. At the completion of the ammonium acetate

addition, 10 mL of water was added to remove residual ammonium

acetate. The transition metals were then eluted using 7 mL of

2.5 M HN03 and collected into clean preweighed 10-mL conventional polyethylene bottles. The bottles were capped with clean polyethylene lined caps and reweighed to determine the weight

of the effluent accurately.

The procedure for the 1-L samples was the same as the 100-mL

samples with minor alterations due to the apparatus (see above). The sample (1018.0 ± 0.5 g) 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 was fitted with

a modified closure (see Figure 1). The bottle was inverted and

the air purged from the system by means of the vent on the column mount. The flow rate was adjusted using the valve and

the height of the reservoir. The flow rate was kept to less than

0.2 mL/min until the shrinkage of the resin was complete. Then

the flow rate was increased to 1.0 mL/min and left overnight to flow through the column. After passing the sample through the column, the valve and tubing were removed at the connector above

the column mount and replaced with a smaller reservoir containing 70 mL of 1.0 M ammonium acetate. The flow rate was adjusted

to 0.5 mL/min until the reagent was exhausted. The resin was

then washed with 10 mL of water. The transition metals were

eluted with two 5-mL portions of 2.5 M HN03 into preweighed

polyethylene bottles as previously described.

Figure 1. Apparatus used (or holding and delivering large volumes of seawater at a controlled rate to Chelex 100 resin. The apparatus

(excluding the column and clamp) was fabricated from Teflon FEP (*) or Teflon TFE (t) which has desirable nonwetting and noncontaminating

properties

screw, allowing the removal of air from the system) as well as an

inlet and was tightly clamped to the column using the lip on the column at point B (See Figure 1). The clamp (a modified glass

joint clamp) and mount provided a seal which allowed the reservoir to be raised above the column to obtain enough pressure to control the flow rate using the pressure of the raised reservoir and the

valve (Figure 1). Column Preparation and Purification Procedure. The

column preparation procedure consisted of precleaning the columns in 1:4 HC1 and then in 1:4 HN03 for one week in each

bath and then rinsing the columns with water after each acid wash. The column was loaded with a slurry of Chelex 100 resin, 200-400 mesh size (sodium form). For 100-mL seawater samples, 3.2 to

3.4 mL of resin was used which covered the lower barrel of the column from point B to point C in Figure 1. For 1-L samples,

5.8 to 5.9 mL of resin was used which filled the column from point

A to point C in Figure 1. The resin was washed with 15 to 20 mL of 2.5 M HN03 (for the small and large resin volumes, re- spectively), in 5-mL portions to elute any trace metal contamination present in the resin. Then two 5-mL volumes of water were used to rinse the resin of excess acid. To transform the resin to the NH4 + form, 10 to 15 mL of 2.0 M NH4 OH was added in 5-mL volumes. After checking the pH of the effluent to ensure

basicity, the column was then rinsed with 10 to 15 mL of water

to remove the excess NH4 OH.

Column Preconcentration and Separation Procedure. For

the 100-mL seawater sample, 101.8 ± 0.2 g was weighed directly into a clean 250-mL Teflon (FEP) beaker and the pH adjusted

to 5.0 to 5.5 with the dropwise addition of NH4 OH. If a spike

(natural or radiochemical) was to be added, it was added prior

to the adjustment of the pH to equilibrate the ions in the acid media; the solution was allowed to equilibrate for a minimum of

1 h after the addition of any spike. Then 0.5 mL of 8 M am- monium acetate was added to aid in buffering the system. Any

necessary agitation of the solution was done with a Teflon stirring rod. A small amount of the seawater was added to the reservoir and column to allow the resin to undergo its natural shrinkage

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 electrothermal device. However, in reality this has not been proved to be true unless the samples are taken from heavily polluted areas. A sample

from the Chesapeake Bay was analyzed 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. Also, when the sample

is evaporated, a small amount of solution may be trapped in the salt crystal lattice which could result in losses due to splattering during the atomization cycle. The absorbances obtained for lead and nickel were very

erratic due to the smoke produced during atomization. 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 modification

to the Chesapeake Bay sample, Cd, Co, Cu, Fe, Mn, and Zn

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 choose a separating agent that can

be purified to produce a low analytical blank. Also, the separating agent should not produce any adverse effects on

the analytes in the GFAAS analysis. The ammonium ion

reacts similarly to the alkali elements, and ammonium nitrate or acetate can be produced from high purity reagents. While both ammonium nitrate and ammonium acetate remove sodium and potassium at identical rates, ammonium

nitrate produced tailing of the calcium and magnesium which

34
ANALYTICAL CHEMISTRY. VOL. 50, NO. 14. DECEMBER 1978 • 2067

Table II. Concentration of Alkali and Alkaline Earth

Metals in Seawater before and after Separation on

Chelex 100 Resin Column

Mg/mL

sample Na K Ca Mg

original 6200 267 283 742

after separation 0 washb h2 o

nh4 no 3 NH.COOCH,

320

0.3

1.0

10

0.7

2.0

350

83

0.25

63.1.3 <0.05

a 100 mL of seawater preconcentrate into 7 mL of 2.5 M HN03

. b Column washed with 50 mL of a given

eluent.

I OM NH,COOCH, pH 5.2 |h,o|- 2 5 M HNOj -j — 10M NH.NO, pH 5.2 |

Figure 2. Comparison of ammonium acetate vs. ammonium nitrate

for the separation of calcium from a Chelex 100 resin column which has previously chelated 100 mL of seawater

left appreciable quantities of these alkaline earths in the final HNO;) effluent (Figure 2) (Table II). However, ammonium

acetate eluted calcium and magnesium from the column with

tailing of only 1 to 2 bed volumes (Figure 2). Manganese,

which has the smallest selectivity coefficient of the transition metals of interest, was not eluted at pH 5.0 by ammonium

acetate or ammonium nitrate. A relatively high concentration

of ammonium acetate in the 2.5 M HN03 effluent produced

a suppression of several of the analytes by GFAAS; however,

the problem was alleviated by washing with 5 to 10 mL of water prior to the stripping of the column with the 2.5 M

HN03 (Figure 2). There is a contribution to the removal of calcium and

magnesium from the resin by the acetate anion which does

not appear with the nitrate ion. Sodium and potassium are

replaced by the ammonium ion, but this cation is only partially

responsible for the complete separation of chelated calcium

and magnesium using ammonium acetate. Effect of pH on the Separation. A study of the pH of the separating agent (1 M ammonium acetate) showed that

a minimum pH of 5.0 was required to retain the transition metal ions on the Chelex 100 resin while removing the alkali and alkaline earth ions. Below pH 5.0, it was found that the

transition metals were eluted by the 1 M ammonium acetate. From pH 5.0 to 5.5, the transition metals Cd, Co, Cn, Fe, Mn,

Ni, Pb, and Zn were retained by the resin while the Na, K,

Ca, and Mg were quantitately eluted (see Figure 3). The chelating efficiency of Chelex 100 increases for the

transition metals from pH 4 to 5 and reaches an optimum at

ml

lO/VJ NH4 COOCH3 2.5M hno3

Figure 3. Comparison of ammonium acetate elution of Ca, Mg, and Mn in the pH range of 3.0 to 5.0. The graph depicts percent of the

total column content of an element eluted with volume

approximately pH 5.0. For most of the transition elements,

this optimum efficiency remains for an increase of several pH

units. However, the chelating efficiency of Chelex 100 for Co

and Cu has been shown to decrease above pH 6.0 ( 29-32). The chelation efficiency of Chelex 100 for Ca and Mg has

been reported to be similar to those of the transition metals

increasing with pH to a maximum at pH 5 in low ionic strength solutions ( 30, 33). However, in high ionic strength

solutions of sodium chloride, there exists a minimum in the

chelation of Chelex 100 for both Ca and Mg 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 for both the preconcentration of the transition elements from the seawater and

the elution of the alkali and alkaline earth elements from the

resin using the ammonium acetate. Separation Parameters for Both 100-mL and 1-L Seawater Samples. The separation parameters, as described

in the Procedure section, are represented graphically for a 100-mL sea water sample in Figure 4, and for a 1-L sample

in Figure 5. The difference between the two systems is approximately double the amount of resin for the 1-L sample.

The larger amount of resin was found to be necessary for quantitative retention of this larger volume, but is still rather small considering a 10-fold increase in the total ionic content

of the larger sample. An increased volume of ammonium

acetate was required for the removal of the greater quantity

of salts occupying more residual sites. Also, a larger volume

of water is required to wash the residual ammonium acetate from the column prior to transition metal elution with nitric

acid. The elimination of ammonium acetate was found to be

necessary to prevent both buffering of the acid wash and a suppression of the GFAAS signal caused by the acetate in the subsequent analysis. The acid fraction did not undergo tailing 35
2068 • ANALYTICAL CHEMISTRY, VOL. 50, NO. 14, DECEMBER 1978

|

I 0(A NHjCOOCHj pH 5 2 jH,o|— 2.5M HNOj —

j

Figure 4. Represents the separation obtained using 1.0 M ammonium

acetate at pH 5.0 to 5.5 for the transition metals from Na, K, Ca, and Mg chelated in a column of Chelex 100 from a 100-mL seawater sample

I

I OM NH.COOCHj pH SO |h,o) 2.5(4 HNOj|

Figure 5. Represents the separation obtained using 1.0 M ammonium

acetate at pH 5.0 to 5.5 for the transition metals from Na, K, Ca, and Mg chelated on a column of Chelex 100 from a 1-L seawater sample

from the transition metals as seen by atomic absorption or by radio tracer studies. The Chelex 100 resin in the presence

of 2.5 M HN03 does not chelate the transition metals and they

are eluted simultaneously into a single small volume of acid. Chelex 100 resin is a dynamic resin, and in the ammonium

form at a pH of 7 to 14, the resin shrinks to approximately

V2 of its original volume when subjected to the seawater sample at pH 5.0 to 5.5. The particle size and subsequent flow

rate were also reduced and the use of the column apparatus

for 1-L samples became necessary to increase the pressure of the sample to obtain a realistic flow rate for both the sample

and ammonium acetate. The flow rate of 1 mL/min was

attained by adjusting the Teflon valve and reservoir height

simultaneously to control the pressure. The residual volume

which would retain any sample in the entire apparatus was

estimated at less than 0.10 mL. The use of all Teflon

components in contact with the sample affords the nonwetting

characteristics and noncontaminating nature of this fluoro- carbon which can be scrupulously cleaned in acid (26). Another important benefit of this apparatus is that during

the preconcentration onto the Chelex 100, the sample and

column are protected from contamination from the envi- ronment; the only entrance into the system is a microbore tube which can be fitted with a filter to exclude particulate contamination. These characteristics make the column apparatus

very attractive for field or shipboard use to prevent con- tamination.

Radiochemical Study. Radiochemical tracers were used

to gain specific information about the behavior of each ion during preconcentration and separation using the Chelex 100. The tracers were added to the seawater as one radioisotope 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 polyethylene bottles. The 1-L samples

were collected in 250-mL bottles and the 100-mL samples were

collected in 125-mL bottles. 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 10-min periods for 7 radiation only (Table III). The counting statistics for each element were optimized by energy discrimination. The concentration of

tracers used gave from 106-107 counts in a 10-min period while background was kept to 102-103 counts during the same

period. The statistical error was obtained using the following

equation (34, 35):“ 100 * V*. +

where Qc = percent experimental error corrected for background, k = number of standard deviations, N = cpm = counts

per minute or period unit time, s = sample including back- ground, and b = background.

This technique enabled the use of ^Cu and “Ni short-lived isotopes as well as

,S9Fe and HMn intermediately-lived isotopes since counting of all fractions could be completed in 40 min.

The error caused by the decay of these isotopes over the course

of the experiment was eliminated; nickel which has a half life of only 2.6 h, decayed beyond usefulness over the 1-day period

of the 1-L experiment.

The counting technique was checked for total recovery using “Zn. The tracer was added to 250 mL of the seawater sample

and counted prior to manipulation. This volume was then

added to 750 mL of seawater and treated as a 1-L “Zn spiked seawater sample. The final acid volume was then counted at the end of the separation as previously described. The total quantity obtained agreed for both the acid fraction and total recovery, 99.99 ± 0.12 and 100.1 ± 0.12, respectively. Thus,

the counting of all effluent fractions and the column itself allows the specific identification of all losses, as well as the

total recovery of the element of interest in the acid fraction. The ammonium acetate separation did not remove a detectable amount of any trace metal with the possible exception

of Fe which could have been in the residual volume from the seawater effluent. Thus, the separation does not affect the maximum efficiency of the concentration alone, and the Na,

K, Ca, and Mg can be eliminated with the same efficiency as the traditional concentration alone. The majority of any minute losses Pb 1.4%, Co 0.3%, and

Fe 6.3% is due to incomplete removal of the transition metal

ions from the seawater. The chelation efficiency of both “Co

and 59Fe was studied by Callahan et al. (32). They found that the two oxidation states of cobalt and iron reacted similarly

and that 100% retention of cobalt and iron could only be

achieved by reduction of Co(III) to Co(II) and Fe(III) to Fe(II) using sodium dithionite (Na2S204 ) at pH 5.0 to 5.3. In natural seawater the approximate concentration of Co(II) was found

to be 96% of the total cobalt. They obtained 96 to 99%

retention for cobalt and 95% for iron without any attempt

to reduce the trivalent ions, which is in agreement with our

findings.

The radiochemical tracer experiments for Cd, Cu, Fe, Ni,

and Zn were repeated several times and all values fell within

the calculated error limits with the exception of those for iron. 36
ANALYTICAL CHEMISTRY, VOL. 50, NO. 14, DECEMBER 1978 • 2069

II

SE

W *

'aE

CO

o

o

to

.S

%

CO

4) cn

42s«

E

jjt S

e

•2 j

S

E

« ° I

°

TJC

COc . E

3

O

o

SC ^

B « O n oo 3 hOS

a

* z

c

* fi C •- E “

J3o

<D

U —

« cE

02

%

aX

u

a

§

4)>

0«

4) CP

5 x c « O <u o O £

r4UE

a

41 z

c

4)3cCm

41U

4)

CO 05

C£> <N CO O TH O 05 6 6 q CO N W

+1 +t : «

©<=>'«

05 <75 • . (N +' +* *

05 05 00 t- 00 CO

05 05 05 t> t> e4

05 05 05 05 05 05

04

i—i ^ o o

o o

V V

cc co O O

o o

V V

IN rH o o

o o

v V

COO 00 1-c O <N O

o o 9 o

+1 -H ® +1 H N * H O H Cl CO

O CO o d

t- -H +C O CO CO o

O O 05 dodo

V V

COO 'O' Ohio

-JOOl

Ti Ori

C^ CO +l +' H H o M

o o

r-H t> CO O

>>

-4-> c o i m

t> 05 r-H 00 CO O O rH O O 00 h

il dodddt”^ 0)o

+1 +1 -H +1 -H OON c

53 Sis 05 CO 05 rH t> +l +1 +' ia <» 0505050505^l/5rH -C C4 05 05 05 05 05 00 05 CO E- 0505050505050505 •O

CO rH eo o o

rH

. o' o

Cfl Tf ® -H -H CONOON * t> rH OOOOONHN odd o' dodo

V V v v v

o

o

•cf (N +l CONNOOHWH OOOOOOO'O' dddo’dddd

V V V V V V V

C'O lOH

o o o O © O © •>*

. do'l®® * . . . O O rH 05 00 + +

CO CO 'O' 05 CO +l +l +l OOOOOOCOCO dodddridcd

V V

S C 5 © 3 £ 0 4) rNSzorob.

JO

C4 ETable IV. Trace Elements in Chesapeake Bay

concentration, ng/mL“

element blank seawater Cd <0.01 0.05 ± O.C Co <0.1 <0.1

Cu <0.1 2.0 ± 0.1 Fe 0.2 ± 0.1 2.1 ± 0.5 Mn <0.1 2.0 ± 0.1 Ni <0.1 1.2 ± 0.1 Pb <0.1 0.3 ± 0.2 Zn <0.05 4.8 ± 0.3

a Replicate analysis of four samples.

Iron exhibited a 2% variation around the average value (Table

III). This could be due to altered ratios of Fe(II) and Fe(III) between samples tested. GFAAS Determination of Trace Elements in Seawater

from the Chesapeake Bay. The reliability of the proposed

separation and preconcentration method was tested by making

replicate analyses on a sample of seawater. These samples

were processed as described in the Separation and Preconcentration Procedure. Then the 8-10 mL of 2.5 N HN03 effluent collected was analyzed for the trace elements by

GFAAS. The instrumental conditions for drying, charring,

and atomizing (Table I) for each analyte were optimized to obtain the maximum sensitivity and precision with the minimum of interferences. The samples (25 mL) were in- troduced into the graphite furnace with the AS-1 which

improved the precision of the analysis with the minimum

amount of contamination. It was necessary to preclean each

sample cup from the AS-1 with 20% HN03 to remove trace contaminants. Pyrolytic and nonpyrolytic coated graphite

tubes were used in this study. The life of the pyrolytic coated tube was extended by a factor of three over the nonpyrolytic coated tube in the presence of 2.5 M HN03

. Background

correction with the deuterium arc lamp was used for each

analyte. For each analysis the hollow cathode lamp was turned on and allowed to stabilize (15 to 60 min). Working standard

solutions of each analyte were prepared in 2.5 M HN03, and

then a three to five point calibration curve was established using the optimum instrumental conditions. After the cal- ibration curve was established, the unknowns were determined

using a sample bracketing technique. As a check for chemical

interferences, each sample was tested by the single standard

addition method (36) and no chemical interferences were

encountered. The results are given in Table IV. Cobalt was

not detected using a 100-mL sample. To obtain an analytical value for cobalt in the Chesapeake Bay Water, a 1-L sample

would be required to be separated and preconcentrated. Some

difficulty was encounted in the GFAAS determination of iron. Iron is known to form carbides in the graphite furnace which

produce erratic results. Also, a high reagent blank was obtained (see Table IV) whereas the reagent blanks for the other elements were below our detection limits. The lead values

are close to the detection limit using a 100-mL sample. With

a 0.5- to 1-L sample, the precision of the lead analysis could be improved.

Recovery of Trace Elements Added to Chesapeake Bay

Seawater. Since there are no samples of seawater with

accurate analytical values for the trace elements under study, the accuracy of the GFAAS technique was checked by adding

0.5 to 2.0 ng/mL of the trace elements to six samples of seawater and processed as previously described. Recoveries

of 90 to 117% were obtained (Table V). The high recovery

value for zinc was due to the low concentration added to the

samples. Since zinc is so sensitive by GFAAS, a 1- to 10-fold dilution of the 2.5 M HN0:) effluent had to be made. Since

37
2070 • ANALYTICAL CHEMISTRY, VOL. 50, NO. 14, DECEMBER 1978

Table V. Recovery of Trace Elements Added to Samples of Seawater by GFAAS

concentration, ng/mLa

av.

ele- recovery, ment present added found %

Cd 0.05 0.5 0.54 i 0.02 98

Co <0.1 1.0 1.07 ± 0.02 107

Cu 2.0 1.0 2.9 ± 0.07 97 Fe 2.1 2.0 3.7 ± 0.4 90

Mn 2.4 2.0 4.2 0.04 95

Ni 1.2 2.0 3.2 ± 0.1 100

Pb 0.3 1.0 1.4 ± 0.07 108 Zn 4.8 0.5 6.2 i 0.09 117

0 Replicate analysis of six samples.

a dilution was required for GFAAS, the original spikes added

to the seawater were too low to obtain accurate recoveries. The

recoveries of the other trace elements are consistent with the known reproducibility of the GFAAS at these concentration

levels. Application of the Technique to Alaskan Seawater

Samples. In addition to the one homogeneous Chesapeake

Bay water sample, other seawater samples were also analyzed

for Cd, Mn, Ni, and Pb. These samples were obtained from

the Gulf of Alaska and ranged in depth from surface to 1500 m. These samples were treated in the same manner and no

alteration in the separation technique was necessary. The

trace metal concentrations from Alaskan seawater were found

to be generally lower in concentration over those of the Chesapeake Bay. The values for Pb and Mn were found to be consistently 1 to 2 orders of magnitude below those reported here for these same elemental concentrations in the Chesapeake Bay.

CONCLUSION

The application of Chelex 100 resin and GFAAS used in this investigation has been shown to provide a new way of determining Cd, Co, Cu, Fe, Mn, Ni, Pb, and Zn in seawater. Chelex 100 resin is known to be an efficient means of sep- arating many of the trace elements from the alkali metals; however, by using an ammonium acetate wash, calcium and

magnesium are also removed. Calcium and magnesium se- verely suppress many analytes in GFAAS and, with their removal, the detection limits of many trace elements by

GFAAS can be extended to subnanogram per milliliter. In our radiotracer study, the recovery of Cd, Cu, Mn, Ni, and Zn was greater than 99.9% while the recovery of Co, Pb, and Fe was 99.5, 98.4, and 93.1%, respectively. The precision of the technique was limited by the GFAAS measurements which

varied with the element and concentration present. Not only has the proposed technique been applied to seawater from

the Chesapeake Bay but the method was applied to the determination of Cd, Mn, Ni, and Pb at the ng/mL level in seawater from the Gulf of Alaska. ACKNOWLEDGMENT

The authors express their gratitude to J. R. Moody, R. Huggett, and W. A. Bowman III for their help in the preparation of materials and seawater collection. LITERATURE CITED

(1) D. E. Leyden, T. A. Patterson, and J. J. Alberts. Anal Cham., 47, 733

(1975).

(2) E. D. Goldbert, "Marine Pollution Monitoring: Strategies for a National Program", NOAA, Washington, D.C., 1972.

(3) C. Lee, N. B. Kim, I. C. Lee. and K. S. Chung, Talanla, 24, 241 (1977).

(4) B. G. Stephens. H. L. Felkel, Jr., and W. M Spinelli, Anal. Chem., 46, 692 (1974).

(5) A. Zirino and S. H. Lieberman, Chapter in "Analytical Methods in Oceanography”, T. R. P Gibbs, Jr., Ed., Adv. Chem. Ser., 147, 1975.

(6) K. R. Sperling, At Absorpt. Newsl. 15, 1 (1976).

(7) P. E. Paus, Fresenius. Z. Anal. Chem., 264, 118 (1973).

(8) D. A. Segar and J. G. Gonzalez. Anal. Chim. Acta. 58. 7 (1972).

(9) B. P. Fabricand. R. R. Sawyer, S. G. Ungar, and S. Adler, Geochim

Cosmochim. Acta. 26, 1023 (1962).

(10) J. P. Riley and G. SkiiTOw, "Chemical Oceanography", Vol. Ill, Academic

Press, New York, 1975.

(11) D. C. Burell, Anal. Chim. Acta. 38. 447 (1967).

(12) K. Kremling and H. Peterson, Anal. Chim. Acta, 70, 35 (1974).

(13) J. P. Riley and D. Taylor, Anal. Chim. Acta. 40, 479 (1968).

(14) E. W. Oavey and A. E. Soper, Chapter in "Analytical Methods in Oceanography", T. R. P. Gibbs, Jr., Ed., Adv. Chem. Ser.. 147, 1975.

(15) T. M. Florence and G. E. Batley, Taianta. 23, 179 (1976).

(16) T. M Florence and G. E. Batley, Taianta. 24, 151 (1977).

(17) T. M Florence and G. E. Batley, Taianta. 22, 201 (1975).

(18) A. S. Douglas and A. Y. Cantillo, Chapter in ' Analytical Methods in Oceanography", T. R. PCGibbs, Jr., Ed., Adv. Chem. Ser.. 147, 1975.

(19) S. Forbug and S. Sundgreen, Anal. Chem.. 23. 1202 (1960).

(20) P. W. J. M. Boumans and F. J. DeBoir, Spectrochim. Acta. Part B, 31, 355 (1976).

(21) P. J. Paulsen, private communication.

(22) R. D. Ediger, G. E. Peterson, and J. D. Kerber, At. Absorpt. News!., 13, 61 (1974).

(23) E. C. Keuhner, R. Alvarez, P. J. Paulsen, and T. J. Murphy, Anal. Chem.,

44, 2050 (1972).

(24) J. W. Useller, NASASP-5074, Office of Technology Utilization, NASA,

Washington, D.C., 1969.

(25) J. A. Dean and T. C. Plains, Ed., "Flame Emission and Atomic Absorption

Spectrometry", Vol. 2, Components and Techniques, Marcel Dekker, New

York, 1971.

(26) J. R. Moody and R. M. Lindstrom, Anal. Chem.. 49, 2264 (1977).

(27) E. J. Maienthal and D. A. Becker, Natl. Bur. Stand. ( U.S.), Tech. Note, 929, 1976.

(28) J. R. Moody, H. L. Rook, P. J. and Paulsen, T. C. Rains, I. L. Barnes, and M. S. Epstein',' Natl. Bur. Stand. {U.S.) Spec. Publ., 464, W. A. Kirchhoff, Ed., 1977.

(29) B. Holymaka, Radiochem. Radioanal. Lett., 17, 313 (1974).

(30) D. E. Leyden and A. L. Underwood., J. Phy. Chem., 68, 2093 (1964).

(31) M. G. Lai and H. A. Goya, U.S. Naval Radiological Defense Laboratory,

Dept, of Commerce, National Technical Information Service, AD-6486185,

1966.

(32) C. M. Callahan, J. M. Pascual, and M. G. Lai, U.S. Naval Radiological Defense Laboratory, Dept, of Commerce, National Technical Information

Service, AD-647661, 1966.

(33) G. H. Luttrel, Jr.rC. More, and C. T. Kenner, Anal. Chem., 43, 1370 (1971). (34) A. C. Kayser, J. Chem. Educ., 36. 128 (1959).

(35) R. E. Lapp and H. L. ''Andrews, "Nuclear Ftadiation Physics”, Prentice-Hall, Englewood Cliffs, N.J., 1959.

(36) J. A. Dean and T. C. Rains, Ed., "Flame Emission and Atomic Absorption

Spectrometry", Vol. 3, Elements and Matrices, Marcel Dekker, New York, 1975.

Received for review July 31, 1978. Accepted September 26, 1978. This paper was taken in part from the dissertation written by H.M.K. and accepted by the graduate school, The

American University, in partial fulfillment of the requirements

for the degree of Doctor of Philosophy in Chemistry. In order

to adequately describe materials and experimental procedures,

it was occasionally necessary to identify commercial products

by manufacturer’s n^lme or label. In no instance does such

identification imply endorsement by the National Bureau of Standards nor does it imply that the particular products or equipment is necessarily the best available for that purpose.

38
form NBS-3U

<u-«)

APPENDIX 4

U.S. DEPARTMENT OF COMMERCE

NATIONAL BUREAU OF STANDARDS

WASHINGTON. D.C. 20234

June 17, 1981

REPORT OF ANALYSIS

To: H. M. Kingston

Subject: Determination of Cadmium, Copper, Lead, Manganese, and Nickel in

Aqueous arid 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 some 60 elements. For some elements

concentrations as low as 10“14

g can be detected [1].

The basic components of AAS are the (1) primary source of radiation,

(2) production of atomic vapor (flame or electrothermal), (3) wavelength

isolator, (4) radiation detector, and (5) readout.

A number of radiation sources are available but the hollow cathode lamp

(HCL), in general,' is satisfactory for most AAS work. For a few elements

which emit 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 HCL.

Historically a flame was the original means of producing 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 so for the forseeable future.

The major advantages of the flameras a means of production of atomic vapor

are: (a) simplicity of the technique, (b) speed 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 required, and (d) sensitivity is limited for many elements.

In general the concentration of most the trace elements in seawater are below the detection limit of flame atomization 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.

39
Massmann [4] constructed a somewhat simpler graphite furnace which is

basically being used by all manufacturers today. Interferences encountered

with electrothermal atomization 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 absorption 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 are 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 port using a metal rod. Adjustments

of the automatic injector tip is made to insure that it does not come 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 monochromator. 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 making readings is

eliminated, and since the digital device employs a decimal -to-bi nary or BCD converter on the output, the signal can be fed to a printer or tape

punched for subsequent computation on a computer.

40
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]. However, concentrations of most trace metals in seawater

are often below the detection limit of even the ETA-AAS method. Also, the

dissolved solids (3.5 g/L) in seawater 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

preconcentration 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 extracted. Extraction is

rapid and concentration factors of 20-50 can be achieved. For successful

extraction the aim is to form a stable complex which has low solubility in

the aqueous phase but has high solubility in the organic phase. The organic

phase should have limited solubility in water. Problems 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 the analytes are collected by

precipitation on a "carrier-precipitate", 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. Columns can be made 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 the separation to be accomplished. Ion-exchange

resins are porous insoluble 3-dimensional polymeric compounds, usually in

the form of powder or small beads. They include firmly bonded organic

functional groups. Associated with these 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]. Kingston et. al . , [12] used Chelex 100 resin and ETA-AAS to

determine Cd, Co, Cu, Fe, Mn, Ni , Pb, and Zn in estuarine water from the

Chesapeake Bay and seawater from the Gulf of Alaska.

41
Procedure

A. Aqueous

A test portion of the estuarine sample from the Chesapeake Bay was preconcentrated by H. M. Kingston and E. S. Beary using the method described by

Kingston et al . , [12]. The eluate from this separation which is 2.5 M HN0 3 was analyzed directly for the analytes by ETA-AAS using the L'vov olatform.

To check for chemical 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 ym filter paper were prepared by

transferring the filter paper to a Teflon beaker. Then, five mL of HN0 3 and one mL of Hf were added and solution warmed. After the paper had

decomposed, five mL of HCIO4 was added and sample solution evaporated to near dryness. The solids were then dissolved in one mL of HN0 3 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 Spectrochemical 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, B. V. Inzhenerno-Fizicheskii Zhurnal , 2 , 44-52 (1959).

[4] Massmann, H. Spectrochimica Acta, 23B , 21 5-226 (1968).

[5] Slavin, W. and Manning, 0. C., Anal. Chem., 51_, 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 (1 980).

L 8 ] Riley, J. P. and Taylor, D., Anal. Chim. Acta, 40, 479 (1968).

[9]

Muzzarelli, R. A. A. and Rocchetti , R., Anal. Chim. Acta, 6£, 35 (1974).

[10] Nix, J., Goodwin, T. , At. Absorp. News!., 9^, 119 (1970).

[11] Dean, J. A., Chemical Separation Methods , Van Nostrand Reinhold,

New York, 1969.

42
[12] Kingston, H. M. , Parnes, I. L., Brady, T. 0., Rains, T.

Chem., 50, 2064 (1578).

T. C. Rains, Research Chemist

'c/.Q. fi-u+j.

T. A. Rush, Chemist

v-y.

///

T.- A. Butler, Chemist

E. L. Garner, Chief

Inorganic Analytical Research Division

Center for Analytical Chemistry

Attachments 2

C. , Anal .

43
Table

1.

Instrumental

Parameters. cO CO CO CO CO CO

•1

*-> o 1 1 1 1 - 1 to ai

Nl to o o o o o

•r— i o o o o o E )— CO CO r-- d o CM CM CM CM CM

4-> d

fOO

O

O

O o O o

CM co

ddd

dd

CM c u

»»— CL) I 1 i . 1 1 1 V- to S- • o • o o O o d <d |— o o o o o

CO Jd co co co oo

ZO CJ o o o o o

CJ

d

d

dd

d

CD

a c a; i l 1 1 1 1

to >> i CO to co CO to

i~ h- CM CM CM CM CM o * r— 1 r—

D.O 5 ~ to S- S- +-> O s- S_ to d d CO r- d d

CO * Ll. i- d

Co c T- • o 4-> to

O) •r— « •o

CO f— to

a c o ro c CM CM CM CO CO •?— o

CO o fd 4- CJ

I/O Cl f“ a> LU X a to UJ o

o8 E o

CM

Cl- s r-» t". t"- CJ CD E • • • • • •r— *-> CO c o o o o o S- to \

•*> t- •a •i— • E 4- sz E

+-> i- c i- CD CO CO o CO o T— o c • • • • • 4- 4-

a> E cod O') CM CO +-> *o

r— c CM CM r-» CO 00 (O 0) •o

0) CM CO CM CM CM r— to ai > O. 3 to

«o 3 > d o O a> > ct- TO - ri: o

+-> CM E c »—»

CL) JO JO JZ

d Ol E -a 3 c •T— JO 4-> zc E

GJ CJ CJ s

z Ou *i— z ro r— »—' cn UJ JO J

44
Table 2. Control Samples.

Sampl e Pb Ni Cu Cd

ng/mL - -

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

Std. Dev. = 2.1 3.4 2. 2 0.8

Rel . Std . Dev . % = 7.6 6.5 14 7.4

Control , SRM 1 643a , Certified Values 27 ± 1 55 ± 3 18 ± 2 10 ±

45
APPENDIX 5

BLANK UNCERTAINTIES AND CORRECTIONS

Correction for the analytical blank must be made along with two other

corrections, one for chemical retention and 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 distribution 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.

Each measurement is presented in two ways, as a point estimate of the

quantity and as an interval estimate that is approximately at the 95% confidence 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 the 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 the 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 standard 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

46
on how many of the blank measurements are below the detectable limit. When

the blank measurements are not normal, the Bonferroni inequality is used.

When most of the blank measurements are below detectable limits, 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 sampling

of 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 blank and sample relationship 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 of 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 procedures. 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 assess- ment 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 and 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 the blank exists unknown.

47
The total data base for the entire project is organized as follows:

TABLE I. ORGANIZATION OF DATA

Elements Determined Elements Determined Instrumental

in the Particulate in the Dissolved Method of

Portion of the Sample Portion of the Sample Determination

Data Subset A Data Subset B Ce Co

Co Cr Neutron

Cr Fe

Fe Mo Activation

Mo Sc

Sc Sn Analysis

Sn Th

Th U (NAA)

U

Zn

Zn

Data Subset C Data Subset D Cd

r N Cd

Cu

Mn

Graphite Furnai

Mn Atomic Absorptii

Ni

Pb

Ni

Pb

Spectrometry

(GFAAS)

Blank 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 origin 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 statistically 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.

48
Cobalt; Dissolved (Data Subset B)

The model of the blank was log normal with a 0.0045 ng/mL shift,

log(X. .-0.0045)^N(u,a2

). This should be read: the logarithm of the blank ' J values X.. minus 0.0045 ng/mL was normally distributed N with mean y and

* J variance a

2

. 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 U=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 C+2. 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(y,a2

)

. The point prediction

* J was P=1 .12 ng/mL with lower limit L=0. 56 ng/mL and upper limit 11=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 — )^N(y,a2

) 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.

49
Thorium; Dissolved (Data Subset B)

The thorium blank values were distributed log normally log(X^ . )^N(y,a 2

) and had a point prediction P of 0.0004 ng/mL and a lower limit L=0.0000 ng/mL

with an upper limit of U=0.0044 ng/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+l .96a)-L] (3)

The values adjusted in this manner resulted in blank corrected data with 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.jj HN(y,a 2

) with a point prediction of 0.06 ng/mL and lower limit

L=0.00 with an upper limit U=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,a2

).

* J The point prediction P was 1.55 ng/mL with a standard deviation a

b

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 o (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/az +a

b

2 (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 was logical

to have obtained a normal distribution.

Scandium; Dissolved (Data Subset B)

The blanks were normally distributed for scandium following X — ^N(y,a 2) with point prediction P=0. 00012 ng/mL. The standard deviation o was 0.00004

50
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.

Batch Preparation Blank Dependence

In the preparation of the dissolved samples for both NAA and GFAAS

analyses the chemical manipulation was complex and time consuming. The time

required to 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 batch 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 data base set B and D the sample numbers were coded to include their batch run number for example 11,001 T, Blank 9 1 and 1 1 ,001 B 1, were all prepared in batch run number 1. The last digit

coming after the space for both data set B and 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 were log normally distributed log(X. . )^N(y . ,a

2

) . The P, L and U values are given in Table II.

* J J

TABLE II. THE P, L, AND U VALUES FOR THE DISSOLVED NICKEL

BLANK CORRECTIONS

Batch Number

- - - - Concentration in ng/mL

Point Prediction P Lower Limit L Upper Limit U

1 0.05 0.02 0.18

2 0.04 0.01 0.12

3 0.23 0.07 0.77

4 0.18 0.05 0.62

5 0.06 0.02 0.20

6 0.06 0.02 0.21

7 0.23 0.07 0.78

8 0.10 0.03 0.32

These P, L, and U values were treated as other blank corrections 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 single point and limits for all batches.

51
Zinc; Dissolved (Data Subset B)

The zinc blanks were modeled using a log normal distribution with a starter component log(X- -+1 .0)^N(y. ,a2

) . The batch component dependent point

1 J J predictions and limits appear in Table III.

TABLE III. THE P, L, OR U VALUES FOR THE DISSOLVED ZINC

BLANK CORRECTIONS

Concentration in ng/mL

Batch Number Point Prediction P Lower Limit L Upper Limit U

1 0.56 0.00 2.12

2 0.88 0.00 2.76

3 0.80 0.00 2.60

4 1.21 0.11 3.42

5 1.09 0.05 3.18

6 1.57 0.29 4.14

7 1 .73 0.37 4.45

8 3.05 1.02 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 . ,a

2

) . The P, L, and U values are presented in Table IV. J

TABLE IV. THE P, L, AND U VALUES FOR THE DISSOLVED MANGANESE

BLANK CORRECTIONS _______ Concentration in ng/mL - - - — - -

Batch Number Point Prediction P Lower Limit L Upper Limit U

1 0.56 0.20 0.93

2 0.73 0.37 1 .10

3 0.00 0.00 0.008

4 0.36 0.00 0.72

5 0.18 0.00 0.56

6 0.00 0.00 0.008

7 0.69 0.25 1.13

8 0.00 0.00 0.008

52
The treatment of these blank corrections and adjustment of the uncertainty on the concentration was as described previously. Batches 1 through 8 were

adjusted using equation 2.

Concentrations Needing No Blank Correction

Molybdenum, Tin, and Uranium; Dissolved (Data Subset B)

Cadmium; Dissolved (Data Subset D)

Manganese; Particulate (Data Subset C)

For each of these elements the blank contribution to the measurement was undetectable in almost all blank samples. It was therefore statistically

impossible to provide even the most minute correction resulting from a blank

component in the given 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 correction given these conditions was insignificant. Therefore supposing the lower

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 values for any blanks and statistically no evaluation could be made. The observation that the blanks for tin were all

below the lower limit of detection gave confidence that the measured concentrations for the samples were significant levels of tin and were real

observations, not artifacts of a variable blank.

There were four cadmium blanks observed just above the detection limit.

The data were not strong enough to 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-l .96a, C, C + 1.96a (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

sample. 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 numbers of filters used to collect the sample was significant. Table V provides the P, L, and U used for the blank correction.

53
To correct the concentrations for blank and obtain the uncertainties to

at least the 95 percent confidence limit equation 2 was used.

TABLE V. THE P, L, AND U VALUES FOR THE PARTICULATE COPPER

BLANK CORRECTION

Concentration in ng/mL

Number of

Filters Point Prediction P Lower Limit L Upper Limit U

1 Q. 23 0.08 0.45

2 Q. 46 0.23 0.76

3 0.68 0.39 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 limit 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 .96a (6)

Nickel; Particulate (Data Subset C)

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 confidence 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 how many filters are in the blanks. With this model, the mean and the

variance of the contamination were both proportional to the number of filters.

That 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

54
V

cone.

ng/mL

Square Root of Zinc Concentration

for Blanks

0 12 3

Number ef Filters = N( -v/n Scale)

55
insufficient to provide any support for the hypothesis of constant variance.

Note that two different filters, Millipore and Ami con, were represented but

could not be distinguished.

Let Z be the amount of contamination and N the number of filters. The

model

/Z = + e ( 7

was fit by ordinary least squares giving the following predictions for the

amount of contamination in the real samples.

TABLE VI. THE P, L, AND U VALUES FOR THE PARTICULATE ZINC

BLANK CORRECTION

Concentration in ng/mL

Number of

Filters Point Prediction P 98.75% Confidence Limits

L U

1 0.20 0 1.30

2 0.41 0 1.80

3 0.61 0 2.27

To obtain limits for the zinc measurements that were at least at the 95%

confidence level, the original values denoted by C ± a were used to obtain

96.25% confidence limits for the concentrations uncorrected for the blanks

C - 2.24a, C, C + 1.96a (8)

Then, subtraction of the upper limit (U) on the blank from C - 2.24a, the

point prediction (P) from C, and the 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 .96a)-L] (3)

The values for P, 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 which the observed concentration could not be

distinguished from 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

56
necessary. The result which is plotted in figure 2 shows clearly that the

Millipore filters contained less chromium than the Ami con 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 contamination mechanisms.

To correct the concentrations for blanks and obtain the uncertainties to

at least the 95% confidence limit, equation 2 was used.

[

( C-2 . 24a ) -U] , (C-P), [ ( C+2 . 24a ) -L] (2)

TABLE VII. THE P, L, AND U VALUES FOR THE PARTICULATE CHROMIUM

BLANK CORRECTION

Concentration in ng/mL

MILLIPORE

N Point Prediction 97.5% Confidence Limits

P L U

1 0.18 0.12 0.46

2 0.35 0.21 0.72

3 0.53 0.33

AMICON

0.97

1 0.71 0.48 1.17

2 1.43 1.04 2.04

3 2.14 1.62 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

hat 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 lower 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+l .96a (11)

This gave at least a 95 percent confidence limit. Any minimum value less

than zero after adjustment was adjusted to zero as a negative was not possible.

57
~|iu/6u

ZO'Q-

•QUOQ/

v

Square Root of Chromium Concentration -0.07

for Blanks

I

1 1

1 0 12 3

Number of Filters = N(«/N Scale)

58
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 l(f 2

. This suggests that the contamination might be as high as 0.0013 ng/mL as with

iron 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 percent confidence limit overall.

C-l :96a, 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 than' 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 contamination 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

appl ied.

To adjust the upper limit and lower limit to yield a final confidence

limit of 95 percent, the samples were adjusted as follows:

C - 1.96a, 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 molybdenum, 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 percent, the samples were adjusted as follows:

C - 1.96a, C, C + 1.96a (5)

This was appropriate because no blank adjustment was necessary.

59
The Correction for Chemical Retention of the Dissolved 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 , Fe, 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)

El ement Percent Retention (R)

Cd 99.99 + 0.071

Co 99.5 + 0.3

Cr 94.94 + 0.33

Cu 99.97 + 0.03

Fe 93.1 + 2.2

Mn 99.99 + 0.11

Mo 98.38 + 0.19

Ni 99.91 + 0.083

Pb 98.4 + 0.48

Sc 84.84 + 0.22

Sn 83.85 + 0.16

Th 82.83 + 0.34

U 98.8 + 0.2

Zn 99.96 + 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 highest

estimate using the form x = ^

where x was the final concentration adjusted for

60
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, Ni , Mn, U, and Zn. Therefore the retention

corrections were made only on Cr, Fe, Mo, Pb, Sc, Sn, and Th.

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

= 9.200

0.8283

= 11.11, x

_ 10.00

" 0.8283 12.02, x 11.00

0.8283

13.28

This was the last adjustment step for the dissolved data subset D and these

concentrations were rounded to the 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 not 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 samples.

The ratio to be multiplied was

1062.5

1Q33.T 1.0285 yv

This correction was made on data sets

The Final Form

C and D during the analysis by GFAAS.

4t

These aforementioned manipulations adjusted the concentration data to at

least the 95 percent confidence limit, compensation for blank and retention

were applied where necessary, producing a final data set in final form.

Two types of data information were left uncorrected after these manipulations, 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

were 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 than" with no discrete mean value or uncertainties.

61
LITERATURE CITED

(1) Eisenhart, Churchill, "Expression of the Uncertainties of Final Results"

NBS Special Publication 300, Vol. 1, page 69-72 (1969).

(2) Currie, Lloyd A. "Limits for Qualitative Detection and Quantitative

Determination, Application to Radiochemistry" Anal. Chem. , 1968, 40.

62
APPENDIX 6

THE CONCENTRATION OF DISSOLVED CADMIUM

(IN NANOGRAMS/MILLILITER)

THE RANGE REPRESENTS AT LEAST

THE 95% CONFIDENCE LIMITS

SAMPLE 1NUMBER MINIMUM BEST VALUE MAXIMUM

11102 8 < 0.007

11101 8 0.081 0.101 0.121

11100 8 0.050 0.062 0.074

11099 8 0 .020 0.024 0.028

1 1 098 8 0.077 0.095 0.113

11097 8 0.034 0.042 0.050

1109b 8 < 0.007

11095 7 < 0.007

11094 7 < 0.007

11093 7 < 0.007

11092 7 0.069 0.087 0.105

11091 7 0.048 0.06O 0.072

11090 7 0.014 0.018 0.022

11089 7 0.068 0.086 0.104

11088 7 0.035 0.045 0.055

11087 7 0.043 0.053 0.063

11086 7 0.067 0.083 0.099

11085 7 0.035 0.045 0.055

11084 7 < 0.007

11083 7 < 0.007

11082 7 < 0.007

11081 7 0.030 0.038 0.046

11080 6 0.059 0.073 0.087

11079 6 < 0.007

11078 6 0.069 0.087 0.105

11077 6 0.068 0.084 0.100

110 7b 6 0.067 0.083 0.099

11075 6 0.050 0.062 0.074

11074 6 0.038 0.048 0.058

11073 6 0.U26 0.032 0.038

11072 6 0.033 0.041 0.049

11071 6 < 0.007

11070 6 < 0.007

11069 6 0.025 0.031 0.037

11068 6 0.024 0.030 0.036

1 1 0b7 5 0.04 3 0.055 0.067

11066 5 < 0.007

11065 5 < 0.007

11064 5 0.035 0.045 0.055

11063 5 < 0.007

11062 5 0.029 0.037 0.045

11061 5 0.019 0.023 0.027

11060 5 0.025 0.031 0.037

1 1 059 5 < 0.007

11058 5 0.020 0.024 0.028

11057 5 < 0.007

11056 5 < 0.007

11055 5 < 0.007

11054 5 < 0.007

11053 5 < 0.007

11052 4 0.044 0.056 0.068

63
Table 1 continued

IHF CONCENTRATION OF DISSOLVED CADMIUM

(IN NANOGRAMS/MILLILITER)

THE RANGE REPRESENTS AT LEAST

THE 95% CONFIDENCE LIMITS

SAMPLE !NUMBER MINIMUM BEST VALUE MAXIMUM

11051 4 0.032 0.040 0.048

11050 4 0.032 0.040 0.04P

1 1049 4 < 0 . 0 0 7

1 1048 4 0.026 0.032 0.038

11047 4 < 0.007

1104b 4 < 0.007

11045 4 0.011 0.015 0.019

11044 4 < 0.007

11043 4 0.024 0.030 0.03b

11042 4 < 0.007

11041 4 < 0.007

11040 4 < 0.007

11039 4 0.048 0 .060 0.072

110 3 8 3 0.019 0.023 0.027

11037 3 0.024 0.030 0.036

11036 3 < 0.007

11035 3 < 0.007

11034 3 < 0.007

11033 3 < 0.007

11032 3 < 0.007

110 31 3 < 0.007

11030 3 < 0.007

11029 3 < 0.007

11028 3 < 0.007

110 2 7 3 < 0.007

11026 3 < 0.007

11025 3 < 0.007

11024 2 < 0.007

110 2 3 2 < 0.007

11022 2 < 0.00 7 110 21 2 o.ou 0.015 0.019

11020 2 0.028 0.034 0.040

110 19 2 0 .032 0.040 0.04H

110 3b 2 0.005 0.007 0.009

110 17 2 0.005 0.007 0.009

1 1C1 6 2 0.012 0 . 0 t 6 0.020

11015 2 < 0.007

11014 2 < 0.007

11013 2 < 0.007

11012 2 < 0.007

11011 2 < 0.007

11010 1 < 0.007

110 0 9 t < 0.007

1 1 0 0 b 1 < 0.007

1 1 0 0 7 1 < 0.0 0 7

1 1 0 0 b 1 < 0.00 7 110 0 5 1 < 0.00 7 11004 1 < 0.007

1 IOC 3 1 < 0.007

11002 1 < 0.007

1 1 0 0 1 1 64 < 0.007
THE CONCENTRATION OF DISSOLVED COBALT

(IN NANOGRAMS/MILLILTTER)

THE RANGE REPRESENTS AT LEAST

THE 95% CONFIDENCE LIMITS

SAMPLE iNUMBER MINIMUM BEST VALUE MAXIMUM

11102 8 0.000 0.049 0.060

11101 8 0.000 0.041 0.050

11100 8 0.077 0.154 0.177

11099 8 0.000 0.068 0.081

11098 8 0.000 0.066 0.079

11097 8 0.000 0.050 0.062

11096 8 0.008 0.076 0.090

11095 7 0.000 0.057 0.069

11094 7 0.079 0.156 0.179

11093 7 0.015 0.082 0.096

11092 7 0.000 0.044 0.055

11091 7 0.000 0.026 0.035

11090 7 0.000 0.025 0.034

11089 7 0.000 0.041 0.050

11088 7 0.000 0.063 0.076

11087 7 0.000 0.048 0.059

11086 7 0.000 0.049 0.060

11085 7 0.429 0.556 0.630

11084 7 0.000 0.029 0.038

11083 7 0.000 0.026 0.035

11082 7 0.000 0.031 0.040

11081 7 0.086 0.165 0.191

11080 6 0.000 0.027 0.036

11079 6 0.008 0.076 0.090

11078 6 0.000 0.056 0.068

11077 6 0.000 0.051 0.063

11076 6 0.000 0.048 0.059

11075 6 0.038 o.no 0.128

11074 6 0.000 0.018 0.025

11073 6 0.128 0.210 0.237

11072 6 0.000 0.021 0.030

11071 6 0.000 0.023 0.031

11070 6 0.000 0.023 0.031

11069 6 0.002 0.070 0.083

11068 6 0.000 0.055 0.067

11067 5 0.108 0.189 0.216

11066 5 0.000 0.054 0.066

11065 5 0.031 0.101 0.117

11064 5 0.000 0.034 0.043

11063 5 0.058 0.133 0.153

11062 5 0.000 0.025 0.034

11061 5 0.000 0.039 0.048

11060 5 0.000 0.030 0.039

11059 5 0.000 0.037 0.046

11058 5 0.000 0.026 0.035

11057 5 0.003 0.071 0.0R4

11056 5 0.000 0.024 0.032

11055 5 0.000 0.038 0.047

11054 5 0.000 0.034 0.043

11053 5 0.000 0.060 0.071

11052 4 0.000 0.055 0.067

65
Table 2 continued

1 HE CONCENTRATION OF DISSOLVED COBALT

(IN NANOGRAMS/MILLILITER)

THE RANGE REPRESENTS AT LEAST

THE 95% CONFIDENCE LIMITS

MPLE NUMBER MINIMUM BEST VALUE MAXIMUM

11051 4 0.000 0.063 0.076

1 1050 4 0.000 0.064 0.077

11049 4 0.007 0.075 0.089

11048 4 0.000 0.059 0.070

11047 4 0.013 0.083 0.099

11046 4 0.014 . 0.081 0.095

11045 4 0.000 0.017 0.024

11044 4 0.000 0.034 0.043

11043 4 0.013 0.083 0.099

110 4 2 4 0.000 0.024 0.032

11041 4 0.020 0.090 0.106

11040 4 0.000 0.02b 0.0 35

1 1039 4 0.021 0.081 0.107

11038 3 0.000 0.021 0.030

11037 3 0.081 0.158 0.181

11036 3 0.000 0.014 0.021

11035 3 0.029 0.099 0.114

11034 3 0.000 0.044 0.055

11033 3 0.027 0.097 0.112

11032 3 0.000 0.060 0.071

11031 3 0.008 0.076 0.090

11030 3 0.028 0.098 0.113

11029 3 0.067 0.144 0.167

11028 3 0.000 0.021 0.030

11027 3 0.000 0.061 0.072

11026 3 0.000 0.055 0.067

11025 3 0.010 0.078 0.092

11024 2 0.000 0.036 0.045

11023 2 0.000 0.045 0.056

11022 2 0.000 0.057 0.069

11021 2 0.010 0.078 0.092

11020 2 0.000 0.044 0.055

11019 2 0.004 0.072 0.085

11018 2 0.000 0.053 0.065

11017 2 0.000 0.040 0.049

1101b 2 0.000 0.016 0.025

11015 2 0.000 0.061 0.072

11014 2 0.000 0.059 0.070

110 13 2 0.000 0.025 0.034

11012 2 0.000 0.049 0.060

11011 2 0.017 0.087 0.103

11010 1 0.000 0.048 0.059

11009 1 0.000 0.055 0.067

1 1 0 0 8 l 0.000 0.042 0.053

11007 1 0.00 0 0.028 0.037

11006 1 0.000 0.028 0.037

1 1005 1 0.000 0.043 0.054

1 1004 1 0.000 0.044 0.055

11003 1 0.000 0.054 0.066

1 1 002 1 0.000 0.057 0.069

11001 1 0.016 0.086 0.102

66
Table 3

THE CONCENTRATION OF DISSOLVED CHROMIUM

(IN NANOGRAMS/MILLILITER)

THE RANGE REPRESENTS AT LEAST

THE 95% CONFIDENCE LIMITS

SAMPLE 1mumbe;r MINIMUM BEST VALUE MAXIMUM

11102 8 0.00 0.19 0.47

11101 8 0.10 0.40 0.70

11100 8 0.11 0.41 0.71

11099 8 0.00 0.21 0.49

1109b 8 o.oo 0.24 0.52

11097 8 0.02 0.32 0.63

11096 8 0.00 0.17 0.45

11095 7 0.03 0.31 0.6 0

11094 7 0.00 0.19 0.48

1 1 093 7 0.00 0.16 0.45

11092 7 0.00 0.26 0.55

11091 7 o.oo 0.14 0.41

11090 7 0.08 0.37 0.65

110 8 9 7 0.00 0.11 0.38

11088 7 0.00 0.14 0.41

11087 7 1.20 1.68 2.15

11086 7 0.00 0.19 0.4R

11085 7 0.00 0.10 0.37

1 1084 7 0.00 0.27 0.56

11083 7 0.00 0.13 0.40

11082 7 0.00 0.03 0.30

11081 7 0.02 0.30 0.59

11080 6 0.00 0.17 0.46

11079 6 0.0 0 0.03 0.30

110 7 8 6 0.00 0.26 0.55

11077 6 0.00 0.17 0.46

11076 6 0.00 0.05 0.33

11075 6 0.04 0.32 0.61

110 7 4 6 0.42 0.74 1.05

11073 6 0.00 0.08 0.35

11072 6 0.07 0.36 0.64

11071 6 0.00 0.05 0.33

11070 6 0.00 0.17 0.46

11069 6 0.17 0.47 0.77

1 10b8 6 0.00 0.00 0.25

11067 5 0.00 0.01 0.28

1 1 06b 5 0.09 0.39 0.69

11065 5 0.00 0.09 0.36

11064 5 0.00 0.10 0.37

11063 5 0.00 0.02 0.29

11062 5 0.00 0.00 0.25

11061 5 0.00 o.ii 0.38

11060 5 0.00 0.12 0.39

11059 5 0.00 0.25 0.5 3

11058 5 0.00 0.14 0.41

11057 5 0.00 0.12 0.39

11056 5 o.oo 0.00 0.2 6

11055 5 0.00 0.02 0.29

11054 5 o.oo 0.00 0.17

11053 5 0.00 0.19 0.48

1 1052 4 0.00 0.02 0.29

67
Table 3 continued

THE CONCENTRATION OF DISSOLVED CHROMIUM

(IN NANOGRAMS/MILLILTTER)

THE RANGE REPRESENTS AT LEAST

THE 95% CONFIDENCE LIMITS

MPLE 1NUMBER MINIMUM BEST VALUE MAXIMUM

11051 4 0.00 0.04 0.32

1 1 050 4 0.00 0.03 0.30

11049 4 0.00 0.04 0.32

11048 4 0.00 0.00 0.22

11047 4 0.00 0.11 0.38

11046 4 0.00 0.09 0.36

11045 4 0.1 1 0.41 0.71

110 4 4 4 0.00 0.00 0.29

11043 4 0.00 0.17 0.46

11042 4 o.oo 0.01 0.29

11041 4 0.00 0.04 0.3?

11040 4 0.00 0.16 0.45

11039 4 0.00 0.28 0.57

110 3 8 3 0.00 0.14 0.41

11037 3 0.00 0.00 0.11

11036 3 0.00 0.11 0.38

11035 3 0.00 0.01 0.28

11034 3 0.00 0.08 0.35

11033 3 0.51 0.84 1.18

11032 3 0.00 0.12 0.39

11031 3 0.00 0.00 0.15

11030 3 0.00 0.04 0.32

11029 3 0.00 0.18 0.47

1 1028 3 0.00 0.14 0.41

11027 3 0.00 0.00 0.26

11026 3 0.00 0.08 0.35

1102b 3 0.02 0.32 0.63

11024 2 0.00 0.01 0.28

11023 2 0.00 0.00 0.14

11022 2 0.00 0.05 0.33

11021 2 0.00 0.03 0.30

11020 2 0.00 0.08 0.35

11019 2 0.00 0.01 0.28

11018 2 0.00 0.06 0.34

11017 2 0.00 0.00 0.24

1101b 2 o.oo 0.00 0.27

11015 2 0.00 0.11 0.38

11014 2 0.00 0.11 0.38

11013 2 0.00 0.00 0.00

11012 2 0.00 0.00 0.11

1101 1 2 0.10 0.40 0.7 0

11010 1 0.00 0.21 0.49

11009 1 0.00 0.00 0.27

11008 1 0.00 0.14 0.43

11007 1 0.14 0.44 0.74

11006 1 0.00 0.14 0.43

11005 1 0.62 0.92 1.22

1 1004 1 0.00 0.00 0.11

11003 1 0.00 0.00 0.23

11002 1 0.00 0.00 0.27

11001 1 0.00 0.01 0.28

68
Table 4

THE CONCENTRATION OF DISSOLVED COPPER

(IN NANOGRAMS/MILLILITER)

THE RANGE REPRESENTS AT LEAST

THE 95% CONFIDENCE LIMITS

SAMPLE 1NUMBER MINIMUM BEST VALUE MAXIMUM

11102 8 0.38 1.50 1.85

11101 8 0.36 1.48 1.83

11100 8 0.52 1.64 1.99

11099 e 0.20 1.29 1.62

11096 6 0.32 1.44 1.79

11097 8 0.22 1.22 1.48

11096 8 0.00 0.85 1.09

11095 7 0.00 0.53 0.65

11094 7 0.00 0.37 0.51

11093 7 0.00 0.78 1.00

11092 7 0.00 0.58 0.76

11091 7 0.00 0.43 0.59

11090 7 0.0 0 0.72 0.94

110 8 9 7 0.00 0.94 1.20

11088 7 0.00 0.35 0.49

11087 7 < 0.08

11086 7 < 0.08

11065 7 0.00 0.05 0.15

11084 7 < 0.08

11063 7 < 0.08

110 6 2 7 < 0.08

11081 7 0.00 0.57 0.75

11080 6 < 0.08

11079 6 < 0.08

11076 6 < 0.08

11077 6 < 0.08

11076 6 < 0.08

11075 6 0.00 0.23 0.35

11074 6 0.00 0.48 0.64

11073 6 < 0.08

11072 6 OiOO 0.45 0.61

11071 6 0.00 0.41 0.57

11070 6 0.00 0.75 0.97

11069 6 0.00 0.46 0.62

11068 6 0.00 0.57 0.75

11067 5 0.00 0.36 0.50

11066 5 0.00 0.44 0.60

11065 5 0.00 0.06 0.16

11064 5 0.00 0.55 0.73

11063 5 0.0 0 0.23 0.35

11062 5 0.00 0.49 0.67

11061 5 0.00 0.50 0.68

11060 5 < 0.08

11059 5 0.00 0.08 0.18

11058 5 0.00 0.28 0.40

11057 5 < 0.08

11056 5 0.00 0.09 0.19

11055 5 0.00 0.12 0.22

11054 5 0.00 0.13 0.23

11053 5 < 0.08

11052 4 < 0.08

69
Table 4 continued

THE CONCENTRATION OF DISSOLVED COPPER

(JN NANOGRAMS/KILLILITER)

THE RANGE REPRESENTS AT LEAST

THE 95% CONFIDENCE LIMITS

SAMPLE NUMBER MINIMUM BEST VALUE MAXIMUM

11051 4 < 0.08

11050 4 < 0.08

11049 4 < 0.08

1104b 4 < 0.08

1 1047 4 < 0.08

1 104b 4 < 0.08

110 4 5 4 < 0.08

11044 4 0.00 0.19 0.31

1 1 0 '4 3 4 0.00 0.18 0.28

11042 4 0.00 0.29 0.43

11041 4 o.oo 0.18 0.28

11040 4 0.00 0.3 3 0.47

11039 4 0.00 0.15 0.25

11038 3 0.00 0.32 0.46

11037 3 0.00 0.11 0.21

1103b 3 0.00 0.35 0.49

11035 3 0.00 0.08 0.18

1 1 034 3 0.00 0.39 0.55

11033 3 0.00 0.31 0.45

11032 3 0.14 1.14 1.40

11031 3 0.00 0.35 0.49

11030 3 0.00 0.44 0.60

11029 3 0.00 0.25 0.37

11028 3 0.57 1.80 2.25

110 2 7 3 0.00 0.22 0.34

1102b 3 0.14 1.14 1 .40

11025 3 0.00 0.2 9 0.43

J 102 4 2 0.00 0.27 0.39

11023 2 o.uo 0.20 0.32

11022 2 0.00 0.19 0.31

110 21 2 0.00 0.30 0.44

11020 2 0.00 0.34 0.48

11019 2 0.0 0 0.17 0.27

1 1 0 1 & 2 0.00 0.21 0.33

Uul7 2 0.00 0.33 0.47

1101b 2 0.00 0.29 0.43

11015 2 0.00 0.27 0.39

11014 2 0.00 0.26 0.38

11013 2 0.00 0.25 0.37

11012 2 0.00 0.33 0.47

11011 2 0.00 0.32 0.46

11010 1 < 0.08

1 1 009 1 0.00 0.47 0.63

lioob 1 0.00 0.17 0.27

11007 1 0.00 0.23 0.35

1 100b 1 0.32 1 .44 1.79

11005 1 0.14 1.14 1.40

11004 1 0.0 3 1.03 1.29

11003 1 0.00 0.58 0.76

11002 1 0.00 0.25 0.37

11001 1 0.00 0.2 3 0.35

70
Table 5

THE CONCENTRATION OF DISSOLVED IRON

(IN NAN OGRA^S/.MILLILITER)

THE RANGE REPRESENTS AT LEAST

THE 95% CONFIDENCE LIMITS

SAMPLE NUMBER MINIMUM BEST VALUE MAXIMUM

11102 6 0.0 0 2.41 3.52

11101 6 0.52 3.84 4.96

1 1100 8 0.00 2.41 3.52

11099 8 0.0 0 2.30 3.41

11098 8 0.00 1.75 2.66

11097 8 0.00 2.06 3.19

11096 8 0.00 2.63 3.74

11095 7 0.52 3.84 4.96

11094 7 0.00 1.41 2.28

110 9 3 7 0.00 1.52 2.64

1 1092 7 0.00 1.30 2.42

11091 7 0.00 0.42 1.53

11090 7 0.8 3 4.40 5.76

110 8 9 7 0.00 0.09 0.95

110 6 8 7 0.00 0.42 1.53

11087 7 o.oo 3.29 4.41

11066 7 0.00 0.75 1.86

1108b 7 61 .42 71.67 79.72

1 1084 7 0.00 1.19 2.06

11083 7 0.00 2.30 3.41

11062 7 0.74 4.07 5.18

11081 7 0.00 2.30 3.41

11080 6 0.00 0.53 1.40

11079 6 0 .00 0.09 1.20

11078 6 0.00 0.53 1.64

11077 6 1.27 4.84 6.20

11076 6 0.00 2.52 3.6 3

11075 6 0.00 2.96 4.07

11074 6 0.00 0.75 1 ,b2

11073 6 25.23 33.01 38.58

11072 6 0.0 0 0.75 1.62

11071 6 0.0 0 1.63 2.75

11070 6 o.oo 1.08 1.95

11069 6 0.00 2.85 3.96

11068 6 0.00 0.97 1.64

11067 5 0.00 2.08 3.19

11066 5 0.00 3.29 4.65

1 1 065 5 0.00 2.96 4.3?

11064 5 0.00 0.97 2.09

11063 5 0.00 0.86 1.98

11062 5 0.00 1.41 2.53

11061 5 0.00 1.75 3.11

11060 5 o.oo 0.20 1.31

11059 5 0.00 1.19 2.31

11059 5 0.00 0.42 1.53

11057 5 0.00 1 .63 2.75

11056 5 0.0 0 0.86 1 .98

11055 5 0.0 0 1.30 2.4?

11054 5 0.00 1 .75 2.66

11053 5 0.00 1.63 2.75

11052 4 2.04 5.61 6.97

71
Table 5 continued

THE CONCENTRATION OF DISSOLVED IRON

(IN NANOGRAMS/MILLILITER)

THE RANGE REPRESENTS AT LEAST

THE 95% CONFIDENCE LIMITS

SAMPLE NUMBER MINIMUM BEST VALUF MAXIMUM

11051 4 0.00 1.86 2.97

11050 4 0.00 2.85 3.96

11049 4 0.38 3.95 5.32

11048 4 0.00 2.74 3.85

11047 4 0.00 1.86 2.97

11046 4 0.00 2.52 3.63

11045 4 0.00 1.30 2.42

11044 4 0.00 1.86 2.72

11043 4 0.00 2.63 3.74

11042 4 0.00 0.97 2.09

11041 4 0.00 2.52 3.63

11040 4 0.00 0.64 1.51

11039 4 0.00 2.41 3.52

11038 3 0.00 0.42 1.29

11037 3 0.00 3.18 4.30

11036 3 0.00 0.31 1.18

11035 3 11.19 16.00 18.59

11034 3 0.00 2.08 3.19

11033 3 1.16 4.73 6.09

11032 3 0.00 1.19 2.06

11031 3 0.00 2.08 3.19

11030 3 0.00 1.52 2.64

11029 3 0.00 3.18 4.30

11028 3 0.00 1.52 2.64

11027 3 0.00 0.97 1.84

11026 3 0.00 0.53 1.64

11025 3 0.00 1.08 1.95

11024 2 0.00 0.09 1.20

11023 2 0.94 4.51 5.87

11022 2 0.00 0.53 1.40

11021 2 10.00 14.56 16.91

11020 2 0.00 0.86 1.98

11019 2 0.00 0.97 2.09

11018 2 0.83 4.40 5.76

11017 2 0.00 0.09 1.20

11016 2 o.oo 0.20 1.31

11015 2 0.00 0.97 2.09

11014 2 0.00 0.64 1.75

11013 2 0.00 0.09 1.20

11012 2 0.00 0.42 1.53

11011 2 0.00 1.30 2.17

11010 1 0.00 2.52 3.63

11009 1 0.00 3.29 4.41

11008 1 2.15 5.72 7.0 8

11007 1 0.00 1.08 2.20

11006 1 0.00 1 .19 2.31

11005 1 0.00 2.96 4.07

11004 1 0.00 1.19 2.31

11003 1 0.83 4.40 5.76

11002 1 0.00 1.30 2.42

11001 1 0.00 1.97 3.08

72
iaDie o THE CONCENTRATION OF DISSOI.VED MANGANESE

(JN NANOGFAMS/M1LLILITER)

THE RANGE REPRESENTS AT LEAST

THE 95% CONFIDENCE LIMITS

MPLE !NUMBER MINIMUM BEST VALUE MAXIMUM

1110 2 8 1.24 1.70 2.15

11101 8 1.64 2.10 2.55

11100 8 6.62 8.20 9.77

11099 8 5.65 7.00 8.34

11098 8 2.80 • 3.70 4.60

11097 8 2.22 2.90 3.57

11096 8 4.95 6.30 7.64

11095 7 2.17 3.51 4.85

11094 7 6.00 8.01 10.02

11093 7 3.73 5.51 7.29

11092 7 0.00 0.61 1.27

11091 7 0.00 0.71 1.60

11090 7 0.00 0.51 1.17

11089 7 0.00 0.41 1 .07

11088 7 0.00 0.71 1 .60

11087 7 2.07 3.41 4.75

11086 7 0.12 1.01 1.90

11095 7 320.67 388.31 455.95

11084 7 0.00 0.81 1.70

110 8 3 7 2.27 3.61 4.95

11082 7 2.65 4.21 5.77

11031 7 5.40 7.41 9.42

11080 6 0.69 0.90 1.10

11079 6 1.82 2.50 3.17

11078 6 2.12 2.80 3.47

11077 6 2.62 3.30 3.97

11076 6 7.85 10.10 12.34

11075 6 86.19 97.40 108.60

11074 6 0.51 0.67 0.83

11073 6 108.59 131.00 153.40

11072 6 0.52 0.68 0.84

11071 6 1.01 1.24 1.46

11070 6 0.45 0.59 0.72

11069 6 38.29 49.50 60.70

11068 6 1.54 2.00 2.45

11067 5 150.64 195. R2 240.80

llObb 5 0.24 0.8 2 1.20

11065 5 31.02 38.12 45.02

11064 5 1.67 2.72 3.57

11063 5 5.07 7.02 8.77

11062 5 1.77 2. 82 3.67

11061 5 2.84 4.12 5.20

11060 5 0.04 0.60 0.96

11059 5 4.10 5.82 7.34

11058 5 0.00 0.38 0.69

110 5 7 5 21.96 26.82 31 .48

11056 5 0.16 0.74 1 .12

11055 5 1.67 2.72 3.57

11054 5 1.29 2.12 2.75

11053 5 2.34 3.62 4.70

11052 4 2.78 4.04 5.3 0

73
Table 6 continued

rnE concentration of dissolvfd manganese

(IN NANOGKAMS/MILLILITER)

THE range represents at least

THE 95% CONFIDENCE LIMITS

SAMPLE lNUMBER MINIMUM BEST VALUE MAXIMUM

11051 4 2.66 3.94 5.20

1 10S0 4 2.36 3.64 4.90

11049 4 4.21 6.14 8.07

110 4 8 4 3.46 4.94 6.42

110 4 7 4 11.29 14.34 17.39

1 1 046 4 16.60 21.44 26.28

11045 4 0.00 0.2? 0.71

110 4 4 4 0.23 1 .04 1 .85

11043 4 3.06 4.54 6.02

1 1 042 4 0.00 0.27 0.76

11041 4 12.52 16.24 19.96

l 1040 4 0.23 0.R1 1.39

11039 4 10.69 13.74 16.79

11038 3 0.7 0 0.91 1.11

110 3 7 3 33.27 40.00 46.72

11036 3 0.50 0.66 0.82

110 3 5 3 12.60 15.30 17.99

11034 3 0.52 0.68 0.84

110 3 3 3 12.40 15.10 17.79

110 3 2 3 0.42 0.56 0.69

11031 3 9.55 11.80 14.04

11030 3 0.68 0,89 1.09

11029 3 58.23 67.20 76.16

11028 3 0.49 0.63 0.76

11027 3 6.30 8.10 9.89

1102b 3 2.80 3.70 4.60

11025 3 6.4b 8.50 10.52

11024 2 0.00 0.57 1.38

110 2 3 2 2.18 3.67 5.1b

11022 2 2.58 4.07 5.55

110 21 2 9.46 12.07 14.67

11020 2 1.03 2.07 3.10

11019 2 7.06 9.67 12.27

11018 2 1.60 2.67 4.13

11017 2 0.55 1.37 2.18

11016 2 0.00 0.00 0.3 2

11015 2 2.20 3.47 4.73

11014 2 2.00 3.27 4.53

11013 2 2.10 3.37 4.63

11012 2 1.43 2.47 3.50

1 101 1 2 3.96 5.67 7.37

1101 0 1 2.37 3.64 4.90

1 1 0 0 9 1 2.77 4.04 5.30

l 1 00 8 1 0.62 1.44 2.25

110 0 7 1 1.12 1.94 2.75

1 1 006 1 0.90 1 .94 2.97

11005 1 1.90 2.94 3.97

110 0 4 1 1 .80 2.84 3.87

1 1 00 3 1 1 . >2 2.04 2.85

11002 1 1.02 1.84 2.65

1 1 0 0

1

1 9.33 11.94 14.54

74
Table 7 THE CONCENTRATION OE DISSOLVED MOLYBDENUM

(IN NANOGRAM S/VILLI LITER)

THE RANGE REPRESENTS AT LEAST

THE 95% CONFIDENCE LIMITS

mplE 1DUMBER MINIMUM BEST VALUE MAXIMUM

11102 6 0.87 0.97 1.07

11101 8 0.7? 0.80 0.89

11100 8 0.69 0.7 7 0.86

11099 8 0.75 0.84 0.92

11098 8 0.59 0.65 0.71

11097 8 0.60 0.66 0.72

11096 8 0.54 0.61 0.67

11095 7 0.80 0.88 0.96

11094 7 0.58 0.64 0.70

11093 7 0.64 0.70 0.76

11092 7 1.50 1.66 1.83

11091 7 1.99 2.20 2.40

11090 7 1.49 1.65 1.82

11089 7 1.26 1.40 1.54

11088 7 1.57 1.78 1 .98

11087 7 1.99 2.20 2.40

11086 7 1.78 1.99 2.19

11085 7 3.04 3.45 3.86

11084 7 1.99 2.20 2.40

11083 7 1.76 1.99 2.19

11062 7 1.89 2.09 2.30

11081 7 2.10 2.30 2.50

11060 6 1.89 2.09 2.30

11079 6 1.99 2.20 2.40

11078 6 1.99 2.20 2.40

11077 6 1.99 2.20 2.40

1 1076 6 2.51 2.72 2.92

11075 6 2.30 2.51 2.71

11074 6 1.99 2.20 2.40

11073 6 3.14 3.55 3.96

11072 6 1.89 2.09 2.30

11071 6 2.30 2.51 2.71

11070 6 2.41 2.61 2.82

11069 6 2.72 2.93 3.13

11068 6 2.20 2.40 2.61

11067 5 2.83 3.24 3.65

11066 5 2.30 2.51 2.71

1 1065 5 3.98 4.39 4.80

11064 5 2.51 2.72 2.92

11063 5 2.20 2.40 2.61

11062 5 2.20 2.40 2.61

11061 5 2.41 2.61 2.82

11060 5 ? . 4

1

2.61 2.82

1 1 059 5 2.62 2.8 2 3.0 3

11058 5 1.99 2.20 2.40

11057 5 2.62 3.03 3.44

11056 5 1.99 2.20 2.40

11055 5 2.52 2.93 3.34

11054 5 2.52 2.93 3.34

11053 5 2.62 3.03 3.44

11052 4 2.41 2.61 2.82

75
Table 7 continued

THE CONCENTRATION OF DISSOLVED MOLYBDENUM

(IN NANQGRAMS/MILLI LITER)

THE HANGF REPRESENTS AT LEAST

THE 95% CONFIDENCE LIMITS

SAMPLE 1NUMBER MINIMUM BEST VALUE MAXIMUM

11051 4 2.62 3.03 3.44

11050 4 2.73 3.14 3.55

11049 4 2.30 2.51 2.71

11048 4 2.73 3.14 3.55

1)047 4 2.73 3.14 3.55

1 1046 4 2.8 3 3.24 3.65

11045 4 2.51 2.72 2.92

11044 4 2.52 2.93 3.34

1 1043 4 3.14 3.55 3.96

11042 4 2.62 3.03 3.44

11041 4 2.94 3.35 3.76

1 1 040 4 2.41 2 . b 2 3.23

11039 4 3.5b 3.97 4.38

110 3 8 3 2.51 2.72 2.92

I 1037 3 3.56 3.97 4.38

1103b 3 2.62 3.03 3.44

11035 3 3.98 4.39 4.80

11034 3 2.73 3.14 3.55

11033 3 3.98 4.39 4.80

110 3 2 3 2.83 3.24 3.65

110 31 3 3.88 4.29 4.70

11030 3 2.94 3.35 3.76

11029 3 4.51 5.12 5.74

110 2 8 3 2.52 2.93 3.34

11027 3 2.94 3.35 3.76

11026 3 3.88 4.29 4.70

11025 3 5.03 5.65 6.26

110 2 4 2 5.45 6.06 6.68

11023 2 5.6 b 6.27 6.89

110 2 2 2 4.61 5.23 5.84

11021 2 4.61 5.02 5.43

110 2 0 2 3.68 4.29 4.70

11019 2 4.50 4.91 5.32

11018 2 4.71 5.12 5.53

11017 2 4.19 4.60 5.01

1101b 2 2.52 2.9 3 3.34

11015 2 5.87 6.48 7.10

11014 2 4.82 5.44 6.05

11013 2 3.5b 3.97 4.38

11012 2 4.09 4.50 4.91

11011 2 5.76 6.38 6.99

11010 1 4.71 5.12 5.53

1 1 009 1 b . bO 7.42 8.2 4

1 1 008 1 6.29 6.90 7.51

11007 1 7.86 8.68 9.50

11006 1 2.41 2.61 2.82

11005 1 3.5b 3.97 4.38

11004 1 4.72 5.33 5.96

11003 1 5.7b 6.38 6.99

1 1 0o2 1 5.0 3 5.65 6.26

11U01 1 5.24 5.85 6.47

76
Table 8

THE CONCENTRATION OF DISSOLVED NICKEL

(IN NANOGRAMS/MILLILITER)

THE RANGE REPRESENTS AT LEAST

THE 95% CONFIDENCE LIMITS

SAMPLE 1NUMBER MINIMUM BEST VALUE MAXIMUM

1110 2 8 0.66 1.15 1.49

11101 8 0.88 1.37 1.71

11100 8 0.88 1.37 1.71

11099 8 1.02 1.58 1.99

1109b 8 0.74 1.23 1.57

11097 8 0.91 1.40 1.74

11096 8 0.60 1.04 1.33

11095 7 0.15 0.92 1.30

11094 7 0.08 0.85 1.23

11093 7 0.35 1.17 1.60

11092 7 1.48 2.59 3.31

11091 7 0.76 1.65 2.15

11090 7 1.04 2.04 2.65

11089 7 0.76 1.65 2.15

110 8 8 7 0.76 1.65 2.15

11087 7 0.85 1.85 2.46

11066 7 0.77 1.66 2.16

11005 7 0.68 1.57 2.07

11064 7 0.77 1.66 2.16

110 6 3 7 0.95 1.95 2.56

110 8 2 7 0.82 1.71 2.21

11081 7 0.56 1.45 1.95

11080 6 0.91 1.40 1.78

11079 6 1.04 1.53 1.91

11078 6 1.03 1.52 1.90

11077 6 0.86 1.28 1.59

1107b 6 1.11 1.60 1.98

11075 6 0.68 1 .10 1.41

110 7 4 6 0.88 1.30 1.61

110 7 3 6 0.95 1.37 1.68

1 1072 6 0.71 1.08 1.34

11071 6 0.57 0.94 1.20

11070 6 0.82 1.24 1.55

11069 6 0.79 1 .16 1.42

11068 6 0.93 1.35 1.66

11067 5 0.87 1.28 1.59

11066 5 1.01 1.49 1.87

11065 5 0.56 0.92 1.18

11064 5 1.05 1.53 1.91

110 6 3 5 0.77 1.13 1.39

11062 5 0.85 1.26 1.57

11061 5 0.93 1.34 1.65

11060 5 0.94 1.35 1.66

11059 5 0.7 0 1.06 1.32

11058 5 0.95 1.36 1.67

11057 5 0.65 t .01 1.27

11056 5 0.86 1.27 1.58

11055 5 0.71 1.07 1.33

11054 5 0.64 1 .On 1.26

11053 5 0.77 1.18 1.49

11052 4 0.38 1.09 1.49

77
Table 8 continued

THE CONCENTRATION OF DISSOLVED NICKEL

(IN NANOGRAMS/MILLILITER)

THE RANGE REPRESENTS AT LEAST

THE 95% CONFIDENCE LIMITS

SAMPLE NUMBFR MINIMUM BEST VALUE MAXIMUM

11051 4 0.29 0.95 1.30

11050 4 0.40 1.11 1.51

1 1049 4 0.30 0.96 1.31

1 1048 4 0.47 1.25 1.72

11047 4 0.0 0 0.59 0.89

1104b 4 0.00 0.56 0.85

11045 4 0.30 0.96 1.31

11044 4 0.6 2 1.40 1.87

11043 4 0.39 1.10 1.50

11042 4 0.36 1.07 1.47

11041 4 0.42 1.13 1.53

11040 4 0.46 1.17 1.57

11039 4 0.38 1.09 1.49

1 1038 3 0.34 1.15 1.58

11037 3 0.06 0.82 1.20

1103b 3 1.31 2.30 2.91

11035 3 0.74 1.62 2.12

11034 3 1.23 2.22 2.83

11033 3 1.11 1.99 2.49

11032 3 0.31 1.12 1.55

11031 3 0.5 7 1.38 1.81

11030 3 0.51 1.32 1.75

11029 3 0.20 0.96' 1.34

11028 3 1.05 1.93 2.43

11027 3 0.42 1.18 1.56

1 1026 3 0.13 0.89 1.27

11025 3 0.2 4 1.00 1.38

11024 2 0.62 0.90 1.13

11023 2 0.61 0.89 1.12

110 2 2 2 0.62 0.90 1.13

11021 2 0.67 0.97 1.22

11020 2 0 . b 5 1 .15 1.40

11019 2 0.95 1.25 1.50

11018 2 0.87 1.17 1.42

11017 2 0.59 0.87 1.10

1101b 2 0.7 0 1.00 1.25

11015 2 0.53 0.81 1.04

11014 2 0.57 0.85 1.08

11013 2 0.53 0.81 1.04

11012 2 0.66 0.94 1.17

11011 2 0.60 0.88 1.11

11010 1 0.47 0.78 0.99

11009 1 0.40 0.71 0.92

1 1008 1 0.55 0.9 8 1.11

1 1 007 1 0.29 0.55 0.71

1100b 1 0.54 0.87 1.10

11005 1 0.47 0.78 0.99

11004 1 0.4 8 0.81 1.04

11003 1 0.64 0.97 1 .20

1 1 0 0 2 1 0.56 0.89 1 .12

11001 1 0.50 0.81 1.02

78
Table 9

THE CONCENTRATION OF DISSOLVED LEAD

(IN NANOGRAMS/MILLILITER)

THE' RANGE REPRESENTS AT LEAST

THE 95% CONFIDENCE LIMITS

MPLE NUMBER MINIMUM BEST VALUE MAXIM

11102 8 0.2 7 0.51 0.63

11101 8 0.00 0.00 0.12

11100 8 0.00 0.00 • 11099 8 0.00 0.08 0.20

11098 8 0.00 0.16 0.31

11097 8 0.10 0.40 0.60

11096 8 0.00 0.10 0.22

11095 7 0.03 0.33 0.52

11094 7 0.00 0.16 0.31

11093 7 0.00 0.04 0.16

11092 7 0.00 0.02 0.14

11091 7 0.00 0.00 0.12

11090 7 0.00 0.00 0.11

11089 7 0.00 0.00 0.07

11088 7 0.00 0.00 0.07

11087 7 0.00 0.21 0.36

1108b 7 0.00 0.00 0.12

11085 7 0.00 0.00 0.09

11084 7 0.00 0.00 0.11

11083 7 0.00 0.00 0.11

11082 7 O.oo 0.00 0.10

11081 7 0.00 0.04 0.16

11080 6 0.00 0.00 0.07

11079 6 0.00 0.00 0.04

11078 6 0.0 0 o.ll 0.23

11077 6 0.00 0.00 0.0 3

11076 6 0.00 0.01 0.13

11075 6 0.00 0.00 0.05

11074 6 0.0 0 0.00 0.12

11073 6 0.00 0.00 0.09

11072 6 0.00 0.00 0.11

11071 6 0.00 0.05 0.17

110 7 0 6 0.00 0.03 0.15

11069 6 0.00 0.03 0.15

11068 6 0.00 0.24 0.41

11067 5 0.08 0.38 0.57

11066 5 0.11 0.43 0.65

11065 5 0.00 0.12 0.27

11064 5 0.00 0.24 0.41

11063 5 0.00 0.13 0.28

11062 5 0.00 0.18 0.33

11061 5 0.00 0.13 0.28

11060 5 0.00 0.10 0.22

11059 5 0 . 0 0 0.08 0.20

11058 5 j . 0 0 0.15 0.30'

11057 5 0.0 0 0.13 0.2 8

11056 5 0.00 0.20 0.35

11055 5 0 . 0 0 0.13 0.28

11054 5 o.oo 0.17 0.32

110 5 3 5 0.19 0.52 0.73

11052 4 0.47 0.98 1.19

79
Table 9 continued

THE CONCENTRATION OF DISSOLVED LEAD

(IN NANOGRAMS/MILLILITER)

THE RANGE REPRESENTS AT LEAST

THE 95% CONFIDENCE LIMITS

SAMPLE 1MUMtJER MINIMUM BEST VALUE MAXIMUM

11051 4 0.00 o.oo 0.11

110 5 0 4 0.00 0.00 0.10

1 1049 4 0.00 0.01 0.13

11048 4 0.00 0.01 0.13

11047 4 o. oo 0.05 0.17

1104b 4 0.00 0.00 0.12

11045 4 0.00 0.05 0.17

1 1044 4 0.00 0.07 0.19

11043 4 0.00 0.03 0.15

1 1042 4 0.00 0.04 0.16

11041 4 0.00 0.03 0.15

11040 4 0.00 0.12 0.27

11039 4 0.00 0.22 0.39

11038 3 0.00 0.05 0.17

11037 3 0.00 0.13 0.28

1 103o 3 0 .00 0.08 0.20

11035 3 0.00 0.05 0.17

11034 3 0.00 0.07 0.19

110 3 3 3 0.00 0.00 0.12

11032 3 0.00 0.10 0.22

1 1 C31 3 0.00 0.06 0.18

11030 3 0.00 0.00 0.11

11029 3 0.00 0.00 0.10

1 1 U 2 B 3 0.00 0.00 0.06

11027 3 0.00 0.04 C. 16

11026 3 0.00 0.16 0.31

1 1025 3 0.95 1.59 2.13

11024 2 0.0 3 0.33 0.52

11023 2 0.0 0 0.20 0.35

11022 2 0.00 0.14 0.29

110 21 2 0.00 0.11 0.23

110 20 2 0.00 0.15 0.30

11019 2 0.00 0.06 0.19

1101« 2 0.00 0.00 0.11

11017 2 0.00 0.04 0.16

11016 2 o.oo 0.09 0.21

11015 2 0.00 0.13 0.25

11014 2 0.00 0.09 0 . 2u

1

0 1 i 2 0.00 0.07 0.19

1 1 u 1 2 2 0.11 0.41 0.61

11011 2 0.00 0.18 0.33

11010 1 o.oo 0.00 0.11

1 1009 1 0.00 0 .no 0.12

1100 8 1 0.00 0.00 0 . 0 ^

1 1 0u7 1 0.00 0.00 0.11

1100c 1 0 .00 0.03 0.15

110 0 5 1 0.00 0.00 0.11

11004 1 0.0 0 0.0 2 0.14

110 0 3 1 0.00 0.08 0.20

11002 1 9.00 o.oi 0.13

11001 1 0.00 0.0 6 0.18

80
Table 10

THE CONCENTRATION OF DISSOLVED SCANDIUM

(IN NANOGPAMS/MILLILITER)

THE RANGE REPRESENTS AT LEAST

THE 95% CONFIDENCE LIMITS

MPLE 1NUMBER MINIMUM BEST VALUE MAXIMUM

11102 8 0.00056 0.00068 0.00080

1 1101 8 0.00098 0.00113 0.00128

11100 8 0.00073 0.00086 0.00100

11099 8 0.00061 0.00074 0.00087

11098 8 0.00084 ' 0.00099 0.00115

11097 8 0.00048 0.00059 0.00071

11096 8 0.00095 0.00110 0.00126

11095 7 0.00090 0.00105 0.00121

11094 7 0.00065 0.00079 0.00092

11093 7 0.00089 0.00104 0.00119

11092 7 0.00046 0,00058 0.00070

11091 7 0.00039 0.00051 0.00063

11090 7 0.00055 0.00067 0.00079

11089 7 0.00051 0.00063 0.00075

11086 7 0.00041 0.00053 0.00065

11087 7 0.00070 0.00084 0.00097

1108b 7 0.00033 0.00044 0.00054

11085 7 0.00069 0.00082 0.00096

11084 7 0.00037 0.00048 0.00060

11083 7 0.00022 0.00033 0.00043

11082 7 0.00020 0.00030 0.00041

11081 7 0.00052 0.00064 0.00076

11080 6 0.00026 0.00036 0.00047

11079 6 0.00021 0.00032 0.00042

11076 6 0.00039 0.00051 0.00063

11077 6 0.00056 0.00068 0.00080

1107b 6 0.00059 0.00073 0.00086

11075 6 0.00058 0.00072 0.00085

11074 6 0.00023 0.00034 0.00045

11073 6 0.00041 0.00053 0.00065

11072 6 0.00028 0.00039 0.00049

11071 6 0.00025 0.00035 0.00046

11070 6 0.00037 0.00048 0.00060

11069 6 0.00026 0.00036 0.00047

11068 6 0.00022 0.00033 0.00043

11067 5 0.00015 0.00025 0.00036

11066 5 0.00023 0.00034 0.00045

11065 5 0.00020 0.00030 0.00041

11064 5 0.00049 0.00061 0.00072

11063 5 0.00044 0.00056 0 .00068

11062 5 0.00058 0.00072 0.00085

1 1061 5 0.00076 0.00090 0.00103

11060 5 0.00017 0.00028 0.00039

11059 5 0.00021 0.00032 0.00042

110 5 6 5 0.00012 0.00023 0.00034

1 1057 5 0.00027 0.00038 0.00048

11056 5 0.00031 0.00041 0 . 0 0 0 5 2 11055 5 0.00034 0.00046 0. 00058

1 1054 5 0.00046 0.00058 0.00070

11053 5 0.00046 0.00059 0.00071

11052 4 0.00048 0.00059 0.00071

81
Table 10 continued

THE CONCENTRATION OF DISSOLVED SCANDIUM

(IN NANOGRAMS/mILLIUTER)

THE RANGE REPRESENTS AT LEAST

THE 95% CONFIDENCE LIMITS

MPLF NUMBER minimum BEST VALUE MAXIMUM

11051 4 0.00031 0.00041 0.00052

11050 4 0.00070 0.00084 0.00097

11049 4 0.00033 0.00044 0.00054

1104b 4 0.00029 . 0.00040 0.00051

11047 4 0.00035 0.00047 0.00059

11046 4 0.00034 0.00046 0.00058

11045 4 0.00025 0.00035 0.00046

11044 4 0.00021 0.00032 0.00042

11043 4 0.00056 0.00068 0.00080

11042 4 0.00017 0.00028 0.00039

11041 4 0.00050 0.00062 0.00074

11040 4 0.00020 0.00032 0.00043

11039 4 0.00038 0.00050 0.00062

1 1038 3 0.00032 0.00042 0.00053

11037 3 0.00018 0.00030 0.00042

11036 3 0.00018 0.00029 0.00040

11035 3 0.00214 0.00240 0.00266

11034 3 0.00017 0.00028 0.00039

11033 3 0.00081 0.00096 0.0011 1 11032 3 0.00031 0.00041 0.00052

11031 3 0.00035 0.00047 0.00059

11030 3 0.00026 0.00036 0.00047

11029 3 0.00045 0.00057 0.00069

11028 3 0.00033 0.00045 0.00057

1 1027 3 0.00032 0.00044 0.00056

1102b 3 0.00021 0.00032 0.00042

11025 3 0.00033 0.00045 0.00057

1 1 024 2 0.00032 0.00042 0.00053

11023 2 0.00089 0.00104 0.00119

11022 2 0.00028 0.00039 0.00049

11021 2 0.00028 0.00039 0.00049

110 20 2 0.00034 0.00046 0.00058

11019 2 0.00037 0.00048 0.00060

noia 2 0.00039 0.00051 0.00063

1 lul7 2 0.00031 0.00U41 0.00052

11016 2 0.00021 0.00032 0.00042

11015 2 0.00025 0.00035 0.00046

11014 2 0.00029 0.00040 0.00051

11013 2 0.00012 0.00023 0.00034

11012 2 0.00022 0.00033 0.0O043

11011 2 0.00103 0.00120 0.00137

1 1010 1 0.00035 0.00047 0.00059

11009 1 0.00033 0.00044 0.00054

11008 1 0.00101 0.001 16 0.00132

11007 1 0.00083 0.00098 0.00113

1 1 00b 1 0.00068 0.00081 0.00095

110 0 5 1 0.00059 0.00073 0.00086

1 1 004 1 0.00069 0.00082 0.00096

110 0 3 1 0.00014 0.00056 0.00068

1 1002 1 0.00034 0.00045 0.00055

11001 1 0.00037 0.00048 0.00060

82
Table 11

THE CONCENTRATION OF DISSOLVED TIN

(IN NANOGRAMS/MILLILITER)

THE RANGE REPRESENTS AT LEAST

THE 95% CONFIDENCE LIMITS

SAMPLE INUMBER MINIMUM BEST VALUE MAXIMUM

11102 8 0.19 0.31 0.4 3

11101 8 1.44 1.61 1.78

11100 8 < 0.40

11099 8 < 0.40

11098 8 0.26 0.50 0.74

11097 8

• < 0.40

11096 8 < 0.40

11095 7 < 0.50

11094 7 < 0.40

11093 7 < 0.40

11092 7 < 0.50

11091 7 < 0.20

11090 7 < 0.30

11089 7 < 0.30

11088 7 < 0.60

11087 7 < 0.60

11086 7 < 0.50

11085 7 < 0.50

11084 7 < 0.90

11083 7 < 0.50

11082 7 < 0.50

11081 7 < 0.60

11080 6 0.13 0.37 0.61

11079 6 < 0.40

11078 6 < 0.50

11077 6 0.74 1.10 1.46

11076 6 0.68 0.97 1.26

11075 6 0.87 1.35 1.83

11074 6 < 0.50

11073 6 < 0.50

11072 6 < 0.40

11071 6 < 0.50

11070 6 < 0.40

11069 6 < 0.50

11068 6 < 0.50

11067 5 < 0.60

11066 5 < 0.50

11065 5 < 0.50

11064 5 < 0.50

11063 5 < 0.60

11062 5 < 0.50

11061 5 < 0.50

11060 5 < 0.50

11059 5 < 0.50

11058 5 < 0.50

11057 5 < 0.50

11056 5 < 0.50

11055 5 < 0.50

11054 5 < 0.50

11053 5 < 0.50

11052 4

83

< 0.40
Table 11 continued

THE CONCENTRATION OF DISSOLVED TIN

(IN N A N OG R A M S / M I L L I L I T F R

)

THE RANGE REPRESENTS AT LFAST

THE 95% CONFIDENCE LIMITS

SAMPLE NUMBER MINIMUM BEST VALUE MAXIMUM

11051 4

11050 4

11049 4

11048 4 11047 4

11046 4 11045 4

11044 4

11043 4

11 C 42 4

11041 4

11040 4

11039 4

11038 3

11037 3 11036 3

11035 3

11034 3 11033 3 11032 3

11031 3 11030 3

11029 3

11028 3

11027 3

11026 3 11025 3

11024 2

11023 2 0.14

11022 2

11021 2

11020 2

11019 2 11018 2

11017 2

11016 2 0.40

11015 2

11014 2

11013 2

11012 2

11011 2

11010 1 11009 1 11008 1 11007 1 11006 1 11005 1 11004 1 11003 1 11002 1 11001 1

< 0.40

< 0.60

< 0.50

< 0.50

< 0.50

< 0.50

< 0.50

< 0.40

< 0.60

< 0.50

< 0.50

< 0.50

< 0.40

< 0.50

< 0.60

< 0.60

< 0.60

< 0.70

< 0.60

< 0.50

< 0.60

< 0.50

< 0.50

< 0.50

< 0.50

< 0.60

< 0.60

< 0.60

0.86 1.58

< 0.60

< 0.60

< 0.60

< 0.60

< 0.60

< 0.40

0.64 O.PR

< 0.40

< 0.60

< 0.40

< 0.40

< 0.50

< 0.40

< O.toO

< 0.70

< 0.60

< 0.50

< 0.60

< 0.50

< 0.30

< 0.40

< 0.40

84
THE CONCENTRATION OF DISSOLVED THORIUM

(IN NANOGRAMS/MILLILITER)

THE RANGE REPRESENTS AT LEAST

THE 95% CONFIDENCE LIMITS

SAMPLE NUMBER MINIMUM BEST VALUE MAXIMUM

1 1102 8 0.00000 0.00137 0.00259

11101 8 0.00000 0.00571 0.00694

11100 8 0.00000 0.00199 0.00346

11099 8 0. 00000 0.00124 0.00223

,110 98 8 0. 00000 0.00137 0.00235

11097 8 < 0.00100

11096 8 0.00000 0.00112 0.00210

11095 7 0.00000 0.00075 0.00222

11094 7 0.00000 0.0^099 0.00246

11093 7 0.00000 0.00099 . o c>? a f 11092 7 0.00000 0.0012 t

• I.Q2 47

11091 7 0.00000 0.00037 0.00136

11090 7 0.00000 0.00025 0.00123

11089 7 0.00000 0.00037 0.00136

11088 7 < 0.00200

11087 7 < 0.00200

11086 7 < 0.00 lOO

11085 7 < 0.00200

11084 7 < 0.00 i 00

11083 7 < 0.00)80

11082 7 0.00000 0.00050 0.00172

11081 7 0.00000 0.00087 0.00185

11080 6 < 0.00080

11079 6 < 0.00090

11078 6 < 0.00090

11077 6 0.00000 0.00161 0.00260

11076 6 0.00000 0.00161 0.00260

11075 6 0.00000 0.00248 0.00347

11074 6 < 0.00090

11073 6 < 0.00090

11072 6 < 0.00080

11071 6 < 0.00090

11070 6 < 0.00090

11069 6 < 0.00090

11068 6 < 0.00090

11067 5 0.00000 0.00112 0.00259

11066 5 0.00000 0.00112 0.00259

11065 5 < 0.00100

11064 5 < o.ooioo

11063 5 < 0.00100

11062 5 < 0.00100

11 061 5 < 0.00100

11060 5 < 0.00100

11059 5 < o.ooioo

11058 5 < 0.00100

11057 5 < 0.0019')

11056 5 < 0.001^0

11055 5 < o.ooioo

11054 5 < 0.00090

11053 5 < 0.00090

11052 4 < 0.00070

85
Table 12 continued

THE CONCENTRATION OF DISSOLVED THORIUM

(IN NANOGRAMS/MILLILITER)

THE RANGE REPRESENTS AT LEAST

THE 95% CONFIDENCE LIMITS

SAMPLE 1dumber MINIMUM BEST VALUE MAXIMUM

11051 4 0.00000 0.00037 0.00136

11050 4 0.00000 0.00075 0.00197

11049 4 < 0.00090

11048 4 < 0.00070

11047 4 < 0.00080

11046 4 < 0.00090

11045 4 0.00000 0.00050 0.00148

11044 4 0.00000 0.00037 0.00136

11043 4 < 0.00090

11042 4 < 0.00070

11041 4 < 0.00080

1 1040 4 < 0.00070

11039 4 < 0.00060

1103* 3 < 0.00080

11037 3 < 0.00080

1 103o 3 0.00000 0.00174 0.00272

110 3 5 3 0.00000 0.00385 0.00508

11034 3 0.00000 0.00161 0.00260

11033 3 0.00000 0.00211 0.00309

1 1032 3 0.00000 0.00211 0.00334

11031 3 0.00000 0.00137 0.00235

11030 3 < 0.00060

11029 3 0.00000 0.00025 0.00123

1 102b 3 < 0.00070

11027 3 < 0.00060

110 2b 3 < 0 . OOO^J

11025 3 < 0.00080

1 1024 2 < 0.00100

11023 2 0.00000 0.00112 0.00234

110 22 2 < 0.00100

110 21 2 < C. 00100

110 2 0 2 0 . u 0 0 0 0 0 .00076 0.00197

11019 2 < 0.001 00

11018 2 < o.ooioo

11017 2 0.00000 0.00025 0.00123

11016 2 0.00000 0.00075 0.00173

11015 2 < 0.00070

11014 2 < 0.00070

11013 2 < 0.00050

11012 2 < 0.00060

11011 2 < 0.00060

11010 1 0.O0000 0.00025 0.00123

110 0 9 1 < 0.00090

1 1008 1 < 0.00100

11007 1 < 0.00100

110 0 6 1 < 0.00070

11005 1 < 0.00090

1 1 0 0 4 1 < 0.00070

1 1 00 3 1 0.00000 O.OOnit 0.00092

11002 1 0.00000 0.00006 0. 0008

11001 1 0 .00000 0.00060 0 . 0 0 1 4 H 86
Table 13

THE CONCENTRATION OF DISSOLVED URANIUM

(IN NANOGRAMS/MILLILITER)

THE RANGE REPRESENTS AT LEAST

THE 95% CONFIDENCE LIMITS

MPLE INUMBER MINIMUM BEST VALUE MAXIMUM

11 102 8 0.124 0.133 0.152

11101 8 0.117 0.130 0.142

11100 6 0.175 0.195 0.216

11099 8 0.146 0.163 0.179

11098 8 0.190 • 0.210 0.230

11097 8 0.161 0.179 0.197

11096 8 0.161 0,179 0.197

11095 7 0.154 0.170 0.186

11094 7 0.168 0.186 0.204

11093 7 0.158 0.176 0.194

11092 7 0.258 0.278 0.298

110 91 7 0.330 0.370 0.411

11090 7 0.237 0.257 0.277

11089 7 0.237 0.257 0.277

110 8 8 7 0.464 0.504 0.544

11087 7 0.464 0.525 0.585

11086 7 0.464 0.504 0.544

11085 7 0.928 1.026 1.129

11084 7 0.474 0.535 0.595

11083 7 0.443 0.483 0.524

110 8 2 7 0.526 0.586 0.647

110 81 7 0.515 0.576 0.636

11080 6 0.536 0.597 0.657

11079 6 0.515 0.576 0.636

11076 6 0.454 0.514 0.575

11077 6 0.485 0.545 0.606

110 7 6 6 0.670 0.751 0.831

11075 6 0.711 0.792 0.873

110 7 4 6 0.577 0.638 0.698

11073 6 1.103 1.224 1.345

11072 6 0.557 0.617 0.678

11071 6 0.598 0.658 0.719

11070 6 0.639 0.699 0.760

11069 6 0.876 0.977 1.078

1 106b 6 0.639 0.72 1 0.801

110 6 7 5 0.742 0.323 0.903

11066 5 0.649 0.710 0.770

11065 5 1 .247 1 .389 1.530

110 6 4 5 0.794 0.974 0.955

1 1063 5 0.773 0.854 0.934

11062 5 0.577 0.638 0.698

11061 5 0.650 0.730 0.811

1 1060 5 0.670 0.751 0.831

11059 5 0.814 0.995 0.975

1 1 0 5 6 5 0 .598 0.659 0.719

110 5 7 5 0.969 1 . 0 9 0 1.191

11056 5 0.5 46 0.60 7 0.667

11 0 6 5 5 0.763 0.843 0.924

110 5 4 5 0.691 0.771 0.852

11053 5 0.732 0.613 0.893

11052 4 0.6? 4 0.905 0.986

87
Table 13 continued

THE CONCENTRATION Of- DISSOLVED URANIUM

(IN NANOGRAM S/MILLILITFR)

THE RANGE REPRESENTS AT LEAST

THE 95% CONFIDENCE LIMITS

MPLE 1NUMBER MINIMUM BEST VALUE MAXIMUM

1 1 ubl 4 0.938 1.039 1.140

11050 4 0.989 1.090 1.191

1 1 049 4 0.814 0.895 0.975

11048 4 1,010 1.111 1.212

11047 4 0.«89 1.090 1.191

11046 4 1.000 1 .100 1.201

11045 4 0.742 0.823 0.903

11044 4 0.608 0.669 0.729

11043 4 1.052 1.172 1.293

11042 4 0.866 0.967 1.068

11041 4 1.371 1.512 1.653

11040 4 0.917 1.018 1.119

11039 4 1.443 1.604 1.766

11038 3 0.691 0.771 0.852

11037 3 1.165 1.286 1.407

11036 3 0.814 0.895 0.975

11035 3 1.217 1 . 359 1.499

11034 3 0.845 0.946 1.047

11033 3 1.237 1.378 1.519

11032 3 0.856 0.957 1.057

11031 3 1 .144 1.265 1.366

11030 3 0.887 0.987 1.088

11029 3 1.412 1.574 1.735

11026 3 0.660 0.741 0.821

110 2 7 3 0.804 0.885 0.965

11026 3 1.185 1.306 1.427

11025 3 1.515 1.676 1.838

11024 2 1.371 1.512 1.653

11023 2 1.464 1.646 1.807

110 2 2 2 1.134 1.255 1.376

11021 2 1.154 1.275 1.396

11020 2 1.000 1.100 1.201

11019 2 1.154 1.275 1.396

11016 2 1.154 1 .275 1.396

11017 2 1.072 1.193 1.314

1 1016 2 0.752 0.833 0.914

11015 2 1.402 1.563 1.725

11014 2 1.505 1.666 1.827

1 1013 2 0.608 0.669 0.729

11012 2 1.258 1 . 399 1 .540

11011 2 1.958 2.160 2.361

11010 1 1.258 1 .399 1.540

1 1009 1 1.525 1.667 1.648

1 1006 1 1.773 1.975 2.176

1 1007 1 2.370 2.571 '2.773

11006 1 0.567 0.62 7 0.688

l luub 1 0.969 1.070 1.170

110 0 4 1 1.196 1.316 1 .437

110 0 3 1 1 .464 1.625 1.786

11002 1 1 .258 1 . 399 1 .540

11001 1 1.350 1 .401 1.632

88
Table 14

THE CONCENTRATION OF DISSOLVED ZINC

(IN NANOGRAMS/MILLILITER)

THE RANGE REPRESENTS AT LEAST

THE 95* CONFIDENCE LIMITS

SAMPLE 1NUMBER MINI M !J M BEST VALUE MAXIMUM

11102 8 0.00 0.00 0.91

11101 e 0.00 0.00 0.71

11100 8 0.00 1.39 3.94

1 1 099 8 0.00 0.67 3.22

1109b 8 0.00 0.00 0.42

11097 8 0.00 0.00 1.55

11096 8 0.00 0.00 1.86

11095 7 0.00 0.69 2.32

11094 7 4.14 8.09 10.64

11093 7 1.80 5.52 7.84

11092 7 0.00 1.92 3.78

11091 7 0.00 2.44 4.30

11090 7 0.00 0.00 1.47

11089 7 0.00 0.69 2.32

11088 7 0.00 2.64 4.50

11087 7 0.00 2.64 4.50

11086 7 0.00 0.38 2.01

11085 7 0.00 1.10 2.73

11084 7 0.00 0.00 0.47

11083 7 0.00 0.00 1.42

11082 7 0.00 0.38 2.01

11081 7 0.00 1.82 3.68

11080 6 0.00 0.25 1.77

11079 6 0.00 0.00 1.06

11078 6 0.00 1.06 2.61

11077 6 0.00 0.65 2.19

11076 6 0.19 3.53 5.54

11075 6 0.00 0.85 2.40

110 7 4 6 0.00 1.06 2.61

11073 6 0.00 0.00 1.01

11072 6 0.00 0.00 0.64

11071 6 0.00 0.00 1.04

11070 6 0.00 0.00 0.65

11069 6 0.00 0.85 2.40

11068 6 0.00 0.36 1.91

11067 5 0.00 2.27 3.8 0

1 1 066 5 0.00 0.33 1.56

1 1 065 5 0.00 0.00 0.86

1 10o4 5 2.31 5.15 6.91

11063 5 0.00 o.oo 1.17

11062 5 0.00 0.00 1.16

11061 5 o.oo 0.07 1.28

11060 5 1.69 4.54 6.30

11059 5 0.00 0.00 1.00

11058 5 0.00 0.38 1.61

11057 5 0.00 0.00 1.02

11056 5 0.00 0.06 1.27

1 1 055 5 o.oo 0.00 1.02

11054 5 1.39 4.23 5.99

1 1053 5 o.oo 0.88 2.18

11062 4 o.oo 0.00 1.17

89
Table 14 continued

THE CONCENTRATION OF DISSOLVEO ZINC

(In NANQGRAMS/M ILL1LITER)

THfc] range

THE 95%

REPRESENTS

CONFIDENCE

AT LF AST

LIMITS

S A M y L K 6 U M B fc H MINIMUM BEST VALUE MAXIMUM

11051 4 0.00 0.00 0.79

1 1 050 4 2.86 6.06 8.11

11049 4 0.00 0.00 1.27

1104a 4 0.00 0.13 1.43

110 4 7 4 0.00 0.00 1.01

1104C 4 0.00 0.31 1.62

110 4 5 4 0.00 0.00 1 .10

1 1044 4 0.00 1.94 3.54

1 lu43 4 0.00 0.20 1.49

11042 4 0.00 0.00 0.91

11041 4 0.00 0.00 1.12

11040 4 0.00 0.21 1.50

11039 4 0.00 1 .02 2.38

1103b 3 0.00 0.81 1.82

110 3 7 3 0.00 0.14 1 .08

11036 3 0.8b 3.19 4.47

11035 3 0.00 0.42 1.38

11034 3 7.87 11.11 13.31

11033 3 0.00 0.75 1.76

11032 3 5.35 8.13 9.87

11031 3 0.00 0.00 0.87

110 30 3 0.00 0.43 1.39

11029 3 0.00 1.09 2.12

1102b 3 0.00 0.98 2.01

11027 3 0.00 0.97 2.00

11026 3 0.05 2.37 3.65

1 1025 3 0.00 0.37 1.33

11024 2 0.00 1.25 2.39

110 2 3 2 0.00 0.06 1.08

11022 2 0.00 0.75 1 .84

110 21 2 0.0 0 0.64 1.73

11020 2 0.00 1.3b 2.49

11019 2 o.uo 1.15 2.29

1 101b 2 0.00 2.2 3 3.65

11017 2 0.00 0.53 1.60

11016 2 0.00 0.00 0.78

1 1015 2 0.00 0.00 0.74

11014 2 0.00 0.43 1.50

11013 2 0.00 0.00 0.77

11012 2 0.00 0.00 0.89

11011 2 0.00 0.22 1.24

11010 1 0.00 0.56 1.27

1 100 9 1 O.O0 0.23 0.89

l 100b 1 o.oo 0.31 0.9 8

1 1007 1 0.00 0.14 o •

or *—

11006 1 0.0 0 1.43 2.24

1 1 005 1 0.0 0 1.36 2.14

1 1004 1 0.47 2.30 3.11

11003 1 0.00 0.92 1.65

11U02 1 5.43 7.96 9.46

11001 1 o.oo 0.41 1.10

90
fable 15

the CONCENTRATION OF particulate CADMIUM

(I* MANOGRAMS/MILLILITER)

THE RANGE REPRESENTS AT LEAST

THE 95% CONF IOENCE LIMITS

SAMPLE NUMBER MINIMUM BEST VALUE MAXIMUM

1 1102 0.016 0.024 0.032

11101 0.075 0.093 0.111

11100 0.002 0.004 0.006

11099 0.011 0.015 0.019

11098 0.030 0.040 0.050

11097 0.050 0.066 0.082

11096 0.013 0.021 0.029

11095 0.016 0.024 0.032

11094 0.045 0.059 0.073

11093 0.091 0.099 0.117

11092 0.011 0.017 0.023

11091 0.012 0.018 0.024

11090 o.ooi 0.003 0.005

11089 0.005 0.009 0.013

11088 0.002 0.006 0.010

11087 0.006 0.010 0.014

11086 0.000 0.001 0.003

11085 < 0.001

11084 < 0.001

11083 0.001 0.003 0.005

11082 0.001 0.00 3 0.005

11081 < 0.001

11080 0.006 0.010 0.014

11079 0.002 0.004 0.00b

11078 0.007 0.015 0.023

11077 0.00 3 0.007 0.011

11076 0.000 0.002 0.004

11075 < 0.001

11074 0.004 0.009 0.012

11073 0.003 0.005 0.007

11072 0.009 0.017 0.025

11071 0.009 0.017 0.025

11070 0.000 0.002 0.004

11069 0.000 0.002 0.004

11068 0.000 0.002 0.004

11067 0.003 0.007 0.011

1 1 066 0.002 0.004 0.006

11065 < 0.001

11064 < 0.001

11063 0.004 0.008 0.012

11062 < 0.001

11061 0.008 0.012 0.016

11060 < 0.001

11059 < 0.001

11058 0.000 0.001 0.003

11057 < 0.001

11056 < o.ooi

11055 < 0.001

11054 < o.ooi

11053 < 0.001

11052 < 0.001

91
Table 15 continued

THE CONCENTRATION OF PARTICULATE CADMIUM

(IN NANOGRAMS/M ILLILITER)

THE RANGE 1REPRESENTS AT LEAST

THE 95 % confidence: LIMITS

sample: NUMBER MINIMUM BFST tfALUE MAXIMUM

11051 < 0.001

11050 < 0.001

11049 < 0.001

11046 0.090 0.110 0.130

11047 0.014 0.020 0.026

1 1 04b 0.001 0.003 0.005

11045 0.017 0.023 0.029

11044 < 0.001

11043 0.005 0.007 0.009

11042 < 0.001

11041 < 0.001

11040 < 0.001

11039 < 0.001

11036 < 0.001

11037 < 0.001

1103b 0.018 0.022 0.026

1 1035 < 0.001

11034 < 0.001

11033 < 0.001

11032 < 0.001

11031 < 0.001

11030 < 0.001

11029 < 0.001

11028 < 0.001

11027 < 0.001

11026 < 0.001

11025 < 0.001

11024 < 0.001

11023 < 0.001

11022 < 0.001

11021 0.040 0.060 0.080

11020 0.000 0.001 0.003

11019 0.005 o.on 0.017

11016 < 0.001

11017 0.000 0.001 0.003

11016 < 0.001

11015 ' < 0.001

11014 < 0.001

11013 < 0.001

11012 < 0.001

11011 0.000 0.002 0.004

11010 < 0.001

11009 0.000- 0.002 0.004

11006 < 0.001

11007 < 0.001

1 1 006 < 0.001

11005 0.001 0.003 0.005

11004 < 0.001

11003 0.002 0.004 0.006

1 1002 < 0.001

11001 0.003 0.005 0.007

92
THE CONCENTRATION OF PARTICULATE CERIUM

(IN NANOGRAMS/MILLILITER)

THE RANGE REPRESENTS AT LEAST

THE 95% CONFIDENCE LIMITS

SAMPLE NUMBER MINIMUM BEST VALUE MAXIMUM

11102 3.608

11101 3.814

11100 1 .165

11099 1.227

11098 2.370

11097 2.682

11096 3.814

11095 3.711

11094 4.431

11093 4.328

1 1092 1.402

11091 2.575

11090 0.783

11089 0.804

11088 0.474

11087 1.031

11086 0.092

11085 0.127

1 1084 0.127

110 8 3 0.144

11082 0.072

1 10H1 0.157

11080 0.057

11079 0.057

11078 0.299

110 7 7 0.309

11076 0.123

11075 0.142

11074 0.065

11073 0.114

110 7 2 0.186

11071 0.278

11070 0.061

11069 0.137

1 1 068 0.154

11067 0.402

11066 0.044

11065 0.155

11064 0.227

1 1 063 0.618

11062 1.814

11061 0.680

11060 0.033

1 1 059 0.037

11058 0.03H

11057 0.175

11056 0.081

11055 0.237

11054 0.392

11053 0.680

11052 0.289

4.011 4.414

4.217 4.620

1.286 1.407

1.368 1.509

2.571 2.773

3.085 3.489

4.217 4 . b20

4.114 4.517

4.834 5.237

4.731 5.134

1.563 1.725

2.777 2.978

0.864 0.945

0.884 0.965

0.535 0.595

1 .152 1.273

0.102 0.112

0.141 0.155

0.141 0.155

0.160 0.177

0.080 0.088

0.175 0.193

0.063 0.069

0.065 0.07 3

0.339 0.380

0.350 0.390

0.137 0.151

0.158 0.175

0.071 0.077

0.127 0.139

0.206 0.2 26

0.298 0.318

0.069 0.077

0.151 0.165

0.170 0.186

0.442 0.483

0.057 0.069

0.175 0.195

0.267 0.30P

0.679 0.739

2.016 2.217

0.761 0.842

0.037 0.041

0.043 0.049

0.0 44 0.050

0.195 0.216

0.089 0.098

0.257 0.277

0.432 0.472

0.761 0.8 42

0.329 0.369

93
Table 16 continued

THE CONCENTRATION OF PARTICULATE CERIUM

(IN NANOGRAMS/MILLILITER)

THE RANGE REPRESENTS AT LEAST

THE 95% CONFIDENCE LIMITS

SAMPLE NUMBER MINIMUM BEST VALUE MAXIMUM

11051 0.279 0.319 0.359

11050 0.485 0.545 0.606

11049 0.454 0.514 0.575

1 1U48 0.258 0.298 0.339

11047 0.794 0.874 0.955

11046 0.039 0.043 0.047

11045 0.969 1.070 1 .170

1 1 044 0.279 0.319 0.359

1 1043 0.783 0.864 0.945

11042 0.035 0.039 0.043

11041 0.268 0.309 0.349

11040 0.030 0.034 0.038

11039 0.938 1.039 1.140

1 1038 0.044 0.052 0.061

11037 0.248 0.288 0.328

1103b < 0.020

11035 0.165 0.185 0.205

11034 0.019 0.023 0.027

11033 0.186 0.206 0.226

11032 0.034 0.040 0.046

11031 0.081 0.094 0.106

110 30 0.144 0.165 0.185

11029 0.763 0.843 0.92 4

11026 0.124 0.144 0.164

11027 0.453 0.494 0.534

11026 0.144 0.165 0.185

11025 0.279 0.319 0.359

11024 0.085 0.095 0.105

11023 0.453 0.494 0.534

11022 0.207 0.247 0.287

11021 0.928 1 .028 1 .129

11020 0.139 0.153 0.167

11019 0.577 0.638 0.698

11018 0.794 0.874 0.955

11017 0.701 0.782 0.862

1 1 016 0.027 0.039 0.051

110 15 0.402 0.442 0.483

11014 0.093 0.113 0.133

11013 0.216 0.2 17 0.257

11012 0.206 0.226 0.246

1 1 0 1

1.010 1.111 1.212

11010 0.105 0. 117 0.129

110 0 9 0.2 37 0.278 0.318

11008 0.155 0.175 0.195

11007 0.247 0.267 0.288

11006 1 .629 1.810 1.992

11005 5.566 6.171 6.775

1 1 uO 4 0.825 0.926 1.026

11003 0.526 0.586 0.647

11002 0.144 0.165 0.185

11001 °- 433

94

0.473 0.513
THE CONCENTRATION OF PARTICULATE COBALT

(IN NANOGRAMS/MILLILITER)

THE RANGE REPRESENTS AT LEAST

THE 95% CONFIDENCE LIMITS

SAMPLE NUMBER MINIMUM BEST VALUE MAXIMUM

11102 1.134 1.255 1 .376

n i o i 1.175 1.296 1.417

11100 0.567 0.627 0.688

11099 0.608 0.668 0.729

11098 1.051 1.172 1.293

11097 1.268 1.409 1.550

11096 1.206 1.347 1.488

11095 1.165 1.286 1.407

11094 2.164 2.365 2.567

11093 2.164 2.365 2.567

11092 0.474 0.535 0.595

11091 1 .103 1.224 1.345

11090 0.340 0.381 0.421

11089 0.350 0.391 0.431

11088 0.175 0.193 0.211

11087 0.402 0.442 0.483

11086 0.048 0.055 0.061

11085 0.027 0.031 0.035

11084 0.053 0.059 0.065

110 8 3 0.057 0.063 0.069

110 8 2 0.040 0.044 0.048

11081 0.068 0.076 0.084

11080 0.030 0.034 0.038

11079 O .034 0.038 0.042

1

1

078 0.065 0.071 0.077

1 1 077 0.064 0.072 0.080

1 1076 0.037 0.043 0.049

1 1075 0.053 0.059 0.065

11074 0.029 0.033 0.037

1 1073 0.015 0.017 0.019

11072 0.04 4 0.050 0.056

1 1071 0.064 0.07 2 0.080

110 7 0 0.026 0.0 30 0.034

11069 0.040 0.044 0.048

1 1068 0.036 0.042 0.048

11067 0.092 0.102 0.112

11066 0.013 0.023 0.033

11065 0.027 0.037 0.047

1 10 6 4 0.013 0.029 0.045

11063 0.054 0.066 0.078

1 1 062 0.289 0.329 0.369

1 1061 0.117 0 . 130

' 0.142

1 1 06 0 0.019 0.023 0.027

110 5 9 0.026 0.030 0.034

1 1 Obft 0.0 18 0.022 0.026

110 6 7 0.035 0.039 0.043

1 !. 0 5 6 0.037 0.045 0.05 3 11055 0.059 0.065 0.071

110 5 4 0.064 0.072 0.080

11053 0.109 0.121 0.133

11062 0.039

g5

0.04 7 0.055
Table 17 continued

the concentration of particulate cobalt

(IN NAr^OGRA MS/MILLILITER)

ThF RANGE REPRESENTS AT LEAST

THE 95% CONFIPPNCE LIMITS

PL E NUMBER MINIMUM BEST VALUE MAXIMUM

110 51 0.053 0.059 0.065

1 1050 0.074 0.084 0.094

110 4 9 0.081 0.092 0.102

1 104b 0.057 0.063 0.069

1 1047 0.128 0.142 0.156

11046 0.022 0.026 0.030

11045 0.164 0.182 0.200

11044 0.063 0.071 0.079

1 1043 0.206 0.226 0.246

11042 0.028 0.032 0.036

11041 0.044 0.050 0.056

1 1040 0.03 3 0.037 0.041

11039 0.156 0.172 0.188

110 3 8 0.036 0.042 0.048

110 3 7 0.043 0.049 0.055

11036 0.028 0.040 0.052

11035 0.029 0.035 0.041

11034 0.019 0.021 0.023

11033 0.040 0.046 0.052

11032 0.023 0.029 0.035

11031 0.064 0.074 0.084

11030 0.040 0.050 0 . 060

1 1 029 0.112 0.127 0.141

1 1 028 0.054 0.062 0.070

11027 0.100 0.112 0.124

11026 0.035 0.041 0.047

11025 0.043 0.051 0.059

11024 0.025 0.031 0 . n 3 7 11023 0.093 0.107 0.121

11022 0.047 0.067 0.087

11021 0.148 0.165 0.181

11020 0.036 0.042 0.048

11019 0.106 0.118 0.130

11018 0.165 0.183 0.201

11017 0.163 0.181 0.199

11016 0.026 0.034 0.042

11015 0.062 0.072 0.082

11014 0.041 0.053 0.06b

11013 0.051 0.057 0.063

11012 0.049 0.059 0.069

11011 0.148 0.165 0.181

11010 0.023 0.029 0.035

1 1009 0.057 0.069 0.081

11008 0.031 0.035 0.039

1 1007 0.047 0.053 0.06Q

1 1006 0.258 0.298 0.339

11005 0.943 1 .049 1.150

1 1 0 o 4 0.155 0.171 0.187

11003 0.097 0.109 0.121

1 1 002 0.039 0.051 0.064

11001 0.072

g6

0.080 0.088
THE CONCENT RATION OF PARTICULATE CHROMIUM

(IN NANOGRAMS/MILLIL ITER

)

THE RANGE REPRESENTS AT LEAST

THE 95% CONFIDENCE LIMITS

SAMPLE NUMBER MINIMUM BEST VALUE M A X I M 1J M

11102 3.58 4.49 5.16

11101 3.45 4.60 5.49

11100 0.82 1.27 1 .49

11099 0.86 1.31 1.53

11098 2.01 2.62 3.00

11097 2.30 3.14 3.74

11096 3.76 4.91 5.60

11095 3.86 5.01 5.91

11094 3.6 3 4.47 5.08

11093 3.63 4.47 5.08

11092 1.52 2.44 3.10

11091 2.55 3.47 4.13

11090 0.47 0.99 1.27

11089 0.43 0.95 1.23

11088 0.17 0.67 0.93

11087 0.8 5 1.44 1.79

1108b 0.00 0.14 0.36

11085 0.00 0.13 0.35

11084 0.00 0.23 0.44

110 8 3 0.00 0.22 0.43

11082 0.00 0.16 0.44

110 8 1 0.00 0.34 0.55

11060 0.00 0.09 0.68

11079 0.00 0.14 0.73

11078 0.00 0.37 1.14

11077 0.00 0.22 0.80

11976 0.00 0.09 0.68

11075 0.00 0.59 1.22

11074 0.00 0.16 0.75

11073 0.00 0.00 0.55

11072 0.00 0.27 0.85

11071 0.00 0.36 0.97

11070 0.00 0.00 0.53

11069 o.oo 0.25 0.83

11068 0.00 0.02 0.56

11067 0.00 0.44 1 .05

11066 0.00 0.00 0.52

11065 0.00 0.11 0.70

11064 0.00 0.15 0.74

11063 0.00 0.44 1.05

1 i 062 0.48 1.71 2.70

11061 0.00 0.00 0.54

11060 0.00 0.00 0.34

11059 0.00 0.00 •0.37

110 58 0.00 0.13 0.72

110 5 7 0.00 0.08 0.67

11056 0.00 0.01 0.57

11055 0.00 0.38 0.99

11054 0.00 0.22 0 .BO

1 1053 0 . UO 0.52 1.16

11052 °.°o

g7

0.39 1.00
Table 18 continued

TrttL' CONCENTRATION OF PARTICULATE CHROMIUM

(IN NANOGRAMS/MILLILITER)

THE RANGE REPRESENTS AT LEAST

THE 95% CONFIDENCE LIMITS

SAMPLE NUMBER MINIMUM BEST VALUE MAXIMUM

11051 0.00 0.14 0.73

1 1 050 0.00 0.07 0.66

11049 0.00 0.22 0.80

1 104B 0.00 0.00 0.46

11047 0.00 0.19 1.00

1 1046 0.00 0.00 0.15

11045 0.00 0.00 0.71

110 4 4 0.00 0.00 0.34

11043 0.00 0.30 1.11

1 1 042 0.00 0.00 0.35

11041 0.0 0 0.00 0.25

i 1040 0.0 0 0.00 0.43

11039 0.73 1.71 2.45

110 38 0.00 0.00 0.19

1 1037 0.00 0.00 0.44

11036 0.00 0.00 0.15

11035 0.00 0.00 0.14

11034 o.oo 0.00 0.49

11033 0.00 0.17 0.76

11032 0.00 0.19 1.00

11031 0.00 0.16 0.75

1 1030 0.00 0.69 1.34

11029 0.06 0.97 1.64

11028 0.00 0.30 0.91

11027 0.0 0 0.14 1.00

11026 0.00 0.00 0.02

11025 0.00 0.74 1.40

11024 0.00 0.22 0.80

11023 0.00 0.60 1.23

11022 0.00 0.15 0.74

11021 0.47 1.42 2.14

11020 0.00 0.47 1.31

11019 0.00 0.38 1.21

11018 0.00 0.8 5 1.73

11017 0.00 0.86 1.74

11016 0.00 0.06 0.62

11015 0.00 0.33 0.94

11014 0.0 0 0.24 0.59

11013 0.00 0.14 0.73

11012 0.0 0 0.42 1.03

1 101

0.00 0.47 1.08

11010 0.00 0.00 0.46

110 0 9 0.00 0.58 1.21

1 1008 0.00 0.17 0.50

11007 0.00 0.22 0.57

11006 0.51 1.46 2.18

11005 3.61 5.31 6.76

1100 4 0.0 0 0.45 1 .29

1 1 w03 0 .00 0.60 1 .45

11002 0 .00 0.01 0.57

lH-'Ul • o UD 00 0.50 1.14
Table 19

THE CONCENTRATION OF PARTICULATE COPPER

(IN NANOGRAMS/M I LLILI IER )

THE RANGE REPRESENTS AT LEAST

THE 95% CONFIDENCE LIMITS

SAMPLE NUMBER MINIMUM BEST VALUE MAXIMUM

11102 0.19 1.02 1.76

11101 0.39 1.22 1 .96

11100 0.43 0.87 1.24

11099 0.33 0.77 1.14

1 1098 0.59 1.34 2.02

11097 0.77 1.74 2.64

11096 0.37 1.42 2.38

11095 0.37 1.42 2.38

11094 0.92 2.34 3.69

11093 1.92 3.34 4.69

11092 0.00 0.62 1 . 36

11091 0.19 1.02 1.76

11090 0.00 0.32 0.73

11089 0.00 0.27 0.68

11088 0.00 0.44 0.87

11087 O.oO 0.42 0.85

11086 0.00 0.00 0.26

11085 0.00 0.00 0.17

11084 0.00 0.00 0.14

11083 0.00 0.00 0.15

11082 0.00 0.00 0.16

11081 0.00 0.00 0.32

11080 0.00 0.00 0.16

11079 0.00 0.00 0.10

11078 0.00 0.00 0.17

11077 0.00 0.00 0.16

11076 0.00 0.00 0.16

11075 0.00 0.00 0.21

11074 0.00 0.01 0.36

11073 0.00 0.00 0.26

11072 0.00 0.00 0.19

11071 0.00 0.00 0.29

11070 0.00 0.00 0.23

11069 0.00 0.00 0.28

1 1068 0.00 0.02 0.36

11067 0.00 0.10 0.46

11066 0.00 0.00 0.34

11065 0.00 0.13 0.49

11064 0.00 0.12 0.48

11063 0.00 0.20 0.59

11062 0.00 0.00 0.24

11061 0.00 0.39 0.81

11060 o.oo 0.11 0.47

11059 0.00 o.oo 0.3 3

11058 0.00 0.00 0.33

11057 0.00 0.15 0.51

11056 o.oo 0.00 0.17

11055 0 .00 0.07 0.41

11054 0.00 0.08 0.42

11053 0.00 0.02 0.36

11052 0.00 9 g 0.02 0.36
Table 19 continued

THE CONCENTRATION OF PARTICULATE COPPER

(IN NANUGRAMS/MILLILITER)

THE RANGE

THE 95*

REPRESENTS

CONFIDENCE

AT LEAST

LIMITS

SAMPLE NUMBER MINIMUM BEST VALUE MAXIMUM110 51 0.00 0.24 0.63

11050 0.00 0.00 0.25

11049 0 .00 0.00 0.23

1 104 R 0.00 0.00 0.11

11047 0.00 0.07 0.54

11046 0.00 0.00 0.20

11045 0.00 0.42 0.93

11044 0.00 0.00 0.27

11043 0.00 0.13 0.60

11042 0.00 0.00 0.29

11041 0.00 0.00 0.34

11040 0.00 0.00 0.3 3 11039 0.00 0.23 0.62

11038 0.00 0.00 0.28

1

037 0.00 0.00 0.28

11036 0.00 0.00 0.28

11035 0.00 0.00 0.15

11034 0.00 0.00 0.13

11033 0.00 0.00 0.30

11032 0.0 0 0.15 0.64

11031 0.00 0.00 0.28

11030 0.00 0.21 0.60

11029 0.00 0.11 0.47

11028 0.00 0.09 0.45

11027 0.00 0.19 0.68

11026 0.0 0 0.00 0.31

11025 0.00 0.06 0.42

11024 0.00 o.oo 0.31

11023 0.00 0.00 0.21

11022 0.00 0.07 0.43

11021 0.00 0.22 0.63

11020 0.00 0.00 0.41

11019 0.00 0.00 0.41

11018 0.00 0.09 0.58

11017 0.00 0.06 0.53

11016 0.00 0.00 0.24

11015 0.00 0.10 0.46

11014 0.00 0.26 0.54

11013 0.00 0.00 0.33

11012 0.00 0.00 0.33

11011 0.00 0.49 0.94

11010 0.00 0.00 0.32

11009 0.00 0.04 0.3 8

1 1008 0.0 0 0.00 0.17

11007 0.00 0.02 0.24

1100 6 0.22 0.74 1 .19

11005 1.32 2.82 4.23

1 1004 0.00 0.2 0 0.69

11003 0.00 0.00 0 . 1 b

1 1002 0.00 0.00 0.33

11001 0.00 100 0.04 0.40
THE CONCENTRATION OF PARTICULATE IRON

(IN NANOGRAMS/VILL1LITFR)

THE RANGE REPRESENTS AT LEAST

ThE 95% CONFIDENCE LIMITS

SAMPLE NUMBER MINIMUM or;st VALUE MAXIMUM

11102 1529 1718 1879

11101 1620 1931 2012

11100 462 535 595

11099 493 566 626

11096 920 1039 1140

11097 1113 1255 1376

11096 1578 1790 1971

11095 1499 1687 1848

11094 1692 190 3 2084

11093 1681 1892 2074

11092 645 740 821

11091 1265 1450 1 591

11090 382 432 472

11089 392 442 483

11068 230 257 277

11087 524 597 657

11066 42 50 54

11085 69 82 90

11064 55 66 72

11083 64 77 85

11082 32 40 44

11061 88 103 113

11080 22 31 35

11079 27 35 39

11076 120 140 154

110 7 7 128 148 162

11076 60 71 77

11075 85 101 111

11074 22 31 35

11073 122 142 156

11072 68 81 89

11071 106 123 136

11070 24 30 3 2

11069 63 99 1 0 9

11068 66 79 87

11067 199 226 246

11066 14 23 27

11065 103 120 132

11064 83 103 117

11063 2 30 257 277

11062 686 782 662

11061 271 298 318

11060 12 19 21

11059 19 25 27

11058 17 23 25

11057 102 119 131

11056 36 44 48

11055 111 129 141

11054 136 158 175

11053 241 267 288

11052 117 144 164

101
Table 20 continued

THE CONCENTRATION OF PARTICULATE IRON

(IN NANOGRAMS/MILLILITER)

THE RANGE REPRESENTS AT LEAST

THE 95% CONFIDENCE LIMITS

SAMPLE NUMBER MINIMUM BEST VALUE MAXIMUM

11051 111 129 141

11050 177 204 224

11049 188 215 235

11048 105 122 1 34

11047 310 360 400

1104b 10 16 1 0 11045 403 453 493

11044 104 121 133

11043 269 319 359

11042 15 22 24

11041 138 160 177

11040 12 18 20

11039 454 504 544

11038 22 31 35

11037 142 165 161

1 10 3b 7 17 24

1 1U35 84 100 110

11034 9 14 16

11033 92 107 117

11032 13 20 22

11031 57 68 74

11030 76 92 102

11029 382 432 472

11028 56 67 7 3

11027 199 226 246

11026 64 77 85

11025 133 155 171

110 24 39 47 51

11023 210 2 37 257

11022 95 110 120

11021 441 514 575

110 2 0 68 81 89

11019 2b9 319 359

11018 362 411 452

11017 331 381 421

11016 15 24 28

11015 173 200 220

11014 53 64 70

11013 101 1 1 8 130

11012 92 107 117

11011 454 504 544

11010 45 56 62

1 1009 118 138 152

11008 72 85 9 3

110 0 7 114 1 34 146

1 1006 747 843 924

11005 2584 2 911 3193

11004 362 432 472

1 1 003 237 270 297

11002 7 0 »3 91

110 01 220 1Q2

247 267
Table 21

THE CONCENTRATION OF PARTICULATE MANGANESE

(IN NANOGRAMS/MILLILITER)

THE RANGE REPRESENTS AT LEAST

THE 95% CONFIDENCE LIMITS

SAMPLE NUMBER MINIMUM BEST VALUE MAXIMUM

11102 92.5

11101 102.5

11100 95.5

11099 106.5

11098 130.6

11097 152.6

11096 157.6

11095 154.6

11094 246.6

11093 311.8

11092 53.9

11091 99.3

11090 35.7

11089 38.3

11088 30.9

11087 60.3

11066 21.0

11085 2.3

11084 21.1

11083 24.3

11082 27.1

11081 29.4

11080 14.6

11079 15.8

11078 15.9

11077 19.0

110 7 6 32.4

110 7 5 34.3

11074 9.7

11073 0.8

11072 12.4

11071 17.6

11070 5.2

11069 8.0

11066 15.4

11067 30.7

11066 5.0

11065 22.9

11064 15.3

11063 2 3.1

11062 2b. 7 11061 45.3

11060 10.0

11059 18.9

11056 10.0

11057 10.0

11056 19.1

11055 18.2

11054 10.8

11053 13.7

1105? 13.8

116.0 139.5

126.0 149.5

119.0 142.5

130.0 153.5

158.0 185.4

182.0 211.4

187.0 216.4

184.0 213.4

276.0 305.4

349.0 386.2

66.2 78.5

115.0 130.7

44.1 52.5

47.3 56.3

37.6 44.3

73.6 86.9

26.1 31.2

2.9 3.5

26.2 31.3

30.2 36.1

33.8 40.5

36.7 44.0

18.1 21.6

19.5 23.2

19.6 23.3

23.7 28.4

40.0 47.6

41.9 49.5

12.1 14.5

1.2 1.6

15.5 18.6

21.3 25.0

6.6 8.0

9.8 11.6

18.9 2 2.4

38.1 45.5

6.4 7.8

28.6 3 4.3

19.2 23.1

28.0 32.9

32.4 38 .

1

52.9 60.5

12.4 14.8

23.4 27.9

12.4 14.8

12.4 14.8

2 3.6 28.1

22.5 26.8

13.3 15.9

16.8 19.9

16.9 20.0

103
Table 21 continued

THE CONCENTRATION OF PARTICULATE MANGANESE

(IN NANOGRAMS/MILLILITER)

THE RANGE REPRESENTS AT LEAST

THE 95% CONFIDENCE LIMITS

SAMPLE NUMBER MINIMUM BEST V A filJE MAXIMUM

11051 15.8 19.3 22.8

11050 lb.

20.2 24.1

1 1 049 18.9 23.4 27.9

J 10 4 8 19.3 23.8 28.3

110 4 7 25.6 31.7 37.8

1 1046 9.7 12.1 14.5

110 4 5 37.7 46.3 54.9

1 1044 21.3 26.6 31.9

11043 27.4 34.1 40.8

11042 9.1 10.1 12.1

11041 7.8 9.8 11 .8

11040 9.2 11.6 14.0

11039 9.5 11.9 14.3

11038 13.5 16.6 19.7

11037 4.9 6.3 7.7

11036 8.0 10.0 12.0

11035 7.5 9.3 11.1

11034 9.3 11.7 14.1

11033 6.5 8.3 10.1

11032 11.0 13.5 16.0

11031 12.4 15.1 17.8

11030 9.8 12.2 14.6

11029 10.0 12.4 14.8

11028 12.2 15.3 18.4

11027 23.4 29.1 34.8

11026 9.4 11.8 14.2

110 2 5 6.1 7.7 9.3

11024 7.0 9.0 11.0

110 2 3 7.5 9.5 11.5

110 2 2 9.0 11.4 13.8

11021 15.0 18.7 22.4

11020 10.7 13.6 16.5

11019 14.4 18.1 21.8

11016 26.3 33.0 39.7

11017 24.1 29.8 35.5

11016 7.3 9.3 11.3

11015 8.5 10.7 12.9

11014 6.8 8.8 3 0.8

11013 11.1 13.8 16.5

11012 8.5 10.9 13.3

11011 22.2 26.9 31.6

11010 5.7 7.3 8.9

11009 7.8 9.8 11.8

1 1 008 4.5 6.1 7.7

1 10C7 6.6 8.6 10.6

11006 16.8 22.5 26.2

1 1 005 X OU • 108.0 117.4

110 0 4 15.4 20.1 23.8

11003 15.5 19.2 22.9

11002 13.5 16.8 20.1

11001 13.0

i na 15.9 1 8 . P
Table 22

THE CONCENTRATION OF PARTICULATE MOLYBDENUM

(IN NANOGRAMS/MILLILITER)

THE RANGE REPRESENTS AT LEAST

THE 95% CONFIDENCE LIMITS

SAMPLE NUMBER MINIMUM BEST VALUE M A X 1 M l! M

11102 < 0.05

11101 < 0.06

11100 0.00 0.02 0.06

11099 0.00 0.02 0.06

11098 % < 0.03

11097 < 0.04

11096 < 0.06

11095 < 0.07

11094 0.00 0.0 8 0.24

11093 < 0.08

11092 0.00 0.01 0.0 3

11091 0.13 0.25 0.37

11090 < 0.06

11089 0.01 0.05 0.0 9

110 8 8 0.00 0.02 0.06

11087 < 0.09

1 lObb < 0.03

11085 < 0.03

11084 < 0.02

11063 < 0.02

11082 < 0.08

11081 o.oo 0.02 0.06

11080 < 0.02

11079 < 0.02

110 7 8 < 0.0 3 11077 < 0.0 3

1 107 6 < 0.0 3 11075 < 0.0 2

110 7 4 < 0.03

11073 < 0.04

11072 < 0.04

11071 < 0.0 3 110 7 0 < 0.03

11069 < 0.02

11068 < 0.06

11067 < 0.05

11066 < 0.05

11065 < 0.04

11064 < 0.04

11063 < 0.05

11062 0.00 0.02 o . o 11061 < 0.04

11060 < 0.02

1 105^ < 0.03

1105b < 0.0 3 110 5 7 < 0.04

11056 < 0.0 3

11055 < 0.05

11054 < 0.02

11053 < 0 . o 3 110 5 2 < 0.04

105
Table 22 continued

THE CONCENTRATION OF PARTICULATE MOLYBDENUM

(IN NANOGRAMS/MILLILITER)

THE PANGE REPRESENTS AT LEAST

THE 95% CONFIDENCE LIMITS

SAMPLE NUMBER MINIMUM BEST VALUE

11051 < 0.06

1 1050 < 0.20

11049 < 0.20

11048 < 0.09

11047 < 0.10

1 104b < 0.05

11045 < 0.80

11044 < 0.60

11043 < 0.05

11042 < 0.03

11041 < 0.10

11040 < 0.0 3

11039 < 0.06

11038 < 0.02

11037 < 0.05

11036 < 0.03

11035 < 0.09

110 3 4 < 0.03

11033 < 0.05

11032 < 0.03

11031 < 0.04

11030 < 0.03

11029 < 0.40

11028 < 0.03

110 2 7 < 0.60

11026 < 0.06

11025 < 0.05

11024 0.00 0.21

11023 < 0.05

11022 < 0.06

11021 < 0.06

11020 < 0.04

11019 < 0.02

11018 < 0.08

11017 o.oi 0.03

11016 < 0.06

11015 < 0.70

11014 < 0.0 6

11013 < 0.06

11012 < 0.06

lion < 0.70

1 1C10 < 0.04

11009 < 0.07

11008 < 0.05

11007 < 0.06

11006 < 0.80

1 1 005 0.00 0.21

1 1 004 < 0.0 7 11003 < 0.0 7 11002 < 0 . 06

110O] < 0.06

MAXIMUM

0.41

0.05

0.61

106
Table 23

THE CONCENTRATION OF PARTICULATE NICKEL

(IN NA NOG RAMS/MILLILITER)

THE RANGE REPRESENTS AT LEAST

THE 95% CONFIDENCE LIMITS

SAMPLE NUMBER MINIMUM BEST VALUE MAXIMUM

11102 1.74

11101 2.04

11100 0.69

1 1099 0.89

11098 1.36

11097 1.96

11096 1.76

11095 1.64

11094 3.14

11093 4.01

11092 0.65

11091 1.16

11090 0.46

11089 0.50

11088 0.26

11087 0.63

11086 0.07

11085 0.00

11084 0.08

11063 0.10

11082 0.08

11081 0.07

11060 0.09

11079 0.04

11078 0.13

11077 0.14

11076 0.03

11075 0.04

110 7 4 0.09

11073 0.00

11072 0.17

11071 0.25

11070 0.09

11069 0.01

1 1 068 0.10

11067 0.19

11066 0.12

11065 0.05

11064 0.0 7 11063 0.28

11062 0.42

11061 0.79

11060 0.0 3

11059 0.04

11058 0.05

11057 U . 1 1 11056 0.0H

11055 0.13

11054 0.11

11053 0.26

11052 0.1 1

2.50 3.09

2.80 3.39

1.00 1.20

1.20 1.40

1.90 2.29

2.50 2.89

2.30 2.69

2.40 2.99

3.90 4.49

5.00 5.78

0.92 1.08

1.70 2.09

0.73 0.89

0.77 0.93

0.46 0.56

0.94 1.14

0.20 0.24

0.11 0.13

0.24 0.30

0.26 0.32

0.24 0.30

0.20 0.24

0.22 0.26

0.17 0.21

0.29 0.35

0.30 0.36

0.16 0.20

0.17 0.21

0.25 0.31

0.10 0.12

0.35 0.43

0.43 0.51

0.22 0.26

0.14 0.18

0.26 0.32

0.36 0.44

0.28 0.34

0.18 0.22

0.20 0.24

0.48 0.58

0.64 0.76

1 .10 1.30

0.16 0.20

0.17 0.21

0.18 0.2 2

0.27 0.33

0.24 0.30

0.29 0.3 5

0.2 7 0.3 3

0.46 0 . 56

0.27 0.33

107
Table 23 continued

THE CONCENTRATION OK PARTICULATE NICKEL

(IN NANOGRAMS/KILLILITER)

rHE RANGE REPRESENTS AT LEAST

THE 95% CONFIDENCE LIMITS

SAMPLI NUMBER MINIMUM BEST VALUE MAXIMUM

11051 0.14 0.30 0.36

1 1 050 0.21 0.39 0.47

1 10<t9 0.19 0.37 0.45

110 4 8 0.16 0.32 0.38

1 1 0 A 7 0.43 0.70 0.86

11046 0.10 0.26 0.32

11045 0.69 1.00 1.20

1 1 044 0.27 0.47 0.57

11043 0.47 0.74 0.90

11042 0.05 0.18 0.22

11041 0.15 0.33 0.41

11040 0.12 0.30 0.38

11039 0.53 0.84 1.04

11038 0.09 0.22 0.26

11037 0.11 0.24 0.28

11036 0.07 0.20 0.24

11035 0.02 0.15 0.19

11034 0.00 0.11 0.15

11033 0.00 0.08 0.10

110 3 2 0.01 0.17 0.23

11031 0.00 0.09 0.11

11030 0.01 0.14 0.18

1 1029 0.22 0.42 0.52

11028 0.00 0.07 0.09

11027 0.19 0.37 0.45

11026 0.03 0.16 0.20

1 1 025 0.01 0.14 0.18

11024 0.00 0.03 0.05

11023 0.03 0.21 0.29

11022 0.01 0.17 0.23

11021 0.39 0.70 0.90

1 1020 0.04 0.22 0.30

11019 0.38 0.63 0.77

11018 0.01 0.19 0.27

11017 0.26 0.46 0.56

11016 0.00 0.14 0.20

11015 0.01 0.19 0.27

11014 0.00 0.14 0.20

11013 0.21 0.41 0.51

11012 0.04 0.17 0.21

11011 0.96 1.50 1.89

11010 0.00 0.11 0.15

11009 0.03 0.21 0.29

11008 0.00 0.07 0.09

1 1 007 0.02 0.15 0.19

11006 0.64 0.95 1.15

11005 0.32 0.63 0.83

11004 0.34 0.6 5 0.85

11 003 0.2 4 0.51 0.67

110 0 2 0.03 0.1^ 0.20

110 01 0.19 0.3 9 0.49

108
THE CONCENTRATION OF PARTICULATE LEAD

(TN NANOGRAMS/MILLILITER)

THE RANGE REPRESENTS AT LFAST

THE 95% CONFIDENCE LIMITS

SAMPLE NUMBER MINI M (J M BEST VA LUE maximum

11102 1.61 2.10 2.49

11101 2.09 2.80 3.39

1 1100 1.01 1.50 1.89

11099 0.91 1 . 10 1.79

11098 1.71 2.20 2.59

11097 2.49 3.20 3.79

11096 3.76 4.70 5.48

11095 5.9 2 7.30 8.48

11094 2.89 3.60 4.19

110 9 5 5.34 6.50 7.48

11092 1.49 2.20 2.79

11091 2.94 4.10 5.08

11090 0.42 0.64 0.80

11089 0.41 0.63 0.79

11088 0.28 0.43 0.5 3

110 8 7 0.67 0.93 1.13

11086 0.00 0.06 0.08

11085 0.0 0 0.05 0.07

11084 0.0 3 0.09 0.11

110 8 5 0.12 0.23 0.29

11082 0.1

1

0.22 0.28

11081 0.08 0.16 0.20

1 J 080 0.00 0.05 0.07

11079 0.00 0.04 0.06

11078 0.04 0.12 0.16

11077 0.06 0.14 0.18

11076 0.06 0.17 0.23

11075 0.03 0.11 0.15

11074 0.00 0.03 0.05

11073 * 0.01 0.07 0.09

11072 0.01 0.07 0.09

11071 0.09 0.20 0.26

11070 0.00 0.02 0.04

11069 0.01 0.07 0.09

11068 0.00 0.06 0.08

11067 0.2 2 0.35 0.43

11066 < 0.01

1106 5 0.12 0.2 3 0.29

11064 0.06 0.17 0.23

11063 0.24 0.39 0.49

11062 0.46 0.68 0.84

11061 0.62 1.00 1.29

11060 0.02 0.08 0.10

11059 0.04 0.10 0.12

11058 0.01 0.07 0.09

11057 0.21 0.34 0.42

1 1056 0.06 0.14 0.18

11055 0.07 0.18 0.24

110 5 4 0.33 0.48 0.58

11053 0.36 0.51 0.61

1 1052 0.47 0.67 0.81

109
Table 24 continued

the: concentration of particulate lead

(IN NANOGRAMS/MILLILITER)

THE RANGE REPRESENTS AT LEAST

ThE 95% CONFIDENCE LIMITS

SAMPLE NUMBER MINIMUM BEST VALUE MAXIM

11051 0.35 0.50 0. 60

11050 0.2 8 0.43 0.53

11049 0.23 0.36 0.44

t 1 0 4 8 0.16 0.29 0.37

11047 0.42 0.64 O.HO

11046 0.05 0.16 0.22

l 1045 0.4 8 0.70 0.86

1 1044 0.33 0.50 0.62

110 4 3 0.48 0.70 0.86

1 1 042 0.0 3 0.09 0.11

11041 0.17 0.28 0.34

11040 0.13 0.24 0.30

1 1039 0.53 0.75 0.91

11038 0.00 0.01 0.03

11037 0.22 0.37 0.47

1 1036 < 0.01

11035 0.00 0.06 0.08

11034 < 0.01

1 1<>33 0.00 0.04 0.06

110 3 2 < o.oi

11031 < 0.01

1 1 0 3 0 0.06 0.14 0.18

11029 0.48 0.70 0.86

11028 0.02 0.10 0.14

11027 0.17 0.30 0.38

1 102b 0.17 0.28 0.34

11025 0.10 0.21 0.27

1 1 u 2 4 0.01 0.09 0.13

11023 0.06 0.14 0.18

11022 0.08 0.16 0.20

110 21 0.10 0.18 0.22

11020 0.08 0.16 0.20

11019 0.15 0.26 0.3 2

1 1018 0.66 0.90 1.08

11017 0.20 0.33 0.41

11016 0.02 0.10 0.14

11015 0.00 0.0 3 0.05

11014 0.04 0.12 0.16

110)3 0.01 0.07 0.09

11012 0.13 0.21 0.25

1 1 0 1 1 0.19 0.32 0.40

1 1 0 1 0 0.11 0.19 0.23

1 1 0 0 9 0.09 0.17 0.21

11008 0.08 0.16 0.20

11007 0.10 0.21 0.27

11006 0.24 0.37 0.45

11005 6.59 7.30 7.89

11004 0.14 0.25 0.31

11003 0.12 0.23 o.29

11002 < 0.01

11001 0.32 0.47 0.57

110
THE CONCENTRATION OF PARTICULATE SCANDIUM

(IN NANOGRAMS/MILLILITER)

THE PANGE REPRESENTS AT LEAST

THE 95% CONFIDENCE LIMITS

SAMPLE NUMBER minimum BEST VALUE MAXIMUM

1 1102 0.5665 0.6068 0 . b 4 7 1 11101 0.5772 0.6376 0.6981

11100 0.1381 0.1543 0.1704

11099 0.1464 0.1625 0.1786

11098 0.2682 0.3085 0.3489

11097 0.3402 0.3805 0.4208

11096 0.4949 0.5554 0 . b 1 58

11095 0.4538 0.5142 0.5747

11094 0.5052 0.5657 0 . 62b

J

11093 0.4949 0.5554 0 . b 1 58

11092 0.1958 0.2160 0.2361

11091 0.4225 0.4628 0.5031

11090 0.1340 0.1481 0.1622

1 1C89 0.1360 0.1502 0.1643

11088 0.0783 0.0864 0.0945

110 8 7 0.1773 0.1975 0.2176

11086 0.0157 0.0175 0.0193

11085 0.0149 0.0166 0.0182

110 8 4 0.0216 0.0237 0.0257

11083 0.0247 0.0267 0.0288

110 8 2 0.0120 0.0134 0.0148

110 81 0.0268 0.0288 C .0308

11080 0.0092 0.0102 0.0112

11079 0.0095 0.0105 0.0115

11078 0.0495 0.0555 0.0616

11077 0.0515 0.0576 0.0636

1 li>7b 0.0186 0.0206 0.0226

110 7b 0.0227 0.0247 0.0267

11074 0.0096 0.0106 0.0116

11073 0.0128 0.0142 0.0156

11072 0.0279 0.0319 0.0359

l 10/1 0.0433 0.0473 0.0513

110 7 0 0.0094 0.0104 0.0114

11069 0.0216 0.0237 0.0257

11068 0.0247 0.0267 0.0288

11067 0.0649 0.0710 0.0770

11066 0.0069 0.0077 0.0085

11065 0.0237 0.0257 0.0277

11064 0.0392 0.0432 0.0472

11063 0.1010 0.1111 0.1212

11062 0.2991 0.3394 0.3797

11061 0.1165 0.1286 0.1407

11060 0.0048 0.0055 0.0061

11059 0.0060 0.0066 0.0072

1 1058 0.0061 0.0067 0.0073

11057 0.0268 0.0288 0.0308

11056 0.0132 0.0146 0.0160

11055 0.0361 0.0401 0.0441

11054 0.0639 0.0720 0.0801

1 1053 0.1093 0.1214 0.1335

11052 0.0485 0.0545 0.06 0 6

111
Table 25 continued

the: concentration of particulate scandium

(IN NANOGRAMS/MILLILITER)

the range REPRESENTS at least

THE 95% CONFIDENCE LIMITS

sample NUMbER MINIMUM BEST VALUE MAXIMUM

1 1 051 0.0453 0.0494 0.0534

11050 0.0742 0.0823 0.0903

11049 0.0742 0.0823 0.0903

11048 0.0402 0.0442 0.0483

11047 0.1258 0.1399 0. 1540

1 1 04b 0.0053 0.0059 0.0065

11045 0.1515 0.1676 0.1838

1 1 0 <* 4 0.0422 0.0463 0.U503

1 1043 0.1165 0.1286 0.1407

11042 0.0045 0.0051 0.0057

110 41 0.0412 0.0453 0.0493

11040 0.0042 0.0046 0.0050

11039 0.1423 0.1584 0.1745

11038 0.0075 0.0083 0.0091

11037 0.0381 0.0422 0.0462

11036 0.0032 0.0036 0 . 0 0 4 0

11035 0.0247 0.0267 0.0288

11034 0.0028 0.0030 0.0032

11033 0.0268 0.0288 0.0308

110 3 2 0.0046 0.0050 0.0054

11031 0.0134 0.0148 0.0162

11030 0.0216 0.0237 0.0257

11029 0.1185 0.1306 0.1427

11028 0.0175 0.0195 0.0216

11027 0.0650 0.0730 0.0811

11026 0.0216 0.0237 0.0257

11025 0.0443 0.0483 0.0524

11024 0.0125 0.0139 0.0153

11023 0.0639 0.0699 0.0760

1 1022 0.0309 0.0350 0.0390

11021 0.1412 0.1553 0.1694

11020 0.0206 0.0226 0.0246

11019 0.0887 0.0987 0 . 1 0 P 8

11018 0.1165 0.1286 0.1407

11017 0. 1U62 0.1183 0.1304

11016 0.0059 0.0065 0.0071

11015 0.0567 0.0627 0.0688

11014 0.0165 0.0185 0.0205

11013 0.0309 0.0350 0.0390

11012 0.0289 0.0329 0.0369

11011 0.1464 0.1625 0.1786

11010 0.0140 0.0156 0.0172

11009 0.0392 0.0432 0.0472

11008 0.0237 0.0257 0.0277

11007 0 . 03b 1 0.0401 0.0441

1 1006 0.2587 0.2869 0.3152

11005 0.8248 0.9256 1 .0264

1 1004 0.1278 0.1419 0. 1560

11003 0.0773 0.0854 0 . 09 34

1 1 002 0.0196 0.0216 0.0236

11001 °.°649 U2 0.0710 0.0770
Table 26

THE CONCENTRATION OF PARTICULATE TIN

(IN NANOGRAMS/MILLILITER)

THE RANGE REPRESENTS AT LEAST

THE 95% CONFIDENCE LIMITS

SAMPLE NUMbFR MINIMUM BEST VALUE

11102 < 3.00

11101 < 3.00

11100 < 0.80

11099 < 0.50

11098 < 1.00

11097 < 2.00

11096 < 2.00

11095 < 3.00

11094 < 2.00

11093 < 2.00

11092 < 2.00

11091 < 1.00

11090 < 0.60

11089 < 0.60

11088 < 0.60

11087 < 2.00

11086 < 0.50

11085 < 0.70

11084 < 0.60

11083 < 0.60

11082 < 0.50

11081 < 0.40

11080 < 0.30

11079 < 0.30

11078 < 0.50

11077 < 0.50

11076 < 0.40

11075 < 0.30

11074 < 0.40

11073 < 0.80

11072 < 0.40

11071 < 0.50

11070 < 0.40

11069 < 0.50

1 1068 < 0.80

11067 < 0.70

11066 < 1.00

11065 < 1.00

11064 < 1.00

11063 < 2.00

1 1 0 o2 < 1.00

11061 < 1.00

11060 < 0.30

11059 < 0.50

1 1058 < 0.50

11057 < 1.00

11056 < 2.00

11055 < 0.70

11054 < 1.00

11053 < 4.00

11052 < 2.00

11051 113 < 0.50

MAXIMUM
Table 26 continued

the: concentration of particulate tin

(IN NANOGRAMS/MILLILITER)

THE RANGE REPRESENTS AT LEAST

THE 95% CONFIDENCE LIMITS

SAMPLE NUMBER MINIMUM PEST VALUE MAXIMUM

11050 < 0.90

11049 < 0.50

11048 < 0.90

11047 < 0.50

11046 < 0.30

11045 < 2.00

1 1 044 < 0.60

11043 < 0.50

11042 < 0.40

11041 < 0.90

11040 < 0.05

11039 < 0.70

11038 < 0.50

11037 < 0.50

11036 < 0.70

110 3 5 < 0.80

11034 < 0.30

11033 < 0.80

11032 < 0.40

11031 < 1.00

11030 < 0.50

11029 < 0.70

11028 < 0.70

11027 < 1.00

11026 < 0.70

11025 < 1.00

110 2 4 < 0.70

110 2 3 < 2.0 0

1 1022 < 2.00

110 21 < 2.00

110 2 0 < 0.7 0

11019 < 0.70

11U18 < 1 .00

11017 < 0.70

11016 < 1.00

11015 < 2.00

11014 < 2.00

1 1 (^1 3 < 0.70

11012 < 0.80

11011 < 2.00

11010 < 0.60

1 1 009 < 1.00

11008 < 0.50

1 1 0 0 7 < 0.50

1 1006 < 2.0 0

110 0 5 < 2.00

11004 < 0.7 0

110 0 3 < 0.30

110 0 2 < 1 .00

110 01 < 0 .60

114
THE CONCENTRATION OF PARTICULATE THORIUM

(IN NANOGRAMS/MILLILITER)

THE RANGE REPRESENTS AT LEAST

THE 95% CONFIDENCE LIMITS

SAMPLE NUMBER MINIMUM BEST VALUE MAXIMUM

11102 0.4538 0.5142 0.5747

11101 0.4846 0.5451 0.6056 * 11100 0.1330 0.1471 0.1612

11099 0.1392 0.1553 0.1714

11098 0.2791 . 0.2983 0.3184

11097 0.3299 0.3702 0.4106

11096 0.4538 0.5142 0.5747

11095 0.4431 0.4834 0.5237

11094 0|4949 0.5554 0.6158

11093 0.4949 0.5554 0.6158

11092 0.1855 0.2057 0.2258

11091 0.3094 0.3497 0.3900

11090 0.0969 0.1070 0.1170

110 8 9 0.1010 0.1111 0.1212

11088 0.0587 0.0648 0.0708

11087 0.1371 0.1512 0.1653

11086 0.0103 0.0123 0.0144

11065 0.0103 0.0123 0.0144

1 1064 0.0155 0.0175 0.0195

110 8 3 0.0165 0.0183 0.0201

11082 0.0094 0.0106 0.0118

11081 0.0196 0.0216 0.0236

11080 0.0066 0.0074 0.0082

11079 0.0067 0.0075 0.0083

11078 0.0422 0.0463 0.0503

11077 0.0443 0.0483 0.0524

1 1 076 0.0147 0.0164 0.0180

110 7 5 0.0173 0.0191 0.0209

11074 0.0075 0.0083 0.0091

11073 0.0098 0.0108 0.0118

11072 0.0247 0.0267 0.02P8

11071 0.0371 0.0411 0.0452

11070 0.0069 0.0079 0.0089

11069 0.0155 0.0175 0.0195

11068 0.0176 0.0216 0.0256

11067 0.0495 O.O 555 0.0616

] 1066 0.0021 0.0041 0.0061

11065 0.0114 0.0154 0.0195

1106 4 0.0289 0.0329 0.0369

110 6 3 0.0835 0.0936 0.1037

1 1 062 0.2472 0.2674 0.2876

11 Obi 0.0948 0.1049 0.1150

1 1 C 6 0 0.0033 0.0044 0.0050

1 1 069 0.0051 0.0063 0.O075

11058 0.0031 0.0043 0 . 0 0 5 5

110 5 7 0.0216 0.0237 0.0257

11056 0.0083 0.0097 0.0111

11055 0.0258 0.0298 0.0339

11054 0.0505 0.0566 0.0626

11063 0.09Q7 0. 1 008 0.11 09

1 t ' > 6 2 0.0371

115

0.0411 0 . 0452
Table 27 continued

THE CONCENTRATION OF PARTICULATF THORIUM

Clw NANOGPAMS/MILLILITER)

THE RANGE REPRESENTS AT LEAST

THE 95% CONFIDENCE LIMITS

SAMPLE NUMBER MINIMUM BEST VALUE MAXIMUM

1 1051 0.0371 0.0411 0.0452

11050 0.0639 0.0699 0.0760

11049 0.0639 0.0720 0.0801

11046 0.0340 0.0381 0.0421

11047 0.1093 0.1214 0.1335

11046 0.0039 0.0045 0.0051

11045 0.1350 0.1491 0.1632

11044 0.0371 0.0411 0.0452

11043 0.1041 0.1162 0.1283

11042 0.0030 0.0040 0.0050

11041 0.0350 0.0391 0.0431

11040 0.0030 0.0034 0.0038

11039 0.1206 0.1347 0.1488

11036 0.0047 0.0063 0.0079

1

037 0.0299 0.0339 0.0380

1103 d < 0.0050

11035 0.0186 0.0226 0.0267

11034 0.0017 0.0023 0.0029

11033 0.0227 0.0247 0.0267

11032 0.0034 0.0044 0.0054

11031 0.0083 0.0103 0.0123

110 3 0 0.0165 0.0185 0.0205

11029 0.0969 0.1070 0.1170

11026 0.0124 0.0144 0.0164

1 1027 0.0526 0.0586 0.0647

110 2 6 0.0186 0.0206 0.0226

1 1025 0.0350 0.0391 0.0431

110 2 4 0.0081 0.0101 0.0121

11023 0.0515 0.0576 0.0636

11022 0.0207 0.0247 0.0287

11021 0.1195 0.1316 0.1437

11020 0.0135 0.0175 0.0215

11019 0.0691 0.0771 0.0852

11016 0.0876 0.0977 0.1078

11017 0.0856 0.0956 0.1057

1 101 b < 0.0050

11015 0.0485 0.0545 0.0606

11014 0.0145 0.0185 0.0225

11013 0.0248 0.0288 0.0328

11012 0.0237 0.0278 0 . 031 R 11011 0.1185 0.1306 0.1427

11010 0.0124 0.0144 0.0164

11009 0.0320 0.0360 0.0400

1 1 0 0 8 0.0186 0.0206 0.0226

1

u 07 0.0268 0.0309 0.0349

11006 0.1711 0.1892 0.2074

110 0 5 0.6163 0.6788 0.7393

11004 0 .0907 0.1008 0.1109

1 1 0 0 3 0.0606 0.0668 0 . 072 °

1 100 2 0.0145 0.0185 0.0225

11001 0.0515 116 0.0576 0.0636
THE CONCENTRATION OF PARTICULATE UR AN T U M

(IN WANOGRAMS/MILLILITER )

SAMPLE NUMBER MINIMUM

11102 0.1144

11101 0.1227

11100 0.0402

11099 0.0402

1109R 0.075?

11097 0.0856

11096 0.1258

11095 0.155b

11094 0.1391

11093 0.1742

11092 0.0577

11091 0.1093

11090 0.0269

11089 0.0289

11088 0.0114

11087 0.0402

11086 0.0036

11085 0.0066

1 1084 0.0044

11083 0.0052

1108?

11081 0.007 3 11080 0.0021

11079 0.0029

11078 0.0122

11077 0.0114

11076 0.0057

11075 0.0000

11074 0.0024

11073 0.0105

11072 0.0063

11071 0.0114

11070 0.0027

11069 0.0000

1 1 l- o 8 0.0032

1 106 7 0.0176

1 l 66 0.0011

1 1 ''6 5 0.0081

1 1 0 6 4 0.0066

1 1 0 6 3 0.0196

11062 0.0691

1 1061 0.0248

11060 0.0014

11059 0.0018

110 5 8 0.0020

11057 0.0067

11056 0.0034

11055 0 . 0 1 0 4

11054 0.0155

11053 0.0237

11052 0.0124

THE RANGE REPRESENTS AT LEAST

THE 95% CONFIDENCE LIMITS

BEST VALUE MAXIMUM

0.1265 0.1386

0.1368 0.1509

0.0442 0.0483

0.0442 0.0483

0.0833 0 . C 9 1 4

0.0956 0.1 057

0.1399 0.1540

0.1718 0.1879

0.1532 0.1674

0.1923 0.2105

0.0638 0 . 0698

0.1214 0.1335

0.0329 0.0390

0.0329 0.0369

0.0154 0.0195

0.0463 0.0523

0.0052 0.0069

0.0084 0.0102

0.0057 0.0069

0.0060 0.0068

< 0.0100

0.0085 0.0097

0.0035 0.0049

0.0039 0.0049

0.0136 0.0150

0.0134 0.0154

0.0073 0.0089

0.0113 0.0315

0.0040 0.0056

0.0119 0.0133

0.0086 0.0105

0.0134 0.0154

0.0041 0.0055

0.0033 0.0204

0.0072 CN o • O

0.0216 0.0256

0.0031 0.0051

0.0095 0.0109

0.0080 0 .0094

0.0237 0 . 0 2 7 7

0.0771 0.0852

0.0288 0.0328

0.0024 0.0034

0.0036 0.0054

0.0034 0 .0048

0.0087 0.0108

0.0046 0 . 0 0 5 8

0.0144 0.0184

0.0175 0.0195

0.0278 0.0318

0.0144 0.0164

117
Table 28 continued

THE C 0 N CENTRATION OF PARTI CULATF URANIUM

(IN NANOGRAMS/MILLILITER)

THE RANGE REPRESENTS AT I-EAST

THE 95% CONFIDENCE LIMITS

LE NUMBER MINIMUM BEST VALUE MAXIMUM

11051 0.0114 0.0134 0.0154

1 1050 < 0.0500

110 4 9 < 0.0300

11048 0.0095 0.0216 0.0337

11047 0.0310 . 0.0370 0.0431

110 4b < 0.0050

1 1045 < 0.1000

11044 < 0.0900

110 4 3 0.0289 0.0329 0.0369

11042 0.0011 0.0031 0.0051

1 1041 < 0.0300

11040 0.0011 0.0031 0.0051

110 3 9 0.0004 0.0206 0.0407

11038 < 0.0020

11037 0.0073 0.0134 0.0194

1103b 0.0018 0.0036 0.0054

11035 < 0.0200

11034 0.0062 0.0082 0.0102

11033 0.0062 0.0082 0.0102

110 3 2 0.0052 0.0072 0.0092

11031 0.0052 0.0072 0.0092

11030 0.0042 0.0062 0.0082

11029 < 0.0500

1 1028 0.0062 0.0082 0.0102

110 2 7 0.0145 0.0185 0.0225

11026 < 0.0100

11025 0.0073 0.0113 0.0153

11024 0.0033 0.0045 0.0057

11023 0.0114 0.0134 0.0154

11022 0.0093 0.0113 0.0133

11021 < 0.0500

110 2 0 0.0052 0.0093 0.0133

11019 0.0155 0.0195 0.0236

11018 0.0217 0.0278 0.0338

11017 0.0196 0.0237 0.0277

11016 < 0.0050

11015 < 0.0900

11014 0.0031 0.0051 0.0072

1 1013 0.0052 0.0072 0.0092

11012 0.0062 0.0082 0.0102

11011 < 0.0800

11010 0.0031 0.0051 0.0072

11009 0.0052 0.0072 0.0092

11008 0.0021 0.0041 0.0061

110 0 7 0.0062 0.0082 0.0102

11006 < 0.1 000

1100 5 0.1341 0.1543 0.1744

11004 0.0146 0.0237 0.0277

11003 0.0165 0.0206 0.024b

11007 0.0052 0.0072 0.0 0 ° 2 11001 0.02.9 n8 0.0329 0.0390
Table 29

THE CONCENTRATION OF PARTICULATE ZINC

(IN NANOGRAMS/MILLILITER)

THE RANGE REPRESENTS AT LEAST

THE 9S% CONFIDENCE LIMITS

SAMPLE NUMBER MINIMUM BEST VALUE MAXIMUM

11102 5.5R 8.22 9.65

1 l 101 5.79 8.42 9.86

11100 1.29 2.88 3.49

11099 1.80 3.39 4.00

11098 4.94 7.29 6.52

11097 6.25 8.83 10.26

11096 7.80 10.89 12.73

11095 7.29 10.38 12.21

11094 12.25 15.52 17.55

11093 10.93 13.96 15.81

1 1092 4.77 7.39 8.83

11091 9.22 12.54 14.58

11090 0.8 8 2.77 3.59

11089 1.60 3.49 4.31

11088 0.70 2.36 2.98

110 8 7 1.88 4.00 5.03

1 108b 0.00 0.15 0.68

11085 0.00 0.33 0.85

11094 0.00 0.55 1.17

11083 0.00 0.45 1.04

11082 0.00 0.42 1.19

11081 0.00 0.73 1.29

11080 0.00 0.73 1.27

11079 0.00 0.50 1.05

11078 0.00 0.87 1.64

11077 0.00 0.74 1.30

11076 0.00 0.60 1.12

11075 0.00 0.53 1.08

11074 0.00 0.53 1.08

11073 0.00 0.07 0.55

11072 0.00 0.59 1.13

11071 0 9 00 0.91 1.44

11070 0.00 0.21 0.75

1 1069 0.00 0.22 0.92

11068 0.00 0.56 1.12

11067 0.00 1.06 1.62

11066 0.00 0.22 0.94

11065 < 1.00

11064 0.00 0.71 1.94

11063 < 2.00

1 10b2 0.50 2.66 3.69

11061 0.00 0,92 1.74

11060 0.00 0.36 0.90

11059 0.00 0.12 0.65

11058 0.00 0.27 0.81

1 1057 0.00 0.34 0.90

11056 0.00 0.37 O.05

J 1055 0.00 0.40 0.98

11054 0.00 0.50 1.33

110 5 3 0 . 0 0 0.95 1.55

11052 1.00

119
Table 29 continued

THE CONCENTRATION OF PARTICULATE ZINC

(IN NANOGRAMS/MILLILITER)

THE RANGE REPRESENTS AT LFAST

THE 95% CONFIDENCE LIMITS

i SAMPLE NUMBER minimum BEST VALUE MAXIMUM

11051 0.00 0.43 1.01

11050 0.00 0.73 1.37

11049 0.00 0.67 1.31

11048 0.00 0.15 0.78

11047 0.00 1.12 2.15

11046 0.00 0.11 0.84

11045 0.00 2.15 3.38

11044 0.00 0.79 1.46

11043 0.00 1.12 2.15

11042 0.00 0.04 0.56

1 1U41 0.00 0.25 0.83

11040 0.00 0.20 0.68

11039 0.00 1.74 2.56

11038 0.00 0.30 0.92

11037 0.00 0.50 1.11

11036 < 0.60

110 3 5 0.00 0.00 0.53

1 1U34 0.00 1.02 1.64

11033 0.00 0.30 0.92

11032 0.00 0.23 1.01

11031 < 0.50

11030 0.00 0.33 0.89

1 1 029 0.00 1.43 2.25

11028 0.00 0.30 0.92

11027 0.00 0.81 1.84

11026 0.00 0.42 1.00

11025 0.00 0.40 1.23

110 2 4 0.00 0.50 1.33

11023 < 0.90

11022 < 2.00

11021 0.00 1.64 2.66

1 10 20 0.00 0.40 1.23

11019 0.0" 1.33 2.3 6

11018 0.00 1 .12 2.15

11017 0.00 1.02 1.85

11016 < 0.40

11015 o.oo 1.22 2.05

11014 < 0.90

1 1 o 1 3 0.00 0.50 1.13

11012 0.00 0.30 0.9 2

11011 0.0 0 1 .64 2.46

11010 < 0.50 i 11009 < 0.90 i 11008 0.0 0 0. 37 0.70

11007 0.5 7 2.16 2/7 7 11(06 2.24 4 .92 6 . 25

1 1 uo5 11.35 1 4 . * 0 17.14

1 1004 0.68 3.08 4.31

1 1003 0.0 0 1 .43 2.26

110 0 2 < 0.90

110 0 1 u . 00 0 .92 1 . 54

120
Table 30

BLANK CONCEN1RA1 ICNS FOR DISSOLVED CADMIUM

(IN NANOGRAMS/MILLILITER)

THE RANGE REPRESENTS THE

ONE SIGMA LEVEL

SAMPLE NUMBER MINIMUM BEST VALUE MAXIMUM

0-3 1 < 0.007

B-9 1 < 0.007

6-9 1 < 0.007

b-11 2 < 0.007

B-b 2 < 0.007

B-7 2 < 0.007

B-U 3 < 0.007

B-3 3 < 0.007

B-7 3 < 0.007

B-17 4 < 0.007

B-l 9 4 < 0.007

6-21 4 0.019 0.021 0.023

b-21 5 < 0.007

B-25 5 < 0.007

B-11 6 < 0.007

B-l 3 6 < 0.007

B-21 6 < 0.007

8-4 7 0.039 0.043 0.047

B-b 7 0.019 0.021 0.023

B-8 7 0.019 0.021 0.023

0-10 8 < 0.007

9-12 8 < 0.007

0-14 8 < 0.007

121
Table 31

BLANK CONCENTRATIONS EUR DISSOLVED COBALT

(IN NANOGRAMS/MILLILITER)

THE RANGE REPRESENTS THE

ONF SIGMA LEVEL

SAMPLE NUMBER MINIMUM BEST VALUE maximum

b-3fc 1 0.0104 o.ono 0.0116

B-7B 1 0.0050 0.0053 0.0056

b-9B 1 0.0068 0.0072 0.0076

B-l 1 A 2 0.0055 0.0058 0.0061

B-bA 2 0.0050 0.0053 0.0056

B-7A 2 0.0082 0.0087 0.0092

B-l lb 3 0.0060 0.0063 0.0066

B-3B 3 0.0117 0.0123 0.0129

b- 7 B 3 0.0055 0.0058 0.0061

B-l 7A 4 0.0280 0.0300 0.0320

B-l 9A 4 0.0069 0.0073 0.0077

6-21 A 4 0.0077 0.0081 0.0085

B-21B 5 0.0074 0.0078 0.0082

B-25B 5 0.0071 0.0075 0.0079

B-7B 5 0.0063 0.0066 0.0069

B-l IB 6 0.0090 0.0095 0.0100

B-13B 6 0.0095 0.0100 0.0105

B-17B 6 0.0380 0.0400 0.0420

B-4 A 7 0.0104 0.0110 0.0116

8-6 A 7 0.0090 0.0095 0.0100

B-HA 7 0.0220 0.0240 0.0260

B-10A 8 0.0152 0.0160 0.0168

B-12A 8 0.0270 0.0280 0.0290

B-14A 8 0.0140 0.0147 0.0154

122
Table 32

BLANK CONCENTRATIONS FOR DISSOLVED CHROMIUM

(IN NANOGRAMS/MILLILITER)

THE RANGE REPRESENTS THE

ONE SIGMA LEVEL

SAMPLE lnumber MINIMUM BEST VALUE MAXIMUM

B-3B 1 1.47 1.55 1.63

B-7B 1 1.30 1.37 1.44

B-9B 1 1.48 1.56 1.64

B-11A 2 1.33 1.40 1.47

b-5 A 2 1.46 1.54 1.62

6-7 A 2 1.26 1.33 1.40

B-11B 3 1.42 1.49 1.56

B-3B 3 1.46 1.54 1.62

B-7B 3 1.50 1.58 1.66

B-17A 4 1.48 1.56 1.64

B-19A 4 1.49 1.57 1.65

B-21A 4 1,46 1.54 1.62

B-216 5 1.36 1.43 1.50

B-25B 5 1.62 1.71 1.80

B-7b 5 1.62 1.71 1.80

6-11B 6 1.46 1.54 1.62

B-13B 6 1.47 1.55 1.63

B-17B 6 1.47 1.55 1.63

B-4A 7 1.40 1.47 1.54

B-6A 7 1.46 1.54 1.62

B-8A 7 1.62 1.71 1.80

8-10A 8 1.59 1.67 1.75

B - 1 2 A 8 1.48 1.56 1.64

B-14A 8 1.59 1.67 1.75

123
Table 33

BLANK CONCL'NI NATIONS FOR DISSOLVED COPPER

(IN nanogpams/milliliter)

THE RANGE REPRESENTS THE

ONE' SIGMA LEVEL

V PLE number MINIMUM BEST VALUE MAXIMUM

P-3 1 < 0.08

P-9 1 < 0.08

P-9 1 < 0.08

b-1 1 2 < 0.08

B-5 2 < 0.08

4-7 2 < 0.08

b-1

3 0.0 7 0.08 0.09

6-3 3 < 0.08

P-7 3 • • • 0-17 4 0.10 0.12 0.1'*

H-l i 4 0.14 0.16 0.1b

6 — 21 4 0.12 0.14 0.16

P-21 5 < 0.08

B-25 5 < 0.08

b-1 1 6 0.39 0.4 3 0.47

b-1 3 6 0.17 0.19 0.21

b-21 6 0.35 0.39 0.43

6-4 7 < 0.06

6-6 7 < 0.08

L-8 7 < 0.08

B-10 8 < 0 .08

b-12 8 < 0.08

b-14 8 < 0.08

124
Table 34

BLANK CONCENTRATIONS FOR DISSOLVED IRON

(IN NANOGRAMS/MILLILITER)

THE RANGE REPRESENTS THE

ONE SIGMA LEVEL

SAMPLE NUMBER MINIMUM BEST VALUE MAXIMUM

b-3B 1 0.94 1.00 1.06

B-7P t 0.96 1.02 1.08

B-9B 1 3.50 3.70 3.90

H-11A 2 1.15 1.25 1.35

8-5A 2 1.20 1.30 1.40

3-7 A 2 0.67 0.75 0.8 3

B-t IB 3 0.52 0.59 0.66

B- 38 3 1.14 1.20 1,26

B-7B 3 0.75 0.80 0.85

B-17A 4 0.84 0.95 1.06

B-19A 4 1.50 1.70 1.90

B - 2 1 A 4 1.00 1.10 1.20

6-21B 5 0.53 0.68 0.63

B-25B 5 1.40 1.50 1.60

9-7B 5 1.00 1.10 1.20

6-1 IB 6 1.44 1.53 1.62

e-1 3b 6 0.83 0.90 0.97

B-178 6 1.0 3 1.10 1.17

R-4A 7 0.80 0.89 0.98

B-6 A 7 1.13 1.24 1.35

B-8A 7 1.76 1.88 1.98

B-10A 8 1.93 2.03 2.13

B-12A 8 0.70 0.79 0.88

B-14A 8 1.40 1.50 1.60

125
Table 35

BLANK CONCEnTPAT IONS FOR DISSOLVED MANGANESE

(TN n AN GG RAMS/ MILLILITER)

THE RANGE REPRESENTS THE

ONE SIGMA LEVEL

MPLE NUMBER MINIMUM BEST VALUE MAXIMUM

H-3 1 0.700 0.770 0.840

B-9 1 0.440 0.480 0.520

6-9 1 0.400 0.440 0.480

0-11 2 0.590 0.700 0.810

H-5 2 0.600 0.700 0.800

H-7 2 0.700 0.800 0.900

0-11 3 < 0.008

8-3 3 < 0.008

B-7 3 < 0.008

8-17 4 0.390 0.430 0.470

8-19 4 0.330 0.370 0.410

b-2i 4 0.240 0.270 0.3O0

8-21 5 0.180 0.200 0.220

8- 2 5 5 0.140 0.160 0.180

b- 1 1 6 < 0.008

B-l 3 6 < 0.008

0-21 6 < 0.008

8-4 7 0.620 0.690 0.760

B-S 7 < 0.008

3-8 7 < 0.008

B-l 0 8 < 0.008

8-12 ft < 0.008

8-14 8 < 0.008

126
Table 36

BLANK CONCENTRATIONS FOR DISSOLVED MOLYBDENUM

THE RANGE REPRESENTS THE

ONE SIGMA LEVEL

SAMPLE NUMBER MINIMUM BEST VALUE MAXIMUM

B-3B 1 B-7B 1 b-9B 1 B-11A 2 0.13

b-5A 2

H-7A 2 B-116 3

B-3B 3 B-7H 3 B-17A 4

B-19A 4

B-21A 4

8-21B 5

8-25B 5

B-7B 5

b-llB 6

tt-13B 6

B-17B 6

6-4A 7

B-6A 7 B-BA 7 B-10A h B-12A 6

B-14A 8

< 0.03

< 0.03

< 0.10

0.14 0.15

< 0.03

< 0.04

< 0.03

< 0.0 3 < 0.04

< 0.03

< 0.04

< 0.04

< 0.04

< 0.02

< 0.03

< 0.05

< 0.03

< 0.04

< 0.03

< 0.03

< 0.03

< 0.05

< 0.0 3 < 0.05

127
Table 37

BLANK CONCENTRATIONS FOR DISSOLVED NICKFL

(IN NANOGRAMS/MILLILITFR)

THE RANGE REPRESENTS THE

ONE SIGMA LEVEL

SAMPLE NUME'EP F I N I M (J M BEST VALUE maximum

HJ

1 0.04 0.05 0.06

b-9 1 0.04 0.05 0.06

b-9 1 0.05 0.06 0.07

b-1 1 2 0.03 0.04 0.05

b-5 2 0.05 0.06 0.07

6-7 2 0.01 0.02 0.03

B-1 1 3 0.09 0.10 0.11

X l 3 0.33 0.37 0.41

h-7 3 0.30 0.3 3 0.36

h-17 4 0.21 0.23 0.25

B-19 4 0.14 0.1b 0.18

b-2 1 4 0.15 0.17 0.19

6- 2 1 5 0.0b 0.08 0.10

B-2 5 5 0.03 0.04 0.05

B-1 1 6 0.05 0.07 0.09

o—13 6 0.05 0.06 0.07 , B-21 6 0.05 0.06 0.07 , b-4 7 0.29 0.33 0.37 ! B- 6 7 0.15 0.17 0.19

b-8 7 0.20 0.22 0.24 i B-10 8 0.13 0.15 0.17

b-12 8 0.05 0.06 0.07 . B-1 4 8 0.08 0.10 0.12 ’

i

128
Table 38

blank concentrations foe dissolved lead

(IN N ANOGR A MS/M I LLIL1TER)

THE RANGE REPRESENTS THE

ONE SIGMA LEVEL

SAMPLE NUMBER MINIMUM BEST VALUE MAXIMUM

B-3 1 0.21 0.23 0.25

B-9 1 0.12 0.14 0.16

B-9 1 0.07 0.09 0.11

8-11 2 0.17 0.19 0.21

8-5 2 0.14 0.16 0.18

d-7 2 0.23 0.25 0.27

B-U 3 0.08 0.10 0.12

B-3 3 0.08 0.10 0.12

fci-7 3 0.12 0.14 0.16

B-17 4 0.11 0.13 0.15

B-19 4 0.08 0.10 0.12

B-2 1 4 0.11 0.13 0.15

B-21 5 0.19 0.21 0.23

8-25 5 0.17 0.19 0.21

d-11 6 0.16 0.18 0.20

B-13 6 0.12 0.14 0.16

B-21 6 0.05 0.07 0.09

B-4 7 0.11 0.13 0.15

b-6 7 0.09 0.10 0.12

B-8 7 0.05 0.07 0.09

B-10 8 0.15 0.17 0.19

8-12 8 0.10 0.12 0.14

B-14 8 0,09 0.11 0.13

129
Table 39

BLANK CONCENTRATIONS FOR DISSOLVED SCANDIUM

(IN NANOGRAMS/MILLILITER)

THE RANGE REPRESENTS THE

ONE SIGMA LEVEL

S A M t> L E NUMBER MINIMUM PEST VALUE MAXIMUM

B-36 1 0.00013

f 0.00014 0.00015

P-7B 1 0.00011 0.00012 0.00013

H-9B 1 0.00018 0.00020 0.00022

6- 1 1 A 2 0.00013 0.00014 0.00015

B-5A 2 0.00011 0.00012 0.00013

r»-7 A 2 0 . 0000b 0.00007 0.00008

B-11H 3 0.00007 0.00008 0.00009

B-3B 3 0.00009 0.00010 0.00011

b-7 6 3 0.00007 0.00008 0.00009

B - 1 7 A 4 0.00004 0.00005 0.00006

b- 1 9 A 4 0.00013 0.00014 0.00015

B-21A 4 0.00008 0.00009 0.00010

B-21B 5 0.00018 0.00020 0.00022

B-25B 5 0.00012 0.00013 0.00014

B — 7 13 5 0.00006 0.00007 0.00008

6-1 IB 6 0.00010 0.00011 0.00012

B- 1 3 B 6 0.00010 0.00011 0.00012

B-17B 6 0.00014 0.00015 0.00016

B-4 A 7 0.00014 0.00016 0.00018

b-6A 7 0.00014 0.00015 0.00016

B-8A 7 0.00009 0.00010 0.00011

B-10A b 0.00009 0.00010 0.00011

B - 1 2 A e 0.00007 0.00009 o.ooOi 1 B-14A 8 0.00015 0.00016 0.00017

130
Table 40

BLANK CONCENTRATIONS FOR DISSOLVED TIN

(IN NANOGRAMS/MILLILITER)

THE RANGE REPRESENTS THE

ONE SIGMA LEVEL

SAMPLE NUMBER MINIMUM BEST VALUE MAXIMUM

tJ-3B 1 H-7B 1 B-9H 1 b-llA 2 8-5A 2

B-7A 2

B-11B 3

B-3U 3 B-7B 3

6-17A 4

B-19A 4

B-21A 4

B-21B 5

B-25B 5

8-7B 5

B-llf* 6

B-13B 6

B-17B 6

B-4A 7 B-6A 7 b-8A 7

8-10A 8

B-12A 8

B-14A 8

< 0.20

< 0.20

< 0.30

< 0.30

< 0.40

< 0.30

< 0.30

< 0.30

< 0.30

< 0.40

< 0.40

< 0.40

< 0.50

< 0.30

< 0.40

< 0.30

< 0.30

< 0.40

< 0.70

< 0.20

< 0.40

< 0.60

< 0.40

< 0.40

131
Table 41

BLANK CONCENTRATIONS FOR DISSOLVED THORIUM

(IN NANOGRAMS/MILLILITER)

THE RANGE REPRESENTS T M E

ONE SIGVA LEVEL

SAMPLE N UVbFR MINIMUM BEST VALUE M A X I M *J

H“ Jd 1 0.00034 0.00042 0 . 0 0 U 5 0

B — 7 8 1 0.00039 0.00047 o . 00055

B — *•* n 1 0.00038 0.0005 J 0.00 062

h- 1 1 A 2 0.00024 0.00036 0 . 0 0 0 4 R b-5A 2 0.00040 0.00050 0.0O060

8-7 4 4. < 0.00040

B-1 IB 3 0.00050 0.00060 0.00070

8-3* 3 0.00410 0. 00*40 0.00470

b-7b 3 0. 00040 0.00050 0.00060

8-1 7A 4 < 0.00050

8- 1 9 A 4 0.00040 0.00050 0.00060

8-21 A 4 < 0.00050

H-218 5 < 0.00070

8-2 bB 5 < 0.00050

8- 7 B S < 0.00050

B-1 lb 6 0.00060 0.00080 0.00100

B- 1 36 6 0.00030 0.0O040 0.00050

B- 1 7 o 6 0.00160 0.00170 0.00180

8-4 A 7 < 0.00080

B-bA 7 < 0.00060

B-8A 7 < 0.00060

B-10A « 0.00030 0. 00050 0.00070

B-1 2 A 8 < 0.00060

B-14A 8 0.00040 0.09060 0.00080

132
Table 42

BLANK CONCENTRATIONS FOR DISSOLVED URANIUM

(IN NANOGRAMS/MILLILITER)

THE RANGE REPRESENTS THE

ONE SIGMA LEVEL

SAMPLE NUMBER MINIMUM BEST VALUE MAXIMUM

B-3B 1 0.0008 0.0013 0.0018

B-7B 1 < 0.0020

6-9B 1 < 0.0060

b-1 1 A 2 0.0310 0.0340 0.0370

B-5A 2 0 . 0032 0.0037 0.0042

6-7 A 2 < 0.0020

6-1 IB 3 < 0.0020

6-3B 3 0.0016 0.0022 0.0028

P-76 3 < 0.0030

B-17A 4 0.0044 0.0049 0.0054

P-19A 4 < 0.0030

6-21 A 4 < 0.0020

D-21B 5 < 0.0030

B-25D 5 < 0.0010

B-7B 5 < 0.0020

B-1 IB 6 < 0.0030

B-13E 6 < 0.0020

6-176 6 < 0.0020

B-4 A 7 0.0013 0.0017 0.0021

B-6A 7 < 0.0020

B- b A 7 < 0.0020

6-10A 8 < 0.0030

6- 1 2 A P < 0.0020

B-14A 8 < 0.0030

133
Table 43

BLANK CONCENTRATIONS FOR DISSOLVED ZI^'C

(IN NANOGRAMS/MILLILITER)

THE RANGE REPRESENTS THE

0*'E S I

G

M A LEVEL

SAMPLE NUMBER MINIMUM BEST VALUE M A X 1 Ml

H-3B 1 0.56 0.59 0.62

B-7B 1 0.59 0.62 0.65

i->-9B 1 0.4b 0.48 0.50

B-l 1 A 2 0.3b 0.38 0.40

H-5A 2 1.19 1.25 1 .31

B-7A 2 1.08 1.14 1.20

B-l 1 B 3 0.7 5 0.79 0.83

b-3B 3 0.76 0.80 0.84

B - 7 B 3 0.78 0.82 0.86

B-l 7 m 4 1 .54 1.62 1.70

B- 1 9 A 4 1.07 1.13 1.19

e - 2 1 a 4 0.89 0.94 0.99

h-2lb 5 1.04 1.10 1.16

B-25B 5 1.3b 1.43 1.50

B-7B 5 0.7 6 0.80 0.84

B-11B 6 2.00 2.10 2.20

B-l 3B 6 1.14 1 .20 1.26

B-l 7B 6 1.42 1.49 1.56

B-4A 7 0.8b 0.91 0.96

H-6A 7 1.07 1.13 1.19

B— 6 A 7 3.80 4.00 4.20

6- 1 0 A b 3.30 3.50 3.70

B-12A 8 2.10 2.20 2.30

B-l 4A 8 3.40 3.60 3.P0

134
Table 44

BLANK CONCENTRATIONS FOR PARTICULATE CADMIUM

(IN NANOGRAMS/MILLILITER)

THE

SAMPLE NUMBER MINIMUM

B- # 9

B-#b

B- # 22

B- # 2 1 B -#20

6-fr 19

6 - # 1 2 B-m

B-# 10

RANGE REPRESENTS THE

ONE SIGMA LEVEL

BEST VALUE MAXIMUM

< 0.001

< 0.001

< 0.001

< 0.001

< 0.001

< 0.001

< 0.001

< 0.001

< 0.001

135
Table 45

BLANK CONCENTRATIONS FOR PARTICULATE CERIUM

(IN NANOGRAMS/MILLILITER)

THE RANGE REPRESENTS THE

ONE SIGMA LEVEL

SAMPLE NUMBER MINIMUM BEST VALUE MAXIMUM

AM-2 < 0.0080

BLANK-1 3 < 0.0040

BLANK- 1

< 0.0030

c LAf.K-15 < 0.0040

PLANK -16 < 0.0050

BLANK- 1 7 0.0050 0.0060 0.0070

BLANK - 1

< 0.0070

bLANK-2 0.0300 0.0320 0.0340

BLANK-26 0.0040 0.0050 0.0060

BLANK- 2b < 0.0020

B L A N K - 5 < 0.0080

bLANK-R < 0.0020

BLK-1 < 0.0080

bLK-7 < 0.0070

LPE < 0.0020

L.PE < 0.0030

L p fc: -< 0.0060

LPE-2 0.0013 0.0014 0.0015

MP-10 < 0.0050

MP-5+MP-9 < 0.0200

136
Table 46

BLANK CONCENTRATIONS FOR PARTICULATE COBALT

(IN NANOGRAMS/MILLILITER)

THE RANGE REPRESENTS THE

ONE SIGMA LEVEL

sample number MINIMUM BEST VALUE MAXIMUM

AM -2 < 0.0040

k L A N K - 1 3 < 0.0060

BLANK-14 0.0020 0.0026 0.0032

Blank- 1

5

< 0.0010

BLANK-16 < 0.0050

BLANK-17 0.0010 0.0016 0.0022

BLANK-16 0.0042 0.0050 0.0058

BLANK-2 0.0130 0.0140 0.0150

BLANK-25 0.0018 0.0028 0.0038

BLANK-26 < 0.0010

BLANK-5 < 0.0050

BLANK-8 < 0.0030

6LK-1 < 0.0040

BLK-7 < 0.0060

LPE < 0.0010

LPE < 0.0060

LPE1

0.0008 0.0012 0.0016

LPE-2 0.0003 0.0005 0.0007

MP-10 0.0020 0.0030 0.0040

MP-5+MP-9 < 0.0040

137
Table 47

BLAMK CONCENTRATIONS FOR PARTICULATE CHROMIUM

(IN NAKOGRAMS/MILLI LITER)

THE RANGE REPRESENTS THE

ONE SIGMA LEVEL

SAMPLE NUMBER MINIMUM BEST VALUE MAXIMUM

AM-2 0.740 0.7 80 0 . H 2 0

BLANK-13 2.170 2.290 2.410

BLANK-14 0.600 0.630 0.660

BLANK-15 0.680 0.720 0.760

BLANK-16 0.230 0.240 0.250

BLANK- 17 1.260 1.330 1.400

BLANK-1 8 0.400 0.420 0.440

BLANK0.270 0.280 0.290

BLANK-25 1.130 1.190 1.250

BLA.nk-26 0.440 0.460 0.480

B L A iV K - 5 2.26C 2.380 2.500

& L A N K - 8 0.360 0.380 0.400

BLK-1 0.710 0.750 0.790

BLK-7 1.790 1.880 1.970

LFE 0.064 0.067 0.070

LPE 0.066 0.070 0.074

LEE0.086 0.092 0.098

LPFJ-2 0.070 0.074 0.078

MP-10 0.220 0.230 0.240

“P-5+MP-9 0.450 0.470 0.490

138
Table 48

BLANK CONCENTRATIONS FOR PARTICULATE COPPER

(IN NANOGRAMS/MILLILITER)

TtlE RANGE REPRESENTS THE

ONE SIGMA LEVEL

SAMPLE NUMBER MINIMUM BEST VALUE MAXIMUM

B-#9 0.17 0.20 0.2 3

B- # 6 0.55 0.63 0.71

B-# 22 0.49 0.55 0.61

B-#21 0.34 0.38 0.42

B-#20 0.57 0.64 0.71

B-#19 0.64 0.71 0.78

B-# 1

2

0.57 0.64 0.71

B-# 1

1

0.30 0.34 0.38

B-# 1

0

0.25 0.28 0.31

139
Table 49

bL ANK CONCENTRATIONS FOR PARTICULATE IRON

(IN NANOGRAMS/MILLILITER)

THE RANGE REPRESENTS THE

ONE SIGMA LEVEL

SAMPLE NUMBER MINIMUM BEST VALUE MAXIMUM

AM-2 < 3.00

BLANK- 13 0.90 1.10 1 . 30

BLANK-14 1.40 1.55 1.70

BLANK-1 5 < 0.80

BLANK- 16 < 3.00

BLANK-17 1.43 1.65 1.87

BLANK-1

0.30 0.50 0.70

BLANK-2 1.80 1.90 2.00

bLANK-25 3.30 3.50 3.70

LLANK-26 0.40 0.50 0.60

BLANK-5 < 3.00

BLANK-8 0.30 0.50 0.70

BLK-1 < 2.00

BLK-7 < 2.00

LPE < 0.60

LPE < 0.70

LPE< 0.60

LPE- 2 0.70 0.75 0.80

MP-10 < 2.00

MP-5+MP-9 < 2.00

140
Table 50

BLANK CONCENTRATIONS FOR PARTICULATE MANGANESE

(IN NANOGRAMS/MILLILITER)

THE RANGE REPRESENTS THE

ONE SIGMA LEVEL

SAMPLE NUMBER MINIMUM BEST VALUE MAXIMUM

B- # 9

B -#6

B - # 2 2

B-#21

B-* 20

B- # 1 9

b- # 1 2

6 - # 1

1

B-#lO

< 0.010

0.052 0.060

< 0.010

< 0.010

< 0.010

0.030 0.040

< 0.010

< 0.010

< 0.010

0.068

0.050

141
Table 51

bLANK CONCENTRATIONS FOR PARTICIPATE MOLYBDENUM

(IN NANOGRAMS/MILLILITER)

SAMPLE NUMBER

AM-2

BLANK-13

BLANK-14

BLANK-1

S

BLANK-16

BLANK-17

BLAiMK-18

B L A N K - 2

BLANK-25

BLANK-26

BLANK-5

HLANK-8

BLK-1

BLK-7

LPE

LPE

LPE-1

LPE-2

MP-10

MP-5+MP-S

THE RANGE REPRESENTS THE

ONE SIGMA LEVEL

MINIMUM BEST VALUE MAXIMUM

<0.0060

<0.0090

<0.0500

< 0.0200

<0.0050

<0.0800

<0.0040

< 0.0200

< 0.1000

< 0.0200

< 0.0060

< 0.0200

<0.0070

<0.0080

< 0.0002

<0.0070

< 0.0200

< 0.0100

<0.0040

<0.0300

142
Table 52

BLANK CONCENTRATIONS FOR PARTICULATE NICKEL

(IN NANOGRAMS/M I LLILITER)

THE RANGE REPRESENTS THE

ONE S I G

A

LEVEL

SAMPLE NUMBER MINIMUM BEST VALUE MAXIM

B- # 9 < 0.02

B-#6 < 0.02

B-*22 < 0.02

B-# 21 0.06 0.07 0.08

b-*20 < 0.02

B-#19 0.0 8 0.09 0.10

B- # 1 2 < 0.02

B-#ll < 0.02

B-#10 < 0.02

143
Table 53

b LANK CONCENTRATIONS FOR PARTICULATE LEAD

(IN NANGGRAMS/MILLILITER)

THE RANGE REPRESENTS THE

ONE SIGMA LEVEL

SAMPLE NUMBER MINIMUM BEST VALUE MAXIMUM

tf - # 9 0.01 0.02

R -# 6 0.03 0.04

*-•22 < 0.01

B - * 2< 0.01

*-#20 < 0.01

B -* 1 9 < 0.01

B -#12 < 0.01

B -# 10.03 0.04

6 - # 1 0 0.02 0.03

0.03

0.05

0.0 5

0.04

144
'll Table 54

BLANK CONCENTRATIONS FOR PARTICULATE SCANDIUM

(IN NANOGRAMS/MILLILITER)

THE RANGE REPRESENTS THE

ONE SIGMA LEVEL

SAMPLE NUMBER MINIMUM BEST VALUE MAXIMUM

AM-2 <0.00030

BLANK-13 0.00011 0.00013 0.00015

BLANK-14 0.00032 0.00034 0.00036

BLANK-15 <0.00009

BLANK-16 <0.00020

BLANK-17 0.00049 0.00053 0.00057

BLANK-18 <0.00005

BLANK-2 0.00030 0.00040 0.00050

BLANK-25 0.00069 0.00076 0.00083

BLANK-26 0.00007 0.00009 0.00011

BLANK-5 <0.00040

BLANK-6 0.00003 0.00004 0.00005

BLK-1 <0.00020

BLK-7 <0.00020

LPE <0.00005

LPE <0.00007

LPE1<0.00001

LPE-2 0.00020 0.00021 0.00022

Mp-10 <0.00020

MP-5+KP-9 0.00015 0.00020 0.00025

145
Table 55

BLANK CONCENTRATIONS FOR PARTICULATE TIN

(IN NANOGRAMS/MILLILITER)

THE RANGE REPRESENTS THF

ONE STGMA LEVEL

SAMPLE NUMBER MINIMUM

AM-2

BLANK-13

BLANK-14

BLANK-15

BLANK-16

BLANK-17

BLANK- 1

BLANK-2

BLANK-25

BLANK-26

BLANK-5

BLANK-6

BLK-1

BLK-7

LPE

LPE

LPE

LPE-2

MP-10

Mp-5-f mP-9

BEST VALUE MAXIMUM

< 0.30

< 0.20

< 0.20

< 0.20

< 0.30

< 0.20

< 0.30

< 0.20

< 0.30

< 0.30

< 0.30

< 0.20

< 0.30

< 0.30

< 0.09

< 0.10

< 0.50

< 0.04

< 0.20

< 0.90

146
Table 56

BLANK CONCENTRATIONS FOR PARTICULATE THORIUM

(IN NANOGRAMS/MILLILITER)

THE RANGE REPRESENTS THE

ONE SIGMA LEVEL

SAMPLE NUMBER MINIMUM BEST VALUE

AM -2 <0.00200

BLANK-1 3 <0.00060

BLANK-14 <0.00050

BLANK-15 <0.00050

BLANK-lb <0.00100

BLANK-17 <0.00050

BLAivK-18 <0.00040

bLANK-2 <0.00040

BLANK-25 0.00100 0.00110

BLANK-26 <0.00020

BLANK-5 <0.00200

B L A N K - « <0.00030

BLK-1 <0.00200

bL.K-7 <0.00010

LPE <0.00050

LPE <0.00060

LPE1

<0.00070

LPE-2 0.00020 0.00024

MP-10 <0.00010

MP-5+MP-9 <0.00200

MAXIMUM

0.00120

0.00020

147
Table 57

BLANK CONCENTRATIONS FOR PARTICULATE URANIUM

(IN NANOGRAMS/MILLILITER)

THE RANGE REPRESENTS THE

ONE SIGMA LEVEL

SAMPLE NUMBER MINIMUM BEST VALUE

A M-2

BLAnK-13

BLANK-14

HLANK-1S

BLANK-16

BLANK-17

BLANK-18

PLANK-2

BLANK-25

BLANK-26

BL.ANK-5

BLANK-8

BL.K-1

BLK-7

LPE

LPE

LPE- 1 LPE-2

MP-10

MP-5+MP-9

<0.00040

<0.00007

< 0.00500

< 0.00200

<0.00030

<0.00800

<0.00030

<0.00300

< 0.01000

< 0.00100

< 0.00100

< 0.00200

< 0.00100

<0.00060

< 0.00020

<0.00070

< 0.00200

< 0.00100

<0.00030

< 0.00200

MAXIMUM
Table 58

BLANK CONCENTRATIONS FOR PARTICULATE ZINC

(IN nanograms/milliliter)

THE RANGE REPRESENTS THE

ONE SIGMA LEVEL

SAMPLE NUMBER MINIMUM BEST VALUE MAXIMUM

AM-2 < 0.300

BLANK-13 0.470 0.500 0.530

BLANK-14 0.280 0.310 0.340

BLANK-15 0.120 . 0.140 0.160

BLANK-16 < 0.300

BLANK-17 0.380 0.420 0.460

BLANK-18 0.890 0.940 0.990

BLANK-2 0.110 0.130 0.150

BLANK-25 0.480 0.530 0.580

BLANK-26 1.500 1.600 1.700

BLANK-5 0.460 0.560 0.660

BLANK-8 0.100 0.110 0.120

bLK-1 < 0.200

ELK-7 0.240 0.290 0.340

LPE < 0.040

LPE < 0.060

LPE-1 < 0.040

LPE2

0.010 0.013 0.016

MP-10 < 0.200

MP-5+MP-9 • • •

149
Table 59

CRUSTAL ENRICHMENT FACTORS FOR PARTICULATE CADMIUM

RELATIVE TO SCANDIUM (WEDEPOHL)

THH RANGE REPRESENTS AT LEAST

THE 90% CONFIDENCE LIMITS

SAMPLE NUMBER MINIMUM BEST VALUE MAXIMUM

1110 2 3.496 5.537 7.869

11101 15.113 20.419 26.837

11100 1.676 3.630 6.040

1 1099 8.684 • 12.923 18.097

110 9 8 12.120 18.150 25.993

11097 lo. 740 24.282 33.612

11096 2.992 5.294 8.159

11095 3.937 6.534 9.824

1 1094 10.124 14.603 20.153

1 1 093 18.496 24.956 32.996

11092 6.593 1 1.020 16.358

11091 3.373 5.445 7.913

110 9 0 0.898 2.836 5.183

1 1089 4.330 8.391 13.296

11088 3.083 9.723 17.731

1108 7 3.911 7.090 10.991

1 1066 0.000 8.007 26.446

11085 <

1 1 084 < 11083 5.063 15.707 28.086

1 1062 9.850 31.414 58.065

11061 <

1 1060 76.070 137.501 212.430

11079 24.839 53.383 87.995

110 7 6 16.277 37.813 64.612

110 7 7 6.776 17.016 29.659

1 1 076 0.248 13.613 29.881

1 1075 < 11074 49.237 105.729 174.101

110 7 3 27.275 49.321 76.234

1 1 0 7 2 35.708 74.650 124.866

110 7 1 24.976 50.307 80.356

11070 0.491 26.956 59.107

11069 0.218 11.837 25.621

11068 0.195 10.471 22.423

1 1067 5.599 13.810 23.550

1 1 Ubb 33.522 72.601 120.803

11065 < 11064 < 110 6 3 4.715 10.083 16.524

11062 < 11061 8.043 13.068 19.137

110 6 0 < 11059 < 11058 0.000 20.942 68.155

1 1057 <

1 1056 <

1 1055 <

1 1054 < 11053 < 110 5 2 < 150
Table 59 continued

CRUSTAL ENRICHMENT FACTORS FOR PARTICULATE CADMIUM

RELATIVE TO SCANDIUM ( WFDEPOHL

)

THE RANGE REPRESENTS AT LEAST

THE 90% CONFIDENCE LIMITS

SAMPLE NUMEER MINIMUM BEST VALUE MAXIMUM

11051 < 11050 < 11049 < 11048 262.272 348.230 451.432

11047 12.838 20.019 28.810

11046 22.514 71.645 132.079

11045 13.043 19.208 26.686

11044 < 11043 5.017 7.623 10.771

11042 < 11041 < 11040 < 11039 < 11038 < 11037 < 11036 632.364 855.650 1135.260

11035 < 11034 < 11033 < 11032 < 11031 < 11030 < 11029 < 11028 < 110 27 < 11026 < 11025 < 11024 < 110 2 3 < 11022 < 11021 33.387 54.090 78.931

11020 0.000 6.188 20.1 06

1 1019 6.588 15.598 26.657

11018 < 11017 0.000 1.18 4 3.903

11016 < 11015 < 11014 < 11013 < 11012 < 11011 0.031 1.723 3.788

11010 < 110 0 9 0.119 6.482 14.156

11008 < 11007 < 11006 < 11005 0.142 0.454 0.842

1 1 004 < 110O3 3.057 6.560 10.794

1100/ < 11001 5.526 9.864 15.010

151
Table 60

CRUSTAL ENRICHMENT FACTORS FOP PARTICULATE CERIUM

RELATIVE TO SCANDIUM (WEDEPOHL)

THE RANGE REPRESENTS AT LEAST

THE 90% CONFIDENCE LIMITS

SAMPLE NUMBER MINIMUM BEST VALUE MAXIMUM

11102 1.04 1.23 1.45

11101 1 .02 1.23 1.49

11100 1.28 1.56 1.90

11099 1.28 - 1.57 1.92

1109b 1.27 1.56 1.93

11097 1.19 1.51 1.91

11096 1 .16 1.42 1.74

11095 1.21 1.49 1.86

11094 1.32 1 .60 1.94

11093 1.31 1.59 1.94

11092 1.11 1.35 1.64

11091 0.96 1.12 1.32

11090 0.90 1.09 1.32

110&9 0.91 1 .10 1.32

1 10bb 0.94 1.16 1.42

11087 0.88 1.09 1.34

11086 0.89 1.09 1.33

1 1085 1.30 1.59 1 .94

11084 0.92 1.11 1.34

11083 0.94 1.12 1.33

11082 0.91 1.12 1.38

11081 0.95 1.13 1.35

11080 0.95 1.15 1.40

11079 0.92 1.15 1.43

11078 0.91 1.14 1.43

11077 0.91 1.13 1.41

110 7 6 1.01 1.24 1.52

11075 0.99 1 .20 1.44

11074 1 .04 1.25 1.50

1 1073 1.37 1.66 2.02

11072 0 ,9b 1.20 1.51

11071 1.01 1.18 1.37

11070 1.00 1.24 1.53

11069 1.00 1.19 1.43

11068 1.00 1.18 1.40

11067 0.97 1 .16 1.39

1 1 066 0.97 1 .37 1.86

11065 1.04 1 .27 1.54

11064 0.90 1.16 1.47

11063 0.95 1.14 1.37

11062 0.89 1.11 1.38

11061 0.90 1.11 1.35

110 6 0 1.02 1.27 1.58

1 1059 0.96 1.22 1 .54

1 105& 0.9 8 1.23 1.54

11057 1.06 1.27 1 .50

11056 0.9 5 1.14 1.38

11055 1 .00 1.20 1.43

1 1054 0.91 1.12 1.38

110 5 3 0.96 1.17 1 .44

110 5 2 0.89 1.13 1.42

152
Table 60 continued

CRUSTAL ENRICHMENT FACTORS FOR PARTICULATE CERIUM

RELATIVE TO SCANDIUM (WEDEPOHL)

THE RANGE REPRESENTS AT LEAST

THE 90% CONFIDENCE LIMITS

SAMPLE NUMBER MINIMUM BEST VALUE MAXIMUM

11051 0.97 1.21 1.48

11050 1.00 1.24 1.52

11049 0.94 1.17 1 .45

11048 1.00 1.26 1.57

11047 0.96 1.17 1.42

11046 1.13 1.38 1.68

11045 0.98 1.19 1.44

11044 1.03 1.29 1.59

11043 1.04 1.25 1.51

11042 1.14 1.42 1.77

11041 1.02 1.27 1.58

11040 1.11 1.37 1 .68

11039 1.00 1.22 1.50

11038 0.91 1.18 1.50

11037 1.00 1.27 1.61

11036 < 11035 1.07 1.29 1.55

11034 1.09 1.42 1.79

11033 1.12 1.33 1.57

11032 1.17 1.49 1.86

11031 0.94 1.18 1.47

11030 1.05 1.30 1.59

11029 1.00 1.21 1.46

11028 1.07 1 .38 1.75

11027 1.04 1.26 1.53

11026 1.05 1.30 1.59

11025 0.99 1.23 1.51

11024 1.03 1.27 1.57

11023 1.11 1.32 1.56

11022 0.99 1.32 1.73

11021 1.02 1.24 1.49

11020 1.05 1.26 1.52

11019 0.99 1.21 1.47

11018 1.05 1.27 1.53

11017 1.00 1.23 1.52

11016 0.71 1.13 1.63

11015 1.09 1.32 1.59

11014 0.85 1.14 1.51

11013 1.04 1.26 1.55

11012 1.04 1.28 1.59

11011 1.06 1.28 1.55

11010 1 .14 1.40 1.72

11009 0.94 1.20 1.52

11008 1.04 1.27 1 .54

11007 1 .05 1.24 1 .49

11006 0.96 1.18 1.44

11005 1.01 1.24 1.53

1 1004 0.99 1.22 1.50

11003 1.05 1.28 1.56

11002 1.14 1 .4? 1 .76

11001 1,05

153

1.24 1.48
Table 61

CRUSTAL ENRICHMENT FACTORS FOR PARTICULATE COBALT

RELATIVE TO SCANDIUM (wEDEPOHL)

THE RANGE REPRESENTS AT LEAST

THE 90% CONFIDENCE LIMITS

AMPLE NUMBER MINIMUM BEST VALUE MAXIMUM

11102 2.04 2.41 2.83

11101 1.96 2.37 2.86

1110 0 3.83 4.74 5.81

110 9 9 3.97 4.80 5.81

1109b 3.52 4.43 5.63

11097 3.51 4.32 5.32

1109b 2.29 2.83 3.51

11095 2.36 2.92 3.62

1 1 094 4.03 4.88 5.93

11093 4.10 4.97 6.05

11092 2.34 2.89 3.55

11091 2.56 3.09 3.71

11090 2.45 3.00 3.66

11089 2.49 3.04 3.70

110 8 8 2.16 2.61 3.15

110 8 7 2.15 2.61 3.18

11086 2.93 3.64 4.51

11085 1.72 2.17 2.72

11084 2.39 2.89 3.49

11083 2.30 2.7 4 3.25

11082 3.17 3.86 4.71

11081 2.58 3.08 3.67

11080 3.12 3.89 4.83

11079 3.45 4.23 5.18

11078 1.23 1.49 1.82

11077 1.17 1.46 1.81

11076 1.92 2.45 3.10

11075 2.30 2.77 3.3 3

11074 2.90 3.62 4.50

110 7 3 1.16 1.44 1.78

11072 1.44 1 .84 2.36

11071 1.45 1.78 2.16

11070 2.64 3. 35 4.21

11069 1.83 2.18 2.60

110 6 8 1.47 1.84 2.28

11067 1.39 1 .67 2.01

11066 1.72 3.42 5.52

11065 1.13 1.68 2.32

110 6 4 0.31 0.78 1.34

1 1063 0.52 0.69 0.90

1 1 0 b 2 0.89 1.13 1.44

11061 0.97 1.18 1.42

11060 3.59 4.84 6.42

11059 4.19 5.29 6.61

11058 2.81 3.77 4.92

11057 1 .33 1.58 1.88

11056 2.71 3.62 4.71

11055 1 .55 1.88 2.29

11054 0.93 1.17 1.46

110 5 3 0.96 1.17 1.42

110 5 2 0.7b 154 1 • 0

1.33
Table 61 continued

crustal enrichment factors for particulate cobalt

RELATIVE TO SCANDIUM (wEDEPOHl.)

THE RANGE REPRESENTS AT LEAST

THF 90% CONFIDENCE LIMITS

SAMPLE NUMBER MINIMUM BEST VALUE MAXIMUM

11051 1 .15 1.39 1.66

11050 0.96 1.20 1.48

11049 1.05 1.30 1.60

1 1048 1.37

' 1.66 2.00

11047 0.97 1.18 1.45

11046 3.91 5.12 6.60

110 4 5 1.04 1.27 1.54

1104 4 1.46 1.79 2.18

11043 1.71 2.05 2.47

11042 5.65 7.23 9.23

11041 1.05 1.30 1.60

1.1040 7.65 9.33 11.34

11039 1.04 1.27 1.54

11038 4.61 5.91 7.48

11037 1.09 1.37 1.70

11036 8.17 13.00 19.05

11035 1.17 1.53 1.94

110 3 4 6.80 8.05 9.47

11033 1.52 1.87 2.28

110 3 2 4.88 6.67 8.77

110 31 4.60 5.83 7.33

11030 1.83 2.49 3.26

11029 0.92 1.13 1.38

11028 2.90 3.68 4.64

11027 1.44 1.79 2.23

11026 1.59 2.03 2.54

11025 0.97 1.24 1.57

11024 1.89 2.59 3.45

11023 1.43 1.78 2.21

110 2 2 1.40 2.23 3.28

11021 1.02 1.24 1.49

11020 1.71 2.17 2.73

11019 1.14 1.40 1.72

11018 1.37 1 .66 2.02

11017 1.46 1.79 2.19

11016 4.26 6.11 8.34

11015 1.05 1 . 34 1.69

11014 2.35 3.37 4.64

11013 1.51 1.89 2.36

11012 1.53 2.08 2.78

11011 0.97 1.18 1.44

11010 1.54 2.15 2.90

11009 1.40 1.86 2.41

110 0 8 1.30 1.59 1.92

11007 1.25 1 .56 1.92

1100b 0.95 1.21 1.53

11005 1.08 1.32 1.63

11004 1.16 1 .40 1.71

1 1 003 1.21 1.49 1.83

11002 1.94 2.78 3.78

110 01 1.09 1 . 32 1.59

155
TaDie oz CRUSTAL ENRICHMENT FACTORS OF PARTICULATE CHROMIUM

AS COMPARED TO SCANDIUM (WEDEPOHL)

THE RANGE REPRESENTS AT LEAST

THE 90% CONFIDENCE LIMITS

SAMPLE NUMBER MINIMUM BEST VALUE MAXIMUM

1 110 2 1.11 1.48 1.82

11101 0.99 1.44 1.90

11100 0.96 1.64 2.15

11099 0.96 1.61 2.09

11098 1.15 1.70 2.23

11097 1.09 1.65 2.20

11096 1.22 1.77 2.34

11095 1.35 1.95 2.60

11094 1 . lo 1.58 2.01

11093 1.18 1.61 2.05

11092 1.29 2.26 3.17

11091 1.01 1.50 1.96

11090 0.58 1.33 1.89

11089 0.52 1.26 1.81

11088 0.37 1.55 2.37

11087 0.7 8 1.46 2.02

11086 0.00 1.65 4.56

110 8 5 0.00 1.61 4.64

11084 0.00 1.91 4.06

11083 0.00 1.62 3.47

11082 0.00 2.46 7.35

11081 0.00 2.36 4.13

11080 0.00 1.82 14.78

110 7 9 0.00 2.75 15.38

11078 0.00 1.33 4.59

11077 0.00 0.75 3.11

11076 o.uo 0.90 7.31

11075 0.00 4.75 10.74

11074 0.00 3.11 15.65

11073 0.00 0.00 8.64

11072 0.00 1.68 6.12

11071 0.00 1.52 4.48

11070 0.00 0.00 11.33

11069 0.00 2.09 7.69

11068 0.00 0.15 4.72

11067 0.00 1.25 3.24

11066 o.oo 0.00 15.09

1 1065 0.00 0.88 5.90

11064 0.00 0.71 3.78

11063 0.00 0.80 2.08

11062 0.25 1.01 1.81

11061 0.00 0.00 0.93

11060 0.00 0.00 14.19

11059 0.00 o.oo 12.54

11058 0.00 4.0 0 23.65

1 1057 0.00 0.57 4.99

11056 0.00 0.14 8.68

11055 0.00 1.90 5.48

11054 0.00 0.60 2.51

11053 0.00 0.86 2.12

11052 0.00 1.43 4.12

156
Table 62 continued

CRUSTAL ENRICHMENT FACTORS OF PARTICULATE CHROMIUM

! AS COMPARED TO SCANDIUM (WEDEPOHL)

THE RANGE REPRESENTS AT LEAST

THE 90% CONFIDENCE LIMITS

SAMPLE NUMBER MINIMUM BEST VALUE MAXIMUM

11051 0.00 0.58 3.22

11050 0.00 0.18 1.77

11049 0.00 0.52 2.16

11048 0.00 0.00 2.29

11047 0.00 0.26 1.58

11046 0.00 0.00 5.84

11045 0.00 0.00 0.94

11044 0.00 0.00 1.63

11043 0.00 0.46 1.91

11042 0.00 0.00 15.61

11041 0.00 0.00 1.22

11040 0.00 0.00 20.29

11039 0.84 2.16 3.45

110 3 8 0.00 0.00 5.04

11037 0.00 0.00 2.30

1 1036 0.00 0.00 9.29

110 3 5 0.00 0.00 1.10

11034 0.00 0.00 35.27

11033 o.oo 1.21 5.68

11032 0.00 7.35 42.98

11031 0.00 2.22 11.19

11030 0.00 5.83 12.42

11029 0.09 1.48 2.77

110 2 8 0.00 3.05 10.35

11027 o.oo 0.39 3.08

11026 0.00 0.00 0.21

11025 0.0 0 3.06 6.30

11024 0.00 3.11 12.85

1 1023 0.00 1.71 3.84

11022 o.oo 0.88 4.78

11021 0.55 1.83 3.04

1 1020 0 .

0

0 4.18 12.69

11019 0.00 0.77 2.74

11016 0.00 1.33 2.98

11017 0.00 1 .46 3.29

11016 0.00 1.90 21.25

11015 0.00 1.05 3.31

11014 o.oo 2.56 7.13

11013 0.00 0.82 4.72

11012 0.00 2.56 7.13

11011 0.00 0.58 1.48

11010 0.00 0.00 6.56

11009 0.00 2.67 6.17

11008 0.00 1.36 4.25

11007 0.00 1.08 3.15

1 1006 0.32 i .02 1.69

110 0 5 0.70 1.15 1.64

11004 0.00 0.64 2.01

11003 0.00 1.40 3.76

11002 0.00 0.10 5.85

11001 0.00 1.42 3.50

157
Table 63

CRUSTAL ENRICHMENT FACTORS FOR PARTICULATE COPPER

RELATIVE TO SCANDIUM (WEDEPOHL)

I

THE RANGE REPRESENTS AT LEAST

THE 90% CONFIDENCE LIMITS

SAMPLE NUMBER MINIMUM BEST VALUE MAXIMUM

11102 0.14 0.78 1.45

11101 0.26 0.89 1.58

11100 1.17 2.63 4.20

11099 0.85 2.21 3.65

11098 0.79 2.03 3.51

11097 0.85 2.13 3.62

11096 0.28 1.19 2.25

110 9 5 0.30 1.29 2.45

11094 0.69 1.93 3.41

11093 1.45 2.81 4.42

11092 0.00 1.34 3.24

11091 0.18 1.03 1.94

11090 0.00 1.01 2.54

11089 0.00 0.84 2.33

11088 0.00 2.38 5.19

11087 0.00 0.99 2.24

11086 0.00 0.00 7.73

11085 0.00 0.00 5.22

11084 0.00 0.00 2.96

11083 0.00 0.00 2.78

11082 0.00 o.oo 6.32

11081 0.00 0.00 5.61

11080 0.00 0.00 7.49

11079 0.00 0.00 4.78

11078 0.00 0.00 1.62

110 7 7 0.00 0.00 1.42

11076 0.00 0.00 3.95

11075 0.00 0.00 4.32

11074 0.00 0.44 17.14

11073 0.00 0.00 9.48

11072 0.00 0.00 3.18

11071 0.00 0.00 3.12

11070 0.00 0.00 11.42

11069 0.00 0.00 6.03

11068 0.00 0.35 6.83

11067 0.00 0.66 3.34

110 6 6 0.00 0.00 23.11

11065 0.00 2.36 9.74

11064 0.00 1.30 5.77

11063 0.00 0.84 2.71 ' 11062 0.00 0.00 0.38

11061 0.00 1.38 3.25

11060 0.00 9.42 45.68

11059 0.00 0.00 25.92

11058 0.00 0.00 25.48

11057 0.00 2.43 8.96

11056 0.00 0.00 5.91

1 1 055 0.00 0.81 5.33 i 11054 0.00 0.52 3.08

1 1053 0.00 0.08 1.55

11052 0.00 0.17 3.49

158
Table 63 continued

CRUSTAL ENRICHMENT FACTORS FOR PARTICULATE COPPER

RELATIVE TO SCANDIUM (WEDEPOHL)

THE RANGE REPRESENTS AT LEAST

THE 90% CONFIDENCE LIMITS

SAMPLE NUMBER MINIMUM BEST VALUE MAXIMUM

11051 0.00 2.28 6.46

11050 0.00 0.00 1.57

11049 0.00 0.00 1.44

11048 0.00 0.00 1.24

11047 0.00 0.23 2.00

11046 0.00 0.00 17.93

11045 0.00 1.17 2.88

11044 0.00 0.00 2.98

11043 0.00 0.47 2.40

11042 0.00 0.00 29.78

11041 0.00 0.00 3.87

11040 0.00 0.00 36.67

11039 0.00 0.68 2.02

11038 0.00 0.00 17.34

11037 0.00 0.00 3.42

11036 0.00 0.00 40.82

11035 0.00 0.00 2.78

11034 0.00 0.00 21.35

11033 0.00 0.00 5.22

11032 0.00 13.89 64.58

11031 0.00 0.00 9.74

11030 0.00 4.14 12.87

11029 0.00 0.39 1.87

11028 0.00 2.15 12.10

11027 0.00 1.21 4.90

11026 0.00 0.00 6.73

11025 0.00 0.58 4.47

11024 0.00 0.00 11.67

11023 0.00 0.00 1.53

11022 0.00 0.93 6.55

11021 0.00 0.66 2.08

11020 0.00 0.00 9.21

11019 0.00 0.00 2.14

11018 0.00 0.33 2.33

11017 0.00 0.24 2.33

11016 0.00 0.00 19.03

11015 0.00 0.74 3.82

11014 u . oo 6.55 15.40

11013 0.00 0.00 5.01

11012 0.00 0.00 5.36

11011 0 .00 1.41 3.01

11010 0.00 0.00 10.72

11009 0.00 0.43 4.55

11008 0.00 0.00 3.44

11007 0.00 0.2 3 3.0 7 11006 0.32 1.20 2.15

11005 0.60 1.42 2.39

11004 n.oo 0.66 2.53

11003 0.00 0.00 0.98

11002 0.00 0.00 7.91

11001 0.00 0.26 2.91

159
Table 64

CRUSTAL ENRICHMENT FACTORS OF PARTICULATE IRON

PELATIVE TO SCANDIUM (WEDEPOHL)

THE RANGE REPRESENTS AT LEAST

THE 90% CONFIDENCE LIMITS

SAMPLE NUMBER MINIMUM BEST VALUE MAXIMUM

11102 0.93 1 .12 1.31

11101 0.92 1.14 1.38

11100 1.07 1.37 1.70

1 1 099 1.09 1.38 1.69

11098 1 .04 1.33 1.68

11097 1.05 1.30 1.60

11096 1.01 1.27 1.58

11095 1.03 1.30 1.61

11094 1.07 1.33 1.63

11093 1.08 1.35 1.66

11092 1.08 1.36 1.66

11091 1.01 1.24 1.49

11090 0.93 1.15 1.39

11089 0.94 1.16 1.40

1 1068 0.96 1.18 1.40

11067 0.95 1.19 1.47

11086 0.86 1.14 1.37

11085 1.51 1.97 2.39

11084 0.85 1 .10 1.31

11083 0.8 8 1.14 1.36

11082 0.85 1.19 1.46

11081 1.12 1.41 1.67

11080 0.79 1.20 1.50

11079 0.91 1.32 1.63

11078 0.77 1.00 1.23

1 1 C 7 7 0.80 1.02 1.24

11076 1.05 1.36 1.64

11075 1.27 1.61 1.93

11074 0.7 7 1.15 1.44

11073 3.09 3.95 4.83

11072 0.75 1.01 1.27

11071 0.81 1.03 1.24

11070 0.82 1.14 1.34

11069 1.28 1.65 1.99

11068 0.91 1.17 1.40

11067 1.02 1.26 1.50

11066 0.66 1.16 1.53

11065 1 .46 1.85 2.21

1 1064 0.69 0.94 1 . 1 H 11063 0.75 0.92 1.09

11062 0.71 0.91 1 .14

11061 0.76 0.92 1.08

11060 0.81 1.34 1.68

11059 1.02 1.48 1.77

11058 0.90 1.34 1 .60

11057 1 . 30 1.64 1 .94

1 1056 0 .86 1.20 1.45

11055 0.99 1.27 1.54

1 1054 0.67 0.87 1.08

11053 0.71 0.87 1.04

11052 0.77 1.04

160

1 .34
Table 64 continued

CRUSTAL ENRICHMENT FACTORS OF PARTICULATE IRON

RELATIVE TO SCANDIUM (WEDEPOHL)

THE RANGE REPRESENTS AT LEAST

THE 90% CONFIDENCE LIMITS

SAMPLE NUMBER MINIMUM BEST VALUE MAXIMUM

11051 0.82 1.03 1.23

11050 0.77 0.98 1.19

11049 0.82 1.03 1.25

11048 0.86 1.09 1.32

11047 0.80 1.02 1.26

11046 0.6 3 1.11 1 .39

11045 0.87 1.07 1.29

11044 0.82 1.04 1.25

11043 0.76 0.98 1.22

11042 1.07 1.66 2.06

11041 1.11 1.40 1.69

11040 0.93 1.51 1.83

11039 1.03 1.26 1.51

11038 0.97 1.46 1.83

11037 1.22 1.54 1.87

11036 0.67 1.92 2.91

11035 1 .16 1 .48 1.76

11034 1.08 1.87 2.20

11033 1.18 1.47 1.73

11032 0.98 1.53 1.84

11031 1.39 1.81 2.18

11030 1.17 1.5 3 1.86

11029 1.06 1.31 1.58

11028 1,03 1.35 1.65

11027 0.97 1.23 1.50

11026 0.99 1.29 1.56

11025 1.00 1.27 1.53

11024 1.01 1.35 1.63

11023 1 .09 1.34 1.59

11022 0.96 1.24 1.54

11021 1.03 1.31 1.61

11020 1.09 1.42 1.71

11019 0.96 1.28 1.60

11018 1.02 1.27 1.53

11017 1 .00 1.27 1.57

11016 0.85 1.44 1.86

11015 0.99 1.26 1.53

11014 1.02 1.36 1.67

11013 1.02 1 .34 1.67

11012 0.98 1.29 1.60

11011 1.01 1.23 1.47

11010 1.03 1.40 1.74

11009 0.99 1 .26 1.53

11008 1.03 1.31 1 .56

11007 1 .02 1 . 12 1 .62

11006 0.94 1.16 1.41

11005 1.00 1.24 1 .53

11004 0.97 1.20 1.46

11003 1.00 1.25 1.52

11002 1.18 1.53 1 .85

11001 1.13 1.38 1.63

161
Table 65

CRUSTAL ENRICHMENT FACTORS FOR PARTICULATE MANGANESE

RELATIVE TO SCANDIUM (wEDEPQHL)

THE RANGE REPRESENTS AT LEAST

THE 90% CONFIDENCE LIMITS

SAMPLE NUMBER MINIMUM BEST VALUE MAXIMUM

11102 2.9 3.9 5.0

11101 3.0 4.0 5.3

1 1100 11.4 15.7 20.9

11099 12.1 16.2 21.3

11098 7.6 10.4 14.0

11097 7.4 9.7 12.6

1109b 5.2 6.8 8.9

11095 5.5 7.3 9.5

11094 8.0 9.9 12.3

11093 10.3 12.8 15.8

11092 4.6 6.2 8.1

1 1091 4.0 5.0 6.3

11090 4.5 6.0 8.0

11089 4.7 6.4 8.4

11086 6.6 8.8 11.5

1 1087 5.6 7.6 9.9

11066 22.1 30.3 40.4

11085 2.6 3.6 4.7

11084 16.7 22.5 29.3

11063 17.2 22.9 29.6

11062 37.2 51.3 66.7

11061 19.4 25.9 33.3

1 1060 26.4 36.1 47.8

11079 27.8 37.7 49.7

11078 5.2 7.2 9.6

110 7 7 6.1 8.3 11.2

11076 29.1 39.5 52.1

11075 26.0 34.4 44.3

1 1074 17.0 23.2 30.6

11073 1.1 1.7 2.5

1 107 2 7.0 9.9 13.6

11071 6.9 9.1 11.7

11070 9.3 12.9 17.2

11069 6.4 8.4 10.8

11068 10.8 14.3 18.4

11067 8.1 10.9 14.2

11066 12.0 16.8 22.8

11065 16.8 22.6 29.4

11064 6,6 9.0 12.0

1 1 0b3 3.9 5.1 6.6

11062 1.4 1.9 2.6

11061 6.5 8.3 10.5

1 1060 33.7 46.2 61.8

1 1059 53.3 72.1 94.7

11056 28.0 37.6 49.2

1 1057 6.6 8.7 11.2

11056 2 4.2 32.8 43.2

11055 8.4 11.4 15.1

11054 2.7 3.7 5.0

11053 2.1 2.8 3.7

11052 4.6 6. i 8.4

162
Table 65 continued

CRUSTAL ENRICHMENT FACTORS FOR PARTICULATE MANGANESE

RELATIVE TO SCANDIUM (WEOEPOHL)

THE RANGE REPRESENTS AT LEAST

THE 90% CONFIDENCE LIMITS

SAMPLE NUMBER MINIMUM BEST VALUE MAXIMUM

J 1051 6.0 7.9 10.2

11060 3.7 5.0 6.6

11049 4.2 5.8 7.6

1 1 0 4 8 8.1 10.9 14.3

11047 3.4 4.6 6.1

11046 30 .

6

41.9 55.8

11045 4.2 5.6 7.4

11044 8.6 11.7 15.3

11043 4.0 5.4 7.1

11042 28.7 39.9 53.9

11041 3.2 4.4 5.8

11040 37.3 50.9 67.0

11039 1.1 1.5 2.0

11038 29.9 40.4 53.2

11037 2.2 3.0 4.1

11036 40.8 56.4 75.9

11035 5.3 7.1 9.1

11034 59.6 79.6 102.5

11033 4.3 5.8 7.6

110 3 2 40.8 54.4 70.2

11031 15.5 20.7 27.0

11030 7.8 10.5 13.6

11029 1.4 1.9 2.5

11028 11.4 15.9 21.3

11027 5.9 8.1 10.9

11026 7.5 10.1 13.3

11025 2.4 3.2 4.2

11024 9.3 13.2 17.8

110 2 3 2.0 2.8 3.6

11022 4.7 6.6 9.0

1 1021 1.8 2.4 3.2

11020 8.8 12.2 16.3

11019 2.7 3.7 5.0

11018 3.8 5.2 6.9

11017 3.8 5.1 6.8

11016 21.0 29.1 38.9

11015 2.5 3.5 4.6

11014 6.8 9.6 13.2

11013 5.8 8.0 10.9

11012 4.7 6.7 9.3

11011 2.5 3.4 4.4

11010 6.7 9.5 12.8

1 1 0U9 3.4 4.6 6.1

11008 3.3 4.8 6 .

6

11007 3.1 4.4 5.9

1 1006 1 .2 1.6 2. J 11005 1.9 2.4 2.9

11004 2.1 2.9 3.8

11003 3.4 4.6 6.0

11002 11.6 15.8 20.9

11001 3.4 4.5 5.9

163
Table 66 i CRUSTAL ENRICHMENT FACTORS FOR PARTICULATE MOLYBDENUM

RELATIVE TO SCANDIUM UEDF.POHL)

THE RANGE REPRESENTS AT LEAST

THE 90% CONFIDENCE LIMITS

SAMPLE NUMBER minimum BEST VALUE MAXIMUM

11102 < 11101 < 11100 o.oo 1.97 6.17

11099 0.00 1.77 5.82

11098 < 11097 < 11096 < 1109b < 11094 0.00 2.04 6.75

11093 < 11092 0.00 0.67 2.18

110 91 3.50 7.47 12.19

11090 < 110 8 9 0.95 4.79 9.44

11086 0.00 3.33 10.88

110 6 7 < 11066 < 11085 < 11084 < 11083 < 11082 < 11061 0.00 10.00 31.83

110 6 0 < 11079 < 11078 < 11077 < 110 7 6 < 110 7 5 < 11074 < 11073 < 11072 < 11071 < 11070 < 11069 <

1 1 066 < 11067 < 11066 < 11065 < 11064 < 11063 < 11062 0.00 0.85 2.85

11061 < 11060 < 11059 < 11056 < 11057 < 11056 <

1 1055 < 11054 < 110 5 3 < 110 5 2 <
Table 66 continued

CRUSTAL ENRICHMENT FACTORS FOR PARTICULATE MOLYBDENUM

RELATIVE TO SCANDIUM (WEDEPOHL)

SAMPLE NUMBER MINIMUM

11051

11050

11049

11048

11047

11046

110 4 5

11044

11043

11042

11041

1 1 040

11039

11038

11037

11036

11035

11034

11033

11032

11031

11030

11029

11028

11027

11026

11025

11024 3.77

11023

11022

11021

11020

11019

11018

11017 1.15

11016

11015

11014

11013

11012

11011

11010

11009

110 0 8 11007

11006

11005 0.00

11004

1100 3

110 0 2

1 1001

THE RAmGE REPRESENTS AT LEAST

THE 90% CONFIDENCE LIMITS

BEST VALUE MAXIMUM

<<<

<

<

<<

<

<<

<

<<

<

<<

<

<<

<

<

<<

<

<<

< 207.41 457.12

<<

<

<<

< 3.65 6.73

<<

<

<

<<

<<

<

<< 3.11 10.33

<

<

<

<

165
Table 67

CRUSTAL ENRICHMENT FACTORS FOR PARTICULATE MCKFL

RELATIVE TO SCANDIUM (WEDEPOHL)

THE RANGE REPRESENTS AT LEAST

THE 90% CONFIDENCE LIMITS

SAMPLE NUMBER MINIMUM BEST VALUE MAXIMUM

11102 0.85 1.31 1.73

11101 0.93 1.40 1.87

1110 0 1.28 2.06 2.75

11099 1.58 2.35 3.03

11098 1.24 1.96 2.72

11097 1.48 2.09 2.70

11096 0.91 1 . 32 1.73

1109b 0.91 1.49 2.10

11094 1.59 2.19 2.83

11093 2.07 2.86 3.72

11092 0.88 1.36 1.75

110 91 0.73 1 .17 1.58

11090 0.90 1.57 2.11

11089 0.97 1.63 2.17

11088 0.87 1.69 2.27

11087 0.92 1.51 2.04

11086 1.08 3.64 4.86

11065 0.00 2.11 2.76

11084 1.03 3.23 4.39

11083 1.14 3.09 4.10

11082 1.78 5.71 7.95

11081 0.67 2.21 2.84

110 8 0 2.42 6.88 8.99

11079 0.97 5.16 7.02

110 7 8 0.69 1 .66 2.24

11077 0.71 1.66 2.21

11076 0.36 2.48 3.42

110 7 5 0.42 2.19 2.94

110 7 4 2.55 7.51 10.25

11073 0.00 2.24 2.98

11072 1.51 3.49 4.89

110 71 1.55 2.89 3.74

11070 2.38 6.74 8.79

1 1069 0.06 1.88 2.64

11068 1.14 3.09 4.10

11067 0.75 1.61 2.15

11066 4.59 11.55 15.61

11065 0.52 2.23 2.94

11064 0.44 1.47 1.94

11063 0.73 1.38 1.82

11062 0.35 0.60 0.81

11061 1.78 2.72 3.54

1 1060 1.32 9.34 13.08

11059 1 ,5b 8.2 2 11.14

11058 1.97 8.57 11.47

11057 1.16 2.98 3.91 !

1 1 05b 1.65 5.23 7.21

11055 0.96 2.30 3.08

11054 0.45 1.19 1.64

11053 0.62 1.21 1 .62

11052 0.59 1.58 2.16
Table 67 continued

CRUSTAL ENRICHMENT FACTORS FOR PARTICULATE NICK FT. RELATIVE TO SCANDIUM (WEDEPOHL)

THE RANGE REPRESENTS AT LEAST

THE 90% CONFIDENCE LI M ITS

SAMPLE NUMBER MINIMUM BEST VALUE MAXIMUM

11051 0.85 1.93 2.52

11050 0.7 4 1.51 2.01

11049 0.67 1.43 1.92

11048 1.07 2.30 3.00

11047 0.89 1.59 2.17

11046 5.06 14.11 19.29

11045 1.19 1.90 2.51

11044 1.69 3.23 4.28

11043 1.07 1.83 2.45

11042 2.50 11.14 15.37

11041 0.97 2.32 3.15

1 1040 7.61 20.63 28.50

11039 0.96 1.69 2.32

11038 2.97 8.40 10.96

11037 0.7 2 1.81 2.33

11036 5.18 17.68 23.81

11035 0.17 1.78 2.43

11034 0.00 11.74 17.07

11033 0.00 0.88 1.18

11032 0.75 10.73 15.70

11031 0.00 1.93 2.60

11030 0.06 1.88 2.64

11029 0.49 1.02 1.39

11028 0.00 1.14 1.63

11027 0.75 1.61 2.20

11026 0.31 2.15 2.93

11025 0.03 0.92 1.29

11024 0.00 0.69 1.27

11023 0.13 0.96 1.44

11022 0.10 1.55 2.35

11021 0.72 1.43 2.02

11020 0.52 3.09 4.61

11019 1.12 2.03 2.75

11018 0.02 0.47 0.73

11017 0.63 1.24 1.67

1 10J 6 0.00 6.88 10.77

11015 0.0 5 0.96 1.51

11014 0.0 0 2.41 3.83

11013 1.70 3.73 5.22

11012 0.30 1.64 2.30

11011 1.71 2.94 4. 11

11010 0.00 2.24 3.39

11009 0.20 1.55 2.34

110 0 8 0.00 0.87 1.20

1 1007 0.11 1.19 1.67

110 0 6 0.64 1 .05 1.41

11005 0.10 0.22 0.32

110 0 4 o • a 1.46 2.11

11003 0.82 1.90 2.74

11002 0.3 4 2.36 3.24

11001 . 0.78 1.75 2. 39

167
Table 68

CRUSTAL ENRICHMENT FACTORS FOR PARTICULATE LEAD

RELATIVE TO SCANDIUM (wEDEPOHL)

THE RANGE REPRESENTS AT LEAST

THE 90% CONFIDENCE LIMITS

SAMPLE NUMBER MINIMUM BEST VALUE MAXIMUM

11102 2.33 3.23 4.11

11101 2.79 4.10 5.48

11100 5.54 9.08 12.78

11099 4.77 8.04 11.43

11098 4.58 6.66 9.02

11097 5.52 7.85 10.39

1 1096 5.70 7.90 10.34

11095 9.61 13.25 17.43

11094 4.30 5.94 7.74

11093 8.09 10.92 14.11

1 1092 5.88 9.51 13.29

11091 5.45 8.27 11.22

11090 2.42 4.03 5.55

11089 2.33 3.92 5.40

1 1088 2.75 4.65 6.29

11087 2.86 4.40 5.93

11066 0.00 3.20 4.74

11085 0.00 2.82 4.35

11064 1.00 3.55 4.73

11083 3.99 8.03 10.90

11082 7.12 15.36 21.76

11061 2.28 5.19 6.94

11060 0.00 4.58 7.08

11079 0.00 3.56 5.87

11076 0.53 2.02 3.00

11077 0.81 2.27 3.24

110 7 6 2.60 7.71 11.51

11075 0.88 4.16 6.14

11074 0.00 2.64 4.83

11073 0.45 4.60 6.54

11072 0.20 2.05 3.00

11071 1.69 3.95 5.58

11070 0.00 1 .80 3.94

110 6 9 0.28 2.76 3.86

11068 0.00 2.09 3.00

110 6 7

1 1066

2.67 4.60

< 6.16

11065 4.13 8.35 11.38

11064 1.24 3.67 5.45

1 1063 1.83 3.28 4.51

110 6 2 1.13 1.87 2.61

11061 4.14 7.26 10.37

11060 2.71 13.70 19.18

11059 4.88 14.18 18.67

11058 0.97 9.77 13.75

11057 6.37 11.02 14.58

11056 3.2 2 8.95 12.68

11055 1.54 4.19 6.18

11054 3.82 6.22 8.44

11053 2.50 3.92 5.19

11052 7.29

168

11.47 15.55
Table 68 continued

CRUSTAL ENRICHMENT FACTORS FOR PARTICULATE LEAD

RELATIVE TO SCANDIUM (*EDEPOHL)

THE RANGE REPRESENTS AT LEAST

THE 90% CONFIDENCE LIMITS

SAMPLE NUMBER MINIMUM BEST VALUE MAXIMUM

11051 o . 0 8 9.45 12.31

11050 2.87 4.88 6.64

11049 2.38 4.08 5.51

11048 3.10 6.12 8.55

11047 2.55 4.27 5.91

11046 7.62 25.47 38.84

11045 2.44 3.90 5.28

11044 6.0 4 10.08 13.64

11043 3.19 5.08 6.87

11042 4.48 16.34 22.54

11041 3.27 5.78 7.67

11040 24.64 48.40 66.01

11039 2.84 4.42 5.95

11038 0.00 1.12 3.67

11037 4.40 8.19 11.45

110 3b < 11035 0.00 2.09 3.00

11034 < 11033 0.00 1 .30 2.08

11032 < 11031 < 11030 2.01 5.52 7.73

11029 3.14 5.00 6.75

110 2 8 0.66 4.78 7.41

11027 1.96 3.83 5.44

11026 6.28 11.05 14.61

1 1025 1.8 3 4.05 5.6b

11024 0.32 6.05 9.67

11023 0.6y 1.87 2.62

11022 1.80 4.27 6.01

110 21 0.52 1.08 1.45

11020 2.85 6.60 9.02

11019 1.31 2.46 3.36

11018 4.37 6.53 8.63

11017 1.43 2.60 3.59

11016 2.00 14.40 22.12

11015 0.00 0.45 0.82

11014 1.60 6.05 9.01

11013 0.18 1 .87 2.70

11012 3.16 5.96 8.05

11011 0.99 1.84 2.54

11010 5.69 11.34 15.26

11009 1.68 3.67 4.99

1 1 008 2.53 5.81 7.85

1 1007 2.17 4.89 6.95

1100b 0.71 1.20 1.62

11005 5.99 7.36 8.93

11004 0.85 1.64 2.25

11003 1.23 2.51 3.49

11002 < 11001 3.85 6.18 6.17

169
Table 69

CRUSTAL ENRICHMENT FACTORS FOR PARTICULATE TIN

RELATIVE TO SCANDIUM (WEDEPOHL)

SAMPLE NUMBER MINIMUM

11102

11101

11100

11099

1109ft

11097

11096

1109b

11094

11093

11092

11091

11090

1 10b9

11088

1 1 0 w 7 11086

11085

11084

11063

1 1082

11081

1 1080

11079

1107ft

11077

11076

11075

11074

11073

11072

11071

11070

11069

11068

11067

11066

11065

11064

11063

1106?

1 1 061

11060

11059

11056

11057

1105b

11055

11054

1 1053

11052

THE RANGE REPRESENTS AT LEAST

THE 90% CONFIDENCE LIMITS

BEST VALUE MAXIMUM

<

<

<

<

<<

<

<<

<

<

<<

<

<<

<

<

<<

<

<

<<

<

<

<<

<

<

<

<

<

<<

<<

<

<

<

<<<

<

<

<

<<

<

<< 170
Table by continued

CRUSTAL ENRICHMENT FACTORS FOR PARTICULATE TIN

RELATIVE TO SCANDIUM (WEDEPOHL)

SAMPLE NUMBER MINIMUM

11051

11050

11049

11049

11047

11046

11045

11044

11043

11042

11041

11040

11039

11039

11037

11036

11035

11034

11033

11032

11031

11030

11029

11028

11027

11026

11025

I 1024

11023

11022

11021

11020

11019

11018

11017

11016

11015

11014

11013

11012

11011

11010

I I 009

11008

11007

11006

11005

11004

11003

11002

11001

THF RANGE REPRESENTS AT LEAST

THE 90% CONFIDENCE LIMITS

BEST VALUE MAXIMUM

<

<

<<

<<

<<

<

<

<

<

<

<

<

<

<<

<<

<

<

<

<<

<

<<

<

<

<<

<

<<

<

<

<<

<<

<<

<

<

<<

<

<

<

< 171
Table 70

CRUSTAL ENRICHMENT FACTORS FOR PARTICULATE THORIUM

RELATIVE TO SCANDIUM (WEDEPOHL)

THE RANGE REPRESENTS AT LEAST

THE 90% CONFIDENCE LIMITS

SAMPLE NUMBER MINIMUM BEST VALUE MAXIMUM

11102 0.89 1.08 1.29

11101 0.88 1.09 1.34

11100 0.99 1.21 1.48

11099 0.99 1.22 1.49

1 1 09b 1.01 1.23 1.51

11097 1.00 1.24 1.54

11096 0.94 1.18 1 .48

11095 0.98 1.20 1.47

11094 1.01 1.25 1.55

1 1 093 1.02 1.27 1.58

11092 1.00 1.21 1.47

11091 0.78 0.96 1.17

1 1 090 0.76 0.92 1.11

11089 0.78 0.94 1.13

11088 0.79 0.95 1.15

11087 0.80 0.97 1.19

1 1 086 0.68 0.90 1.17

11085 0.72 0.95 1.22

11084 0.77 0.94 1.15

11083 0.73 0.87 1.04

1108? 0.81 1.01 1 .26

1 108 J 0.81 0.95 1 .12

11080 0.75 0.93 1.14

11079 0.74 0.91 1.12

1 1U78 0.87 1.06 1.29

11077 0.89 1.07 1.29

1 1 076 0.83 1.01 1.23

11075 0.83 0.99 1.18

1 1 074 0.83 1.00 1.21

11073 0.80 0.97 1.18

11072 0.b8 1.07 1.31

11071 0.92 l.U 1.33

110 7 0 0.7 7 0.97 1.21

11069 0.77 0.94 1.15

1 1068 0.78 1.03 1 .32

11067 0.82 1.00 1.21

1 10b6 0.31 0.68 1.13

110 6 5 0.52 0.76 1.05

11064 0.78 0.97 1.20

11063 o •

JO JO 1.07 1.31

11062 0.83 1 .00 1.22

11061 0.86 1 .04 1.26

11060 0.80 1.03 1.32

11059 0.90 1.21 1 .59

11058 0.54 0.82 1.16

11057 0.89 1 .05 1.22

1 1056 0.66 0.84 1.07

1 1056 0.74 0.95 1.19

11054 0.80 1 .00 1.25

110 5 3 0.»7 1 .06 1.29

1105? 0.78 0.96 1 .19

172
Table 70 continued

CRUSTAL ENRICHMENT FACTORS FOR PARTICULATE THORIUM

RELATIVE TO SCANDIUM (WEDEPOHL)

THE RANGE REPRESENTS AT LEAST

THE 90% CONFIDENCE LIMITS

SAMPLE NUMBER MINIMUM BEST VALUE MAXIMUM

11051 0.88 1.06 1 .27

11050 0.90 1.08 1.30

11049 0.90 1.11 1.37

11048 0.90 1.10 1.33

11047 0.90 1.10 1.35

11046 0.77 0.98 1.24

11045 0.94 1.13 1.37

11044 0.94 1.13 1 . 36

11043 0.94 1.15 1.40

11042 0.67 0.99 1.41

11041 0.91 1 .10 1.33

11040 0.76 0.93 1.14

11039 0.88 1.08 1.33

11038 0.65 0.96 1.33

11037 0.82 1.02 l.?7

11036 < 11035 0.82 1.08 1.37

11034 0.66 0.97 1.31

11033 0.94 1.09 1.27

11032 0.80 1.12 1.49

110 31 0.65 0.88 1.17

11030 0.82 1.00 1.21

11029 0.86 1.04 1.26

1 1028 0.73 0.94 1.19

11027 0.83 1.02 1.27

11026 0.92 1.11 1.33

11025 0.85 1.03 1.24

11024 0.67 0.92 1.23

11023 0.86 1.05 1.27

1 1022 0.67 0.90 1.18

11021 0.90 1.08 1.30

1 1020 0.69 0.98 1.33

11019 0.81 0.99 1.2 2 11018 0.79 0.97 1.18

11017 0.84 1.03 1.27

11016 < 11015 0.90 1.11 1.36

11014 0.90 1.27 1.74

11013 0.81 1.05 1.35

11012 0.82 1.07 1.40

11011 0.84 1.02 1.24

11010 0.91 1.17 1.49

110 0 9 0.86 1.06 1.30

110 0 8 0.85 1.02 1.21

11007 0.77 0.98 1.23

1 1 0 0 o 0.69 0.84 1.0?

110 0 5 0.7 7 0.9 3 1 .14

1)004 0.74 0.90 1.10

1100 3 0.8 3 1 .no 1 .20

1100? 0.78 1.09 1.47

11U01 0.85 1 .03 1.25

173
Table 71

crustal enrichment factors for particulate uranium

RELATIVF TO SCANDIUM (WEDEPOHL)

THF RANGE REPRESENTS AT LEAST

THE 90% CONFIDENCE LIMITS

SAMPLE NUMBER MINIMUM BEST VALUE MAXIMUM

1 1102 0.71 0.83 0.98

11101 0.70 0.86 1.05

11100 0.94 1 .15 1.40

11099 0.90 1.09 1.32

1109b 0.86 1.08 1.36

11097 0.81 1.01 1.24

11096 0.82 1.01 1.24

11095 1.08 1.34 1.66

11094 0.89 1.08 1 .33

11093 1.13 1.39 1.70

11092 0.98 1.18 1.43

11091 0.87 1.05 1.26

11090 0.66 0.89 1 .16

11089 0.70 0.88 1.09

110 8 8 0.48 0.71 0.99

11087 0.74 0.94 1.18

11086 0.75 1.20 1.75

1 1085 1.46 2.04 2.74

11084 0.69 0.96 1.27

11083 0.72 0.89 1 .10

11082 < 11081 0.95 1.19 1.46

11080 0.75 1.37 2.14

11079 1.01 J .49 2.07

11078 0.79 0.98 1.21

11077 0.71 0.93 1.19

11076 1.01 1.42 1.92

11075 0.0 0 1.83 5.55

110 7 4 0.83 1.51 2.35

11073 2.70 3.36 4.1«

11072 0.76 1.08 1.50

110 71 0.88 1.13 1.42

11070 0.95 1.58 2.36

11069 0.00 1.41 3.78

11068 0.44 1.08 1.82

11067 0.91 1 .22 1.58

11066 0.50 1.60 2.95

11065 1.16 1.47 1.84

11064 0.56 0.74 0.96

11063 0.65 0.85 1.10

11062 0.7 3 0.91 1.14

11061 0.70 0.90 1.13

11060 0.90 1.74 2.78

11059 0.99 2.19 3.62

11056 1.09 2.0 3 3.16

11057 0.87 1.21 1.61

11056 0.85 1 .27 1.77

11055 0.94 1 .44 2.04

110 5 4 0.77 0.97 1.22

110 5 3 0.71 0.92 1.16

1 1052 0.8 2 1 .06 1.35

174
Table 71 continued

CRUSTAL ENRICHMENT FACTORS FOR PARTICULATE URANIUM

RELATIVE TO SCANDIUM (WFDEPOHL)

THE RANGE REPRESENTS AT LEAST

THE 90% CONFIDENCE LIMITS

SAMPLE NUMBER MINIMUM BEST VALUE MAXIMUM

11051 0.85 1.08 1.36

11050 < 11049 < 11046 0.79 1.95 3.35

11047 0.80 1.06 1.37

11046 < 11045 < 11044 < 11043 0.82 1.02 1.27

11042 0.74 2.40 4.50

11041 < 11040 0.85 2.67 4.83

11039 0.01 0.52 1.15

11038 < 11037 0.63 1.27 2.04

11036 1.78 4.00 6.77

11035 < 11034 7.80 11.03 14.73

11033 0.81 1.14 1 .53

11032 3.81 5.71 7.95

11031 1.28 1.94 2.75

11030 0.65 1.04 1.51

11029 < 11028 1.15 1.68 2.34

11027 0.71 1.01 1.39

11026 < 11025 0.56 0.94 1.39

11024 0.87 1.30 1.84

11023 0.60 0.76 0.96

11022 0.95 1.29 1.72

11021 < 11020 0.85 1.64 2.58

11019 0.57 0.79 1 .06

11018 0.62 0.86 1.16

11017 0.60 0.80 1.04

11016 < 11015 < 11014 0.61 1.11 1.74

11013 0.53 0.82 1.19

11012 0.67 1.00 1 .42

11011 <

1 1010 0.73 1.32 2.04

1 1009 0.44 0.67 0.94

11008 0.30 0.64 1 .03

11007 0.56 0.82 1.14

11006 < 11005 0.52 0.67 0.86

11004 0.50 0.67 0. 87

11003 0.71 0.96 1.27

11002 0.88 1 .33 1.88

11001 ‘• 40

175

1 .86 2.40
Table 72

CRUSTAL ENRICHMENT FACTORS FOR PARTICULATE ZINC

RELATIVE TO SCANDIUM (WEDFPOHL)

THE RANGE REPRESENTS AT LEAST

THE 90% CONFIDENCE LIMITS

SAMPLE number MINIMUM BEST VALUE MAXIMUM

11102 2.02 3.16 3.98

11101 1 .94 3.08 3.98

1110 0 1.76 4.36 5.89

110 9 9 2.35 4.87 6.38

110 9 8 3.30 5.51 7.41

11097 3.47 . 5.42 7.04

11096 2.96 4.58 6.00

110 9 5 2.96 4.71 6.28

11094 4.56 6.40 8.11

11093 4.14 5.87 7.45

11092 4.71 7.99 10.52

1 1091 4.27 6.32 8.05

11090 1.26 4.36 6.25

11089 2.27 5.42 7.39

11088 1.72 6.36 8.87

11087 2.02 4.73 6.62

1108b 0.00 2.06 10.08

110 8 5 0.00 4.64 13.29

11084 0.00 5.38 12.60

11083 0.00 3.95 9.77

11082 0.00 7.36 23.22

11081 0.00 5.92 11.27

11080 0.00 16.73 32.37

11079 0.00 11.21 25.75

11070 0.00 3.67 7.74

11077 0.00 3.00 5.90

11076 0.00 6.77 14.07

11075 0.00 5.06 11.09

110 7 4 0.00 11.78 26.23

11073 0.00 1.18 10.12

1 1072 0.00 4.29 9.46

11071 0.00 4.01 7.74

11070 0.00 4.62 18.62

11069 0.00 2.13 9.92

110 6 8 o.on 4.85 10.55

11067 0.00 3.48 5.83

1 1066 0.00 6.5 3 31.76

11065 < 11064 0.00 3.83 11.54

11063 < 11062 0.30 1.83 2.8P

11061 0.00 1.66 3.49

11060 0.00 15.41 43.46

11059 0.00 4.37 25.21

11058 0.00 9.33 31 .08

11057 0.00 2.75 7.86

11056 0.00 5.92 16.86

1 1 U 5 5 0.00 2.33 6.36

11054 0.00 1.63 4.85

11053 0.00 1 .H2 3.31

11052 < 176
Table 72 continued

CRUSTAL ENRICHMENT FACTORS FOR PARTICULATE ZINC

RELATIVE TO SCANDIUM (WEOEPOHL)

THE RANGE REPRESENTS AT LEAST

THE 90% CONFIDENCE LIMITS

sample number MINIMUM BEST VALUE. MAXIMUM

11051 0.00 2.04 5.22

11050 0.00 2.07 4.32

11049 0.00 1.90 4.12

11046 0.00 0.81 4.51

11047 0.00 1.87 3.99

11046 0.00 4.50 37.34

11045 0.00 2.99 5.21

11044 0.00 3.99 8.04

11043 0.00 2.03 4.31

11042 0.00 1.87 28.98

11041 0.00 1.27 4.70

1 1040 0.00 9.85 37.42

11039 o.oo 2.56 4.20

11038 0.00 8.35 28.58

11037 0.00 2.79 6.77

11036 < 11035 0.00 0.00 5.02

11034 0.00 79.66 137.72

11033 0.00 2.42 8.03

11032 0.00 10.48 51.08

11031 < 11030 0.00 3.25 9.62

11029 0.00 2.55 4.44

11028 0.00 3.56 12.27

11027 0.00 2.60 6.62

11026 0.00 4.16 10.83

11025 0.00 1.94 6.46

11024 0.00 8.47 24.86

11023 < 11022 < 11021 0.00 2.46 4.40

11020 0.00 4.14 13.93

11019 0.00 3.14 6.20

11016 0.00 2.03 4.31

11017 0.00 2.01 4.06

11016 < 11015 0.00 4.55 8.43

11014 < 11013 0.00 3.36 8.50

11012 0.00 2.11 7.45

11011 0.00 2.35 3.92

11010 < 11009 < 11008 0.00 3.36 6.86

110 0 7 3.00 12.56 17.91

11006 1.66 3.92 5.64

1 1005 2.58 3.76 4.85

11004 1.01 5.06 7.86

1 100 3 0.00 3.91 6.82

11002 < 11001 0.00 3.01 5.53

177
APPENDIX 7

77D30M 77D10M 76D50M 76D30M 76D10M 75050M 75D30M

178
77D30M 77D10M 76D50M 76D30M 76D10M 75D50M 75D30M

179
77D30M 77D10M 76D50M 76D30M 76D10M 75D50M 75D30M

180
77D30M 77D10M 76D50M 76D30M 76D10M 75D50M 75D30M

181
77D30M 77D10M 76D50M 76D30M 7601 OM 75050M 75030M

182
77D30M 39D40M

-

77D10M 76D50M 76D30M 7601 OM 75D50M

39D25M

-

39D5M •

38D45M

38D25M38D5M -

37D45M37D25M37D5M

36D45MTHE CONCENTRATION OF DISSOLVED

IRON (IN NANOGRAMS/MILL I L I TER) AREA OF CIRCLE IS DIRECTLY PROPORTIONAL TO CONCENTRATION

75D30M

r 39D40M

39D25M

39D5M

38D45M

38D25M

38D5M

37D45M

37D25M

37D5M

36D45M

77D30M 77D10M 76D50M 76D30M 7601 OM 75D50M 75D30M

183
77D30M

39D40M

77D10M 76D50M 76D30M 76D10M 75D50M

39D25M39D5M

38D45M

38D25M38D5M

37D45M37D25M37D5M -

36D45M

TOP

THE CONCENTRATION OE DISSOLVED

HANOANESE (IN NANOORAMS/HILLIL1TER)

AREA OF CIRCLE IS DIRECTLY PROPORTIONAL TO CONCENTRATION

75D30M 39D40M

3902SM

39D5M

38D45M

38D25M

38D5M

37D45M

-37D25M

37D5M

36D45M

77D30M 77D10M 76D50M 76D30M 76D10M 75D50M 75D30M

184
77D30M 77D10M 39D40M 1 76D50M 76D30M

TOP

76D10M 75D50M

39D25M39D5M

38D45M

38D25M38D5M -

37D45M37D25M37D5M -

36D45M

77D30M 77D10M 76D50M 76D30M 76D10M 75D50M

75D30M

39D40M

39D25M

39D5M

38D45M

38D25M

38D5M

37D45M

37D25M

37D5M

36D45M

75D30M

185
77D30M 39D40M - 77D10M 76D50M 76D30M 76D10M 75D50M

39D25M

39D5M

38D45M

38D25M

38D5M

37D45M

37D25M37D5M -

36D4 5MTHE CONCENTRATION OF DISSOLVED

NICKEL (IN NANOORAHS/M1LLILITER)

AREA OF CIRCLE IS DIRECTLY PROPORTIONAL TO CONCENTRATION

75D30M

39D40M

39D25M

39D5M

38D45M

38D25M

38D5M

37D45M

37D25M

37D5M

36D45M

77D30M 77D10M 76D50M 76D30M 76D10M 75D50M 75D30M

186
77D30M 39D40M i 77D10M 76D50M 76D30M 76D10M 75D50M

39D25M

39D5M -

38D45M

38D25M

38D5M •

37D45M37D25M37D5M

36D45MTHE CONCENTRATION OF DISSOLVED

LEAD (IN NANOGRAF1S/M! LL IL 1 TER) AREA OF CIRCLE IS DIRECTLY PROPORTIONAL TO CONCENTRATION

75D30M

• 39D40M

39D25M

- 39D5M

38D45M

38D25M

•38D5M

• 37D45M

37D25M

37D5M

36D45M

77D30M 77D10M 76D50M 76D30M 76D10M 75D50M 75D30M

187
77D30M 77D10M 76D50M 76D30M 7601 OM 75D50M 75D30M

188
77D30M

39D40M

-

77D1 OM 76D50M 76D30M 76D10M 75D50M

39D25M

39D5M

38D45M

-

38D25M

38D5M

37D45M37D25M37D5M

36D45M

TOP

THE CONCENTRATION OF DISSOLVED

THORIUM (IN NANOGRAMS/MILL 1 L 1 TER) AREA OF CIRCLE IS DIRECTLY PROPORTIONAL TO CONCENTRATION

75D30M

39D40M

1- 39D25M

• 39D5M

-38D45M

38D25M

-38D5M

37D45M

-37D25M

-37D5M

36D45M

77D30M 77D10M 76D50M 76D30M 76D1 OM 75D50M 75D30M

189
THE CONCENTRATION OF DISSOLVED URANIUM (IN NANOCRAMS/M1LL1LI TER) AREA Of CIRCLE IS DIRECTLY PROPORTIONAL TO CONCENTRATION 39D25M39D5M

BOTTOM

I .35 NO/ML

77D30M

39D40M - 77D10M 76050M 76D30M 76D10M 75D50M 75D30M 39D40M

39D25M

39D5M

38D45M - 38D45M

38D25M 38D25M

38D5M - 38D5M

37D45M- 37D45M

37D25M- 37D25M

37D5M 37D5M

TOP

36D45M-1 77D30M 77D10M 76D50M 76D30M 76D10M 75D50M

36D45M

75D30M

190
77D30M 39D40M - 77D10M 76D50M 76D30M 76D10M 75D50M

39D25M

39D5M -

38D45M

38D25M

38D5M

37D45M37D25M

37D5M •

36D45MTOP

THE CONCENTRATION OF DISSOLVED

ZINC (IN NANOGRAMS/MI LL 1 L I TER) AREA OF CIRCLE IS DIRECTLY PROPORTIONAL TO CONCENTRATION

75D30M

-39D40M

39D25M

39D5M

38D45M

38D25M

38D5M

37D45M

37D25M

37D5M

36D45M

77D30M 77D10M 76D50M 76D30M 76D10M 75D50M 75D30M

191
77D30M 39D40M

77D10M 76D50M 76D30M 76D10M 75D50M

39D25M

39D5M

38D45M

38D25M

38D5M -

37D45M37D25M37D5M -

36D45MTHE CONCENTRAT ION OF PARTICULATE CADHlUn (IN NANOCRAnS/nlLLlllTER)

AREA OF CIRCLE IS OIRECTLT PROPORTIONAL TO CONCENTRATION

75D30M

3904OM

39D25M

39D5M

3804 5M

38D25M

38D5M

37D45M

37D25M

37D5M

36D45M

77D30M 77D10M 76D50M 76D30M 7601 OM 75D50M 75D30M

192
77D30M

39D40M

-

77D10M 76D50M 76D30M 76D10M 75D50M

THE CONCENTRATION OF PARTICULATE CERIUM (IN NANOGRAMS/MILLILITER)

AREA OF CIRCLE IS DIRECTLY PROPORTIONAL TO CONCENTRATION 39D25M39D5M -

38D45M -

38D25M -

38D5M

37D45M

-

37D25M37D5M

J6D45M75D30M

-39D40M

39D25M

39D5M

38D45M

38D25M

38D5M

37D45M

37D25M

37D5M

36D45M

77D30M 77D10M 76D50M 76D30M 76D10M 75D50M 75D30M

193
39D25M 39D25M

39D5M 39D5M

3804 5M

38D25M

38D5M

37D45M

37D25M 37D25M

37D5M 37D5M

36D45M

77D30M 7701 OM 76D50M 76D30M 7601 OM 75D50M

36D45M

75D30M

77D30M 39D40M i 77D10M 76D50M 76D30M 7601 OM 75D50M

38D45M

38D25M

38D5M -

37D45M

TOP

THE CONCENTRAT 1 04 OF PARTICULATE

COBALT (IN NANOCRAHS/HI LL IL I TER) AREA OF CIRCLE IS DIRECTLY PROPORTIONAL TO CONCENTRATION

BOTTOM SAMPLE

75030M 39D40M

BOTTOM

0-02 NC/ML

1.17 NC/ML

2-40 NG/Ml

194
77D30M 39D40M

-

77D10M

39D25M -

39D5M -

38D45M

-

38D25M

38D5M -

37D45M

37D25M37D5M -

36D45M

76D50M

TOP

76D30M 7601 OM 75D50M

0.00 NC/HL

2.65 NC/ML

75D30M

r 39D40M

39D25M

39D5M

38D45M

3802 5M

38D5M

37D45M

37D25M

37D5M

77D30M 77D10M 76D50M 76D30M 76D10M 75D50M 36D45M

75D30M

195
75D30M 39D40M

39025M

39D5M

38D45M

38D25M

38D5M

37D45M

37D25M

37D5M

36D45M

75D30M

77D30M

39D40M

39D25M

39D5M

38D45M38D25M

38D5M -

37D45M

37D25M37D5M

36D45M-I 77D30M

7701 OM

77D10M

76D50M

76D50M

76D30M

76D30M

7601 OM 75D50M

7601 OM 75D50M

[

THE CONCENTRATION OF PARTICULATE

COPPER (IN NAN00RAMS/H1LULITER)

AREA OF CIRCLE IS DIRECTLY

PROPORTIONAL TO CONCENTRATION

BOTTOM

+ 0.00 NG/NL

1 .67 NG/ML

196
77D30M 39D40M

77D10M 76D50M 76D30M 76D10M 75D50M

39D25M BOTTOM

39D5M

25.00 NC/ML

1468-00 NG/Ml

38D45M -

38D25M

38D5M -

37D45M37D25M37D5M

36D45M75D30M 39D40M

39D25M

39D5M

38D45M

38D25M

38D5M

37D45M

37D25M

37D5M

77D30M 77D10M 76D50M 76D30M 76D10M 75D50M

36D45M

75D30M

197
77D30M 39D40M

77D10M 76050M 76D30M 76D10M 75D50M

TOP

THE CONCENTRATION OF PARTICULATE

MANGANESE (1N NANOCRAMS/Hl LL 1 L I TER) AREA OF CIRCLE IS DIRECTLT PROPORTIONAL TO CONCENTRATION 39D25M39D5M

38D45M

38D25M38D5M -

37D45M37D25M37D5M

36D45M75D30M 39D40M

39D25M

39D5M

38D45M

38D25M

38D5M

37D45M

37D25M

37D5M

77D30M 77D10M 76D50M 76D30M 76D10M 75D50M

36D45M

75D30M

198
77D30M

39D40M

•

77D10M 76D50M 76D30M 76D10M 75D50M

39D25M

39D5M

38D45M -

38D25M

38D5M

37D45M

37D25M

37D5M

36D45MTHE CONCENTRATION OF PARTICULATE MOLYBDENUM (IN NANOGRAMS/MILLILITER)

AREA OF CIRCLE IS DIRECTLY PROPORTIONAL TO CONCENTRATION

75D30M

k39D40M

39D25M

39D5M

38D45M

38D25M

38D5M

37D45M

37D25M

37D5M

36D45M

77D30M 77D10M 76D50M 76D30M 76D10M 75D50M 75D30M

199
77D30M 39D40M

77D10M 76D50M 76D30M 76D10M 75D50M

39D25M

39D5M

38D45M

38D25M

38D5M -

37D45M

37D25M

37D5M -

36D45MTHE CONCENTRATION OF PARTICULATE

NICKEL (IN NANOGRAHS/MILL 1L 1 TER) AREA OF CIRCLE IS DIRECTLY PROPORTIONAL TO CONCENTRATION

75D30M 39D40M

39D25M

39D5M

38D45M

38D25M

< 38D5M

37D45M

37D25M

•37D5M

77D30M 7701 OM 76D50M 76D30M 7601 OM 75D50M

36D45M

75D30M

200
77D30M 39D40M

-

77D10M 76D50M 76D30M 76D10M 75D50M

39D25M

39D5M

38D45M

38D25M

38D5M -

37D45M37D25M

37D5M

36D45M

TOP

THE CONCENTRATION OF PARTICULATE

LEAD (IN NANOGRAHS/MI LL IL I TER) AREA OF CIRCLE IS DIRECTLY PROPORTIONAL TO CONCENTRATION

75D30M

•39D40M

-39D25M

39D5M

•38D45M

38D25M

38D5M

37D45M

-37D25M

37D5M

36D45M

77D30M 77D10M 76D50M 76D30M 76D10M 75D50M 75D30M

201
THE CONCENTRATION OF PARTICULATE SCANDIUM (IN NANOCRAMS/MILLILITER)

AREA OF CIRCLE IS DIRECTLY PROPORTIONAL TO CONCENTRATION 39D25M39D5M

38D45M

38D25M

38D5M -

37D45M

37D25M

37D5M

36D45MBOTTOM

o.oi nc/m.

0.47 NC/ML

0-93 NC/ML

77D30M 77D10M 76D50M 76D30M 76D10M 75D50M

77D30M

39D40M - 77D10M 76D50M 76030M 76D10M 75D50M 75D30M 39D40M

39D25M

39D5M

38D45M

38D25M

38D5M

37D45M

37D25M

37D5M

36D45M

75D30M

TOP

202
77D30M 39D40M - 77D10M

39D25M

39D5M

38D45M

38D25M

-

38D5M -

37D45M37D25M

37D5M

36D45M76D50M

TOP

76D30M 76D10M 75D50M

• 0.01 NC/ML

0.34 NC/ML

75D30M

-39D40M

39D25M

39D5M

38D45M

38D25M

38D5M

37D45M

37D25M

37D5M

77D30M 77D10M 76D50M 76D30M 76D10M 75D50M 36D45M

75D30M

203
77D30M 39D40M

77D10M 76D50M 76D30M 7601 OM 75D50M

39D25M

39D5M

38D45M38D25M -

38D5M

37D45M37D25M37D5M

3604 5M

THE CONCENTRATION OF PARTICULATE URANIUM UN NANOGRAHS/MILLILITER)

AREA OF CIRCLE IS DIRECTLY PROPORTIONAL TO CONCENTRATION

75D30M

3904OM

39D25M

39D5M

38D45M

38D25M

38D5M

37D45M

37D25M

37D5M

77D30M 7701 OM 76D50M 76D30M 76D10M 75D50M

36D45M

75D30M

204
77D30M

39D40M

-

77D10M 76D50M 76D30M 76D10M 75D50M

39D25M

39D5M

38D45M -

38D25M

38D5M

37D45M37D25M

37D5M

36D45MTHE CONCENTRATION OF PARTICULATE

ZINC (IN NANOGRAhS/MIlLILITER)

AREA OF CIRCLE IS DIRECTLY PROPORTIONAL TO CONCENTRATION

75D30M

39D40M

39D25M

• 39D5M

38D45M

38D25M

•38D5M

37D45M

1 37D25M

-37D5M

77D30M 77D10M 76D50M 76D30M 76D10M 75D50M 36D45M

75D30M

205
77030M

39D40M7701 OM 76D50M 76D30M 7601 OM 75D50M

39025M

39D5M

38D45M

38D25M

38D5M

37D45M37D25M37D5M

36D45M

75D30M 39D40M

39D25M

39D5M

38D45M

38D25M

• 38D5M

37D45M

-37D25M

37D5M

36D45M

77D30M 7701 OM 76D50M 76D30M 76D10M 75050M 75D30M

206
77D30M

39D40M

-

77D10M 76D50M 76D30M 76D10M 75D50M 75D30M

• 39D40M

TOP

CRUSTAL ENRICHMENT FACTOR FOR CERIUM

RELATIVE TO SCANDIUM (WEDEPOHL) AREA OF CIRCLE IS OIRECTLT PROPORTIONAL TO ENRICHMENT FACTOR 39D25M39D5M

38D45M38D25M38D5M

37D45M37D25M37D5M -

36D45M-

-39D25M

-39D5M

38D45M

38D25M

38D5M

•37D45M

• 37D25M

37D5M

77D30M 77D10M 76D50M 76D30M 76D10M 75D50M 36D45M

75D30M

207
39D25M

crustal enrichment factor for cobalt RELATIVE TO SCANDIUM (UEDEPOHL) AREA OF CIRCLE IS OIRECTLT PROPORTIONAL TO ENRICHMENT FACTOR

BOTTOM SA»LE (PARTICULATE)

39D5M

38D45M

38D25M38D5M

37D45M37D25M37D5M

36D45MBOTTOM

s.ss

13.00

77D30M 77D10M 76D50M 76D30M 7601 OM

77D30M

39D40M - 7701 OM 78D50M 76D30M 7601 OM 75D50M 75030M

3904OM

39D2SM

39D5M

38D45M

38D25M

38D5M

37D45M

37D25M

37D5M

75D50M

36045M

75D30M

TOP

208
77D30M 77D10M 76D50M 76D30M 76D10M 75D50M 75D30M

209
77D30M 39D40M - 77D10M 76D50M 76D30M 76D10M 75D50M

39D25M

39D5M

38D45M

38D25M

38D5M

37D45M37D25M37D5M -

36D45MCRUSTAL ENRICHMENT FACTOR FOR COPPER RELATIVE TO SCANDIUM (WEOEPOHL) AREA OF CIRCLE IS DIRECTLY PROPORTIONAL TO ENRICHMENT FACTOR

75D30M

-39D40M

39D25M

39D5M

38D45M

38D25M

38D5M

37D45M

37D25M

37D5M

36D45M

77D30M 77D10M 76D50M 76D30M 76D10M 75D50M 75D30M

210
77D30M 39D40M - 77D10M 76D50M 76D30M 76D10M 75D50M

39D25M

39D5M -

38D45M -

38D25M -

38D5M

37D45M37D25M37D5M -

36D45MCRUSTAL ENRICHMENT FACTOR FOR IRON RELATIVE TO SCANDIUM (MEOEPOHL) AREA OF CIRCLE IS DIRECTLY PROPORTIONAL TO ENRICHMENT FACTOR

75D30M

•39D40M

39D25M

39D5M

38D45M

38D25M

38D5M

37D45M

37D25M

37D5M

36D45M

77D30M 77D10M 76D50M 76D30M 76D10M 75D50M 75D30M

211
39D25M

39D5M

38D45M

38D25M -

38D5M

37D45M37D25M

37D5M -

CRUSTAL ENRICHMENT FACTOR FOR MANGANESE RELATIVE TO SCANDIUM (WEDEPOHL) AREA OF CIRCLE IS OIRECTLY PROPORTIONAL TO ENRICHMENT FACTOR

BOTTOM

40.00

BO. 00

77D30M

39D40M

77D10M 76D50M 76D30M 76D10M 75D50M 75D30M

39D40M

39D25M

39D5M

38D45M

38D25M

38D5M

37D45M

37D25M

37D5M

3604 5M

77D30M 7701 OM 76D50M 76D30M 7601 OM 75D50M

36D45M

75D30M

TOP

212
77D30M 39D40M

-

77D10M 76D50M 76D30M 76D10M 75D50M

39D25M

39D5M -

38D45M

38D25M38D5M

37D45M

•

37D25M

37D5M

36D45M

TOP

CRUSTAL ENRICHMENT FACTOR FOR MOLYBDENUM

RELATIVE TO SCANOIUM (WEOEPOHL) AREA OF CIRCLE IS DIRECTLY PROPORTIONAL TO ENRICHMENT FACTOR

75D30M 39D40M

39D25M

39D5M

38D45M

38D25M

38D5M

37D45M

37D25M

37D5M

36D45M

77D30M 77D10M 76D50M 76D30M 7601 OM 75D50M 75D30M

213
77D30M 77D10M 76D50M 76D30M 7601 0M 75D50M 76D30M

214
77D30M 77D10M 76D50M 76D30M 76D10M 75D50M 75D30M

215
39D25M

39D5M

38D45M

38D25M38D5M -

37D45M37D25M37D5M

36D45M

CRUSTAL ENRICHMENT FACTOR FOR THOR1 RELATIVE TO SCANDIUM (WEDEPOHL) AREA OF CIRCLE IS DIRECTLY

PROPORTIONAL TO ENRICHMENT FACTOR

BOTTOM

77D30M 7701 OM 76D50M 76D30M 76D10M 75D50M

77D30M 39D40M

77D10M 76D50M 76030M 78D10M 75D50M 75030M

3904OM

39D25M

39D5M

38D45M

38D25M

38D5M

37D45M

37D25M

37D5M

36D45M

75D30M

TOP

216
77D30M 77D10M 76D50M 76D30M 70D1OM 75D50M 75D30M

217
77D30M 39D40M - 77D10M 76D50M 76030M 76D10M 75050M

39D25M39D5M

38D45M

38D25M

38D5M

37D45M37D25M

37D5M

36D45M

TOP

CRUSTAL ENRICHMENT FACTOR FOR ZINC RELATIVE TO SCANDIUM (VEDEPOHL) AREA OF CIRCLE IS DIRECTLY PROPORTIONAL TO ENRICHMENT FACTOR

75D30M 39D40M

39D25M

39D5M

38D45M

38D25M

38D5M

37D45M

37D25M

37D5M

77D30M 77D10M 76D50M 76D30M 7601 OM 75D50M

36D45M

75D30M

218
NBS-114A REV. 2-80

U.S. DEPT. OF COMM.

BIBLIOGRAPHIC DATA

1. PUBLICATION OR

REPORT NO.

2. Performing Organ. Report No. 3. Publication Date

SHEET (See instructions) NBSIR 83-2698 November 1983

4. TITLE AND SUBTITLE

The Characterization of the Chesapeake Bay: A Systematic Analysis of Toxic

Trace Elements

5 . author(S)

Howarcj Kingston, Robert R. Greenberg, Ellyn S. Beary, Billy R. Hardas,

John R. Moody, Theodore C. Rains, and Walter S. Liggett

6. PERFORMING ORGANIZATION (If joint or other than NBS, see in struction s) 7. Contract/Grant No. NATIONAL bureau of standards

DEPARTMENTOF COMMERCE 8. Type of Report & Period Covered

WASHINGTON, D.C. 20234

9. SPONSORING ORGANIZATION NAME AND COMPLETE ADDRESS (Street. City. State, ZIP)

same as above

10.

SUPPLEMENTARY NOTES

Document describes a computer program; SF-185, FIPS Software Summary, is attached.

11. ABSTRACT ( A 200-word or less factual summary of most si gn if i cant information. If document includes a significant

bibliography or literature survey, mention it here) p ar{ 0 f a mU 1 t i d 1 SC i p 1 l' na Ty Study Of the

Chesapeake Bay, the National Bureau of Standards (NBS) was asked to develop the techniques and procedures necessary to measure the trace and toxic element concentrations

within the water column through the entire 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, Ce, Co, Cr, Cu, Fe, Mn, Mo, Ni, Pb, Sc, Sn, Th,

U, and Zn), including some elements at concentrations consistently below one picogram

per milliter (part per trillion). The characterization of the Chesapeake Bay can be

divided into five major phases. First step was 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. The second phase consisted

of sampling, chemical stabilization, and storage of the samples in the field. The total

complement of 102 samples was obtained, filtered, acidified, and stabilized. A series

of over 30 blanks were also prepared and integrated with the 102 water samples to be

analyzed. The third major phase of activity consisted of the chemical separation and

preparation of samples for the analytical instrumental methods. The fourth major phase

consisted of the instrumental analysis of the samples for the trace elements. This

phase places most of the burden for analysis on NAA and GFAA. The fifth major phase

involved data reduction, evaluation of the statistical significance of the blank, and

adjustment of the concentration data to at least the 95% confidence limit.

12. KEY WORDS Six to twelve entries; alphabet! cal order; capitali ze only proper names; and separate key words by semicolon Si chemical separation; clean room chemistry; Chesapeake Bay; dissolved elements; graphite

furnace atomic absorption; matrix modification; natural water; neutron activation

analaysis; particulate elements; trace elements.

13. AVAILABILITY 14. NO. OF

PRINTED PAGES

Uni imi ted For Official Distribution. Do Not Release to NTIS

Order From Superintendent of Documents, U.S. Government Printing Office, Washington, D.C.

20402. 15. Price

Order From National Technical Information Service (NTIS), Springfield, VA. 22161

USCOMM-DC 6 0 4 3 -P 80
'

.

--