A Summary of Oil and 

Gas Production and 

Reserve Histories of the 

Appalachian Basin, 1859-1972

GEOLOGICAL SURVEY BULLETIN 1409

mo

AUG27

A Summary of Oil and 

Gas Production and 

Reserve Histories of the 

Appalachian Basin, 1859-1972

9' By BETTY M. MILLER

GEOLOGICAL SURVEY BULLETIN 1409

UNITED STATES GOVERNMENT PRINTING OFFICE, WASHINGTON : 1975
UNITED STATES DEPARTMENT OF THE INTERIOR 

ROGERS C. B. MORTON, Secretary

GEOLOGICAL SURVEY 

V. E. McKelvey, Director

Library of Congress Cataloging in Publication Data

Miller, Betty M.

A summary of oil and gas production and reserve histories of the Appalachian basin

1859-1972.

(Geological Survey Bulletin 1409) 

Bibliography: p. 

Supt.ofDocs.no.: 119.3:1409

1. Petroleum Appalachian region. 2. Gas, Natural Appalachian region. 

I. Title: A summary of oil and gas production II. Series: United States Geological

Survey Bulletin 1409. 

QE75.B9 no. 1409 [TN872.A5] SS7.3'08s [338.2V280974] 75-619101

For sale by the Superintendent of Documents, U. S. Government Printing Office

Washington, D. C. 20402 

Stock Number 024-001-02670-8
CONTENTS

Page

Abstract __________________________________________ 1

Introduction __________________________^____________ 2

Purpose and scope of report ___________________________ 2

Previous investigations ____________________^_________ 3

Methods of investigation _____________________________ 3

General geology _____________________________________ 4

Structure ______________________________________ 4

Stratigraphy _____________________________________ 4

Oil and gas production and reserves _______________^._________ 7

Historical comment ________________________________ 7

Annual production of oil and gas ________________________ 11

Distribution of known oil and gas production by geologic age ________ 15

Distribution of known recoverable reserves by geologic age _________ 15

Distribution of total hydrocarbons by geologic age ______________ 17

Speculations on wastage ______________________________ 20

Drilling and production information _______________________ 24

References cited _____________________________________ 25

Selected references ___________________________________ 27

ILLUSTRATIONS

Page

FIGURE 1, . Map of the Applachian Basin ____________________ 5

Graph showing annual oil production for the Applachian basin, .

1859-1972______________________________ 13 

Graph showing annual natural gas production for the Applachian

basin, 1882-1972. _______________.________ 15

ra
IV CONTENTS

TABLES

Page TABLE 1. Principal oil- and gas-producing pay zones in the Appalachian

basin _________________________________ 8

2. Estimated annual crude oil production in the Appalachian basin,

1859-1972 _______________________________ 12

3. Estimated annual natural gas production in the Appalachian

> basin, 1882-1972 ___________________________ 14

4. Known cumulative oil and natural gas liquids production in the

Appalachian basin, 1859-1972 _________________^_ 16

5. Known cumulative gas production in the Appalachian basin,

1882-1972 _______________________________ 16

6. Estimated ultimate recoverable oil reserves in the Appalachian

basin __________________________________ jg

7. Estimated original oil-in-place in the Appalachian basin ____ jg

8. Estimated ultimate natural gas reserves in the Appalachian basin 19

9. Estimated ultimate recoverable reserves of natural gas in the Appalachian basin ___________________________ 19

10. Estimated total recoverable hydrocarbons in the Appalachian

basin _________________________________ 21

11. Estimated total hydrocarbons in the Appalachian basin, calculated

using original oil-in-place _____________________ 21

12. Deepest drilling and production depths for oil or gas in States of the

Appalachian basin, through 1973 ____^____________ 24

CONVERSION TO METRIC SYSTEM

In this report the main units of measurement are barrels (petroleum), miles, feet, and 

cubic feet. These and other units may be converted to the metric system by multiplying 

by the following factors:

English unit Metric unit

To convert Multiply by To obtain

Acres ________________ 0.4047 Hectares

Barrels (petroleum) ________ 0.16 Cubic metres

Btu ____^____________ 0.252 Kilogram calories

Cubic feet1 ____________ 0.0283 Cubic metres

Feet _______^_________ 0.3048 Metres

Miles ________________ 1.609 Kilometres

Square feet _____________ 0.09 Square metres

'Barrel equivalents for cubic feet of natural gas are based on the Btu equivalent of methane gas, 5,426 cubic feet per 

barrel.
A SUMMARY OF

OIL AND GAS PRODUCTION

AND RESERVE HISTORIES

OF THE APPALACHIAN BASIN, 1859-1972

By BETTY M. MILLER

ABSTRACT

The Appalachian basin extends over 100 million surface acres from the Adirondack 

Mountains in New York southward into northern Alabama. This Paleozoic sedimentary 

basin was the birthplace of the modern petroleum industry in the United States, and its 

oil and gas fields have the longest production history of any on the North American Continent. The Appalachian basin's commercial development dates from the discovery of oil in 

a stray sand of Late Devonian age in the Drake well in Pennsylvania, August 1859; the 

first commercial gas production was recorded in 1882.

This report presents a comprehensive compilation of the oil and gas production and 

reserve histories of the Appalachian basin from 1859 through 1972, based chiefly upon 

published information from State and Federal agencies, private agencies, and petroleum 

companies. A detailed bibliography accompanies the report.

Beginning in 1859, with 2,000 barrels, the annual oil production in the basin increased 

to a peak of 36.3 million barrels in 1900. After 1900 the annual oil production declined irregularly over the years until in 1972 it was 21.3 million barrels. Total cumulative oil 

production for the Appalachian basin through 1972 was approximately 2.7 billion barrels.

Annual production of natural gas in the Appalachian basin was recorded as 1.3 billion 

cubic feet in 1882. Gas production reached a peak in 1917 with more than 522 billion cubic 

feet, and then declined to approximately 460.4 billion cubic feet in 1972. Total cumulative 

natural gas production for the basin through 1972 is approximately 31.2 trillion cubic feet.

The known cumulative oil and natural gas production from 1859 through 1972 is 

categorized by geologic age for each State within the basin and for the total basin. The 

major oil and gas reservoirs are of Devonian age, and have produced 70.6 percent of the oil 

and 45.4 percent of the natural gas. The Mississippian is the second most important section, and accounts for 14.7 percent of the oil and 32.4 percent of the natural gas production. Silurian reservoirs are third in importance, having yielded 10.2 percent of the oil and 

15.1 percent of the gas produced. The three major oil-producing States in the basin are 

Pennsylvania, with a cumulative total of 1.3 billion barrels, West Virginia, with 507.7 million barrels, and Ohio, with 317.9 million barrels. The major gas-producing States are 

West Virginia, with a total production of 14.2 trillion cubic feet, Pennsylvania, with 8.7 

trillion cubic feet, Ohio, with 4.9 trillion cubic feet, and eastern Kentucky, with 2.8 trillion cubic feet

1
2 OIL AND GAS PRODUCTION OF THE APPALACHIAN BASIN

Summary compilations categorized by State and geologic age are reported for the distribution of the estimated total proved recoverable hydrocarbons (oil, natural gas, and 

natural gas liquids) in the Appalachian basin. The four most potentially productive 

States are West Virginia, 3.853 billion barrels equivalent; Pennsylvania, 3.258 billion barrels equivalent; Ohio, 1.494 billion barrels equivalent; and eastern Kentucky, 1.008 billion 

barrels equivalent. Total proved recoverable hydrocarbons for the basin are estimated at 

10 billion barrels equivalent. Of this total, approximately 8 percent of the recoverable oil 

reserves and 27 percent of the recoverable gas reserves have not yet been produced. 

Categorized by geologic age, the sources of these recoverable reserves are as follows: Devonian, approximately 52.2 percent; Mississippian, 27.7 percent; and Silurian, 13.8 percent 

of the total.

Original oil-in-place data were also used in separate studies of distribution by geologic 

age in determining the estimated recovery factor for the basin. The average percentage of 

ultimate hydrocarbon recovery in the Appalachian basin, based upon past and present 

technology, is approximately 20 percent, as compared with 31.4 percent for the entire 

United States.

Estimates of wastage of oil and natural gas in the Appalachian basin, based upon old 

published accounts, may be as high as 100 million barrels of crude oil and natural gas liquids (approximately 3 percent or more of the total proved reserves for 1859-1972); and 

nearly 10 trillion cubic feet of natural gas (more than 25 percent of the total proved gas 

reserves for 1882-1972).

Drilling reports for each State are summarized for deepest drilling records, production 

depth records, and annual average footage per well drilled. The deepest drilling in the 

basin through 1972 was in Pennsylvania, where a well was drilled to 18,834 feet. Since 

1972 several deeper wells have been drilled in West Virginia, reaching depths greater than 

20,000 feet. The deepest known production was from a hole drilled in 1964 in Pennsylvania at 11,458 feet in the Silurian Tuscarora Sandstone. The average footage per well 

drilled within the Appalachian basin during the period 1947-68 was approximately 2,662 

feet.

Stripper well production surveys are summarized for each State. Records show that 100 

percent of the production from Pennsylvania and West Virginia, the leading hydrocarbonproducing States, is from stripper wells. Ohio has 82 percent of its production from stripper wells, Kentucky, 94 percent, and New York, 100 percent.

All production, reserve, and estimated oil-in-place data are based upon known reservoirs. Projections or extrapolations into unexplored or currently nonproductive formations within the Appalachian basin are outside the scope of this report.

INTRODUCTION

PURPOSE AND SCOPE OF REPORT

This report is a comprehensive summary of the oil and gas production 

and reserve histories of the Appalachian basin from 1859 through 1972. 

These histories were used in making a regional synthesis of Appalachian basin data to evaluate the basin's petroleum potential and to 

delineate potentially productive areas within selected stratigraphic intervals in the basin.

The Appalachian basin, as the term is used by the petroleum industry in the United States, comprises those Paleozoic sedimentary 

rocks lying between the west face of the Blue Ridge Mountains on the 

east and the crests of the Cincinnati and Findlay arches and of the
INTRODUCTION 3

Nashville dome on the west, and stretching from the Canadian border 

on the north to the northern border of the overlapping Cretaceous rocks 

in Alabama on the south. This report on the Appalachian basin encompasses production and reserve data from all of West Virginia and parts 

of New York, Pennsylvania, Ohio, Maryland, Virginia, Kentucky, and 

Tennessee. Because no significant production occurred in those parts of 

the Appalachian basin that fall within the States of North Carolina, 

Georgia, Alabama, and New Jersey, these States are not included in the 

data compilations. The production in Ontario, Canada, is not included 

in this report. It should be noted that all production and reserve data 

pertaining to the Lima-Findlay (Trenton) fields on the FindlayCincinnati arch in Ohio and all data for the western side of the 

Nashville dome in Kentucky and Tennessee are excluded here from the 

Appalachian basin records because these areas lie outside the basin. 

This will account for differences between data reported here and 

production and reserve data for the Appalachian basin published in 

other sources in which these two areas were included in the totals for the 

Ohio and Kentucky records.

This report presents information on the oil and gas developments in 

the Appalachian basin from 1859 through 1972 for all the States included within the basin and also for geologic age categories. The report 

includes data on oil and gas production, proved reserves, original oil-inplace, number of wells drilled, deepest drilling records, average footage 

drilled, and percent stripper-well production.

PREVIOUS INVESTIGATIONS

A detailed compilation of the oil and gas production and reserve 

histories for the entire Appalachian basin from 1859 through 1972 has 

not been previously published. Although many individual State agencies and U. S. Bureau of Mines reports (U. S. Bureau of Mines, 1924- 

1931, 1932-1971) provide piecemeal information, there are no comprehensive summary reports for the entire basin.

METHODS OF INVESTIGATION

This report is based chiefly upon published information from State 

and Federal agencies, the American Gas Association (AGA), the 

American Petroleum Institute (API), the American Association of 

Petroleum Geologists (AAPG), the Independent Petroleum Association 

of America (IPAA), the Interstate Oil Compact Commission (COMPACT), and on many other published reports from miscellaneous 

sources. Additional information was provided by correspondence with 

some industrial companies and other private organizations and through 

communications with various officials of State geological surveys. A 

detailed list of published references and other sources of information is 

included at the end of this report.
4 OIL AND GAS PRODUCTION OF THE APPALACHIAN BASIN

GENERAL GEOLOGY

STRUCTURE

The Appalachian basin is a large spoon-shaped geologic feature extending southwestward from approximately the Adirondack Mountains 

in New York into northern Alabama (see fig. 1). The basin is bounded 

on the west by the Cincinnati arch in western Ohio and on the east by 

the Blue Ridge Mountains of Virginia. Structurally, the Appalachian 

basin extends to the Blue Ridge on the east; however, there is evidence 

to indicate that Paleozoic strata lie below the thrust plates of 

metamorphic rocks of the Blue Ridge and that the eastern boundary of 

the Appalachian basin in southwestern Virginia and North Carolina 

may lie as much as 50 miles east of the west edge of the Blue Ridge anticlinorium. The boundaries of the Appalachian basin coincide roughly 

with the boundaries of the Appalachian Plateau and the Valley and 

Ridge physiographic provinces, although along its northwestern, 

western, and southwestern margins, the basin extends beyond the 

Plateau. The greatest length of the basin is approximately 900 miles. Its 

greatest width is about 300 miles; however, in most places it is much 

narrower. The entire area as reported by Roth (1968, p. 1707) comprises 

at least 100 million surface acres.

The Appalachian basin originated as a sedimentary trough or depression on the Precambrian surface which was covered by Cambrian seas. 

Large quantities of marine and continental sediments were deposited in 

the basin throughout most of the Paleozoic Era. The sediments were 

derived primarily from landmasses to the east, although some detritus 

was derived from sources to the north and west of the basin. During the 

Paleozoic there was a sequence of depositional settling, subsidence, and 

elevation in the basin. During the Paleozoic, the seas encroached 

westward and then receded as epeirogenic movements occurred. The 

Cincinnati arch was an important influence in the formation of the Appalachian basin, acting as a barrier to the westward migration of the 

seas and the clastic materials which they carried and functioning as a 

fulcrum during the orogenies occurring during the basin's formation 

(Roth, 1968, p. 1707).

STRATIGRAPHY

All systems of the Paleozoic Era are represented in the Appalachian 

basin. The youngest beds in the central part of the basin are of Permian 

age, surrounded by outcrops of Pennsylvanian rocks. The Pennsylvanian caps the major part of the Appalachian Plateau south of the New 

York-Pennsylvania border. Mississippian, Devonian, Silurian, and 

older strata crop out in sequence along the western, northern, and 

southeastern margins (Fettke, 1953, p. 71). At the southwestern end of
GENERAL GEOLOGY

100 200 300 KILOMETRES

EXPLANATION

Nashville-Cincinnati-FindlayAlgonquin arch

Perimeter of Appalachian basin 

Western margin of the Atlantic

Coastal Plain

Metamorphic and igneous rocks 

of the Blue Ridge and 

Piedmont

Appalachian structural front 

(from Roth, 1968)

FIGURE 1. Map of the Appalachian basin (modified from Colton, 1961, and Roth, 1968).
6 OIL AND GAS PRODUCTION OF THE APPALACHIAN BASIN

the basin in Alabama the Paleozoic beds pass underneath the 

Cretaceous and Tertiary beds of the Gulf Coastal Plain.

Along the Allegheny Front, which forms the eastern edge of the Appalachian Plateau, and east of it in the closely folded Appalachian 

Mountains of central Pennsylvania, the exposed Upper Cambrian to 

Mississippian section inclusive has a thickness of over 21,000 feet (Fettke, 1953, p. 71). As much as 5,000 feet of post-Mississippian rock is present in the folded anthracite district in the Valley and Ridge of Pennsylvania. Due to the westward thinning of most of the formations and 

the truncating of others by unconformities, the corresponding interval 

in central Ohio includes less than 5,000 feet of strata. In the southwest 

corner of Pennsylvania, the Pennsylvanian System has a thickness of 

1,500 feet and the Permian, 1,100 feet (Fettke, 1953, p. 71).

The succession and nature of the principal oil- and gas-producing pay 

zones within the major part of the Appalachian basin are shown in 

table 1.

The reservoir rocks in which oil and gas have been found in commercial quantities in the Appalachian basin range in age from Pennsylvanian to Cambrian.

Sandstones of Pennsylvanian age have yielded substantial volumes of 

gas and oil in southeastern Ohio, western Pennsylvania, northwestern 

West Virginia, and eastern Kentucky and a little gas in Virginia.

Mississippian sandstones and, to a lesser extent, limestones have 

been important producers of both oil and gas in eastern Ohio, western 

Pennsylvania, western West Virginia, eastern Kentucky, and eastern 

Tennessee, and have produced some gas in Virginia. The Berea Sandstone, near the base of the Mississippian System, has been a major 

producer of oil in Pennsylvania, Ohio and West Virginia.

Major oil and natural gas production in New York has been confined 

to sandstones in the Upper Devonian Series. The major part of the oil 

production in Pennsylvania and much of that in West Virginia has also 

come from Upper Devonian sandstones; large volumes of natural gas 

have also been produced from these sandstones. Upper and Middle 

Devonian black shales in eastern Kentucky and southwestern West 

Virginia have been a major source of gas. Substantial volumes of gas 

have been encountered in fractured Huntersville Chert (of Price, 1929) 

and Oriskany Sandstone of Middle and Early Devonian age, respectively, in southwestern Pennsylvania, western Maryland, and 

northeastern West Virginia. The Lower Devonian Oriskany Sandstone 

has been the source of large volumes of gas in south-central New York, 

north-central Pennsylvania, and western West Virginia. Gas and some 

oil have also been produced from the Oriskany Sandstone in eastern 

Ohio.

The Newburg sand, a porous zone correlated with rocks in the Middle 

Silurian Lockport Dolomite of New York, produces considerable gas
OIL AND GAS PRODUCTION AND RESERVES 7

and some oil in northern Ohio. The so-called Corniferous limestone of 

eastern Kentucky consists of two dolomites, the Peebles and the Lilley 

(of Foerste, 1917) of the Middle Silurian Lockport Group, and is a major 

producer of petroleum. The Big Six sand, which is thought to correlate 

with the Keefer Sandstone of the Middle Silurian, is a source of gas in 

eastern Kentucky. The "Red", "White", and "Gray Medina" sands of 

the Albion Group of the Lower Silurian have been an outstanding 

source of gas in western New York and in central and eastern Ohio. In 

Ohio, where these sands are commonly called Stray, Red, and White 

Clinton sands by drillers, some oil has also been produced (Calvert, 

1964a, b).

To date, rocks older than the Silurian have contributed relatively 

small amounts (less than 2 percent) of oil and gas to the total production of the Appalachian basin. A little gas has been produced from the 

Trentor Limestone of the Middle Ordovician on the southwest flank of 

the Adirondack Mountains in New York.

Limestones of Trenton, Black River, and Stones River ages (Middle 

Ordovician) have produced a little oil and gas in south-central Kentucky and north-central Tennessee. Gas in commercial volumes has 

been discovered in eastern Kentucky in a sand that occurs a short distance above the unconformity at the top of the Lower Ordovician Knox 

Dolomite. A small oil field in Virginia produces from fractured Trenton 

Limestone. A little oil and gas have been obtained from the Knox 

Group of Early Ordovician and Late Cambrian age in central Tennessee 

and shows of oil occur in this dolomite in eastern Kentucky (Fettke, 

1953, p. 72).

To date, the most encouraging production in rocks older than 

Silurian are the recent discoveries and good yields from the 

Trempealeau Dolomite in central Ohio in the uppermost unit of the 

Cambrian sequence.

OIL AND GAS PRODUCTION AND RESERVES

HISTORICAL COMMENT

The modern petroleum industry in the United States began in the 

Appalachian basin and the oil and gas fields of this basin have the 

longest production history of any on the North American Continent. 

Although the basin's commercial development dates from the discovery 

of oil in a stray sand of Late Devonian age at a depth of 69 feet in the 

Drake well along Oil Creek south of Titusville in northwestern Pennsylvania in August 1859, the first recorded reference to petroleum in 

this area was reported in 1627. Joseph Delaroche Daillon, a French missionary, having penetrated into the Lake Erie Wilderness, now a part of 

New York State, wrote in a letter dated July 18, 1627, that he had seen 

"a good kind of oil which the Indians called Antonontons" coming from
8 OIL AND GAS PRODUCTION OF THE APPALACHIAN BASIN

TABLE 1. Principal oil- and gas-producing

[Correlation between units for each State not implied. Maryland omitted as it has only limited production from 

two horizons in the Lower Devonian. Table modified from Meyer and Edgerton (1968, table 51). Data from Calvert 

(1961, 1964b), Cardwell and others (1970), Cram (1971), Hunter (1955,1964), Kreidler (1953), Landes (1970), Lytle 

(1950), McGuire and Howell (1963), Milhous (1960), Sitler and Wehmeyer (1962), Thomas and Nosow (1960),

Southern New York Southeastern Ohio

(No production)

Murphy sd 

Little Dunka 

Big Dunkard

Carroll sd 

Goose Run sd 

Mitchell sd 

Wolf Creek sd

First Cow Run sd 

Buell Run sd 

Macksburg 300-fc

PF.NNSYI.VANIAN Freeport sd 

Kittanning sd 

Clarion sd 

"First Salt" sd 

"Second Salt" sd

Second Cow Run sd 

Macksburg 500-foot 

Macksburg 700-foot 

Germantown sd 

Schram sd 

"First Salt" sd 

"Second Salt" sd 

Brill sd

"Maxton" sd "Maxton" sd

Upper

"Big Lime"

(Greenbrier Ls)

"Big Lime" 

Lime sd

MISSISSIPPI AN

Lower

Lime sd

Big tnjun sd

Squaw sd

Second sd

Berea Ss

MurrysvilleThirty Foot sd

Keener sd

Big Injun sd

Squaw sd

Hamden sd

Weir sd

Berea Ss

"Second Berea" ss

Bradford First sd 

Sugar Run sd 

Chipmunk sd 

Bradford Second sd

Ha risburg Ru

Richburg sd

DEVONIAN 

(PART) Upper

Gantz sd

Hundred footFirst Venango sd

Nineveh sds

Red Valley sd

Thirty footSecond Venango sd

Snee sd

Knox Third sd

Knox Fourth sd

Knox Fifth sd

Gordon Stray sd

Gordon-Third Venango s

McDonald Fourth sd

McDonald Fifth sd

Bayard sd

Elizabeth sd

Warren First sd

Warren Second sd

Bradford First-GladeQueen-Eighty Ft sds

Clarendon sd

Speechley sd

Balltown sd

Tiona sds

Bradford Second sd

Cooper sd

Bradford Third sd

Kane sds

Haskill sds
OIL AND GAS PRODUCTION AND RESERVES

pay zones in the Appalachian basin

Wilson (1968), Weaver (1962), and Wallace Dewitt, Jr. (written commun., 1974). Abbreviations are as follows: Fm, 

formation; Mbr, member; Ls, limestone; Ss or ss, sandstone; Dol or dol, dolomite; Gp, group; Sh or sh, shale; sd(s), 

sand(s). Quotation marks (") mean local or driller's name].

West Virginia Virginia

Carroll sd

Sewickley coal

Pittsburgh coal

Minshall sd

Murphy sd

MoundsviHe sd

First Cow Run sd

Big Dunkard sd

Burning Springs sd

"Peeker" sdSecond Cow Run sd

Horseneck sd

"First Salt" sd 

"Second Salt" sd

"Maxton" sd

Princeton ,sd

Ravencliff sd 

Maxton sd

"Big Lime"

Keener sd

Big Injun sd

Squaw sd

Weir sd

Salt sd Beaver sd

Horton sd

Pike sd

"First Salt" sd

"Second Salt" sd , '" 

"Third Salt" sd (part)

Ravencliff sd Maxton or "Maxon" sd Unnamed sds

Maxton sd Cirkin ("Gasper") Fm Glen Dean Ls

("Big Lime") St. Louts Ls St. Louis Ls

Little Valley Ls (sds) Warsaw Ls Warsaw Ls

Berea Ss Keener sd- Fort Payne Chert

Fort Payne Chert Borden sd

Red Injun sd

Big Injun sd

Bere Ss

Murrysville sd

Gantz sd

(now gas storage) 

Fifty foot sd 

Thirty foot sd 

Gordon Stray sd 

Gordon sd

McDonald Fourth sd 

McDonald Fifth sd 

Sixth-Bayard sd 

Seventh-Elizabeth sd 

Warren First sd 

Burnside sd 

Warren Second sd 

Clarendon sd 

Speechley (Tiona) sd 

Balltown-Cherry Grove 

Riley sd

Elk-Porter sd 

"Kane" sd 

"Childress zone" sd

Weir sd

Sunbury Sh

Berea Ss

Beaver sd-Beaver Creek sd

Borden sd

Chattanooga Sh

sh (Black sh)
10 OIL AND GAS PRODUCTION OF THE APPALACHIAN BASIN

TABLE 1. Principal oil- and gas-producing

System Series Southern New York

...... Hamilton Fm Middle Onondaga Ls

DEVONIAN . . (PART) Oriskany Ss

Lower

Salina Gp 

Upper

Lockport Dol 

SILURIAN Mlddlfi

"Gray Medina" sd 

"Red Medina" sd 

Lower "White Medina" sd

Pennsylvania Southeastern Ohio

Onondaga Ls

Huntersville Chert Oriskany Ss 

Oriskany Ss

Salina Fm Salina Gp 

Newburg Dol

"Lockport" Dol "Lockport" Dol 

"Packer ShellLittle Lime"

"Red Medina" sd Stray Clinton sd 

"White Medina" sd Red Clinton sd 

(Albion Sd) 

White Clinton sd 

Medina sd

Upper

Ls of Trenton Gp

Beekmantown Dol Beekmantown Dol

Trenton Dol 

Black River Ls 

Glenwood Fm 

St. Peter Ss

Beekmanto Dol

Upper

Gatesburg Fm

Middle (No production)

Copper Ridge Dol

(Trempealeau Dol) 

Mount Simon Ss

a spring near the present town of Cuba in Allegany County, N. Y. 

(Carll, 1887, p. 575).

Prior to the Drake well, the presence of oil and gas had been observed 

at a number of scattered localities in the basin and had been utilized on 

a small scale for illuminating, lubricating, and medicinal purposes. The 

literature relating to the early history of the salt industry in the Appalachian basin cites many instances of both natural gas and oil having 

been found during drilling for brine. According to the U. S. Geological 

Survey (1885), the salt industry made the first commercial use of gas at 

Maiden, W. Va., where brine was evaporated by use of natural gas from 

wells drilled in 1807 and 1808. Because crude oil was considered a 

nuisance which greatly hampered the extraction of salt from the brine, 

the salt well drillers attempted to avoid finding oil in their drilling. 

Many of their tools, however, which were developed for drilling brine 

wells, were used to drill the early oil wells.

Although the salt industry used the natural gas byproducts from 

brine wells, historians generally agree that the first well drilled for the 

express purpose of finding natural gas was near the town of Fredonia, 

Chautauqua County, N. Y., in 1821 (Roth, 1968, p. 1702). In spite of 

these early uses it was not until about 1882, when gas was transported
OIL AND GAS PRODUCTION AND RESERVES

pay zones in the Appalachain basin Continued

11

West Virginia Virginia Central and eastern Kentucky Tennessee

"Brown" sh 

Hamilton Fm

Huntersville Chert Oriskany Ss 

Oriskany Ss 

Healing Springs Ss Mbr 

of New Scotland Ls

Unnamed dol 

Williamsport sd 

Newburg sd

"Lockport" Dol 

Big Six sd (Reefer Ss)

"Onondaga" Ls ^ 

(Irvine sd) r

I

^

Salina Fm "c 

Peebles sd o

"Lockport" Dol "Lockport" Dol 

' Big Six sd

Clinton sd

(Tuscarora Ss)

Clinton sd 

Brassfield Ls

Lelpers Ls

Trenton Dol 

Black River Ls

Trenton Ls Sunnybrook sd- 

"Black River" (Witten) Ls Granville sd 

Moccasin Ls "Black River" Ls 

"St. Peter" Ss

Trenton Ls 

"Black River" Ls 

Stones River Ls

"Beekmantown" Dol 

(Knox Dol)

Knox Cp

Rome Fm 

"Basal" sd

to Pittsburgh, Pa., from a gas well about 15 miles east of the city, that 

the natural gas industry began. By 1885 the natural gas industry was 

well established in the Appalachian area.

ANNUAL PRODUCTION OF OIL AND GAS

For the purposes of this report, the first recorded oil production in the 

Appalachian basin began in 1859, and the first recorded gas production 

in 1882. Any production or wastage figures prior to these dates are 

highly speculative for reasons which will be commented on later in this 

report.

Beginning in 1859 with 2,000 barrels, the annual oil production in the 

Appalachian basin rose until it reached a peak of 36.3 million barrels in 

1900. This represented 57 percent of the total oil production of the 

United States in that year. By the end of 1900, or during the first 40 

years of the petroleum industry's history, 73.5 percent of the total 

cumulative oil production in the United States had come from this 

basin.

After 1900, oil production declined until, in 1915, it had dropped to a 

low of 24.8 million barrels. An upward trend followed the introduction 

of secondary recovery methods, particularly waterflooding, which was
12 OIL AND GAS PRODUCTION OF THE APPALACHIAN BASIN

used in the Bradford field of Pennsylvania, and in 1937 production was 

37.6 million barrels. Production again declined until 1960, when it was 

approximately 19.3 million barrels. An upward surge in 1964 to 31.9 

million barrels reflected the new discoveries in the Cambrian of Ohio. 

Since then the trend has again been gradually downward.

The annual oil production for 1972 was approximately 21.3 million 

barrels, representing only 0.65 percent of the total U. S. oil production 

that year. At the end of 1972, the cumulative production of the Appalachian basin accounted for only 2.75 percent of the total cumulative 

production of the United States, in contrast to 73.5 percent at the end of 

1900. This change in the relative importance of Appalachian basin oil 

fields emphasizes the rapidity with which the American oil industry has 

grown and the magnitude it has attained since the beginning of the present century.

TABLE 2. Estimated annual crude oil production in the Appalachian basin, 1859-1972

[Reported in thousands of barrels]

Year

1859

1860

1861

1862

1863

1864

1865

1866

1867

1868

1869

1870

1871

1872

1873

1874

1875

1876

1877

1878

1879

1880

1881

1882

1883

1884

1885

1886

1887

1888

1889

1890

1891

1892

1893

1894

1895

1896

Production

2

520

2,133

3,076

2,631

2,136

2,517

3,617

3,367

3,666

4,235

5,280

5,225

6,313

9,913

10,946

8,807

9,128

13,344

15,389

19,901

26,253

27,568

30,227

23,307

23,956

21,534

26,624

22,878

16,942

22,356

30,066

35,849

33,432

31,366

30,783

30,960

33,971

Year

1897

1898

1899

1900

1901

1902

1903

1904

1905

1906

1907

1908

1909

1910

1911

1912

1913

1914

1915

1916

1917

1918

1919

1920

1921

1922

1923

1924

1925

1926

1927

1928

1929

1930

1931

1932

1933

1934

Production

35,230

31,717

33,069

36,295

33,618

32,883

32,472

31,882

30,800

28,834

27,628

27,435

28,468

29,069

25,969

27,825

27,457

25,791

24,753

25,087

27,643

27,745

34,344

32,745

32,588

31,210

30,379

29,074

29,550

30,452

32,163

32,640

35,308

35,417

31,516

30,732

28,513

31,509

Year

1935

1936

1937

1938

1939

1940

1941

1942

1943

1944

1945

1946

1947

1948

1949

1950

1951

1952

1953

1954

1955

1956

1957

1958

1959

1960

1961

1962

1963

1964

1965

1966

1967

1968

1969

1970

1971

1972

Total

Production

33,303

35,080

37,585

35,314

34,842

34,167

30,652

30,110

29,249

26,434

24,639

26,479

25,719

25,832

24,002

23,826

23,202

23,223

22,931

21,365

21,368

22,028

22,545

22,585

21,486

19,294

21,739

21,510

21,473

31,916

28,208

25,540

23,722

24,424

23,525

22,444

20,339

21,300

2,738,000

'Annual crude oil production data for the Appalachian basin States were compiled from many sources (see, 

for example, U.S. Bureau of Mines references) and exclude the greater part of the Lima-Trenton production in Ohio 

and the production in western Kentucky after oil was discovered there in 1943. However, it was impossible to trace all of 

the Lima-Trenton production on an annual basis in the data for Ohio's total annual production. This difficulty and 

the many sources of data account for the minor differences between total cumulative production figures given here and 

those given in table 4.
OIL AND GAS PRODUCTION AND RESERVES 13

Table 2 shows the estimated annual crude oil production for the Appalachian basin from 1859 through 1972. The estimated total production for each year consists of a summation of the oil production data for 

each respective State withiri the basin compiled from many different 

sources of reference. These annual production figures were adjusted to 

eliminate the major part of the Lima-Trenton production in Ohio and 

the oil production from the western side of the Nashville dome in Tennessee and Kentucky areas which are not considered as a part of the 

Appalachian basin in this report. The data in table 2 were used to plot 

the oil-production curve for the Appalachian basin for the years 

1859-1972 as shown in figure 2.

40

35-

w30

'25-

§ 

220

Q

O15

DC

YEAR

FIGURE 2. Annual oil production for the Appalachian basin, 1859-1972.
14 OIL AND GAS PRODUCTION OF THE APPALACHIAN BASIN

Beginning in 1882, with a reported annual production of natural gas 

of 1.3 billion cubic feet, the Appalachian basin reached its peak natural 

gas production in 1917 with more than 522 billion cubic feet reported. 

Production declined to approximately 460.4 billion cubic feet produced 

in 1972, a figure which represents approximately 2 percent of the total 

natural gas production for the United States for that year. At the end of 

1972 the cumulative natural gas production of the entire Appalachian 

basin accounted for about 7 percent of the total cumulative gas production of the United States, in contrast to approximately 63 percent of the 

total at the end of 1917.

Table 3 shows the estimated annual natural gas production for the 

Appalachian basin from 1882 through 1972. The estimated total 

production figure for each year is derived from natural gas production 

data compiled from a variety of sources for each respective State within 

the basin. The data in table 3 were used to plot the natural gas production curve for the Appalachian basin for the years 1882-1972 as shown 

in figure 3.

TABLE 3. Estimated annual natural gas production in the Appalachain basin, 1882-1972

[Reported in millions of cubic feet]

Year Production Year Production Year Production

1882 .

1883 .

1884 .

1885 .

1886 .

1887 .

1888 .

1889 .

1890 .

1891-.

1892 .

1893 .

1894 .

1895 .

1896 .

1897 .

1898 . 1899:l .

1900 .

1901 .

1902 .

1903 .

1904 .

1905 .

1906 .

1907 .

1908 .

1909 .

1910 .

1911 .

1912 .

1,282

3,419

21,154

120,232

224,176

313,562

400,601

261,185

242,743

Total

production: 

2,844,922

Estimated 

annual

average: 

203,209

204,543

306,337

314,837

295,375

354,150

373,173

371,726

419,945

1913

1914

1915

1916

1917

1918

1919

1920

1921

1922

1923

1924

1925

1926

1927

1928

1929

1930

1931

1932

1933

1934

1935

1936

1937

1938

1939

1940

1941

1942

425,266

425,863

446,852

509,835

522,116

461,737

420,995

436,223

319,891

360,867

388,695

354,616

342,201

352,124

335,589

341,432

335,660

333,951

291,658

251,435

247,822

285,131

328,288

351,850

419,325

365,902

401,722

428,187

465,856

487,318

1943

1944

1945

1946

1947

514,388

471,062

430,250

440,124

465,566

1948

1949

1950

1951

1952

1953

1954

1955

1956

1957

1958

1959

1960

1961

1962

1963

1964

1965

1966

1967

1968

1969

1970

1971

1972

443,512

379,078

411,179

449,580

404,911

412,391

449,894

429,808

413,892

421,677

426,158

435,517

455,910

437,683

420,203

426,280

405,630

418,900

429,360

441,428

465,588

450,727

478,811

471,165

460,413

Total ___ 31,672,854

'Annual natural gas production data for the Appalachian basin States were compiled from many sources (see, 

for example, U.S. Bureau of Mines references). This method accounts for differences between total cumulative 

production figures given here and those given in table 5.

-Annual production figures for the years 1891 through 1901 were not available on a yearly basis. However, total 

production for this 14-year span is available and is reported accordingly.

:l Unpublished data on gas production for Ohio and West Virginia for the years 1899-1905 were obtained through 

written communications with J. R. Ebright (East Ohio Gas Company, Cleveland, Ohio, January 1974) and G. C. Grow, 

Jr. (Transcontinental Gas Pipe Line Corporation, Newark, N. J., September 1973).
ARSENIC IN VEGETATION 15

PROCEDURES

PREPARATION OF SAMPLE SOLUTION

REAGENTS

Hydrochloric acid, concentrated, A.C.S.

Hydrochloric acid, 6 M.

Magnesium oxide-magnesium nitrate slurry. Suspend 37.5 g magnesium 

oxide and 52.5 g magnesium nitrate hexahydrate in enough water to 

make 500 ml. Shake vigorously immediately before using.

Nitric acid, concentrated, A.C.S.

Oxalic acid, reagent grade, 5 percent. Dissolve 5 g of dihydrate in 100 

ml water.

Perchloric acid, 70-72 percent.

Potassium iodide. Prepare by dissolving 15 g of salt in 100 ml water. 

Store in dark bottle.

Stannous chloride. Prepare by dissolving 4 g of dihydrate in 10 ml concentrated hydrochloric acid.

Sulfuric acid, concentrated, A.C.S.

DRY IGNITION

1. Weigh 1 to 2 g of ground air-dried vegetation in an evaporating dish 

and wet with small amount of water.

2. Add 10 ml of magnesium oxide-magnesium nitrate slurry and mix 

well.

3. Place dish on hot steam bath and dry.

4. Transfer dish to preheated muffle furnace and ignite the vegetation 

at 550°-600°C for 2 to 4 hours.

5. Remove dish from muffle furnace, cool, moisten ash with minimum 

amount of water, and cover dish with cover glass. Add about 15 

ml 6 M hydrochloric acid.

6. Heat dish and contents on steam bath until sample dissolves.

7. Filter hot acid solution through Whatman No. 41 filter paper into 

a 125-ml Erlenmeyer flask. Rinse dish and filter with several portions of hot water and continue until filtrate has a volume of about 

60ml.

8. To the filtrate, add 8 ml concentrated hydrochloric acid, 2 ml of potassium iodide, and 0.5 ml stannous chloride. Mix and heat in 

boiling water bath about 5 minutes. Cool flask and contents.

9. Distill arsine as described under the headings entitled "Molybdenum 

Blue Reaction" and "Silver Diethyldithiocarbamate Reaction."

WET IGNITION

1. Weigh 1 to 2 g of air-dried vegetation into a 250-ml Erlenmeyer flask.

2. Add 15 ml concentrated nitric acid, mix, and add 25 ml of 1+1 mixture
16 TRACE ANALYSIS IN GEOCHEMICAL EXPLORATION

of concentrated sulfuric acid and concentrated (70-72 percent) perchloric acid.

3. Heat flask and contents on hotplate until white fumes evolve. If, 

during heating, brown fumes cease evolving and sample turns 

brown, discard and start over, using a larger volume (20-25 ml) 

of concentrated nitric acid.

4. After about one-half hour and while white fumes are still evolving, 

remove flask from hotplate. Cool, add 10 ml oxalic acid solution 

and return flask to hotplate.

5. Heat flask and contents until white fumes evolve freely.

6. Remove flask from hotplate, cool, and add 2- by 50-ml portions of 

water twice and mix well.

7. Add 2 ml potassium iodide and 0.5 ml stannous chloride, mix and 

allow mixture to stand 15 minutes.

8. Distill arsine as described under the headings entitled "Molybdenum 

Blue Reaction" and "Silver Diethyldithiocarbamate Reaction."

DISTILLATION AND ESTIMATION

MOLYBDENUM BLUE REACTION 

REAGENTS

Acetic acid, glacial

Ammonium molybdate. Dissolve 1.5 g of the reagent in 100 ml of 1+9 

sulfuric acid. Prepare fresh daily.

Arsenic standard solution, 1,000 /ng/ml. Dissolve 0.132 g of arsenious 

oxide in 2 ml of 1 M sodium hydroxide. Dilute with 5-10 ml water, 

add 3 ml concentrated hydrochloric acid, and make up to 100 ml with 

water. From this stock solution, prepare less concentrated standard 

solutions as needed by dilution of appropriate volumes with water.

Hydrochloric acid, 1 M. Prepare by diluting 8.3 ml of concentrated acid 

with water to 100 ml.

Hydrazine sulfate. Prepare by dissolving 1 g of reagent-grade salt in 100 

ml of water.

Lead acetate. Prepare by dissolving 17.5 g of salt in 100 ml of water 

containing 5 ml glacial acetic acid.

Potassium iodide-iodine reagent, stock solution, 0.02 N. Prepare by dissolving 8 g potassium iodide and 2.54 g iodine in 25 ml water. Dilute 

to 1 1 with water and store in the dark.

Potassium iodide-iodine reagent, 0.002 N. Prepare by diluting 10 ml of 

stock solution to 100 ml with water. Store in the dark.

Sodium meta-bisulfite. Prepare daily by dissolving 0.5 g of the reagent 

in 10 ml water.

Zinc, mossy, arsenic-free.
ARSENIC IN VEGETATION 17 

APPARATUS

The distillation apparatus used was described by Kingsley and 

Schaffert (1951) and is commercially available from Corning Glass 

Works, 1 Corning, N.Y. Catalog No. 33680.

1. Assemble the distillation apparatus of Kingsley and Schaffert, using 

a 250-ml Erlenmeyer flask containing sample solution prepared 

by either wet or dry ignition. Place lead acetate-saturated glass wool 

in the trap and 15 ml of 0.0002 N potassium iodide-iodine reagent 

in collecting test tube.

2. Separate sample flask from apparatus and add 4-6 g arsenic-free zinc 

and quickly connect flask to trap.

3. Allow the evolved arsine and hydrogen to bubble through the iodine 

solution for 45 minutes.

4. After about 45 minutes, remove test tube receiver from apparatus and 

add the following:

2 ml LM hydrochloric acid

2 ml ammonium molybdate reagent

2 drops hydrazine sulfate reagent

5. Mix reagents of step 4 and add 1-2 drops of sodium meta-bisulfite 

reagent.

6. Make volume up to 25 ml with water, mix, and place test tube in 

boiling water bath for 10 minutes.

7. Cool and read absorbance at 835 nm.

8. Compare the absorbance of an unknown with that obtained from 

standard solutions, prepared as follows:

To a series of 125-ml flasks each containing 8 ml concentrated 

hydrochloric acid add individually 0.0, 1, 2, 4, 8, and 16 ng of 

arsenic. Make each up to 60 ml with water and continue with step 

8 under dry ignition to prepare a series of standard solutions. Plot 

absorbance values versus concentration and use resulting curve for 

comparison in step 7.

SILVER DIETHYLDITHIOCARBAMATE REACTION 

REAGENTS

Arsenic standard solution, 1,000 /jg/ml. See "Reagents" under "Molybdenum Blue Reaction."

Lead acetate. See "Reagents" under "Molybdenum Blue Reaction."

Pyridine, reagent grade.

Silver diethyldithiocarbamate absorbing solution. Prepare by dissolving 

250 mg of the carbamate in 50 ml reagent-grade pyridine.

Zinc, granular, 20-mesh, arsenic-free.

'Use of a specific company name does not necessarily constitute endorsement of the company by the U.S. 

Geological Survey.
18 TRACE ANALYSIS IN GEOCHEMICAL EXPLORATION

APPARATUS

Arsine generator. The distillation apparatus is described in the Fisher 

Scientific Co. catalog (1974).

1. Assemble distillation apparatus, marketed by Fisher Scientific Co., 

with sample solution in 125-ml generating flask, a piece of lead 

acetate-saturated glass wool in scrubber (trap) and 3 ml of carbamate reagent in the absorber. Lubricate standard taper joints with 

water to assure a tight seal.

2. Disconnect generating flask from scrubber, add 6 g of zinc to flask 

and quickly connect flask to scrubber and pass the evolved arsine 

through the trap and the absorbing solution.

3. After 30 minutes, disconnect generating flask from scrubber and 

transfer the absorbing solution to a 1-cm cuvette and measure 

absorbance at 540 nm using absorbing solution in null cell.

4. Obtain arsenic concentration by referring the measured absorbance 

of sample solution to a standard curve prepared as follows:

To a series of 125-ml Erlenmeyer flasks, each containing 60 ml 

water, 8 ml concentrated hydrochloric acid, 2 ml potassium iodide, 

and 0.5 ml stannous chloride, add individually 0.5, 1.0, 2.0, 3.0, 

6.0, 8.0, and 10.0 /ng of arsenic. Mix and heat in boiling water 

bath about 5 minutes. Cool flask and contents. Distill contents of 

each flask as in steps 1, 2, and 3, collecting the evolved arsine 

in the pyridine solution of silver diethyldithiocarbamate. Plot 

absorbance values versus concentration to prepare standard curve.

DISCUSSION

In the presence of relatively large amounts of hydrochloric acid, such 

elements as antimony and germanium form volatile chlorides and may 

possibly distill with the arsine. Phosphine may distill also, and all these 

elements interfere with the molybdenum blue reaction. On the other 

hand, phosphine does not interfere with the reaction of arsine with silver 

diethyldithiocarbamate, and antimony forms a compound having a different color and, thus, is not a serious interference. Bhargava, Donovan, 

and Hines (1972) found that up to 0.1 percent antimony did not interfere 

when the sample solution was accomplished with acid mixtures containing sulfuric acid as one component.

EXPERIMENTS

The effect of different amounts of sulfuric acid is significant at the 

wavelength used to measure the absorbance of the blue compound. 

Sandell (1959) suggested 0.25 N as the optimum concentration, but, 

under the conditions of our method, we observed a range in sulfuric
ARSENIC IN VEGETATION 19

acid concentration from 0.1 to 0.4 N over which the absorbance was constant. Such a range was observed at 10- and 20-/jg levels of arsenic, and 

this range suggests more flexibility in the molybdenum blue reaction 

than heretofore observed.

RESULTS

A scarcity of analyzed samples of vegetation precludes adequate comparison of results of our procedure with those obtained by other procedures. Arsenic values reported by Bowen (1967) on a standard kale 

sample are inconsistent, varying from about 0.1 to nearly 2 ppm. The 

Standard Reference Orchard Leaves of the National Bureau of Standards 

(Meinke, 1971) was unavailable at the time our procedures were being 

tested.

Repeatability of the proposed procedures was tested by repeat determinations on limited amounts of samples from the southwestern United 

States. The data given in table 3 were obtained using the wet ignition 

procedure of, and subsequent measurement by, the molybdenum blue 

reaction.

TABLE 3 Repeatability of arsenic determinations (molybdenum blue)

Sample 

No.

399

435

433

432

438

440

446

Material

...do...........................

...do...........................

Sage..........................

...do...........................

...do...........................

Number 

of determinations

8

6

13

7

7

8

10

Low 

(ppm)

2

6

5

10

10

12

23

High

(ppm)

3

9

12

13

17

18

30

Average 

(ppm)

2.1

7.0

7.8

11.9

12.5

15.5

25.8

Standard 

deviation 

(ppm)

0.4

1.1

2.2

.9

2.6

2.2

2.7

Relative 

standard 

deviation 

(percent)

19

16

28

8

21

14

10

The standard deviation of sample Nos. 433 and 432 appears to be out 

of line for undetermined reasons; otherwise, the relative standard deviation seems to be in the range of 10 to 20 percent. This range is in better 

accord with our experience using the kinds of methods presented in this 

bulletin.

The data in table 4 show that both the molybdenum blue reaction 

and the silver diethyldithiocarbamate reaction give essentially the same 

results. A casual examination of these data suggests that small amounts 

of arsenic are lost on dry ignition; however, the differences are small 

and one may not draw any such conclusion with certainty.
20 TRACE ANALYSIS IN GEOCHEMICAL EXPLORATION

TABLE 4. Determination of arsenic by molybdenum blue and carbamate

Sample 

No. 

(ADD-)

407....-

399

439.....

441.....

437.....

445

430.....

436.....

442.....

431

Arsenic (ppm)

Molybdenum blue 

wet ignition

............ 1

............ 2

............ 4

............ 4

5

5

............ 6

............ 6

............ 6

7

Silver 

diethyldiihiocarbamate 

dry ignition

1

4 

2 

4 

3 

7 

4 

8 

5

Arsenic (ppm)

Sample 

No. 

(ADD-)

435......

433......

429......

434.......

432 .......

444.......

438 .......

440.......

446.......

Molybdenum blue 

wet ignition

........... 7

.. .. 9

........... 10

........... 12

15

........... 16

........... 18

...........28

Silver 

diethyldithiocarbamate 

dry ignition

7

9 

10 

9 

10 

16 

12 

18 

24

REFERENCES CITED

Bhargava, O. P., Donovan, J. F., and Hines, W. G., 1972, Rapid spectrometric determination of arsenic in iron and steel: Anal. Chemistry, v. 44, no. 14, p. 2402-2404.

Bowen, H. J. M., 1967, The determination of antimony, cadmium, cerium, iridium, 

and silver in biological material by radioactivation: Analyst, v. 92, no. 1091, p. 

118-123.

Burbank, W. S., Luedke, R. G., and Ward, F. N., 1972, Arsenic as an indicator element 

for mineralized volcanic pipes in the Red Mountains area, western San Juan Mountains, Colorado: U.S. Geol. Survey Bull. 1364, 31 p.

Delavault, R. E., and Manson, R. J., 1971, Spectroscopic determination of arsenic in 

geochemical samples, in Geochemical exploration (International Geochemical Exploration Symposium, 3d, Proc.): Canadian Inst. Mining and Metallurgy Spec. v. 

11, no. 11, p. 552-553.

Kingsley, G. R., and Schaffert, R. R., 1951, Microdetermination of arsenic and its application to biological material: Anal. Chemistry, v. 23, no. 6, p. 914-919.

Meinke, W. W., 1971, Standard reference materials for clinical measurements: Anal. 

Chemistry, v. 43, no. 6, p. 28A-47A.

Sandell, E. B., 1959, Colorimetric determination of traces of metals [3d ed.]: New York, 

Interscience Publishers, 1032 p.

Warren, H. V., Delavault, R. E., and Barakso, J., 1964, The role of arsenic as a pathfinder 

in biogeochemical prospecting: Econ. Geology, v. 59, p. 1381-1385.

Warren, H. V., Delavault, R. E., and Cross, C. H., 1967, Some problems in applied 

geochemistry, in Cameron, E. M., ed., Symposium on geochemical prospecting, 

Ottawa, 1966, Proc. (sponsored by Natl. Advisory Comm. on Research in the Geological Sciences): Canada Geol. Survey Paper 66-54, p. 253-264.
NEW AND REFINED METHODS OF TRACE ANALYSIS 

USEFUL IN GEOCHEMICAL EXPLORATION

FLAMELESS ATOMIC ABSORPTION METHOD

FOR DETERMINATION OF TRACE AMOUNTS

OF MERCURY IN VEGETATION

By JOHN B. McHuGH and ROBERT L. TURNER

CONTENTS

	Page

Abstract........................................................................................................................... 21

Introduction.................................................................................................................... 22

Laboratory reagents and apparatus................................................................................ 22

Reagents................................................................................................................... 22

Apparatus................................................................................................................. 23

Procedure........................................................................................................................ 24

Sample preparation...............................................................:................................. 24

Sample digestion..................................................................................................... 24

Standards preparation ............................................................................................. 24

Estimation of mercury............................................................................................. 24

Discussion of procedure.................................................................................................. 25

Results............................................................................................................................. 25

Recovery of added mercury ..................................................................................... 25

Precision .................................................................................................................. 26

Accuracy................................................................................................................... 26

References cited............................................................................................................... 27

TABLES

Page

TABLE 5. Absorbance obtained with known amounts of mercury............................... 25

6. Recovery of added mercury............................................................................ 25

7. Precision of determinations........................................................................... 26

8. Accuracy comparison..................................................................................... 26

ABSTRACT

Mercury is determined by a flameless atomic absorption procedure on solutions of 

vegetation which were obtained through digestion with sulfuric acid and hydrogen 

peroxide under controlled temperature conditions. Mercury is reduced to the elemental 

state, vaporized, passed through an absorption cell at a controlled rate, and vented.

21
22 TRACE ANALYSIS IN GEOCHEMICAL EXPLORATION

A detection limit of 25 parts per billion is achieved with good accuracy, and a precision 

of about 30 percent relative standard deviation. This method can be used to analyze 

as many as 25 samples per day.

INTRODUCTION

The analysis of vegetation and other organic-rich materials for mercury is useful in biogeochemical exploration, and exploitation of this 

use demands an analytical method with greater sensitivity than is now 

available. The length of the method is also a factor shorter methods 

usually prove to be more useful. Flameless atomic absorption methods 

are generally short and provide the needed sensitivity for mercury.

Although plants do not appear to be efficient in concentrating mercury from soils of medium mercury content (50-300 ppb), these same 

plants do accumulate high concentrations of mercury if their root systems are in contact with cinnabar or soils having a relatively high 

mercury content. Under these conditions, mineralized areas can be 

detected by measuring the mercury content of the vegetation (Shacklette, 

1970).

A single-extraction colorimetric method for determining mercury in 

vegetation was devised by Ward and McHugh (1964) and has proven 

useful in geochemical exploration. About 10 samples could be prepared 

and analyzed per day with a sensitivity of about 400 ppb. At that time, 

the speed and sensitivity were adequate, but recent demands for greater 

speed and sensitivity emphasized the need for a new method. Such 

demands are met in the atomic absorption methods and especially in 

those utilizing the flameless measurements; for example, those in which 

ground-state atoms of the sample are introduced as a vapor and not as 

a fine dispersion of sample solution. Using the flameless approach, 

Hatch and Ott (1968) devised the first of several methods which are capable of more than 5 times greater output at increased sensitivities of 

about 25 ppb. The procedure proposed here differs from that by Hatch 

and Ott primarily in the aeration of mercury vapor during absorption 

measurement. Our procedure is a single pass method, whereas the procedure of Hatch and Ott circulates the evolved mercury vapor through 

a closed system.

A method devised by Vaughn and McCarthy (1964), especially for 

determining mercury in soils and rocks, is capable of greater output and 

with increased sensitivity, 10 ppb, but organic material interferes; hence, 

the method is limited to materials with low organic content and cannot 

be used for vegetation.

LABORATORY REAGENTS AND APPARATUS

REAGENTS

Standard mercury solution (1,000 jug/ml): Dissolve 0.1354 g of mercuric 

chloride in 100 ml of 1 N sulfuric acid.
23

Standard mercury solution (100 jug/ml): Dilute 10.0 ml of 0.1 percent 

mercury solution to 100 ml with I'N sulfuric acid. Prepare fresh 

monthly.

Standard mercury solution (1 /ug/ml): Dilute 1.0 ml of 0.01 percent mercury solution to 100 ml with 1 N sulfuric acid. Prepare fresh weekly.

Hydrochloric acid, concentrated, reagent grade.

Hydrogen peroxide, 50 percent, reagent grade.

Hydroxylamine sulfate, reagent grade.

Potassium permanganate solution: Dissolve 5 g of potassium permanganate in 100 ml of demineralized water.

Sodium chloride-hydroxylamine sulfate solution: Dissolve 30 g each of 

sodium chloride and hydroxylamine sulfate in demineralized water 

and dilute to 1 litre.

Stannous chloride solution (10 percent): Dissolve 100 g of stannous 

chloride in 170 ml concentrated hydrochloric acid, dilute to 1 litre 

with demineralized water.

Sulfuric acid, concentrated, reagent grade.

Sulfuric acid, 1 N: Dilute 28 ml of concentrated sulfuric acid to 1 litre 

with demineralized water.

APPARATUS

Atomic absorption spectrophotometer, Perkin-Elmer, model 403 or

equivalent. 1 

Absorption cell, cylindrical cell, 100-mm length, 22-mm O.D., quartz

window, inlet and outlet ports to fit f 7/15 ground-glass joint. 

Reaction bottle, B.O.D. bottle, 300-ml capacity, with Coleman

model MAS-50 bubbler.

Water bath, Blue M Electric Co., model MW 1110A, 115 v, 50/60 cycle 

A.C., ambient to 100°C temperature range.

The Perkin-Elmer model 403 atomic absorption spectrophotometer 

was operated under the following parameters, as suggested for flame 

atomic absorption method (Perkin-Elmer Corp., 1968): 

Wavelength: 2,537A 

Slit: 3 (0.3 mm)

Lamp: Mercury hollow cathode run at 10 mA 

Air pressure and flow: 20 Ib/in2g on incoming line. Air is obtained 

by disconnecting the nebulizer oxidant tube from the atomic 

absorption unit and connecting this tube to the reaction bottle. 

Air flow is set at 1.8 litres/min by adjusting air pressure and flowmeter on the control box.

Absorption cell: The cell is secured to the 4-inch flat-top burner head 

with two rubber bands. The inlet port is attached to the reaction

'Use of a specific brand name does not necessarily constitute endorsement of the product by the U.S. Geological Survey.
24 TRACE ANALYSIS IN GEOCHEMICAL EXPLORATION

bottle with Tygon tubing and the exit port vented to the exhaust 

hood with Tygon tubing.

PROCEDURE 

SAMPLE PREPARATION

The freshly collected plants are dried 1 to 2 days at 35°C and ground 

in a Wiley mill to approximately 2 mm size.

SAMPLE DIGESTION

To a 150-ml beaker containing 2 g of dried and ground vegetation, 

add 25 ml concentrated sulfuric acid. After the sample is well coated 

by the acid, add about 30 ml of hydrogen peroxide in small increments, 

maintaining the temperature below 95°C during the addition. Upon 

completion of the peroxide addition, place sample in a constant-temperature water bath, set for 95°C, and allow sample to cook for about 

6 hours or until elimination of excess peroxide. Remove the sample from 

the water bath, cool slightly, and test for peroxide elimination by adding 

1 drop of potassium permanganate. Brown coloration, possibly accompanied by precipitation of manganese dioxide, indicates incomplete 

elimination of peroxide; if such occurs, return sample to water bath and 

continue heating until test shows complete elimination of peroxide. 

Finally, remove the sample from the water bath, cool slightly, and slowly 

add 75 ml demineralized water. Cool sample solution to room temperature.

STANDARDS PREPARATION

From the l-/ug/ml mercury standard, pipet 0, 0.1, 0.5, 1.0, and 3.0 

ml into a series of 150-ml beakers, each containing 25 ml concentrated 

sulfuric acid. To each beaker add one drop of hydrogen peroxide. Place 

the standards in the constant-temperature water bath for 30 minutes at 

95°C. Remove the standards from the water bath, cool slightly, and 

slowly add 74 ml of demineralized water. Proceed with estimation of 

mercury.

ESTIMATION OF MERCURY

Estimation of mercury is the same for standards and samples.

To the cooled solutions, add potassium permanganate solution, 

stirring until a pink coloration persists. Add 20 ml sodium chloridehydroxylamine sulfate solution to each. Pour the solution into the reaction bottle, add 10 ml stannous chloride solution, mix well, and attach 

the aerator. Begin the aeration of the solution using the air-pressure 

tube from the atomic absorption instrument. Maximum absorption 

values are recorded for both standards and samples. The preparation 

and estimation of standards and samples should be done on the same 

day.
MERCURY IN VEGETATION 25

DISCUSSION OF PROCEDURE

The rate of air flow through the reaction system must be known and 

calibrated on a particular unit and must be maintained at a constant 

rate for all standards and samples. The air-flow rate for the system in 

this experiment which produced a maximum absorbance is 1.8 1/min. 

A faster air-flow rate produces a lower absorbance because the mercury 

vapor passed through the absorption cell too fast for the meter to respond 

properly. A slower air-flow rate produces a dilution of the mercury vapor 

by pushing smaller portions of vapor per unit of time through the absorption cell. The slower rate produces a lower maximum reading. Note 

that the data in table 5 are unique for this particular system and will 

vary due to the total free air volume of the system.

TABLE 5. Absorbance obtained with known amounts of mercury

Mercury (fig) Absorbance

0.0....................................................................................0.006

.1.................................................................................... .023

.2.................................................................................... .044

.5.................................................................................... .097

1.0.................................................................................... .183

2.0.................................................................................... .350

3.0.................................................................................... .500

The temperature of standard and sample solutions must be maintained at 95°C during digestion. Experiments were run with standard 

solutions digested at temperatures ranging from 80° to 145°C. At 145°C, 

70 percent of the mercury was lost. At 125°C, 50 percent of the mercury 

was lost. At 95° and 80°C there was no detectable mercury loss. Digestion 

of the samples was slower at 80°C than at 95°C; therefore, the latter temperature was found to be the most advantageous. The samples are heated 

to 95°C in the water bath after the plant material has been destroyed 

and are maintained at this temperature for 30 minutes, or until the excess 

hydrogen peroxide has been broken down.

RESULTS 

RECOVERY OF ADDED MERCURY

To test our procedure, a given amount of mercury was added to three 

different portions of three plant samples, and the portions were analyzed. 

The results are shown in table 6.

TABLE 6. Recovery of added mercury

[Three determinations on each sample]

X-5..

NA-5 ..

NA-2 ..

Plant 

Sample 

No.

Merrury found in 

plant sample

(US)

0.025

.55

1.60

Total amount of mercury 

standard added to 

plant sample 

(Mg)

0.10

1.0

1.0

Mercury found in plant 

sample after 

standard addition 

(Mg)

0.15

1.58

2.60
26 TRACE ANALYSIS IN GEOCHEMICAL EXPLORATION

PRECISION

The precision of our procedure was found by analyzing 6 samples 

5 times each. The results are given in table 7. In the table the data under 

the column head "absorbance" are given in terms of absorbance units 

in order to include the less-than values on the last two samples of mesquite and cottonwood. The range in concentration, expressed in parts 

per million, corresponding to these absorbance values is included in 

table 4 under the column head "Atomic Absorption Method."

The relative standard deviations ranged from 5.4 to 33.9 percent, and 

such precision compares favorably with that of an earlier dithizone procedure (Ward and McHugh, 1964).

TABLE 7. Precision of determinations

Sample 

No

NA-1 .......

NA-2.......

NA-S .......

NA-5 .......

X-5 .......

X-6 .......

Plant name and

.... ...do............ .......................

.... ...do. ..................................

Absorbance 1

Range

0.246-0.317 

.243-0.290 

.474-0.544 

.046-0.086

.006-0.012 

.006-0.017

Mean

0.283 

.261 

.511 

.065

.010 

.014

Relative standan 

deviation 

(percent)

9.6

7.8 

5.4 

24.8

25.0 

33.9

i Mean 

(ppm)

1.4 

1.2

2.9

.4

.025 

.025

ACCURACY

The accuracy of the proposed procedure was tested by comparing the 

results obtained on four samples with those obtained earlier by the dithizone procedure. The results are given in table 8.

TABLE 8. Accuracy comparison 

[Five determinations on each sample]

Sample

No.

NA-1 .......

NA-2 .......

NA-3 .......

NA-5 .......

Plant 

name

.... ...do...... ..................

.... ...do........................

Dithizone method 

(ppm)

Range 

of values

........... 1.6-2.2

1 9-1 8

2 3-2 7

........... .4-0.7

Mean

1.8 

1.2 

2.5 

.6

Atomic absorption method 

(ppm)

Range 

of values

1.2-1.6 

1.1-1.4 

2.7-3.1 

.3-0.5

Mean

1.4 

1.2 

2.9

.4

A range of values obtained on each sample by both procedures is considered to be more meaningful than a single number simply because 

of the small amounts of mercury present in these materials. Despite the 

handicap of working with nearly mercury-free samples, the recovery data,
MERCURY IN VEGETATION 27

the precision data, and the comparison data attest to applicability and 

usefulness of our procedure.

Although the procedure and equipment described have proved useful 

in acquiring the sort of data given in this paper, other commercially 

available equipment, such as the Perkin-Elmer mercury analyzer, is 

equally useful and, indeed, preferable if available.

REFERENCES CITED

Hatch, R. W., and Ott, W. L., 1968, Determination of sub-microgram quantities of

mercury by atomic absorption spectrophotometry: Anal. Chemistry, v. 40, no. 14,

p. 2085-2087. 

Perkin-Elmer Corp., 1968, Analytical methods for atomic absorption spectrophotometry:

Norwalk, Conn., Perkin-Elmer Corp., 522 p. 

Shacklette, H. T., 1970, Mercury content of plants, in Mercury in the environment:

U.S. Geol. Survey Prof. Paper 713, p. 35-36. 

Vaughn, W. W., and McCarthy, J. H., Jr., 1964, An instrumental technique for the

determination of submicrogram concentrations of mercury in soils, rocks, and gas,

in Geological Survey research 1964: U.S. Geol. Survey Prof. Paper 501-D, p.

D123-D127. 

Ward, F. N., and McHugh, J. B., 1964, Determination of mercury in vegetation with

dithizone A single extraction procedure, in Geological Survey research 1964: U.S.

Geol. Survey Prof. Paper 501-D, p. D128-D130.

NEW AND REFINED METHODS OF TRACE ANALYSIS 

USEFUL IN GEOCHEMICAL EXPLORATION

ATOMIC ABSORPTION DETERMINATION 

OF MOLYBDENUM IN PLANT ASH

By H. M. NAKAGAWA, J. R. WATTERSON, and F. N. WARD

CONTENTS

Page

Abstract........................................................................................................................... 29

Introduction.................................................................................................................... 30

Reagents and apparatus.................................................................................................. 31

Working standard solutions.................................................................................... 31

Optimum working range........................................................................................ 32

Operating conditions............................................................................................... 32

Procedure........................................................................................................................ 32

Results............................................................................................................................. 32

References cited............................................................................................................... 35

TABLES

Page

TABLE 9. Absorbance of standard molybdenum solutions......................................... 33

10. Repeatability of molybdenum determinations in ash of trees arid

plants........................................................................................................ 33

11. Molybdenum in plant ash, Death Valley, Calif.......................................... 34

12. Molybdenum in plant ash, Catheart Mountain, Maine............................. 34

ABSTRACT

Trace amounts of molybdenum in plant ash are determined by atomic absorption 

spectrometry after sample breakdown with hot hydrochloric acid. The molybdenum 

is extracted into MIBK (4-methyl-2-pentanone) and atomized into a nitrous oxideacetylene flame. With a threefold scale expansion and a limited volume of extractant, 

as little as 0.1 part per million of molybdenum in the ash can be measured with relative 

standard deviations of 5-10 percent. Such sensitivity is comparable to that of existing 

colorimetric procedures, and this feature plus the attainable speed and simplicity of 

the method commends the atomic absorption method to widespread application in biogeochemical prospecting.

29
30 TRACE ANALYSIS IN GEOCHEMICAL EXPLORATION

INTRODUCTION

During the last decade or two Warren and Delavault (1965) in Canada, 

and Kovalevskii (1969) and Malyuga (1958) in the U.S.S.R., and perhaps 

others, have established the usefulness of the molybdenum content of 

vegetation as a diagnostic parameter in biogeochemical exploration. 

Trees and smaller plants take up varying amounts of molybdenum depending on several factors which include species, soil conditions, and 

availability of molybdenum to plant roots, for example, from molybdenum-bearing bedrock and outcrops.

Because the molybdenum content of trees and plants is small, it is 

moderately difficult to measure. Initially, such amounts were measured 

in the plant ash by optical emission spectrographic methods requiring 

precision instruments and skilled analysts, which, in turn, limited the 

analytical output and hindered widespread application to biogeochemical prospecting. In time, colorimetric procedures, simpler methods of analysis based on the reaction of molybdenum with a color-forming 

reagent both inorganic and organic were developed to supplement 

the optical emission methods (Reichen and Ward, 1951; Stanton and 

Harwick, 1967).

The availability and dependability of both types of determinations 

of molybdenum in plant ash provided a choice for the prospector who 

depended chiefly on knowledge gained by experience. For example, the 

optical emission methods were used by Brooks and Lyon (1966) to determine molybdenum in plant ash, and these methods seem to be preferred 

by most Soviet workers; a colorimetric procedure, however, was used 

by Griffitts and Ward (1970) when the analyses had to be made in the 

field.

Colorimetric and optical emission methods of determination of 

molybdenum in plant ash have generally proved adequate for the problems at hand. Gradually, these procedures are being replaced with 

atomic absorption methods in geochemical and biogeochemical exploration for elements, such as copper, zinc, and manganese. This trend 

has not been so pronounced for molybdenum, partly because of the 

relatively poor sensitivity of molybdenum in an air-acetylene flame. 

David (1961) achieved a sensitivity of 3 jug/ml of molybdenum for 1 

percent absorption using a fuel-rich air-acetylene flame. Later, Mostyn 

and Cunningham (1967) attained a sensitivity of slightly more than 1 

ppm for 1 percent absorption.

The luminosity of the fuel-rich flame produces a high background 

radiation that affects the responsive surface of the photomultiplier 

cathode and causes operator fatigue (Kirkbright, Peters, and West, 1966; 

Kirkbright, Smith and West, 1966). The latter workers adopted a suggestion of Willis (1965) and used a nitrous oxide-acetylene flame that 

not only provided better sensitivity but exhibited fewer interferences^ 

notably the depressive effect of phosphate on calcium.
MOLYBDENUM IN PLANT ASH 31

Initially, nitrous oxide-acetylene flames showed a tendency to frequent 

flashbacks. Most instrument manufacturers have now developed means 

to minimize the danger of flashbacks. Because of this improvement in 

technology, chemists are less reluctant to use nitrous oxide-acetylene 

flames for refractory elements, such as molybdenum. The nitrous oxideacetylene flame has the advantage of a higher temperature than airacetylene without the greater flame velocity of oxyacetylene flames.

Our atomic absorption procedure is potentially a good replacement 

for the existing colorimetric method because of its suitability to larger 

batch-type operations and because of the achievable sensitivities.

Analysts in our laboratory use a nitrous oxide-acetylene flame and 

a threefold scale expansion. They routinely achieve a sensitivity of about 

0.05 ju g of molybdenum for 1 percent absorption, with minimum effort 

to optimize the atomic absorption measurement. With a 1-g sample of 

plant ash and 5 ml of MIBK as suggested in our procedure, the conversion factor is 5, and as little as 0.25 ppm molybdenum in plant ash 

can be determined. If the molybdenum is extracted into 2 ml of MIBK, 

which is about the minimum volume needed for measurement, as little 

as 0.1 ppm molybdenum in the ash can be determined.

REAGENTS AND APPARATUS

Molybdenum standard solution, 100 ppm. Prepare by dissolving 0.075 

g pure molybdic anhydride in 10 ml of 1 M sodium hydroxide, dilute 

with water, add 1 M hydrochloric acid drop by drop until solution 

is slightly acid, then dilute to 500 ml with 6 M hydrochloric acid.

Molybdenum standard solution, 10 ppm. Prepare by diluting 10 ml of 

the 100-ppm standard to 100 ml with 6 M hydrochloric acid.

Molybdenum standard solution, 1 ppm. Prepare by diluting 10 ml of 

the 10-ppm standard to 100 ml with 6 M hydrochloric acid.

Hydrochloric acid, concentrated.

Hydrochloric acid, 6 M. Mix equal volumes of concentrated acid and 

demineralized water.

Sodium hydroxide, 1 M. Prepare by dissolving 4 g of reagent in 100 ml 

of demineralized water.

MIBK, reagent grade.

Test tubes, screwcap, 16 by 150 mm.

Hotplate.

Beakers, 50-ml capacity.

Pipets, 5 ml.

Centrifuge useful but not essential.

Atomic absorption instrument, Perkin-Elmer model 303 or equivalent.

WORKING STANDARD SOLUTIONS

1. Using 100-ppm molybdenum solution, pipet 0.5-, 0.25-, and 0.1-ml 

aliquots into 16- by 150-mm screwcap tubes each containing 10
32 TRACE ANALYSIS IN GEOCHEMICAL EXPLORATION

ml of 6 M hydrochloric acid. Add 5 ml MIBK, cap and shake tube 

for 1 minute. Allow phases to separate and atomize upper layers 

of each tube to calibrate instrument. Upper layer in each tube contains, respectively, 10, 5, and 2 ppm molybdenum.

2. Using 10-ppm molybdenum solution, pipet 0.5-, 0.25-, and 0.1-ml 

aliquots into 16- by 150-mm screwcap tubes each containing 10 

ml 6 M hydrochloric acid and proceed as in solution 1. Upper 

layers contain respectively 1, 0.5, and 0.2 ppm molybdenum.

3. Using 1-ppm molybdenum solution, pipet 0.5-, 0.25-, and 0.1- ml 

aliquots into 16- by 150-mm screwcap tubes each containing 10 

ml 6 M hydrochloric acid and proceed as in solution 1. Upper 

layers contain, respectively, 0.1, 0.05, and 0.02 ppm molybdenum.

OPTIMUM WORKING RANGE

Ix 0.2-10 ppm. 

3 x 0.02-1 ppm.

OPERATING CONDITIONS

Wavelength: 313. 3 nm.

Source: HC.

Lamp Current: 30 mA.

Slit: 4 (0.7 nm).

Flame: Nitrous oxide-acetylene, reducing (rich red).

PROCEDURE

1. Place a weighed sample up to 1.0 g in a 50-ml beaker and add 3 ml 

concentrated hydrochloric acid. Place beaker on hotplate and at 

moderate heat evaporate concentrated acid to dryness.

2. Remove beaker from hotplate, cool, and add 5 ml of 6 M hydrochloric 

acid. Return beaker to hotplate and warm for few minutes.

3. Transfer contents of beaker to a 16- by 150-mm screwcap tube and 

wash beaker with 5 ml of 6 M hydrochloric acid. Add wash acid 

to the tube.

4. Add 5 ml MIBK to tube, cap, and shake tube for 1 minute.

5. Let tube stand or centrifuge to separate the phases. Aspirate the clear 

upper layer into a nitrous oxide-acetylene flame of an atomic absorption instrument.

6. Measure the molybdenum concentration after calibration of the 

instrument with working standard solutions and observing the recommended operating parameters.

RESULTS

Under the conditions in our laboratory we measured absorbances, as 

shown in table 9. These values are indicative of the sensitivity achieved
33

TABLE 9. Absorbance of standard molybdenum solutions

[Leaders (...) indicate measurement not made]

Molybdenum

(jUg/ml)

0.02

.05

.1

.2

.5

1.

2.

5.

10.

None

0.0044

.0088

.0223

.0419

.0851

.2048

.3979

Scale expansion

Threefold

0.0015

.0029

.0058

.0107

.0252

.0480

in a routine situation, but under different conditions the actual sensitivities achieved will differ slightly.

The precision of our procedure was established by repeat determinations of molybdenum in the ash of fir, alfalfa, and desertholly (table 

10). Generally, the relative standard deviations are in the order of 5-10 

percent. The value on sample CR-9 probably results from fortuitous 

circumstances and does not seem to signify a trend to lower relative 

standard deviations with higher levels of molybdenum.

TABLE 10. Repeatability of molybdenum determinations in ash of trees and plants

Molybdenum (ppm)

Sample

No.

CRT-48.....

A-4 ............

A-2 .............

A-3 ............

A-l ............ 

A-5 ............. 

CR-9..........

P-26............

Name

. Fir...............

. Alfalfa.........

. ...do.............

. ...do.............

. ...do............. 

. ...do............. 

. Fir...............

Desertholly..

Low

0.50 

19' 3 6 

23 

35 

45 

125 

250

High

0.65 

5.0 

23 

26 

39 

51 

130 

300

Mean

0.60 

4.2 

20.7 

24.5 

36.2 

48.2 

128 

270

Standard 

deviation

0.05 

.4 

1.4 

1.2 

1.5 

2.8 

2.7 

19.2

Relative 

standard 

deviation, 

(percent)

8.3 

9.5 

6.8 

4.9 

4.1 

5.8 

2.1 

7.1

The accuracy and validity of this atomic absorption method were 

established by comparing the results with those obtained earlier by 

colorimetric and spectrographic methods, as shown in tables 11 and 12. 

The colorimetric procedures differ primarily in the method of sample 

attack (methods are described in the footnotes of the tables). The validity, 

sensitivity, and production potential of this procedure are characteristics 

that suggest its use in a service function, where results are the chief objective and methods development is of secondary consideration.
34 TRACE ANALYSIS IN GEOCHEMICAL EXPLORATION

TABLE 11. Molybdenum in plant ash, Death Valley, Calif.

Sample

No

P-l........ .............

P-3

P-7...... ...............

P-9...... ...............

P-12......... ..........

P-I7...................

P-6.... .................

P-ll......... ..........

P-5...... ...............

P-4...... ...............

Name

... Rush.................

... Desertholly........

... Arrow weed........

... ...do..... ..............

Emission 

spectrographic 

method1

5

5

5

7

7

10

20

20

50

50

Molybdenum (ppm)

Colorimetric 

method2

6

4

6

8

16

12

16

24

32

48

Atomic absorption 

(this paper)

5

2

4

6

10

8

18

26

25

32

"Analyses made in 1961 by Uteana Oda.

2Analyses made by colorimetric method in 1961 by H. M. Nakagawa using a lithium nitrate fusion of plant 

ash, followed by solution in hot dilute hydrochloric acid.

TABLE 12. Molybdenum in plant ash, Catheart Mountain, Maine

No.

CRT-47...................

CR-12......................

CR-11. ...... ............ ...

CR-10. .....................

CRT-28...................

CR-9.........................

CRT-39....................

CR-8.........................

CR-7.. ...... ..........:.....,

CR-6.........................

CRT-29....................

CR-5.. .......................

CRT-31....................

CRT-37. ...... ............ .

CR-19.......................

 j

Colorimetric 

method1

Fir

4

60

140

200

240

Spruce

20

20

4

ilolybdenum (ppm)

Colorimetric 

method2

3

5

60

120

150

150

230

230

10

15

20

40

150

5

Atomic absorption 

(this paper)

<0.4

4

4

58

113

130

175

200

240

6

15

20

48

160

2.2

! Hot hydrochloric acid digestion of samples; analyses made in 1968 by C. S. E. Papp. 

2Bisulfate fusion of samples; analyses made in 1970 by G. A. Nowlan.
MOLYBDENUM IN PLANT ASH 35

REFERENCES CITED

Brooks, R. R., and Lyon, G. L., 1966, Biogeochemical prospecting for molybdenum 

in New Zealand: New Zealand Jour. Sci., v. 9, no. 3, p. 706-718.

David, D. J., 1961, The determination of molybdenum by atomic-absorption spectrophotometry: Analyst, v. 86, p. 730-740.

Griffitts, W. R., and Ward, F. N., 1970, Observations on the geochemistry of molybdenum at Eagle Mountain, Guyana, in Geochemical prospecting methods and 

techniques seminar, 2d, 1970, Proc., Mineral Resources Development Ser. 38, 

Economic Commission for Asia and the Far East: United Nations [N.Y.], p. 166-169.

Kirkbright, G. F., Peters, M. K., and West, T. S., 1966, Determination of small amounts 

of molybdenum in niobium and tantalum by atomic-absorption spectroscopy in 

a nitrous oxide-acetylene flame: Analyst, v. 91, p. 705-708.

Kirkbright, G. F., Smith, A. M., and West, T. S., 1966, Rapid determination of molybdenum in alloy steels by atomic-absorption spectroscopy in a nitrous oxide-acetylene 

flame: Analyst, v. 91, p. 700-704.

Kovalevskii, A. L., 1969, Biogeochemical prospecting for molybdenum [in Russian]: 

Geol. Geofiz., no. 9, p. 124-126.

Malyuga, D. P., 1958, An experiment in biogeochemical prospecting for molybdenum 

in Armenia: Geochemistry, no. 3, p. 314-337.

Mostyn, R. A., and Cunningham, A. F., 1967, Determination of antimony by atomicabsorption spectrometry: Anal. Chemistry, v. 39, no. 4, p. 433-435.

Reichen, L. E., and Ward, F. N., 1951, Field method for the determination of molybdenum in plants: U.S. Geol. Survey Circ. 124, 4 p.

Stanton, R. E., and Harw.ick, A. J., 1967, Colorimetric determination of molybdenum 

in soils and sediments by zinc dithiol: Analyst, v. 92, p. 387-390.

Warren, H. V., and Delavault, R. E., 1965, Further studies of the biogeochemistry of 

molybdenum: Western Miner, v. 38, no. 10, p. 64-72.

Willis, J. B., 1965, Nitrous oxide-acetylene flame in atomic-absorption spectroscopy: 

Nature, v. 207, p. 715-716.