Notes
Suspended marine clay mineral identification by scanning
electron microscopy and energy-dispersive X-ray analysis
Abstract-A technique enabling qualitative
identification of clay mineral species com-
monly found in marine environments,
particle-by-particle basis, permits
microscopic and X-ray analysis examination
of specific clay particles, without
either their morphology or association,
membrane ultrafilters containing
0.2 mg of particulate matter.
Investigators of marine suspended mat-
ter have long recognized the importance of
characterizing both the morphology and
the geochemical composition of its constit-
uent particles. Unfortunately, the standard
techniques used required separate sample
preparations for optical examination and
chemical analysis (Jackson 1956). Quanti-
tative clay-mineral study by X-ray dif-
fraction methods requires the filtration of
several hundred liters (Jacobs and Ewing
1965; Birks et al. 1966). Recently, with
the advent of high-resolution scanning elec-
tron microscopes (SEM) coupled with en-
ergy-dispersive X-ray analyzers (EDXR), it
has become possible to do simultaneous
morphological and elemental studies. With
few exceptions, clay minerals cannot be
identified by morphology alone. The tech-
nique of combined morphologic and X-ray
analysis allows characterization of clay
mineral composition without the need of
large volume or multiple sampling and
eliminates the necessity of separate prep-
arations for morphology and mineralogy.
This paper presents the first application of
SEM/EDXR capabilities to the study of
suspended marine clay.
Energy-dispersive X-ray is a semiquanti-
tative microanalytical technique for the
identification of elemental composition.
The impinging electron beam excites the
samples, and discrete quanta of energy,
termed characteristic radiation (X-rays), are
emitted. The characteristic X-rays of the
elements vary systematically according to
their atomic number and appear as peaks
against the background level. A complete
133
discussion of energy-dispersive analysis is
given by Russ ( 1971).
on a
electron I am indebted to E. L. Thurston and the
staff of the Texas A & M University Elec-
affecting tron Microscopy Center for their help. Por-
on tions of this work were funded by a grant
as little as
from the Dean’s Fund, Northern Illinois
University.
Total suspended matter was sampled
throughout the water column in the central
Caribbean Sea. Seawater was collected in
30-liter Niskin bottles and pressure filtered
through Millipore membrane ultrafilters of
0.45pm nominal pore size (Fig. 1). A com-
plete description of the sampling procedure
is given in Bassin et al. (1972) and Harris
( 1972). In the laboratory, a piece of each
filter was mounted on a brass stub with
silver paint and then coated with carbon
and gold-palladium alloy. Examination was
made with a JEOL JSM-U3 SEM and cou-
pled EDAX model 5 energy-dispersive X-
ray analyzer.
Low magnification ( 1,000-3,000X ) was
used for a quick overview of the sample.
Usually there is a significant amount of
overlap between particles, resulting from
the filtration. During subsequent X-ray, it
is necessary to avoid such particles in order
not to have spurious results due to un-
derlying particles. Figure 2 illustrates this
problem, as well as showing the spectrum
of particle types encountered. When a
cIay particle is seen, magnification is in-
creased to fill the area of the viewer (7,000-
10,000~), and a photograph is taken. The
instrument is then switched from scanning
to EDXR mode and the scanning area
reduced to the maximum enclosed square
within the particle, as shown by the in-
scribed squares in Figs. 3-5. The particles
were analyzed for 400 set at 15 kV.
After each particle analysis, an equiva-
lent area of a nearby section of the stub
that is free of particulates is X-rayed and
the data are stored in a computer. Back-
ground counts of silver, gold, palladium,
 Notes 135

nizable. From the original peak height, a

Fig. 5. Sample 177-28, talc.
sium, silicon, aluminum, calcium, iron, and
other elements may be semiquantitatively
evaluated.
Elements were identified using energies
of the principal emission lines for each by
referring to a published chart (Nuclear Di-
odes 1971). Total counts for each element
represent the integrated area under the dis-
tribution curve and are therefore propor-
tional to the concentration of the element.
Often, however, a broad peak may mask
the presence of a smaller one with similar
energy. When this occurs the larger peak
is skewed, and the effect therefore recog-
gaussian curve is generated on the com-
puter for each main peak and is then
stripped from the original. This leaves a
smaller peak resulting from a masked ele-
ment. The area of the generated peak is
taken to be the true amount of that ele-
ment in the particle, and this process is
continued until the remaining small peak
is gaussian and identified. The amplitudes
of the new peaks revealed by spectral
stripping are proportional to the originals
and may be apportioned directly in the
elemental ratios.
Table 1 lists the clay analysis for each of
the three samples by element, peak energy,
total count, and the ratio of each element
to silicon: the last is simply the percentage
of each elemental count to that of silicon.
This system is superior to total percentage
because it does not include the lighter ele-
ments, and remnant background noise may
be safely ignored. Table 2 lists the sili-
con-normalized elemental ranges of known
clays common in the ocean, compiled from
published chemical analyses ( Grim 1968).
By direct comparison of the unknowns with
these controls the mineral species can be
identified.
The analytical precision of the EDXR
was reported by Russ (1972) to have a
standard deviation of *0.67%, and a mini-
mum detectable limit of lo-l3 g.
It is rare for a clay to have precisely its
theoretical composition. Isomorphic substi-

Table 1. Energy-dispersive X-ray analyses of three clay particles. “Ratio” is the proportion of each
element to silicon, normalized to 100.

177-26 177-27 177-28

Element Energy counts ratio counts ratio counts ratio

1.74 28,736 100 54,659 100 476,537 100

i; 1.49 9,065 31.5 23,886 43.7 -- --
Fe 6.40 8,132 28.3 1,973
Mg 1.25 5,165 18.0 14,036 2;:; 357,oG Y4.9
Ca 3.69 5,625 19.6 877 1.6 -- --
Na 1.04 500 1.7 -- -- -- --
K 3.31 629 2.2 -- -- 472 Tr
Ti 2.27 2,821 9.8 3,830 7.0 642 0.1
Cr 5.41 1,637 5.7 -- -- -- --
Ni 7.47 197 0.7 -- -- -- --
Zn 1.01 -- -- 269 0.5 -- _-
RE mixed 4,671 8.5 -- --
136 Notes

Table 2. Elemental ranges from common marine clays, as a ratio to silicon (after Grim 1968).

Illite Kaolinite Chlorite Vermicul. Montmoril. Nontronite Saponite

max min max min max mi n max min max min max min max min
Al 58.8 17.4 84.4 55.2 98.3 47.3 46.4 29.7 62.7 32.3 26.5 8.2 24.1 18.5
Fe 57.3 3.7 3.7 0.7 224.1 37.7 10.2 12.7 0.1 78.0 40.9
Mg 16.8 2.7 1.0 0.0 119.7 10:; 68.8 54.1 13.0 4.5 4.8 Tr 5:'; 5ZT;
Ca 3.2 0.0 2.3 0.3 14.0 0': 12 00 63 20 47 00 4'5 1'4
Cr __ __ __ __ 5.2 1- -1 I, -1 I- ,I 1, -1
Na 2.8 0.0 0.9 0.0 -- -: -- -- -- -- -- --
K 17.1 7.9 3.2 0.0 -- --
Ti 12.5 0.0 4.9 0.0 -- -- 0:; ;:O 0:; 010
Ni __ __ __ -- __ __ 6.3 0.0 _- -- -- -- -- -.

tution of aluminum for silicon in the tetra- nesic bedeillite [ (OH)~(Si6.3~A11.66)Al~O~~]:

hedral layer is common, as well as replace-
ment of aluminum in the octahedral layer
by magnesium, calcium, iron, titanium, etc.
The presence of interlayer cations such as
potassium, calcium, and rare earths makes
individual chemical formulation tenuous.
With these dangers in mind, mineralogic
identifications of the unknowns are detailed
below.
Sample 177-26 (Fig. 3) most nearly fits
the elemental composition of illite.
though its aluminum concentration is simi-
lar to that of illite, vermiculite, or mont-
morillonite, its iron content is too high for
montmorillonite, and its magnesium too low
for vermiculite. The illite (mica) minerals
are isomorphs of the theoretical mineral
(OH).&( SiAl)sA1,OZ,j. Grim (1968) stated
that poorly crystallized micas are likely to
have about 15% replacement of aluminum
for silicon in the tetrahedral layer, and cal-
cium, titanium, sodium, etc. may replace
potassium in the interlayer. The elements
in sample 177-26 may be distributed as fol-
lows, preserving the chemical integrity of
an illite: interlayer-( Car .ZK,j.INao.lTio.~;) 2;
tetrahedral layer-(Si F.3-1A11.6(i)X; octahedral
layer-( Mg1.1Fet.xAl(,.~Cr,,.~)~.
Sample 177-27 (Fig. 4) has aluminum
values which could make it either illite or
smectite (montmorillonite) while its mag-
nesimll puts it within range of only the
smectites. The smectites are the most
difficult to analyze because of the vast
amount of chemical substitution and the
wide ranges permitted to each element.
Sample 177-27 (Fig. 4) is probably an al-
tered dioctahedral smectite, perhaps a mag-
tetrahedral layer-(Sis.c;r;A11.3&; octahedral
layer: (All.nMg,.,Feo.2Cao.1Tio.4Zno.lREo.4)4.
Talc, with the formula OH&MgGOzo is
one of the easiest clay minerals to identify
by composition. Sample 177-28 (Fig. 5),
with only trace amounts of potassium and
titanium, is composed entirely from silicon
and magnesium : tetrahedral layer-( Si) 8;
octahedral layer-( Mg,.:,Ti, Kc)., )(j.
Although clay minerals can be recog-
Al- nized by their characteristic aluminumo-
silicate nature, precise formulation of clay
mineral composition is difficult from chem-
istry alone. A combination of energy-dis-
persive X-ray analysis and morphological
study effectively serves to differentiate be-
tween biogenic (carbonates and amorphous
silicates) and nonbiogenic (mineralogic)
constituents of marine suspended matter.
N. Jay Bassin
Department of Oceanography
Texas A & M University
College Station 77843
Refe re rices
BASSIN, N. J., J. E. HARRIS, ASD A. H. BOUMA.
1972. Suspended matter in the Caribbean
Sea: A gravimetric analysis. h4ar. Geol. 12:
h1l-5.
BIRKS, L. S., J. S. GROSSO, R. J. LAURIE, J. W.
SANDELIS, AND D. J. i%\;AGEL. 1966. Charac-
terizatiou of particulate matter in the ocean.
U.S. Na\~l Res. Lab. Rep. 6398, p. l-20.
Gmi, R. E. 1968. Clay mineralogy, 2nd ed.
h4cGraw-Hill.
HARRIS, J. E. 1972. Characterization of sus-
pended matter in the Gulf of Mexico-l.
Spatial distribution of suspended matter.
Deep-Sea Res. 19: 719-726.
 Notes 137

JACKSON, M. L. 1956. Soil chemical analysis, ysis on the scanning electron microscope, p.
advanced course. M. L. Jackson, Soils Dep. 154-179. In Energy dispersion X-ray analy-
Univ. Wis., Madison. sis and electron probe analysis. Am. Sot.
JACOBS, M. B., AND M. EWING. 1965. Mineral- Testing Mater. Spec. Pub. 48.5.
ogy of particulate matter suspended in sea -. 1972. Elemental X-ray analysis of ma-
water. Science 149: 179-180. -terials. EDAX Lab., Raleigh, N.C. 89 p.
NUCLEAR DIODES. 1971. EDAX peak identifica-
tion chart. EDAX Lab., Raleigh, N.C. 7 p. Submitted: 22 March 1974
Russ, J. C. 1971. Energy dispersion X-ray anal- Accepted: 24 September 1974

A continuous turbidity monitoring system

for coastal surface waters1
Abstract-A continuous, time-referenced
turbidity monitoring system utilizes a keel
mounted optical transmissometer with a mod-
ified strip chart recorder; it allows detailed
study of the distribution of suspended par-
ticles in surface waters.
It is of interest to measure turbidity
continuously in surface waters of channels,
bays, and estuaries. Drake ( 1972) used an
in situ optical transmissometer to monitor
turbidity for his studies of the distribution
and transport of suspended matter in the
Santa Barbara Channel. Ludwick and Mel-
char (1972) clearly demonstrated the value
of spot-monitoring turbidity with an opti-
cal transmissometer by delineating many
circulation patterns in the mouth of Chesa-
peake Bay. We have extended the use of
the optical transmissometer for surface cir-
culation studies by coupling the instrument
to the keel of a research vessel so that
turbidity can be monitored continuously
over a short time, providing a way of re-
solving small-scale surface circulation struc-
ture over a wide area if repeated traverses
of the area are made. Such small-scale sur-
face circulation studies have been almost
impossible with spot turbidity measure-
ments, and we have found no similar
system reported in the literature. The con-
tinuous surface turbidity monitoring sys-
tem can be used by itself or to complement
’ This work was supported in part by the Na-
tional Aeronautics and Space Administration, Earth
Resources Technology Satellite programs, contract
NAS 5-21816, MMC 299-2.
the traditional technique of spot measure-
ments by vertical casts.
We wish to express our appreciation to
J. C. Ludwick and J. R. Melchor for their
advice and assistance on the instrument
modifications, to T. Gardner for technical
help in metal fabrication, and to R. Bray
and the crew of the RV Linwood Ho&on
for shipboard assistance.
To continuously monitor turbidity we
have devised a system that couples a modi-
fied dual-beam optical transmissometer
probe and an automatic null-balancing cir-
cuit with a modified strip chart recorder.
It is operated aboard a research vessel on
which the transmissometer probe is keel
mounted so that it will pass through an un-
disturbed portion of the top surface layer
(Fig. 1).
We measure turbidity with a Bendix/Ma-
rine Advisers C-2 transmissometer probe.
This instrument gives a direct indication
of light transmittance in water, the degree
of light attenuation with a fixed-beam path-
length, expressed generally as the attenu-
ation coefficient, ac, where
1
In (transmittance)
a! = - (beam path-length)
for a homogeneous medium. The beam
path-length of our probe has been reduced
from the standard 1 m to 0.430 m to make
it operable in the turbid waters character-
istic of the Chesapeake Bay and other es-
tuarine environments. Figure 2 shows the
optical construction of the probe. Only