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Spectrophotometry: Turbidimetry and

nephelometry

Chapter December 2005

DOI: 10.1016/B0-12-369397-7/00718-4

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 SPECTROPHOTOMETRY / Turbidimetry and Nephelometry 343
possible as the differentiation is dened un-
changeable by the resistor and the capacitor of the
differentiating circuit [7].
Analogous to the adjustment of the window width,
different modulation amplitudes a [8] can be chosen
in optical derivative spectroscopy. According to [12],
larger derivative signals and hence better signal-
to-noise ratio can be gained by increasing a. This was
conrmed experimentally; however, a signal increase
comes along with a washing out of derivative shapes
and minute derivative features are lost (Figure 7).
The values for the modulation amplitude given in
Figure 7 are typical examples. Thus, the modulation
amplitude can be optimized for different applica-
tions: if several analytes in mixtures have very similar
and overlapping absorption spectra, a small modu-
lation amplitude helps to pronounce minor differ-
ences for discrimination. If, however, clearly different
absorption spectra are present, a large modulation
amplitude is selected for improved signal-to-noise
ratio.
See also: Chemometrics and Statistics: Multivariate
Calibration Techniques. Optical Spectroscopy: Radia-
tion Sources; Wavelength Selection Devices; Detection
Devices. Spectrophotometry: Overview.
Further Reading
Bosch OC, Sanchez RF, and Cano PJ (1995) Recent
developments in derivative ultraviolet/visible absorption
spectrophotometry. Talanta 42: 11951214.
Brown C, Vega-Montoto L, and Wentzell P (2000)
Derivative preprocessing and optimal correction for
Turbidimetry and Nephelometry
D M Lawler, University of Birmingham, Birmingham, UK
& 2005, Elsevier Ltd. All Rights Reserved.
Introduction
Turbidity is an expression of the optical property of a
medium, which causes light to be scattered and ab-
sorbed rather than transmitted in straight lines
through the sample. The International Organization
for Standardization (ISO) denes turbidity as the
reduction of transparency of a liquid caused by
the presence of undissolved matter. It is, therefore,
the opposite of clarity. The medium concerned is
normally a uid (but may be solid) in which light is
baseline drift in multivariate calibration. Applied Spectro-
scopy 54: 10551068.
Dixit L and Ram S (1985) Quantitative analysis by
derivative electronic spectroscopy. Applied Spectroscopy
Review 21: 311418.
Fell A (1983) Biomedical applications of derivative spectro-
scopy. Trends in Analytical Chemistry 2(3): 6366.
Hager R and Anderson R (1970) Theory of the derivative
spectrometer. Journal of the Optical Society of America
60: 14441449.
Hawthorne A and Thorngate J (1978) Improving analysis
from second-derivative UV-absorption spectrometry. Ap-
plied Optics 17: 724729.
Knowles A and Burgess C (1984) Practical Absorption
Spectrometry/Ultraviolet Spectrometry. New York: Chap-
man & Hall.
OHaver TC and Begley T (1981) Signal-to-noise in higher
order derivative spectrometry. Analytical Chemistry 53:
18761878.
Sassenscheid K, Klocke U, Marb C, et al. (1998) Dynamic
derivative UV-spectroscopy for combustion monitoring.
Proceedings of SPIE 3535: 204214.
Sassenscheid K, Klocke U, Marb C, et al. (1998) Enhanced
selectivity and sensitivity in UV-analysis of volatile org-
anic compounds. Proceedings of SPIE 3533: 222233.
Savitzky A and Golay M (1964) Smoothing and differen-
tiation of data by simplied least squares procedures.
Analytical Chemistry 36: 16271639.
Steiner J, Termonia Y, and Deltour J (1972) Smoothing and
differentiation of data by simplied least square proce-
dure. Analytical Chemistry 44: 19061909.
Vogt F, Klocke U, Rebstock K, et al. (1999) Optical UV
derivative-spectroscopy for monitoring gaseous emis-
sions. Applied Spectroscopy 53: 13521360.
Williams D and Hager R (1970) The derivative spectro-
meter. Applied Optics 9: 15971605.
scattered by matter usually small particles sus-
pended in the light path. Measurements of turbidity
can be used in many analytical elds to determine the
mass concentration of suspended particles in a sam-
ple and, for some simple contexts, particle size dis-
tributions. The eld is hampered, however, by a lack
of standardization in units, measurement devices and
calibration techniques. Analytical determinations of
concentrations tend to be empirical. Such method-
ological problems have recently driven a profusion of
technical papers.
This article reviews turbidity theory, measurement
principles, instrumentation systems, and applica-
tions, with particular reference to suspended sedi-
ment concentrations (SSCs) in natural waters (e.g.,
rivers, estuaries, and nearshore zones).
344 SPECTROPHOTOMETRY / Turbidimetry and Nephelometry
Definitions and Applications
Measurement Definitions
Turbidity can be measured using the techniques of
turbidimetry or nephelometry (from nephelo cloud
(Greek)). Turbidimetry is the measurement of tur-
bidity by quantifying the degree of attenuation of a
beam of light of known initial intensity. It is usually
applied to media of fairly high turbidity in which the
scattering particles are relatively large (e.g., natural
waters), for reasons, which will be addressed below.
Nephelometry is the measurement of turbidity by
the direct evaluation of the degree of light scattering
taking place in the medium. It is much more appro-
priate to media of lower turbidity in which the
suspended particles are small. Turbidimetry and
nephelometry can offer considerable time-saving
advantages over gravimetric methods for the deter-
mination of particle concentrations, and are non-
destructive techniques.
Typical Applications
Turbidimetry and nephelometry have found many
applications in scientific laboratories and in the
chemical, pharmaceutical, foodstuffs, and beverage
industries. In addition, turbidimetry and nephelome-
try are well-established procedures wherever ltra-
tion processes have to be effected, monitored, and
controlled. Within the hydrological sciences, and
water supply and wastewater management indus-
tries, turbidity values can act as simple and conveni-
ent surrogate measures of the concentration of
suspended solids, sulfate ions (which are precipitat-
ed as BaSO4 in acidic media (HCl) with barium
chloride), and other particulate material, and remain
one of the most common applications of turbidime-
try. Also, atmospheric and space physicists effect ne-
phelometric analyses because of the importance of
dust particles to radiation and other processes. In
quantitative chemical and biological analysis, appli-
cations are common, especially the calculation of
absolute molecular weights and dimensions of pol-
ymers in solution, as well as particle size determina-
tions of suspended matter. Chemical proles can also
be obtained by observing turbidity changes deliber-
ately induced by the addition of specific substances
to the solution. Within microbiology, cell and bac-
teria growth can be monitored through the media
turbidity changes such activity causes. In foodstuff
manufacturing, turbidimetry is often used to monitor
product quality and treatment process efciency, es-
pecially in the dairy and brewing industries. Clarity
(and hence turbidity) is also a key concern in the
petrochemical industries. Determining turbidity
components turbidity apportionment has advan-
ced with recent technological developments.
Principles and Theory
Light passing through a liquid medium may be scat-
tered and absorbed by inhomogeneities in the light
path, especially suspended particles of silt, clay, algae
and other plankton, microbes, organic matter, and
other ne insoluble particulate substances. Bubbles
and density discontinuities can also scatter light.
Scattering occurs when a minute particle interacts
with incident light by absorbing the light energy and
then, as if a point light source itself, reradiating the
light energy in all directions. Absorption takes place
when light is converted to other energy forms (e.g.,
heat) within the particle. Scattered light includes that
reected from the surface of the particle and that
refracted within the particle, possibly after many in-
ternal reections. Scattering is often accompanied by
absorption.
The direct relationship, however, between turbid-
ity data and suspended solids concentrations is
weakened by the complex interactions of light energy
with suspended particles. This interplay is heavily
dependent on many factors, including:
* concentration of scattering particles suspended in
the medium;
* size distribution of the scattering particles;
* shape, orientation, and surface condition of the
scattering particles;
* refractive index of the scattering particles;
* refractive index of the suspension medium;
* wavelength of the light source employed.
Consequently, separate bodies of theory have been
developed to describe the many different processes
that result. At its simplest level, light intensity is re-
duced during transmission through a collection of
scattering particles in a sample according to an at-
tenuation function of the form:
I I0 e
tl 1
where I0 is the initial beam intensity, I the beam in-
tensity after passing through a medium of length l,
and t the turbidity coefcient of the medium. Equa-
tion [1] ignores losses of light through true absorp-
tion by suspended particles or reection from the
sides of the sample container.
Light-Scattering Theory and the Inuence
of Particle Size
Appropriate light-scattering theory is governed by
the diameter, D, of the scattering elements in relation
 SPECTROPHOTOMETRY / Turbidimetry and Nephelometry 345
Incident beam Incident beam
(A) Small particles (B) Large particles
Figure 1 Inuence of particle size on the angular distribution of scattered light: (A) small particles (D o 0.1l); (B) large particles
(D B 0.25l); and (C) larger particles (D 4 1l). (From Vanous RD, Larson PE, and Hach CC (1982) The theory and measurement
of turbidity and residue. In: Minear RA and Keith LH (eds.) Water Analysis, vol. 1, pp. 163234. New York: Academic Press.)
to the wavelength, l, of the light emitted by the me-
asuring instrument. Indeed, theory is often specied
in terms of the Mie size parameter a 2pR=l,
where R is particle radius. Particle size thus forms an
appropriate basis for the subdivision of the theoret-
ical discussion that follows.
Small Particles
For particles where Do0.05l, Rayleigh scattering
theory of 1871, originally developed for gases, is
applicable to liquids with low concentrations of sus-
pended particles which do not interact with each
other. For such small particles, relatively symmetrical
light-scattering distributions are obtained (Figure
1A). If a visible light source (i.e., l 0.40.7 mm) is
employed, then it follows that this theory is appli-
cable for particles where DoB0.03 mm.
The Rayleigh equation describing the angular dis-
tribution of resultant scattering is:
iy =I0 fn0 =n
1g2 NV 2 =l4 r2 1 cos2 y 2
where iy is the intensity of light scattered at angle y,
I0 is the initial light source intensity, n0 is the refr-
active index of the particles, n is the refractive index
of the suspension medium, r is the distance from the
particles to the point of measurement, in terms of the
number, N, of particles, each of volume V. Rayleighs
work thus shows that the intensity of scattered light
varies: (1) with the square of the particle volume
and thus with the sixth power of the particle radius,
assuming spherical shapes; and (2) inversely with the
fourth power of the light wavelength used. Rayleigh
theory has since been developed to allow relative
molecular masses and sizes to be determined.
Large Particles
For larger particles, however, where 0.1loDo0.8l,
the angular distribution of scattered light becomes
asymmetrical. Destructive interference of light scat-
tered in the backward direction leads to a bias in
forward-scattered light (Figure 1B). In these con-
texts, Mie scattering theory of 1908 for larger
spheres becomes more appropriate. For such larger
Incident beam
(C) Larger particles
1.0
Light absorbance (i c )
<5 m
0.3
68 m 1218m
3050 m
0.1
0.03
30 100 300 1000 3000 10 000
Suspended sediment concentration (mg l1)
Figure 2 Inuence of sediment particle diameter on light ab-
sorbance by samples of different concentrations. Note how a
given concentration effects much greater absorbance at the
smaller particle diameters. (Reproduced with permission from
Ward PRB and Chikwanha R (1980) Laboratory measurement of
sediment turbidity. Proceedings of the American Society of Civil
Engineers, Journal of the Hydraulics Division 106: 10411053.)
particles, scattering intensity is less dependent on
wavelength.
Very Large Particles
For larger particles still, where D40.8l, the Mie
equations are still workable, although for particles
larger than B0.4 mm in diameter wide oscillations in
scattering patterns emerge. For particles of D41 mm,
extreme concentration of scattering in the forward
direction emerges (because of mutually destructive
backscattering effects), along with secondary peaks
in the angular distribution of scattered light (Figure 1C).
Theory and practice also demonstrate that the
most efcient scattering elements are those of a dia-
meter similar to the light wavelength used. Also, a
given mass of small particles causes much greater
light attenuation than the same mass of large parti-
cles (Figure 2).
One complexity is that much classical theory has
been developed for identically sized spherical parti-
cles conditions that may not be obtained in all
laboratory or eld situations. Indeed, many natural
346 SPECTROPHOTOMETRY / Turbidimetry and Nephelometry
waters, like the atmosphere, contain an ensemble of
variably sized, irregularly-shaped, and randomly
oriented particles, for which theory is still being
developed. Furthermore, processes become highly
complex when concentrations are so great that mul-
tiple scattering occurs (i.e., particles receive light
previously scattered from other particles: this nor-
mally increases opportunities for light absorption).
Instrumentation
Range of Turbidimetric and Nephelometric
Systems
Early procedures were based on manual operation of
analytical systems and visual turbidity assessment
(e.g., the Secchi disk). Several instruments are now
available, however, for quantitative turbidity deter-
mination in a variety of scientific, industrial, and
process management applications. Choice will de-
pend largely on the analytical aims (e.g., mass con-
centration, particle size distribution, molecular
dimensions, or crystal/cell growth), the nature of
the scattering elements and suspension medium, and
whether eld or laboratory measurement is needed.
Turbidimeters also vary in optical geometry, mode of
operation, sample handling capabilities, data record-
ing options (e.g., automatic/manual or analogue/
digital) and portability. Ultraviolet-visible spectro-
photometry can also be used for turbidimetric
measurements by measuring the absorption of light
by particles at a xed wavelength or full spectrum
(e.g., for kinetic studies of the time decay of species).
The discussion that follows focuses on the use of
turbidimetric instrumentation to estimate the mass
concentration of suspended matter in liquid samples,
with particular reference to sediment in natural
waters.
Basic Elements of Measurement Systems
Modern measurement devices use photosensitive
cells to quantify scattered and/or transmitted light.
Figure 3 illustrates that most laboratory bench in-
struments usually have ve basic components: a light
source of known, constant intensity, and given
wavelength characteristics; a lens to collimate the
light beam; a sample cell; photosensor(s); and a me-
ter or logger to record the output signals from the
photosensor(s). Versions for continuous monitoring
of turbidity values (e.g., for online industrial systems
or process measurement in environmental sciences)
include some kind of ow-through measurement
chamber (instead of a static sample cell) and out-
puts for a datalogger. The two basic measuring in-
struments are the nephelometer and the turbidimeter.
5.9
Photocell
Lens
Lamp Sample cell
(vertical view)
(A)
Transmitted
detector
Lamp Sample
Filter Lens cell
(B)
90 Detector Forward
scatter
Transmitted
detector
Lamp Sample
Filter Lens cell
(C)
Figure 3 Three basic designs of turbidity meter: (A) the ne-
phelometer, which directly measures light scattered (usually at
901 to the beam direction) by suspended particles; (B) the tur-
bidimeter, where the transmitted light is detected, in relation to
initial beam intensity; (C) the ratio turbidimeter in which both
transmitted and scattered light is detected. (Reproduced with
permission from Hach CC, Vanous RD, and Heer JM (1982)
Understanding turbidity measurement. Technical Information
Series, Booklet No. 11, 1st edn., 11pp. Hach Chemical Co.)
A nephelometer measures directly the intensity of
light scattered by the sample, which is proportional
to the amount of matter suspended in the light path,
though the inuence of size, shape, and refractive
index of the scattering particles is also important.
With nephelometers, the sensor is mounted at an
angle to the traversing beam (often 901) to record
scattered light in one part of the angular distribution
(Figure 3A). Some more sophisticated versions can
monitor scattering intensity at many different angles:
this allows angular summation values to be checked
against initial and attenuated signals. Nephelometers
usually provide better precision and sensitivity than
turbidimeters and are normally used for samples of
low turbidity containing small particles.
A turbidimeter, sometimes called a transmisso-
meter, absorptiometer, or turbidity meter (the latter
term is commonly used for eld instruments in the
earth and environmental sciences), measures the
 SPECTROPHOTOMETRY / Turbidimetry and Nephelometry 347
intensity of the beam after it has passed through the
sample, i.e., it quanties the amount of transmitted
light remaining (Figure 3B). Suspended matter in the
light path causes scattering and absorption of some
light energy, which reduces the incident illumination
falling on the photocell. These instruments are more
appropriate for relatively turbid samples in which the
scattering particles are large in relation to the light
wavelength used. This is because a signicant reduc-
tion in the intensity of incident light is needed to
yield precise results.
Some newer instruments, called ratio turbidi-
meters, incorporate measurement systems for light
which is side-scattered (usually at 901), forward-
scattered, and transmitted (Figure 3C). The turbidity
value is obtained as the ratio of the 901 signal to
the sum of forward-scattered and transmitted
values. The ratio feature has a number of advantages:
it increases the long-term stability of the sensor
(by reducing effects of instrumental drift); it com-
pensates for ageing of, and deposits on, the optics;
it reduces the inuence of temperature changes in
the electronics; it minimizes the need for repeated
recalibration; and it limits the effect of sample color
on readings. This can be more appropriate for
strongly and/or variably colored liquids, or for sam-
ples of high turbidity. A four-beam instrument vers-
ion has emerged recently, which reduces error still
further.
Recent developments include laser-based turbidi-
meters, reectometers, or ber-optic systems. The
development of the optical backscatter sensor (OBS)
has become popular for eld deployment in the hy-
drological and oceanographic sciences: this instru-
ment monitors water turbidity through the
backscattering of pulsed infrared light emitted from
the OBS instrument head. Also, remotely sensed tur-
bidity measurement, using satellite or air borne
instruments (e.g., the CASI (Compact Airborne Spec-
trographic Imager) system deployed by the UK
Natural Environment Research Council), has recent-
ly eased the mapping of turbidity patterns over large
spatial scales.
There is a strong dependency of scattering ef-
ciency on light wavelength (see above). Consequent-
ly, for a given detector, light sources of short
wavelength are more sensitive to, and therefore more
useful for, the detection of small particles. Convers-
ely, longer wavelengths are more appropriate for
samples containing large particles (e.g., sediment in
many earth or environmental science systems). The
sourcedetector relationship can vary widely be-
tween instruments, and is cited as the key reason
explaining the different readings obtained on the
same sample by different devices.
Units of Measurement and Instrument Calibration
The eld is hampered by a nonstandard, ill-dened,
and historically changing unit of measurement. The
Nephelometric Turbidity Unit (NTU) is the most
common unit employed. The precision with which
turbidity data should be reported depends on how
turbid the sample is, but should be to the nearest
110%, approximately, of the NTU value deter-
mined. For example, NTU values for distilled water,
tap water, and raw water are 0.08, 0.54, and
3.52, respectively, but much higher values, well
above 150 NTU, are common in many hydrological
systems.
Formazin polymer, developed in 1926, can be used
for turbidimeter calibration, and is straightforward
to prepare, control, and reproduce. Standard proce-
dures for the production of a stock formazin turbid-
ity suspension of 400 NTU are given in American
Public Health Association. Other calibration materi-
als can be used (e.g., Fullers Earth or Hach Gelex
xed standards metal oxide particles permanently
and statically suspended in silica gel) and may
provide suitable alternatives, especially given the
health concerns voiced in some quarters over form-
azin use.
Field Calibration
In natural waters, suspended material may largely
consist of particles in the size range of clay
(Do2 mm), silt (2oDo63 mm), or even sand
(63oDo2000 mm). It may also include organic mat-
ter and compounds and microscopic organisms. For
eld applications in hydrology or oceanography, an-
alysts should preferably calibrate turbidity readings
against known mass concentrations of the suspended
sediment typical of that context, and declare
the strength of the diagnostic statistics for derived
relationships. Such correlations can be weak,
reecting temporal changes in suspended load
composition (and hence its light-scattering efcien-
cy), water color, or bubble presence. Predictive
relationships can be strengthened by accounting
for such changes (especially in sediment load parti-
cle size distribution), which can occur over various
timescales (e.g., interannual, seasonal, subseasonal,
ood event). It may even be necessary to produce
multivariate or separate calibration equations to in-
corporate the effects of, for example, changing ow
levels, sediment source areas, and season on sediment
load constitution. For such eld applications, the
turbidimeter reading (often in arbitrary units) is
converted to estimated SSC using a site-specific
calibration curve.
348 SPECTROPHOTOMETRY / Turbidimetry and Nephelometry
Turbidity Meters for Continuous Field Operation
For unattended automated eld use a range of suit-
able turbidity meters with additional instrumental
features are available. The measurement cell is re-
placed by a ow-through chamber, which must
prevent stray light from reaching the photosensor.
Instruments can be boom-mounted directly in the
ow, or at the end of pump-lines connecting sa-
mpling point to measurement system.
Turbidity meters with narrow-band near infrared
(NIR) light sources (peak output at 0.86 mm; spectral
bandwidth o0.06 mm) are recommended by ISO.
Such instruments reduce problems of algal build-up
on the optical surfaces, are less affected by color, and
are more sensitive to the slightly larger particles typ-
ical of sediment transport systems. However, some
relaxation of the infrared protocol is tolerable for
eld instruments operating in continuous monitoring
mode.
To limit further the impact of problematic algal
growth on the optics, eld turbidimetric systems can
be equipped with a pulsed light source, antifouling
chemicals or lms, and/or wiper blades for conveni- equipped with an appropriate input channel and
ent (sometimes automated) cleaning of optical
surfaces. Alternatively, a dual-beam (twin-gap)
instrument to compensate for these effects can be
deployed.
Power requirements for eld instruments are im-
portant considerations. The use of low-consumption
light-emitting diodes (LEDs) in sensors, and pho-
tovoltaic sensors which convert incident light directly
into electrical energy, reduces power needs to a min-
imum. Solar panels are useful to trickle-charge in-
struments and dataloggers.
Some instruments are temperature sensitive, lar-
gely because LEDs can emit more strongly when
warm, and photovoltaic detectors convert photons
into electrons more efciently at low temperatures.
Given, for example, the annual range of river
temperature in the UK is typically B2025 K, some
correction procedures may be necessary.
Figure 4 also demonstrates that many turbidi
meters are relatively insensitive to very ne or very
coarse particulate matter. Because most instruments
work in the visible or NIR spectrum this means that
the most readily detectable particles are those where,
B0.2oDo1.8 mm. In standard sedimentological
and engineering classications, these are clay-sized
particles, and hence the occasionally used term silt-
meter for turbidimetric instruments is not entirely
appropriate.
Turbidity meters need to be interfaced with port-
able multimeters, dataloggers, or computers for
recording and storage of turbidity data. Dataloggers
400
HF DRT-1000
Instrument response (NTU)
300
200
Hach 2100A
100 5 103 wt. % conc.
0
0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0
Particle diameter (m)
Figure 4 Sensitivity of two turbidity meters to particle diameter
(HF H.F. instruments). Test material here is spherical latex
particles of very narrow size distribution. (From Vanous RD,
Larson PE, and Hash CC (1982) The theory and measurement of
turbidity and residue. In: Minear RA and Keith LH (eds.) Water
Analysis, vol. 1, pp. 163234. New York: Academic Press.)
needing minimal power for operation are heavily
used today. They provide quasi-continuous digital
data on temporal variations in turbidity, which are
ideal for computational analysis and the study of
turbidity dynamics. Telemetry systems for real-time
data acquisition, alarm facilities, and remote down-
loading capabilities are becoming increasingly
common.
Many eld scientists, however, despite the range of
commercially available turbidity instrumentation,
still recognize a need for low cost, rugged, and re-
liable systems. This is especially so when a network
of instruments is required for permanent installation
to dene a turbidity eld, for simultaneous manual
turbidity measurements by a research team, or for
specialist applications such as in subglacial environ-
ments. This has led many researchers to custom-
build their own instruments.
Hydrological Applications
of Turbidimetry
The monitoring of turbidity and SSCs in rivers, es-
tuaries, lakes, reservoirs, nearshore zones, etc. is att-
racting increasing attention from hydrologists,
limnologists, geomorphologists, freshwater ecolo-
gists, engineers, oceanographers, glaciologists, water
resource managers, and policy makers. Such meas-
urement programs can allow inferences to be made
about upstream hydrogeomorphological processes,
 SPECTROPHOTOMETRY / Turbidimetry and Nephelometry 349
catchment erosion rates, downstream uvial proc-
esses and sedimentation impacts, pollutant and con-
taminant transfer, and aquatic habitat quality. The
recreational value of water bodies can be partly
linked to their clarity, as demonstrated in the Lake
Tahoe turbidity reports of 200102. Increasingly,
there is a legal requirement for environmental impact
assessments and water supply managers to consider
the possibility of short- or long-term turbidity
increases resulting from proposed development
schemes.
Automated, in-stream, high-frequency turbidity
monitoring has become increasingly popular, main-
ly because the alternative practice of sampling and
subsequent laboratory processing of samples is labo-
rious and resource-intensive. Sampling approaches
thus inevitably constrain the level of temporal and
spatial detail possible, making it difcult to reveal
the patterns, dynamics, and processes present. Re-
cent advances in the understanding of the hydrody-
namics of ne-sediment transport in river, tidal, and
nearshore environments, for example, would have
been impossible without very high frequency (e.g.,
5 Hz) monitoring of transient turbidity changes. In
remote environments, and in the developing world, a
likely paucity of suitable sample analysis facilities
underlines the need for an automated and direct
eld-based method.
Three example applications of continuous moni-
toring are outlined below: river turbidity varia-
tion during rainstorms; very short-lived turbidity
pulsing in glacial and coastal waters; and the
definition of the estuarine turbidity maximum. These
illustrate the many advantages of turbidity instru-
mentation over sampling-based approaches in
quantifying and understanding complex temporal
and spatial patterns of suspended sediment uxes.
They also demonstrate the substantial variations of
turbidity and SSCs in natural systems in space and
time.
River Turbidity Variation through Individual
Storm Events
SSC in streams can change appreciably over seasonal
timescales and during high-ow events. Automated
river turbidity monitoring is very useful in refining
calculations of suspended sediment loads, because it
detects the short-lived, but very important order-of-
magnitude changes in SSC that occur in many rivers
during complex storm events (e.g., Figure 5). The
1-min datalogging scan interval used in Figure 5
dened all peaks and troughs in turbidity for most
events. Following calibration, this permitted the full
definition of exhaustion phenomena in SSCs, and
100
Concentration (mg I1) Discharge (Is1)
75
50
Sediment concentration
25
Discharge
0
12 12 12
18.11.1986 19.11.1986 20.11.1986
Figure 5 Continuous record of stream suspended sediment
concentration, in relation to river discharge changes during storm
events, derived from calibration of a Partech turbidity record.
(From Gippel CJ (1989) The use of turbidity instruments to
measure stream water suspended sediment concentration,
Monograph Series No. 4, Department of Geography and
Oceanography, University College, University of New South
Wales, Australian Defence Force Academy, Canberra, 204pp.)
hysteresis effects in relation to the discharge series
(hitherto undetected for the system by earlier work-
ers using a conventional sampling program). This
led, in turn, to more securely based explanations of
ne-sediment delivery processes.
Turbidity Pulsing in Rivers and Nearshore Zones
Turbidimetric instrumentation also facilitates the de-
tection of very short-lived pulsing of suspended sed-
iment, which characterizes many systems, especially
proglacial meltwater environments. The example in
Figure 6, for the Jokulsa a Solheimasandi glacial river
in southern Iceland, shows two substantial sediment-
pulsing events detected by a 2-min turbidity scanning
program. These were unrelated to river ow variat-
ions, and showed that other signicant sediment
mobilization processes were present in the system.
The alternative approach of ow-triggered automat-
ed sampling is unsatisfactory in these situations
where many sedimentux perturbations are un-
related to water discharge.
One strength of automated turbidity monitoring is
that the logging system can also be used to record, on
the same time base, data on associated or explana-
tory variables. For glacial meltwater studies (Figure
6), these typically include energy budget components
relevant to glacial ablation, rainfall intensity, river
discharge, temperature, and electrical conductivity,
and, with Photo-Electronic Erosion Pin (PEEP) sen-
sors, even the erosion events themselves which gene-
rate sediment plumes. Such data can strengthen the
350 SPECTROPHOTOMETRY / Turbidimetry and Nephelometry

100 5000

Suspended sediment concentration (mg I1)

Discharge
80 4000

Discharge (m3 s1)

60 3000

40 2000
Concentration

20 1000

0 0
18:00 20:00 22:00 00:00 02:00
GMT (also Icelandic time)
Figure 6 Two-minute scanning of turbidity and river discharge (89 Aug 1988) showing a compound pulsing of suspended sediment
concentration, unrelated to ow variations, in the Jokulsa a Solheimasandi glacial river in southern Iceland. (Reproduced with
permission from Lawler DM and Brown RM (1992) A simple and inexpensive turbidity meter for the estimation of suspended sediment
concentrations. Hydrological Processes 6: 159168; & John Wiley and Sons Ltd.)
OBS output (mV)
1700 1950 2200

OBS output

20 10 0 10 20
v (cm s1)
V
60 80 100 120
U (cm s1)

0 1 2 3 4 5 6 7 8 9 10
Time (min, from 16:57 h PST)
Figure 7 A high-frequency, 5 Hz, 10-min time series of OBS turbidity alongside river ow components (u, streamwise; v, normal to
the bed) for the Fraser River, near Mission, BC, Canada. (Reproduced with permission from Lapointe M (1992) Burst-like sediments
suspension events in the sand bed river. Earth Surface Processes and Landforms 17: 253270; & John Wiley and Sons Ltd.)

process-inference capabilities of the whole exercise. Estuarine Turbidity Maxima

Thus, the correlation of high-frequency velocity and
OBS turbidity series (Figure 7) allowed a clearer un-
derstanding of river sediment transport events to be
gained. In coastal zones, very high frequency (5 Hz)
monitoring of OBS turbidity, wave height, and
currents (Figure 8), facilitated the definition of the
critical ow velocities required to mobilize bed sed-
iment. Knowledge of these threshold conditions is
important for the stability, engineering, and protec-
tion of coastlines and their ecosystems.
The estuarine turbidity maximum is the term given
to the clear peak in mean SSC observable in many
estuaries around the limit of saline intrusion. Im-
proved explanations of turbidity elds in estuarine
systems, including the nature, location, and migration
of the turbidity maximum, and the tidal pumping
processes responsible, have recently been obtained by
supplementing water sampling approaches with de-
tailed automatic turbidity monitoring. Furthermore,
 SPECTROPHOTOMETRY / Inorganic Compounds 351

for any spatial survey, the fact that turbidity values

U (m s1)
0.5 0.2
U
V (m s1)
0 are obtained at the eld sites themselves, rather
0 V 0.2
than in the laboratory subsequently, can allow in-
0.5 stant decisions to be made regarding any further
200

SSC (mg l1)

3 environmental sampling (including turbidity) that
2 100 may be desirable. Figure 9 illustrates the value of
SSC
H S (m)

0
repeated estuarine turbidity measurement in revea-
1
ling the spatial and temporal structure of the turbi-
Hs
0 dity maximum.
0 50 100 150 200 250 300 350 400
Start Time (h) Finish See also: Color Measurement. Environmental Analy-
04.02.96 19.02.96 sis. Geochemistry: Sediment. Particle Size Analysis.
12:00 08:00 Sensors: Photometric. Water Analysis: Particle Charac-
terization.
Figure 8 A high-frequency, 5 Hz record averaged to hourly time
series of OBS turbidity (SSC), in relation to signicant wave
height, Hs; cross-shore current, U; and longshore current, V, for
the North Sea nearshore zone at Holderness, UK. Data from Feb. Further Reading
1996; water depth 16.8 m. The OBS here has been deployed
within BLISS (Boundary Layer Intelligent Sensor System). (From American Public Health Association (1998) Turbidity.
Blewett J and Huntley D (1999) Measurement of suspended Standard Methods for the Examination of Water and
sediment transport processes in shallow water off the Holderness Wastewater. American Public Health Association, Amer-
coast, UK. Marine Pollution Bulletin 37(37): 134143.) ican Water Works Association, and Water Pollution
Control Federation.
180 Davies-Colley RJ and Smith DG (2001) Turbidity, suspe-
nded sediment, and water clarity: a review. Journal
160
of American Water Resources Association 37(5):
140 10851101.
Bottom
ISO (International Organisation for Standardization)
120
Turbidity (NTU)

(1984). Water Quality Determination of Turbidity,

100 1st edn., 5pp. ISO 7027 1984(E).
Top Mitchell SB, Lawler DM, West JR, and Couperthwaite JS
80
(2003) Use of continuous turbidity sensor in the predic-
60 tion of ne sediment transport in the turbidity maximum
of the Trent Estuary, UK. Estuarine Coastal and Shelf
40
Science 58: 643650.
20 Schuerman DW (ed.) (1980) Light Scattering by Irre-
0
gularly Shaped Particles, 334pp. New York: Plenum
0 2 4 6 8 10 12 14 16 18 Press.
Distance from mouth (km) Van de Hulst HC (1981) Light Scattering by Small
Particles, 2nd edn., 470pp. New York: Dover Publica-
Figure 9 Relationship between estuarine turbidity in NTU and
tions.
distance from the mouth of St. Lucia Estuary, Natal, on a rising
tide on 20 March 1981, showing a clear turbidity maximum Walling DE (1977) Limitations of the rating curve tech-
B812 km from the estuary mouth for both near-bed (bottom) nique for estimating suspended sediment loads, with
and surface (top) waters. (From Cyrus DP (1988) Turbidity and particular reference to British rivers. Erosion and Solid
other physical factors in Natal estuarine systems. Part 1: selected Matter Transport in Inland Waters. International
estuaries. Journal of the Limnological Society of southern Africa Association of Hydrological Sciences Publ. No. 122,
14(2): 6071.) pp. 3448.

Inorganic Compounds
M A Zezzi-Arruda and R J Poppi, University of Introduction
Campinas, Campinas, Brazil
Spectrophotometry is an excellent alternative for
the determination of inorganic compounds. It is
& 2005, Elsevier Ltd. All Rights Reserved. characterized by a wide analytical working range,