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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- baseline drift in multivariate calibration. Applied Spectro-
changeable by the resistor and the capacitor of the scopy 54: 10551068.
differentiating circuit [7]. Dixit L and Ram S (1985) Quantitative analysis by
Analogous to the adjustment of the window width, derivative electronic spectroscopy. Applied Spectroscopy
different modulation amplitudes a [8] can be chosen Review 21: 311418.
Fell A (1983) Biomedical applications of derivative spectro-
in optical derivative spectroscopy. According to [12],
scopy. Trends in Analytical Chemistry 2(3): 6366.
larger derivative signals and hence better signal- Hager R and Anderson R (1970) Theory of the derivative
to-noise ratio can be gained by increasing a. This was spectrometer. Journal of the Optical Society of America
conrmed experimentally; however, a signal increase 60: 14441449.
comes along with a washing out of derivative shapes Hawthorne A and Thorngate J (1978) Improving analysis
and minute derivative features are lost (Figure 7). from second-derivative UV-absorption spectrometry. Ap-
The values for the modulation amplitude given in plied Optics 17: 724729.
Figure 7 are typical examples. Thus, the modulation Knowles A and Burgess C (1984) Practical Absorption
amplitude can be optimized for different applica- Spectrometry/Ultraviolet Spectrometry. New York: Chap-
tions: if several analytes in mixtures have very similar man & Hall.
and overlapping absorption spectra, a small modu- OHaver TC and Begley T (1981) Signal-to-noise in higher
order derivative spectrometry. Analytical Chemistry 53:
lation amplitude helps to pronounce minor differ-
18761878.
ences for discrimination. If, however, clearly different Sassenscheid K, Klocke U, Marb C, et al. (1998) Dynamic
absorption spectra are present, a large modulation derivative UV-spectroscopy for combustion monitoring.
amplitude is selected for improved signal-to-noise Proceedings of SPIE 3535: 204214.
ratio. Sassenscheid K, Klocke U, Marb C, et al. (1998) Enhanced
selectivity and sensitivity in UV-analysis of volatile org-
See also: Chemometrics and Statistics: Multivariate anic compounds. Proceedings of SPIE 3533: 222233.
Calibration Techniques. Optical Spectroscopy: Radia- Savitzky A and Golay M (1964) Smoothing and differen-
tion Sources; Wavelength Selection Devices; Detection tiation of data by simplied least squares procedures.
Devices. Spectrophotometry: Overview. Analytical Chemistry 36: 16271639.
Steiner J, Termonia Y, and Deltour J (1972) Smoothing and
Further Reading differentiation of data by simplied least square proce-
dure. Analytical Chemistry 44: 19061909.
Bosch OC, Sanchez RF, and Cano PJ (1995) Recent Vogt F, Klocke U, Rebstock K, et al. (1999) Optical UV
developments in derivative ultraviolet/visible absorption derivative-spectroscopy for monitoring gaseous emis-
spectrophotometry. Talanta 42: 11951214. sions. Applied Spectroscopy 53: 13521360.
Brown C, Vega-Montoto L, and Wentzell P (2000) Williams D and Hager R (1970) The derivative spectro-
Derivative preprocessing and optimal correction for meter. Applied Optics 9: 15971605.

Turbidimetry and Nephelometry


D M Lawler, University of Birmingham, Birmingham, UK scattered by matter usually small particles sus-
& 2005, Elsevier Ltd. All Rights Reserved. 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
Introduction of standardization in units, measurement devices and
Turbidity is an expression of the optical property of a calibration techniques. Analytical determinations of
medium, which causes light to be scattered and ab- concentrations tend to be empirical. Such method-
sorbed rather than transmitted in straight lines ological problems have recently driven a profusion of
through the sample. The International Organization technical papers.
for Standardization (ISO) denes turbidity as the This article reviews turbidity theory, measurement
reduction of transparency of a liquid caused by principles, instrumentation systems, and applica-
the presence of undissolved matter. It is, therefore, tions, with particular reference to suspended sedi-
the opposite of clarity. The medium concerned is ment concentrations (SSCs) in natural waters (e.g.,
normally a uid (but may be solid) in which light is rivers, estuaries, and nearshore zones).
344 SPECTROPHOTOMETRY / Turbidimetry and Nephelometry

Definitions and Applications components turbidity apportionment has advan-


ced with recent technological developments.
Measurement Definitions
Turbidity can be measured using the techniques of
Principles and Theory
turbidimetry or nephelometry (from nephelo cloud
(Greek)). Turbidimetry is the measurement of tur- Light passing through a liquid medium may be scat-
bidity by quantifying the degree of attenuation of a tered and absorbed by inhomogeneities in the light
beam of light of known initial intensity. It is usually path, especially suspended particles of silt, clay, algae
applied to media of fairly high turbidity in which the and other plankton, microbes, organic matter, and
scattering particles are relatively large (e.g., natural other ne insoluble particulate substances. Bubbles
waters), for reasons, which will be addressed below. and density discontinuities can also scatter light.
Nephelometry is the measurement of turbidity by Scattering occurs when a minute particle interacts
the direct evaluation of the degree of light scattering with incident light by absorbing the light energy and
taking place in the medium. It is much more appro- then, as if a point light source itself, reradiating the
priate to media of lower turbidity in which the light energy in all directions. Absorption takes place
suspended particles are small. Turbidimetry and when light is converted to other energy forms (e.g.,
nephelometry can offer considerable time-saving heat) within the particle. Scattered light includes that
advantages over gravimetric methods for the deter- reected from the surface of the particle and that
mination of particle concentrations, and are non- refracted within the particle, possibly after many in-
destructive techniques. ternal reections. Scattering is often accompanied by
absorption.
The direct relationship, however, between turbid-
Typical Applications
ity data and suspended solids concentrations is
Turbidimetry and nephelometry have found many weakened by the complex interactions of light energy
applications in scientific laboratories and in the with suspended particles. This interplay is heavily
chemical, pharmaceutical, foodstuffs, and beverage dependent on many factors, including:
industries. In addition, turbidimetry and nephelome-
try are well-established procedures wherever ltra- * concentration of scattering particles suspended in
tion processes have to be effected, monitored, and the medium;
controlled. Within the hydrological sciences, and * size distribution of the scattering particles;
water supply and wastewater management indus- * shape, orientation, and surface condition of the
tries, turbidity values can act as simple and conveni- scattering particles;
ent surrogate measures of the concentration of * refractive index of the scattering particles;
suspended solids, sulfate ions (which are precipitat- * refractive index of the suspension medium;
ed as BaSO4 in acidic media (HCl) with barium * wavelength of the light source employed.
chloride), and other particulate material, and remain
one of the most common applications of turbidime- Consequently, separate bodies of theory have been
try. Also, atmospheric and space physicists effect ne- developed to describe the many different processes
phelometric analyses because of the importance of that result. At its simplest level, light intensity is re-
dust particles to radiation and other processes. In duced during transmission through a collection of
quantitative chemical and biological analysis, appli- scattering particles in a sample according to an at-
cations are common, especially the calculation of tenuation function of the form:
absolute molecular weights and dimensions of pol-
ymers in solution, as well as particle size determina- I I0 etl 1
tions of suspended matter. Chemical proles can also where I0 is the initial beam intensity, I the beam in-
be obtained by observing turbidity changes deliber- tensity after passing through a medium of length l,
ately induced by the addition of specific substances and t the turbidity coefcient of the medium. Equa-
to the solution. Within microbiology, cell and bac- tion [1] ignores losses of light through true absorp-
teria growth can be monitored through the media tion by suspended particles or reection from the
turbidity changes such activity causes. In foodstuff sides of the sample container.
manufacturing, turbidimetry is often used to monitor
Light-Scattering Theory and the Inuence
product quality and treatment process efciency, es-
of Particle Size
pecially in the dairy and brewing industries. Clarity
(and hence turbidity) is also a key concern in the Appropriate light-scattering theory is governed by
petrochemical industries. Determining turbidity the diameter, D, of the scattering elements in relation
SPECTROPHOTOMETRY / Turbidimetry and Nephelometry 345

Incident beam Incident beam Incident beam

(A) Small particles (B) Large particles (C) Larger 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-


1.0
asuring instrument. Indeed, theory is often specied

Light absorbance (i c )
in terms of the Mie size parameter a 2pR=l,
<5 m
where R is particle radius. Particle size thus forms an
0.3
appropriate basis for the subdivision of the theoret- 68 m 1218m
ical discussion that follows. 3050 m

Small Particles 0.1

For particles where Do0.05l, Rayleigh scattering


theory of 1871, originally developed for gases, is
0.03
applicable to liquids with low concentrations of sus- 30 100 300 1000 3000 10 000
pended particles which do not interact with each Suspended sediment concentration (mg l1)
other. For such small particles, relatively symmetrical
Figure 2 Inuence of sediment particle diameter on light ab-
light-scattering distributions are obtained (Figure sorbance by samples of different concentrations. Note how a
1A). If a visible light source (i.e., l 0.40.7 mm) is given concentration effects much greater absorbance at the
employed, then it follows that this theory is appli- smaller particle diameters. (Reproduced with permission from
cable for particles where DoB0.03 mm. Ward PRB and Chikwanha R (1980) Laboratory measurement of
sediment turbidity. Proceedings of the American Society of Civil
The Rayleigh equation describing the angular dis-
Engineers, Journal of the Hydraulics Division 106: 10411053.)
tribution of resultant scattering is:

iy =I0 fn0 =n  1g2 NV 2 =l4 r2 1 cos2 y 2


particles, scattering intensity is less dependent on
where iy is the intensity of light scattered at angle y, wavelength.
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 Very Large Particles
particles to the point of measurement, in terms of the For larger particles still, where D40.8l, the Mie
number, N, of particles, each of volume V. Rayleighs equations are still workable, although for particles
work thus shows that the intensity of scattered light larger than B0.4 mm in diameter wide oscillations in
varies: (1) with the square of the particle volume scattering patterns emerge. For particles of D41 mm,
and thus with the sixth power of the particle radius, extreme concentration of scattering in the forward
assuming spherical shapes; and (2) inversely with the direction emerges (because of mutually destructive
fourth power of the light wavelength used. Rayleigh backscattering effects), along with secondary peaks
theory has since been developed to allow relative in the angular distribution of scattered light (Figure 1C).
molecular masses and sizes to be determined. Theory and practice also demonstrate that the
most efcient scattering elements are those of a dia-
Large Particles
meter similar to the light wavelength used. Also, a
For larger particles, however, where 0.1loDo0.8l, given mass of small particles causes much greater
the angular distribution of scattered light becomes light attenuation than the same mass of large parti-
asymmetrical. Destructive interference of light scat- cles (Figure 2).
tered in the backward direction leads to a bias in One complexity is that much classical theory has
forward-scattered light (Figure 1B). In these con- been developed for identically sized spherical parti-
texts, Mie scattering theory of 1908 for larger cles conditions that may not be obtained in all
spheres becomes more appropriate. For such larger laboratory or eld situations. Indeed, many natural
346 SPECTROPHOTOMETRY / Turbidimetry and Nephelometry

waters, like the atmosphere, contain an ensemble of 5.9


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- Photocell
tiple scattering occurs (i.e., particles receive light
previously scattered from other particles: this nor-
mally increases opportunities for light absorption).

Lens
Instrumentation Lamp Sample cell
(vertical view)
Range of Turbidimetric and Nephelometric (A)
Systems

Early procedures were based on manual operation of


analytical systems and visual turbidity assessment Transmitted
detector
(e.g., the Secchi disk). Several instruments are now Lamp Sample
available, however, for quantitative turbidity deter- Filter Lens cell
mination in a variety of scientific, industrial, and (B)
process management applications. Choice will de-
pend largely on the analytical aims (e.g., mass con- 90 Detector Forward
scatter
centration, particle size distribution, molecular
dimensions, or crystal/cell growth), the nature of
Transmitted
the scattering elements and suspension medium, and detector
whether eld or laboratory measurement is needed. Lamp Sample
Turbidimeters also vary in optical geometry, mode of Filter Lens cell
(C)
operation, sample handling capabilities, data record-
ing options (e.g., automatic/manual or analogue/ Figure 3 Three basic designs of turbidity meter: (A) the ne-
digital) and portability. Ultraviolet-visible spectro- phelometer, which directly measures light scattered (usually at
901 to the beam direction) by suspended particles; (B) the tur-
photometry can also be used for turbidimetric bidimeter, where the transmitted light is detected, in relation to
measurements by measuring the absorption of light initial beam intensity; (C) the ratio turbidimeter in which both
by particles at a xed wavelength or full spectrum transmitted and scattered light is detected. (Reproduced with
(e.g., for kinetic studies of the time decay of species). permission from Hach CC, Vanous RD, and Heer JM (1982)
The discussion that follows focuses on the use of Understanding turbidity measurement. Technical Information
Series, Booklet No. 11, 1st edn., 11pp. Hach Chemical Co.)
turbidimetric instrumentation to estimate the mass
concentration of suspended matter in liquid samples,
with particular reference to sediment in natural A nephelometer measures directly the intensity of
waters. light scattered by the sample, which is proportional
to the amount of matter suspended in the light path,
Basic Elements of Measurement Systems
though the inuence of size, shape, and refractive
Modern measurement devices use photosensitive index of the scattering particles is also important.
cells to quantify scattered and/or transmitted light. With nephelometers, the sensor is mounted at an
Figure 3 illustrates that most laboratory bench in- angle to the traversing beam (often 901) to record
struments usually have ve basic components: a light scattered light in one part of the angular distribution
source of known, constant intensity, and given (Figure 3A). Some more sophisticated versions can
wavelength characteristics; a lens to collimate the monitor scattering intensity at many different angles:
light beam; a sample cell; photosensor(s); and a me- this allows angular summation values to be checked
ter or logger to record the output signals from the against initial and attenuated signals. Nephelometers
photosensor(s). Versions for continuous monitoring usually provide better precision and sensitivity than
of turbidity values (e.g., for online industrial systems turbidimeters and are normally used for samples of
or process measurement in environmental sciences) low turbidity containing small particles.
include some kind of ow-through measurement A turbidimeter, sometimes called a transmisso-
chamber (instead of a static sample cell) and out- meter, absorptiometer, or turbidity meter (the latter
puts for a datalogger. The two basic measuring in- term is commonly used for eld instruments in the
struments are the nephelometer and the turbidimeter. earth and environmental sciences), measures the
SPECTROPHOTOMETRY / Turbidimetry and Nephelometry 347

intensity of the beam after it has passed through the Units of Measurement and Instrument Calibration
sample, i.e., it quanties the amount of transmitted
The eld is hampered by a nonstandard, ill-dened,
light remaining (Figure 3B). Suspended matter in the
and historically changing unit of measurement. The
light path causes scattering and absorption of some
Nephelometric Turbidity Unit (NTU) is the most
light energy, which reduces the incident illumination
common unit employed. The precision with which
falling on the photocell. These instruments are more
turbidity data should be reported depends on how
appropriate for relatively turbid samples in which the turbid the sample is, but should be to the nearest
scattering particles are large in relation to the light
110%, approximately, of the NTU value deter-
wavelength used. This is because a signicant reduc-
mined. For example, NTU values for distilled water,
tion in the intensity of incident light is needed to
tap water, and raw water are 0.08, 0.54, and
yield precise results.
3.52, respectively, but much higher values, well
Some newer instruments, called ratio turbidi-
above 150 NTU, are common in many hydrological
meters, incorporate measurement systems for light
systems.
which is side-scattered (usually at 901), forward-
Formazin polymer, developed in 1926, can be used
scattered, and transmitted (Figure 3C). The turbidity for turbidimeter calibration, and is straightforward
value is obtained as the ratio of the 901 signal to
to prepare, control, and reproduce. Standard proce-
the sum of forward-scattered and transmitted
dures for the production of a stock formazin turbid-
values. The ratio feature has a number of advantages:
ity suspension of 400 NTU are given in American
it increases the long-term stability of the sensor
Public Health Association. Other calibration materi-
(by reducing effects of instrumental drift); it com-
als can be used (e.g., Fullers Earth or Hach Gelex
pensates for ageing of, and deposits on, the optics;
xed standards metal oxide particles permanently
it reduces the inuence of temperature changes in
and statically suspended in silica gel) and may
the electronics; it minimizes the need for repeated provide suitable alternatives, especially given the
recalibration; and it limits the effect of sample color
health concerns voiced in some quarters over form-
on readings. This can be more appropriate for
azin use.
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
Field Calibration
further.
Recent developments include laser-based turbidi- In natural waters, suspended material may largely
meters, reectometers, or ber-optic systems. The consist of particles in the size range of clay
development of the optical backscatter sensor (OBS) (Do2 mm), silt (2oDo63 mm), or even sand
has become popular for eld deployment in the hy- (63oDo2000 mm). It may also include organic mat-
drological and oceanographic sciences: this instru- ter and compounds and microscopic organisms. For
ment monitors water turbidity through the eld applications in hydrology or oceanography, an-
backscattering of pulsed infrared light emitted from alysts should preferably calibrate turbidity readings
the OBS instrument head. Also, remotely sensed tur- against known mass concentrations of the suspended
bidity measurement, using satellite or air borne sediment typical of that context, and declare
instruments (e.g., the CASI (Compact Airborne Spec- the strength of the diagnostic statistics for derived
trographic Imager) system deployed by the UK relationships. Such correlations can be weak,
Natural Environment Research Council), has recent- reecting temporal changes in suspended load
ly eased the mapping of turbidity patterns over large composition (and hence its light-scattering efcien-
spatial scales. cy), water color, or bubble presence. Predictive
There is a strong dependency of scattering ef- relationships can be strengthened by accounting
ciency on light wavelength (see above). Consequent- for such changes (especially in sediment load parti-
ly, for a given detector, light sources of short cle size distribution), which can occur over various
wavelength are more sensitive to, and therefore more timescales (e.g., interannual, seasonal, subseasonal,
useful for, the detection of small particles. Convers- ood event). It may even be necessary to produce
ely, longer wavelengths are more appropriate for multivariate or separate calibration equations to in-
samples containing large particles (e.g., sediment in corporate the effects of, for example, changing ow
many earth or environmental science systems). The levels, sediment source areas, and season on sediment
sourcedetector relationship can vary widely be- load constitution. For such eld applications, the
tween instruments, and is cited as the key reason turbidimeter reading (often in arbitrary units) is
explaining the different readings obtained on the converted to estimated SSC using a site-specific
same sample by different devices. calibration curve.
348 SPECTROPHOTOMETRY / Turbidimetry and Nephelometry

Turbidity Meters for Continuous Field Operation 400

For unattended automated eld use a range of suit- HF DRT-1000

Instrument response (NTU)


able turbidity meters with additional instrumental 300
features are available. The measurement cell is re-
placed by a ow-through chamber, which must
prevent stray light from reaching the photosensor. 200
Instruments can be boom-mounted directly in the Hach 2100A
ow, or at the end of pump-lines connecting sa-
mpling point to measurement system. 100 5 103 wt. % conc.
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. 0
Such instruments reduce problems of algal build-up 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0
on the optical surfaces, are less affected by color, and Particle diameter (m)
are more sensitive to the slightly larger particles typ- Figure 4 Sensitivity of two turbidity meters to particle diameter
ical of sediment transport systems. However, some (HF H.F. instruments). Test material here is spherical latex
relaxation of the infrared protocol is tolerable for particles of very narrow size distribution. (From Vanous RD,
eld instruments operating in continuous monitoring Larson PE, and Hash CC (1982) The theory and measurement of
turbidity and residue. In: Minear RA and Keith LH (eds.) Water
mode. Analysis, vol. 1, pp. 163234. New York: Academic Press.)
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 needing minimal power for operation are heavily
surfaces. Alternatively, a dual-beam (twin-gap) used today. They provide quasi-continuous digital
instrument to compensate for these effects can be data on temporal variations in turbidity, which are
deployed. ideal for computational analysis and the study of
Power requirements for eld instruments are im- turbidity dynamics. Telemetry systems for real-time
portant considerations. The use of low-consumption data acquisition, alarm facilities, and remote down-
light-emitting diodes (LEDs) in sensors, and pho- loading capabilities are becoming increasingly
tovoltaic sensors which convert incident light directly common.
into electrical energy, reduces power needs to a min- Many eld scientists, however, despite the range of
imum. Solar panels are useful to trickle-charge in- commercially available turbidity instrumentation,
struments and dataloggers. still recognize a need for low cost, rugged, and re-
Some instruments are temperature sensitive, lar- liable systems. This is especially so when a network
gely because LEDs can emit more strongly when of instruments is required for permanent installation
warm, and photovoltaic detectors convert photons to dene a turbidity eld, for simultaneous manual
into electrons more efciently at low temperatures. turbidity measurements by a research team, or for
Given, for example, the annual range of river specialist applications such as in subglacial environ-
temperature in the UK is typically B2025 K, some ments. This has led many researchers to custom-
correction procedures may be necessary. build their own instruments.
Figure 4 also demonstrates that many turbidi
meters are relatively insensitive to very ne or very
coarse particulate matter. Because most instruments Hydrological Applications
work in the visible or NIR spectrum this means that
the most readily detectable particles are those where,
of Turbidimetry
B0.2oDo1.8 mm. In standard sedimentological The monitoring of turbidity and SSCs in rivers, es-
and engineering classications, these are clay-sized tuaries, lakes, reservoirs, nearshore zones, etc. is att-
particles, and hence the occasionally used term silt- racting increasing attention from hydrologists,
meter for turbidimetric instruments is not entirely limnologists, geomorphologists, freshwater ecolo-
appropriate. gists, engineers, oceanographers, glaciologists, water
Turbidity meters need to be interfaced with port- resource managers, and policy makers. Such meas-
able multimeters, dataloggers, or computers for urement programs can allow inferences to be made
recording and storage of turbidity data. Dataloggers about upstream hydrogeomorphological processes,
SPECTROPHOTOMETRY / Turbidimetry and Nephelometry 349

catchment erosion rates, downstream uvial proc- 100

Concentration (mg I1) Discharge (Is1)


esses and sedimentation impacts, pollutant and con-
taminant transfer, and aquatic habitat quality. The
recreational value of water bodies can be partly 75
linked to their clarity, as demonstrated in the Lake
Tahoe turbidity reports of 200102. Increasingly,
50
there is a legal requirement for environmental impact
assessments and water supply managers to consider Sediment concentration
the possibility of short- or long-term turbidity 25
increases resulting from proposed development
schemes. Discharge
Automated, in-stream, high-frequency turbidity 0
monitoring has become increasingly popular, main- 12 12 12
18.11.1986 19.11.1986 20.11.1986
ly because the alternative practice of sampling and
subsequent laboratory processing of samples is labo- Figure 5 Continuous record of stream suspended sediment
rious and resource-intensive. Sampling approaches concentration, in relation to river discharge changes during storm
events, derived from calibration of a Partech turbidity record.
thus inevitably constrain the level of temporal and (From Gippel CJ (1989) The use of turbidity instruments to
spatial detail possible, making it difcult to reveal measure stream water suspended sediment concentration,
the patterns, dynamics, and processes present. Re- Monograph Series No. 4, Department of Geography and
cent advances in the understanding of the hydrody- Oceanography, University College, University of New South
namics of ne-sediment transport in river, tidal, and Wales, Australian Defence Force Academy, Canberra, 204pp.)
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 hysteresis effects in relation to the discharge series
likely paucity of suitable sample analysis facilities (hitherto undetected for the system by earlier work-
underlines the need for an automated and direct ers using a conventional sampling program). This
eld-based method. led, in turn, to more securely based explanations of
Three example applications of continuous moni- ne-sediment delivery processes.
toring are outlined below: river turbidity varia-
Turbidity Pulsing in Rivers and Nearshore Zones
tion during rainstorms; very short-lived turbidity
pulsing in glacial and coastal waters; and the Turbidimetric instrumentation also facilitates the de-
definition of the estuarine turbidity maximum. These tection of very short-lived pulsing of suspended sed-
illustrate the many advantages of turbidity instru- iment, which characterizes many systems, especially
mentation over sampling-based approaches in proglacial meltwater environments. The example in
quantifying and understanding complex temporal Figure 6, for the Jokulsa a Solheimasandi glacial river
and spatial patterns of suspended sediment uxes. in southern Iceland, shows two substantial sediment-
They also demonstrate the substantial variations of pulsing events detected by a 2-min turbidity scanning
turbidity and SSCs in natural systems in space and program. These were unrelated to river ow variat-
time. ions, and showed that other signicant sediment
mobilization processes were present in the system.
The alternative approach of ow-triggered automat-
River Turbidity Variation through Individual
ed sampling is unsatisfactory in these situations
Storm Events
where many sedimentux perturbations are un-
SSC in streams can change appreciably over seasonal related to water discharge.
timescales and during high-ow events. Automated One strength of automated turbidity monitoring is
river turbidity monitoring is very useful in refining that the logging system can also be used to record, on
calculations of suspended sediment loads, because it the same time base, data on associated or explana-
detects the short-lived, but very important order-of- tory variables. For glacial meltwater studies (Figure
magnitude changes in SSC that occur in many rivers 6), these typically include energy budget components
during complex storm events (e.g., Figure 5). The relevant to glacial ablation, rainfall intensity, river
1-min datalogging scan interval used in Figure 5 discharge, temperature, and electrical conductivity,
dened all peaks and troughs in turbidity for most and, with Photo-Electronic Erosion Pin (PEEP) sen-
events. Following calibration, this permitted the full sors, even the erosion events themselves which gene-
definition of exhaustion phenomena in SSCs, and 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- The estuarine turbidity maximum is the term given
derstanding of river sediment transport events to be to the clear peak in mean SSC observable in many
gained. In coastal zones, very high frequency (5 Hz) estuaries around the limit of saline intrusion. Im-
monitoring of OBS turbidity, wave height, and proved explanations of turbidity elds in estuarine
currents (Figure 8), facilitated the definition of the systems, including the nature, location, and migration
critical ow velocities required to mobilize bed sed- of the turbidity maximum, and the tidal pumping
iment. Knowledge of these threshold conditions is processes responsible, have recently been obtained by
important for the stability, engineering, and protec- supplementing water sampling approaches with de-
tion of coastlines and their ecosystems. 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,

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