14.

23 Wet Chemical Methods (pH, Electrical Conductivity, Ion-Selective

Electrodes, Colorimetric Analysis, Ion Chromatography, Flame Atomic
Absorption Spectrometry, Inductively Coupled Plasma-Atomic Emission
Spectroscopy, and Quadrupole Inductively Coupled Plasma-Mass Spectrometry)
C Chagué-Goff, University of New South Wales, Sydney, NSW, Australia, and Australian Nuclear Science and Technology
Organisation, Kirrawee DC, NSW, Australia
HKY Wong, Australian Nuclear Science and Technology Organisation, Kirrawee DC, NSW, Australia
r 2013 Elsevier Inc. All rights reserved.

14.23.1 Introduction 274

14.23.2 Pretreatment of Samples 275
14.23.3 Water for Analytical Methods 275
14.23.4 pH 275
14.23.5 Electrical Conductivity 276
14.23.6 Ion-Selective Electrodes 276
14.23.7 Colorimetric Analysis 277
14.23.8 Ion Chromatography 278
14.23.9 Flame Atomic Absorption Spectrometry 278
14.23.10 Inductively Coupled Plasma Spectrometries 278
14.23.10.1 Interferences 279
14.23.11 Summary 280
References 280

Glossary pH Negative logarithm of the concentration of hydrogen

Anions Negatively charged ions (e.g., Cl and SO42). ions in solution (in normal dilute solutions), pH ¼  log
Cations Positively charged ions (e.g., Na þ and Ca2 þ ). [H þ ].
Electrical conductivity Measure of the concentration of
soluble salts (cations and anions) in solution, expressed as
mS cm1 or mS m1 (1 mS m1 ¼10 mS cm1).

Abstract

A summary of wet chemical methods commonly used in geomorphological studies is presented. Instructions and tips are
provided for the determination of pH and electrical conductivity in the laboratory. General information is presented about
the principles of ion-selective electrodes, colorimetric analysis, ion chromatography, FAAS, ICP-AES, and Q-ICP-MS,
together with some examples. References to specialized textbooks and standard analytical methods are provided for each
analytical technique.

14.23.1 Introduction material, weathering, contamination, and spatial and tem-

Analysis of water and soil/sediment extracts is commonly
conducted in geomorphology, as it can provide information
about many aspects relevant to the discipline, such as the
present and past environmental conditions, source of
Chagué-Goff, C., Wong, H.K.Y., 2013. Wet chemical methods (pH, electrical
conductivity, ion-selective electrodes, colorimetric analysis, ion
chromatography, flame atomic absorption spectrometry, inductively
coupled plasma-atomic emission spectroscopy, and quadrupole inductively
coupled plasma-mass spectrometry). In: Shroder, J. (Editor in Chief),
Switzer, A.D., Kennedy, D.M. (Eds.), Treatise on Geomorphology. Academic
Press, San Diego, CA, vol. 14, Methods in Geomorphology, pp. 274–281.
poral changes. Wet chemical methods cover a large range of
analyses, from pH and electrical conductivity (EC) analysis of
single analytes to multielemental analysis using standard la-
boratory instruments. The aim of this chapter is to provide an
insight in some of the most common analytical techniques,
although acknowledging that the list is not exhaustive. Readers
are referred to the (Standard Methods for the Examination
of Water and Wastewater, 2005, online edition, http://
www.standardmethods.org/) for specific analytical techniques
and details on methodology. Numerous textbooks on soil
chemical analysis also exist, such as Rowell (1994), Sparks
(1996), and Rayment and Lyons (2010).

274 Treatise on Geomorphology, Volume 14 http://dx.doi.org/10.1016/B978-0-12-374739-6.00391-2


Tip: Always refer to the manufacturer’s handbook and
notes for appropriate instrument operating parameters.
14.23.2 Pretreatment of Samples
Numerous rules must be followed when bringing water or
soil/sediment samples from the field to the laboratory. First,
the batch of samples should be accompanied by detailed in-
formation indicating the number of samples and details per-
tinent to their collection, as well as analysis to be carried out.
Characteristically many problems occur as the analyses are
undertaken in commercial laboratories by people who do
not know the environment the samples were collected in, or
the environmental conditions the collected material has ex-
perienced subsequent to field collection. Transportation time
needs to be kept to a minimum and depending on the analysis
required, samples need to be preserved, either cool on ice or
acidified to opH 2. Although they may be frozen in certain
cases, advice needs to be sought from the analyzing laboratory
prior to sample collection.
Measurements of pH and conductivity of water have to be
carried out on unfiltered samples. However, samples need to
be filtered immediately after collection or as soon as practical
for a number of analyte determinations (e.g., dissolved nu-
trients and metals). Again, advice is to be sought from the
laboratory regarding the pore size of the filter to be used.
Where and when possible, pH should be measured in situ (for
both water and soil), but for a number of reasons, such as
unavailability of a pH meter, time constraints in the field, or
soil too dry to allow pH determination in the field, it is
commonly necessary to measure water pH in the laboratory
and for soil to be suspended in liquid to allow measurement
of pH.
Soil samples should be oven-dried below 35 1C (or
air-dried), and then ground and sieved to less than 2 mm
(Rayment and Higginson, 1992) before further analysis.
14.23.3 Water for Analytical Methods
Analytical methods commonly prescribe the use of distilled
water for mixing or rinsing. However, distilled water is not
always available in laboratories, where purification of water
is now commonly obtained through reverse osmosis (RO) and
deionization. Furthermore, there also appears to be some
misunderstanding about the level of purity of the water (RO,
deionized, and distilled water). Thus, definitions are provided
below: RO water is water that has undergone reverse osmosis.
RO is a process by which water moves across a membrane
against the concentration gradient. It results in the removal of
ions (e.g., Ca2 þ , Cl, and Na þ ) and large molecules. De-
ionized water is also called demineralized water. Deionization
is a physical process that uses specially manufactured ion ex-
change resins to remove mineral ions. Because the majority of
water impurities are dissolved salts, deionization results in
high purity water that is generally similar to distilled water.
Distilled water is water that has undergone distillation,
whereby water is boiled and the steam is condensed into a
clean container. Distillation produces very pure water, with
Wet Chemical Methods 275
distilled water having an EC of less than 10 mS cm1. In
modern laboratories, distillation units are replaced with de-
ionized water units. Type 1 water, identified as ultrapure water,
with a resistivity reading of at least 18 mO cm1 and a total
organic carbon (TOC) content of less than 10 mg l1 (Milli-
pore, 2011a), is used for ultra-trace metal analysis. Type 2
water, identified as pure water, has a resistivity reading 45
mO cm1 and a TOC content of less than 30 mg l1 (Millipore,
2011b), and is used for general laboratory applications.
14.23.4 pH
pH is defined as the negative logarithm of the activity of
hydrogen ions in solution. Note that, except in saline solu-
tions, where the activity is smaller than the concentration, in
normal dilute soil solutions, the activity is equivalent to the
concentration of H þ [H þ ] in mol l1 (Rowell, 1994) and thus
pH ¼  log [H þ ]. pH is measured using a glass electrode and a
reference electrode (which are commonly manufactured as
a single combination electrode), and a pH meter, which is a
millivoltmeter. The pH meter needs to be calibrated using
at least two buffer solutions, usually with pH values of 4 and
7, or 7 and 10, depending on the values to be determined.
Before and after sample measurements, all standards should
be checked to ensure readings indeed indicate the correct
pH value.
pH measurement is made either in water, or using a sus-
pension made generally of approximately 10 g of dried soil
(o2 mm) and 50 ml of deionized water (soil:water ratio of
1:5), which is stirred for at least 15 min before measurement.
The suspension should also be stirred during measurement.
The electrodes should be thoroughly washed with deionized
water before and after calibration and between measurements.
The measurement should be carried out in duplicate, of sep-
arate subsamples, and replicate results should be within
0.1 pH unit. It is best that samples, buffers, and electrodes
are at the same temperature, but a temperature difference of
2–5 1C is acceptable in most cases, as the difference in pH
reading between 20 and 25 1C, for example, is less than 0.1 pH
unit (Barron et al., 2010). Refer to the manufacturer’s hand-
book and data on buffer solutions for corrections for each
specific instrument.
The measurement of pH is generally seen as one of the
simplest methods in soil chemistry. However, it is not that
easy, as the pH theory applies to dilute solutions of simple
electrolytes (Bates, 1962), whereas the measured value for any
soil sample is dependent on procedures used in the laboratory,
such as the soil:water ratio, stirring or not during measure-
ment, and position of the electrode during measurement
if no stirring (e.g., Blakemore et al., 1987; Sumner, 1994). The
soil:water ratio alone is a matter for debate, and various ratios
are provided by different authors (e.g., Rayment and Higgin-
son, 1992; Rowell, 1994; Sumner, 1994; Kissel et al., 2009).
We suggest a soil:water ratio of 1:5 as it allows the use of a
common pH electrode. Researchers might choose a different
ratio, in particular if comparing with previous results. How-
ever, one needs to be aware that a soil:water ratio of 1:2.5
results in samples being more like a paste, thus requiring the
use of a paste pH electrode.
276 Wet Chemical Methods
Tips: The important points to consider when carrying out
pH analysis are to make sure that: (1) the pH meter is cali-
brated with at least two buffers, (2) the electrodes are washed
before and after calibration, as well as between measurements,
and (3) the difference in temperature between standard buffer
solutions and samples is no more than 5 1C.
A simple way to check if the electrode is working properly
is to dilute the pH 7 calibration solution 10 times. The reading
should be 7.270.05. If the reading is different, refer to the
electrode manual for cleaning and maintenance requirement.
Note that the electrode should always have a minor amount of
saturated KCl crystals as a conditioning requirement. If it is
not the case, refill the electrode by adding saturated KCl (with
crystals) into the electrode through the opening on the side.
The working range for the electrode sensitivity should be
97–100%. If it is below this value, the electrode needs to
be cleaned. After cleaning and refilling the electrode, the pH
meter should be recalibrated. Also note that there should not
be any air bubbles between the crystals or at the reference
element. Refer to the manufacturer’s handbook for more de-
tails in trouble shooting and cleaning to improve faster re-
sponse, better accuracy, and reproducibility of the electrode.
14.23.5 Electrical Conductivity
EC provides a measure of the concentration of soluble salts
(cations and anions) in solution. It is the specific conductance,
or ability of a solution to carry electricity, and is the inverse of
the resistivity. The SI unit for EC is siemens per m (S m1).
However, depending on the ion concentration in solution, it is
generally expressed in microsiemens per cm (mS cm1) or
millisiemens per m (mS m1), with 1 mS m1 ¼10 mS cm1.
EC is temperature dependent, and is reported at 25 1C. If
measured at a different temperature, the correction of the
value to 25 1C is made using the following equation:
ECðmScm1 Þ ¼ km =ð1 þ 0:0191ðt  25ÞÞ,
where km is the measured conductivity at temperature t (in 1C)
(method 2510B – Standard Methods for the Examination of
Water and Wastewater, 2005). However, modern instruments
generally have an automatic temperature compensation.
EC is determined with a conductivity cell by measuring the
electrical resistance of water or a soil suspension made up with
10 g of dried soil (o2 mm) and 50 ml of deionized water (soil:
water ratio of 1:5), which has been stirred for 1 h (Rayment and
Higginson, 1992). The conductivity cell must be first calibrated
using the KCl reference solution at the same temperature as the
water sample or soil suspension, and rinsed with deionized
water before use. After allowing the soil suspension to settle for
20–30 min, the EC of the supernatant is measured with the
conductivity cell, and the reading is taken once the system has
stabilized. EC of water samples can be measured after the
reading of the electrode immersed in water has stabilized.
Tips: When calibrating the EC meter, take into consider-
ation the conductivity of the sample. Always calibrate the
meter using standards of similar value to the sample. The
reading needs to be repeated if the sample conductivity is
greater than or less than 75% of the conductivity of the
standard used. Record the units on the EC meter when taking
a reading, as the meter may automatically convert from one to
another (either mS m1 or mS cm1).
14.23.6 Ion-Selective Electrodes
Ion-selective electrodes (ISEs) allow quick and cost-effective
determination of ion activity. Compared to many other ana-
lytical techniques, they are relatively inexpensive, simple to
use, and offer a wide range of applications and concentration
ranges; they are not sensitive to color, viscosity, and suspended
solids, and allow the quick measurement of changes in con-
centrations (e.g., Pretsch, 2002; Bedlechowicz et al., 2005).
The ISE, which comprises a special ion-sensitive membrane
that interacts with the ion of choice, is used in combination
with a reference electrode of constant potential and both are
immersed into the aqueous solution with ions to be meas-
ured. Both electrodes are connected to a millivoltmeter, which
measures the potential difference that develops across the ISE
membrane. The measured voltage is proportional to the
logarithm of the concentration. The electrodes are first cali-
brated using solutions of known concentrations, and a graph
of mV versus concentration is plotted. The concentration of
the unknown solution is determined by plotting its mV value
on the graph. The temperature of the standard solutions and
sample should be kept within a few degree centigrades, to
keep with good laboratory practices.
Although the pH membrane in the pH electrode only
allows the passage of hydrogen ions, other ISEs are not en-
tirely ion specific, thus leading to issues with interfering ions.
See also the manufacturer’s instructions, which provide in-
formation of the interfering ion to each measured ion. In di-
lute solutions, it might not be a problem. Otherwise, the
interference can be corrected either by removing the inter-
fering ion through precipitation or complexation prior to
analysis, or by the fixed interference method, whereby the
concentration of the primary ion is changed whereas the
background concentration of the interfering ion is kept con-
stant (e.g., Salt and Vora, 1991).
ISEs are one of the most popular and widely used method
for the determination of fluoride (e.g., Wen et al., 1998;
Konieczka et al., 2000; Standard Methods for the Examination
of Water and Wastewater, 2005 – method 4500), and a sum-
mary of the method is described here. The fluoride electrode is
used in combination with a standard calomel reference elec-
trode (sleeve-type) and a pH meter with an extended millivolt
scale. A series of fluoride standards is first prepared by diluting
a known fluoride standard solution made from a stock
solution of anhydrous sodium fluoride (NaF) with known
volumes of deionized water.
The effects of interfering ions, namely aluminum and iron,
but also hydroxide, can be minimized by adding a known
volume of fluoride buffer (e.g., Konieczka et al., 2000;
Standard Methods for the Examination of Water and Waste-
water, 2005) to standards and samples, which should be at the
same temperature. Readers are referred to Standard Methods
for the Examination of Water and Wastewater (2005) for exact
concentration and pH requirements of the buffer solution,
which is available commercially. Formation of hydrogen
 Wet Chemical Methods 277

fluoride complex, which can occur in acid solutions, can be
minimized by maintaining pH above 5. Hydroxide inter-
ference, which can occur in alkaline solutions, can also be
avoided as long as the pH is maintained between 5.3 and 5.5,
which is achieved by the buffer (Standard Methods for the
Examination of Water and Wastewater, 2005).
Electrodes are immersed into each standard solution,
which is then stirred with a magnetic stirrer. Readings of
potential in mV are taken after 3 min in the standard solutions
and the samples. Electrodes have to be washed with deionized
water and blotted dry between each reading. If a direct-reading
measurement instrument is not used, the measurements of
the standard solutions are plotted (potential mV) against
concentration on logarithmic paper. The concentration of
the unknown samples is then read using the potential value
reading on the graph. Another commonly used method is
the standard addition method, whereby known solutions
of standard are added to each sample. The reader is referred
to Pungor (1998), Pretsch (2002), and Standard Methods
for the Examination of Water and Wastewater (2005), to
name a few, for further details on the principles and uses of
ISEs.
Although there are many advantages in using ISEs, as their
name indicates, they are ion selective, and thus they are ideal if
only one or a few ions have to be determined, or if it is re-
quired to measure the change in concentration in the field. If
the determination of more ions are required, then more time-
effective, analytical techniques include ion chromatography
(IC) (for anions and cations), inductively coupled plasma-
atomic emission spectroscopy (ICP-AES) (for cations), or in-
ductively coupled plasma-mass spectrometry (ICP-MS) (for
cations and isotope ratios), which also provide more precise
results and better detection limits. See Table 1 for examples of
analytes and methods of analysis.
colored substance, a characteristic portion of the wavelength is
absorbed and the remaining light has the complementary
color of the absorbed wavelength (e.g., Skoog and Leary,
1992).
A colorimeter is an instrument that determines the con-
centration of a solution by measuring its absorbance of
a specific wavelength of light, as the concentration is pro-
portional to the absorbance (Beer–Lambert law). A spectro-
photometer measures the light intensity as a function of
the color, or more specifically, the light source wavelength.
Spectrophotometers use a monochromator containing a dif-
fraction grating that splits the spectrum into a large number of
bands, and can read each band to define a more detailed
spectral graph (Figure 1).
Colorimetric methods have long been used for the analysis
of many elements (see Table 1 for examples of analytes).
Nitrite, for example, can be determined through formation
of a reddish purple dye formed through complexation of
diazotized sulfanilamide with NED dihydrochloride, and
photometric measurement at 543 nm with a 1-cm light path
(Standard Methods for the Examination of Water and Waste-
water, 2005 – method 4500-NO2 B). The concentration is
calculated using a standard curve prepared by plotting the
absorbance of standards versus NO2–N concentrations,
which follows Beer–Lambert law up to 180 mg N l1. Nitrate
can be determined using a UV spectrophotometric technique,
whereby the absorbance of NO3 is measured at 220 nm.
However, this technique is mainly used for screening samples
with low organic content (due to the interference of dissolved
organic matter at 220 nm), although a second measurement
may be made at 275 nm to determine the interference and
correct the NO3 value (Standard Methods for the Examin-
ation of Water and Wastewater, 2005 – method 4500-NO3 B).

Monochromator
14.23.7 Colorimetric Analysis Detector
Light source Sample in cuvette Recorder
Colorimetric methods are based on the measurement of
electromagnetic spectra absorbed by chemical substances. Al-
though we see white light as uniform in color, it is actually
composed of a broad range of radiation wavelengths from
ultraviolet (UV), visible, and infrared (IR) portions of the
spectrum. The visible spectrum covers a range of approxi-
mately 380–750 nm, with the shortest visible wavelength Figure 1 Schematic diagram of the main elements of a
violet and the longest red. When white light passes through a spectrophotometer.

Table 1 Examples of analytes and possible/preferred methods of analysis, as well as detection limits. Colorimetric¼colorimetric analysis,
ISE¼ion-selective electrodes, IC ¼Ion Chromatography ( subject to type of column used), FAAS¼Flame Atomic Absorption Spectrometry, ICP-
AES¼Inductively Coupled Plasma – Atomic Emission Spectroscopy, Q-ICP-MS¼Quadrupole-Inductively Coupled Plasma – Mass Spectrometry

Method Analytes Detection limit

Colorimetric NO2, 
P , Li , Na , Ca , K , NH4þ , Mg2 þ , Cu2 þ
Br , NO3, þ þ þ 2þ þ
Sub mg l1
ISE Br , Ca , Cl , CN, Cu2 þ , F, I, K þ , Na þ , NH4þ , NO3, Pb2 þ , S2
 2þ 
Sub mg l1
IC F, Cl, NO2, Br, NO3, SO42, PO43, Li þ , Na þ , Ca2 þ , K þ , NH4þ , Mg2 þ , Sr2 þ , Ba2 þ Sub mg l1
FAAS Most metals Sub mg l1
ICP-AES Most metals and some non-metals mg l1 to mg l1
Q-ICP-MS Most metals and some non metals Sub mg l1

Note: parts per million (ppm) ¼ mg l  1 or mg kg  1; parts per billion (ppb) ¼mg l  1 or mg kg  1; 1%¼ 10 000 ppm (mg l  1 or mg kg  1).
278 Wet Chemical Methods
14.23.8 Ion Chromatography
IC is an analytical technique for the determination of the
common cations and anions. It is also known as a liquid–solid
chromatographic method where the eluent (liquid) is passed
through a column of inorganic or polymeric organic resin
(solid) and then to a flow-through detector (Figure 2).
A fixed amount of water sample using a sample loop of
10–100 ml is injected into the eluent via the switching valve. The
eluent is continuously pumped through the preconditioned
column at a constant flow rate of approximately 1–2 ml min1.
The column, which is packed with uniform resin, is 2–4 mm
wide with a typical length of 15 cm. The anions or cations in
the sample are chemically bound to the resin before being re-
placed by the counter ions of the same charge from the eluent.
The elution characteristics are determined by the ion exchange
capacity of the resin and the concentration of competing ions in
the eluent. As the sample flows through the column, it begins to
separate into its individual components. The sample com-
ponents that are weakly bound by the resin travel rapidly with
the flow of the eluent. The components travel through the
column at different rate and enter the detector at different
times. A flow-through membrane device known as the sup-
pressor is added after the column to reduce the background
noise and improve detection limit. This is achieved by changing
the highly conductive strength of the eluent to a weaker acid.
The conductivity detector senses the sample components and
produces a chromatogram. By determining the peak area or
peak height, one can quantify the concentration by comparing
it with known standards.
Readers are referred to Haddad and Jackson (1990), Smith
(1990), and Skoog and Leary (1992) for details on the prin-
ciples and applications of IC. The technique has been used in
a number of studies assessing the effect of anthropogenic ac-
tivities on soil and water quality, either for the analysis of
cations and anions in water, or the determination of analytes
(e.g., Cl, S, and F) after extraction from soil samples. For ex-
ample, IC was used in a study investigating the efficiency of a
small wetland treating domestic wastewater (Chagué-Goff
et al., 1999). Data showed that sulfate concentrations had
decreased after passage through the land treatment area,
whereas phosphate concentrations had not, due to release of
phosphorus by the sediment.
Sample
Eluent Pump Column
Waste
Figure 2 Schematic diagram of ion chromatography.
14.23.9 Flame Atomic Absorption Spectrometry
Flame atomic absorption spectrometry (FAAS) is based on a
sample being aspirated into a flame and atomized. A light
beam is directed through the flame, then into a mono-
chromator, and then onto a detector that measures the
amount of light absorbed by the atomized element in the
flame (Standard Methods for the Examination of Water
and Wastewater, 2005). Each metal has its own characteristic
absorption wavelength, thus a source lamp made of that
particular element is used for each element to be analyzed,
which also reduces interferences. The amount of energy at
that characteristic wavelength absorbed in the flame is pro-
portional to the concentration of the element, but only over a
limited concentration range. Many metals can be determined
using an air-acetylene flame (e.g., Ca and Mg), with chemical
interferences being reduced or eliminated by adding specific
compounds to the sample solution. Some elements (e.g., Al, P,
and Sr) require a hotter flame for complete dissociation, and
nitrous oxide-acetylene flame is thus used. Standard solutions
of known metal concentrations are also prepared in a similar
matrix of that of the sample.
Readers are referred to Skoog and Leary (1992) for details
on the principles of FAAS and Standard Methods for the
Examination of Water and Wastewater (2005) (method 3111)
for details on the analytical technique, flame gas required,
preparation of standards, and interferences. Although FAAS
used to be the preferred method of analysis for most metals,
due to its simplicity of use and relatively low cost, it is time
consuming as only one element can be analyzed at one time.
Thus, the method has now most often been superseded by
ICP-AES and ICP-MS (see Section 14.23.10), in particular for
multielement analysis.
14.23.10 Inductively Coupled Plasma
Spectrometries
Inductively coupled plasma-atomic emission spectrometry
(ICP-AES) and quadrupole-inductively coupled plasma-mass
spectrometry (Q-ICP-MS) have become the most popular
techniques used today for multielement analysis, due to the
following reasons (e.g., Montaser, 1998):
Suppressor Detector Data processing
= Switching vial with sample loop
 Wet Chemical Methods 279

1. Better detection limits than FAAS. The detector measures the light (ICP-AES) or ions (Q-ICP-
2. Improved sample throughput and number of elements MS) and converts them to electrical signal as counts per second
under one set of conditions. (cps) that can be measured. The signal is proportional to
3. Greater linear dynamic range (up to 8 orders of magnitude). the concentration of the element and one can quantify the
4. Isotope analysis is possible with ICP-MS. concentration by comparing the signal intensities to known
5. Lower interferences due to higher temperature than the concentrations.
flame (B2–3 times greater). ICP-AES and ICP-MS are used in a number of studies in-
vestigating natural and anthropogenic changes in marine,
Basically, the sample compartments and plasma of the ICP-
coastal, and freshwater environments, such as that of Pas-
AES and ICP-MS are very similar (Figure 3). The sample, in a
ternack and Brown (2006), who used ICP-AES to reconstruct
liquid form, is pumped or self aspirated via suction into the
the Holocene geochemical history of a floodplain in California.
nebulizer. If the sample to be analyzed is a solid, it is first
dissolved/digested and then analyzed. The liquid forms an
aerosol of fine droplets (1–10 mm) with argon gas using the 14.23.10.1 Interferences
nebulizer. Large droplets are separated from the fine droplets
ICP-AES: spectral – due to the large amount of emission
in the spray chamber. The argon gas carries the fine droplets
spectral lines (greater than 50 000), there are occasions when
into the plasma, where the sample is vaporized, atomized, and
one overlaps another. Interelement correction could reduce
ionized (Figure 4). The plasma is a spherical ball of ionized
the errors but has limited success. Background correction with
argon gas at around 8000–10 000 K.
sophisticated equations could improve the accuracy. The best
Emission Spectroscopy is based on light produced from
option is to find another emission line without the inter-
excited atoms and ions when they return to their ground state
ference. Thus, the resolution of the instrument is important to
or to lower excitation state. An element will emit light with a
resolve the spectral overlap and reduce these interferences.
set of characteristic wavelengths that can be used to identify
Matrix effect – spray chamber effects and viscosity differ-
the element. The spectrum light passes through the mono-
ence between samples and calibration standards could also
chromator containing lens, mirrors, gratings/prisms, slits, and
affect the accuracy of the results. That is, the efficiency of
detectors. The primary function of the monochromator is to
samples carried up to the plasma is different for the standards
isolate light to its specific wavelength of interest, where the
and the samples. One way to overcome this matrix problem is
detector can measure the intensity of the wavelength. There are
to matrix match the standards to the samples or perform a
two basic types of ICP-AES, sequential and simultaneous. The
standard addition instead of the normal external calibration.
sequential instrument as the name implies measures the
Q-ICP-MS – there are less interferences identified than by
wavelengths one by one, whereas the simultaneous instrument
ICP-AES. These interferences occur when species has a similar
measures a large number of wavelengths at the same time.
mass to the analyte. Some of the examples are shown below:
Detection limits have improved by a factor from 2 to 10
through axial viewing (end-on) of the plasma instead of radial 1. Isobaric or elemental interferences – 40Ar on 40Ca,
(side-on) (e.g., Montaser, 1998). Readers are referred to 2. Polyatomic or matrix interferences – 40Ar16O on 56
Fe,
40 35
Montaser and Golightly (1987), Varma (1991), and Skoog Ar Cl or 40Ca35Cl on 75As, and 40Ar37Cl on 77Se,
and Leary (1992) for details on principles and applications of 3. Doubly charged ions – 88Sr2 þ on 44Ca,
ICP-AES. 4. Matrix effects similar to the ICP-AES.
The Q-ICP-MS generally has a much lower detection limit
than the ICP-AES. Excited ions produced in the plasma
are extracted into the mass spectrometer via an ion lens
system. Light is excluded from the quadrupole filter and de-
tector region via a photon stop or through bending ions into
the quadrupole filter to reduce background noise. The quad- Aerosol
rupole mass filter consists of four cylindrical rods of ap-
proximately 1 cm in diameter and 15 cm in length. By varying
the voltage of AC and DC applied to the rods, only ions of a
Ions Atoms Gas Solid Liquid
specific mass to charge ratio are allowed through onto the
detector at any one time. The Q-ICP-MS is a fast sequential
instrument which can separate up to 2400 atomic mass units
(Ionization) (Atomization) (Vaporization) (Desolvation)
(amu) per second. Readers are referred to Skoog and Leary
(1992) and Montaser (1998) for details on principles and Figure 4 Schematic diagram of the inductively coupled
applications of Q-ICP-MS. plasma torch.

Monochromator/mass filter
Sample Nebulizer Spray chamber Plasma
+ detector

Figure 3 Schematic diagram of the principles of inductively coupled plasma – atomic emission spectroscopy and quadrupole-inductively
coupled plasma–mass spectrometry.
280 Wet Chemical Methods
To minimize these interferences, one could: choose another
mass/isotope which is free of the interference; optimize the
instrument to minimize the oxides and doubly charged ions;
use lower power (cool plasma) or shield torch interface setting
to reduce the polyatomic interferences with argide ions; or use
internal standards to minimize matrix effects. In the modern
instruments today, a collision or reaction cell is installed in the
system to further reduce the matrix effects from chloride and
argide formation. The use of high resolution (HR) ICP-MS
would also reduce these matrix effects, but the cost is ap-
proximately double that of a Q-ICP-MS.
Tips: Always assess if the detection limit by any specific
method is sufficient for the measurements required. Generally,
instrumental methods are more sensitive than the colorimetric
and ISE method. Always include a procedural blank with each
set of samples. A procedural blank, which is a reagent water
blank containing acids, is included in any digestion steps. As
part of the quality assurance, if possible include a reference
material of a known certified concentration that is similar
in matrix to the sample. This will ensure that digestion and
analytical methods are working properly. A good practice is
to include quality controls checks (i.e., known concentra-
tion standards) when analyzing samples to check for instru-
ment drifts.
14.23.11 Summary
Wet chemical methods are widely used in geomorphological
studies. They range from pH and EC measurements to the
analysis of elements in water and soil/sediment extracts.
Techniques presented allow for the analysis of single elements
as well as the simultaneous determination of multianalytes.
Although advances have been made in the development
of analytical techniques (e.g., Laser Ablation-ICP-MS), wet
chemical methods described above are suitable to fulfill the
requirements of most geomorphological studies.
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 Wet Chemical Methods 281

Biographical Sketch

Dr Catherine Chagué-Goff is a Senior Research Fellow at the Australia-Pacific Tsunami Research Centre, University
of New South Wales and at the Australian Nuclear Science and Technology Organisation. Her current research
interests include recent and past environmental changes, with particular emphasis on chemical and isotopic
signatures.

Henri Wong is the Manager of the Inorganic Analytical Laboratory in the Institute for Environmental Research, at
the Australian Nuclear Science and Technology Organisation. He is involved in a number of research projects
ranging from studies of groundwater to tracing of contaminant sources. He has 15 years experience working with
ICP-AES and ICP-MS.