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Water Analysis: Seawater—Inorganic Compounds for the Environmental

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Water Analysis: Seawater—Inorganic Compounds for the Environmental

Analysis☆
Guang-Yuan Lu and Wen-Xiong Wang, Shenzhen Research Insistute, HKUST, Shenzhen, China; HKUST, Hong Kong, China
© 2018 Elsevier Inc. All rights reserved.

Introduction 1
Sampling, Pretreatment, and Storage 1
Macroelements 2
Nutrients 3
Dissolved Oxygen 3
Trace Metals 4
Techniques 5
Further Reading 5

Introduction

The oceans cover approximately 71% of the Earth’s surface and 90% of the Earth’s biosphere. The Ocean also reserved about 1.35
quintillion metric tons water resource, equivalent to 97% of Earth’s water. However, because humans live only on the terrestrial
land and due to the difficulty of marine research, only 5% of the World Ocean has been studied and explored. With the rapid
increase of marine development by human beings, the coastal areas and open seas are used as mariculture, petroleum exploitation,
and port construction, consequently the pollution has seriously affected ocean health and ecological safety. It is a big analytical
challenge for measuring many substances in seawater during environmental monitoring, which is the basic support and cornerstone
for marine management and protection. This article will introduce the inorganic analysis of seawater, including major ions, carbon,
nitrogen, phosphorus, silicon, dissolved oxygen, trace elements, and some rare earth elements in estuarine, coastal, and open sea
waters. Sodium ion (Naþ, 55%), chloride (Cl, 31%), sulfate (SO2 2þ 2þ
4 , 8%), magnesium ion (Mg , 4%), calcium ion (Ca , 1%),
þ
and potassium ion (K , 1%) were the six major ions about >99% of the total dissolved in seawater. The components of major ions
in the seawater are listed in Table 1 (modified data from https://www.sedgeochem.uni-bremen.de/standards_seawater.html).
All macroelements (Na, Mg, Ca, K, Br, Sr, S, Cl, B, F, and Si) in seawater are present at concentrations  103 mg/kg, while some
microelements are present at much lower concentrations ranging from 106–1012 mg/kg. Among these microelements, some
nutrient elements such as Zn, I, Fe, and Mn play important roles in marine organism metabolism, and some toxic or harmful
elements such as Cd, Ni, Pb, and As are considered as the pollutants of marine environments. The chemical analyses of seawater are
to measure or monitor the concentrations of ions or compounds (inorganic or organic) at submicromolar to millimolar
concentrations.

Sampling, Pretreatment, and Storage

Clean sampling is firstly essential for inorganic compounds in seawater analysis. The dissolved fractions are conventionally and
operationally defined as those passing through filters of about 0.22–0.45 mm pore diameter. However, some colloids in seawater are
also included in the dissolved phase. In some studies, measurements have been made on unfiltered samples with storage after
acidification for total inorganic analysis, such as total nitrogen and phosphorus. The shallow water samplers directly collect the
seawater samples at the target area from the upwind head, taking great care to avoid metals or oil contamination. For dissolved
oxygen or dissolved gas compounds analysis, the sampling needs to use siphon tube to collect water without gas bubble and air
disturbance. When using boat or ship for sampling, reversing water sampler or nonmetallic, free flushing water sampler is
recommended for general-purpose water sampling of PVC body. The most commonly used water samplers include Van Dorn
Bottle, Nansen Bottle, Niskin Bottle, Go-Flo, ground-glass stoppered flask (all sample cases as http://www.oceantestequip.com/
water-samplers.php, http://www.generaloceanics.com/water-sampling-bottles/, http://www.marinebio.net/marinescience/01intro/
tosamp.htm). On a large research ship with a need of large volume of water for preconcentration, full closure devices capable of
continuously pumping the uncontaminated water into the ship’s in situ laboratories are necessary. The most difficult sampling in
the deep sea is the collection of different layers of several kilometers under the sane conditions of in-situ original temperature and
pressure. In the deep sea, sampling requires the solid strength and high corrosion-resistant material of sampling frames to support
sampling bottles.
For dissolved inorganic analysis, the organisms such as phytoplankton or zooplankton, suspended inorganic particles, and
organic detritus are separated from the water samples through 0.22–0.45 mm pore-size filters. The dissolve part is defined as the

☆
Change History: September 2018. Guang-Yuan Lu and Wen-Xiong Wang updated text and references. Update of T. D. Jickells and A. R. Baker. Water Analysis |
Seawater—Inorganic Compounds. Encyclopedia of Analytical Science, 2nd Edition, 2005, pages 283–289. https://doi.org/10.1016/B0-12-369397-7/00657-9.

Encyclopedia of Analytical Science, 3rd Edition https://doi.org/10.1016/B978-0-12-409547-2.14498-1 1

 2 Water Analysis: Seawater—Inorganic Compounds for the Environmental Analysis
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Table 1 Main composition of standard seawater (salinity of 35%)

Element Concentration Concentration range Molar concentration (density of 1.05 g/cm3)

As 1.7 mg/kg 1.1–1.9 mg/kg 22.69 nmol/kg (23.82 nmol/L)

Al 0.54 mg/kg 0.01–1.2 mg/kg 0.020 mmol/kg (0.021 mmol/L)
B 4.5 mg/kg Average 416.3 mmol/kg (437.09 mmol/L)
Ba 14 mg/kg 4–20 mg/kg 0.102 mmol/kg (0.107 mmol/L)
Br 67 mg/kg Average 838.5 mmol/kg (880.5 mmol/L)
C_total 27.6 mg/kg 24–30 mg/kg 2.298 mmol/kg (2.412 mmol/L)
Ca 412 mg/kg Average 10.279 mmol/kg (10.793 mmol/L)
Cd 0.08 mg/kg 0.0001–0.12 mg/kg 0.71 nmol/kg (0.75 nmol/L)
Cl 19,354 mg/kg Average 545.95 mmol/kg (573.25 mmol/L)
Cs 0.29 mg/kg Average 2.18 nmol/kg (2.29 nmol/L)
Cu 0.25 mg/kg 0.03–0.4 mg/kg 3.93 nmol/kg (4.13 nmol/L)
F 1.3 mg/kg Average 68.42 mmol/kg (71.84 mmol/L)
Fe 0.055 mg/kg 0.005–0.140 mg/kg 0.98 nmol/kg (1.03 nmol/L)
Hg 0.001 mg/kg 0.0004–0.002 mg/kg 4.98 pmol/kg (5.23 pmol/L)
I 50 mg/kg 25–65 mg/kg 0.394 mmol/kg (0.414 mmol/L)
K 399 mg/kg Average 10.20 mmol/kg (10.71 mmol/L)
Li 0.174 mg/kg Average 25.07 mmol/kg (26.32 mmol/L)
Mg 1290 mg/kg Average 53.06 mmol/kg (55.72 mmol/L)
Mn 0.014 mg/kg 0.005–0.2 mg/kg 0.255 nmol/kg (0.268 nmol/L)
Na 10,770 mg/kg Average 468.46 mmol/kg (491.89 mmol/L)
N 0.42 mg/kg 1–0.63 mg/kg 29.98 mmol/kg (31.48 mmol/L)
Ni 0.5 mg/kg 0.1–0.7 mg/kg 8.52 nmol/kg (8.94 nmol/L)
P 70 mg/kg 0.1–110 mg/kg 2.26 mmol/kg (2.37 mmol/L)
Pb 0.002 mg/kg 0.001–0.035 mg/kg 9.65 pmol/kg (10.135 pmol/L)
Rb 0.12 mg/kg Average 1.404 mmol/kg (1.474 mmol/L)
S_total 904 mg/kg 2712 mg/kg SO4 28.19 mmol/kg (29.60 mmol/L)
Si 2.8 mg/kg 0.02–5 mg/kg 99.68 mmol/kg (104.66 mmol/L)
Sr 7.9 mg/kg Average 90.16 mmol/kg (94.67 mmol/L)
U 3.3 mg/kg Average 0.0139 mmol/kg (0.0145 mmol/L)
Zn 0.4 mg/kg <0.01–0.6 mg/kg 6.12 nmol/kg (6.42 nmol/L)

filtrate, although it may also contain the colloidal components. The colloids in seawater play an important role in microbial activity
and deep-sea food web. The flow field-flow fractionation, such as Eclipe Asymmetric Flow Field-Flow Fractionation (AF4) system or
Hollow-Fiber Flow Field-Flow Fractionation (HF5), is a uniquely versatile ways of size-based separations, capable of fractionating
and characterizing the proteins and aggregates, liposomes, emulsions, viral particles, colloidal particles, among others. It can further
separate true soluble, macromolecules, colloidal or insoluble nanoparticle components over a wide size range of 1 >1000 nm
with excellent resolution. This technique can avoid adverse interactions with column packing beads and short analysis time, and
provide numerous advantages over other conventional column separation techniques. For trace metal or rare earth metal analysis,
some useful pre-concentration procedures can be applied to improve the detection concentrations. Co-precipitation with iron (III)
“hydroxide” or cobalt pyrrolidinedithiocarbamate, complexation with dithiocarbamates, 8-quinolinol, and dithizone extraction
into a range of solvents, or chelating column like Chelex-100, Nobia-chelate PA-1®, are the most widely used and efficient method
for preconcentrating a substantial concentration at 10–100 fold of original seawater with minimal interferences.
Because of the difficult in-situ analysis of some components, it needs cryopreservation of sample for storage to avoid component
degradation or production by microbial activities and adsorption/desorption processes. To stabilize the variable components in
seawater, many strategies have been applied during the storage period. To prevent the potential wall-adsorption of sample
containers, samples need to be routinely acidified to about pH ¼ 2.0. In some instances, the online-preconcentration techniques
can be used to estimate the speciation of metals in seawater by analyzing samples directly without acidification. However,
acidification process before storage will disturb the ion speciation or other inorganic components in seawater. Ultralow temperature
and mercury (II) chloride could slow down all reactions of biological process. Some components will settle under the low
temperature, such as some silicate or metal hydrate/chelate. For notices, some gas components or speciation analysis need a stable
anoxic condition, and the sample will be pretreat by inert gases such as nitrogen (N2) or Argon (Ar) for avoiding redox environment
change.

Macroelements

Major ions (or macroelements, including Naþ, Mg2þ, Ca2þ, Kþ, Br, Sr2þ, SO2    
4 , Cl , H3BO4 , F , and HCO3 ) are defined as
elements concentration > 1 ppm or 0.001 (>1 mg/kg). These ions are the main contribution to the standard salinity seawater
(35%). Naþ and Cl account for >86% of the total salt content. The units of g/kg allows to determine the contribution to salinity of
seawater. Chemists prefer to use mole concentrations as mmol/kg or mmol/L by considering the chemical reaction, which is related
 Water Analysis: Seawater—Inorganic Compounds for the Environmental Analysis 3

to the temperature and pressure. The major ions are relatively constant in seawater, thereby it is normally unnecessary to measure
their concentrations. Individual major ions are determined by atomic absorption spectrometry (AAS) or inductively coupled
plasma-optical emission spectrometry (ICP-OES).
The carbonate system contains dissolved carbon dioxide (DIC), carbonic acid (H2CO3), bicarbonate (HCO 3 ), carbonate
(CO23 ), and some complexes. Basically, the system includes the dissolution of carbon dioxide gas (CO2) and carbonate minerals
into the seawater. Seawater is an aqueous mixed electrolyte. It attains its chemical composition through a variety of chemical
reactions and physio-chemical processes: including acid-base reactions, gas absorption and desorption process, precipitation and
dissolution of solids and adsorption processes between different interfaces.

CO2 ðgÞ Ð CO2 ðaq:Þ

CO2 ðaq:Þ þ H2 O Ð H2 CO3
H2 CO3 Ð HCO3 þ Hþ
HCO3 Ð CO3 2 þ Hþ

The difficult part of carbon analysis is the accuracy of CO2 determination. Recently, an efficient method has been applied. DIC can
be extracted from water samples as gaseous CO2 using a vacuum extraction (Macchia et al., 2013), and this system is fitted with a
graduated cylinder for injecting water and orthophosphoric acid. Three vessels are used to trap and transport the extracted CO2, and
the released CO2 gaseous mixture is firstly removed from water vapor by the 80  C water trap, and then CO2 can be frozen into the
liquid nitrogen trap. Nowadays there are concerns over the CO2 emission from different continents and seas, which is related to the
climate change and greenhouse effect. It requires extremely accurate and precise measurements of the carbon dioxide system.

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Nutrients

In seawater, some ions are essential for the growth of phytoplankton that form the primary production of marine food web. Unlike
macroelements, nutrient elements such as nitrogen, phosphorus, and silicon are presented at relatively low concentrations, which
can limit the growth rate of phytoplankton in seawater. In oligotrophic areas, which cover approximately 40% of the world’s oceans,
nutrient concentration can drop to nanomolar levels or even lower due to the biological uptake. Highly sensitive methods and
technologies are urgently needed for nutrient measurements in these areas. Although some researchers demonstrated that special
trace metals and dissolved organic matters can also limit algal growth, the traditional view is that nitrogen, phosphorus, and silicon
are nutrient elements, because of their key roles in the growth metabolism, physiological and biochemical reaction, and skeleton
construction to resist climate change and maintenance the balance of the marine ecosystems. These elements are also important for
environmental management of wastewaters discharged into the seawater, coupled with the alarming environmental problems of
harmful algal blooms, eutrophication, and hypoxia-zone in coastal and estuarine waters. Nitrogen is present as nitrate, nitrite,
ammonium, amino acid, polypeptide, and protein in seawater. Phosphorus is present as phosphate, polyphosphate, phosphine,
and phospholipid in seawater. Silicon is present mainly as silicate in seawater. Nitrogen and phosphorus are the required nutrients
for all phytoplankton, and silicon is required for diatoms. In tropical and subtropical ocean, silicate in the euphotic zone can be
seasonally or chronically depleted to <0.1–0.6 mmol/L, which limits the diatom productivity that export of carbon from surface to
the deep sea. Nitrogen gas (N2) in seawater is usually unavailable to most algae, but some cyanobacterium like Trichodesmium has
the ability of nitrogen fixation. Algae use nitrate, nitrite, ammonium, and dissolved amino acid. Colorimetric determination
methods of phosphate, nitrate, nitrite, ammonium and silicate are well established and used at measurement of seawater in coastal
waters, with acceptably high sensitivity of both manual detection and automatic procedures. Nutrient elements are often depleted to
the detection limits of the colorimetric methods by phytoplankton in the euphotic layer. Therefore, the precipitation preconcentra-
tion, catalytic spectrophotometry, flow injection analysis combined with fluorescence method have been developed for lower
concentration detection.

Dissolved Oxygen

There are three common method for measuring the dissolved oxygen concentration, involving electrochemical, optical sensor, and
colorimetric method. The colorimetric method offers a basic approximation of dissolved oxygen concentrations in a water sample.
The conventional measurement of dissolved oxygen in freshwater systems is Winkler Method, which is considered as the most
accurate and precise method for many years. Electrochemical sensors contain polarographic, pulsed polarographic and galvanic
sensors. Optical dissolved oxygen sensors measure the interaction between oxygen and certain luminescent dyes. When exposed to
blue light, these dyes become excited (electrons gaining energy) and emit light as the electrons return to their normal energy state.
When dissolved oxygen is present, oxygen will interact with the dye, thus the returned wavelengths are limited or altered. The
Winkler Method uses titration to determine the dissolved oxygen by fixing a series of reagents that form an acid compound.
Although this method has human error and is more difficult in in-situ determination, particularly in the field, it is still used today.
When applying this method in seawater analysis, the reagent manganese (II) sulfate is used instead of manganese (II) chloride. This
method is suitable for the measurement of oceanic levels of 1–400 mmol/kg in uncontaminated seawater, but is unsuitable in
seawater containing hydrogen sulfide such as in hydrothermal vent and cool seep of deep sea. The principle of the Winkler
 4 Water Analysis: Seawater—Inorganic Compounds for the Environmental Analysis

procedure is that oxygen oxidize iodide ion to iodine quantitatively (in the presence of manganese (II) ion under alkaline
conditions), and then the fixed equivalent iodine is determined by titration with a standard thiosulfate solution. The end-point
is located using starch indicator for the presence of iodine from color indigo carmine to colorless.
Relevant titration reactions are the following:
Mn2þþ2OHÐMn(OH)2 #
Mn(OH)2 þ 1/2O2ÐMnO(OH)2 #
MnO(OH)2 þ Mn(OH)2 Ð2 H2O þ MnMnO3 # (brown and yellow)
MnMnO3 þ 6Hþþ2IÐ2Mn2þþI2 þ 3H2O

I2 þ 2S2O2
3 Ð2I þ S4O6 (Starch indicator, from indigo carmine to clear and colorless)
2

Other sensor methods can be found in https://www.fondriest.com/environmental-measurements/equipment/measuring-water-

quality/dissolved-oxygen-sensors-and-methods/.

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Trace Metals

Heavy metals are often referred to as trace metals, occurring at low concentrations in seawater or organisms (Burton and Stratham,
2018). Because of the universally low (nmol/L or less) concentration of trace metals, it is a major challenge to achieve reliable and
accurate determinations of these trace metals in seawater. In previous studies, behaviors of dissolved trace metals in the ocean have
been divided into three principal categories reflecting their chemical and geochemical characteristics.
Group I: these metals behave conservatively or show minor divergences, which are highly influenced by local sources (e.g.
estuary inputs, glacial metaling). They showed a significantly mixing impacts of different water bodies in boundary regions. This
characteristic reflects their low geochemical reactivity, which are due to their long-time mixing residence (>105 years) as major ions
such as sodium, chloride, and potassium, but relatively low concentrations in crustal rocks. Metals in this group include lithium (Li,
25 mmol/kg), rubidium (Rb, 1.4 mmol/kg), cesium (Cs, 2.2 mmol/kg), molybdenum (Mo, 90–135 nmol/L), and uranium (U,
13.9 nmol/kg).
Group II: nutrient-like metals; they behave like some micronutrient, phosphate, nitrate, or dissolved silicon in the open sea by
depletion in surface waters to deep waters. They reflect the vertical profiles of the metals of biogenic particulates, which transmit the
primary productivity of phytoplankton from euphotic layer to deeper sea, where they are released by microbial activities in the
bottom waters. These metals behave intermediate residence times and have recycling style. Metals in this group included cadmium
(Cd, like dissolved phosphate profile), zinc (Zn, like dissolved biogenic silica or phosphate), germanium (Ge, like dissolved
silicon), nickel (Ni, like micronutrients), copper [Cu, Cu (þI) or Cu (þII), shows the inverse pattern of the recycled elements, rest
with its valence state], selenium [Se, Se (þIV) or Se (þVI) occur as the oxy-anions, selenite and selenite, organic selenide, Se (-II)],
arsenic [As, As(þV) (arsenate), and As(þIII) (arsenite), methylate forms, like dissolved phosphate].
Group III: these metals behave markedly non-conservative and short residence time (103 years), which reflect efficient removal
behavior of particles by oxidative or hydrolytic scavenging, or enhanced concentrations in surface waters. Metals in this group
included aluminum (Al, 21 nmol/L), gallium (Ga, 7–56 pmol/L), manganese [Mn, Mn (þIV) in which the solubility of oxidation
state is very low, or Mn (þII) under reducing conditions], cobalt (Co, 10–100 pmol/kg), iron [Fe, Fe(þII) occurs at high
concentrations in hydrothermal fluids], lead (Pb, atmospheric deposition), mercury (Hg, atmospheric deposition). In the deep
ocean waters, the trace metal concentration show little variation with depth.
Among these metals, iron play a special role in the ocean, with approximately 40% of the world’s surface waters are high-nutrient
and low chlorophyll (HNLC) due to the iron limitation, the most important being the Southern Ocean, the Equatorial Pacific and
the Subarctic Pacific. John Martin advanced the “Iron Limitation Hypothesis” in 1991 based on an inverse correlation between
carbon dioxide and iron in Vostok ice cores linked with glacial and interglacial transitions. Martin proposed that increased Fe input
to HNLC oceans could stimulate the primary production, and many studied have tested this hypothesis in the Equatorial Pacific,
Subarctic Northeast Pacific and Southern Ocean by seeding low concentrations of dissolved iron. These works showed a signifi-
cantly triggering of large phytoplankton blooms, with a subsequent large drawdown flux of atmospheric carbon from surface water
to the deep sea. Size fractionation is important due to the broad variety of Fe species in seawater, including macromolecules,
colloidal phases, nanoparticles. The development of trace metal clean ultra-filtration techniques improves the Fe size fractions
analysis. Iron usually have a nutrient-type vertical distribution in open ocean HNLC waters, with surface water depleting by
organisms to a very low concentration of <0.2 nmol/L. In recent years, high resolution (magnetic sector) ICP-MS has become the
preferred atomic spectrometric method of iron determination with high sensitivity and short time efficiency. Isotope dilution is
frequently used for quantification, co-precipitation preconcentration methods required minimal use of reagents, and the dispersive
liquid-liquid micro extraction offers advantages for lower iron detection. High resolution ICP-MS or a Nobia Chelate PA1® resin
combine preconcentration can improve the detection limit of 2 pmol/L and 14 pmol/L. The off-line preconcentration system of
solid-phase extraction SPE 100 (Hiranuma Sangyo) has been developed for single step preconcentration of Al, Mn, Fe, Co, Ni, Cu,
Zn, Cd, and Pb analysis in a nanomolar concentration.
 Water Analysis: Seawater—Inorganic Compounds for the Environmental Analysis 5

Techniques

Based on the procedure of water pretreatment, methods of inorganic compounds fall into two ways: pre-concentration method and
direct method. The pre-concentration method requires a variety of pretreatment such as atomic absorption spectroscopy (AAS), gas
chromatography, and mass spectrometry. Direct methods are spectrophotometric, chemiluminescence, and fluorimetric proce-
dures, electrochemical methods, including Inductively Coupled Plasma-Mass Spectrometry (ICP-MS) and–Atomic/Optical Emis-
sion Spectrometry (ICP-AES or ICP-OES). A variety of analysis method has been applied in metal analysis in seawater, among
which, the most common analysis one is the atomic absorption spectroscopy (AAS), which is the earliest method. The light source
radiates the characteristic spectrum of the special elements for measurement. When the light passes the atomic vapor from the
atomization of the sample, it will be absorbed by the ground state atoms, and the content of the elements can be determined by the
weaken degree of the characteristic spectrum. The negative limits of atomic spectrometric determination of seawater analysis are the
large interferences of the major ion in substratum of seawater. Today, the ICP-MS and ICP-OES are widely used in the elements
analysis in the laboratory. The ionization process of metals under the ultra-high temperature (8000–10,000 K) of mass spectrom-
etry can resolve the most interferences. The inductively coupled plasma has an analytical nebulizer, which can produce excited
atoms. The ions from plasma flame emit electromagnetic radiation with specific nano-scale wavelengths characteristics of elements.
The intensity of the emission from sample is indicative of the metal concentrations in the samples. The optical emission
spectrometry and mass spectrometry are different electromagnetic detectors, and ICP-OES have the lower sensitivity to measure
trace elements than ICP-MS. Compared to OES, MS has greater speed, precision, and sensitivity of low concentration as one part in
1015 (part per quadrillion, ppq) on non-interfered low-background isotopes.
Chemiluminescence is using the illuminating effects of the metal reactions without extra light source, with is the most different
aspect from fluorimetric method. This method is often used along with flow injection analysis (FIA) technology in the determina-
tion of trace metals in the laboratory. Spectrophotometric technique is a basic and widely application method by using the metal
combination with ligands to form a colored complex with high molar absorptivity.
Significant improvements have been made in the determination of low concentration of metals in seawater. However, expensive
costs of cumbersome equipment and complex pretreatment make these methods difficult to be applied in situ at sea. ICP-MS and
AAS have a limited range for use and are not suitable for on-site measurement. Colorimetry and chemiluminescence combined with
FIA have a lower detection limit for some metals and different speciation, but they require complicated pre-treatment procedures
and matrix removal. Stripping voltammetry is a classic electrochemical method for metal analysis of auto-detection of Cu, Zn, Pb,
Cd, Hg, As in situ, however, this method have a relative low stability and anti-interference ability of the working electrode. The
Voltammetric In situ Profiling system (VIP) firstly developed by Tercier et al. (1998) provides a solution to the above problems and
has now been commercialized for continuous in situ analysis of trace metals. An improve VIP called the Multi Physical Chemical
Profiler (MPCP) has been developed for in situ monitoring of trace metal species in various environment. MPCP has been
successfully used in Cu and Pb speciation analysis in the Po estuary of the Adriatic Sea. These two system have been shown to
provide reliable, real-time monitoring of metals and their species with less than 10% variations over a continuous filed survey for up
to 8 days without renewal of the sensor. A new strategy for metal determination in low cost and reliable long-term monitoring
method of in situ sensor is an autonomous spectrophotometric analyzer capable of providing vertical profiles by Milani et al.
(2015). In situ sensors have great potentials for quantifying the basic distribution of metals in seawater. Further development is still
need to improve the sensor reliability and accuracy for long-term stable operation, and wireless techniques and real-time
transmission technologies of information science provide a broad prospects for future studies.
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Further Reading
Burton, J. D.; Stratham, P. J. Trace Metals in Seawater. In Heavy Metals in the Marine Environment; Furness, R. W., Rainbow, P. S., Eds.; Taylor & Francis Group, 1990; pp 5–26.
Bruland, K. W. Trace Elements in Sea-Water. In Chemical Oceanography; Riley, J. P., Chester, R., Eds.; Vol. 8, Academic Press: London,1983, p 157.
Hatje, V.; Bruland, K. W.; Flegal, A. Determination of Rare Earth Elements after Pre-Concentration Using NOBIAS-Chelate PA-1W Resin: Method Development and Application in the
San Francisco Bay Plume. Mar. Chem. 2014, 160, 34–41.
Biller, D. V.; Bruland, K. W. Analysis of Mn, Fe, Co, Ni, Cu, Zn, Cd, and Pb in Seawater Using the Nobias-Chelate PA1 Resin and Magnetic Sector Inductively Coupled Plasma Mass
Spectrometry (ICP-MS). Mar. Chem. 2012, 130-131, 12–20.
Balcerzak, M. Sample Digestion Methods for the Determination of Traces of Precious Metals by Spectrometry Techniques. Anal. Sci. 2002, 18, 737–750.
Fisher, A.; Kara, D. Determination of Rare Earth Elements in Natural Water Samples-a Review of Sample Separation, Preconcentration and Direct Methodologies. Anal. Chim. Acta
2016, 935, 1–29.
Zhang, Q.; He, M.; Chen, B.; Hu, B. Preparation, Characterization and Application of Saussurea Tridactyla Sch-Bip as Green Adsorbents for Preconcentration of Rare Earth Elements in
Environmental Water Samples. Spectrochim. Acta, Part B 2016, 121, 1–10.
Anastopoulos, I.; Bhatnagar, A.; Lima, E. C. Adsorption of Rare Earth Metals: A Review of Recent Literature. J. Mol. Liq. 2016, 221, 954–962.
Ma, J.; Adornato, L.; Byrne, R. H.; et al. Determination of Nanomolar Levels of Nutrients in Seawater. Trends Anal. Chem. 2014, 60, 1–15.
Worsfold, P. J.; Lohan, M. C.; Ussher, S. J.; et al. Determination of Dissolved Iron in Seawater: A Historical Review. Mar. Chem. 2014, 166, 25–35.
Lin, M.; Hu, X.; Pan, D.; et al. Determination of Iron in Seawater: From the Laboratory to In Situ Measurements. Talanta 2018.
Mader, M.; Schmidt, C.; van Geldern, R.; et al. Dissolved Oxygen in Water and its Stable Isotope Effects: A Review. Chem. Geol. 2017.
Wong, G. T. F. Removal of Nitrite Interference in the Winkler Determination of Dissolved Oxygen in Seawater. Mar. Chem. 2012, 130, 28–32.
Rafelski, L. E.; Paplawsky, B.; Keeling, R. F. Continuous Measurements of Dissolved O2 and Oxygen Isotopes in the Southern California Coastal Ocean. Mar. Chem. 2015, 174,
94–102.
Milani, A.; Statham, P. J.; Mowlem, M. C.; et al. Development and Application of a Microfluidic In-Situ Analyzer for Dissolved Fe and Mn in Natural Waters. Talanta 2015, 136, 15–22.
 6 Water Analysis: Seawater—Inorganic Compounds for the Environmental Analysis

Tercier-Waeber, M. L.; Confalonieri, F.; Riccardi, G.; et al. Multi Physical-Chemical Profiler for Real-Time In Situ Monitoring of Trace Metal Speciation and Master Variables:
Development, Validation and Field Applications. Mar. Chem. 2005, 97 (3–4), 216–235.
Fighera, M. Microengineered Electrochemical Tools for In-Situ Monitoring of Marine Environment. EPFL. 2017.
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