38 Thinking Cap
Monitoring Environmental
Contaminants in
Wastewater
SUMMARY
The combination of ion chromatography
(IC) and inductively coupled plasma mass
spectrometry (ICP/MS) provides a rapid,
reliable, and sensitive speciation analysis
of the extent to which iron flocculation
in wastewater treatment, releases toxic
ions from magnetic resonance imaging
(MRI) chelates. This IC-ICP/MS analysis
proceeds without requiring costly
sample preparation, thus provides
important information on the entry,
degradation, and fate of contrast media
in (waste)water. The method is highly
suitable for determining compounds
containing gadolinium in biological
matrixes such as urine, blood or other
biological fluids. Additionally, IC-ICP/
MS is a powerful tool for monitoring
iodine-containing ionic oxidation by-
products (OBP) of unknown toxicity, that
formed during conventional oxidative
waste treatment technologies, such as
ozonation of iodinated X-ray contrast
media.
INTRODUCTION
Sur veillance and protection of
aquatic resources have improved to
ensure safe drinking water supplies.
Besides the inorganic, physical, and
microbiological water quality, attention
has increasingly focused on organic
substances in water. Formerly, sum
parameters such as dissolved organic
carbon (DOC) or absorbable organic
halogen compounds (AOX) were used
to describe the water quality. Since
1990s, liquid chromatography can
be feasibly coupled to mass selective
detectors, thus enable the ultra-trace
detection of wide myriads of single
September October 2015
Monitoring of wastewater
from patients treated
with contract agents for
non-invasive diagnostics:
iodine- and gadolinium-
based contrast media in
water treatment facilities
P. Pfundstein1, C. Martin2, W. Schulz3, D.
Flottmann1, A. Steinbach4, A.K. Heng5.
1
Aalen University, D-73430 Aalen, Germany.
2
Leibniz Center for Marine Tropical Ecology
(ZMT), D-28359 Bremen, Germany.
3
Zweckverband Landeswasserversorgung,
D-89129 Langenau, Germany.
4
Metrohm International Headquarter
CH9100 Herisau /Switzerland.
5
Metrohm Regional Support Centre
Asia, 608608, Singapore.
Corresponding author: A. K. HENG,
Asia Product Manager,
organic compounds in water, a quantum
leap forward, to facilitate monitoring
environmental contaminants as well
as pharmaceutical compounds. Among
the latter, there are the biologically inert
iodinated X-ray contrast media (ICM) and
gadolinium chelates, which are used as
contrast media in magnetic resonance
imaging (MRI).
The use of contrast agents in non-
invasive diagnostic provides a specific
and detailed picture of body organs,
to make it possible to differentiate
between diseased and healthy tissues.
The radiocontrast agents changes the
x-ray absorption of the radiographed
organ relative to its surrounding tissues,
while contrast agents for MRI are based
on the use of magnetic fields resulted
by charged elementary particles,
such as protons and electrons. Thus,
compared to traditional X-ray, MRI uses
no ionising radiation. However, MRI is
based on the same principles as nuclear
magnetic resonance spectroscopy: thus
takes advantage of the absorption and
emission of energy in the radiofrequency
range.
These contrast media are applied
in high amounts and are excreted
in non-metabolised form via urine
into wastewater. They are suspected
to be non-degradable in most
conventional water treatment plants
and consequently accumulate in aquatic
systems. While considered harmless to
the human body, their long-term eects
on the environment are still unknown,
hence for this reason their removal is
mandatory.
Implication of Iron Flocculation
Gadolinium contrast agents, primarily
administered intravenously, give
excellent in vivo and in vitro stability. With
a half-life of approximately two hours,
the chemical are excreted unchanged
through the kidney-urine pathway and
are thus emitted into the wastewater.
In the city sewage treatment plants
where flocculation with Fe3+ or Al3+ salts
is carried out to improve the settling
behavior of dissolved and suspended
colloidal material, the added trivalent
metal ions will compete with Gd 3+
ions for the organic ligands. Subjective
to the thermodynamic complex
stability, addition of the trivalent
metal salts produces recomplexing
(transmetallation) in the MRI contrast
agents and thus releases highly toxic
Gd3+ ions.
Water & Wastewater Asia
 Thinking Cap 39

This article explores the possible channel whereby

contaminants are introduced into environment. For example, Overlay of a chromatogram of a 100 g/L Gadovist and a
the addition of competitive Fe3+ ions in the wastewater 100 g/L Magnevist solution
treatment - flocculation step, enhances the displacement of Column : Metrosep A Supp 3 - 250/4.6
gadolinium from its chelate complexes. Thereby, highly toxic Column temp. : 25 C
Gd3+ ions are released. Similarly, ICMs are commonly destroyed Eluent : 7.2 mmol/L sodium
by oxidative treatment technologies using ozonation or UV carbonate
radiation. Instead of complete ICM mineralisation, ozonation 6.8 mmol/L sodium
hydrogen carbonate
leads to several unidentified iodine-containing ozonation by-
Flow : 1.0 mL/min
products (OBPs) of unknown toxicity. In this studies, the eects Loop : 100 L
of flocculation and ozonation were evaluated, respectively, for RF power : 1200 W
gadolinium-containing (e.g., Gadovist, Magnevist) and iodine- Plasma gas flow : Ar, 13 L/min
containing (e.g., Iomeprol, Amidotrizoic Acid) contrast media. Auxiliary gas flow : Ar, 1 L/min
Speciation analysis of iodinated and gadolinium species was Nebulizer gas flow : Ar, 1 L/min
performed using IC-ICP/MS. Detection, m/z : 156Gd, 158Gd, 160Gd

METHODS
For Gadolinium-containing contrast media, depending on the Iron(3+) and Gadolinium(3+)
thermodynamic complex stability, addition of the trivalent Aliquot of 100ul of dierent samples were injected into
metal salts within the flocculation process produces trans- Cation-exchange column, Nucleosil 5SA-125/4.0.
metallation in the gadolinium chelates and consequently
results in the release of toxic gadolinium ions. Using aqueous
solutions of the model components Gadovist and Magnevist
(each 1 mg/L), the present study looks at the extent to which
the bench-scale Fe3+ flocculation liberates free gadolinium ions.
For Iodinated X-ray contrast media, aside from the
destruction of pathogenic bacteria and other microorganisms,
water ozonation aims at the degradation of organic compounds.
Applying a dissolved ozone concentration of 3 mg/L, the impact
of bench-scale ozonation on unbuered aqueous solutions of
the ICMs, Amidotrizoic acid and Iomeprol, (both 20 mg/L)
was evaluated.
The Instrumentation involved the coupling of Metrohm 850
Ion Chromatography system with Thermo VG PQ Excell ICP-
MS system, using dierent columns for various contaminants
investigation. Three different analytical methods were
developed.

Gadolinium Complexes
100ul aliquot of samples harvested from various stages
of treatment were injected into anion exchange column,
Metrosep A Supp 3 -250/4.6.

1 mg/L Gadovist solution, 5 mg/L Fe3+

Column: Nucleosil 5 SA - 125/4.0
Column temp.: 30 C
Eluent: 10 mmol/L 2-hydroxyisobutyric acid
2 mmol/L ethylenediamine
Flow: 1.5 mL/min
Loop: 100 L

Water & Wastewater Asia September October 2015

40 Thinking Cap

Ozonation By-products (OBPs)

Samples were injected into anion-exchange column
Metrosep A Supp 3 250/4.6.

Table 1.2 Ionic Amidotrizoic acid

Overlay of three chromatograms obtained for a 100 g/L

iodate/iodide standard and two ozonated (60 and 120 min)
aqueous Iomeprol solutions (20.4 mg/L)
IC Column: Metrosep A Supp 3 - 250/4.6
Column temp.: 30C
Eluent: 7.2 mmol/L sodium carbonate
Table 1.3 Non-ionic Iomeprol
0.8 mmol/L sodium hydrogen
carbonate
Flow: 1.0 mL/min
RF power: 1200 W
Plasma gas flow: Ar, 13 L/min
Auxiliary gas flow: Ar, 1 L/min
Nebulizer gas flow: Ar, 1 L/min
Detection, m/z: 127I

RESULTS AND DISCUSSION

Gadolinium-containing contrast media
For both Magnevist and Gadovist, gadolinium displacement
increases as Fe3+ concentration rises. The extent of this
exchange, however, is very pronounced for Magnevist (> 80%)
and relatively small for Gadovist (< 10%). The reason lies in
the structure: the linear DTPA ligand of Magnevist provides
less shielding for the Gd atom than the crown-ether-like
polyamino-polycarboxylic acid ligand of Gadovist, which is
spherically arranged around the gadolinium ion.
Iodinated X-ray contrast media Ionic Amidotrizoic acid
With proceeding ozonation time, concentration of amidotrizoic
acid decreased in the same way as iodate concentration
increased. After 120 min ozonation, approximately 8% of
nondegraded ICM and 95% iodate were found, resulting in a
recovery rate of approximately 103%. Ozonation cleaves the
aromatic carbon-iodine bond leading to short-lived iodide
that is directly ozonated to iodate.
Iodinated X-ray contrast media Non-ionic Iomeprol
Iomeprol degradation proceeds much faster than iodate
formation. After 120 min ozonation, 84% of Iomeprol was
degraded, whereas iodate concentration only increased to
14%, which means a recovery rate of only 30%.
In accordance with the ion-exchange chromato-gram, the
poor recovery is attributed to the formation of still unknown
ozonation by-products (OBPs) other than iodate. Identification
of these OBPs is a major future research task.
CONCLUSIONS
IC-ICP/MS is a powerful tool for monitoring and investigation
of trace level environment contaminants, for example, OBPs
generated by disposal of treated contrast media used in
magnetic resonance imaging (MRI), such as Gadolinium
containing or iodine-containing contrast media. WWA

September October 2015 Water & Wastewater Asia