Development of a Multi-Isotope Tracer Tool for Aquatic
Ecosystems on the Example of the German Wadden Sea
Johanna Irrgeher1,2, Daniel Proefrock1, Thomas Prohaska2, Andreas Zitek2, Ulrike Kleeberg3,
Hans-Burkhard Erbsloeh1, Andreas Prange1
1 Helmholtz-Centre
for Materials and Coastal Research, Institute of Coastal Research, Dept. Marine Bioanalytical Chemistry, D-21502 Geesthacht, Germany
2 University of Natural Resources and Life Sciences, Vienna, Dept. of Chemistry, Division of Analytical Chemistry, VIRIS Laboratory, A-3430 Tulln, Austria
3 Helmholtz-Centre for Materials and Coastal Research, Institute of Coastal Research, Modelling for the Assessment of Coastal Systems, D-21502 Geesthacht, Germany
1 Background
2 Analytical Methodology
The goal of this study is the development of isotope tracer tools for elements in the marine ecosystem
of the German Wadden Sea based on the isotopic variation of Sr and Pb. These isotopic systems can be
used to discriminate and trace geogenic and anthropogenic sources in enduringly contaminated, highly
anthropogenically impacted ecosystems.
•  Study area: German Wadden Sea catchment including the main tributaries (Elbe, Weser, Rhine)
• Sample compartments: Sediments, suspended particulate matter, water, biota
• Analytical method: (multi collector) inductively coupled plasma mass spectrometry – ((MC) ICP-MS)
• Approach: Creation of isotopic and elemental distribution maps of the investigated systems; visualization
of the spatial variation of elemental and isotopic pattern (isoscapes) using GIS-based analysis
ISOTOPIC MAPPING of Pb, Sr, Mo and N TRACING OF CONTAMINANTS and NUTRIENTS samples
sediment - NOAH fields (ca. 8 x 8 km)
(North Sea-Observation and Assessment of Habitats)
sampling by box-grabs
5 sampling spots (n = 3) / field
http://wiki.coast.hzg.de
(FS Heincke, 2014 ship sampling campaign He422)
freezing (-20 °C)
Laser-based particle size determination
(Analysette 22 MicroTec Plus, Fritsch)
wet-sieving
(PTFE sieve cascade, extraction of fine fraction via continuous centrifugation)
microwave-assisted acid digestion
of < 22 µm sediment fraction
(CEM Mars Express, Kamp-Lintfort)
SEDIMENTS WATER SUSPENDED PARTICULATE MATTER BLUE MUSSELS calibraKon column chemistry (LA)-­‐MC ICP-­‐MS SAMPLE PREPARATION validaKon / uncertainty digesKon, extracKon SAMPLING ANALYTICAL METHOD DEVELOPMENT Fig 1: Schematic of the essential aspects addressed within the overall project.
The project sub-tasks presented in this poster are displayed in blue.
.
3 Results
3.1 Elemental pattern
207Pb/206Pb 3.2 Isotopic pattern: Pb
0.852
0.850
0.848
I
0.846
0.844
H
0.842
0.840
2.070 2.075
E
C
B
D
A
F
G
2.080 2.085
208Pb/206Pb
2.090
Fig 3: 207Pb/206Pb vs 208Pb/206Pb isotope ratio plot of NOAH sediment
field samples (fields A – I). Error bars correspond to combined
uncertainties uc (k = 1).
3.3 Isotopic pattern: Sr
0.7170 H 87Sr/86Sr 0.7150 0.7140 0.7130 G I E C F D Sr isotopes: Sr/matrix-separation
using a Sr specific resin
(Eichrom Technologies)
elemental analysis
ICP-QQQ-MS
(Agilent 8800, Agilent Technologies)
Sr and Pb-isotope ratio measurements
MC ICP-MS (Nu Plasma II, Nu Instruments Ltd.)
combination of internal and external calibration of isotope ratios
using NIST SRM 987 + Zr (Sr) and NIST SRM 981 + Tl (Pb)
3.4 Multi-layer elemental and isotopic pattern
Fig 2: Elements underlying
isotopic variation in nature
and detected at relevant
mass fractions in sediment
samples are highlighted in
green. These elements
represent potential tracer
systems in the German
Wadden Sea.
0.7160 DEVELOPMENT and APPLICATION of ISOTOPIC TOOLS for tracing elemental pathways from source to sink in marine, coastal and estuary ecosystems Sr, Pb, Mo and N ISOTOPES in the WADDEN SEA B A 0.7120 -­‐0.50 -­‐0.25 0.00 0.25 0.50 0.75 1.00 δ88Sr/86SrSRM987 Fig 4: 87Sr/86Sr isotope ratios vs δ88Sr/86SrSRM987 of sediment samples.
Error bars correspond to combined uncertainties uc (k = 1).
87Sr/86Sr
(Layer 6)
< 0.7130
0.7131 - 0.7137
0.7138 - 0.7143
87
86
L6: Sr/ Sr
0.7144 - 0.7151
0.7152 - 0.7161
Sr (µg g-1) (Layer 5)
227 - 230
L5: Sr (µg g-1)
231 - 260
261 - 295
296 - 330
331 - 365
208Pb/206Pb (Layer 4)
L4: 208Pb/206Pb
L3: 207Pb/206Pb
2.072 - 2.073
-1
L2: Pb (µg g )
2.074 - 2.076
L1: sediment type
2.077 - 2.079
I
2.080 - 2-082
2.083 - 2.085
207Pb/206Pb (Layer 3)
0.842 - 0.843
H
G
0.844 - 0.845
0.846 - 0.847
F
0.848 - 0.849
A
0.850 - 0.851
E
B
Pb (µg g-1) (Layer 2)
D
< 46
C
47 - 55
56 - 65
66 - 75
76 - 115
sediment type (Layer 1)
mud
sand/shells
Fig 5: Multi-layer elemental and isotopic pattern of NOAH sediment fields (A – I) in the German Bight (North
sand
Sea); 87Sr/86Sr, Sr mass fraction, 208Pb/206Pb, 207Pb/206Pb and Pb mass fraction are given in a multi-layer
fine sand
display. The 87Sr/86Sr spatial isotope interpolation map (isoscape) created by ArcGIS® shows the modeled
coarse sand
distribution in the investigated area.
4 Summary
5 Outlook
•  The Sr isotope and Pb isotope ratios showed a
clear differentiation between the investigated
samples originating from different sediment
fields.
•  No significant within-site heterogeneity was
observed for Pb and Sr isotopes.
•  Mapping of tributaries (e.g. Elbe catchment)
•  Determination of possible sources of Sr and Pb via
isotopic analysis; differentiation between natural
and anthropogenic origin
•  Investigation of other sample compartments
•  Analysis of additional isotopic systems (e.g. N, Mo)
Helmholtz-Zentrum Geesthacht • Max-Planck-Straße 1 • 21502 Geesthacht / Germany • Phone +49 (0)4152 87-0 • Fax +49 (0)4152 87-1403 • contact@hzg.de • www.hzg.de
Contact: Dr. Johanna Irrgeher • Phone +49 (0)4152 87-1832 • johanna.irrgeher@hzg.de