Development of integrative sampling strategies for the
determination and effect-based evaluation of contaminants
in marine and coastal environments
Daniel Pröfrock, Heike Helmholz, Stephan Lassen, Burkhard Erbslöh, Christiane Ruhnau, Andreas Prange
Helmholtz-Zentrum Geesthacht, Institut of Coastal Research, Marine Bioanalytical Chemistry
Introduction
The determination of persistent toxic contaminants represents an important issue related to the assessment of the environmental quality status of marine water bodies. Due to their tendency to bioaccumulate and thus their potential toxic effects on marine organisms it is essential to analyse their concentration and bioavailability in different environmental compartments but also their potential
hazardous effects, especially when they occur in sublethal concentrations, which may cause cumulative and long term effects. Spot sampling is still an important component of different monitoring
tasks, however such techniques are limited since they represent only a minute view of the current status, in particular when focussing on the analysis of a dynamic environment such as the German
North Sea. This limitation can be overcome by the parallel application of techniques based on passive and active sampler as integrating tools, which reflect variations of the environmental
contamination level more consistently. In addition combined approaches, which utilise biota such as transplanted blue mussels allow also the detection of hazardous effects or new potential
biochemical indicators related to the targeted pollutants, utilizing powerful tools such as proteomics. Here first results related to the development and implementation of an integrative sampling
approach are described. Therefore stations have been installed on the island of Helgoland in the Germany Bight acting as a reference sampling site as well as at the estuary of the river Elbe, which
represents a heavily impacted station, respectively. The instrumentation, has been installed in May 2011 and since then regular sampling campaigns, which include transplanted mussels as well as
water samples have been performed every six weeks. Corresponding long term hydrological data were acquired 24 h per day during the whole year at both sites utilizing the COSYNA network,
which allows the precise observation of the physical environmental conditions.
Design of a new sampling infrastructure and related challenges
MarGate underwater experimental field
COSYNA station Cuxhaven
A crucial point in monitoring programs are high-resolution
measurements over long time periods, since most ship- or diver
supported methods are only suited for short term campaigns and often
provide a fragmented picture of processes and mechanisms inside the
marine environment. In the framework of COSYNA (Coastal
Observation Network for Northern and Arctic Seas), the Alfred
Wegener Institute for Polar and Marine Research (AWI) together with
the Helmholtz-Zentrum Geesthacht (HZG) realized “MarGate”, a new
underwater experimental and monitoring area near Helgoland in about
10 m water depth. There, active and passive sampling devices as well
as electronic equipment can be easily exposed and maintained year
round by specially trained scientific divers. Furthermore, underwater
electric power (max. 48V) and underwater data connection for
standard UW sensors.
Further sampling infrastructure has been realized next to the COSYNA station Cuxhaven. The
system includes a winch operated universal sampling platform, which could be easily
submerged or retrieved from the Elbe estuary. Different sampling tools such as cages for the
deployment of preconditioned mussel cultures, passive samplers (e.g. silicone rubber sheets,
DGT etc.) or SPM traps can be deployed in parallel. At both station automated measuring
systems (FerryBox) are installed, which provide online data for important parameters (e.g.
temperature, salinity, current etc.) allowing an improved data interpretation.
BSH
HZG
Universal
titanium
based
sampling
system
for
deployment
of
e.g.
preconditioned
mussel
cultures, passive samplers or
sediment traps.
Examples for available online data continuosly aquired at both sampling locations via
automated measuring systems (FerryBox).
a.)
Winch
operated
universal
sampling
platform
at the
COSYNA station Cuxhaven.
b.)
c.)
e.)
d.)
Currently available sampling tools: a.) Universal mounting, b.) DGT holder, c.) holder for
polymer sheet passive samplers, d.) Protective housing for cylindrical SPM traps, e.) cage
for mussel deployment
Location and structure of the MarGate underwater experimental site. Tetrapodes are used as robust platforms to carry the
different experimental infrastructure (Pictures kindly provided by Philipp Fischer, AWI Helgoland).
Inconsist deployment periods
For the reason of weather conditions, especially in autumn/winter periods, marine sampling in temperate zones is unpredictable
regarding length of sampling periods. The sampling capacity of the passive samplers has to be sufficient to buffer for a varying
deployment time.
Biofouling
Especially in summer bio-fouling occurs on the samplers. The used open cage construction nonetheless guarantees a high flow rate.
Freely shifting samplers are less overgrown than fixed ones.
Workflow and targets
50000
Time integrated sampling of selected emerging contaminants
SRM 2257 PBDE Congeners detected using
GC-ICP-MS
pH 4
200 kDa
Signal (cps)
45000
40000
79Br
35000
81Br
Environmental
contaminant
cocktail
30000
~pI / ~MW
116 kDa
Spot 1
4,7 / 38 kDa
Spot 2
5,5 / 45 kDa
Spot 3
5,6 / 32 kDa
pH 7
67 kDa
25000
45 kDa
20000
2
15000
1
10000
1800
2000
2200
2400
Time (s)
Development of new quantification approaches for PBDEs in
marine water samples using GC-ICP-MS and 81Br labeled internal
standards. (Poster TH 116)
Extraction/Digestion
Enrichment and
Chemical analysis
Concentrations
in the
environment
160
140
120
100
80
ICP-MS, GC-MS, LC-MS/MS, MALDI-MS
60
40
20
0
Al / 27 Cr / 53 Mn / 55 Fe / 56 Co / 59 Ni / 60 Cu / 63 Zn / 66 As / 75 Rb / 85 Sr / 88 Ag / 107 Cd / 111 Pb / 208
[#3]
[#2]
[#2]
[#3]
[#2]
[#3]
[#3]
[#2]
[#1]
[#1]
[#2]
[#3]
[#2]
[#1]
3
29 kDa
Blue mussel
Concentration of bioavailable
compounds (body burdens)
180
g
Recovery (%) SRM 2976
200
Concentration of dissolved
compounds (water phase)
Search for hazardous effects on the molecular level using proteomics
Proteome analysis of different tissue samples obtained from
blue mussels from differentialy contaminated coastal regions
for biomarker/effect determination using 2D GE and MALDI
mass spectrometry (see Poster WE 317 and TU 377)
Cu (cps)
1600
63
1400
Intensity 48SO and
1200
Cd (cps)
1000
114
DGT, Polymer Sheets
0
Active sampling
Intensity 66Zn and
Passive sampling
5000
Development of new approaches for multi element and
element species analysis in marine samples
Conclusion
Development of new quantification approaches for selected
protein biomarkers via LC-ICP-MS
A modular, easy accessible underwater sampling infrastructure has been realised, which allows the continuous deployment of either active and passive sampling devices. The open design of the
deployment cages helps to minimise both mechanical stress and bio-fouling and permits high flow rates throughout the deployment period.
Sensoric infrastructure provides high resolution oceanographic data sets, opening new possibilities for the interpretation of the results obtained by active and passive sampling.
The combination of active and passive sampling strategies may allow a better assessment of environmental contamination levels and will provide insight into possible contaminant related effects on
the molecular level.
Helmholtz-Zentrum Geesthacht • Max-Planck-Straße 1 • 21502 Geesthacht • Phone +49 (0)4152 87-0 • Fax +49 (0)4152 87-1403 • www.hzg.de
Contact: Dr. Daniel Pröfrock, daniel.proefrock@hzg.de
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