3- Field and
experimental studies of biological, physical and chemical factors controlling
trace element circulation
3- Field and
experimental studies of biological, physical and chemical factors controlling
trace element circulation
CABE
is involved with several field or simulated field studies in which the
long-term goal is to contribute to the understanding of the mechanisms
which control the circulation and bioavailability
of vital and detrimental elements and compounds in aquatic systems (water,
sediment, soil). Because natural organic matter (NOM) is implicated in
essentially every reaction in the natural environment, much of our recent
research has concentrated on the role NOM may play in some of the important
processes which
occur in the natural freshwaters. For example, although it is well established
that NOM plays a key role in the circulation and bioavailability of trace
elements, quantitative predictions of the effects of NOM in a given ecosystem
are presently impossible, because the specific properties of NOM are poorly
understood or even totally unknown. For example, the formation rate and
structure of the aggregates depends on the nature (size, conformation,
chemical reactivity) of the organic macromolecules present in the system
of interest. At least two types of organic macromolecules play very different
(sometimes opposite) roles in lakes: the soil-derived fulvics (small highly
charged macromolecules; Mw~1000) and the water-borne polysaccharides
(large macromolecules; Mw>10000). The processes of interest
to our group are schematised in Figure 1:
Figure
1: Schematic representation of some of the important processes
determining metal bioavailability
and transport
Research which is now underway examines some of the different roles of NOM in the natural environment by attempting to relate macromolecular structure to function in freshwater systems.
This research includes :
THE
CHARACTERISATION OF NATURAL ORGANIC MATTER USING NON-PERTURBING TECHNIQUES
For several years, we have been developing
techniques which allow the characterisation of NOM by transmission
electron microscopy. Novel techniques are now being developed which
will allow the separation, characterisation and study of interactions of
NOM components under relatively non perturbing conditions. For example,
the morphological characterization of organic macromolecules by atomic
force microscopy
(AFM)
is now well underway. Fluorescence
Correlation Spectroscopy (FCS) is being developed in order to determine
how solution physicochemistry affects the conformation and transport of
NOM while Capillary Electrophoresis
(CE) is being used to relate the structure of different components
to their electrophoretic mobility and their ability to bind metallic pollutants.
These techniques are complemented by voltammetric, size distribution (PCS)
and ultracentrifugation techniques in order to characterise as completely
as possible the NOM based upon its size and morphology.
THE
ROLE OF NOM COMPLEXATION ON METAL BIOAVAILABILITY
Although bioavailability-chemical
speciation relationships have been well-studied with simple synthetic
complexants such as EDTA, the role of natural complexing macromolecules
with complicated structures, like fulvic
or humic compounds, is poorly understood; published results are, for
the most part, contradictory or qualitative. Two novel techniques have
been
developed in our laboratories for measurements of trace metal speciation
in the presence of complexing ligands: gel-covered voltammetric microelectrodes
(GCVM), and the supported liquid membrane (SLM). These techniques are presently
being exploited for the determination of trace metal bioavailability to
aquatic microorganisms in the presence of humic and fulvic compounds.
THE
ROLE OF NOM IN COLLOID
AGGREGATION / FLOCCULATION AND SEDIMENTATION
We will continue to examine how the interactions
of large NOM macromolecules influence the aggregation
of small inorganic colloids under field and simulated field conditions.
Figure 2: Aggregate of
natural organic matter and small inorganic colloids (Bar represents 500nm)
Figure 3: Hard-working graduate student (A. Jozroland) during field study on Lake Bret.
Determination of the conformation of natural organic macromolecules using
atomic
force and transmission electron microscopy
Roles of the various organic biopolymers in environmental processes in
aquatic systems
Characterization of organic biopolymers using novel applications of fluorescence
spectroscopy
Trace metal bioavailability to aquatic microorganisms in the presence of
humic substances
Mechanisms determining trace metal bioavailability to aquatic microorganisms
The AFM page
S.E.J. Buikx, M.A.G.T. van
den Hoop, R.F.M.J. cleven, J. Buffle and K.J. Wilkinson. 2000. Particles
in natural surface waters : Chemical composition and size distribution.
Intern.
J. Environ. Anal. Chem. 77, 75-93.
K.J. Wilkinson and F. Cuenod.
2000. Optimization of the hydrolysis of freshwater polysaccharides.
Intern. J. Anal. Chem. 77, 323-335.
J. Lead, K.J. Wilkinson,
E. Balnois, C. Larive, B. Cutak, S. Assemi and R. Beckett. 2000. Diffusion
coefficients and polydispersities of the Suwanee River Fulvic acid. Comparison
of fluorescence correlation spectroscopy, nuclear magnetic resonance, flow
field-flow fractionation and atomic force microscopy. Environ. Sci.
Technol. 34, 3508-3513.
E. Balnois, S. Stoll, K.J.
Wilkinson, J. Buffle, M. Rinaudo and M. Milas. 2000. Conformational
transformation of succinoglycan as observed by atomic force microscopy.
Macromolecules. 33, 7440-7447.
N. Mirimanoff and K.J. Wilkinson.
2000. Regulation of Zn accumulation by a freshwater Gram-positive bacterium
(Rhodococcus
opacus). Environ. Sci. Technol. 34, 616-622.
J. Lead, Wilkinson, K.J.,
Starchev, K., Canonica, S. and Buffle, J. 2000. Diffusion coefficients
of humic substances as determined by fluorescence correlation spectroscopy:
Role of solution conditions. Environ. Sci. Technol. 34, 1365-1369.
X. Gayte, D. Fontvieille
and K.J. Wilkinson. 1999. Bacterial stimulation in mixed cultures of
bacteria and organic carbon coming from river and lake waters. Microbiol.
Ecol. 38, 285-295.
E.
Balnois, K.J. Wilkinson, J.R. Lead and J. Buffle. 1999. Atomic force
microscopy of humic substances. Effects of pH and ionic strength. Environmental
Science and Technology, 33, 3911-3917 (abstract)
K.J. Wilkinson,
E. Balnois, G.G. Leppard and J. Buffle. 1999.
Characteristic features
of the major components of freshwater colloidal organic matter revealed
by transmission electron and atomic force microscopy. Colloids and
Surfaces A: Physicochemical and Engineering Aspects, 155, 287-310
(abstract)
J.R. Lead, E. Balnois,
M. Hosse, R. Menghetti and K.J. Wilkinson. 1999. Characterization
of Norwegian natural organic matter : size, diffusion coefficients and
electrophoretic mobilities. Environ. Int. 25, 245-258
(abstract)
J. Buffle,
Wilkinson K.J., Stoll S., Filella M. and Zhang J. 1998.
A
generalized description of aquatic colloidal interactions: The 3
colloidal component approach. Environ. Sci. Technol. 32, 2887-2899
(abstract)
P.H. Santschi,
Balnois E., Wilkinson K.J., Zhang J., Buffle J. and Guo L. 1998.
Fibrillar
polysaccharides in marine macromolecular organic matter, as imaged by atomic
force microscopy and transmission electron microscopy.
Limnol Oceanogr.
43,
896-908 (abstract)
Person
to contact:
| Kevin
Wilkinson
Address :
|
(41) 22 702 6051
|
(41) 22 702 6069
