monitoring of subsurface pollution by use of vegetation samples · 2007-04-09 · monitoring of...
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Monitoring of subsurface pollution by use of vegetation samples
Stefan Trapp1, Ulrich Karlson2 & Dietmar Pieper3
1 Environment & Resources
Technical University of Denmark
2 NERI 3 GBF
Stefan Trapp CV
1962 * Germany
1986 dipl geoecology
1992 PhD botany
1998 habil mathematics
1998 DTU applied ecology
2004 BIOTOOL
Table of Contents
Monitoring of subsurface pollution by use of vegetation samples
1 The BIOTOOL project
2 Effects on plants
3 Uptake into plants
4 Conclusions
http://www.gbf.de/biotools/index.html
Coordinator Dietmar Pieper, GBF
BIOTOOLBiological procedures for diagnosing the status
and predicting evolution of polluted environments
Dietmar Pieper German Research Centre for Biotechnology, DVictor de Lorenzo CSIC, ESStefan Trapp Technical University of Denmark, DKChristof Holliger Ecole Polytechnique Federale de Lausanne, CHVladimir Brenner Czech Academy of Sciences, CZUlrich Karlson National Environmental Research Institute, DKHermann Heipieper Centre for Environmental Research, D Jan Jurak KAP Ltd, CZJuan Rodriguez BIONOSTRA S.L., ES
some BIOTOOL partners
Howard Junca & Dietmer Pieper
Victor de Lorenzo Ulrich KarlsonHermann, Nadja, Janett UFZ
Maria Brennerova
Chris Hollinger
Natural attenuation is predominantly a biologically driven process
We require information on
- whether it can occur
- whether it is actually occurring at a significant rate
- which mechanisms and pathways are involved
- how it will behave in the future
Biological fate of tetrachloroethene
Cl
Cl Cl
Cl
tetrachloroethene(PCE) Testing in microcosms
for 5 months2[H]HCl
Cl
Cl Cl
H
trichloroethene(TCE)
2[H]HCl
H
Cl Cl
H
cis-1,2-dichloroethene(cis-1,2-DCE)
Under identical physico/chemical conditions, different metabolic reactions are observed
PCE transforming activity seems to be ubiquitous, vinylchloride transformation not
H
Cl H
H
2[H]HCl
vinyl chloride(VC)
H
H H
H
2[H]HCl
etheneMAROC, Holliger et al.
Opening the black box of environmental microbiology
Biological markers of degradation
H
Cl Cl
H
H
Cl H
H
H
H H
H
Cl
Cl Cl
Cl
Bacteria In some cases specific groups of bacteria are known to be predominantly responsible for a certain metabolic capability
DNA Catabolic genes can be detected by culture-independent analyses
RNA Shows which genes are actually expressed and thus indicates activity
Proteins Indicators for the status of the cell
Lipids Adaptation of bacteria to stress and pollutants
The problem
Insufficient tools to assess, evaluate and predict biological mediated natural attenuation processes
The solutionBiological procedures for diagnosing the status and
predicting evolution of polluted environments
Objective
To develop instruments for diagnosis of the catabolic status and prediction of site biodegradation trends
COOH
X
OH
XX
X
OCH2COOH
X
NH2
X
X
CH3
X
COOH
X
OH
O O O
X X
OHOH
XCOOH
OH
CHOX
X
COOHCOOH
Metabolic networks
Catabolic gene fingerprinting gives information on
Genes abundant at the site of interestDiversity of genesand generally the catabolic gene landscape
Catabolic gene arrays to rapidly analyze catabolic gene landscapesare under development
Detection of mRNA
A B C A B C
rRNA
rRNAextract without purification
extract after purification
BIOTOOL specific objectives
- Design and utilization of DNA and DNA–arraytechnology for examining the catabolic potential ofsamples
- Access and analysis of the soil/groundwater meta-proteome as biomarker
- Use of lipid biomarkers as prediction instruments ofstress/toxicity on soil and groundwater microorganisms
-Establishment of the correlation betweensoil/groundwater contamination and plant contamination
Overview of BIOTOOL field sites
Denmark
Glostrup, former rain water lagoon; TCE
Axelved, former petrol station; diesel & gasoline
Vassingerød, former asphalt works; diesel and PAH
Søllerød, former gas works; CN, PAH and BTX
Czech Republik
Hradcany, former USSR-air base; jet fuel
SAP, carcasses disposal plant; PCE
Field sites in Denmark
former tank station former asphalt works
Axelved: gasoline & diesel
Vassingerød:diesel & PAH
Former gas works Søllerød
Cyanides PAH, BTEX
1951
2001
Field site in Czech Republik: Hradcany(former Russian military airport)
Hradcany airport
Pollution: jet fuel
BIOTOOL workpackage 2
Plant monitors to analyze subsurface contamination
The normal engineer makes many bore holes
to find sub-surface pollution
The lazy engineer takes plant samples
... but will it help him?
Hypothesis 1If soils are polluted,
effects on plants indicate subsurface pollution
Louise
Henning
Example 1: Gas works waste
Photo: Gas works waste in Amager
Composition of gas works waste
Typically
Iron cyanide FexCNyup to 50 g/kg
PAH up to 1000 mg/kg
Sulphur up to 50%
Evil substrate!
Field observation 1
This gas works waste was deposited > 30 years ago.
Still no plants grow on it.
Is gas works waste toxic to plants?
Field observation 2
Vegetation established well on other gas workswaste.
Is gas works wastenon-toxic to plants ?
What now?
Photo: Tim Mansfeldt
Laboratory tests on phytotoxicityWillow tree transpiration test
Lab results
Iron cyanide is quite non-toxic to plants.
PAH (≤ 1600 mg/kg soil) are non-toxic, too.
What is the toxic principle?
Louise's result
Low pH (< 2) kills the plants. At pH > 3.3 plants can grow.
After liming, all tested species could grow in this gas works waste
S H2SO4 pH 2
Example 2: Axelved, former petrol station
Photo: Axelved 1999 (2nd season)
Axelved 1999, plume center
In 1 – 3 m depth ~ 3000 mg diesel / kg soil
Tree height 2000 (3rd season)
Plume center
Tree height measurements winter 2005
Method
• Height measurement with a telescopic bar
• Average distance between trees 0.5 m
• Comparison to chemical data from student excursions
Ulrich Reiter, ETH
Correlation between tree height and soil contamination in Axelved 2005
Not significant !
R2 < 0.1
Laboratory test of phytotoxicity
Soil samples from Axelved
with diesel + gasoline from 500 to 20 000 mg/kg
were lab-tested for toxicity with willow trees.
Tox-criterion was inhibition of transpiration.
Helle Christiansen
Phytotoxicity of samples from Axelved
0
0.2
0.4
0.6
0.8
1
1.2
100 1000 10000 100000
C5-C28 mg/kg
I
LogNorm curve fit Observed values EC50 EC10
outsite 2005
Conclusion: Contamination in Axelved 2005 is too low to show effects on tree growth.
Example 3: Asphalt works Vassingerød
Tree grows on free-phase diesel
normal tree
Uli Karlson
Positive relation contamination – growth?
Example 3: Asphalt works Vassingerød
N
former building structure seems to determine tree growth (not contamination)
Preliminary conclusions for hypothesis 1
"If soils are polluted, effects on plants indicate subsurface pollution"
1 What is toxic for us is not toxic to trees (CN, PAH ...)
2 What is toxic to trees (pH, salt etc.) is not necessarily our problem
3 Many variables influence the growth of trees, the correlation to pollution can be uncertain (weak)
Hypothesis 2
If soil and/or ground-water are polluted
chemicals will be found in stem, leaves or fruits
and may be used to indicate subsurface pollution.
Translocation upwards
A ”standard plant” transpires 500 L water for the production of 1 kg dry weight biomass!
= approx. 1 L/day/m2
good chance for upwards-transport of chemicals
Correlation between soil and plant contamination
Measuring campaign starts June 2005
No own data available yet
Pre-selection of compounds with models
Modeling uptake of pollutants into plants
Relevant processes
Uptake by diffusion
Uptake by advection
Transport in xylem
Volatilization from stem and leaves
Metabolism by plant & bacteria
Advective uptake into roots
Change of mass in roots =
+uptake with water – transport to shoots
dmR/dt = CWQ – CXyQ
where Q is water flow [L d-1]
Diffusion across the peel is neglected!
Dilution by growth
0
25
50
75
100
0 24 48 72
Time
Plan
t mas
s,
conc
entr
atio
n
M (kg) m/M (mg/kg)
Chemical mass: m = constant
Plant Mass: M(t) = M(0) x e+kt
m/M = Concentration in plant: C(t) = C(0) x e-kt
Root concentration
Change of concentration in roots =
+ uptake with water
– transport to shoots
– dilution by growth
dCR/dt = CWQ/M – CXyQ/M – kCR
where k is growth rate [d-1] and CXy is the concentration in xylem = CR/KRW
Root model steady-state (dC/dt=0)
W
RW
R CkM
KQ
QC+
=
RRWRWR CkMQKCMQC
dtdC
×−×−×= ///
)(/ kMK
QCMQCRW
RW −×
×=×
Growth
Root to soil - steady-state
0.0
0.5
1.0
1.5
2.0
1 2 3 4 5 6log Kow
BCF
root
to s
oil
(fre
sh w
eigh
t)
Equilibrium C Carrot
WS
RW
WSW
R
Soil
R KkM
KQ
QKCC
CC
BCF ×+
=×==
no growth, k = 0
with growth
Translocation upwards in the xylem
Transpiration stream concentration factor TSCF
RW
RW
RWW
R
W
Xy KkM
KQ
QKCC
CC
TSCF //+
===
0
0.4
0.8
1.2
-1 0 1 2 3 4 5 6
log Kow
TSC
F
Briggs B+S CXy
Tree model
Influx with xylem = Q x CW x TSCF
Q is transpired water (m3/a)
Loss with xylem = Q × CStem /KWood
WoodStemWStem KCQTSCFCQ
dtdm
/×−××+=
Sorption to wood
Kwoodlog
KWood = CWood / Cw
log KWood = – 0.27 + 0.632 log KOW(oak)
log KWood = – 0.28 + 0.668 log KOW(willow)
Lignin is a good sorbent for lipophilic chemicals!
Movement in stem relative to water Delayed due to retention in the stem
Source: Trapp, Miglioranza, Mosbæk Env. Sci. Technol. 2001
Conclusion from modeling
Only
persistent
non-volatile and
water-soluble chemicals
will be efficiently translocated to stem and leaves !
Promising indicator compounds
Heavy metals: copper, cadmium
Many herbicides & other pesticides
TCE and its metabolite TCAA
IRON for FexCNy
Naphthalene as only PAH
RDX explosive
For diesel & gasoline ??
All results are preliminary – this project has just started!
SummaryMonitoring of subsurface pollution by use of vegetation
... might be more difficult as it seems at firstbut provides the chance to save many boreholes!