organic sewage tracers
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Organic Sewage Tracers
• Sterols are components of cells & are synthesized by most organisms
• In humans cholesterol is biohydrogenated by intestinal microflora to 5cholestrol
• Other animals also produce 5cholestrol but at much lower concentrations
• Herbiverous animals produce 24-ethyl coprostanol in greater concentrations
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2324 25
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A B
C D
Sterol structure
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Assessment of Faecal Contamination Using Sterol Molecular Markers
Attenborough Ponds Nature: Long Term Effects of River Diversion
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Conneries datingAttenborough ponds CN
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0.00 1.00 2.00 3.00 4.00 5.00 6.00 7.00 8.00 9.00 10.00
Cs-137 concentration (Bq/kg)
Dept
h (c
m)
1 sigma errors shown
1986 ?
1963 ?
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TOC vs Sterol Concentration
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Identification of Sewage Markers
17.5 20.0 22.5 25.0minutes
2.5
5.0
7.5
10.0
12.5
15.0
GCounts
Target mix
22.2 22.3 22.4 22.5 22.6 22.7 22.8minutes
2.5
5.0
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12.5
GCounts
01020304050607080
MCounts
0
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100
125MCounts
0
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MCounts
TIC
m/z = 333Cholesterol-d6
m/z = 231Coprostan-3-one
m/z = 329Cholesterol
Resolving co-elution
17.5 20.0 22.5 25.0minutes
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50GCounts
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40MCounts
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MCounts
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Sediment Sample
coprostanol
m/z 333
m/z 231
m/z 329
est
ron
e
estr
adio
l
5-c
hole
stan
e
copr
osta
nol
5-e
pico
pros
tano
l
5-c
hole
stan
olca
mpe
ster
olst
igm
aste
rol
fuco
ster
ol +
s
itost
erol
5-s
tigm
asta
nol
Environment & Human Health Theme
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•Ten of eleven sewage markercompounds were identifiedin the Attenborough cores
•5-cholestane not detected
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sterolR=H: cholest-5-en-3 ; (cholesterol); [57-88-5]; mammalsR=CH : 24 ; (campesterol); [474-62-4]; plantsR=C H : 24-ethylcholest-5-en-3 ; ( -sitosterol); [83-46-5, 19044-06-5]; plants
β-olα-methyl-5-cholesten-3β-ol
β-ol β3
2 3
HO
R
5 ...stanolβ-R=H : 5 ; (coprostanol); [360-68-9]
C 24-methyl- ampe ???-??-?C 24-ethyl- stigma
β-cholestan-3β-olR= H : 5 ; (5 c stanol), [ ]R= H : 5 ; (5 stanol); [19466-47-8]
β-cholestan-3β-ol β-β-cholestan-3β-ol β-
2 5
3
HHO
R
5 epi...stanolβ-Intensive microbial reworking of faecal material in waters and sediments in the environment
Intestinalmicrobialreduction
Microbial reduction in the natural environment
R=H: ; ( epicoprostanol); [516-92-7]C5β-cholestan-3α-ol
R= H : (epi- campestanol); [???-??-?]R=C H : - -cholestan- -ol; (epi- stigmastanol); [???-??-?]
55 5
β-β 3α β-2 5 24-ethyl
5β-
3
HHO
R
5 ...stanolα-R=H: 5 ; ( cholestanol); [80-97-7]
C campe camp ???-??-?stigma stigma
-cholestan-3 -olR= H : 5 ; (5 estanol); [ ]R=C H : 5 ; (5 stanol); [???-??-?]
α- stan-3β-ol α-α- stan-3β-ol α-2 5
α β α-5
3
HHO
R
5α-stanone (intermediate)
HO
R
Δ4 stenone (intermediate)-
O
R
5β-stanone (intermediate)R=H: 5β-coprostanone; [601-53-6]
HO
R
Δ5 stenone (intermediate)-
O
R
cholest-5-en-3 -d (cholesterol-2,2,3,4,4,6-d ); [92543-08-3]β-ol6; 6
HD
2
2D
DD
HO
Sterol & Stanol Marker Pathways
Intestinal (5)
Environmental (5)
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1. Sitosterol: Clifton and Church = Input from plants & or avian FM2. Stigmastanol: Conneries = Input from ruminants / manure, slurry ?3. Coprostanol: Concs. >0.5ug/g = received appreciable amounts of sewage
1 2 3
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HH O
Coprostanol
H O
Cholesterol
Ratios >0.2 indicative of feacal contam ination (Grim alt & A lbaiges, 1990)
HH O
Cholestanol
HH O
Coprostanol
HH O
Coprostanol
1) M easure of sewage contam ination
HH O
Coprostanol
HH O
Epicoprostanol
HH O
Coprostanol
HH O
Epicoprostanol
HH O
Cholestanol
Ratios 0 .7 indicative of feacal contam ination
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H HHO
Coprostanol
Epicoprostanol
HHO
Coprostanol
HO
Cholesterol
2) Measure of sewage treatment or age
Ratios 0 to 0.5 sewage old or treated Ratios 1.5 to 3 sewage fresh or untreated (Mudge etal., 1999)
H HHO
Coprostanol
Epicoprostanol
3) Combined 1 & 2
4) Other sterol markers - Terrestiral plants
HO
Presence of sitosterol indicator of terrestrial run-off(may indicte non-point source diffuse pollution from agricultural areas)
HO
HO
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1. Coprostanol/Cholesterol: human sewage >0.2 criteria= Only Conneries
2. Coprostanol/(Coprostanol+Cholestanol) human sewage >0.7= Conneries
3. Epicoprostanol/coprostanol:treatment or age in environ. =Church &
Clifton little sewage or high degree of treatment
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1.5
1.0
0.5
0.00.5 1.0 1.5 2.0 2.50.0
HH O
Coprostanol
H O
Cholesterol
HH
HO
Cop
rost
anol
Epi
cop
rost
anol
HO
Low sewage, old or treated
High sewage, untreated
Bi-plot of sewage marker compounds
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•Ratio 5Cholestanol/Cholesterol:anaerobic process marker
•Conneries possible more reducing environ at 20 to 50 cm ?
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