Yueming LU, Coralie BIACHE and R. Paul Philp

Transcription

1 Yueming LU, Coralie BIACHE and R. Paul Philp School of Geology & Geophysics, University of Oklahoma, Norman, OK7319, USA LIEC, University of Lorraine, Vandoeuvre-lès-Nancy, 5456, France. Session: Water and Soil Conservation

2 Cimarron Upper Arkansas Neosho Grand 2

3 Fecal materials Water quality deterioration: * concentration of nutrients for algae * number of pathogenic micro-organisms (E. colis & Enterococci) Indicator of fecal contamination: * Bacterial enumeration: : e.g. E. colis & Enterococci * Sterol distributions: + : do not require immediate and long-term analysis : specific molecular biomarker -> indicator of source(s) of contamination HO 3

4 What are sterols? * Cyclic organic compounds (4 rings) Cholesterol HO * Synthesized by most organisms (e.g. plants, animals, fungi) * Vital component of cell membranes * Ubiquitous compounds Specific sources of sterols: * Sitosterol, campesterol & stigmasterol vascular plants * Cholesterol vegetable and animal kingdoms Sterols Stanols : in the guts of some warm-blooded animals 4

5 µg/g dw Coprostanol Epicholestanol Epicoprostanol Coprostanone Cholesterol Cholestanol 5β-stigmastanol 5β-epistigmastanol 24- Ethylcoprostanol Campesterol 24- Ethylepicoprostanol Campestanol Stigmasterol Stigmastanol Sitosterol Sitostanol % of total sterols Distribution and concentration of the sterols vary in different warm-blooded animal feces (Leeming et al., 1996) Chicken Cow Pig (Leeming et al., 1996) Human (Leeming et al., 1996) Sterol Abundance Major sterols - chicken feces: sitosterol - cow feces: 24-ethyl and 24- ethylepicoprostanol; - pig and human: coprostanol and 24-ethylcoprostanol Total sterols Human Chicken Major sterols are the same for pig and human Total concentration of the sterols: human feces = 5 x pig feces Pig 1 Cow 5

6 Distribution and concentration of sterols vary in different warm-blooded animal feces (Leeming et al., 1996) 3 controlling factors: * Diet: each diet present different sterol profile e.g. Herbivore Carnivore * Endogenous sterols: sterols are biosynthesized and discharged to the digestive tract * Anaerobic bacteria: transform the sterols into stanols with various isomeric configurations 6

7 HO HO Cholesterol Bacteria in the guts H Coprostanol HO β-sitosterol Bacteria in the guts HO H 24-ethylcoprostanol & 24-ethylepicoprostanol HO β-sitosterol Bacteria in the guts HO β-sitosterol Sterol fingerprints (distribution & concentration) = indicator of fecal contamination 7

8 Western Ave S Walker Ave S Robinson Ave Sterol fingerprints in Oklahoma River and Illinois River Oklahoma River Illinois River North Canadian River OKLAHOMAARKANSAS Siloam Spring S6 S5 S3 S4 Compost plant S1 S9 S6S7S8 S8 Tahlequah S9 Eldon S7 S2 S1 Fayetteville Watershed boundary Streams Stockyards River Roads Sediment sampling sites S1 S2 S3 S Shield Bvd S5 S4 1 km 1 mile Lake Tenkiller Miles Kilometers Lake Stateline Sediment sampling sites Towns 8

9 % of total sterols % of total sterol Sterol fingerprints in Oklahoma River and Illinois River Sterol proportions Oklahoma River OKRS1 OKRS2 OKRS7 OKRS Illinois River ILRS2 ILRS5 ILRS8 Chicken manure 1 Similar fingerprints to the sterol distribution of chicken manure 9

10 F2 (31,77 %) Statistical treatment on the proportion of the different sterols * Principal Component Analysis: discriminating different groups within a data set Swan Chicken manure Rosella Duck Cow manure Buffalo Horse Cow Sheep WWTP Effluent WWTP Influent Cat Magpie Dog Seagull -3 Pig -4 Human F1 (44,68 %) Data from Leeming et al. (1996) Illinois River Sediments 1

11 δ 13 C Carbon Compound Specific Isotope Analysis (CSIA): provide additional information concerning the origin of sterols that are non-characteristic of feces (e.g. cholesterol, stigmasterol and sitosterol) Cholestanol Stigmasterol Sitosterol Sitostanol C4 plants (Chikaraishi et al., 24) -2 CHICKEN ILRS1 ILRS2-25 ILRS3 ILRS4-3 ILRS5 ILRS6 ILRS7 ILRS8-35 ILRS9-4 C3 plants : >85% of plant species (all trees, wheat, sugar beat, tobacco, a lot of herbaceous ) C3 plants (Chikaraishi et al., 24) C4 plants : <5% of plant species (corn, sorghum, millet, sugarcan e) 11

12 δ 13 C Carbon Compound Specific Isotope Analysis (CSIA): provide additional information concerning the origin of sterols that are non-characteristic of feces (e.g. cholesterol, stigmasterol and sitosterol) Cholestanol Stigmasterol Sitosterol Sitostanol C4 plants (Chikaraishi et al., 24) -2 CHICKEN ILRS1 ILRS2-25 ILRS3 ILRS4-3 ILRS5 ILRS6 ILRS7 ILRS8-35 ILRS9-4 C3 plants (Chikaraishi et al., 24) Mixed signature with C4 plant contribution contribution from chicken feces 12

13 Cimarron Upper Arkansas Neosho Grand Upper Canadian 13

14 Monitoring water quality depends on some other factors e.g. seasonal variation, special rainfall events, land change or agriculture practices Sampling areas Cimarron Upper Arkansas Neosho Grand Upper Canadian 1. Dead Indian Cr. 2. Cottonwood Cr. 3. Red Rock Cr. 4. Council Cr. 5. Beaver Cr. (Osage Co.) 6. Turkey Cr. (Wood Co.) 7. Persimmon Cr. 8. Turkey Cr. (Upper) 9. Duckpond Cr. 1. Yellowstone Cr. 1 Hogshooter Cr. 2. Delaware Cr. 3. Chouteau Cr. 4. Little Cabin Cr. 5. Buck Cr. 6. Tar Cr. 7. Hominy Cr. 8. California Cr. 9. Ranger Cr. 1. Fivemile Cr. 1. Buggy Cr. 2. Walnut Cr. 3. Hackberry Cr. 4. Trail Cr. 5. Deer Cr. - Sampling Once a month during one year (June 212 April 213) > 23 water samples were collected 14

15 Cimarron Upper Arkansas Upper Canadian 15

16 Water sample Filtration Water with dissolved organic matter Suspended particles Extraction of organic matter Solid Phase Extraction Sonication Separation (Liquid chromatography on alumina & silica gel columns) Aliphatic, Aromatic, Polars - Sampling - Experiment Analysis & Quantification (GC-MS or Gas Chromatography-Mass Spectrometry; internal calibration) 16

17 μg/l μg/l μg/l June Cimarron Upper Arkansas Non fecal sterols Fecal sterols NG1 NG2 NG3 NG4 NG5 NG6 NG7 NG8 NG9 NG1 CUA1 CUA2 CUA3 CUA4 CUA5 CUA7 CUA8 CUA9 8 Upper Canadian Concentration of the sterols: Neosho Grand > Cimarron Upper Arkansas > Upper Canadian UC1 UC2 UC4 UC5 Low proportion of the fecal sterols 17

18 Coprostanol/Cholestanol Coprostanol/Cholestanol Coprostanol/Cholestanol Fecal contamination: if Coprostanol/Cholestanol >,4 (Leeming et al., 1997, Shah et al., 27) Upper Canadian UC1 UC2 UC4 UC Cimarron Upper Arkansas Fecal contamination.8.6 Cimarron Upper Arkansas Neosho Grand Upper Canadian - Sampling - Experimental Dead Indian Cr. 2. Cottonwood Cr. 8. Turkey Cr. (Upper) 9. Duckpond Cr. 2. Delaware Cr. 5. Buck Cr. 6. Tar Cr. 7. Hominy Cr. 8. California Cr. 1. Buggy Cr. 2. Walnut Cr. 4. Trail Cr. 5. Deer Cr. - Results 18

19 NG3 NG6 NG1 Coprostanol Epicoprostanol Cholesterol Cholestanol 24-ethylcoprostanol 24-ethyepicoprostanol Campesterol Campestanol Stigmasterol Stigmastanol Sitosterol Sitostanol High proportion of Phytosterols & Cholesterol Phytosterol (e.g. β-sitosterol & campesterol): originating from plants, bird or herbivore feces (not assimilated during digestion). Low proportion of Coprostanol & Epicoprostanol Coprostanol: reduced from cholesterol by bacterial activities in the guts of warmblooded animals. - Sampling 24-Ethylcoprostanol: characteristic of herbivore feces (Leeming et al., 1996; Derrien et al., 211). - Experimental - Results 19

20 NG3 NG6 NG1 Coprostanol Epicoprostanol Cholesterol Cholestanol 24-ethylcoprostanol 24-ethyepicoprostanol Campesterol Campestanol Stigmasterol Stigmastanol Sitosterol Sitostanol UC1 UC4 UC5 Upper Canadian Coprostanol Epicoprostanol Cholesterol Cholestanol 24-ethylcoprostanol 24-ethyepicoprostanol Campesterol Campestanol Stigmasterol Stigmastanol Sitosterol Sitostanol 6 4 CUA1 CUA3 CUA7 Cimarron Upper Arkansas 2 Coprostanol Epicoprostanol Cholesterol Cholestanol 24-ethylcoprostanol 24-ethyepicoprostanol Campesterol Campestanol Stigmasterol Stigmastanol Sitosterol Sitostanol 2

21 NG3 NG6 NG1 Chicken manure Coprostanol Epicoprostanol Cholesterol Cholestanol 24-ethylcoprostanol 24-ethyepicoprostanol Campesterol Campestanol Stigmasterol Stigmastanol Sitosterol Sitostanol UC1 UC4 UC5 Chicken manure Upper Canadian Coprostanol Epicoprostanol Cholesterol Cholestanol 24-ethylcoprostanol 24-ethyepicoprostanol Campesterol Campestanol Stigmasterol Stigmastanol Sitosterol Sitostanol 6 4 CUA1 CUA3 CUA7 Chicken manure Cimarron Upper Arkansas 2 Coprostanol Epicoprostanol Cholesterol Cholestanol 24-ethylcoprostanol 24-ethyepicoprostanol Campesterol Campestanol Stigmasterol Stigmastanol Sitosterol Sitostanol 21

22 * Fecal contamination evidence: several localities in Neosho Grand, Cimarron Upper Arkansas and Upper Canadian * Sterol fingerprint in studied Oklahoma watersheds in June 212 dominated by phytosterols and cholesterol similar to that in chicken manure * Continue the sterol fingerprint analysis Seasonal variation Land use or Agricultural practice 22

23 Thanks to Jason Ramming and all members of the Water Quality Division of the Oklahoma Conservation Commission for the sample collections during one year. 23