Ch.3 유기물 분석 Extraction of OM Rock-Eval (Pyrolysis) Elemental analysis GC, HPLC & MS SIRMS

Extraction of OM Outline of extraction procedures in IHSS

method Step 1. Equilibrate the sample to a pH value between 1-2 with 1 M HCl at

room teperature. Adjust solution volume with 0.1 M HCl to provide a final concentration that has ratio of 10 mL liquid/1 g dry sample. Shake the sus-pencion for 1 hour.

Step 2. Separate supernatant from the residue by decantation after allow-ing solution to settle (or by low speed centrifugation). Save supernatant for XAD-8 isolation.

Step 3. Neutralize the soil residue with 1 M NaOH to pH=7.0 then add 0.1 NaOH under an athmosphere of N2 to give a final extractant to soil ratio of 10:1.

Step 4. Extract the suspension under N2 with intermittent shaking for a minimum of 4 hours. Allow the alkaline suspension to settle overnight and collect the supernatant by means of decantation or centrifugation.

Step 5. Acidify the supernatant with 6 M HCl with constant stirring to pH=1.0 and then allow the suspension to stand for 12-16 hours.

Step 6. Centrifuge to separate the humic acid (precipitate) and fulvic acid (supernatant - FA Extract 2) fractions.

Step 7. Redissolve the humic acid fraction by adding a minimum volume of 0.1 M KOH under N2. Add solid KCl to attain 0.3 M (K+) and then centrifuge at high speed to remove suspended solids.

Step 8. Reprecipitate the humic acid as in step 5. Centrifuge and discard supernatant.

Step 9. Suspend the humic acid precipitate in 0.1 M HCl/0.3 M HF solution in a plastic container. Shake overnight at room temperature.

Step 10. Centrifuge and repeat HCl/HF treatment(step 9), if necessary, un-til the ash content is below 1 percent.

Step 11. Transfer the precipitate to a Visking dialysis tube by slurring wiyh water and dialyze against distilled water until the dialysis watr gives a nagative Cl- test with the AgNO3. Step 12. Freeze-dry the humic acid.

Step 13. Pass the supernatant from step 2 through a column of XAD-8 (0.15 ml of resin per gram of initial sample dry weight at a flow rate of 15 bed volumes per hour). Discard the effluent, rinse the XAD-8 column containing sorbed fulvic acid with 0.65 column volumes of distilled water.

Step 14. Back elute the XAD-8 column with 1 column volume of 0.1 M NaOH, followed by 2-3 column volumes of distilled water.

Step 15. Immediately acidify with 6 M HCl to pH=1. Add concentrated HF to a final concentration of 0.3 M HF. Solution volume should be sufficient to maintain fulvic acid solubility.

Step 16. Pass the supernatant from step 6 through a column of XAD-8 (1.0 mL of resin per gram of initial sample dry weight).

Step 17. Repeat steps 14 and 15

Step 18. Combine the final eluates from steps 15 and 17 and pass this so-lution through XAD-8 resin in glass column (column volume should be 1/5 of sample volume). Rinse with 0.65 column volumes of distilled water.

Step 19. Back elute with 1 column volume of 0.1 M NaOH followed by 2 column volumes of distilled water. Pass eluate through H+- saturated cation exchange resin (Bio-Rad AG-MP-5) using three times the mole of Na ions in solution).

Step 20. Freeze-dry the eluate to recover the H+- saturated fulvic acid.

from http://karnet.up.wroc.pl/~weber/ekstrak2.htm

http://karnet.up.wroc.pl/~weber/ekstrak2.htm

http://www.google.co.kr/url?sa=i&rct=j&q=&esrc=s&frm=1&source=images&cd=&cad=rja&uact=8&ved=0CAcQjRw&url=http://forum.skyscraperpage.com/showthread.php?t%3D214067%26page%3D4&ei=guclVdvTJ4jr8gWi_4GgCA&bvm=bv.90237346,d.dGc&psig=AFQjCNEukKkQKlu8BgIKYKznRzbG4Suhfw&ust=1428633641306656

http://jmbe.asm.org/index.php/jmbe/article/view/656/html

Soxhlet extraction

Rock-Eval (pyrolysis) 무산소 가열로 유기물의 분해를 측정하는 것 .

근원암의 평가에 많이 이용

http://www.vinci-technologies.com/prod-ucts-explo.aspx?IDR=82289&idr2=82568&IDM=536784

http://wiki.aapg.org/Rock-Eval_pyrolysis

Peak Is a measurement of… Comment

S1 mg Hc/g rock The free hydrocarbons present in the sample before the analysis

Can be thought of as a residual hydrocarbon phase. When S1 is large relative to S2, an alternative source such as migrated hydrocarbons or contamination should be suspected

S2 mg Hc/g rock The volume of hydrocarbons that formed during thermal pyrolysis of the sample

Used to estimate the remaining hydrocarbon generating potential of the sample

S3 mg Co2/g rock The CO2 yield during thermal breakdown of kerogen Most prevalent in calcareous source rocks.

S4 mg carbon/g rock The residual carbon content of the sample

Residual carbon content of sample has little or no potential to generate hydrocarbons due to a lack of hydrogen and the chemical structure of the molecule

%TOC=[0.082(S1+S2)+S4]/10 http://wiki.aapg.org/Rock-Eval_pyrolysis

http://www-odp.tamu.edu/publications/tnotes/tn30/tn30_f5.htm

Elemental analysis Combustion CHNX analysis

http://www.chemistryland.com/CHM151S/03-Counting/ElementalAnalysis/ElementalAnalysis.htm

http://facstaff.gpc.edu/~mkim/C1211&1212Lec/C1211_Lecture.htm

http://www.weiku.com/products/10367454/Automatic_Carbon_Hydrogen_Nitrogen_Analyzer_SDCH235.html

Elemental Analyzer (EA)

The elemental analyzer is for routine analysis of organic samples for δ15/14N, δ13/12C, %N, and %C. A sample is combusted in an Oxygen stream at 1100C,then passed through oxidation and reduc-tion tubes to form CO2 and N2 gas. The peaks are separated on a chromatography column allowing both C and N isotope composition to be determined on a single sample. The precision is better than 0.2 for C and 0.4 for N. The disadvantage of the elemental analyzer is that it is not as precise as the dual inlet. The advantages are that sample prep is much easier, many more samples can be analyzed per day, and δ15/14N, δ13/12C, %N, and %C are measured on each sample.

http://www.uark.edu/ua/isotope/equipment.php

http://cool.conservation-us.org/jaic/articles/jaic33-02-008.html

http://www.rsic.iitb.ac.in/Chn.html

GC-MS Combination of GC and MS

http://en.wikipedia.org/wiki/Gas_chromatography%E2%80%93mass_spectrometry

http://academics.wellesley.edu/Chemistry/chem211lab/Orgo_Lab_Manual/Appendix/Appendix/Instruments/GCMS/gcms.html

http://blog.restek.com/wp-content/uploads/2011/03/chromatogram-fig21.jpg

www.avivanalytical.com

SIRMS Nowadays, combined w/ EA, Laser, GC, etc

http://inside.mines.edu/~jhumphre/Isotope_Lab.html

http://www.gwadi.org/tools/tracers/methods

Others IR NMR ESR XRD UV etc.