For the analysis of soil organic carbon by WB method,I have used 1 g soil with 10 ml of 0.1667M K2Cr2O7 solution, 20 ml concentrated H2SO4,200 ml water for dilution,10 ml H3PO4,10 ml of NaF solution,diphenylamine as an indicator,0.5M FeSO4 solution as a titrant.
During dilution,different soil sample shows a variation in colour i.e. some are orange and some are dark green,but with the same end point of light greenish colour after titration.Why is this colour variation takes place in different soil samples,Is this not an appropriate procedure for soil organic carbon?
1)Transfer 1 g air dried soil into a 500ml conical flask.
2) Add 10 ml 1N K2Cr2O7 solution and 20 ml concentrated H2SO4.
3) Swirl the content of the flask 2 or 3 times and allow the flask to stand for 30min. for the reaction to complete.
4) Add 200ml distilled water to the flask to dilute the suspension.
5 ) Add 10ml of orthophosphoric acid or 0.5gof NaF and 1ml of diphenylamine indicator. A deep violet color will appear.
6) Titrate it with 0.5N ferrous ammonium sulphate till the color changes from violet to blue and finally bright green.
7) Note the vol. of the ferrous ammonium sulphate used in titration.
8) Carry out a blank titration (without soil), the same way.
Calculations-
Organic carbon% in soil=(X-Y)ml× 0.003 × 100 ÷ 2×W=Z
Organic carbon% in soil= Z×1.3= R
Where, X= blank titration reading.
Y= sample reading, W= Weight of soil used
* Assume that organic matter contains 58% carbon, thus the organic matter content of the soil will be calculated as -
Organic matter in soil (%) = R × 1.724
different colour means variation in OC content in soil. Your procedure is right. These variations may also be due to wrong pipetting.
My Dear Priyanka Ji, Here are few links which will help you in your research. Regards
http://epa.gov/esd/cmb/research/papers/bs116.pdf
http://www.agvise.com/educational-articles/soil-organic-matter-a-choice-of-methods/
http://aesl.ces.uga.edu/protected/methods/details/stl-soil/12.html
This normal because different color is an indicator for different organic C concentration
The Walkley-Black method may result in low test results for soils with very high in organic matter, due to the incomplete oxidation of the organic carbon in the sample. The Loss on Ignition method is better suited to soils with greater than 6.0% organic matter. In this method there is no chemical reaction which could be limiting since we are only measuring weight loss of the sample at high temperatures. But the Walkley-Black method is more accurate and more precise on soils with less than 2.0% organic matter.
Dear Priyanka, the dark green colour means that your soil sample contains more organic carbon than your other samples. According to WB procedure you need to add 10 ml K2CrO7 more on this sample until dark green colour changes to brown.
The following method is helpful for the estimation of SOC. Best of luck.
Please go through the book on soil analysis by WB method as written by M.L.Jackson,1967 or 1963
1) Take 2 g air dried soil into a conical flask.
2) Add 10 ml 1N K2Cr2O7 solution and carefully add 10 ml concentrated H2SO4 and mix thoroughly with slight rotating.
3) Allow the mixture to cool for half an hour with occasional slight shaking. (If the colour of the mixture appears green then add an additional 10 ml of 1N K2Cr2O7 solution. Green colour is an indication that all oxidizing agent added is used up to oxidize organic carbon.)
4) Add 150 ml dw, 10 ml H3PO4 (85%) and 0.2 g NaF in sequence.
5) Add 3 ml diphenylamine (Dissolve 0.25 g indicator into 10 ml dw and slowly add 50 ml concentrated H2SO4 into it) indicator prior to titration. The mixture appears deep violet in colour.
6) Titrate excess K2Cr2O7 solution left in the flask with FeSO4.7H2O solution (1N).
7) Run a blank titration (This step is essential to standardize FeSO4.7H2O solution against standard K2Cr2O7 solution).
C in soil (%) = [(B-T) × S × 0.003 × 1.3 × 100] ÷ W
Where,
B = Amount of FeSO4 required in blank titration.
T = Amount of FeSO4 required in soil titration.
S = Strength of FeSO4 (from blank titration).
W = Weight of the soil.
Organic matter in soil (%) = % organic C × 1.724
Thanks to all of you for your attention,But I am still confused with the above mentioned procedure, that results come with that above mentioned method is write or wrong,because both colour gives a titration value and thus soil organic carbon value.But is that value of soil organic carbon is authenticated or not.
You cannot use "green" samples. You should try to take 1/2 of the soil sample and remake the analysis.
Hi Priyenka
Light greenish colour appeared after titration is perfect for most soils, but some soils give bit different colour so soil colour notation is important before analysis if it happened. Instead, you can use Total carbon measurement using 0.5 mg of fine soil powder by combustion using a Fissions Instruments NA1500 NCS analyser , you can get the similar result. you can use this machine for total carbon, nitrogen and sulphur analysis.
Some of the preceding comments are correct and your intuition that the test is approximate is also correct. There must be excess reagent remaining and the usual procedure is to decrease the quantity of sample until this is the case. For reasons I will not go into here, the intensity of the green color is a better and simpler measure of the amount of OM oxidised than the titration. Like all soil tests, W & B is operationally defined, i.e. you MUST follow the procedure even down to the sizes and shapes of the containers, the surface that they sit on etc. THis is important because it affects the rate of cooling and hence the completeness of the oxidation. (The oxidation is incomplete, e.g. see Heanes DL (1984) Determination of total organic carbon in soils by an improved chromic acid digestion and spectrophotometric procedure. Communications in Soil Science and Plant Analysis: 15, 1191-1213.
If you want an exactly measure of SOC, better do not use this procedure:
- This fails when you have a good content of SOM (e. g., > 2 %), specially you your soil is clayey.
- In addition, this procedure yields strong pollution (by Cr).
If you cannot measure SOC by a dry method, better use KMnO4 as oxidant, errors are similar and you avoid environmental pollution!
Thanks to all of you,
Dear sir @ Pere Rovira, Please also give some suggestions for the variation in colour during analysis of organic carbon by above mentioned method.The reading come out with the already greenish soil sample, is acceptable or not.
Thanks sir, for such a beautiful explanation.This is really helpful in clarifying basic concepts involved in this reaction.
Dear Dr, Kumari Priyanka, many times we are also facing the same situation, after final calculation, it showed (dark green color) higher organic carbon. In this case you can use 0.5 g soil samples for analysis.
Thanking you
hi. did anyone find any relevant material for the correct procedure on carrying out SOC estimation? what depth is recommended for the study. i am also quite interested in pursuing it but in a tropical forest in kenya
Hi Rael Adhiambo,
The depth of soil sampling depends on your objectives. Usually it is based on the rooting depth if you are to handle agricultural crops and their nutrient dynamics.
Cheers.
The most correct way for this method is do not use the K2Cr2O7, because Cr is very high contaminant. Please do not use this method any more. You can change the oxidant, e. g., using KMnO4. Even better, please use a dry method for determining SOC.
Thanks, Dr. Gallardo Lancho.
This is the problem every soil science student in India faces and still overlooks and moves forward.
Rael Adhiambo, you first perform a hole in your soil for seeing the soil profile. After that, you should sample the soil according the 'black zone' you have. If this layer is narrow, please sample only -15 cm, maximum -20 cm. If this black layer is depth, it is recommendable to select two horizons (e. g., 0-15 & 15-30 cm). Then, the soil morpholgy can show you what sampling your soil.
In continuation of suggestion given by Dr. Milton Halder regarding addition of extra 10 ml 1N K2Cr2O7 solution, if the colour of the mixture turns green initially.
My query is that the extra 10 ml of 1N K2Cr2O7 solution added initially during above case need to considered while calculating % organic carbon or not.
regards
On the topic of 'active carbon'. Which is the best method - hot water extraction or KMNO4? I understand both are qualitative. I have never done it, so am open to suggestions.
1)Transfer 1 g air dried soil into a 500ml conical flask.
2) Add 10 ml 1N K2Cr2O7 solution and 20 ml concentrated H2SO4.
3) Swirl the content of the flask 2 or 3 times and allow the flask to stand for 30min. for the reaction to complete.
4) Add 200ml distilled water to the flask to dilute the suspension.
5 ) Add 10ml of orthophosphoric acid or 0.5gof NaF and 1ml of diphenylamine indicator. A deep violet color will appear.
6) Titrate it with 0.5N ferrous ammonium sulphate till the color changes from violet to blue and finally bright green.
7) Note the vol. of the ferrous ammonium sulphate used in titration.
8) Carry out a blank titration (without soil), the same way.
Calculations-
Organic carbon% in soil=(X-Y)ml× 0.003 × 100 ÷ 2×W=Z
Organic carbon% in soil= Z×1.3= R
Where, X= blank titration reading.
Y= sample reading, W= Weight of soil used
* Assume that organic matter contains 58% carbon, thus the organic matter content of the soil will be calculated as -
Organic matter in soil (%) = R × 1.724
Organic carbon% in soil=(X-Y)ml× 0.003 × 100 ÷ 2×W=Z
Organic carbon% in soil= Z×1.3= R
Why Organic carbon % in soil at both places? The last one should be Total organic carbon % in soil, though the factor 1.3 is not same for all soils.
Please do not use this method any more. You provoke a high contamination by Cr. For that you should change the oxidant substance, e. g., using permanganate (KMnO4). Alternatively, if you have too much SOC content you can using a furnace and determining the SOM by loss of weight; on opposite, if you have low amount of SOC you can use that wet oxidant determination using KMnO4. That is my opinion..., by the way, please use mL (not ml); and in observing colours, please look for helping a woman! She differentiates better the colour changes (presence of oxidant or reducing substances).
Can I use the Walkley-Black method of organic carbon analysis method with slight modification (viz., KMno4) for sludge and sediment samples?
I have a doubt that sludge and sediments samples will consume more of KMnO4 compared to soil samples as they are rich in organic matter.
I said, if your sediments have a lot of SOC, please use the dry procedure using a furnace. But take in account that you measure SOM, not SOC. In adition, if you have carbonates, you need to eliminate them previously. Dichromate or permanganate destroy reducing substances, then soils, sediments or sludges is not the matter; in some cases protecting substances, as clays, could produce interferences if the oxidant power is low. For that I recommend you the dry way (furnace), because in this case all the SOM is burnt (if the C content in samples is relatively high). Please, do not forget the carbonates as interferences!!!
The core of the question was about the colour change. This is related to the reaction of the oxidant (dichromate, orange) which is converted to chromium oxidation state +3 (green) in the course of the reaction. If you observe the green colour, this means that all of your oxidant is consumed and you cannot be sure if all of organic (oxidable) matter is really oxidised and thus covered by your experiment (means that the result is not reliable).
However, keep in mind that the orange dichromate is highly toxic (stated before several times), therefore this method might be regarded a little bit outdated.
Can another indicator except for Diphenylamine indicator can be used ?
1- Weight 1 g air air-dry soil (0.15mm) into a 500_ml beaker
2- Add 10 ml 1N potassium dichromate solution on using a pipette, add 20 ml concentrated H2SO4 using a dispenser, and swirl the beaker to mix the suspension.
3- Allow to stand for 30 minutes.
4- Add about 200 ml DI water, then add 10 ml concentrated H3PO4 using a dispenser, and allow the mixture to cool.
5- Add 10_15 drops diphenylamine indicators, add a Teflon _coated magnetic stirring bar, and place the beaker on a magnetic stirrer.
6- Titrate with 0.5 M ferrous ammonium sulfate solution, until the color changes from violet blue to green.
7- Prepare two blanks, containing all reagents but no soil, and treat them in exactly the same way as the soil suspension.
Measure 1 g of 0.2 mm soil sample in 500 mL conical flask. Add 10 mL of Potassium dichromate and 20mL Sulphuric acid. Mix gently and the reaction to complete for 30 minutes. Dilute with 200 mL distill water and 10 mL orthophosphoric acid. Add 1 mL diphenylamine indicator. Titrate the solution with ferrous ammonium sulphate solution to a brilliant green colour. A blank without soil is run simultaneously.
Dear Rohan Oak, 1.25% Ag2SO4 is applied for saline soils to avoid the error that could be produced by Chloride ion. Used oxidizing agent could be consumed to oxidize Chloride ions (present at higher concentration in saline soil). That will give a erroneous result.
Dear Tahanyat Naeem Satti you can use Ferroin indicator also. In that case As the end point is approached, the solution takes on a greenish colour and then changes to a dark green. At this point, add the ferrous sulphate drop-by-drop until the colour changes sharply from blue-green to reddish-grey.
Dear Dr. Zafar,
A modification of this method, yes. Look up any of multiple reference methods for Chemical Oxygen Demand. You'll need the catalyst to help degrade the plastics.
Appearance of green color means that all the oxidizing materials are reduced by organic matter and in this cases, more amount of oxidizing agent should be added. Soil contains various types and nature of organic compounds and during oxidation of these compounds so many intermediate products having different light absorption abilities are formed. This results various coloration of the solutions.
Marc Pansu_ Jacques Gautheyrou - Handbook of Soil Analysis_ Mineralogical_ Organic and Inorganic Methods-Springer (2006)
Hello,
please can someone kindly tell me how to separate soil organic carbon from total soil carbon (TC - SOC) and if there is a calculation, equation or formula that can be used for this. Also will appreciate any journal.
example: if you have TC = 4.322%; 3.399%; 2.974... e.c.t how do you determine the SOC?
Thank your
This method is good, my research data process of Walkley-Black method
The determination of soil organic carbon is based on the Walkley-Black chromic acid wet oxidation method. Oxidisable matter in the soil is oxidised by 1 N K2Cr2O7 solution. The reaction is assisted by the heat generated when two volumes of H2SO4 are mixed with one volume of the dichromate
1) Take 0.5 or 1.0 g 0.2 mm sieved soil sample into a 500 ml capacity conical flak.
2) Add 10 ml of 1 N potassium dichromate solution and 20 ml of concentrated sulphuric acid, gently mixed and keep the contents for 1/2 hour.
3) After 30 min, add 200 ml distilled water, 10 ml phosphoric acid, about 0.2 g NaF and 8 to 10 drops of diphenylamine indicator.
4) Titrate the contents against the standard ferrous sulfate or ferrous ammonium sulfate till it becomes bright green in colour.
5) Run a blank titration by following all the above steps without soil.
6) After noting down the burette readings of both blank and sample titrations, calculate the organic carbon present in the soil using the following formula
Refer the link for correct information
https://journals.lww.com/soilsci/citation/1934/01000/an_examination_of_the_degtjareff_method_for.3.aspx
Else, for further details you directly contact me. The analysis is also dependent upon the carbon content of the soil sample.
1.0 g of soil taken in 500 ml conical flask, 10 ml of N K2Cr2O7 solution and 20 ml concentrate (96%) H2SO4 were added. The solution was shaken for a minute and allowed to cool down for about 30 minutes in dark place, after that added 200 ml of distilled water and added 10 ml of 85% pure H3PO4 than add 1.0 ml diphenylamine indicator solution. The dark brown coloured solution was titrated against N/2 ferrous ammonium sulphate solution until the deep violet colour changed to purple and finally to green. In the same way a blank determination without soil was also carried out...
Calculation
1 ml of 1 N K2Cr2O7 = 0.003g Carbon
Organic carbon percent in soil =
{10(B – S)×0.003/B× wt . of soil samples}× 100
1) Take 0.5 or 1.0 g 0.2 mm sieved soil sample into a 500 ml capacity conical flak.2) Add 10 ml of 1 N potassium dichromate solution and 20 ml of concentrated sulphuric acid, gently mixed and keep the contents for 1/2 hour.3) After 30 min, add 200 ml distilled water, 10 ml phosphoric acid, about 0.2 g NaF and 8 to 10 drops of diphenylamine indicator.4) Titrate the contents against the standard ferrous sulfate or ferrous ammonium sulfate till it becomes bright green in colour.5) Run a blank titration by following all the above steps without soil.6) After noting down the burette readings of both blank and sample titrations, calculate the organic carbon present in the soil using the following formula
Pr: Eetela Sathya Narayana Thank you so much for your good explanation, but I think that you forgot the correction factor of the amount of oxidized organic carbon 100/77 in the cacule formula !?
- Badges
- Science topic
- Similar topics
- Agriculture
- Soil Science