Methylene Blue Method for aqueous sulfide measurement

Using a 100ml volumetric flask:

1. Add 20ml of a 2% Zinc Acetate Solution
2. Add Sulfide Solution (fixed as ZnS)
3. Add 80ml of distilled water
4. Add 10ml of dimethyl-p-phenylenediamine sulfate solution (0.2% in 20%
H2SO4)
5. Immediately swirl it (gently)
6. Add 0.5 ml of FeNH4(SO4)2 solution (10% in 2% H2SO4)
7. Shake mixture and allow it to stand for 10 minutes

Zeiss Spectrophotometer: Analyze at 670 mu (Utsumi et al)
Eppendorf Photometer: Analyze at 644 mu


How it works

The Methylene Blue color complex occurs when sulfide reacts with dimethyl-p-
phenylenediamine. It is necessary to prepare a stock solution and measure
different concentrations of sulfide in order to obtain a calibration curve and then
compare the curve to the absorbance obtained from the sample to be measured
(Lindsay & Baedecker 1988). The pH should be kept stable because it can
interfere on the readings (Kuban Dasgupta and Marx 1992). The acidic pH is
essential to release trapped H2S (Pluth et al 2013)(Check image below)




References

Image comes from (it was not possible to download and/or copy the content):
http://books.google.ca/books?hl=pt-BR&lr=&id=l-
1gCPtxJ_AC&oi=fnd&pg=PA349&dq=Spectrophotometric+determination+of+hyd
rogen+sulfide-
methylene+blue+method&ots=jxzk3U2zWc&sig=9rcelvh8z17YOZgygZ4TCzDlgK
w#v=onepage&q&f=false

Guenther Johnson and Coale 2001 - Focus on a method that actually doesn't use
Methylene Blue, but it has a small comparison and description of the method.
(Highlighted)

Pluth et al 2013: Description and comparison of different strategies to detect
H2S. Methylene Blue method is highlighted.

Reese et al 2011: Background history of the Blue Methylene Method. Description
and how it changed over time.

Kuban Dasgupta and Marx 1992: Description on how the amount of acid, iron
and other reagents can alter the results of the measurement.

Utsumi et al: Comparison of Methylene Blue Method and UV method

Juliana Carla Robi: Step by step description of method (highlighted). This is not a
scientific paper. This is a internship report. (In portuguese)


Most of the methods presented cite, at some moment, the Standard Methods for
the Examination of Water and Wastewater book. There is a 2012 edition of the
book, but I was able to find the 1999 version only. It doesn't have an index, which
made it hard to find information about the sulfide measurement. I could not find
anything but some recommendations to measure Hydrogen Sulfide by the gas
method.