HOW TO GUIDE:Testing for Hydrogen Sulfide Using Photographic Paper

Protocol from:Horwell, C.J., Allen, A.G., Mather, T.A., Patterson, J.E., 2004. Evaluation of a simple passive sampling technique for monitoring volcanogenic hydrogen sulphide. J. Environ. Monitor. 6, 630 - 635.

This guide describes how to make your own test for Hydrogen Sulfide Gas using strips of photographic paper. The method was developed by Horwell et. al. and described in their 2004 paper. We are adapting and developing the protocol for use in communities impacted

by natural gas development. This protocol should be used to further develop the accuracy and usefulness of this test for gas patch communities. We have not yet standardized or calibrated this assay. Therefore NO RESULTS FROM THIS PROTOCOL SHOULD BE TAKEN AS CONCLUSIVE EVIDENCE AT THIS STAGE. Consider this a “prototyping process” in which we will be further developing the test, to examine questions such as: 1. What positive and negative controls should we include? How do we know what positive results looks like? How can we make sure the test strips are working accurately? 2. What are possible false positives and negatives, i.e. what gases or substances other than H2S might cause the test strips to darken? In what conditions might this test fail to detect H2S that the human nose or other sensor might detect?3. Do different test strip containers produce different results? What is the best design for a test strip container?4. What are cases of hydrogen sulfide exposure like in the gas patch? Does H2S emerge continually from a point source? Does the smell come and go? How should this test be best adapted to serve the needs to Gas Patch communities?5. How does this test perform in different experimental conditions? I.e. around a point source? In a home? On a person?6. How should we develop this test for ease of use, maximum accuracy, verifiability, and adaptability?

Materials - (with links) 1) Ilford Multigrade IV RC Deluxe MGD.1M B&W Paper (35 sheets $18) herehttp://www.google.com/products/catalog?q=Ilford+Multigrade+IV+RC+Deluxe+MGD.1M+B%26W+Paper&hl=en&safe=off&prmd=imvns&bav=on.2,or.r_gc.r_pw.r_cp.,cf.osb&biw=1047&bih=706&um=1&ie=UTF-8&tbm=shop&cid=1635077024732872642&sa=X&ei=V6-mTtzsC8Le0QHY2c2XDg&ved=0CG8Q8wIwAw 2) Glycerol: as it should seem that Glycerol and Glycerine are roughly the same compounds we will use Glycerine as it is more readily available. (8oz $1) herehttp://www.google.com/products/catalog?q=glycerin&um=1&ie=UTF-8&tbm=shop&cid=14151160970879363122&sa=X&ei=5LGmTsaCGer30gGJxuG3Dg&ved=0CGsQ8gIwAw 3) Kodak Photoflo 200 (16oz $8) herehttp://www.google.com/products/catalog?hl=en&safe=off&q=kodak+photo+flo+200&bav=on.2,or.r_gc.r_pw.,cf.osb&biw=1047&bih=706&um=1&ie=UTF-8&tbm=shop&cid=14456853804540069997&sa=X&ei=x7KmTum8BOH10gGkw_WEDg&ved=0CF4Q8wIwAAMaterials Safety Data Sheet: http://www.tedpella.com/msds_html/26950msds.htm 4) Salt: sodium chloride 5 grams 5) Photographic fixing solution: Kodak Fixer, Powderhttp://www.bhphotovideo.com/bnh/controller/home?is=REG&sku=27603&Q=&O=&A=detailsMaterials Safety Data Sheet: http://www.emsdiasum.com/microscopy/technical/msds/74300.pdf 6) 1 Gallon Plastic Jug for Storing Fixer and a Sharpie to label the Jug 7) Access to a dark room or set up your own minimal darkroom: There are a number of videos on YouTube about how to set up your own darkroom. For this assay we aren’t fully developing pictures but merely preparing and fixing photographic paper so you don’t need an enlarger or any developing chemicals. You just need a dark space where you can mix solutions, dispose of them safely and hang test strips to dry.Safelight: http://www.google.com/products/catalog?q=darkroom+safe+light&cid=8561709536343219570&ei=zpB0T_OXGcOisAe0xayhBg&ved=0CBQQrRI

8) Gloves: household rubber gloves, or surgical gloves will do.

9) Tongs for handling the strips: http://www.bhphotovideo.com/c/product/762104-REG/Dot_Line_DL_0301_Print_Tongs_3_Pack_.html

10) Dishes: You will need some kind of container to mix the two solutions in, any deep plastic tray should work or you can order one like this. You might consider getting 2 trays so you can process multiple strips.http://www.bhphotovideo.com/c/product/65420-REG/Arkay_603530_8R_Plastic_Developing_Tray.html 11) Scissors or paper cutter 12) Paper Towels 13) A Timer or Watch (make sure it doesn’t emit light) 14) Camera for documenting work

15) Public Laboratory account for sharing results: http://publiclaboratory.org/getting-started 14) Dark containers for holding photostrips during testing. We are currently experimenting with which containers make the best samplers. Design parameters for the canister are:1. They need to allow air access but not allow light to access the test strips. 2. They need to be sealable so you can open the canister at the time of testing and close it after the testing period to be fixed. This could be achieved by taping the box or canister thoroughly at the conclusion of the testing period.3. It would be great if they were easily shippable. Megan has designed one using black VHS boxes: http://www.tapestockonline.com/plasvhsboxwi.html

Alternatively, Horwell et. al. stuck the paper strips in the bottom of film canister and left them open in dark spaces like mail boxes, or open but upside down in light areas to prevent light access. Film canisters can be bought in bulk though often photo stores will just give them to you: http://www.ebay.com/sch/i.html?_nkw=film+canister

As different canisters are developed we will test them in controlled laboratory conditions to compare and contrast them. Horwell et. al. found no significant differences between the

different canister arrangements they tried.

Procedure For Making the test strips: 1. In a dark room, cut black and white resin-backed photographic paper into strips. 2. Make the glycerol solution:

2.1) Wear plastic gloves and use tongs while making this mixture and handling the strips. Work in a room with good ventilation.

2.2) Make a 50/50 mix of water and glycerol in a trayAdd 5 grams of Sodium Chloride (optional)Add 5 drops of surfactant Kodak Photoflo 200.(MSDS for Kodak Photo Flo 200)Stir until salt is dissolved.

3. Use plastic tweezers to place the strips face down in the glycerol solution (to reduce the effects of any light in the darkened room) for five minutes. 4. Remove the strips from the solution and let them drain onto a paper towel. Leave strips to drain for five minutes. 5. Transfer strips to rack or pin up to dry in a dark room for twelve hours (we have been hanging them using clothes pins) 6. After 12 hours, in the dark room place the strips with tongs into containers for storage and testing. Replace container lids during storage. The samplers remain inactive until exposed to H2S-laden air. 7. Waste Disposal: If you are working in a school or professional darkroom, follow their procedures for safe disposal of the Photo Flo Mixture. If you are setting up your own darkroom, contact a local photography store or darkroom or local officials to discuss safe disposal of the mixture and the fixative solution you will make to fix the strips upon completion. Using the Test Strips: This is the area where we should be experimenting at present to see what we can find out. The basic protocol is to:1. Plan an experiment (ideas suggested below)2. place the open canister in a site where you are interested in testing for Hydrogen Sulfide, ensuring that light is not entering the canister but air is able to circulate.3. Record the date, time, temperature and humidity at time of opening4. Record on a daily basis as long as the canister is open the temperature range and humidity

range.5. Once test strips have been exposed to H2S laden air, the canisters containing the strips should be resealed so they can be fixed in a dark room. Horwell et. al. 2005 article describes how these strips were placed all around a city in New Zealand for 1 week and following that for 1 month. After this period of time they collected the strips and used them to make maps like the one shown here.

Experiments to try: 1. Opening a canister when there is a smell event and closing it after the smell dissipates, and then fixing the sample. It is also important to document the date, daily temperature and humidity throughout such an experiment. 2. Placing canister all around home and property where H2S smells have been reported. It is important to record the exact location of each test strip and place them in a variety of locations. It will be important to label each sample canister and each testing strip to ensure there is no confusion when the strips are all fixed. To plan this a piece of property could be balloon mapped to generate a markable satellite image of the site. It is also important to document the date, daily temperature and humidity throughout such an experiment. 3. Placing canisters around a suspected point source. Again it is important to map the suspected point source and note where each sample is placed. It will be important to label each

sample canister and each testing strip to ensure there is no confusion when the strips are all fixed. To plan this a suspected point source or piece of property could be balloon mapped to generate a markable satellite image of the site. It is also important to document the date, daily temperature and humidity throughout such an experiment. 4. To document personal exposure a canister could be worn or carried an open canister over a period of time? It is also important to document the date, daily temperature and humidity throughout such an experiment.

Fixing the Test Strips: Gather up test strips and in a dark room fix them by: 1. Mixing up the fixative, we have tried:Kodak Fixer for Black & White Film & Paper this powder when makes 1 Gallon (3.8L) of fixer.

1.1 Put on gloves and follow the directions on the back of the packet1.2 mix 3 L of water with the powder (not 3.8 L of water then adding the powder as I did

on my first try). 1.3 Stir the mixture gently until it the powder dissolves completely so the liquid looks clear. This took us about 10 minutes on first try.

2. Establish an order to your fixing process so you know which strips came from which canisters. This could be done by doing canisters one at time, or marking the strips. We scratched roman numerals into the strips before fixing them but that is difficult in the dark. 3. According to your plan, place the strips into the fixer for five minutes. 3. Remove the strips from the fixer and wash the strips twice with cold water. 4. Leave the strips on a rack or hang them to dry for 12 hours. As they are now fixed they can

be dried in light or in the dark. 5. The fixer is reusable so store it in a 1 gallon light safe jug. This should be poured in carefully using a funnel so you don't splash it around too much. Wash skin thoroughly if you get any on you. 6. Once outside the darkroom- use a camera or scanner to record your results. Post your results and your experimental design on Publiclaboratory.org as a research note. Describe what didn’t work as well as your successes so others can learn from your mistakes.