Bromide Analysis Lab

In this lab...

You will be analyzing bromide content in water using microfluidic devices. The device will have the design of a flow through chip where all the reagent layers are stacked on top of each other. The sample is inserted through the top and the colorimetric reaction is observed on the bottom layer. Excess bromide in water can signify harmful contaminants in your drinking water. This water pollution is often a negative ramification of hydraulic fracturing and oil drilling.

Watch this video to see how polluted water can be highly flammable (and extremely unsafe to ingest!)

Learning Objectives:

  1. Determine the necessary procedures to produce an analytically reproducible measurement of bromide concentration.

  2. Elucidate the critical factors involved in constructing a flow through microfluidic device.

  3. Compare different methods of colorimetric image analysis in terms of analytical figures of merit.


To Do List:

Step 1: Read lab background below

Step 2: Read lab procedure

Step 3: Watch corresponding lab tutorial

Step 4: Answer pre-lab questions

Step 5: Perform lab experiment

Step 6: Answer post-lab questions

What is Hydraulic Fracturing?

To access the fossil fuels, cracks in and below the Earth’s surface are opened and widened by injecting water, chemicals, and proppant (sand or other small incompressible particles1) at high pressure. Today the process uses approximately 60,000 gal of fluid and 100,000 lbm of propping agent per fracture treatment, with the largest treatments exceeding 1 million gal of fluid and 5 million lbm of proppant.2 Once the injection process is completed, the internal pressure of the rock formation causes fluid to return to the surface through the drilling site.1 This fluid is known as "flowback" and may contain the injected chemicals plus naturally occurring materials such as brines (salts dissolved in water), metals, radionuclides, and hydrocarbons.1 The amount of flowback typically ranges from 10% to 25% of the injected volume, however, it can also yield over 70% or exceed the injected volume of hydraulic fracturing fluid3. Flowback is not safe to be released into local rivers and streams so it is typically stored on site in tanks or pits before it is treated, disposed of or recycled. In many cases, it is injected underground, into porous geologic formations, for disposal.1 Studies have shown that fluids have leaked, spilled, and migrated underground as well as contaminated nearby ecosystems due to inadequate treatment and disposal of wastewater.4

This image chronicles the hydrofracking well pad activities. In chronological order: water acquisition, chemical mixing, well injection, flowback and produced waters (wastewaters), wastewater treatment and waste disposal. A close up view of the underground of hydrofracking well says "natural gas flows from fissures into well" depicting the small fissures in the ground.

Hydrofracking well pad water activities14

Hydraulic fracturing wastewaters typically contain halides (specifically chloride, bromide, and iodide) and alkaline earth ions (like calcium or magnesium), radioactive species and heavy metals (like mercury or lead).3 The total dissolved salts content of produced water ranges based on location but all show concentrations that are significantly above background levels.4,6 High concentrations of bromide, chloride, iodide, and ammonium have been found in wastewater, which could directly contaminate surface waters from spills or wastewater disposal but also make them an excellent analytical target.5 In this experiment, bromide will be used as the ion that can be used to detect hydrofracking infiltration. Using microfluidic devices, the concentration of bromide in the sample can be found.

Health Effects of Hydraulic Fracturing

While hydrofracked natural gas still contributes significantly to global climate change, it provides some benefits compared to traditional carbon-based energy sources, like coal burning, such as lower electricity costs and decreased carbon emissions.7 However, as hydrofracking gains popularity, more studies begin to show the harmful effects it causes to both humans and the environment.

This infographic shows pathways from hydrofracking exposure to various health outcomes.

Of the 632 chemicals involved in natural gas operations:

  • more than 75% are harmful to skin, eyes, sensory organs, the respiratory system, and the gastrointestinal system8

  • An estimated 50% are hazardous to the nervous system, immune system, cardiovascular system, and the kidneys8

  • 25% of these chemicals are expected to be carcinogens8



Associations have been drawn between proximity to a hydrofracking site and the increased prevalence of birth defects such as congenital heart defects and neural tube defects.9 The extraction process includes over 100 know endocrine-disrupting chemicals which can greatly affect estrogen and androgen receptors in humans and animals if they reach surface or ground water and are consumed.10 Silica levels in air samples from hydraulic fracturing sites are on average 84% above the Occupational Safety and Health Administration’s proposed standard.11 This puts hydrofracking site workers, and those living in adjacent areas a higher ricks of developing silicosis and other silica related illnesses such as lung cancer, end-stage renal disease, chronic obstructive pulmonary disease, tuberculosis, and connective tissue disease.11 Most of these health effects are long-term and would not show expression immediately, therefore given hydrofracking’s rise in the 2000s, clinicians will likely just now start to see the effects of these hazards. Additionally, these illnesses will more severely effect those individuals and communities with pre-existing conditions an lack of accessibility to quality healthcare.

Where is this happening?

At least 15.3 million people live within one mile of a drilling site built since 2000.12 Many of these sites are located in the Marcellus Shale, a large rock formation spanning more than 90,000 square miles, which covers areas of New York, Pennsylvania, Ohio, and West Virginia.13 Environmental injustice related to hydrofracking appears most prominently in areas of Pennsylvania near the Marcellus Shale.13 Although the hydraulic fracturing industry claims these hydrofracking wells are placed in predominantly poor, rural areas out of necessity, with a selling point that they could promote economic growth, populations below the poverty line are disproportionally bearing the negative affects associated with these wells.13 Additionally, elderly, poor, and lower-education populations in West Virginia, and youth populations in Ohio have been found to be disproportionately impacted by gas wells.13 This is especially concerning because these populations generally have less access to information and resources, as well as less mobility in regard to relocation.


Environmental Effects of Hydrofracking

The ways in which the hydrofracking flowback water is disposed of also has significant environmental effects. Coupled with wastewater from other oil and coal related processes, fluid waste from hydrofracking is often injected deep into the ground below the ground water level.15 These injections have been shown to increase seismic activity in areas of the United States that are not naturally prone to earthquakes.15 Oklahoma specifically has had a surge of M3+ earth quakes between 2014 and 2017 that surpassed the earthquake rate in California.15

Professionals in the Field:

Watch this video of Professor Hannah Shafaat from Ohio State University from when she was researching hydrogen-producing enzymes at the Max Planck Institute of Bioinorganic Chemistry in Mülheim, Germany.

Get Involved!

Learn more about organizations like:


References:

  1. The Process of Unconventional Natural Gas Production https://www.epa.gov/uog/process-unconventional-natural-gas-production.
  2. Montgomery, C. T.; Smith, M. B. Hydraulic Fracturing: History of an Enduring Technology. J. Pet. Technol. 2010, 62 (12), 26–40. https://doi.org/10.2118/1210-0026-JPT.
  3. Zwiener, D. C. 20.07.2016 Prof. Dr. Wolfgang Rosenstiel. 218.
  4. Vengosh, A.; Jackson, R. B.; Warner, N.; Darrah, T. H.; Kondash, A. A Critical Review of the Risks to Water Resources from Unconventional Shale Gas Development and Hydraulic Fracturing in the United States. Environ. Sci. Technol. 2014, 48 (15), 8334–8348. https://doi.org/10.1021/es405118y.
  5. Vengosh, A.; Kondash, A.; Harkness, J.; Lauer, N.; Warner, N.; Darrah, T. H. The Geochemistry of Hydraulic Fracturing Fluids. Procedia Earth Planet. Sci. 2017, 17, 21–24. https://doi.org/10.1016/j.proeps.2016.12.011.
  6. Zolfaghari, A.; Dehghanpour, H.; Noel, M.; Bearinger, D. Laboratory and Field Analysis of Flowback Water from Gas Shales. J. Unconv. Oil Gas Resour. 2016, 14, 113–127. https://doi.org/10.1016/j.juogr.2016.03.004.
  7. Leighton Walter Kille, Journalist's Resource November 14. “Fracking, Shale Gas and Health Effects: Research Roundup.” Journalist's Resource, 29 Mar. 2017, journalistsresource.org/studies/environment/energy/fracking-shale-gas-health-effects-research-roundup/.
  8. “Natural Gas Operations from a Public Health Perspective” Colborn, Theo; Kwiatkowski, Carol; Schultz, Kim; Bachran, Mary. Human and Ecological Risk Assessment, September 2011, 1039-1056. doi: 10.1080/10807039.2011.605662
  9. “Birth Outcomes and Maternal Residential Proximity to Natural Gas Development in Rural Colorado” McKenzie, Liza M.; Guo, R.; Witter, R.Z.; Savitz, D.A.; Newman, L.S.; Adgate, J.L. 2014. Environmental Health Perspectives. doi: 10.1289/ehp.1306722. , 122, 412-417.
  10. “Estrogen and Androgen Receptor Activities of Hydraulic Fracturing Chemicals and Surface and Ground Water in a Drilling-Dense Region” Kassotis, Christopher D.; Tillitt, Donald E.; Davis, J. Wade; Hormann, Annette M.; Nagel, Susan C. Endocrinology, December 2013. doi: 10.1210/en.2013-1697.
  11. Hydraulic Fracturing and the Risk of Silicosis” Rosenman, Kenneth D. Clinical Pulmonary Medicine, July 2014, Vol. 21, Issue 4. doi:10.1097/CPM.0000000000000046.
  12. Gold, Russel. “How Many People Are Affected By Fracking?” Forbes, Forbes Magazine, 24 Mar. 2014, www.forbes.com/sites/quora/2014/03/24/how-many-people-are-affected-by-fracking/#6f64c8423aec.
  13. Bienkowski, Brian. “Poor Communities Bear Greatest Burden from Fracking.” Scientific American, Scientific American, 6 May 2015, www.scientificamerican.com/article/poor-communities-bear-greatest-burden-from-fracking/.
  14. Gorski, Irena, and Brian S. Schwartz. “Environmental Health Concerns From Unconventional Natural Gas Development.” Oxford Research Encyclopedia of Global Public Health, 25 Feb. 2019, oxfordre.com/publichealth/view/10.1093/acrefore/9780190632366.001.0001/acrefore-9780190632366-e-44
  15. “Oklahoma Has Had a Surge of Earthquakes since 2009. Are They Due to Fracking?” USGS Science for a Changing World, U.S. Department of the Interior , www.usgs.gov/faqs/oklahoma-has-had-a-surge-earthquakes-2009-are-they-due-fracking?qt-news_science_products=0#qt-news_science_products.
  16. Loh, L. J.; Bandara, G. C.; Weber, G. L.; Remcho, V. T. Detection of Water Contamination from Hydraulic Fracturing Wastewater: A ΜPAD for Bromide Analysis in Natural Waters. The Analyst 2015, 140 (16), 5501–5507. https://doi.org/10.1039/C5AN00807G.