Ocean Acidification
From A Geological and Chemical Perspective
  Timeframe
  1 Fifty minute class period
                                                Description
  Target Audience                               This lesson plan emphasizes balance between natural geologic process-
  High school chemistry or earth science        es and human activities affecting ocean seawater acidity, as measured
  students (grades 9-12)                        by pH, and discusses how human activities are altering these processes
  Materials                                     to cause a rapid decline in ocean pH (termed ocean acidification).
  - PowerPoint presentation
                                                Objectives
  For each group:
  - 1 Student Data Sheet (at back of
                                                •	   Students will develop a basic understanding of the logarithmic pH
    lesson)                                          scale and how an increase in CO2 in the ocean will lead to a de-
  - 4 Erlenmeyer Flasks or other clear               crease in pH (increase in acidity).
    containers (500mL capacity)
  - 4 types of water (see “Activity” sec-       •	   Students will be able to identify how differences in ocean alkalinity
    tion for further instruction on making
                                                     affect the rate at which ocean acidification occurs.
    waters):
   1. Fresh water (tap is ok, store-bought
                                                •	   Students will gain experience developing a testable hypothesis and
      distilled (DI) water is best)
   2. Cretaceous seawater (fresh water
                                                     testing that hypothesis with an experiment.
      with 5g baking soda added per 10L
      or seawater with 2.5g baking soda         Teacher Background
      added per 10L)
                                                Carbon is an element that is the chemical backbone of all known life.
   3. Modern seawater (fresh water with
                                                What does that mean? All known life forms rely on carbon. Our Earth has a
      ~2.5g baking soda added per 10L,
      seawater, or artificial seawater)         carbon cycle. That means carbon is always on the move. Plants use
   4. Estuary water (approximated by            carbon dioxide (CO2) and sunlight to generate energy and grow. The
      filling the flask with half fresh water   carbon then becomes part of the plant. When we eat plants (or eat
      and half modern seawater)
                                                things that eat plants), some of the carbon becomes part of us, some
  - Bromothymol blue pH indicator dye
                                                is exhaled in our breath. When plants die theysometimes are buried
  - Straws or tubes for blowing into water
                                                and turn into fossil fuels like coal and oil over millions of years. . In fact,
  - Bromothymol blue pH color reference
    scale (on student data sheet)
                                                during the Carboniferous Period in the distant past, roughly 360 to 300
  - Stopwatch                                   million years ago, nearly all of the fossil fuels we use today were begin-
Contact:                                        ning to be formed. When we burn fossil fuels much of this long-stored
SMILE Program
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   Teacher Background (Continued)
   carbon quickly (re)enters the atmosphere as carbon dioxide. This is in
   contrast to the carbon dioxide we exhale, which was only obtained by
   plants in the food we eat within the past couple of years.
   	       One of the most critical jobs the oceans have is to store carbon.
   The oceans contain the largest reactive pool of carbon on the planet,
   and without the benefit of carbon storage in the oceans, the current            Key Vocabulary
   atmospheric carbon dioxide levels would be at least 25% higher than             pH
   they are today. Carbon in the form of carbon dioxide can be removed
                                                                                   CO2
   from the atmosphere when absorbed by the ocean through a physical
                                                                                   Ocean acidification
   process called diffusion. Diffusion occurs when there is more of some-
                                                                                   Alkalinity
   thing in one area relative to another, and that material moves to the
                                                                                   Corrosivity
   area with less. Prior to the combustion of fossil fuels the oceans were
   actually a small source of CO2 to the atmosphere, but they have be-             Buffering capacity
   come a large “sink” for CO2. In fact, in the last 150 years, 25-35% of all
   CO2 from the burning of fossil fuels has ended up in the ocean, and it
   will stay there for a long time.
   	      The oceans are naturally equipped to absorb large amounts of
   carbon dioxide from the atmosphere with little change to seawater
   chemistry. This is possible due to the natural buffering system of the
   oceans. The same way antacids buffer a sour stomach, the ocean’s
   buffering capacity slows changes in the ocean chemistry. To explain
   the ability of the oceans to store carbon and the buffering capacity of
   seawater we need to understand what happens when carbon dioxide
   enters the ocean.
   	      Several chemical reactions occur when the oceans absorb car-
   bon dioxide. The first is that carbon dioxide (CO2) reacts with seawater
   (H2O) to form carbonic acid (H2CO3). The carbon from the carbon diox-
   ide has been colored orange to illustrate the storage effect.
   		CO2 + H20 ↔ H2CO3                   				                        (1)
   	       Carbonic acid is a weak acid and separates (or more exactly,
   dissociates) to form one bicarbonate ion (HCO3-), and one hydrogen ion
   (H+) is released into the seawater.
   		CO2 + H2O ↔ H2CO3 ↔ HCO3- + H+                     		           (2)
   	      Bicarbonate is the primary form of inorganic carbon in the
   ocean and is one of the two “products” shown in the above reaction
   (the other is the hydrogen ion). Consider that we have only shown one
Ocean Acidification From a Geological & Chemical Perspective	                   Oregon State University | SMILE Program| 2
   Teacher Background (Continued)
   reaction from one molecule of carbon dioxide. There are actually MANY
   of these reactions taking place, one for each molecule of carbon di-
   oxide, and after these many reactions occur, some hydrogen ions will
   remain free floating in the seawater while others will react with an-
   other carbon ion in seawater (detailed in reaction (4) below). The more
   hydrogen ions that float freely in seawater, the more acidic the sea-          How Do We Measure
   water becomes. Looking back to our first equation, this means when
                                                                                  Acidity?
   CO2 increases the seawater will become more acidic (more CO2 being
                                                                                  The pH scale is used to measure the
   absorbed by the oceans ultimately leads to more hydrogen ions - see            acidity of a solution, like seawater, and
   pH equation to the right). This process, the uptake of carbon dioxide          is based on the negative logarithmic
   by the oceans and concurrent change in chemistry, has been named               concentration of hydrogen ions. It is
                                                                                  important to note that the pH is ef-
   ocean acidification.
                                                                                  fectively an indicator of the acid-base
   	      Note that a product of the above reaction includes bicarbon-            balance of any solution. In seawater
   ate, which is how the ocean so effectively stores carbon, because the          pH reflects the relative abundance of
                                                                                  carbonic acid and associated (inorgan-
   carbon in the CO2 gas initially absorbed into seawater is now in bicar-
                                                                                  ic) carbon molecules.
   bonate form. After this happens, more room will have been created for
                                                                                  pH = -log10[H+]     (3)
   even more CO2 gas form the atmosphere to be absorbed by the oceans.
                                                                                  As the concentration of hydrogen ions
   We are steadily increasing the concentration of CO2 in the atmospherei
                                                                                  goes up, pH goes down, and acidity
   by burning fossil fuels primarily, but also because of loss of vegetation      increases. A 10-fold increase in the
   (land use changes). The increase in atmospheric CO2 is directly respon-        concentration of hydrogen ions means
                                                                                  a decrease of 1 unit in the pH scale.
   sible for increasing mean global temperature through the amplification
                                                                                  The mean global pH of seawater is
   of a natural process, called the greenhouse effect. The increase in glob-      8.1. However, in the last 150 years,
   al temperature caused by the intensification of the greenhouse effect is       the pH of the ocean has decreased
   called climate change (also, global warming).                                  by 0.1 units. That does not sound like
                                                                                  much of a change, but because pH is
   	       Remember that free-floating hydrogen ion shown in reaction             measured on a logarithmic scale, this
   (2)? Instead of being free-floating, some of these ions will combine           equals an approximate 30% increase
   with another important ion in seawater, carbonate (CO₃²-), to form into        in acidity!
   another bicarbonate ion.
   		CO2 + H2O ↔ H2CO3 ↔ HCO3- + H+ ↔ CO3²- ↔ 2H+ (4)
   	       In the above reaction you can now see all components of the
   dissolved inorganic carbon system in seawater. The formation of an-
   other bicarbonate ion, resulting from the initial absorption of atmo-
   spheric CO2 by the oceans, is the primary way that the ocean naturally
   slows the increase in acidity on immediate time-scales. We call the
   ability of the ocean to take up (or “sequester”) hydrogen ions and
   prevent the pH from dropping its buffering capacity. We talk about the
   buffering capacity of seawater because it is linked to the amount of
Ocean Acidification From a Geological & Chemical Perspective	                  Oregon State University | SMILE Program| 3
   Teacher Background (Continued)
   ions that can react with hydrogen ions, and that is what we call alka-
   linity. Alkalinity in the oceans is approximately 97% due to the total
   amount of bicarbonate and carbonate ions.
   	       We know that the concentration of CO2 is changing on times-
   cales of years, but how fast does alkalinity change? The main process
   adding alkalinity compounds (like bicarbonate and carbonate ions)                 Can We Just Add Biocar-
   to the oceans is the erosion and weathering of rocks on land through              bonate?
   the hydrologic cycle. In very small amounts over long periods of time,            In the ocean, pH is effectively a result
   rivers carry “alkalinity” to the oceans and leave it there, once water            of the ratio of two main components
                                                                                     of the dissolved inorganic carbon sys-
   evaporates. Over very long time scales, 100,000’s of years, the weath-
                                                                                     tem: the combined CO2 and H2CO3 in
   ering of continental rocks increases the alkalinity of seawater and               proportion to CO3²-. It is important to
   increases the ability of seawater to offset pH decreases. While it may            note that while alkalinity or buffering
                                                                                     capacity helps prevent changes in pH,
   seem like a viable solution to the ocean acidification problem to simply
                                                                                     simply adding bicarbonate to normal
   dump “alkalinity” into the sea, a large mismatch between time-scales              seawater will actually initially lower
   exists. Therefore, on the time scales important to humans (tens to                pH, because a solution of bicarbon-
   hundreds of years), these processes are not fast enough to significantly          ate only has equal parts of CO2 and
                                                                                     CO3²- and will have a pH of about 7.7.
   buffer against ocean acidification. In other words, the buffering capac-
                                                                                     Typically that solution will have excess
   ity of the planet can’t keep up with the amount of CO2 being put into             CO2, and if that outgasses (more CO2 in
   the atmosphere, and ultimately the oceans. This is essentially because            the solution than in the atmosphere),
                                                                                     the pH will rise to a value closer to
   the normal changes in CO2 in the geologic past have occurred on much
                                                                                     modern ocean pH (depending on how
   longer time scales, more similar to rates of weathering.                          much bicarbonate is initially added).
   	     We don’t yet know how ocean acidification impacts all marine
   ecosystems, but we do know that some organisms that build shells
   (mussels, oysters, clams) or other body-parts (corals, sea urchins)
   made out of calcium carbonate (CaCO3) are affected negatively. Why is
   that?
   	        Remember that the more hydrogen ions free-floating in sea-
   water from CO2-enrichment (more and more CO2 being absorbed by
   the oceans), the more carbonate ions react with hydrogen ions to form
   bicarbonate. This means that the amount of carbonate ions in the sea-
   water will decrease. The more carbonate ions in seawater, the easier
   it is to make their calcium + carbonate shells, through a process called
   calcification. A term called “corrosivity” is determined by how many
   carbonate ions are in seawater. Similar to a glass of water that salt
   is added to, initially the water is corrosive to the salt and dissolves it.
   After adding more and more salt, at some point the glass of salty water
   will not dissolve any more salt. At this time the solution is saturated
Ocean Acidification From a Geological & Chemical Perspective	                    Oregon State University | SMILE Program| 4
   Teacher Background (Continued)
   with respect to salt. Fortunately for marine organisms that build shells,
   the oceans are saturated in most places with respect to calcium
   carbonate, but the decrease in carbonate ions from ocean acidifica-
   tion lowers the saturation state and makes it harder for organisms to
   make shells, and in some cases may make waters corrosive to exist-
   ing calcium carbonate structures with enough CO2.
   	       We know that ocean pH was lower in the Earth’s past (pa-
   leo-oceanographers can determine the acidity of the ocean back
   as far as 400 million years ago), although it hasn’t been as acidic in
   the last 1 million years. More importantly, ocean acidity has never
   changed as fast as it is changing today, even though during some
   periods in Earth’s history, such as the Cretaceous, the levels of CO2
                                                                                     Each group will need: 4 cups or flasks,
   were up to four times greater than today. Still, during that time a lot of
                                                                                     bromothymol blue (with dropper), bro-
   shell building organisms evolved and thrived! What do you think was               mothymol blue pH color reference, and 4
   happening? The alkalinity of the ocean was twice what it is today!                straws. Not shown: Student Data Sheet,
                                                                                     water samples, pen for labling, and stop-
   Preparation                                                                       watcb
   Because tap water can be rich in minerals (and thus have a high alka-
   linity) it is better to start with distilled water. Purchase two 2.5gal jugs
   of distilled water from the store. The first jug will serve as the source of
   fresh water. The second jug will be made into the Cretaceous water. To            Guiding Questions:
   this jug, add 5g (1 teaspoon) of baking soda (the recipe for this water is        Activity Introduction
   5g baking soda per 10L fresh water, and 10L = 2.5gal). Label each jug!
                                                                                     - Gauge students' understanding
   This can all be done before the activity is to start.                               of pH. Review pH as a logarithmic
                                                                                       scale:
   Activity Introduction                                                             	        pH = -log10[H+]
   One of the most critical jobs the oceans have is to store carbon. Today           - If we have a pH of 7, is our material
   we will do an experiment to understand how an increase in carbon                    basic, acidic, or neutral?
   dioxide leads seawater to become more acidic, a process called ocean              - If the acidity of a substance increas-
                                                                                        es to 10 times as much, what hap-
   acidification. We will also learn that ocean acidification is partially
                                                                                        pens on the pH scale? It decreases
   managed by the alkalinity of the ocean.                                              by 1 unit.
   •	   When carbon dioxide (from sources such as the burning of fossil              - In the last 150 years, the pH of the
        fuels) is added to the ocean, seawater becomes more acidic. This                ocean has decreased from 8.2 to
                                                                                        8.1. What percentage of increase in
        hurts the ocean's ecosystem and ocean-related industries.	
                                                                                        acidity does this equal? 30%!
   •	   Differences in Alkalinity, or the carbonate chemistry of the ocean,
        controls the ocean's ability to buffer the increase in CO2 and slow
        down acidification.
Ocean Acidification From a Geological & Chemical Perspective	                     Oregon State University | SMILE Program| 5
   •	   Unfortunately, changes in alkalinity occur across geologic times-
        cales (caused by the erosion of rocks on land and deposition of
        erosive materials in the ocean), and cannot keep up with changes in
        CO2 levels which increase on a seemingly daily basis! For example,
        in the Cretaceous, CO2 levels were up to 4 times greater than today,
        but the alkalinity of the ocean was twice what it is today, so shells
        and other marine life flourished.
   •	   The air we breathe out is 100 times more concentrated in CO2 than
                                                                                      Testing the CO2 levels of human breath
        our modern atmosphere. An exhaled human breath is about 3.7%
        CO2ii while the modern atmosphere is ~0.04% CO2iii. We can use
        the fact that our breath is high in CO2 to investigate what happens
        when CO2 is added to waters with different alkalinities or buffering
        capacities. Using baking soda (sodium bicarbonate) we can create
        different types of water masses.
   Activity:
   Instructions written for 4 students groups. These can be expanded for
   more groups by starting with more water in the Preparation.                        Activity Set-up: 4 cups labeled with
                                                                                      different water types, bromothymol blue
        1. Ask students to label their flasks (or clear cups) and fill them with
                                                                                      color pH reference, straws, dropper
            the water to create one of each of four types of water. This will
            be an exercise in how to create dilutions:
           1.	 Fresh water
           2.	 Cretaceous seawater                                                    Guiding Questions:
                                                                                      Pre-Experiment!
           3.	 Modern seawater - The students will have to dilute the
                                                                                      - Ask students about the characteris-
               Cretaceous water to make this type. This could be done                   tics of the four kinds of water. What
               by adding ½ Cretaceous water and ½ fresh water to their                  do they think are the differences
               container. If students are measuring out amounts of water                between the four types of water
                                                                                        with regard to pH, CO2 content, and
               (this is ideal), have them add 250mL Cretaceous water and
                                                                                        alkalinity? Which has the highest
               250mL fresh water to their container (500mL total).                      alkalinity? The lowest?
           4.	 Estuary water – The students will have to dilute the Creta-            - What is the difference between
                                                                                        Cretaceous Seawater and Modern
               ceous water to make this type. This could be done by adding
                                                                                        seawater? Why?
               ¼ Cretaceous water and ¾ fresh water to their container. If
                                                                                      - What is an estuary? Why did we mix
               students are measuring out amounts of water (this is ideal),             the Cretaceous seawater with fresh
               have them add 125mL Cretaceous water and 375mL fresh                     water to make Estuary water?
               water to their container (500mL total).                                - What properties of the water affect
                                                                                        its alkalinity?
        2.	 Have students add a straw or length of tubing to each flask for
            blowing. Ask students about the characteristics of the different
            types of water using the Guiding Questions to the right.
Ocean Acidification From a Geological & Chemical Perspective	                      Oregon State University | SMILE Program| 6
   Activity Continued
       3.	 Have students write hypotheses about what will happen to
           the different kinds of water when CO2 is introduced via blow-
           ing.
       4.	 Ask students to add bromothymol blue to each water sample
           (start with 2 drops but keep adding until they see a notice-
           able color change) to measure the initial pH. Record onto data
           sheet at Time 0.
       5.	 Conduct the experiment! Begin blowing and every 30 sec-
           onds, use the bromothymol blue indicator chart on the data
           sheet to record the change in pH in relation to the addition of      Using a dropper to add bromothymol blue
                                                                                to each water type
           CO2 for each water sample.
   Activity Wrap Up:
       1.	 What did you notice about the level of pH changes
           between the four types of water? Are the colors the
           same in all types of water? Why or why not?
       2. How long did it take to change each type of water?
          Which type took the longest to change? Which type
          changed most quickly?
       3. Do your observations match what you hypothe-
          sized?
                                                                                The water samples with bromothymol
       4.	 Let’s review how the alkalinity differed between each type of        blue - which water type is the most
           water. How do you think the alkalinity of water plays a role in      acidic?
           the ability for increased CO2 to cause ocean acidification?	
   It should take the most time to change the Cretaceous seawater and
   the least time to change the fresh water. The end point will look
   different in each treatment too – the fresh water will turn all the
   way yellow almost immediately, while students will have to huff
   and puff for a long time to get the Cretaceous seawater to turn a
   muddy green.
   Water with higher alkalinity is more resistant to changes in pH
   when an acid (in this case H2CO3, or carbonic acid) is added. This
   example demonstrates one of the more commonly used defini-
   tions of alkalinity — which can be simplified to: “its quantitative
   ability to titrate an acid”iv.                                               After addition of CO2, note color change!
Ocean Acidification From a Geological & Chemical Perspective	                Oregon State University | SMILE Program| 7
       Next Generation Science Standards                                                 THANKS TO THE
       DISCIPLINARY CORE IDEAS:                PRACTICES:                                 FOLLOWING
       ESS2.D: Weather and Climate             •	   Developing and Using Models          CONTRIBUTORS:
                                               •	   Planning and Carrying Out
       PERFORMANCE EXPECTATIONS:                    Investigations                   Elizabeth Brunner
       HS-ESS2-4: Use a model to               •	   Analyzing and Interpreting       Iria Gimenez
       describe how variations in the flow          Data                             Annaliese Hettinger
       of energy into and out of Earth’s                                             Rebecca Mabardy
       systems result in changes in            CROSSCUTTING CONCEPTS:
                                                                                     Stephanie Smith
       climate.                                •	   Cause and Effect
                                               •	   Stability and change             George Waldbusser
       HS-ESS2-5: Plan and conduct an
       investigation of the properties         •	   Scale, Proportion, & Quantity
                                                                                     This project is supported by
       of water and its effects on Earth
                                                                                     Dr. George Waldbusser's re-
       materials and surface processes.
                                                                                     search group in the College
                                                                                     of Earth, Ocean, and Atmo-
                                                                                     spheric Sciences at Oregon
                                                                                     State University.
                                                                                            POTENTIAL
                                                                                           EXTENSIONAL
                                                                                             ACTIVITY:
                                                                                        Think about how
                                                                                        ocean acidification
                                                                                        affects Oregon’s coast-
                                                                                        al industries: https://
                                                                                        www.youtube.com/
        SMILE Teachers blowing into their water samples at the 2016 Winter Teach-       watch?v=7h08ok3hFSs
        ers' Workshop!
       Resources:
         ihttp://www.ipcc.ch/
         iihttp://cdiac.esd.ornl.gov/pns/faq_othr.html
         iii Dr. Pieter Tans, NOAA/ESRL http://www.esrl.noaa.gov/gmd/ccgg/trends
         ivhttp://en.wikipedia.org/wiki/Alkalinity
         For a more comprehensive treatment of alkalinity, see Zeebe and Wolf-Gladrow, “CO2 in seawa-
         ter: equilibrium, kinetics and isotopes” Elsevier Oceanography Series 65.
Ocean Acidification Resources	                                                      Oregon State University | SMILE Program| 8
     	
  	
  	
  	
  	
  	
  	
  	
  	
  	
  	
  	
  	
  	
  	
  	
  	
  	
  	
  	
  	
  	
  	
  	
  	
  	
  	
  	
  	
  	
  	
  	
  	
  	
  	
  	
  	
  	
  	
  	
   	
  	
  	
  	
  	
  	
  	
  	
  	
  	
  	
  	
  	
  	
  	
  	
  	
  	
  	
  	
  	
  	
  	
  	
  	
  	
  	
  	
  	
  	
  	
  	
  	
  	
  	
  	
  	
  	
  	
   	
  	
  	
  	
  	
  	
  	
  	
  	
  	
  	
  	
  	
  	
  	
  	
  	
  	
  	
  	
  	
  	
  	
  	
  	
  	
  	
  	
  	
  	
  	
  	
  	
  	
  	
  	
  	
  	
  	
   	
  	
  	
  	
  	
  	
  	
  	
  	
  	
  	
  	
  	
  	
  	
  	
  	
  	
  	
  	
  	
  	
  	
  	
  	
  	
  	
  	
  	
  	
  	
  	
  	
  	
  	
  	
  	
  	
  	
   	
  	
  	
  	
  	
  	
  	
  	
  	
  	
  	
  	
  	
  	
  	
  	
  	
  	
  	
  	
  	
  	
  	
  	
  	
  	
  	
  	
  	
  	
  	
  	
  	
  	
  	
  	
  	
  	
  	
   	
                                                                                                                                                                                                                                                                                                           Student Data Sheet
     Hypotheses:
     Add the Bromothymol blue indicator and record your pH level! Then blow into your water
     samples!
            Time                                                                   pH                                                                        pH                                                                             pH       pH                                                                                                                                                                                                                                                                                                                     Observations
            (sec.)                                                                Fresh                                                                    Estuary                                                                        Modern Cretaceous
                                                                                  water                                                                     water                                                                        seawater seawater
Ocean Acidification Handouts	                                                                                                                                                                                                                                                                                                                                                                                                                                                                                                                                                                            Oregon State University | SMILE Program | 9