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- Herausgeber: John Wiley & Sons
- Kategorie: Wissenschaft und neue Technologien
- Sprache: Englisch
Covers the essentials of environmental chemistry and focuses on measurements that can be made in a typical undergraduate laboratory
- Provides a review of general chemistry nestled in the story of the Big Bang and the formation of the Earth
- Includes a primer on measurement statistics and quantitative methods to equip students to make measurements in lab
- Encapsulates environmental chemistry in three chapters on the atmosphere, lithosphere and hydrosphere
- Describes many instruments and methods used to make common environmental measurements
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Veröffentlichungsjahr: 2017
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Table of Contents
Cover
Title Page
Copyright
PREFACE
ABOUT THE COMPANION WEBSITE
INTRODUCTION
CHAPTER 1: ORIGINS: A CHEMICAL HISTORY OF THE EARTH FROM THE BIG BANG UNTIL NOW—13.8 BILLION YEARS OF REVIEW
1.1 INTRODUCTION
1.2 THE BIG BANG
1.3 SOLAR NEBULAR MODEL: THE BIRTH OF OUR SOLAR SYSTEM
1.4 LIFE EMERGES
1.5 REVIEW MATERIAL
1.6 IMPORTANT TERMS
EXERCISES
BIBLIOGRAPHY
CHAPTER 2: MEASUREMENTS AND STATISTICS
2.1 INTRODUCTION
2.2 MEASUREMENTS
2.3 PRIMARY AND SECONDARY STANDARDS
2.4 SAMPLE AND POPULATION DISTRIBUTIONS
2.5 HYPOTHESIS TESTING
2.6 METHODS OF QUANTITATION
2.7 QUANTITATIVE EQUIPMENT
2.8 LINEAR REGRESSION LITE
2.9 IMPORTANT TERMS
EXERCISES
BIBLIOGRAPHY
CHAPTER 3: THE ATMOSPHERE
3.1 INTRODUCTION
3.2 AN OVERVIEW OF THE ATMOSPHERE
3.3 THE EXOSPHERE AND THERMOSPHERE
3.4 THE MESOSPHERE
3.5 THE STRATOSPHERE
3.6 THE TROPOSPHERE
3.7 TROPOSPHERIC CHEMISTRY
3.8 CLASSICAL SMOG
3.9 ACID DEPOSITION
3.10 OZONE DESTRUCTION IN THE STRATOSPHERE
3.11 THE OZONE HOLE
3.12 CFC REPLACEMENTS
3.13 CLIMATE CHANGE
3.14 MEASUREMENTS OF ATMOSPHERIC CONSTITUENTS
3.15 IMPORTANT TERMS
EXERCISES
BIBLIOGRAPHY
CHAPTER 4: THE LITHOSPHERE
4.1 INTRODUCTION
4.2 SOIL FORMATION
4.3 METALS AND COMPLEXATION
4.4 ACID DEPOSITION AND SOIL
4.5 MEASUREMENTS
4.6 IMPORTANT TERMS
EXERCISES
BIBLIOGRAPHY
CHAPTER 5: THE HYDROSPHERE
5.1 INTRODUCTION
5.2 THE UNUSUAL PROPERTIES OF WATER
5.3 WATER AS A SOLVENT
5.4 THE CARBON CYCLE
5.5 THE NITROGEN CYCLE
5.6 THE PHOSPHORUS CYCLE
5.7 THE SULFUR CYCLE
5.8 WATER QUALITY
5.9 WASTEWATER TREATMENT
5.10 MEASUREMENTS
5.11 IMPORTANT TERMS
EXERCISES
BIBLIOGRAPHY
APPENDIX A: REVIEW EXAMPLES AND END-OF-CHAPTER EXERCISES
A.1 Solutions to In-Chapter Review Examples
A.2 Questions about the Big Bang, Solar Nebular Model, and the Formation of the Earth
APPENDIX B: EXAMPLES AND END-OF-CHAPTER EXERCISES
B.1 SOLUTIONS TO IN-CHAPTER EXAMPLES
B.2 SOLUTIONS TO END-OF-CHAPTER EXERCISES
APPENDIX C: CHAPTER 3 EXAMPLES AND END-OF-CHAPTER EXERCISES
C.1 SOLUTIONS TO IN-CHAPTER EXAMPLES
C.2 SOLUTIONS TO END-OF-CHAPTER EXERCISES
APPENDIX D: CHAPTER 4 EXAMPLES AND END-OF-CHAPTER EXERCISES
D.1 SOLUTIONS TO IN-CHAPTER EXAMPLES
APPENDIX E: CHAPTER 5 EXAMPLES
E.1 SOLUTIONS TO IN-CHAPTER EXAMPLES
E.2 SOLUTIONS TO END-OF-CHAPTER EXERCISES
APPENDIX F: COMMON CHEMICAL INSTRUMENTATION
F.1 UV-VIS SPECTROPHOTOMETERS
F.2 FLUOROMETERS
F.3 ATOMIC ABSORPTION SPECTROPHOTOMETERS
F.4 INDUCTIVELY COUPLED PLASMA INSTRUMENT
F.5 CHROMATOGRAPHY
F.6 INFRARED SPECTROMETRY
EXERCISES
F.7 Answers to Common Instrumentation Exercises
BIBLIOGRAPHY
APPENDIX G: DERIVATIONS
G.1 THE EQUAL VOLUME METHOD OF MULTIPLE STANDARD ADDITIONS FORMULA
G.2 TWO-POINT VARIABLE-VOLUME METHOD OF STANDARD ADDITION FORMULA
G.3 VARIABLE-VOLUME METHOD OF MULTIPLE STANDARD ADDITIONS FORMULA
APPENDIX H: TABLES
H.1 STUDENT's
t
TABLE
H.2 TEST TABLE
APPENDIX I: CHEMICAL AND PHYSICAL CONSTANTS
I.1 PHYSICAL CONSTANTS
I.2 STANDARD THERMOCHEMICAL PROPERTIES OF SELECTED SPECIES
I.3 HENRY's LAW CONSTANTS
I.4 SOLUBILITY PRODUCT CONSTANTS
I.5 ACID DISSOCIATION CONSTANTS
I.6 BASE DISSOCIATION CONSTANTS
I.7 BOND ENERGIES
I.8 STANDARD REDUCTION POTENTIALS
I.9 OH OXIDATION RATE CONSTANTS VALUES
BIBLIOGRAPHY
Index
End User License Agreement
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Guide
Cover
Table of Contents
Preface
Begin Reading
List of Illustrations
CHAPTER 1: ORIGINS: A CHEMICAL HISTORY OF THE EARTH FROM THE BIG BANG UNTIL NOW—13.8 BILLION YEARS OF REVIEW
Figure 1.1 Another view of the solar radiation spectrum showing the difference between the radiation at the top of the atmosphere and at the surface. Source: Robert A. Rhode http://en.wikipedia.org/wiki/File:Solar_Spectrum.png. Used under BY-SA 3.0 //creative commons.org/licenses/by-sa/3.0/deed.en
Figure 1.2 A glowing electric stove element. Courtesy K. Overway.
Figure 1.3 While visible radiation cannot penetrate the plastic bag, the infrared radiation, generated by the blackbody radiation of the man's body, can. Source: NASA.
Figure 1.4 A thermal camera used to find cold spots in a leaky house. Source: Passivhaus Institut “http://en.wikipedia.org/wiki/File:SONEL_KT-384.jpg” Used under BY- SA 3.0 //creativecommons.org/licenses/by-sa/3.0/deed.en.
Figure 1.5 A solar spectrum showing the absorption lines from elements that compose the outer atmosphere of the Sun. Notice the sodium “D” lines, the hydrogen “C” line, and the “A” and “B” lines associated with . Source: https://en.wikipedia.org/wiki/File:Fraunhofer_lines.svg
Figure 1.6 Relative abundances of the elements in the universe. Note that the -axis is a logarithmic scale. Source: http://en.wikipedia.org/wiki/Abundance_of_the_chemical_elements. Used under BY-SA 3.0 //creativecommons.org/licenses/by-sa/3.0/deed.en.
Figure 1.7 The onion-like layers of a giant star develop as it ages and approaches a supernova explosion. Source: http://commons.wikimedia.org/wiki/File:Massive_star_cutaway_pre-collapse_%28pinned%29.png. Used under CC0 1.0 //creativecommons.org/publicdomain/zero/1.0/deed.en.
Figure 1.8 This photograph of the Earth, titled the Pale Blue Dot, was taken by the Voyager spacecraft on February 14, 1990, from somewhere near the edge of our solar system, about 6 billion kilometer from Earth. The Earth appears as a pixel against the vast background of empty space. Source: NASA.
Figure 1.9 This stratigraphic chart shows the chronology of the history of the Earth, with the latest eon, the Phanerozoic eon, broken into eras and epochs. Our ancestors began using tools (2.6 Ma) in the Pliocene, mastered fire (800 ka) and invented agriculture (12 ka) in the Pleistocene, and emerged from the last ice age (10 ka) in the Holocene. Some scientists have proposed a new epoch to recognize the global impact humans have had on the Earth since the Industrial Revolution. Courtesy K. Overway, 2013.
Figure 1.10 A diagram of the reaction vessel that Stanley Miller used to produce organic molecules from simple inorganic reactants. The Miller–Urey experiment proved conclusively that organic molecules could be made with very simple ingredients. Source: Yassine Mrabet http://en.wikipedia.org/wiki/Miller-Urey_experiment. Used under BY-SA 3.0 //creativecommons.org/licenses/by-sa/ 3.0/deed.en.
Figure 1.11 Common table sugar, sucrose, is a polymer of two simpler sugars. The monomers glucose and fructose link together to form sucrose. Courtesy NEUROtiker, 2007.
Figure 1.12 Phospholipids, which can be characterized as having separate hydrophilic and hydrophobic regions, spontaneously form bilayers, micelles, and vesicle in aqueous solutions. Courtesy Ties van Brussel and Mariana Ruiz Villarreal, 2010.
Figure 1.13 This reaction diagram shows the energetic difference between the uncatalyzed and catalyzed conversions of a generalized reaction. Notice the height of the activation energy () for each mechanism. The catalyzed reaction is much faster because the activation energy is much lower. Source: Smokefoot. http://en.wikipedia.org/ wiki/Catalysis. Used under CC0 1.0 // creativecommons.org/publicdomain/ zero/1.0/deed.en.
Figure 1.14 The Beer–Lambert Law, or just Beer's Law, relates the absorption of electromagnetic radiation by matter. Courtesy CarlosRC, 2008.
CHAPTER 2: MEASUREMENTS AND STATISTICS
Figure 2.1 Signal and noise can sometimes be indistinguishable. The 3 line above the baseline is the threshold between signal and noise.
Figure 2.2 Measurements from a blank in (a) a cuvette fluorometer, (b) a 96-well plate fluorometer, (c) an atomic absorption spectrophotometer (
N>
100 in each case). The bars represent the distribution of the actual measurement, and the line is a Gaussian curve fitted to the average and standard deviation of the data.
Figure 2.3 The noise in most measurements has a Gaussian distribution based on the calculated average and standard deviation of the noise. This is due to the Central Limit Theorem.
Figure 2.4 Replicate measurements allow an analyst to convey a level of uncertainty in the reported results. In this case, one can conclude that a penny weighs, on average, g.
Figure 2.5 Histograms of (a) 4, (b) 20, (c) 100, and (d) 200 randomly generated numbers. The vertical line represents the calculated average (the true average is 5).
Figure 2.6 The method of external standards requires a stock solution and calibration standards produced separately from any unknown samples.
Figure 2.7 Internal standards (IS) are usually related to the analyte. In example (a), the analyte is naphthalene and the IS is 2,3,6,7 tetrafluoronaphthalene. In example (b), the analyte is ethanol and the IS is 1-propanol. In each example, the IS is structurally similar to the analyte but exotic enough not to be found in the matrix. Fluorinated hydrocarbons are unusual in nature and would not be found with naphthalene in a coal sample, for example. The natural fermentation in wine production would produce ethanol but not 1-propanol.
Figure 2.8 A chromatogram for ethanol (EtOH) analysis of a fermentation process might resemble this with 1-propanol (1-PrOH) as the IS.
Figure 2.9 The Actual Analyte Peak Areas of the calibration standards are plotted versus their concentration in (a). Using the ratio between the Actual Analyte Peak Area and the Actual IS Peak Area, a corrected calibration curve is plotted in (b).
Figure 2.10 The method of multiple standard additions requires a stock solution of the primary standard to be added, in increasing amounts, to several flasks of equal aliquots of the unknown sample. The
x
intercept of the Signal versus Volume of Standard Added graph yields an indirect measurement of the unknown.
Figure 2.11 Graphs that result from the method of multiple standard additions. In (a), the
x
axis is the Volume of Added Standard, which yields an
x
intercept that is the volume. In (b), the
x
axis is the Concentration of Added Standard (after dilution) yielding an
x
intercept that is the concentration.
Figure 2.12 The result of a variable-volume multiple standard additions experiment.
Figure 2.13 The two errors caused by chemical interferences in the matrix of the sample are constant errors and proportional errors – here compared to the error-free sample blank spiked with known amounts of a primary standard in the method of standard additions.
Figure 2.14 The absorbance spectra of the most common cuvettes are shown here. All measurements in the visible region can be accomplished with the inexpensive, disposable polystyrene cuvettes. Glass is useful in the visible region when organic solvents are needed. For aqueous solutions measured in part of the UV spectrum, the
p
oly
m
ethyl
m
eth
a
crylate (PMMA) and other UV cuvette brands are appropriate and inexpensive. Quartz cuvettes provide the best spectral transmission and solvent compatibilities but are very expensive.
Figure 2.15 In this section of the regression spreadsheet for the method of external standards, you will use various built-in functions to establish a minimal regression analysis.
Figure 2.17 The replicates section includes all of the replicate measurements for a single unknown sample. The signals go in the signal column, and formulas replace the *** markers in the other columns.
Figure 2.18 This is the regression analysis section of the method of multipoint internal standard.
Figure 2.20 This is the replicates section of the method of multi-point internal standard.
Figure 2.21 This is the data section of the regression spreadsheet for the method of multiple standard additions. The “Conc of Std” column is useful if you are going to use the alternative method of plotting the result of this method (Signal versus Conc. of Added Standard). You can disregard it if you are going to plot Signal versus Volume Standard Added.
Figure 2.22 This is the regression analysis section of the spreadsheet. It does not contain any calculation of errors in the slope or intercept.
Figure 2.23 Unknown samples whose concentration is close to the middle of the calibration curve will have the smallest uncertainty. The uncertainty curve shows that the uncertainty is at a minimum in the middle of the standards and increases as the unknown concentration gets larger or smaller than the center.
CHAPTER 3: THE ATMOSPHERE
Figure 3.1 Gases in the atmosphere of the Earth absorb solar radiation in different regions of the electromagnetic spectrum and form distinct layers as a result. Source: http://www.srh.noaa.gov/jetstream/atmos/atmprofile.htm.
Figure 3.2 Solar radiation up to about 100 nm strikes the thermosphere and is absorbed by several different gases, the most concentrated of which are molecular nitrogen and oxygen. The vertical axis, labeled Absorption Cross Section, represents the absorption efficiency. The traces labeled I.E. represent the low energy end of the ionization energy continuum. Source: O
2
data from Hegelund
et al
. (Hegelund
et al
. (2005)); O
3
data from Ackerman (Ackerman (1971)); N
2
data from Chan
et al
. (Chan
et al
. (1993c)).
Figure 3.3 Thermodynamic calculations only reveal the difference between the initial and final states (B.E. calculated by ), not the activation energy. Photolysis requires activation energy. The difference between the and the B.E. goes to the kinetic energy of the products and manifests itself as heat.
Figure 3.4 Major and minor components of the mesosphere begin to absorb solar radiation that penetrates the thermosphere – mostly with wavelengths greater than 100 nm. Source: Data from Keller-Rudek
et al
. (Keller-Rudek
et al
. (2013)).
Figure 3.5 The radiation available to cause atmospheric reactions is referred to as the actinic flux. The thermosphere and mesosphere remove most of the <180 nm radiation (see the 50 km line). Much of the rest is absorbed by the stratosphere at various altitudes. Source: NASA.
Figure 3.6 The UV spectrum is divided into ranges. The UV-C range will be the focus of discussions from the top of the atmosphere until the troposphere. Source: NASA.
Figure 3.7 This absorbance spectrum of molecular oxygen contains two of the features mentioned in Section 3.3 – the ionization continuum beginning at 103 nm and the absorbance from 130–175 nm. Much less intense but still significant is the absorption from 200 nm to 250 nm. Each region is labeled with a representational reaction. Source: Keller-Rudek http://www.earth-syst-sci-data.net/5/365/2013/essd-5-365-2013.html. Used under CC BY 3.0 https://creativecommons.org/licenses/by/3.0/.
Figure 3.8 The Sun's photosphere produces energy according to Planck's Law, but it diffuses over a great distance when it arrives at the Earth. This diffuse energy strikes a cross-sectional area the size of Earth's shadow, but since the Earth is a globe, the area is spread out over an area four times larger than the shadow. Courtesy K. Overway, 2013.
Figure 3.9 Solar radiation that is absorbed by the surface causes the Earth to emit IR radiation as a blackbody radiator. Greenhouse gases in the troposphere absorb a significant portion of the IR radiation coming from the surface. Source: NASA.
Figure 3.10 The Lewis structures of , O, and show that and are nonpolar while O is polar if viewed as static molecules.
Figure 3.11 During one of its vibrational modes, the normally nonpolar CO
2
becomes temporarily polar and generates an electric field, which matches the frequency of IR radiation.
Figure 3.12 Carbon dioxide has three different vibrational modes. Two modes are “IR active” and the other (symmetric stretch) is “IR inactive.”
Figure 3.13 Water has a permanent dipole moment, but its vibrational modes show that the dipole oscillates during the vibrations. Examine the length or angle of the dipole arrow carefully and you will see it changes as the molecule vibrates. All modes are IR active.
Figure 3.14 The IR absorption spectrum for carbon dioxide. The
x
axis is in wave numbers. The two IR-active vibrational modes from Figure 3.12 (plus a combination of the two modes) show absorption peaks in the spectrum. Source: Original spectrum by NIST, modified by K. Overway.
Figure 3.15 The resonance structures for SO
2
and a depiction of the net dipole moment.
Figure 3.16 The IR spectrum of SO
2
. (Courtesy NIST)
Figure 3.17 The Lewis structure of CCl
2
F
2
. Courtesy NIST.
Figure 3.18 The IR spectrum of CCl
2
F
2
.
Figure 3.19 The absorption spectrum of ozone showing what photolytic reactions are produced from the different absorption regions. The excited states are more accurately described with the equations to the left and were first introduced in Table 3.5 on page 100. Source: Data from Ackerman (1971).
Figure 3.20 Terpenes are a common class of biogenically produced VOCs. Their presence produces the characteristic fragrance of many plants. -pinene (a) is produced by conifers, limonene (b) is present in the rind of citrus fruits, and isoprene (c) is emitted by several classes of trees such as palm, oak, eucalyptus, and aspen.
Figure 3.21 The process of coalification converts fulvic and humic acids (decaying plant material) into coal by removing oxygen and increasing aromatic ring structures under intense heat and pressure. Courtesy Michal Sobkowski (2010) and Yikrazuul (2009), respectively.
Figure 3.22 The Chapman cycle and several of the catalytic reactions that interfere with ozone production.
Figure 3.23 CFCs and halons are hydrocarbons with many or all of the hydrogens replaced by a halogen. They are usually very stable, inert, and revolutionized refrigeration by indoor climate control, degreasing, and fire extinguishing.
Figure 3.24 Since the late 1970s the ozone minimum above Antarctica was getting worse until around 2005 when ozone thickness was starting to trend upward (b). Above the Northern Hemisphere, ozone levels appeared to be normal (a). Note that the Montreal Protocol was signed in 1987 and went into effect in 1989. Ozone levels are just now returning to pre-1987 levels. Source: NASA.
Figure 3.25 The bottom graph compares the winter temperatures above each of the poles. PSCs are not as common above the Arctic, so ozone destruction is much less but still not zero as the upper graph suggests. Courtesy FaheyD.W., and M.I. Hegglin (Coordinating Lead Authors), Twenty Questions and Answers About the Ozone Layer: 2010 Update, Scientific Assessment of Ozone Depletion: 2010, 72 pp., World Meteorological Organization, Geneva, Switzerland, 2011. Source: Reproduced with permission of World Meteorological Organization (WMO).
Figure 3.26 The chemical structure of two of the molecules that have replaced CFCs.
Figure 3.27 Levels of CFCs are beginning to decrease since the Montreal Protocol in 1985, according to the data from World Meteorological Organization. Source: Reproduced with permission of World Meteorological Organization (WMO).
Figure 3.28 The addition of a CFC and an HCFC fills one of the open spectral windows where no GHG currently absorbs. Source: Data from NIST.
Figure 3.29 Temperature reconstruction over the last millennium, highlighting the warmer Medieval Climate Anomaly (MCA), the cooler Little Ice Age (LIA), and the 20th century (20C). Source: Reproduced with permission of IPCC.
Figure 3.30 Concentration trends for the three most important greenhouse gases. The data was obtained from the National Oceanic and Atmospheric Administration. Source: Data from NOAA ESRL Global Monitoring Division, Boulder, Colorado, USA (http://esrl.noaa.gov/gmd/).
Figure 3.31 Variations of deuterium (D) in Antarctic ice, which are a proxy for local temperature, and the atmospheric concentrations of the greenhouse gases carbon dioxide (CO
2
), methane (CH
4
), and nitrous oxide (N
2
O) in the air trapped within the ice cores and from recent atmospheric measurements. Data cover 650,000 years, and the shaded bands indicate the current and previous interglacial warm periods. Source: Reproduced with permission of IPCC.
Figure 3.32 Sea level rise over the past 20 years has been steady according to a few different measuring techniques. Source: Reproduced with permission of IPCC.
Figure 3.33 The steady rise in carbon dioxide, seen in (a), inevitably leads to an increase in carbonic acid and a decrease in pH as more of the atmospheric is dissolved in the oceans, seen in (b). Source: Reproduced with permission of IPCC. Dorea
et al
. (2009).
Figure 3.34 Milankovitch Cycles encompass several different irregular patterns in the orbit of the Earth. These irregularities result in predictable changes in the distance between the Earth and the Sun, which lead to changes in climate. The E cycles occur every 100,000 and 400,000 years. The T cycle and P cycle occur at intervals of 41,000 and 20,000 years, respectively. Source: Reproduced with permission of IPCC.
Figure 3.35 Data obtained from the DOME C Antarctic ice cores reveal a very dynamic climate over the past 800,000 years. The traces show (starting from the top) methane, dust, carbon dioxide, and temperature levels. The temperature scale is relative to the current average temperature and the others are absolute scales. Source: Data from NOAA ESRL Global Monitoring Division, Boulder, Colorado, USA (http://esrl.noaa.gov/gmd/).
Figure 3.36 Graph (a) shows only the number of named hurricanes (Frequency) as a function of year. The slope of the data is positive (increasing frequency) but does not rise above . Graph (b) shows the average maximum wind speed for all of the hurricanes in a given year. A trend here is also hard to see. Source: Data from National Hurricane centre.
Figure 3.37 Given the temperature trends observed in various parts of the globe (black line), GCMs are unable to model the data using only natural forcings (darker shading). When anthropogenic forcings (such as anthropogenic greenhouse gas emissions) are included in the calculation, then GCMs are able to model the data sufficiently (lighter shading). Source: Reproduced with permission of IPCC.
CHAPTER 4: THE LITHOSPHERE
Figure 4.1 A vertical soil profile usually has several horizons. Organic matter tends to be most abundant in the top layer (horizon O). Horizon A tends to be a mixture of mineral and organic components and contains much of the biological activity. Horizon B contains dramatically more inorganic material that consists of clays and other small particles. Horizon C tends to be strictly inorganic material with larger weathered particles from the parent rock. Finally, a layer of bedrock undergirds the soil. Other intermediate layers are possible. Source: http://en.wikipedia.org/wiki/File:SOIL_PROFILE.png. Used under BY-SA 3.0 //creative commons.org/licenses/by-sa/3.0/deed.en.
Figure 4.2 In this aluminosilicate sheet, you can see the two layers made from silicate tetrahedrons that form the top and bottom of a sandwich layer with an octahedral sheet of aluminum in between. The aluminum atoms are explicitly shown in the center of the octahedral structures. The silicon atoms are not explicitly shown but reside at the centers of the tetrahedral oxygen structures. Spaces between these layers can contain exchangeable cations. Source: http://wwww.intechopen.com/books/nanocomposites-new-trends-and-developments/polymer-nanocomposite-hydrogels-for-water-purification.
Figure 4.3 Silica, with an empirical formula of , really is a network covalent structure of units. Each O atom is shared by two Si atoms, giving the empirical formula. At the end of the polymer chain (left side), the SiO group terminates with an H atom to balance the charge. If the polymer continues (right side) then the O atoms form a neutral polar surface.
Figure 4.4 Lignin (a) provides much of the rigidity that allows woody plants to grow extensive structures. Its hydro- phobicity (derived from phenylalanine (b)) makes it resistant to degradation, but some fungi and bacteria are able to convert it into humic and fulvic acids, as seen in Figure 3.21 found on page 133. The total combination of all of the organic material in soil is collectively called
humus
. Source: http://en.wikipedia.org/wiki/File:Lignin_structure.svg. Used under BY-SA 3.0 //creativecommons.org/licenses/by-sa/ 3.0/deed.en.
Figure 4.5 A pictorial summary of the inorganic buffering mechanisms found in soil. Variations in the limestone (top left), silicate and cation exchange (middle), and aluminum buffering mechanisms (bottom right) generate three different ranges of buffer center points, with a large amount of overlap in the lower two buffers. The graph simulates the titration of a soil sample assuming that all three inorganic buffering mechanisms are present.
Figure 4.6 Microwave bombs provide a fast and efficient means of acid digestion. A sample and a digesting acid are placed in the PTFE canister, which is inserted into the bomb vessel. High temperatures and pressures can be safely achieved in minutes. Courtesy Ken Overway, 2013.
CHAPTER 5: THE HYDROSPHERE
Figure 5.1 The Lewis structure of water shows a molecule in the tetrahedral orbital group with a bent molecular shape having an average bond angle of 104.5.
Figure 5.2 The density of liquid water reaches its maximum at about 4C. As it warms, the density continues to decrease. Notice the large change in density when it freezes. Source: Data from Eric W. Peterson, Illinois State University.
Figure 5.3 Understanding the hydrosphere requires an understanding of chemical equilibria of several types, some of which were shown earlier. The exchange of gases between air and water is described by Henry's Law (). Acid–base reactions are integral to water chemistry ( and ). The exchange of salts and metals between the surrounding soil and the aqueous phase is a function of solubility products () and complex ion formations (). Finally, solutes distribute themselves between the water and hydrophobic solutes and sediment as described by a distribution coefficient ().
APPENDIX B: EXAMPLES AND END-OF-CHAPTER EXERCISES
Figure B.1 Spreadsheet analysis using general statistics.
APPENDIX C: CHAPTER 3 EXAMPLES AND END-OF-CHAPTER EXERCISES
Figure C.1 The IR spectrum of methane.
Figure C.2 The formation of nitric acid from N
2
O
5
and H
2
O.
Figure C.3 The decomposition of N
2
O
4
.
APPENDIX E: CHAPTER 5 EXAMPLES
Figure E.1 A graphical depiction of the data found in Table E.1.
Figure E.2 A graphical depiction of the data found in Table E.2.
APPENDIX F: COMMON CHEMICAL INSTRUMENTATION
Figure F.1 The Spectronic-20 (top, larger spectrometer) has been the preferred instrument in general biology and chemistry laboratories for decades. In many cases, they are now being replaced by smaller spectroscopes, such as the Vernier Colorimeter (bottom, smaller spectrometer) due to significantly lower cost. Source: Courtesy Ken Overway.
Figure F.2 UV-Vis spectrophotometers are common in biology and chemistry departments, and in upper-level lab courses, students are more likely to use more sophisticated instruments compared to the Spectronic 20. A schematic example of one such instrument uses a combination of lamps to deliver UV-vis radiation to the sample. A monochromator narrows the radiation to a specific band of wavelengths, chosen by the analyst, and thereby increases the instrument sensitivity and selectivity. While mirrors and other optics turn the light, the essential absorption instrument has a linear path from source to detector. Source: Courtesy Sobarwiki.
Figure F.3 A fluorescence spectrophotometer or fluorometer. Source: Courtesy Sobarwiki.
Figure F.4 A simplified block diagram of an atomic absorbance spectrometer. Source: Courtesy K05en01.
Figure F.5 A simplified diagram of a gas chromatograph. Source: Courtesy Offnfopt.
Figure F.6 A
chromatogram
(a) shows the analyte signal as a function of time since the sample mixture is separated by the chromatography method and detected as each analyte elutes from the column. The peak height and peak area are proportional to the concentration of the analyte. When a mass spectrometer is used as the detector, ionization of the analyte weakens the molecular bonds and causes a reproducible fragmentation pattern. This
mass spectrum
can be compared to a library of patterns previously recorded from known samples. Computer software allows the analyst to click on a peak in the chromatogram to display the mass spectrum of the analyte (b). A search of the library can provide a probable identification of the compound (c).
Figure F.7 A diagram of the interferometer of a Fourier Transform infrared spectrometer. Source: Courtesy Sanchonx
Figure F.8 (a) Infrared spectra are often recorded as % Transmittance versus Wave number. (b) A more useful graph for quantitation is one of Absorbance versus Wave number. The peak height and peak area are proportional to the analyte concentration, but peak area is often more useful when the absorption shows a complex structure, as is the case for this spectrum of carbon monoxide.
List of Tables
CHAPTER 1: ORIGINS: A CHEMICAL HISTORY OF THE EARTH FROM THE BIG BANG UNTIL NOW—13.8 BILLION YEARS OF REVIEW
Table 1.1 Certain regions of the electromagnetic (EM) spectrum provide particular information about matter when absorbed or emitted
Table 1.3 Melting points and densities of the major constituents of the mantle and crust
Table 1.4 Selected radioisotopes and their half-lives
Table 1.2 Common metric prefixes and their numerical values
Table 1.5 Atomic structure example with answers
Table 1.6 You will be reading about many different ionic compounds throughout this textbook, and you need to be able to derive the formula from the name and vice versa
Table 1.7 Names of some ionic compounds
Table 1.8 Name the following ionic compounds
Table 1.9 Greek cardinal prefixes
Table 1.10 Common covalent compound names
Table 1.11 Name the following covalent compound
Table 1.12 Free energy of some nitrogen compounds
Table 1.13 Strong acids and bases commonly used in the laboratory
Table 1.14 Some common weak acids, their formulas, weak acid reactions, and equilibrium constants
Table 1.15 Common equilibrium constant expressions
Table 1.16 Simulated equilibrium experiments
CHAPTER 2: MEASUREMENTS AND STATISTICS
Table 2.1 These probabilities represent the
confidence levels
for a Gaussian distribution.
Table 2.2 A set of numbers from a Gaussian distribution.
Table 2.3 A set of simulated data for the measurement of a blank and two samples.
Table 2.4 Systematic errors generally depend on the training of the analyst, the instrumentation, and the method used to process the samples and standards.
Table 2.5 Some prices for various samples of calcium carbonate.
Table 2.6 A table of volumes used to make a set of calibration standards.
Table 2.7 This Table contains Student's
t
values for different sample sizes and confidence levels.
Table 2.8 Simulated fructose measurements for two brands of soft drinks.
Table 2.9 Simulated replicate analyses of a CaCO
Table 2.10 Simulated replicate mercury analyses of sediment.
Table 2.11 Simulated calibration curve results using the method of external standards.
Table 2.12 Simulated calibration curve results using the method of multipoint internal standards.
Table 2.13 Results from a simulated method of multiple standard additions.
Table 2.14 Results from a simulated variable-volume method of multiple standard additions.
Table 2.15 Two important comparisons were made between the two-point and the multipoint variants of the method of standard additions.
Table 2.16 Comprehensive simulated results from a method of external standards experiment, including the calibration standards, nonreplicate sample measurements, and replicate sample measurements.
Table 2.17 Comprehensive simulated results from a method of multipoint internal standard experiment, including the calibration standards, nonreplicate sample measurements, and replicate sample measurements.
Table 2.18 Simulated results from an experiment using the equal-volume variant of the method of multiple standard additions.
CHAPTER 3: THE ATMOSPHERE
Table 3.1 The general composition of the atmosphere is summarized.
Table 3.2 Estimated maximum number density (concentration) values for several important trace gases in the upper atmosphere.
Table 3.3 Some of the photolytic reactions that predominate in the thermosphere where photon energies are very high.
Table 3.4 Some of the photolytic reactions that predominate in the mesosphere.
Table 3.5 The various forms of oxygen and the way they will be referred to in this textbook.
Table 3.6 Kinetic data for Reaction R3.21 as a function of altitude.
Table 3.8 The electron counting system for drawing Lewis structures.
Table 3.9 Emissions from a Yamaha 232-cc two-cylinder, four-stroke outboard motor and a Suzuki 211-cc two-cylinder, two-stroke outboard motor without catalytic converters.
Table 3.10 Emissions from two Volkswagen Golf cars with different four-stroke engines.
Table 3.11 Emission differences for various blends of gasoline and ethanol compared to 100% gasoline.
Table 3.12 Emissions of a John Deere 4276T, four-cylinder, four-stroke, turbocharged diesel engine running at 1400 RPM compared to using No. 2 diesel fuel.
Table 3.13 Rate constant values for Eq. (3.11) as a function of the angle of the Sun (zenith).
Table 3.14
Table 3.15 The Free Energy values presented for each of the forms of nitrogen and sulfur suggest the thermodynamic fate for each in an oxidizing atmosphere.
Table 3.16 The data in this Table shows the removal of various trace species in the troposphere by the hydroxyl radical. Source: Monks (2005).
Table 3.17 The elemental composition and heat content of the different stages in the process of coalification show a trend of increasing %C, decreasing %O and %H, and increasing heat content.
Table 3.18 The four reactions of the Chapman cycle.
Table 3.19 The properties of some selected Class I and Class II ozone-depleting substances.
Table 3.20 Important bond energies for HCFC analysis.
Table 3.21 Important heats of formation for HCFC analysis.
Table 3.22 The lifetime of carbon dioxide is difficult to estimate and has become a controversial topic.
Table 3.23 Gases that can be measured using a Cavity Ring-Down Spectroscopy, along with the characteristic wavelength that gets absorbed by each gas, and the Limit Of Detection (LOD).
Table 3.24 Small-scale ambient spectrometers are available to quantitate gases in the lab or atop monitoring stations. These instruments have comparable detection limits to the satellite and ground-based measurements.
Table 3.7 Planetary average albedos and albedo estimates of surface features. Source: Lissauer, 2013.
CHAPTER 4: THE LITHOSPHERE
Table 4.1 The composition and elemental analysis of a volcanic soil from the British West Indies (van Baren, 1931)
Table 4.2 The composition and elemental analysis of the top layer (horizon A) of a limestone soil from the Netherlands (van Baren, 1930)
Table 4.3 A few examples of primary minerals and their chemical formulas
Table 4.4 Lewis structure and line-angle formulas of some of the common organic functional groups
Table 4.5 Microbial respiration reactions for aerobic, anaerobic, and methanogenic organisms. When these reactions are placed on a cell potential scale, they are commonly referred to as the redox ladder
Table 4.6 This metal classification schema, currently preferred by environmental scientists, more naturally separates metals by their toxicity than the meaningless term “heavy metals.”
Table 4.7 Several plants, referred to as
hyperaccumulators
, can be used in
phytoremediation
processes for the removal of some toxic contaminant.
Source:
Puget Sound (1992).
Table 4.8 Equilibrium pH values, as calculated from Example 4.3, for water that is saturated with CO
2
and these carbonate minerals
Table 4.9 A select set of minerals, which represent the range of aluminosilicate minerals participating in the aluminum soil buffer, with the pH they maintain in the presence of aqueous acid, as calculated by successive approximations
Table 4.10 Simulated compositional analysis of some soil samples
Table 4.11 Simulated water analysis after a contamination of organic waste
CHAPTER 5: THE HYDROSPHERE
Table 5.1 Major constituents of various waterbodies
Table 5.2 Approximate elemental composition of the human body
Table 5.3 Phosphate minerals are quite insoluble, which means that, in typical aquatic environments, where cations such as calcium and magnesium are present, levels of dissolved orthophosphate will be low
Table 5.4 The free energy of the common hydrospheric forms of sulfur
Table 5.5 Common parameters of water quality
Table 5.6 A modified recipe from DelValls and Dickson (1998) for a seawater TRIS buffer having a salinity of 35.2‰ and a pH of 8.09
Table 5.7 An example BOD experiment with three dilutions
Table 5.8 The results of a simulated BOD experiment
Table 5.9 (
A
b-sorbance
U
nits) is the integrated peak area, from 3800 to 3400 cm, taken from the absorbance spectrum of CO
2
APPENDIX A: REVIEW EXAMPLES AND END-OF-CHAPTER EXERCISES
Table A.1 Atomic structure example with answers.
Table A.3 Name the following covalent compounds.
Table A.4 Simulated equilibrium experiments and answers.
APPENDIX B: EXAMPLES AND END-OF-CHAPTER EXERCISES
Table B.1 A set of numbers in Gaussian distribution
Table B.2 A set of simulated data for the measurement of a blank and two samples.
Table B.3 A Table of volumes used to obtain a set of calibration standards.
Table B.4 Simulated calibration curve results from using the method of external standards.
APPENDIX D: CHAPTER 4 EXAMPLES AND END-OF-CHAPTER EXERCISES
Table D.2 Simulated water analysis after contamination of organic waste.
APPENDIX E: CHAPTER 5 EXAMPLES
Table E.1 A theoretical prediction of the value of and DO levels as a function of temperature
Table E.2 A theoretical prediction of the DO levels of a freshwater and seawater system as a function of temperature
Table E.3 A simulated analysis
Table E.4 (
U
nits) is the integrated peak area, from 3800 to 3400 cm, taken from the absorbance spectrum of CO
2
APPENDIX F: COMMON CHEMICAL INSTRUMENTATION
Table F.1 Typical light sources found in common absorption and fluorescence spectrophotometers
Table F.2 A select list of some of the common organic functional groups and gases and their generalized absorption bands
APPENDIX H: TABLES
Table H.1 Student's
t
values for one-tailed and two-tailed comparisons
Table H.2 Test data from MedCalc at http://www.medcalc.org/manual/f-table.php
APPENDIX I: CHEMICAL AND PHYSICAL CONSTANTS
Table I.1 These values come from the National Institute of Standards and Technology Reference on Constants, Units, and Uncertainty, physics.nist.gov/cuu/index.html
Table I.2 The values come from
CRC Handbook of Chemistry and Physics
, 89th ed.; Lide, D.R., Ed.; CRC Press: Boca Raton, FL, 2008; Section 5
Table I.3 Henry's law equilibrium constants
Table I.4 Solubility product constants
Table I.5 Acid dissociation constants
Table I.6 Base dissociation constants
Table I.7 Average bond energies (enthalpies) for some common single, double, and triple bonds
Table I.8 Environmentally useful reduction potentials from the 92nd CRC
Table I.9 Kinetic rate constants for VOC oxidation against the hydroxyl radical
ENVIRONMENTAL CHEMISTRY
An Analytical Approach
KENNETH S. OVERWAY
Copyright © 2017 by John Wiley & Sons, Inc. All rights reserved
Published by John Wiley & Sons, Inc., Hoboken, New Jersey
Published simultaneously in Canada
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Library of Congress Cataloging-in-Publication Data
Names: Overway, Kenneth S., 1971- author.
Title: Environmental chemistry : an analytical approach / Kenneth S. Overway.
Description: Hoboken : John Wiley & Sons, Inc., [2017] | Includes bibliographical references and index.
Identifiers: LCCN 2016034813 (print) | LCCN 2016036066 (ebook) | ISBN 9781118756973 (hardback) | ISBN 9781119085508 (pdf) | ISBN 9781119085492 (epub)
Subjects: LCSH: Environmental chemistry.
Classification: LCC TD193 .O94 2017 (print) | LCC TD193 (ebook) | DDC 577/.14–dc23
LC record available at https://lccn.loc.gov/2016034813
Cover Design: Wiley
Cover Images: Earth © NASA;
Graphs courtesy of author
PREFACE
Careful readers of this textbook will find it difficult to avoid the conclusion that the author is a cheerleader for collegiate General Chemistry. I have taught General Chemistry at various schools for over a decade and still enjoy the annual journey that takes me and the students through a wide array of topics that explain some of the microscopic and macroscopic observations that we all make on a daily basis. The typical topics found in an introductory sequence of chemistry courses really do provide a solid foundation for understanding most of the environmental issues facing the world's denizens. After teaching Environmental Chemistry for a few years, I felt that the textbooks available were missing some key features.
Similar to a movie about a fascinating character, an origin story is needed. In order to appreciate the condition and dynamism of our current environment, it is important to have at least a general sense of the vast history of our planet and of the dramatic changes that have occurred since its birth. The evolution of the Earth would not be complete without an understanding of the origin of the elements that compose the Earth and all of its inhabitants. To this end, I use Chapter 1 to develop an abridged, but hopefully coherent, evolution of our universe and solar system. It is pertinent that this origin story is also a convenient occasion to review some basic chemical principles that should have been learned in the previous courses and will be important for understanding the content of this book.
As a practical matter when teaching Environmental Chemistry, I was required to supplement other textbooks with a primer on measurement statistics. My students and I are making environmental measurements soon after the course begins, so knowing how to design an analysis and process the results is essential. In Chapter 2, I provide a minimal introduction to the nature of measurements and the quantitative methods and tools used in the process of testing environmental samples. This analysis relies heavily on the use of spreadsheets, a skill that is important for any quantitative scientist to master. This introduction to measurements is supplemented by an appendix that describes several of the instruments one is likely to encounter in an environmental laboratory.
Finally, the interdependence of a certain part of the environment with many others becomes obvious after even a casual study. A recursive study of environmental principles, where the complete description of an environmental system requires one to back up to study the underlying principles and the exhaustive connections between other systems followed by a restudy of the original system, is the natural way that many of us have learned about the environment. It does not, however, lend itself to the encapsulated study that a single semester represents. Therefore, I have divided the environment into the three interacting domains of The Atmosphere (Chapter 3), The Lithosphere (Chapter 4), and The Hydrosphere (Chapter 5). In each chapter, it is clear that the principles of each of these domains affect the others. Studies of the environment beyond a semester will require a great deal of recursion and following tangential topics in order to understand the whole, complicated picture. Such is the nature of most deep studies, and this textbook will hopefully provide the first steps in what may be a career-long journey.
Shall we begin?
Ken OverwayBridgewater, VirginiaDecember, 2015
ABOUT THE COMPANION WEBSITE
This book is accompanied by a companion website:
www.wiley.com/go/overway/environmental_chemistry
The website includes:
Powerpoint Slides of Figures
PDF of Tables
Regression Spreadsheet Template
INTRODUCTION
You are “greener” than you think you are. What I mean is that you have been twice recycled. You probably are aware that all of the molecules that make up your body have been recycled from the previous organisms, which is similar to the chemical cycles you will read about later in this book, such as the carbon cycle and the nitrogen cycle. The Earth is nearly a closed system, and it receives very little additional matter from extraterrestrial sources, except for the occasional meteor that crashes to the Earth. So, life must make use of the remains of other organism and inanimate sources in order to build organism bodies.
What you may not have been aware of is that the Earth and the entire solar system in which it resides were formed from the discarded remains of a previous solar system. This must be the case since elements beyond helium form only in the nuclear furnace of stars. Further, only in the core of a giant star do elements beyond carbon form, and only during the supernova explosion of a giant star do elements beyond iron form. Since the Earth contains all of these elements, it must be the result of at least a previous solar system. This revelation should not be entirely unexpected when you examine the vast difference between the age of the universe (13.8 billion years old) and the age of our solar system (4.6 billion years old). What happened during the 9.2 billion year gap? How did our solar system form? How did the Earth form? What are the origins of life? To answer these questions, the story of the chemical history of the universe since the Big Bang is required. Much of what you learned in General Chemistry will help you understand the origin of our home planet. It may seem like it has been 13.8 billion years since your last chemistry course, so a review is warranted. Ready?
