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ENVIRONMENTAL
ORGANIC CHEMISTRY
Third Edition

René P. Schwarzenbach
Philip M. Gschwend
Dieter M. Imboden
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 is available.
ISBN: 978-1-118-76723-5
CONTENTS
Preface
About the Companion Website
Chapter 1 General Topic and Overview
1.1 Introduction
1.2 Assessing Organic Chemicals in the Environment
1.3 What is This Book All About?
1.4 Bibliography
Part I Background Knowledge
Chapter 2 Background Knowledge on Organic Chemicals
2.1 The Makeup of Organic Compounds
2.2 Intermolecular Forces Between Uncharged
Molecules
2.3 Questions and Problems
2.4 Bibliography
Chapter 3 The Amazing World of Anthropogenic Organic
Chemicals
3.1 Introduction
3.2 A Lasting Global Problem: Persistent Organic
Pollutants (POPs)
3.3 Natural but Nevertheless Problematic: Petroleum
Hydrocarbons
3.4 Notorious Air and Groundwater Pollutants:
Organic Solvents
3.5 Safety First: Flame Retardants All Around Us
3.6 How to Make Materials “Repellent”:
Polyfluorinated Chemicals (PFCs)
3.7 From Washing Machines to Surface Waters:
Complexing Agents, Surfactants, Whitening Agents,
and Corrosion Inhibitors
 3.8 Health, Well-Being, and Water Pollution:
Pharmaceuticals and Personal Care Products
3.9 Fighting Pests: Herbicides, Insecticides, and
Fungicides
3.10 Our Companion Compounds: Representative
Model Chemicals
3.11 Questions
3.12 Bibliography
Chapter 4 Background Thermodynamics, Equilibrium
Partitioning and Acidity Constants
4.1 Important Thermodynamic Functions
4.2 Using Thermodynamic Functions to Quantify
Equilibrium Partitioning
4.3 Organic Acids and Bases I: Acidity Constant and
Speciation in Natural Waters
4.4 Organic Acids and Bases II: Chemical Structure and
Acidity Constant
4.5 Questions and Problems
4.6 Bibliography
Chapter 5 Earth Systems and Compartments
5.1 Introduction
5.2 The Atmosphere
5.3 Surface Waters and Sediments
5.4 Soil and Groundwater
5.5 Biota
5.5 Questions
5.7 Bibliography
Chapter 6 Environmental Systems: Physical Processes and
Mathematical Modeling
6.1 Systems and Models
6.2 Box Models: A Concept for a Simple World
6.3 When Space Matters: Transport Processes
 6.4 Models in Space and Time
6.5 Questions and Problems
6.6 Bibliography
Part II Equilibrium Partitioning in Well-Defined Systems
Chapter 7 Partitioning Between Bulk Phases: General
Aspects and Modeling Approaches
7.1 Introduction
7.2 Molecular Interactions Governing Bulk Phase
Partitioning of Organic Chemicals
7.3 Quantitative Approaches to Estimate Bulk Phase
Partition Constants/Coefficients: Linear Free Energy
Relationships (LFERs)
7.4 Questions
7.5 Bibliography
Chapter 8 Vapor Pressure (pi*)
8.1 Introduction and Theoretical Background
8.2 Molecular Interactions Governing Vapor Pressure
and Vapor Pressure Estimation Methods
8.3 Questions and Problems
8.4 Bibliography
Chapter 9 Solubility (Csatiw) and Activity Coefficient
(γsatiw)in Water; Air–Water Partition Constant (Kiaw)
9.1 Introduction and Thermodynamic Considerations
9.2 Molecular Interactions Governing the Aqueous
Activity Coefficient and the Air–Water Partition
Constant
9.3 LFERs for Estimating Air–Water Partition
Constants and Aqueous Activity Coefficients/Aqueous
Solubilities
9.4 Effect of Temperature, Dissolved Salts, and pH on
the Aqueous Activity Coefficient/Aqueous Solubility
and on the Air–Water Partition Constant
 9.5 Questions and Problems
9.6 Bibliography
Chapter 10 Organic Liquid–Air and Organic Liquid–Water
Partitioning
10.1 Introduction
10.2 Thermodynamic Considerations and Comparisons
of Different Organic Solvents
10.3 The Octanol–Water System: The Atom/Fragment
Contribution Method for Estimation of the Octanol–
Water Partition Constant
10.4 Partitioning Involving Organic Solvent–Water
Mixtures
10.5 Evaporation and Dissolution of Organic
Compounds from Organic Liquid Mixtures–
Equilibrium Considerations
10.6 Questions and Problems
10.7 Bibliography
Chapter 11 Partitioning of Nonionic Organic Compounds
Between well-Defined Surfaces and Air Or Water
11.1 Introduction
11.2 Adsorption from Air to Well-Defined Surfaces
11.3 Adsorption from Water to Inorganic Surfaces
11.4 Questions and Problems
11.5 Bibliography
Part III Equilibrium Partitioning in Environmental Systems
Chapter 12 General Introduction to Sorption Processes
12.1 Introduction
12.2 Sorption Isotherms and the Solid–Water
Equilibrium Distribution Coefficient (Kid)
12.3 Speciation (Sorbed versus Dissolved or Gaseous),
Retardation, and Sedimentation
12.4 Questions and Problems
 12.5 Bibliography
Chapter 13 Sorption from Water to Natural Organic Matter
(NOM)
13.1 The Structural Diversity of Natural Organic Matter
Present in Aquatic and Terrestrial Environments
13.2 Quantifying Natural Organic Matter–Water
Partitioning of Neutral Organic Compounds
13.3 Sorption of Organic Acids and Bases to Natural
Organic Matter
13.4 Questions and Problems
13.5 Bibliography
Chapter 14 Sorption of Ionic Organic Compounds to
Charged Surfaces
14.1 Introduction
14.2 Cation and Anion Exchange Capacities of Solids in
Water
14.3 Ion Exchange: Nonspecific Adsorption of Ionized
Organic Chemicals from Aqueous Solutions to Charged
Surfaces
14.4 Surface Complexation: Specific Bonding of
Organic Compounds with Solid Phases in Water
14.5 Questions and Problems
14.6 Bibliography
Chapter 15 Aerosol–Air Partitioning: Dry and Wet
Deposition of Organic Pollutants
15.1 Origins and Properties of Atmospheric Aerosols
15.2 Assessing Aerosol–Air Partition Coefficients
(KiPMa)
15.3 Dry and Wet Deposition
15.4 Questions and Problems
15.5 Bibliography
Chapter 16 Equilibrium Partitioning from Water and Air to
Biota
 16.1 Introduction
16.2 Predicting Biota–Water and Biota–Air
Equilibrium Partitioning
16.3 Bioaccumulation and Biomagnification in Aquatic
Systems
16.4 Bioaccumulation and Biomagnification in
Terrestrial Systems
16.5 Baseline Toxicity (Narcosis)
16.6 Questions and Problems
16.7 Bibliography
Part IV Mass Transfer Processes in Environmental Systems
Chapter 17 Random Motion, Molecular and Turbulent
Diffusivity
17.1 Random Motion
17.2 Molecular Diffusion
17.3 Other Random Transport Processes in the
Environment
17.4 Questions and Problems
17.5 Bibliography
Chapter 18 Transport at Boundaries
18.1 The Role of Boundaries in the Environment
18.2 Bottleneck Boundaries
18.3 Wall Boundaries
18.4 Hybrid Boundaries
18.5 Questions and Problems
18.6 Bibliography
Chapter 19 Air–Water Exchange
19.1 The Air–Water Interface
19.2 Air–Water Exchange Models
19.3 Measurement of Air–Water Exchange Velocities
19.4 Air–Water Exchange in Flowing Waters
 19.5 Questions and Problems
19.6 Bibliography
Chapter 20 Interfaces Involving Solids
20.1 The Sediment–Water Interface
20.2 Transport in Unsaturated Soil
20.3 Questions and Problems
20.4 Bibliography
Part V Transformation Processes
Chapter 21 Background Knowledge on Transformation
Reactions of Organic Pollutants
21.1 Identifying Reactive Sites Within Organic
Molecules
21.2 Thermodynamics of Transformation Reactions
21.3 Kinetics of Transformation Reactions
21.4 Questions and Problems
21.5 Bibliography
Chapter 22 Hydrolysis and Reactions with Other
Nucleophiles
22.1 Nucleophilic Substitution and Elimination
Reactions Involving Primarily Saturated Carbon Atoms
22.2 Hydrolytic Reactions of Carboxylic and Carbonic
Acid Derivatives
22.3 Enzyme-Catalyzed Hydrolysis Reactions:
Hydrolases
22.4 Questions and Problems
22.5 Bibliography
Chapter 23 Redox Reactions
23.1 Introduction
23.2 Evaluating the Thermodynamics of Redox
Reactions
23.3 Examples of Chemical Redox Reactions in Natural
Systems
 23.4 Examples of Enzyme-Catalyzed Redox Reactions
23.5 Questions and Problems
23.6 Bibliography
Chapter 24 Direct Photolysis in Aquatic Systems
24.1 Introduction
24.2 Some Basic Principles of Photochemistry
24.3 Light Absorption by Organic Compounds in
Natural Waters
24.4 Quantum Yield and Rate of Direct Photolysis
24.5 Effects of Solid Sorbents (Particles, Soil Surfaces,
Ice) on Direct Photolysis
24.6 Questions and Problems
24.7 Bibliography
Chapter 25 Indirect Photolysis: Reactions with
Photooxidants in Natural Waters and in the Atmosphere
25.1 Introduction
25.2 Indirect Photolysis in Surface Waters
25.3 Indirect Photolysis in the Atmosphere
(Troposphere): Reaction with Hydroxyl Radical (HO•)
25.4 Questions and Problems
25.6 Bibliography
Chapter 26 Biotransformations
26.1 Introduction
26.2 Some Important Concepts about Microorganisms
Relevant to Biotransformations
26.3 Initial Biotransformation Strategies
26.4 Rates of Biotransformations
26.5 Questions and Problems
26.6 Bibliography
Chapter 27 Assessing Transformation Processes Using
Compound-Specific Isotope Analysis (CSIA)
 27.1 Introduction, Methodology, and Theoretical
Background
27.2 Using CSIA for Assessing Organic Compound
Transformations in Laboratory and Field Systems
27.3 Questions and Problems
27.4 Bibliography
Part VI Putting Everything Together
Chapter 28 Exposure Assessment of Organic Pollutants
Using Simple Modeling Approaches
28.1 One-Box Model: The Universal Tool for Process
Integration
28.2 Assessing Equilibrium Partitioning in Simple
Multimedia Systems
28.3 Simple Dynamic Systems
28.4 Systems Driven by Advection
28.5 Bibliography
Appendix A Mathematics
Appendix B Physical Constants and Units
Appendix C Physical Properties of Organic Compounds
Appendix D Temperature Dependence of Equilibrium Constants
and Rate Constants
Appendix E Estimation of Gas-Phase Hydroxyl Radical Reaction
Rate Constants of Organic Chemicals
Index
EULA

List of Tables
Chapter 1
Table 1.1
Chapter 2
Table 2.1
 Table 2.2
Table 2.3
Table 2.4
Table 2.5
Chapter 3
Table 3.1
Chapter 4
Table 4.1
Table 4.2
Table 4.3
Table 4.4
Table 4.5
Table 4.6
Table 4.7
Table 4.8
Table 4.9
Table 4.10
Chapter 5
Table 5.1
Table 5.2
Table 5.3
Table 5.4
Table 5.5
Table 5.6
Table 5.7
Table 5.8
Table 5.9
 Table 5.10
Chapter 6
Table 6.1
Table 6.2
Table 6.3
Chapter 7
Table 7.1
Table 7.2
Table 7.3
Table 7.4
Chapter 8
Table 8.1
Table 8.2
Chapter 9
Table 9.1
Table 9.2
Table 9.3
Table 9.4
Table 9.5
Table 9.6
Chapter 10
Table 10.1
Table 10.2
Table 10.3
Table 10.4
Table 10.5
Table 10.6
 Table 10.7
Chapter 11
Table 11.1
Table 11.2
Chapter 13
Table 13.1
Table 13.2
Table 13.3
Chapter 14
Table 14.1
Table 14.2
Chapter 15
Table 15.1
Table 15.2
Table 15.3
Table 15.4
Chapter 16
Table 16.1
Table 16.2
Table 16.3
Table 16.4
Table 16.5
Chapter 17
Table 17.1
Table 17.2
Table 17.3
Chapter 19
 Table 19.1
Table 19.2
Chapter 21
Table 21.1
Chapter 22
Table 22.1
Table 22.2
Table 22.3
Table 22.4
Table 22.5
Table 22.6
Table 22.7
Table 22.8
Table 22.9
Chapter 23
Table 23.1
Table 23.2
Table 23.3
Table 23.4
Table 23.5
Table 23.6
Chapter 24
Table 24.1
Table 24.2
Table 24.3
Table 24.4
Table 24.5
 Table 24.6
Chapter 25
Table 25.1
Chapter 26
Table 26.1
Table 26.2
Table 26.3
Chapter 27
Table 27.1
Table 27.2
Table 27.3
Table 27.4
Table 27.5
Table 27.6
Table 27.7
Table 27.8
Table 27.9
Table 27.10
Table 27.11
Table 27.12
Table 27.13
Chapter 28
Table 28.1
Table 28.2
Table 28.3
Table 28.4
Table 28.5
 Table 28.6
Appendix A
Table A.1
Appendix B
Table B.3a
Table B.3b
Appendix C
Table C.1
Table C.2
Appendix D
Table D.1
Table D.2

List of Illustrations
Chapter 1
Figure 1.1 Historical records of the sales/production
volumes of DDT and PCBs, and the similarity of these time-
varying trends to the accumulation rates of these chemicals
in the sediments of Lake Ontario; adapted from Eisenreich
et al. (1989). The major metabolites DDE and DDD
accumulated more or less concurrently with the parent
compound DDT, indicating transformation of this
compound.
Figure 1.2 Key features and commonalities of exposure
and effect assessment of organic chemicals in the
environment. Both assessments hinge on knowledge of the
same compound properties and intrinsic reactivities.
Adapted from Schwarzenbach et al. (2006).
Figure 1.3 Processes that determine the distribution,
residence time, and sinks of an organic chemical i in a lake.
This example illustrates the various physical, chemical, and
 biological processes that a compound is subjected to in the
environment.
Chapter 2
Figure 2.1 Some simple molecules (type 4 from Table 2.3)
exhibiting double and triple bonds.
Figure 2.2 Examples of bond angles in some simple
molecules. Data from Hendrickson et al. (1970) and March
(1992).
Figure 2.3 Rotation about a σ-bond leading to various
spatial arrangements of the atoms in a molecule.
Figure 2.4 The two enantiomers of the herbicide
mecoprop. The asymmetric carbon center is indicated by
the asterisk; Ar denotes the aromatic substituent.
Figure 2.5 Simplified picture of the electron clouds of the
π-electrons of a (a) double and (b) triple bond.
Figure 2.6 Cis/trans isomerism at double bonds
exhibiting two substituents.
Figure 2.7 Geometric isomers in ring systems with two
(cis/trans) or more substituted carbons (α-, β-, γ-isomers of
1,2,3,4,5,6-hexachloro-cyclohexane (HCH).
Figure 2.8 Different possible conformations of a six-
membered ring (e.g., cyclohexane).
Figure 2.9 Schematic picture of π-electron delocalization
in propenal (acrolein). The blue balls represent the carbon
atoms, the gray ones the hydrogen atoms, and the read one
the oxygen atom.
Figure 2.10 Some additional examples of aromatic ring
systems in organic compounds (in parentheses number of
π-electrons).
Figure 2.11 Some functional gro- ups (“functionalities”)
commonly found in organic compounds.
Figure 2.12 Illustration of the various molecular
interactions arising from uneven electron distributions: (a)
 dispersive forces, (b) dipole–induced dipole forces, (c)
dipole–dipole forces, and (d) electron acceptor-electron
donor forces.
Chapter 3
Figure 3.1 Some members of the so-called “legacy POPs,”
the “dirty dozen.”
Figure 3.2 Examples of aliphatic, alicyclic, and olefinic
hydrocarbons.
Figure 3.3 Examples of aromatic hydrocarbons.
Figure 3.4 Gas chromatograms of (a) the original oil from
the Macondo Well; (b) a surface slick taken a two months
after the blow up; (c,d,e) weathered oil samples collected
one year later. On the x-axes, retention times are given in n-
alkane units (retention time of the sharp peaks
corresponding to the elution of the respective linear
alkane). The y-axes provide the relative abundances of the
components within the sample analyzed. The different
chromatograms cannot be compared quantitatively. Figure
from Aeppli et al. (2012).
Figure 3.5 Structures of the gasoline additives methyl-t-
butyl ether (MTBE), ethyl-t-butyl ether (ETBE), and
methyl-t-amyl ether (TAME).
Figure 3.6 Structures of some common polychlorinated
solvents causing major groundwater contamination issues.
Figure 3.7 General structures of (a) cyclic and (b) linear
polydimethylsiloxanes. (c) D5 is the most common
polydimethylsiloxane present in personal care and
household products and is used as a dry cleaning solvent.
Figure 3.8 Some prominent flame retardants, plasticizers,
and related compounds.
Figure 3.9 Some prominent perfl-uorinated compounds.
Figure 3.10 Examples of laundry and dish detergent
components, including complexing agents, surfactants,
whitening agents, and corrosion inhibitors.
 Figure 3.11 Some prominent pharmaceuticals of
environmental concern, particularly with respect to water
pollution.
Figure 3.12 Some ingredients of personal care products of
environmental concern, particularly with respect to water
pollution.
Figure 3.13 Examples of frequently used pesticides:
herbicides, insecticides, and
fungicides.
Figure 3.14 The air–water and octanol–water equilibrium
partition constants for our companion compounds (data
from Appendix C) illustrating the wide range of physical-
chemical properties encountered when assessing organic
pollutants in the environment.
Chapter 4
Figure 4.1 Conceptualization of the potential functions in
a hydrostatic system and in a simple chemical system. (a) In
the unequilibrated hydrostatic system, water will flow from
reservoir 2 of higher hydrostatic potential (=gh2, where g is
the acceleration due to gravity and h2 is the observable
height of water in the tank) to reservoir 1 of lower
hydrostatic potential; total water volumes (i.e., total
potential energies W1 and W2) do not dictate flow.
Similarly, benzene molecules move from liquid benzene to
the headspace in the unequilibrated chemical system, not
because there are more molecules in the flask containing
the liquid, but because the molecules initially exhibit a
higher chemical potential in the liquid than in the gas. (b)
At equilibrium, the hydrostatic system is characterized by
equal hydrostatic potentials in both reservoirs (not equal
water volumes) and the chemical system reflects equal
chemical potentials in both flasks (not equal benzene
concentrations). In the hydrostatic system, m is the mass,
W the weight, and gh is the hydrostatic potential. In the
chemical system, ni is the number of moles of compound i,
G is the Gibbs free energy, and i is the chemical potential.
 Figure 4.2 Conceptualization of the fugacity of a
compound i (a) in an ideal gas; (b) in a pure liquid
compound i; (c) in an ideal liquid mixture; and (d) in a
nonideal liquid mixture (e.g., in aqueous solution). In (b),
(c), and (d), the gas and liquid phases are in equilibrium
with one another.
Figure 4.3 Fraction in acid form as function of pH. At pH
= pKia, the acid and base forms are present at equal
concentrations, i.e., [HA] = [A−]; [BH+] = [B].
Figure 4.4 Effect of delocalization on the pKia of an –OH
group.
Figure 4.5 Influence of the position of a nitro substituent
on the pKia of a phenolic hydrogen.
Figure 4.6 Example of a proximity effects on the acidity
constant: hydrogen bonding.
Figure 4.7 Effects of ring substituents on the pKa of
benzoic acid, phenyl acetic acid, and phenol.
Figure 4.8 Hammett plots for meta- and para-substituted
phenols, phenylacetic acids, and 3-phenylpropionic acids;
data from Serjeant and Dempsey (1979).
Chapter 5
Figure 5.1 The atmosphere is divided into horizontal
layers (troposphere, stratosphere, mesosphere and higher
layers not shown) that are confined by heights where the
temperature gradient changes sign (tropopause and
stratopause). Under special weather conditions,
temperature in the troposphere increases with height; such
conditions, called inversions, are zones of suppressed
vertical mixing.
Figure 5.2 Schematic of average atmospheric circulation.
(a) In both hemispheres, large differences in surface
heating by sunlight from the equator to the poles leads to
three circulation cells of rising warm air and descending
cold air (Hadley, Ferrel and Polar cells). Air pressure is low
and cloud formation high where rising air meets another
circulation cell. The boundaries between the circulation
cells, especially at the equator, are zones where north-south
transport is limited. Graphic: NOAA (2011). (b) The Earth's
rotation deflects air flows near the surface from the north-
south axis into the latitudinal direction, thus leading to a
distinct pattern of latitudes with westerly and easterly
winds. Graphic: Niemi (2002).
Figure 5.3 Electron micrographs (not at the same scale) of
three “primary” aerosol components: (a) pollen, (b) sea salt
from sea spray, and (c) soot. Primary aerosol components
arise directly from the Earth surface, while secondary
components are formed in the atmosphere. Micrographs
from USGS, UMBC (Chere Petty), and Arizona State
University (Peter Buseck) accessed at Voiland (2010).
Figure 5.4 Schematic of annual global water flows in 1012
m3 yr−1. Adapted from Bengtsson (2010).
Figure 5.5 Layers of the ocean as illustrated for the
Atlantic Ocean: (1) surface layer of a few hundred meters
during the winter, (2) intermediate water at about 1000 m,
(3) North Atlantic Deep Water (NADW) flowing south at
about 3000 m, and (4) Antarctic Bottom Water (AABW)
flowing north along the ocean bottom.
Figure 5.6 The global scale transport of seawater, referred
to as the “Global Conveyor Belt;” graphic from Broecker
(1987, 1991). Cold, salty water sinks in the Arctic/North
Atlantic, flows south (blue) until it turns east and moves
toward the Indian and Pacific Oceans. The deep water flows
northward until it arrives in the vicinity of India or Alaska
where it rises to the ocean surface for its shallow return flow
(red) back to the North Atlantic.
Figure 5.7 Typical seasonal stratification cycle of a
freshwater lake. Not every lake undergoes a complete
overturn. Some lakes are permanently stratified. Usually,
this effect is caused by a vertical gradient in the
 concentration of total dissolved solids. Adapted from
Campbell et al. (2002).
Figure 5.8 Depiction of the land compartment with the
uppermost soil zone, the unsaturated or vadose zone, the
capillary fridge, where groundwater seeps up via capillary
action, and the saturated zone where groundwater flows.
Adapted from Heath (1983).
Figure 5.9 (a) Schematic depiction of horizons in the soil
zone and (b) photograph of a corresponding soil section.
(Photo: Jim Turenne accessed at Turenne, 2014.)
Figure 5.10 Typical pH and electrode potential (EH) for a
range of different types of soils. Adapted from Baas-Becking
(1960).
Figure 5.11 Impact of heterogeneity on transport in porous
media. Three important mechanisms of transport and
mixing are (a) inter-pore dispersion caused by mixing
between pore channels, (b) intra-pore dispersion caused by
non-uniform velocity distributions and mixing in individual
channels, and (c) dispersion and retardation of solute
transport by molecular diffusion between open and dead-
end pores. Such effects also develop from slow exchanges
between strata of differing hydraulic conductivities, such as
a clay layer in a sandy aquifer.
Chapter 6
Figure 6.1 A mathematical model is defined by a boundary
(solid line) that separates a subunit of the world (IN) from
the rest of the world (OUT). The state of the system is
characterized by a set of variables (state variables). The
dynamics of these variables is determined by internal
processes and by external forces. The impacts of the system
on the rest of the world are called outputs. An essential
aspect of the representation of the world as IN and OUT is
that the effect of the output on the external forces is
neglected. The figure gives a general view of a system with
three state variables. The lines with arrows show the
interactions between the components; sometimes these
interactions are negligible.
Figure 6.2 (a) Concentrations of tetrachloroethene (PCE)
as a function of depth measured in Mystery Lake, Cleanland
on two consecutive sampling dates (August 15 and
September 4). Maximum depth of the lake is 35 m. The
water samples in the vertical are taken every 2.5 m (15
samples). The green area represents the PCE that
disappeared from the epilimnion between the two sampling
dates; the brown area represents the PCE that moved into
the hypolimnion. (b) Schematic view of Mystery Lake and
vertical temperature profile in August/September. The
thermocline (boundary between epilimnion and
hypolimnion, see Fig. 5.7), is between 10 and 15 m depth.
Figure 6.3 Three different models to describe
tetrachloroethene (PCE) in Mystery Lake, Cleanland.
Characteristic data of the models are given in Table 6.1. (a)
Model A has one state variable (mean concentration of PCE
in lake), (b) Model B has two state variables (mean
concentrations of PCE in epilimnion and hypolimnion), and
(c) Model C has 15 state variables (concentrations at 15
depths, each 2.5 m apart). The models have no external
forces. Output processes are air–water exchange and
flushing from the surface layer; internal processes are
mixing between water layers.
Figure 6.4 Schematic representation of a well-mixed box.
A chemical is introduced into the system via the inlet and by
production processes (total rate Ptot [MT−1]) and removed
via the outlet and by internal removal processes (Rtot
[MT−1]). Although Ptot an Rtot are in situ production and
removal processes, the corresponding arrows are drawn
across the system boundary to indicate that the chemical is
added to or removed from the box. [M] is the total mass
of the compound in the volume V [L ], C and Cin [ML−3] are
3
concentrations in the box and in the inlet, respectively, Q
[L3T−1] is the flow rate through the box. The concentration
in the outlet is equal to the concentration in the box, since
the box is well mixed.
Figure 6.5 Solution to the first-order linear
inhomogeneous differential equation (FOLIDE) (Eq. 6.7).
C0 = initial value at t = 0, C∞ = J/k is the steady-state value.
(a) Growth curve for C0 = 0; (b) Decay curve for C0 = 1, J =
0; (c) general case for C0 = 0.3. The time axis is in units of
1/k. The remaining difference to steady state drops from
37% at t = 1/k to 14% and 5% for each additional time
interval 1/k.
Figure 6.6 (a) System consisting of two boxes (two-box
model) described by one state variable in each box (total
mass, 1 and 2, or mean concentration C1 and C2). V1
and V2 are the volumes of the boxes. In addition to the
usual processes of the one-box model (external forces,
outputs), mass fluxes 12 and 21 exist between the boxes.
(b) Same as (a), but all processes are zero except the mass
fluxes between the boxes (pure exchange model). Since
there are no fluxes between the system (IN) and its
environment (OUT), total mass, tot = 1 + 2, is
constant with time (Eq. 6.13), but the sum of the
concentrations, C1 and C2, is not constant, unless the box
volumes are equal.
Figure 6.7 Water exchange between two lake basins that
are separated by a channel. If the channel gets long and
shallow, the backward flux 21 becomes zero. The flow from
Basin 1 to Basin 2 is then purely advective, the influence
from Basin 2 on Basin 1 disappears and the system becomes
hierarchical.
Figure 6.8 Schematic picture showing how a m-box model
consisting of m horizontal layers (boxes) turns into a model
with a continuous description of concentration C along the
spatial axis under consideration (in this case, it is the z-
axis). Fn,n+1 and Fn+1,n are the downward and upward
 fluxes, respectively, across the boundary between layer n
and layer n+1.
Figure 6.9 A cube with dimension δ (control volume)
illustrates Gauss' theorem (Eq. 6-33). The concentration
change within the cube results from the differences between
input and output fluxes, Fjin – Fjout, calculated for the three
Cartesian coordinates j = x, y, z.
Figure 6.10 Qualitative relations between the sign of
concentration change at location x0 due to advection and
diffusion, respectively. Advection (upper panels): A
concentration profile along the x-axis is shifted to the right
(thin line) due to advection in the positive x-direction (vx >
0). This leads to a decrease of C at x0 if the slope of C(x) is
positive (left panel), and to an increase of C if the slope is
negative (right panel). Diffusion (lower panels): According
to the Fick's second law (Eq. 6.34b), diffusion always shifts
a concentration profile to its concave side.
Figure 6.11 Schematic one-dimensional concentration
profiles resulting from the diffusion/advection/reaction
equation at steady state (Eq. 6-39) for different parameter
values D (diffusion coefficient), vx (advection velocity along
the x-axis), and k (first-order reaction rate constant). The
profiles obey the boundary conditions Co = C(0), CL = C(L).
The four ‘pure’ situations are determined by the size of the
Damköhler Number, Da (Eq. 6-40), and the Peclet Number,
Pe (Eq. 6-41).
Chapter 7
Figure 7.1 Partitioning of a compound i from an ideal gas
phase (air, subscript “a”) into a bulk liquid (subscript “ℓ”).
Figure 7.2 Plots of the logarithms of the hexadecane–air
(a), octanol–air (b), water–air (c), and octanol–water (d)
partition constants of series of apolar, monopolar, and
bipolar compounds (our “test set”) versus their molar
volumes, Vi.
 Figure 7.3 Plot of the logarithms of (a) the hexadecane–air
(Kihexadecane–air) versus the octanol–air (Kioa) partition
constants, and (b) the logarithms of the hexadecane–water
(Kihexadecane–water) versus octanol–water (Kiow) partition
constants at 25°C for our test set.
Figure 7.4 Predicted (using Eq. 7-13) versus experimental
Kiow values of our test set.
Chapter 8
Figure 8.1 Vapor pressure at 25°C of n-alkanes as a
function of chain length. The subcooled liquid vapor
pressures have been calculated by extrapolation of p*iL
values deter-mined above the melting point (Eq. 8-7). Data
from Daubert (1997) and Lide (1995).
Figure 8.2 Simplified phase diagram of a pure organic
chemical. The boundary between the solid and liquid phase
has been drawn assuming the chemical's melting point (Tm)
equals its triple point (Tt), the temperature–pressure
condition where all three phases coexist. In reality, Tm is a
little higher than Tt for some compounds and a little lower
for others.
Figure 8.3 Open (a) and closed (b) vessel containing a
pure condensed phase and a vapor phase. In case (a), the
total pressure (1 bar) is exerted by the compound's
molecules and by other gaseous species (e.g., O2, N2), which
do not significantly alter the composition of the condensed
phase. In case (b), the total pressure is equal to the vapor
pressure of the compound; that is, no other gaseous species
are present.
Figure 8.4 Effect of temperature on vapor pressure for
some organic compounds. The decadic logarithm is used,
thus the factor 1/2.303 (ln p*i = 2.303log pi*).
Figure 8.5 Plot of ΔvapHi and TΔvapSi versus ΔvapGi for a
wide variety of organic compounds at 25°C. At the intercept
 (ΔvapGi = 0) the value for ΔvapHi (= TΔvapSi) obtained from
a linear regression analysis is 25.8 kJ mol−1.
Figure 8.6 Plot of ΔvapHi versus ln p*iLfor a large number
of apolar, monopolar, and bipolar compounds (some
bipolar outliers not included). Data from Goss and
Schwarzenbach (1999).
Figure 8.7 Fitted (Eq. 8-19) versus experimental p*iL
values for 200 apolar, monopolar, and bipolar compounds
taken from Appendix C.
Chapter 9
Figure 9.1 Thermodynamic cycles relating partition
constants between air (a), water (w), pure organic liquid (L)
or solid (s), and an organic solvent (ℓ) at saturated
(superscript “sat,” left) and (infinitely) dilute (superscript
“∞,” right) conditions.
Figure 9.2 Standard enthalpy and entropy changes for the
transfer of an organic compound from water to air (aw),
and from the pure organic liquid to air (vap) and water (w)
respectively.
Figure 9.3 Effect of salt concentration on the aqueous
solubility of benzene and naphthalene. Data from McDevit
and Long (1952) and Gordon and Thorne (1967a).
Figure 9.4 Schematic representation of the total aqueous
solubility of (a) an organic acid and (b) an organic base as a
function of pH. For simplicity, the same pKa values and
maximum solubilities of the neutral and charged (salt)
species have been assumed.
Chapter 10
Figure 10.1 Plot of the logarithms of the octanol–water
partition constants (log Kiow) versus the aqueous activity
coefficients (log ) for a variety of apolar, monopolar, and
bipolar compounds. The diagonal lines indicate where the
activity coefficients in octanol ( ) (calculated from Eq. 10-
2) equal 0.1, 1, 10, or 100.
Another random document with
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 “Sure, people buying things for school. Grouchy Greenway was in,
he bought a lot of homework paper—pity the fellers in the third
grade. Ruth Binney’s scared of that ladder that rolls along—oh
bimbo, that’s my middle name. I can take a running jump and ride it
all the way to the back of the store.” He did not mention that he
played the harmonica for the girls to dance; he was a good sport and
did not tell tales out of school.
“I think Ruth and Annie Terris will miss you when you go to
Montana,” said Mr. Walton playfully.
“Such nonsense,” said Mrs. Walton. “Don’t put those ideas back
into his head.”
“I may go sooner than you think,” said Hervey.
He stood in the doorway to the dining room, pausing before
making his late evening attack on the apple barrel. A blithe, carefree
figure he seemed, his eyes full of a kind of gay madness. One
rebellious lock of hair sprawled over his forehead as he suddenly
pulled off his outlandish hat in deference to his stepmother. He never
remembered to do this as a regular duty; he remembered each time
separately, and then with lightning inspiration. He could not for the
life of him adapt his manners or phraseology to his elders.
“You know me, Al,” he said.
“Are you going to wash your face when you go in the kitchen?”
Mrs. Walton inquired.
“Sure, is there any pie?” he asked.
They heard him fumbling in the kitchen, then trudging up the
stairs.
“I think it would be just as well not to harp on Montana,” said Mrs.
Walton. “It’s odd how he hit on Montana.”
“One place is as good as another,” said Mr. Walton. “I’m glad it’s
Montana, it costs so much to get there. If he had Harlem in mind, or
Coney Island, I might worry.”
“He talks of them both,” said Mrs. Walton. “Yes, but I think his
heart is in the big open spaces, where the fare is about a hundred
dollars. If it were the Fiji Islands I’d be content.”
“Do you think he’d like to go to Europe with us next summer?”
Mrs. Walton asked. “I can’t bear to leave him alone.”
 “No, I’m afraid he’d want to dive from the Rock of Gibraltar,” said
Mr. Walton. “He’ll be safe at Temple Camp.”
“He seems to have just no balance-wheel,” Mrs. Walton mused.
“When I look in his eyes it seems to me as if they saw joys, but never
consequences.”
“Sort of near-sighted in a way, eh?”
“I do wish he had stayed in the Scouts, don’t you?”
“No, I don’t,” said Mr. Walton in a matter-of-fact way. “He didn’t
see it. Some day he’ll see it, but it won’t be because anybody tells
him. The only way Hervey can learn that a tree is high is for him to
fall out of it. That’s what I mean by his being near-sighted in a way.”
“Do you think those railroad workers are a good set?”
“Oh, they’re a good lot; good, strong men.”
“Well, I don’t care for that Hinkey, do you?”
Mr. Walton did not go into raptures over anybody from New York.
He was a good New Englander. Nor had he been carried off his feet
by the “million dollar theatre.” But being a true New Englander he
was fair in judgment and of few words, especially in the field of
criticism. His answer to this last question was to resume reading his
book.
 CHAPTER XXIV
IN THE SILENT NIGHT
In his own room Hervey opened the satchel which circumstances
had caused him to carry home. He thought that since kind fate had
brought the opportunity, he would like to give one exceedingly low
blast on a real musical instrument. He was astonished to find that
there was no musical instrument in the satchel, but a tin box
containing a small account book, a number of bills with a rubber
band around them, and an envelope containing some loose change.
He contemplated this treasure aghast. Counting the bills he found
them to be in amount a trifle over a hundred dollars. Never before
had he handled so much money. He was a little afraid of it. He shook
the sealed envelope which was fat with coins; that alone seemed to
contain a fortune. He glanced at the book and found it to full of
figures, entries of receipts and expenditures. On the flyleaf was
written:
Farrelton Merry Medley Serenaders,
Horton Manners, Treasurer.
He was greatly excited by this revelation. Here was a serious
business, a very grave consequence of a mischievous act. To be
sure, the bringing home of the satchel that did not belong to him
would have been the same in any case regardless of its contents.
But just the same the sight of so much money come into his
possession in such a way, frightened him. He had not thought of
such a thing as this. You see Hervey never thought at all—ever.
But he thought now. He had “colloped” (whatever that meant) the
treasury funds of this musical organization and he felt uneasy that he
should have to be the custodian of such a princely sum over night.
Money that did not belong to him! Would his wanton act be
construed as just harmless mischief? He had always wanted to have
a hundred dollars, but now he was almost afraid to touch it. He
replaced the box in the satchel and put the satchel under his bed.
Then he pulled it out again and put it in his dresser. Then he closed
and locked the window. When he was half undressed, he took the
satchel out of his dresser and stood holding it not knowing where to
put it. Then he put it back in the dresser.
He thought of going downstairs and telling his stepfather and
getting this awful fortune off his hands. But then he would have to tell
how he had come by it. Well, was that so very bad? Tripping a fellow
up? But would any one understand? He was very angry at the
deserter Hinkey. And he was equally angry that this dextrous little
tripping stunt should bear such consequences. It seemed to him that
even poor Horton Manners had taken a mean advantage.
He resolved that he would hunt up the musical treasurer in the
morning and return the satchel to him. He would hang on to it pretty
carefully going down the street, too. He did not know Horton
Manners, but he could find him. Of course, he would have to tell the
man that he was sorry he had tripped him up. And his explanation of
why he had carried the satchel home might sound rather queer. He
was not too considerate of the tripping treasurer. He was doomed to
a sleepless night on account of that “bimbo.” It was odd, more than it
was significant, that Hervey, who was afraid of no peril, was in panic
fear of this hundred and some odd dollars. He was just afraid of it.
Several times during that long night, he arose and groped his way
to the dresser to make sure that the satchel was safe. In the wee
hours of the night he was sorry that he had not hunted up Horton
Manners immediately after his escapade. But then he might have got
home too late. On every hand he seemed confronted with the high
cost of mischief.
He wondered if the tripping treasurer was searching for the culprit
with the aid of the police. He felt sure that no one dreamed he was
the culprit. Would they, might they not already, have traced Hinkey?
And what would Hinkey say? He had a reassuring feeling that
Hinkey could not be identified as one of the culprits. He certainly
would not tell on Hinkey. And he hoped that Hinkey would not be
incriminated and tell on him before he had a chance to return the
satchel. But surely Mr. Horton Manners had not gone home and to
bed, doing nothing about the theft of more than a hundred dollars. To
the young treasurer the affair was a plain robbery. Of course, Hervey
could not sleep when his imagination pictured the whole police and
detective force of the town aroused by a bold hold-up.
In the hour just before dawn Hervey, in his troubled half-sleep,
heard a knocking sound. Trembling all over, he pulled on his shirt
and trousers, crept stealthily downstairs and with a shaking hand
and pounding heart opened the front door.
 CHAPTER XXV
LIFE, LIBERTY⸺
No one was there. Hervey looked out upon the dissolving night;
already the familiar scene was emerging in the gray drawn—the
white rail fence, the gravel walk with its bordering whitewashed
stones, the big whitewashed tub that caught the rain-water from the
roof trough. He smelled the mist. There was no one anywhere about;
no sound but the slow dripping into the tub. Drop, drop, drop; it was
from the rain of two or three days ago. How audible it was in the
stillness! He crept upstairs again and went to bed. But he did not
sleep. He wished that dreadful satchel were off his hands. Over a
hundred dollars!
He arose in the morning before the household was astir and stole
out with his guilty burden. He knew that Kipp’s Railroad Lunch was
open all night and that it had a telephone. He would look in the
telephone book for Manners. That way he would find the address.
He thought of leaving the satchel at the Manners’ door, ringing the
bell, and running away. The recovery of the money would end the
trouble. But suppose the satchel should be stolen again—not again;
but suppose it should be stolen? Of course, it had not been stolen
before.... Just the same he was desperate to get it off his hands.
Things looked strange about the station so early in the morning;
there were so few people to be seen, and no shops open. Somehow
the very atmosphere imparted a guilty feeling to Hervey. He felt a
little like a fugitive.
He could not find the name of Manners in the ’phone book and
thus baffled, he felt nervous. For while he was losing time, the victim
and the authorities were probably not wasting any time. He thought
he would wait in the station a little while and try to decide what to do.
He knew that the family of Denny Crothers, a scout, was identified
with the big white church. There was an idea! Denny would know
where Horton Manners lived, or could soon find out. Perhaps he
might even take Denny into his confidence. It is worth considering
that in his extremity he was willing not only to use, but to trust, this
scout whose troop he had repudiated.
Well, he would sit in the station a little while (it was still very early)
and if he could not think of any other plan, he would go to Denny’s
house. It would seem strange to the Crothers, seeing him there so
early. And it would seem stranger still to Denny to be approached by
an arch enemy. But Hervey’s troubled thoughts could not formulate
any better plan.
The station was not yet open and he strolled back and forth on the
platform where a very few people were waiting for the early train—a
workman wearing a reefer jacket and carrying a dinner-pail, a little
group of girls who worked in the paper mill at Brierly, and a couple of
youngish men near the end of the platform. These two were chatting
and one of them gave a quick glance at Hervey. It seemed to him
that the talk which followed had reference to himself. He wished that
the station would open, for it was a raw fall morning; there was a
penetrating chill in the air. He wanted to sit down; he was tired of
holding that dreadful satchel, yet he would not set it down for so
much as a moment.
Suddenly, a rattling old car drove up and a brisk young man in an
overcoat got out and dragged two huge oilcloth grips to the platform.
He looked as if he might be a salesman who had completed his
assault on Farrelton. He stopped and lighted a cigarette, and while
he was doing this the two men strolled over and spoke to him. He
seemed annoyed, then laughed as he took out some papers which
the two men examined. Hervey overheard the word hardware. And
he overheard one of the men say, “K.O., Buddy.” They handed back
the papers, nodded sociably, and moved away. It seemed by the
most casual impulse that they approached Hervey. But he trembled
all over.
“You’re out early, kiddo,” said one of them. “Waiting for the train?”
Why, oh why, did he flush and stammer and answer without
thinking? “No—y-yes—I guess it’s late, hey?”
 “Guess not,” said the man with a kind of leisurely pleasantry.
“What you got in the bag, kiddo?”
“Bimbo, do I have to tell you?” Hervey demanded with the air of
one whose rights are outraged.
“Might be just as well,” said the man. “What’s your name
anyway?”
“My name is Hervey Willetts and you let go of that!” Hervey
shouted, tugging at the satchel. “You let go of that, do you hear!” He
not only pulled, but he kicked. “You let go of that or you’ll get in
trouble, you big⸺”
He was the center of a little group now; it was astonishing what a
number of persons were presently on the scene considering the few
early morning stragglers. The men put a quick end to Hervey’s ill-
considered struggle by taking the satchel while one held him firmly
by the collar. There is not a decent person in the world but rebels
against this collar grip which seems the very essence of effrontery.
Few boys so held will fail to use that potent weapon, the foot, and
Hervey, squirming, administered a kick upon his captor’s shin which
made the burly fellow wince and swear.
But it was all to no avail. They opened the satchel and noted its
contents. Hervey’s sense of indignity now quite obliterated every
other feeling. His struggles subsided into a wrathful sullenness; he
could not, or he would not, explain. He knew only that he was being
held and that fact alone aroused the demon in him. Of course, if
Walton could not manage him, and the Scouts could not win and
hold him, it was hardly to be expected that these low-bred detectives
could get closer to him than to hold him by the collar. A dog would
have understood him better. He was not the kind of boy to grab by
the collar.
These two detectives, apprised of the “robbery,” had taken their
stand at the station to note if any suspicious looking strangers were
leaving town on the first train. The boy had almost escaped, because
of his youth.
And escape was the one thought in his mind now. Twice he might
have explained; first to his good stepfather, and again to these
minions of the law. But they had the grabbing instinct and (oh, the
pity of it) had diverted his thoughts from honest restitution to a
maniac desire to beat them and baffle them, to steal indeed his
liberty if nothing else, and let the satchel with its fortune go hang! He
would steal; yes, he would forget all else now in this crazy mixup! He
would steal what was the very breath of life to him—his freedom. He
forgot the whole sorry business in this dominant thought—Horton
Manners, the satchel, everything. They had grabbed him by the
collar and he could feel the tightness in his neck.
As long as the squirrel has teeth to bite, he will bite. You cannot
tame a squirrel. The fact that he is caught stealing in your tree is
quite a secondary matter. Hervey Willetts never thought of stealing
anything in his life—but just the one thing.
Freedom!
So he did a stunt. With both hands he tore open his shirt in front,
and as he felt the loosening grip in back he sprang forward only to
feel a vice-like hand catch hold of his arm. And that hand he bit with
all his vicious might and main. Like lightning he dodged both men
and was off like a deer while the circle of onlookers stood aghast.
Around the end of the freight platform he sped and those who
hurried there beheld no sign of him—only a milk-can lying on its side
which he had probably knocked over.
Off bounded one of the detectives; the other lingered, sucking the
cut in his hand. He didn’t know much about wild life, poor man. This
was a kind of stealing he had never seen before—the only kind that
interested Hervey Willetts. The only thing that interested him—
freedom. As long as the squirrel has teeth to bite, he will bite.
You cannot tame a squirrel.
 CHAPTER XXVI
OUT OF THE FRYING PAN
But they caught him, and caged him. They found him in the camp
of railroad workers near Clover Valley where he had spent a week or
so of happy days. And they left nothing undone. They investigated
the histories of that rough and ready crew, for they were after the
man higher up, the “master mind” in back of the robbery.
They unearthed the fact that one of them, Nebraska Ned, had
been a sailor and had deserted his ship to assist in a revolution in
South America. It was then that Hervey made a most momentous
decision. He abandoned Montana quite suddenly and chose South
America as the future theatre of his adventurous career.
No master mind was discovered, not even the true master mind,
Harlem Hinkey. He was not implicated and he neglected to uphold
the chivalrous honor of Harlem by coming forward as the originator
of the prank which had such a grave sequel. In the hearing in court,
Hervey never mentioned his name. And there you have Hervey
Willetts. You may take your choice between the “million dollar
theatre” and South America.
There was a pathos about the quiet resignation, the poise and
fairness in face of all, which Mr. Walton presented in that memorable
scene at the hearing. I like Mr. Walton, good man that he was. He
sat, a tall, gaunt figure, one lanky limb across the other, and listened
without any outward show of humiliation. His tired gray eyes, edged
by crow’s-foot wrinkles singularly deep, rested tolerantly on the prim
young man, Horton Manners, who was having his day in court with a
vengeance.
And Hervey, too, looked upon the young treasurer musician with
interest, with dismay indeed, for he recognized in him the very same
young man into whose lap he had stumbled on the train coming
home after his triumphal season at helpless Temple Camp. Horton
Manners looked down from his throne on the witness box, gazing
through Hervey rather than at him, and adjusted his horn spectacles
in a way that no one should do who is under fifty years old. He held
one lapel of his coat and this simple posture, so common with his
elders, gave him somehow the absurd look of an experienced
business man of about twenty-two years.
He was not in the least embarrassed. He testified that he was
treasurer of the Farrelton Band and confessed that he played a small
harp. If he had said that he played a drum nobody would have
believed him. He said that he had lived in Farrelton but a short while
and made his home with his married sister. Then, on invitation of the
likely looking young man representing the prosecutor, he told how
Hervey had mentioned on the train that he was going to Montana
and that he was going to “collop” the money to get there.
“And when did you next see him?”
“Not till this very day; in fact—here in court.”
“When he spoke of Montana, did he ask you how much it would
cost to get there?”
“He did, and I informed him that it would cost at least a hundred
dollars. I advised him against going.” There was a slight titter of the
spectators at this.
“I think that’s all, your Honor,” said the interrogator. “Since the boy
admits he took the satchel, we need not prove that.”
“Just one moment,” drawled Mr. Walton, drawing himself slowly to
his feet. He had employed no lawyer, and would not, unless his
stepson were held for trial on the serious charge of robbery.
“You say you live with your married sister?” he drawled
ruminatively.
“Mrs. Winton C. DeGraw, yes.”
“Then your name would not be in the ’phone book?”
“Presumably not.”
“Hmph.”
“I don’t see any significance in that,” said the young prosecutor.
“I simply want to find out if my boy has told me the truth,” said Mr.
Walton. “This isn’t a trial, of course. When I have satisfied myself
about certain matters I will ask the court to hear me. One more
question, Mr. Horton—I mean Mr. Manners. Do you know the
meaning of the word collop?”
“I never investigated it.”
“Well, I have investigated it,” said Mr. Walton, with the faintest
twinkle in his eye. Hervey looked rather surprisedly at his stepfather.
“It does not mean to steal. It means to earn or to get by the
performance of a foolhardy act—what boys call a stunt. Do you know
what a stunt is?”
“I suppose when I was knocked down⸺”
“You mean tripped.”
“Well, tripped. I suppose that was a stunt.”
“Exactly,” said Mr. Walton. “That’s all it was and nothing more. I
have talked with boys and I find that if a boy jumps from a high fence
to get another boy’s jack-knife, he collops it. It’s a long time since
you and I were boys, Mr. Horton Manners,” Mr. Walton added with a
smile. “Do you really want to charge this youngster with a felony?” he
continued in a tone of quiet kindness. “Isn’t the case hard enough
without that? Did you never perform a stunt?”
Oh, Hervey Willetts, if you had no thrill in that moment for the
patient, kindly, harassed man—your friend and counselor; then
indeed was there no hope for you! But he had a thrill. For the first
time in all his life his eyes filled and brimmed over as he looked at
the man who wanted only to make sure of him, to know that he was
not dishonest; who could stand for anything save that.
“I think, your Honor,” said Mr. Walton quietly, “that this affair
simmers down to a piece of mischief with an unintendedly serious
consequence. I know, of course, about the recent affair of the fire.
My boy gave himself up because he would not be despicable. He
does not lie, much less steal. I believe the story he told me; that he
thought the satchel contained a musical instrument and that he
intended to blow it and cause panic to those gathered in the church.
He saw the police officer, thought he was watched, and carried out
the part of innocence by bringing the satchel home. It proved an
elephant on his hands, a guilty burden to one really innocent. He told
me he could not find this young man’s name in the ’phone book and
it develops that the name is not there. I have here two men who saw
him looking in the ’phone book in a lunch room near the station⸺”
The judge interrupted and surprised him. “I think we need not
prolong this,” said he. “I think the boy had no intention of committing
a serious crime, or any crime at all. I believe the story he told when
arrested. I’d like to think the consequence will prove a lesson to him.
But do you think it will?”
“I’m afraid it will not,” said Mr. Walton. “And I may say now that it is
my intention to send him somewhere where he will be under rigid
discipline. I think I may be left to deal with him.”
“Well, the charge of robbery is dismissed,” said the judge. Then he
appeared to ruminate. “But the boy is still with us and there’s the
problem. This is the second time he has been brought into court. He
kicked up quite a rumpus and bit an officer. Where is this kind of
thing going to end?” He seemed kindly and spoke rather sociably
and not as an official. “Why don’t you put him in the Boy Scouts?” he
added.
“The Boy Scouts haven’t given him a knockout blow yet,” smiled
Mr. Walton. “I’m always hoping they’ll reach him. But I suppose
they’ll have to do a stunt that pleases him. Meanwhile, I’m going to
send him to a military school. It seems like a confession of defeat,
but I’m afraid it’s the only thing to do.”
The judge turned to Hervey. “You’d better go home with your
father,” said he. “And you take my advice and get into the Boy
Scouts while there is time, or the first thing you know you’ll land in a
reformatory. So you want to go to Montana, eh?”
“Sure, they have train robbers out there?” said Hervey.
“And how do you like having a hundred dollars that doesn’t belong
to you?”
“Nix on that stuff,” Hervey said gayly.
“Yet you like train robbers.”
“Bimbo, that’s different.”
Mr. Horton Manners, still sitting like an owl on the witness stand,
gazed at Hervey with a look of utter bewilderment.
“But in South America they have rebellions,” said Hervey.
“Well, let us have no more rebellion here,” smiled the judge.
And he winked at Mr. Walton.
 CHAPTER XXVII
AT LAST
Of course, Hervey was never in any danger of being sent to prison
for robbery. As soon as he was arrested and made to tell his story,
Mr. Walton annoyed, but unruffled, saw the thing in its true light. He
went to the all night lunch room near the station and made sure that
Hervey had gone there; then he verified the boy’s statement that the
name of Manners was not in the ’phone book.
Quietly he even inquired among boys the meaning of collop. And
he learned on the highest juvenile authority that it did not signify
stealing nor an intent to steal. But Horton Manners had made the
charge of robbery and so the whole business had to be aired in
court. Mr. Walton was a man of few words; it would be interesting to
know what he really thought of Horton Manners.
As for Hervey, he quite forgot the affair within an hour of the time it
was over. He had been appalled to find himself the custodian of a
hundred and more dollars, but now that he had got it off his hands,
he went upon his way rejoicing. He never looked either backward or
forward; the present was good enough for him. It is significant that
he bore no malice toward Horton Manners. Once or twice he referred
to him as Arabella; then he forgot all about him. He could not be
bothered hating anybody; nor caring a great deal about anybody
either.
A few prominent townspeople financed the Firemen’s Carnival
and it was held after all. Shows and acts were engaged, the merry-
go-round revolved to the accompaniment of its outlandish music, the
peanut and lemonade men held form; you could see the five-legged
calf for “a dime ten cents,” and Biddle’s field presented a gala scene.
The boys of Farrelton went round and round trying to stab the brass
ring, they drank red lemonade and time after time gazed spellbound
at the five-legged calf.
Hervey did not care about seeing the five-legged calf unless he
could sneak in under the canvas fence, and he could not manage
that because of the man who kept shouting and slapping the canvas
with his stick. In common with all the other boys he was thrilled at the
sight of Diving Denniver who ascended a ladder to a dizzy height
and dived from it into a small tank directly below. Diving Denniver did
this thing twice a day, and his night performance was the more
thrilling because it was in the glare of a searchlight whose long beam
followed him in his slow ascent of the frail looking ladder and showed
him in a circle of light when he paused for one thrilling moment at the
top. He earned his living in this way, going around exhibiting at
carnivals and amusement parks, and he was the big feature of the
Farrelton carnival.
Hervey was not content simply to behold this daredevil exploit. He
saw it twice in the daytime and once at night, and he could not stand
the strain of being restricted to the enjoyment afforded a gaping
audience. That is where he differed from other boys. It was this
something in his nature that prevented him from reading boys’
books; he could not intrude into the hair-raising adventures and so
he had no use for them. The most thrilling stories were utterly dead
stuff to Hervey.
But here he could intrude. It was after he saw the night
performance that he felt the urge to penetrate to the hallowed spot
whence that enchanted daredevil emerged in his theatrically
cautious ascent of the ladder. The nature of the spectacular feat
required that it be performed at a distance from the body of the
carnival. As soon as the band started playing Up in the air mid the
stars, the long column of light was directed on the ladder which
appeared as if by magic a hundred yards or so from the thronged
area of the carnival. Every eye was then fixed with expectancy as a
white figure arose into view, moving up, up, up, to a little
surmounting platform. Then the sensational dive, after which the
pleasure seekers ate, drank and were merry again.
But Hervey could not go back to any merry-go-round after that,
and red lemonade had no solace for him. He wandered off from
those festoons of electric lights, away from the festive groups, into
the darkness. Before him, down near the edge of Biddle’s field, was
a tiny light. Soon he came to a rope fence which cut off the end of
the field from the public. Beyond this were wagons and huge cases
standing in the darkness, the packing and transporting paraphernalia
of the motley shows. In a monstrous truck that stood there the multi-
colored prancing horses of the merry-go-round would be loaded and
have a ride themselves.
On an upright of this rope fence was a sign which read
POSITIVELY NO ADMITTANCE. Hervey entered just where the sign
was placed. A hundred or so paces brought him to the holy of holies,
a little tent at the foot of the towering, slender ladder. In the darkness
its wire braces, extending away on each side to their anchorages in
the earth, could not be seen. Almost at the foot of the ladder was a
tank perhaps fifteen or eighteen feet square. Close by the tent was a
Ford sedan, and Hervey crept reverently up to it and read the words
on the spare tire cover DIVING DENNIVER. On the lower part of the
circumference was printed THREE HUNDRED FOOT DIVE. Diving
Denniver believed in advertising. In that tent lived the enchanted
mortal.
Hervey lingered in awe as a pilgrim might linger at a shrine before
entering. Then he walked rather hesitatingly to the open flap of the
tent. On a mattress which lay atop a huge red chest reclined Diving
Denniver in a bath robe. The chest had DIVING DENNIVER printed
on it, as also did a large leather grip, which bore the additional
information WONDER OF TWO CONTINENTS. If the world could
not see Diving Denniver on his dizzy perch, it at least could read
about him. Besides the makeshift divan the tent contained a rough
table formed by a red board laid on two saw horses.
On this was a greasy oil-stove and one or two plates and cups. In
his illicit wanderings, Hervey had at last trespassed through the
golden gates into heaven.
“I was walking around,” said he, rather unconvincingly.
Diving Denniver, a slim young man of about thirty, was smoking a
cigarette and looking over a magazine. It seemed incredible that he
should be thus engaged so soon after his spectacular descent.
 “Bimbo, that was some pippin of a dive,” said Hervey. Then, as
Diving Denniver made no attempt to kill him, he ventured to add, “Oh
bambino, that’s one thing I’m crazy about—diving.”
“Didn’t the cop see you?” the marvel asked.
“Leave it to me,” said Hervey. “There isn’t any cop there anyway.
Cops, that’s one thing I have no use for—nix.”
“Yere?” queried Diving Denniver, aroused to slight amusement.
“Do you—do you feel funny?” Hervey ventured as he gazed upon
the wonder of two continents.
“Where did yer git that hat?” asked the god of the temple. “What’s
all them buttons you got on it?”
“I climbed way down a cellar shaft to get one of those buttons,”
said Hervey, anxious to establish a common ground of professional
sympathy with this celebrity. “That’s the one,” he indicated, as he
handed Denniver his hat; “the one that says VOTE FOR TINNEY. He
didn’t get elected and I’m glad, because his chauffeur’s a big fool; he
chased me, but he couldn’t catch me. Some of those holes I cut out
with a real cartridge shell, like you cut cookies. I bet you feel funny,
hey?”
“Yere?” said Diving Denniver, examining the hat. “Well, do you
think yer could go back up there where the big noise is and then
come back here again—without gettin’ stopped?”
“You mean you dare me to?”
Diving Denniver roused himself sufficiently to reach over to a box
and grope in the pocket of a pair of ordinary trousers, the kind that
mortals wear. Then he tossed a quarter to Hervey. “Chase yourself
back there and get a frankfurter,” he said; “get a couple of ’em. And
don’t leave the cop see yer.”
So the wonder of two continents ate frankfurters—and scorned
cops. More than that, he and Hervey were going to eat a couple of
frankfurters together. At last Hervey felt that he had not lived in vain.
 CHAPTER XXVIII
THE LAW AGAIN
Hervey felt that he and Diving Denniver were pretty much alike
after all. The wonder of two continents beat all the boy scouts put
together. And he had now a fine precedent for his repudiation of
authority. Diving Denniver cared naught for cops and signs. Hervey
would have been glad to go into any court and cite this high
authority, confounding the powers with this frankfurter episode. He
was sorry he had not told Diving Denniver of his swimming across
the lake at Temple Camp (during rest period which was against the
rules). Instead of an honor he had received a reprimand for that. He
was a little afraid that some of the other boys would visit the wonder
in his tent, but in fact there wasn’t much danger of that. The wonder
was too much off the beaten track for most boys. Their thoughts did
not carry behind the scenes.
Hervey was now in much perplexity whether to witness the thrilling
exploit from the audience the next night or to view it from the
sanctum of the hero. In either case he intended to visit the remote
scene of enchantment with two frankfurters. He decided that he
would not demean himself by gazing at his hero with the idle throng.
He even negotiated an extra hour out from Mr. Walton in anticipation
of his second visit to the hermit of the ladder.
He could not possibly reach the place in the daytime, and besides,
he had to take up some bulbs for his stepmother the next day. For
this and other services he was to receive fifty cents. Twenty-five of
this would pay his admission to the carnival. With the other twenty-
five he intended to furnish forth a banquet of frankfurters for his hero
and brother daredevil. He could not afford to go twice in the day. He
had some thought of effecting an entrance over the high fence into
the field and having his entire fifty cents for the post-exploit feast. But
reckless as he was, he was cautious in this matter of reaching the
tent—there was so much at stake! So he decided to go respectably
in through the entrance and then cross the rope fence where the
“Positively No Admittance” sign was placed. It was not often that he
showed such a conservative spirit.
At half past eight, he found Diving Denniver strolling around in his
bathrobe outside the tent. Within, the odor of fried bacon and coffee
still lingered.
“You back again?”
“Sure, I want to see you from right here, and afterward I’m going
to go and get some more frankfurters. After you’re finished will you
let me go about ten or fifteen steps up the ladder and try it?”
Diving Denniver did not trouble himself to answer, but he ruffled
Hervey’s hair good-humoredly as he ambled about smoking his
cigarette. “Much of a crowd over there?” he asked.
“Oh bimbo, they’re all waiting. They stop dancing even when you
go up,” Hervey said.
“You’re a pretty slippery kid, all right, ain’t yer?” Denniver said.
“Ain’t there no guy up there at the rope?”
The words were scarcely out of his mouth when both he and
Hervey became aware of a policeman who had just come around the
side of the tent. But Hervey, though astonished, was not perturbed,
for he believed that the wonder of two continents would protect him.
One word from Diving Denniver and he would be safe. He even
ventured a defense himself.
“I’m going to do an errand for him,” he said.
“You can ask him yourself. So I’ve got a right to be here.”
But it appeared that it was Diving Denniver with whom the officer
had business. “Are you Charles McDennison?” he asked.
“Yere, what’s the dope?” the wonder asked, with a kind of
weariness in his voice.
Hervey was astonished, not to say shocked, that Diving Denniver
acknowledged the name of Charles McDennison.
“Let’s look at your permit,” said the officer.
Mr. McDennison entered the tent, presently emerging with a
paper.