The roles of humic substances in soil and crop sciences, discussed in detail in the preceding chapters of this book, are summarized here. The topics addressed include: the extraction, composition, characterization, and formation of soil humic substances. Particular attention is focused on the application of 13C-NMR spectroscopy to these materials. Other subjects addressed are the stabilization of soil organic matter through humification, sorption of nonionic compounds by soil organic matter, and sewage sludge humic materials. The influences of humic substances on soil fertility and plant growth are also discussed. The chapter concludes with an ecological view of humic substances that provides a rationale for their highly intractable nature.

3-D topographic surfaces ("topos") can be generated to visualize how pH behaves during titration and dilution procedures. The surfaces are constructed by plotting computed pH values above a composition grid with volume of base added in one direction and overall system dilution on the other. What emerge are surface features that correspond to behavior in aqueous solutions. Equivalence point breaks become cliffs that pinch out with dilution. Buffer effects become plateaus. Dilution alone generates 45 degrees ramps. Limitations of the Henderson-Hasselbalch equation can be seen by noting the conditions over which a plateau remains relatively flat. Because dissociation is driven by dilution, the surfaces demonstrate when the solution of a weak acid becomes indistinguishable from that of a strong acid. Surfaces are presented for hydrochloric acid, HCl (a strong acid); acetic acid, CH3COOH (a weak monoprotic acid); oxalic acid, HOOCCOOH (a weak diprotic acid) and L-histidine dihydrochloride, C6H9N3O2. 2HCl (a weak triprotic acid). Supplementary materials include suggested use of topos in lecture, as worksheets and in support of laboratory activities for first-year college courses and third-year analytical chemistry courses. Also provided is pH TOPOS, the macro-enabled spreadsheets that quickly generate surfaces for any mono-, di-, or triprotic acid desired. Only a change of acid dissociation constants, K-a values, is required.

Two characteristics of batteries, their delivery of nearly constant voltage and their rapid failure, are explained through a visual examination of the Nernst equation. Two Galvanic cells are described in detail: (1) a wet. cell involving iron and copper salts and (2) a mercury oxide dry cell. A complete description of the wet cell requires a three-dimensional Nernst surface because the potential is a function of two variables: the activities of both the oxidized and reduced forms in each redox couple. Dry cell potentials, which utilize solid or pure liquid species, are functions of only one variable and can be described by a pair of traces in a traditional plot. Plots of the Nernst potential are relatively flat for most activities, but they exhibit cliffs under extreme conditions. The flat spots are responsible for the fairly constant voltage that batteries deliver; the cliffs explain why batteries fail so quickly.

Two principles are presented that define the molecular nature and ecological role of humic substances (HS). The First Principle (i) accounts for and organizes an extensive body of apparently disparate data relating to the inability to purify and establish a molecular structure for HS; (ii) offers a conceptual framework for dealing with HS and for evaluating the applicability and limitations of various experimental methods; and (iii) identifies molecular heterogeneity, in combination with pronounced chemical reactivity, as constituting the essence of HS. Five corollaries to the First Principle spell out its consequences in more specific detail. New definitions of HS that offer greater insight into the molecular nature of these materials arise from the First Principle. The inapplicability of the molecular structure concept to HS is explained. The concept of hypothetical pseudostructures is introduced to help visualize the chemical reactions and interactions of HS without the unjustified assignment of specific structures to the material as a whole. Constraints in the design of experiments and in the interpretation of experimental data caused by the heterogeneous nature of HS are discussed. The Second Principle makes a connection between the molecularly heterogeneous and chemically reactive nature of HS and the ecological need for a reactive and persistent medium for plant growth. Concepts presented herein have broad implications in many fields, including chemistry, geochemistry, environmental and soil sciences, and ecology.

The binding of uranium(VI) by Suwannee River humic and fulvic acids was studied at pH values of 4.0 and 5.0 in 0.10 M NaClO4using an ion-exchange technique. Few data sets currently exist for metal binding to different molecular weight fractions from the same source. The complexation of U(VI) by citric acid was also studied under the same experimental conditions in order to "calibrate" the experimental and modeling approaches. For the citric acid system, the experimental results were analyzed using Schubert´s ion-exchange method, which indicated the formation of only a 1:1 uranyl-citrate complex. Close agreement was found for the values of log β1,1(6.69±0.03 at I = 0.10) determined from nonlinear regression of data collected at pH values of 4.0 and 5.0. This value represents a more direct measurement of the binding constant for the 1:1 uranyl-citrate complex than do other existing literature values derived from experimental data requiring the simultaneous consideration of 1:1 and 2:2 species.Both humic and fulvic acids were demonstrated to strongly bind U(VI), with humic acid forming slightly stronger complexes and exhibiting greater pH dependence. Analyses of the data for the humic and fulvic acid systems using the Schubert´s equation previously applied to the citrate system result in an apparent nonintegral number of ligands binding the uranyl ion. Schubert´s method is only appropriate for interpreting mononuclear complexes with integral moles of binding ligands. Thus, a more elaborate binding model was required and the data were interpreted assuming either: (1) a mixture of 1:1 and 1:2 uranyl-ligand complexes or (2) a limited number of high affinity sites forming a 1:1 complex. While both of these modeling approaches are shown to provide excellent fits to the data, the second is deemed more appropriate given the large size of humic and fulvic acid molecules as well as previous results obtained with other metal cations, such as Cu(II).

The equilibrium binding of Ca2+, Ni2+, Cd2+, Cu2+ and Zn2+ with unfractionated Suwannee river fulvic acid (SRFA) and an enhanced metal binding subfraction of SRFA was measured using Schubert’s ion-exchange method at pH 6.0 and at an ionic strength (μ) of 0.1 (NaNO3). The fractionation and subfractionation were directed towards obtaining an isolate with an elevated metal binding capacity or binding strength as estimated by Cu2+ potentiometry (ISE). Fractions were obtained by stepwise eluting an XAD-8 column loaded with SRFA with water eluents of pH 1.0 to pH 12.0. Subfractions were obtained by loading the fraction eluted from XAD-8 at pH 5.0 onto a silica gel column and eluting with solvents of increasing polarity. Schuberts ion exchange method was rigorously tested by measuring simultaneously the conditional stability constants (K) of citric acid complexed with the five metals at pH 3.5 and 6.0. The logK of SRFA with Ca2+, Ni2+, Cd2+, Cu2+ and Zn2+ determined simultaneously at pH 6.0 follow the sequence of Cu2+>Cd2+>Ni2+>Zn2+>Ca2+ while all logK values increased for the enhanced metal binding subfraction and followed a different sequence of Cu2+>Cd2+>Ca2+>Ni2+>Zn2+. Both fulvic acid samples and citric acid exhibited a 1:1 metal to ligand stochiometry under the relatively low metal loading conditions used here. Quantitative 13C nuclear magnetic resonance spectroscopy showed increases in aromaticity and ketone content and decreases in aliphatic carbon for the elevated metal binding fraction while the carboxyl carbon, and elemental nitrogen, phosphorus, and sulfur content did not change. The more polar, elevated metal binding fraction did show a significant increase in molecular weight over the unfractionated SRFA.

The relationship between acidity, Cu(II) binding and sorption to XAD resin was examined using Suwannee River fulvic acid (SRFA). The work was based on the hypothesis that fractions of SRFA eluted from an XAD column at various pH’s from 1.0 to 12.0 would show systematic variations in acidity and possibly aromaticity which in turn would lead to different Cu(II) binding properties. We measured equilibrium Cu(II) binding to these fractions using Cu2+ ion-selective electrode (ISE) potentiometry at pH 6.0. Several model ligands were also examined, including cyclopentane-1,2,3,4-tetracarboxylic acid (CP-TCA) and tetrahydrofuran-2,3,4,5-tetracarboxylic acid (THF-TCA), the latter binding Cu(II) much more strongly as a consequence of the ether linkage. The SRFA Cu(II) binding properties agreed with previous work at high ionic strength, and binding was enhanced substantially at lower ionic strength, in agreement with Poisson–Boltzmann predictions for small spheres. Determining Cu binding constants (Ki) by non-linear regression with total ligand concentrations (LTi) taken from previous work, the fractions eluted at varying pH had Ki similar to the unfractionated SRFA, with a maximum enhancement of 0.50 log units. We conclude that variable-pH elution from XAD does not isolate significantly strong (or weak) Cu(II)-binding components from the SRFA mixture.

researchers in three previously disparate areas of research (vascular biology, neuroscience and immunology) all stumbled on the same molecule.Within a short period of time, it was realized that NO was involved in the regulation of blood vessels, in communication in the brain, and in immunological defence against invading organisms.Now, NO impinges on almost all areas of biology.Not only is it important physiologically as a messenger that conveys signals from one cell to another in many different tissues but, through its toxic effects, it is also a likely player in many pathological processes.So it was decided that we need to have a journal devoted specifically to the molecule, Nitric Oxide: Biology and Chemistry.But do we?It could also be said that, because of its importance to so many areas of biology, a journal solely concerned with NO is a nonstarter: NO is really only interesting in context.After all, we don't have, or need, journals specifically about glutamate or acetylcholine or inositol trisphosphate.Viewed from this perspective, there is no shortage of journals in which to publish and read about NO research.In fact, almost any one will do.Nitric Oxide: Biology and Chemistry is a spin-off from Archives of Biochemistry and Biophysics and is also referred to as 'Part B' of that journal.The first issue appeared in February 1997 and, so far, only eight issues have been published (six of which were from last year) so it is possibly a little early to expect the journal to have found its flavour.The editors would like it to be a repository of papers about all aspects of the biology and chemistry of NO, but this is probably unrealistic.To date, there have been a few reviews, and a modest number (up to ten) of research papers per issue (except the latest: volume two, number two, which is a book of abstracts).Some of the better papers have come from the editorial advisory board's research groups.These aside, the journal appears to be falling into its default guise, which is Archives of Biochemistry and Biophysics Part B. The parent journal has long had a penchant for chemically oriented research into reactive free radicals, and NO does have this chemical characteristic (although it is not very reactive).Of course it is important that the chemistry of NO and related species, such as the much more reactive peroxynitrite anion, does become better understood.Indeed, it is just this type of research that one imagines could find a home in a journal devoted exclusively to NO.The problem is that, when the chemistry is not constrained within a biological framework, you can get free radicals to do almost anything.

Fulvic acid, isolated from the Suwannee River, Georgia, was assessed for its ability to bind Ca2+, Cd2+, Cu2+, Ni2+, and Zn2+ ions at pH 6 before and after extensive fractionation that was designed to reveal the nature of metal binding functional groups. The binding constant for Ca2+ ion had the greatest increase of all the ions in a metal binding fraction that was selected for intensive characterization for the purpose of building quantitative average model structures. The “metal binding” fraction was characterized by quantitative 13C NMR, 1H NMR, and FT−IR spectrometry and elemental, titrimetric, and molecular weight determinations. The characterization data revealed that carboxyl groups were clustered in short-chain aliphatic dibasic acid structures. The Ca2+ binding data suggested that ether-substituted oxysuccinic acid structures are good models for the metal binding sites at pH 6. Structural models were derived based upon oxidation and photolytic rearrangements of cutin, lignin, and tannin precursor...