1.

Humic Substances : Structures, Models and Functions

Edited by
Elham A. Ghabbour
Soil, Waterand Environmental Research Institute, Alexandria, Egypt
and Northeastern University,Boston, USA
Geoffrey Davies
Northeastern University,Boston, USA

 humic substances (HSs), the remarkable brown biomaterials in animals,

coals, plants, sediments, soils and waters.
 HSs buffer pH, retain water, are photo-active, are redox catalysts, sorb
solutesand bind metals.
 Nature can switch these properties on or off, depending on the
circumstances. In other words, HSs can respond when nature demands
 HSs are nimble species with a strong tendency to congregate.
THE FIRST PRINCIPLE OF HUMIC SUBSTANCES
Humic substances comprise an extraordinarily complex, amorphous
mixture of highly heterogeneous, chemically reactive yet refractory molecules,
produced during early diagenesis in the decay of biomatter, and formed
ubiquitously in the environment via processes involving chemical reaction of
species randomly chosen from a pool of diverse molecules and through random
chemical alteration of precursor molecules.
Corollary A. Humic substances are devoid of a regularly recurring,
extended skeletal entity.
 no long-range chemical order recognizable
 no identifiable backbone or skeletal structure

Corollary B. Humic substances cannot be purified in the conventional

meaning of purity.
Corollary C. The essence of humic substances resides in the combination
of their extreme molecular heterogeneity and pronounced chemical
reactivity.
Corollary D. Humic substances from different sources display a
remarkable uniformity in their gross properties.
Corollary E. It is not possible to write a molecular structure, or set of
structures, that fully describes the connectivity within molecules of a humic
substance

1. The terms heterogeneous and heterogeneity, as used in the principle and

throughout this paper, include the lack of structural regularity within
and among the humic molecules.
2. The term refractory means that the substrate resists decomposition by
microorganisms
 microbial degradation of humic substances is considerably slower than that
of discrete biopolymers
 The formation of humic substances occurs during early diagenesis of
biomatter
 Materials that do not originate from the decay of biomatter in soil, sediment or
natural waters should not be considered as humic substances
Chemical Reactivity
Humic substances
 Have an abundance of carboxyl groups and also possess
weakly acidic phenolic groups
 Acidity, complexation, redox active and ion-exchange
properties of humic materials
 Possess free-radicals
 Can bind small molecules through both hydrogen bonding and nonpolar
interactions
 Exhibit both hydrophobic and hydrophilic characteristic sand can bind to
mineral surfaces
Inability to Separate and purify
 from classical methods such as fractional precipitation" to
the more modern separation techniques including
chromatography, electrophoresis and field-flow
fractionation
 molecules in a humic system differ gradually from one
another in their ] chemical and physical properties in a
continuous manner : inability to separate these materials into
pure components
 highly complex and heterogeneous nature
 highly heterogeneous and molecular complexity :
refractory nature
Molecular Nature
 made up of a series of molecules of different sizes, few having
precisely the same structural configuration or array of
reactive functional groups
 perhaps no two molecules of humic substances are exactly alike
Composition of humic substances (e.g. Functional group
contents)
 Chemical and Thermal degradative methods and chemical
derivatization.
 Identifying aromatic and aliphatic components among the
degradation products.
 no molecular entity has been identified as constituting a
molecular backbone of the molecules in humic substances.

Model for the formation of humic substances

1) microbial decomposition of the biomatter into smaller

molecules.
2) small molecules are then consumed as an energy and
carbon source by microbes with the release of other small
molecules.
3) formative step: some of the initial degradation products
and the microbially-produced diverse small molecules,
chosen randomly from the mixture, undergo Condensation
reactions to generate
substances that, unlike the initial biological matter,
resist breakdown by the organisms themselves.
That is, refractory materials are produced.
Other proposed models for the formation of humic
substances
  involve chemical alteration at sites along polymer chains
of biomolecules such as lignin or partially degraded lignin.
 These alterations could include condensation, hydrolytic
or oxidative processes.
 Such reactions, occurring randomly, would contribute to
increased heterogeneity within a system

 (Swaby and Ladd) : humus "is not synthesized enzymatically,

but by heterogeneous chemical catalysis ...I1involving
"...chaotic chemical combination of monomers produced
enzymatically".
 humic substances are formed ... via processes involving
chemical reaction of species randomly chosen from a pool of
diverse molecules and through random chemical
alteration of precursor molecules. This random feature in the
humic formation processes contributes to the molecular
heterogeneity that is intrinsic to humic substances.
Uniformity and Variability Among Humic Substances
Common features
 The uniformity is evident in many humic properties
despite the diversity in geographic location, botanic
origin and climatic conditions:
 Elemental compositions of humic substances from all over
the world are remarkably similar. All humic substances
exhibit the same general array of functional groups and
there are no major compositional differences between old
and recent humic materils.
 All humic substances exhibit the same types of reactions
and interactions
 Molecularly heterogeneous but macroscopically
homogenized mixture, regardless of the source material.
Equilibrium Mixture
 A given humic sample in the aqueous state would then
represent an equilibrium condition that could be disturbed by
a fractionation, after which a new equilibrium would be
established in the resulting fractions.
 Contributing to the inability to purify and to establish
detailed structural features of humic substance.
 Include various types of noncovalent forces such as
hydrogen bonding.
 While humic substances as a whole are persistent
materials, some of the individual molecules may have a more
transitory existence

Four features contribute to the heterogeneity of a mixture

I. The multiplicity of the system, i.e. The number of
structurally different molecules (per mole or per stated
number of moles) in the system;
II. The molecular diversity, i.e. The extent to which those
molecules differ from each other;
III. Polydispersity, i.e., the range of molecular weights
displayed by the molecules, and
IV. Chemical equilibrium in which molecules constantly
associate and dissociate.
Humic substance as a Supermixture
 Macroscopic system comprising an ensemble of molecules
where no two molecules have identical molecular
structures would have an extremely high multiplicity, but
would not necessarily represent a very high degree of
complexity.
 Ensemble of molecules lacking a common, regularly
recurring, identifiable skeletal structure or other long-
range order
 larger the constituent molecules, the greater the
statistical opportunity for increased molecular diversity.
 variations in molecular weight among the species
(polydispersity) would add another dimension to the
complexity.
A supermixture is defined in conceptual terms as a mixture
having a degree of complexity and heterogeneity equivalent to
that of a large ensemble of molecules where no two molecules
are identical, where the molecules are essentially devoid of a
regularly recurring, extended skeletal entity and display a high
degree of molecular diversity
 Supermixture has both a high multiplicity and a high
diversity, and it generally would be Polydisperse

Ceramic Membranes
 for ultrafiltration and microfiltration.
 microporous membranes
 made from aluminum, titanium, or silicon oxides.
 Advantages: chemically inert and stable at high temperatures,
 suitable for food, biotechnology, and pharmaceutical applications in
which membranes require repeated steam sterilization and cleaning with
aggressive solutions
  Pore diameters :0.01 to 10 μm
 made by a slip coating-sintering procedure.
Slip coating-sintering process, a porous ceramic support tube is made by
pouring a dispersion of a fine-grain ceramic material and a binder into
a mold and sintering at high temperature.

Chapter 1: Overview of Membrane Science and Technology

1. Historical Development of Membranes
2. Types of Membranes
 Isotropic Membranes
 Anisotropic Membranes
  Ceramic, Metal, and Liquid Membranes

Chapter 2.: Membrane Transport Theory

 The Solution-Diffusion Model
 The Pore-Flow Model
 Permeation in Ultrafiltration and Microfiltration Membranes
 Knudsen Diffusion and Surface Diffusion in Microporous
Membranes.

Chapter 3: Membranes and Modules

 Isotropic Membranes
 Isotropic Nonporous Membranes
 Isotropic Microporous Membranes
 Anisotropic Membranes
 Phase separation membranes
 Interfacial Polymerization Membranes
 Solution-Coated Composite Membranes
 Repairing Membrane Defects
 Metal, Ceramic, Zeolite, Carbon, and Glass Membranes
 Hollow Fiber Membranes
 Membrane Modules
 Plate-and-Frame Modules
 Tubular Modules
 Spiral-Wound Modules
 Hollow Fiber Modules
 Other Module Types
 Module Selection

Chapter 5: Reverse Osmosis

 Introduction and History
 Theoretical background
 Membranes and Materials
 Cellulosic Membranes
 Noncellulosic Polymer Membranes
 Interfacial Composite Membranes
 Reverse Osmosis Membrane Categories
 Seawater and Brackish Water Desalination Membranes
 Nanofiltration Membranes
 Hyperfiltration Organic Solvent Separating Membranes
 Membrane Selectivity
 Membrane Modules
 Membrane Fouling Control
  Scale, Silt, Biofouling, Organic Fouling
 Membrane Cleaning
 Brackish Water Desalination, Seawater Desalination, Ultrapure Water,
Wastewater Treatment, Nanofiltration. Organic Solvent Separation