Modern Techniques in Water and Wastewater Treatment

INTRODUCTION AND OVERVIEW OF APPROACHES

A.J. Priestley

CSIRO, Division of Chemicals and Polymers,

Private Bag 10, Rosebank MDC, Clayton, VIC 3168 Australia

INTRODUCTION

The papers presented at the CSIRO/UNIDO workshop on Modern Techniques in Water and Wastewater Treatment and contained in this publication cover a variety of aspects of water and wastewater treatment from both a scientific and practical point of view. The authors range from research scientists, through technical consultants to industry practitioners and their papers thus provide a wide range of viewpoints on the subject. The main segments of the workshop covered physicochemical and biological approaches to treatment as well as aspects of sludge/residue treatment and disposal. With the obvious diversity of subjects addressed, it is informative to identify the key scientific and technical elements which underlie all of these approaches to water and wastewater treatment.

APPROACHES TO WATER AND WASTEWATER TREATMENT

Any attempt to unify the many approaches to treating water and wastewater must firstly look at the nature of the impurities which need to be removed from the polluted water. There are many possible ways to classify these impurities. One approach which can be easily related to the different treatment processes is given in Table 1 and is based on a matrix of chemical nature of the impurity versus its particle size. This approach is discussed in detail in the paper by Kolarik and Booker on page 7. Some examples of pollutants are given in each size category.

The chemical or biological nature of the pollutant is important in selecting the treatment process. Inorganic pollutants, ranging from dissolved solids to dispersed clays and grit are usually not chemically reactive, but need to be removed for a variety of reasons. For example, dissolved salts are undesirable in drinking water and boiler feed water applications, while dispersed clays can harbour infective microorganisms and other impurities on their surface.

Table 1. Categorisation of water pollutants and examples

Because of their chemically unreactive nature, removal of inorganic pollutants must involve a phase separation step, with the separation becoming more difficult as the particle size decreases. Organic pollutants are, in general, more reactive, both chemically and biologically, than inorganic pollutants and consequently can also be removed by chemical or biological reactions as well as phase separation. Particularly for the dissolved organic impurities, the reaction approach may be more desirable. The major concern with biological impurities usually involves their pathogenicity, which can be destroyed by a number of techniques e.g. heat, time, radiation, oxidising conditions. However, as the reduction in pathogenicity can never be guaranteed to be complete, a phase separation of the inactivated microorganism is still necessary. Again in general, the smaller the microorganism the more difficult it is to separate.

As illustrated by the papers in this book, there are basically two approaches to removing pollutants from water, either destroy them or separate them into a semi-solid sludge. The basic properties of these two approaches are outlined in Tables 2 and 3 and identify particular technologies which have been developed around each approach. As indicated in the previous paragraph, the more reactive pollutants can be destroyed or transmuted to another form by either a reduction or oxidation step. Both chemical and biological means can be utilised to achieve this goal, with the approach taken depending on particular circumstances. As biological reactions are generally much slower than chemical reactions, the former approach involves more capital equipment but has a much lower operating cost. However, nearly all approaches eventually have to rely on some form of phase separation and the technologies listed in Table 3 form the basis of much water and wastewater treatment technology. While the listing given in Table 3 is not exhaustive, it does demonstrate the wide range of technologies which can be applied to this problem. Again, the removal of the finer particles represents a more difficult task and, consequently, most technical developments are concentrated on this more challenging end of the spectrum.

Table 2. Methods for destruction of water pollutants

Table 3. Methods for separation of water pollutants

Another aspect of water and wastewater treatment, which is becoming increasingly important, is the treatment and final disposal of the sludge generated by the treatment operation. Virtually all treatment processes generate a final residue, which is a concentration of the pollutants removed from the water. As treatment processes become more widely adopted, much more attention will have to be focussed on the ultimate disposal of this residue. As illustrated in the article by Chris Burt on Sludge Disposal, Options Study for the Sydney Water Board, many avenues will have to be explored before the optimum disposal route is identified. Technologies, both simple and complex, are being developed to handle sludges and some are described in the workshop papers. In general, local conditions and economics are vital to the selection of the most suitable technology.

The papers presented in this workshop give an insight into the characteristics and applicability of each technology. Understanding the suitability of a technology for a particular application really only comes from experience. However, it is hoped that these proceedings, by providing examples of both theory and practice, will contribute to the transfer of the knowledge and understanding which underlies every successful technology.

Section 1

PHYSICO-CHEMICAL PROCESSES IN WATER AND WASTEWATER TREATMENT

FUNDAMENTALS OF COAGULATION–FLOCCULATION PROCESSES IN WATER TREATMENT

L.O. Kolarik and N. Booker

CSIRO Division of Chemicals and Polymers,

Private Bag 10, Rosebank MDC, Clayton, VIC 3169 Australia

ABSTRACT

Coagulation and flocculation processes are widely used in water and wastewater treatment to remove undesirable particulate colloidal and suspended impurities.

The size and surface characteristics of a particulate impurity are both important parameters affecting its separation from solution. The efficiency of the physico-chemical processes for removing such impurity increases with increasing size and decreasing surface charge. Coagulation and flocculation processes are used to reduce the surface charge and to promote the agglomeration of the colloidal or suspended impurity to form large, settlable, floatable and/or filterable agglomerate called flocs.

The chemical-physical and engineering aspects of the coagulation–flocculation processes are discussed in this paper.

WATER-BORNE IMPURITIES

The aim of any water purification process is the removal of undesirable contaminants. Knowledge of the physico-chemical characteristics of the water-borne constituents is important for an understanding of the process.

We can classify the constituents of natural waters and wastewaters in accord with their size and origin. The size spectrum of water-borne contaminants is rather broad, ranging from simple molecules to large suspended particles. The impurities can be divided into three broad size categories based on nominal diameter:

There are no rigorous boundaries between the three groups.

Size is an important general parameter, since it determines the physico-chemical properties of various components and governs selection of the process for their removal from solution. The data in Table 1 emphasise the importance of particle size in the ease of separation from water.

While particles larger than 10 μm can be removed by filtration or sedimentation, the smaller ones will not settle to any significant extent. Submicron particles can be removed by a suitable membrane filtration or by their agglomeration and sedimentation.

The water-borne contaminants are derived from various sources. Inorganic and organic substances are always present in varying proportions and concentrations. They are introduced into water by land erosion, dissolution of minerals, the decay of organic matter, and from domestic and industrial discharges.

Table 1. Sedimentation rates of spherical silica particles of various diameters (density = 2.5 g cm−3)

Coarse and dissolved impurities

The coarse suspended impurities do not cause a serious problem in water treatment and can be removed readily by coagulation, sedimentation and filtration.

The dissolved contaminants can be separated into three groups: organic, inorganic and gases. The term ‘organic matter’ in water represents literally thousands of organic compounds often present in minute quantities. These are naturally occurring substances and compounds introduced by man.

Naturally occurring substances such as geosmin, 2-methyl isoborneol, sesquiterpene alcohols and n-heptanal for example are the products of algae and fungi metabolism.¹ Such substances often contribute to the taste and odour of the water. The colour of the water is usually caused by a group of substances — humic substances — which will be discussed later.

Attention is currently focused on the substances introduced into water by man. Synthetic organic contaminants in natural water are derived from two principal sources: (a) products of chlorination of drinking water, such as trihalomethanes, and (b) from direct or indirect industrial discharges, agricultural sources and runoff. This latter field is being intensely studied because of the toxicity or potential toxicity of such substances.

A diversity of inorganic constituents and gases are present in any water or wastewater. The presence and concentration of various components are responsible for the physico-chemical characteristics of water. A number of parameters must be considered prior to distribution and/or treatment. These include the heavy metals content, toxicity, total concentration of dissolved ions, pH, alkalinity, turbidity and colour.

Colloidal dispersions

The coagulation–flocculation processes remove mainly the suspended particulates of colloidal dimension. Most of the colloidal systems can be described as systems consisting of a homogeneous continuous phase in which dispersed particles are suspended. The properties, classification and characterisation of the colloidal state have been presented in a number of texts.²–⁴ The dispersed particles are large compared with small molecules of inorganic salts. While size is an important characteristic of the colloidal state, there is no sharp distinction between colloidal and non-colloidal systems at either end of the spectrum. With decreasing particle size, surface area of particles per unit volume increases sharply and so does the proportion of molecules situated at the interface. With diminishing size the properties of the interface become increasingly significant. The factors that contribute most to the overall nature of a colloidal system are: particle size, shape and flexibility, surface charge, particle–particle and particle–solvent interaction. Due to such interactions the particles form a stable dispersion and will not settle in a reasonable time. The size effects for submicron particles are also demonstrated by kinetic and optical properties such as Brownian motion and light scattering (Tyndall effect). Light scattering or turbidity is the simplest optical parameter that can be measured in water. A nephelometric method of turbidity measurement that uses synthetic colloidal latex-formazine as a standard is commonly used in water research and in industry.⁵ The measurement is empirical and qualitative only, but indicates the presence of suspended particles in water and thus indicates the effectiveness of a water treatment process.

Classification of colloidal systems in natural waters

The colloidal matter in natural waters can be broadly classified by its nature as shown in Table 2.

There are certain characteristics typical of each group. Particulate colloids usually have geometric shapes. For example, Fe2O3 and clays are platelike particles⁴,⁶ usually of limited porosity. When suspended in water they acquire characteristic surface properties as will be discussed later. Metal hydroxides have some special properties and can be categorised as an intermediate group having characteristics common to both particulate and macromolecular materials. They are usually amphoteric, three dimensional fairly rigid structures compared with insoluble organic macromolecules. The hydrolysis products of Fe³+ and Al³+ ions form polymeric species as precursors to either amorphous or crystalline precipitates.⁷ The particulate fraction of the colloidal system can readily be removed by coagulation and filtration.

As a rule the substances belonging to the macromolecular group are more difficult to remove than the particulates. Depending on their size they may elude the purification process. Humic substances, which are by-products of decomposition of natural organic matter in soil and water, are a typical and most common example belonging to this category. Such substances are an extremely complex and diverse group of organic materials. Despite significant efforts their structures are still not well defined, but the nature of their major functional groups is well established. Generally they are described as amorphous, polymeric hydrophilic, acidic polydisperse substances of molecular weights ranging from several hundred to tens of thousands.⁸ Traditionally they are divided into three broad groups on the bases of their solubility in dilute acid, base and ethyl alcohol.⁹ The term humic acids generally refers to the fraction that is soluble in alkali but insoluble in acid or alcohol. The compounds of the acid soluble fraction are called fulvic acids and that material which is precipitated by acid but soluble in alcohol is made up of hymatomelanic acids.

Table 2. Classification of colloidal matter in natural waters

Fulvic acids are usually associated with the lower molecular weight material present in water, while the humic acids are the higher molecular weight fraction. However, it is impossible to categorise these substances quantitatively. While the smaller molecular fraction belongs in the soluble organic group, the macromolecular substances are legitimate representations of the colloidal state. It also appears that the fulvic acid group is not completely removed by coagulation processes and is thought to be responsible for the residual dissolved organic carbon (DOC) in the product water.

Humic substances were first associated by Rook¹⁰ and Bellar¹¹ with the formation of trihalomethanes in drinking water. Another important characteristic of these substances is their ability to complex with various metal ions including iron and aluminium.¹² Humic substances contribute to the colour of water and their concentration is expressed in units based on similarly coloured platinum-cobalt based standards.⁵

The foregoing classification of the constituents of natural waters is an arbitrary one, designed to simplify the description of a system because the components may interact with each other. The physico-chemical characteristics of a particular water reflect the interplay of the various fractions.

Colloidal dispersions play the dominant role in water clarification processes, and their removal is usually the main aim of a process. Coagulation–flocculation–sedimentation–filtration processes are currently the most effective means for removal of colloidal dispersions on the large scale.

TERMINOLOGY

Particles in natural waters and wastewaters can remain as individual entities for an appreciable time only if they are prevented from agglomerating on collision. The like electric charge that they carry will cause repulsion when they approach each other. Alternatively, the particles are coated by an adsorbed layer of a substance (e.g. a polymeric material) that forms a barrier to their collision. These two mechanisms are called electrostatic and steric stabilisation, respectively, where the term stability refers to the aggregation behaviour of the system. However, if the collisions, for some reason, result in aggregation of the particles, the system is colloidally unstable and such a process is called coagulation.⁴

There is no fully defined and universally accepted use of the terms coagulation and flocculation in the water treatment industry. Both terms usually describe a process of aggregation of colloidal particles. Often the terms are used interchangeably, irrespective of the mechanisms involved.

There is a good reason, however, for separation of these two terms in the context of water treatment. Regardless of the mechanism, destabilisation of a colloidal system leads to its coagulation. In practice, small aggregates are formed that would still not settle in a reasonable time. Further contact has to be provided to allow formation of large enough agglomerartes — flocs — that can be removed. Thus the process of agglomeration consists of two distinct steps which must be successfully accomplished to achieve efficient clarification of water.¹³

Coagulation is the process of destabilisation of a colloidal dispersion in which the forces causing stability of a given system are overcome. This is, in practice, carried out by the addition of inorganic or organic substances: primary coagulants such as aluminium sulfate or a suitable cationic polyelectrolyte.

Flocculation is the process in which destabilised particles, or particles formed as a result of destabilisation, are further contacted to form larger flocs. Flocculation is often aided by the addition of flocculant aids — polyelectrolytes that accelerate the rate of floc formation and make the flocs mechanically more stable. Formation of larger settlable flocs is the desired product of the two processes.

ASPECTS OF SURFACE AND COLLOID CHEMISTRY

The classification presented above illustrates the complex chemistry of natural and wastewaters and shows that the colloidal fraction is able to exist in a dispersed state. Such colloidal systems are said to be stable in that the colloidal particles remain as independent entities to produce a dispersed system.³

Origin of surface charges and the formation of an electrical double layer

Particulate matter in contact with water acquires a surface electric charge. This charge in turn influences the distribution of ions on the solution side of the interface. The process of charge redistribution is described as the formation of an electrified interface or electrical double layer (edl).

The surface charge on particles can be generated by:¹⁴

• The ionisation of functional groups such as -COOH to -COO−;

• The solid may dissolve unequal quantities of ions of one charge, e.g. Agl;

• The solid may adsorb ions of one kind unequally; and

• Adsorption and orientation of dipolar molecules.

Inorganic oxides and hydroxides develop their surface charge potential and the edl by the unequal adsorption of H+ and OH− ions. For such systems H+ and OH− are called potential determining ions. The adsorption mechanism is attributed to the amphoteric reaction of the surface hydroxyl groups >M–OH. Depending on the pH, the surface acquires a positive, (>M– ), or negative (>M–O−) charge. The total surface charge of oxides can be determined by an acid-base potentiometric titration that also gives the point of zero charge (pzc), a pH value specific for each oxide.

Clay minerals derive a great part of their fixed surface charge from isomorphic substitution of, for example, Si⁴+ by Al³+. This process produces negatively charged platelets.⁶ The charge on clays is a bulk charge in contrast to the surface charge structure of oxide and is usually expressed as an ion exchange capacity. While the platelet surfaces are negatively charged due to the isomorphic substitution the edges can be positive through oxide-like dissociation.

As noted earlier, there is a general tendency for dispersed particles in natural waters to acquire adsorbed films of inorganic and organic polymeric species. Dissociation of the functional surface groups, rather than the nature of the original particle, will then be the main charging mechanism. The charge is usually negative, but in the case of amphoteric materials (proteins) the particle can also become positively charged and show a pzc. This charging mechanism also applies to biocolloids, i.e. viruses, algae and bacteria.¹⁵

The surface charge on colloidal particles must be balanced by a counter charge. The counter-ion charge depends on the composition of the electrolyte solution. A negative charge will be balanced by counter charge of cations in a ratio depending on the bulk concentration of different cations and valency. Various models of the particle-solution interface showing the potential as a function of distance from the surface and the planes of adsorption have been discussed in detail by Hunter.⁴

Electrokinetic or zeta potential (ζ)

The surface potential of a particle is not a readily accessible parameter. It is often preferable to work with another double layer potential which can be determined experimentally with relative ease, i.e. with the electrokinetic or zeta potential (ζ). The significance and measurement of ζ have been reviewed extensively in the literature.¹⁴,¹⁶,¹⁷

Electrokinetic phenomena are associated with a movement of two phases relative to each other. The ζ is the potential at the ‘shear’ or ‘slipping’ plane between those two charged phases when one of the phases is moved tangentially to the other. It is now accepted that ζ measures the electrostatic potential at, or very near to, the beginning of the diffuse part of the double layer. Electrokinetic techniques such as electrophoresis, electroosmosis and streaming current/potential are used to measure this potential. The most common methods are electrophoresis in which the liquid is stationary and the particles are moved by an applied electric field, and streaming potential, where electrolyte is moved relative to the immobilised solid phase. The electrokinetic data can be used for quantitative measurements of various surface parameters of the particles by postulating mathematical models.

An important parameter also derived from the electrokinetic measurements is the isoelectric point (iep) of the surface. The iep is defined as the concentration of potential-determining ions at which ζ = 0 when only surface inactive ions from an indifferent electrolyte are present. During electrophoretic measurements, when the mobility of a particle is determined as a function of pH, there is a certain pH value at which the electrophoretic mobility is zero. This pH is called the iep. At the iep the net surface charge is zero. From this definition and from the definition of pzc, it can be seen that these two terms are not interchangeable except in the case of an indifferent electrolyte being present. The important point is that the iep and pzc are solely dependent on the properties of the particle surface and the solvent. They are characteristic parameters for such a surface.

Double layer interactions and coagulation of particles

The properties of the double layer control, to a large extent, the interaction between colloidal particles, and the adsorption of charged chemical species from the suspending medium. The various forces that are involved when two colloidal particles or two double layers approach one other have been examined in detail by Hunter.⁴

The term colloid stability is used to cover the interaction of dispersed particles and their aggregation or resistance to aggregation. It is closely related to the properties of the electrical double layer at the solid-solution interface. A colloidal system may be considered stable if there is no change in the total number of particles with time. Thus kinetically, many dispersions have a high degree of stability, and the aggregation of such particles is extremely slow. This is due to a repulsive interaction between the electrical double layers which limits the rate of coagulation. The stability of a dispersion is determined by the properties of the double layers of interacting particles, e.g. by the magnitude of their respective ζ.

Most stability theories have been derived for idealised dispersions and have been studied under strict laboratory conditions. The assumptions made, such as uniformity of shape and surface properties and interaction under controlled electrolyte composition, differ from conditions existing in natural waters. There, because of the broad particle size range and the irregular shape of particles, the almost limitless combination of water-borne constituents makes evaluation difficult.

Colloidal stability is a result of a balance of the forces acting within the system. The main forces of interaction between particles may be separated into three categories:

1. An electrostatic force (Vr) that arises from the overlap of double layers on particles during collision. Such force can be attractive or repulsive, depending on whether particles are of opposite or the same sign of charge.

2. Attractive London-van der Waals force (Va); and

3. The repulsive force caused by solvation, adsorbed large molecules, etc.

The most widely accepted theory of colloidal stability was independently derived by Deryaguin and Landau¹⁸ and Verwey and Overbeek,¹⁹ and is known as the DLVO Theory. Based on the interaction of electric double layers of colliding lyophobic (insoluble) particles, this theory considers only electrostatic repulsion and van der Waals attraction, to give a total energy of interaction Vt = Vr + Va. Other forces, now called non-DLVO forces, such as hydration, hydrophobic and steric interaction and polymer bridging were not considered. The theory also offers an explanation of the valency effect of the counterions on stability, i.e. Schulze-Hardy rules, as discussed in detail by Hunter,⁴ and with an emphasis on water treatment, by Gregory.²⁰

Here it will suffice to say that the DLVO theory provides a quantitative explanation of interactions in colloidal systems and colloid stability under restricted conditions. It also defines the concentration of specific electrolyte required to just coagulate a colloidal dispersion, the critical coagulation concentration. According to the experimental Schulze-Hardy rule this effect is determined by the counter ion and is strongly influenced by the ion valency, as is also predicted by this theory. The energy relationships, as applied in DLVO theory, i.e. Vt VS distance of separation, can be used for the assessment of stability of a colloidal system. However, they do not give direct information on the coagulation rate that is a more useful criterion of colloidal stability.

To make predictions of the behaviour of a particular colloidal dispersion, it is necessary to know:

• the surface characteristics of the particles — the ζ is usually used as an approximation,

• the magnitude of the attractive forces between the particles, and

• the dimensions of the particles.

In aqueous systems these three parameters control the potential energy relationships. When the combination of ζ of the particles and the ionic strength of the solution is such that the repulsion is stronger than the attraction, the particles will repel one other. There is a potential energy barrier preventing collision of the particles and their coagulation. When this energy barrier is reduced by increasing the ionic strength thus reducing the magnitude of ζ, the particles can agglomerate more readily. By removing the barrier altogether, theoretically, each collision will result in attachment. The system is destabilised and undergoes a rapid coagulation.

PRACTICAL IMPLICATIONS

The DLVO theory cannot be easily applied to control water purification processes. This is mainly due to the complexity of natural water and wastewater systems in which a variety of solids of different materials, dimensions and shapes is suspended in complex electrolyte matrixes, and to the relatively complicated and expensive experimental methods needed, e.g. measurement of ζ. Hence coagulant or flocculant doses are still being determined empirically rather then calculated from the measured surface characteristics of the dispersion. However, the theoretical considerations derived from pure well defined systems give us an understanding of the coagulation process in general terms.

Colloidal dispersions can be destabilised by increased electrolyte concentration, boiling, ultrasound, addition of an excess of hydrophobic colloid, adsorption of ions or particles at the interface and, sometimes, by just agitating the suspension with or without pH control. However, the main destabilising mechanisms that are applicable for water treatment on a large scale are:²¹,²²

• Charge neutralisation via specific adsorption of positively charged