EP 99-5266 Removal of Heavy Metals From Wastewater

SIEP 995266 ii Restricted
Summary
Environment and Resource Technology Ltd. was contracted by SIEP, The Netherlands to carry out a
desk study on treatment methods for the removal of heavy metals from wastewaters.
As well as information on treatment methods, analytical methods for the detection and determination
of heavy metals were identified.
There are a number of areas in which the development of systems for the removal of heavy metals has
been carried out. Most of this has been in the areas of land remediation and treatment of non-saline
waters. Though treatment methods for a number of solid and liquid effluents were looked at, the
focus of this study was on systems suitable for offshore oil and gas production waters.
Heavy metal removal processes were grouped into a number of treatment types
 adsorption and absorption,

 advanced affinity chromatography,
 biological treatment,
 chemical treatment,
 distillation treatment,
 electrochemical treatment,
 reverse osmosis,
 ion exchange,
 filtration,
 combined systems.
For each treatment technology, three different status areas were identified:
 vendor systems commercially available;

 research currently undertaken;
 patents available.
In general, response from equipment vendors was disappointing. Therefore, the internet sites for these
vendors were located and as much information as possible was extracted in this way.
The information obtained indicated that a large proportion of the work in the removal of heavy metals
remains at the research and development stage. Of the limited number of systems currently available,
few are likely to be capable of being used offshore on produced waters. The particular properties of
produced waters that present difficulties for heavy metal removal are:
 salinity
 presence of free oil
 high temperatures,
 low concentrations of heavy metal ions in relation to other ions.
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In particular, highly saline produced waters, will affect the different treatment types in the following
ways:
 adsorption and absorption – altered chemistry of the water alters the required chemistry of the
adsorption or absorption media,
 advanced affinity chromatography – saline reduction would be required prior to
chromatographical treatment,
 biological treatment – inhibition of bacterial performance under saline conditions,
 chemical treatment – different water chemistry and thus chemical treatment chemistry between
saline and non-saline waters,
 distillation treatment – removes all salts, thus high salinity has little effect, but large volumes of
waste salt concentrates are produced
 electrochemical treatment – may result in large amounts of chlorine gas being produced with
saline waters,
 reverse osmosis –can remove all ions, thus the higher the salinity, the larger the plant,
 ion exchange – media would require specific acceptor sites to remove the heavy metal ions in
preference to highly concentrated sodium ions,
 filtration – difficult to separate only heavy metals in the presence of high concentrations of the
other cations by pH adjustment and/or chemical coalescence and precipitation,
 combined systems – any of the above.
The main reason for the limited interest in the removal of heavy metals from oil and gas production
water appears to be the lack of legislation in controlling such discharges. Future legislation and the
adoption of ‘zero discharge’ policies may soon require heavy metal discharge control. Therefore,
research into systems specific for offshore produced water treatment is required where conditions of
high salinity, oil contamination up to 40 ppm (or greater) and low concentrations of heavy metals are
predominant. Systems so far developed are mainly for treatment of freshwater and industrial
wastewater systems where low salinity and high concentrations of heavy metals are the norm.
Thus, to summarise, for specific treatment of produced water, heavy metal removal is required to be
undertaken in conditions of high salinity, oil contamination and temperatures possibly above 50 oC.
These conditions restrict the use of most of the systems identified in this report. Treatment methods to
show the most potential will be systems that will remove heavy metals in preference to the more
abundant alkaline and alkaline-earth metals. The most suitable systems should therefore include one
or more of the following technologies:
 adsorption and absorption,

 chemical treatment (with filtration),
 advanced affinity chromatography.
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Contents
SUMMARY II
1 INTRODUCTION 1
2 DEFINITION OF HEAVY METAL 2
3 CHEMISTRY OF HEAVY METALS 3
3.1 Sources of heavy metals in aquatic environments 3
3.2 Types of heavy metal compounds in the aquatic environment 4
3.3 Behaviour of heavy metals in the aquatic environment 6
3.4 Heavy metals in North Sea produced water 7
4 TOXIC EFFECTS OF HEAVY METALS 10
4.1 Toxicity 10
4.2 Health effects 12
4.3 Environmental effects 13
4.4 Irrigation 14
4.5 Environmental fate/mode of transport 15
5 ASSESSMENT OF TREATMENT TECHNOLOGIES 16
5.1 Adsorption and absorption 17
5.2 Advanced affinity chromatography 21
5.3 Biological treatment 22
5.4 Chemical treatment 25
5.5 Distillation treatment 35
5.6 Electrochemical treatment 36
5.7 Reverse osmosis 38
5.8 Ion exchange 39
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5.9 Filtration 42
5.10 Combined systems 43
6 ANALYTICAL TECHNIQUES 47
6.1 Atomic Absorption Spectrometry (AAS) 47
6.2 Plasma Emission Spectrometry (PES) 48
6.3 High Pressure Liquid Chromatography (HPLC) 49
6.4 Other Methods 51
7 REFERENCES 53
APPENDIX (See SIEP 99-5282)
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1 Introduction
The term ‘heavy metals’ (or ‘trace metals) includes the elements cadmium, chromium, copper, lead,
nickel, mercury and zinc (Alloway & Ayres, 1997). Heavy metal pollution of water has a number of
sources including the processing of ores and metals, the industrial use of metal compounds (chromium
from tanneries, for example) and, in particular, leaching from domestic and industrial waste dumps,
excessive land disposal of domestic sewage, mine tailings, contaminated bottom sediments and
leaching from lead pipes. This kind of leaching has potentially acute consequences. Acidified or
saline water increases the dangers by enhancing metal mobility, so drawing more lead, or other metals,
from piping and vessels into a form more readily absorbed and stored in living tissues, thus amplifying
the toxic effects of leaching. Heavy metals have so far affected water quality only on a local or
regional rather than global scale, though pollution from lead now occurs widely in coastal and marine
environments (Manahan, 1992b).
'Safe' levels of metal concentrations are hard to establish and vary according to the type and degree of
exposure and the state and toxicity of the metal in question (Ferguson, 1990). Acute human
intoxication from heavy metal pollution is not yet common though it has been seen in cases such as the
mercuric contamination of Minamata Bay in Japan (Alloway & Ayres, 1997). Toxicity is particularly
difficult to measure because the effects in humans may not show up for many years, or levels may
become toxic to humans only through the ingestion of bioaccumulated matter in aquatic organisms
such as shellfish (Rainbow & White, 1989). Sometimes the effects may be seen far sooner, eg when
sea food, that has absorbed methylated mercury to a level toxic to humans, is eaten exclusively or
excessively.
Urban stormwater contains heavy metals such as lead, mercury, zinc and copper, which may
concentrate in sediment and bioaccumulate in living organisms (Rainbow & White, 1989).
Atmospheric discharges from industry and vehicle emissions (particularly lead petrol emissions) are
major sources of road surface runoff contamination. These metals accumulate on road surfaces and
are washed into the stormwater system by rainfall (Manahan, 1992b).
To date, limited work has been carried out on the monitoring and removal of heavy metals from
produced waters (Ray & Engelhardt, 1992). The work that has been done has been concerned
primarily with the two most toxic metals/semi-metals, namely mercury and arsenic (Okland, 1993;
Wilding, 1993).
The aim of this report is to outline the technologies available for heavy metal removal and potential
processes that may be used to treat produced waters in particular.
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2 Definition of heavy metal

(References: Alloway and Ayres, 1997; Kazantis, 1980; Langard, 1980; Manahan, 1992a; Manahan,
1992b; Manahan, 1993; Solheim, 1994.)
The term ‘heavy metals’ is generally interpreted to include those metals from periodic table groups IIA
through to VIA. Heavy metals have atomic weights between 63.546 and 200.590, and a specific
gravity greater than 4.0. The semi-metallic elements boron, arsenic, selenium, and tellurium are often
included in this classification. At trace levels, many of these elements are necessary to support life.
However, at elevated levels they become toxic, may build up in biological systems, and become a
significant health hazard. The most important metals and non-metals in toxicity are listed below.
Table 2.1 Important metals and semi-metals (metalloids) (CAS version)
Series Symbol Element Atomic Atomic

Number Weight
IIA (Alkali Earth Metals) Be Beryllium 4 9.01
Ca Calcium 20 40.08
Mg Magnesium 12 24.31
IB-VIIB (Transition Metals) Cd Cadmium 48 112.40
Cr Chromium 24 52.40
Co Cobalt 27 58.93
Cu Copper 29 63.55
Hf Hafnium 72 178.49
Fe Iron 26 55.85
Mn Manganese 25 54.94
Hg Mercury 80 200.59
Mo Molybdenum 42 95.94
Ni Nickel 28 58.71
Os Osmium 76 190.20
Pt Platinum 78 195.09
Rh Rhodium 45 102.91
Ag Silver 47 107.87
Ta Tantalum 73 180.95
Ti Titanium 22 47.90
V Vanadium 23 50.94
Yb Yttrium 39 88.91
Zn Zinc 30 65.37
Zr Zirconium 40 91.22
(Actinide Series) Th Thorium 90 232.04
U Uranium 92 238.03
IIIA (Earth Metals) B Boron 5 10.81
IVA Sn Tin 50 118.69
Pb Lead 82 207.20
VA As Arsenic 33 74.92
Bi Bismuth 83 208.98
VIA Se Selenium 34 78.96
Te Tellurium 52 127.6
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3 Chemistry of heavy metals

(References: Alloway and Ayres, 1997; Beger, 1994; Bowen, 1979; Kazantis, 1980; Langard, 1980;
Manahan, 1992a; Manahan, 1992b; Manahan, 1993; Marlow, 1993; Okland, 1993; Ray and
Engelhardt, 1992; Sarrazin et. al., 1993; Solheim, 1994; Tibbetts et. al., 1989; Wilding, 1993.)
3.1 Sources of heavy metals in aquatic environments

Geochemical sources. In geological terms heavy metals are included in the group of elements referred
to as 'trace elements', which together constitute less than 1 % of the rocks in the earth's crust. These
trace elements occur as impurities in the crystal lattice of many minerals. There is a possibility that
high levels of heavy metals in the aquatic environment in a polluted locality may have developed
‘naturally’ from rocks with high concentrations of heavy metals. Freshwater generally demonstrates a
wider range of heavy metal levels than sea waters owing to the effect of salinity in controlling
solubility products.
Anthropogenic sources. The aquatic environment is affected by heavy metal pollution from various
sources. One of the main sources of man-made heavy metal pollution is mining. Other significant
sources of heavy metal pollution are agriculture and combustion of fossil fuels. Electronics, metal
finishing and waste disposal also contribute to the heavy metal pollution of water. Industrial effluents
may be treated without sufficient reductions in heavy metal levels, and such waters are often
discharged into the aquatic environment. Heavy metals discharged to rivers are carried downstream to
estuaries and cause pollution of the sea and silts in the coastal areas.
Cadmium in water, for example, may arise from industrial discharges and mining wastes.
Chemically, cadmium is very similar to zinc, and these two metals frequently undergo geochemical
processes together. Both metals are found in water in the +2 oxidation state. Cadmium and zinc are
common water and sediment pollutants in harbours surrounded by industrial installations.
Concentrations of these elements of more than 100 ppm dry weight sediment have been found in
harbour sediments.
Mixing of bay water from outside the harbour and harbour water by high winds during the winter
results in de-sorption of cadmium from harbour sediments by aerobic bay water. This dissolved
cadmium is carried out into the bay, where it reacts with suspended solid materials, which then
become incorporated with the bay sediments. This is an example of the sort of complicated interaction
of hydraulic, chemical solution-solid, and micro-biological factors involved in the transport and
distribution of a pollutant in an aquatic system.
Inorganic lead arising from a number of industrial and mining sources occurs in water in the +2
oxidation state. Lead from leaded gasoline has in the past been a major source of atmospheric and
terrestrial lead, much of which eventually enters natural water systems. In addition to pollutant
sources, lead-bearing limestone and galena (PbS) contribute lead to natural waters in some locations.
Mercury is found as a trace component of many minerals, with continental rocks containing an
average of around 80 ppb, or slightly less, of this element. Cinnabar, red mercuric sulphide, is the
chief commercial mercury ore. Fossil fuel coal and lignite contain mercury, often at levels of 100 ppb
or even higher which has been a matter of some concern with increased use of these fuels as energy
sources. Metallic mercury is used as an electrode in the electrolytic generation of chlorine gas, in
laboratory vacuum apparatus, and in other applications. Large quantities of inorganic mercury and
mercury compounds are used annually.
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Organic mercury compounds used to be widely applied as pesticides, particularly fungicides. These
mercury compounds include aryl mercurials such as phenyl mercuric dimethyldithiocarbamate (used
in paper mills), and alkyl mercurials such as ethylmercuric chloride used as a seed fungicide. The
alkyl mercury compounds tend to resist degradation and are generally considered to be more of an
environmental threat than either the aryl or inorganic compounds.
Metalloid arsenic occurs in the Earth's crust at an average level of 2-5 ppm. The combustion of fossil
fuels, particularly coal, introduces large quantities of arsenic into the environment, much of it reaching
natural waters. Arsenic occurs with phosphate minerals and enters into the environment along with
some phosphorus compounds. Some formerly used pesticides, particularly those from before World
War 2, contain highly toxic arsenic compounds. The most common of these are lead arsenate, PbS
(AsO4)2; sodium arsenite, Na3AsO3; and Paris Green, Cu3(AsO3)2. Another major source of arsenic is
mine tailings. Arsenic produced as a by-product of copper, gold, and lead refining greatly exceeds the
commercial demand for arsenic, and it accumulates as waste material. Like mercury, arsenic may be
converted to more mobile and toxic methyl derivatives by bacteria.
3.2 Types of heavy metal compounds in the aquatic environment

All heavy metals exist in waters in colloidal, particulate, and dissolved phases, although dissolved
concentrations are generally low. The colloidal and particulate metal may be found as:
1) hydroxides, oxides, silicates, or sulphides; or

2) adsorbed to clay, silica, or organic matter.
The soluble forms are generally ions (commonly denoted as Mn+) or organometallic chelates or
complexes. Main factors influencing uptake of heavy metals in the environment are salinity, redox
potential and pH. The solubility of trace metals in water is predominately controlled by the water pH,
the type and concentration of ligands on which the metal could adsorb, and the oxidation state of the
mineral components and the redox environment of the system.
3.2.1 Inorganic heavy metal compounds

A bare metal ion does not usually exist as a separate entity in water. In order to secure stability of
their outer electron shells, metal ions in water are weakly bonded to water molecules in forms such as
hydrated metal cations M (H2O)xn+. Metal ions in the water can be transformed into more stable forms
by means of the following chemical reactions:
 Acid-base;
 Precipitation;
 Oxidation-reduction.
3.2.2 Organically bound metals and metalloids

The interaction of metals with organic compounds is of high importance in determining the role played
by the metal in an aquatic system. There are two major types of metal-organic interactions to be
considered in an aquatic system. The first of these is complexation, or chelation, when organic
ligands are involved. Chelation by organics in natural water and wastewater systems is a process in
which metal ions associate reversibly with an organic complexing species as a function of hydrogen
ion concentration. It is described by the following chemical process:
ML + 2H+  M2 + + H2L
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where M2+ is a metal ion and H2L is the acidic form of a complexing (and frequently chelating) ligand,
L2-, illustrated here as a compound that has 2 ionizable hydrogens.
Organometallic compounds, on the other hand, contain metals bound to organic entities by way of a
carbon atom and do not dissociate reversibly at lower pH or greater dilution. Furthermore, the
organic component, and sometimes the particular oxidation state of the metal involved, may not be
stable except as the organometallic compound. A simple way to classify organometallic compounds
for the purpose of discussing their toxicology is the following:
1 Those in which the organic group is an alkyl group such as ethyl in tetraethyl lead, eg Pb(C 2H5)4;
2 Carbonyls, some of which are quite volatile and toxic, having carbon monoxide bonded to metals;
3 Those in which the organic group is a  electron donor, such as ethylene or benzene.
Combinations exist of the three general types of compounds outlined above, the most prominent of
which are arene carbonyl species in which a metal atom is bonded to both an aromatic entity such as
benzene and to several carbon monoxide molecules.
A large number of compounds exist that have at least one bond between the metal and a C atom on an
organic group, as well as other covalent or ionic bonds between the metal and atoms other than
carbon. Because they have at least one metal-carbon bond, as well as properties, uses, and
toxicological effects typical of organometallic compounds, it is useful to consider such compounds
along with organometallic compounds. Examples are monomethyl mercury chloride, CH 3HgCl in
which the organometallic CH3Hg+ ion is ionically bonded to the chloride anion. Another example is
phenyldichloroarsine, C6H5AsCl2, in which a phenyl group is covalently bonded to arsenic through an
As-C bond, and two Cl atoms are also covalently bonded to arsenic.
A number of compounds exist that consist of organic groups bonded to a metal atom through atoms
other than carbon. Although they do not meet the strict definition thereof, such compounds can be
classified as organometallics for the discussion of their toxicology and aspects of their chemistry. An
example of such a compound is isopropyl titanate, Ti(i-OC3H7)4 also called titanium isopropylate, a
colourless liquid melting at 14.8oC and boiling at 104oC. Its behaviour is more that of an
organometallic compound than that of an inorganic compound, and by virtue of its titanium content it
is not properly classified as an organic compound. The term "organometal" is sometimes applied to
such a compound, which for environmental considerations may be regarded as an organometallic
compound.
The interaction of trace metals with organic compounds in natural waters is too vast an area to cover
in detail in this section. However, it may be noted that metal-organic interactions may involve organic
species of both pollutant (such as EDTA) and natural (such as fulvic acids) origin. These interactions
are influenced by, and sometimes play a role in, redox equilibria; formation and dissolution of
precipitates; colloid formation and stability; acid-base reactions; and micro-organism-mediated
reactions in water. Metal-organic interactions may increase or decrease the toxicity of metals in
aquatic ecosystems, and they have a strong influence on the growth of algae in water.
Of all the metals, tin has the greatest number of organometallic compounds in commercial use, with
global production on the order of 40,000 metric tons per year. In addition to synthetic organotin
compounds, methylated tin species can be produced biologically in the environment.
Major industrial uses of organotin compounds include applications of tin compounds in fungicides,
acaricides, disinfectants, anti-fouling paints, stabilisers to lessen the effects of heat and light in PVC
plastics, catalysts, and precursors for the formation of films of Sn0 2 on glass. Tributyl tin chloride and
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related tributyl tin (TBT) compounds have bactericidal, fungicidal, and insecticidal properties and are
of particular environmental significance because of growing use as industrial biocides. In addition to
tributyl tin chloride, other tributyl tin compounds used as biocides include the hydroxide, the
naphthenate, bis(tributyltin) oxide, and tris(tributylstannyl) phosphate. A major use of TBT is in boat
and ship hull coatings to prevent the growth of fouling organisms. Other applications include
preservation of wood, leather, paper, and textiles. Anti-fungal TBT compounds are used as slimicides
in cooling tower water. Because of their applications near or in contact with bodies of water, organotin
compounds are potentially significant water pollutants.
3.3 Behaviour of heavy metals in the aquatic environment

The behaviour of metals in natural waters is a function of the substrate sediment composition,
suspended particles, and the water chemistry. Sediment composed of fine sand and silt will generally
have higher levels of adsorbed metal than will quartz, feldspar, and carbonate-rich sediment. Metals
also have a high affinity for humic acids, organo-clays, and oxides coated with organic matter.
The water chemistry of the system controls the rate of adsorption and desorption of metals to and from
sediment. Adsorption removes the metal from the water column and stores the metal in the substrate.
Desorption returns the metal to the water column, where re-circulation and bio-assimilation may take
place. Metals may be de-sorbed from the sediment if the water experiences increases in salinity,
decreases in redox potential, or decreases in pH.
Often, metals will be driven off into the overlying water. Estuaries are prone to this phenomenon
because of fluctuating river flow inputs. A decreased redox potential, as is often seen under oxygen
deficient conditions, will change the composition of metal complexes and release the metal ions into
the overlying water. A lower pH increases the competition between metal and hydrogen ions for
binding sites. A decrease in pH may also dissolve metal-carbonate complexes, releasing free metal
ions into the water column.
The adsorption of metal ions or ionic complexes (whether in true solution or in colloidal suspension,
eg oxides of iron or manganese) onto particle surfaces is a potent mechanism for removing trace
elements from the seawater solution. Adsorption results from the mutual attraction between the
charges on the ions and suitable bonding sites on the surfaces of the particles.
In the aquatic environment adsorption is mostly onto the surfaces of bacteria, which make up nearly
half of the total amount of particulate organic matter. They are thus very abundant, and their small
size ensures that their total surface area is large. For particles less than 5 µm in diameter, the total
surface area amounts to about 10 m2 per gram. It has been variously estimated that in the upper ocean
something like 90% of the active surface area of suspended particles is on living bacteria; and that the
total surface area of freely suspended bacteria is two orders of magnitude greater than that of
inorganic particles.
Heavy metal ions adsorbed onto small particles are removed from the water column as larger particles
which capture the small ones and carry them downwards - a process called scavenging (the term to
encompass both parts of the process: adsorption and capture). It is important to stress scavenging is a
passive process so far as the bacteria are concerned. The particles and bacteria act merely as an agent
of transport, but do not make use of the elements they adsorb from solution. The trace elements
adsorbed onto particle surfaces are generally in great demand for the metabolic requirements of other
marine organisms; and though they will be ingested along with the particles by filter-feeding
organisms, they are soon excreted again, to become available for further scavenging.
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Scavenging is the main natural mechanism in removing heavy metals from the water column. The
mean lifetime of small particles in seawater is about 7.5 years. The mean residence times for
scavenged elements are rather longer, because adsorption is not a one-way process: there are
adsorption-desorption equilibria between ions in solution and those attached to particles; so
scavenging cannot be 100% efficient. All the same, the residence time for the scavenged elements is
invariably less than 103 years, and for many it is less than 100 years.
As the mean oceanic mixing time is about 500 years, and residence times for most scavenged elements
are much less than this, these elements cannot be uniformly mixed throughout the oceans. Their
distribution must, to a very high extent, reflect the influence of their sources within the water column.
So, the discharge of produced waters polluted with heavy metals could have local effect for quite a
long time.
The water chemistry of the system controls the rate of adsorption and desorption of metals to and from
sediment. Adsorption removes the metal from the water column and stores the metal in the substrate.
Desorption returns the metal to the water column, where recirculation and bioassimulation may take
place. Metals may be desorbed from the sediment if the water experiences increases in salinity,
decreases in redox potential, or decreases in pH.
1 Salinity increase: Elevated salt concentrations create increased competition between cations
and metals for binding sites. Often, metals will be driven off into the overlying water.
(Estuaries are prone to this phenomenon because of fluctuating river flow inputs).
2 Redox Potential decrease: A decrease in redox potential, as is often seen under oxygen
deficient conditions, will change the composition of metal complexes and release the metal
ions into the overlying water.
3 pH decrease: A lower pH increases the competition between metal and hydrogen ions for
binding sites. A decrease in pH may also dissolve metal-carbonate complexes, releasing free
metal ions into the water column (Connell et al, 1984).
3.4 Heavy metals in North Sea produced water
Produced waters contain a wide range of both cations and anions. There have been several studies by
both industry and government to try to determine the quantity of various heavy metals in produced
water. Anion composition was not analysed on a regular basis with more data available on the
cationic composition (Table 3.1). The data contains concentrations averaged for a number of effluents
in a specific area. This appeared the only way to get an overall picture of the enormous amount of
data collected. A disadvantage is, however, that differences between effluents in a specific area or
concentrations below the detection limit, can no longer be directly seen.
All effluents showed similar patterns of concentration for the different metals. The measured alkaline
(Na, K, and Li), earth (only B) and alkaline-earth (Ba, Ca, Mg and Sr) metals showed the highest
concentrations in all cases. Sodium appeared the dominant cation, but calcium, magnesium and
potassium were also present in high concentrations. The concentration of calcium was in most
instances higher than that of magnesium, i.e., reversed compared to seawater. Although not apparent
from the averaged data in Table 3.1, some effluents from oil platforms showed a Ca/Mg ratio <1,
indicating a significant breakthrough of injected seawater. All effluents also contained appreciable
quantities of boron, strontium and barium. However, particularly in effluents from oil platforms with
a significant "water cut", the barium content was much lower than in effluents with less or no
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breakthrough of seawater. This was probably a consequence of precipitation of barium sulphate scale
following contact with seawater.
Although the relative proportions of heavy metals in effluents from oil platforms closely resembled the
composition of North Sea water (compare data in Table 3.1), the actual concentrations were a factor
of up to about 1000 higher in produced water than in seawater.
Table 3.1 Average concentrations of metals (mg/l) in produced waters discharged into the
North Sea
Element Northern sector Central North UK Sector Dutch Sector North Sea
Sea (average background
levels)
oil gas
Al 0.83 2.33 4.48 nd 0.16-1.9
As nd nd nd 0.005 0.003-0.024
B 26.49 81.55 1.7 82.61 4.4
Ba 1.92 3.44 0.66 6.6 0.05
Be nd nd nd 0.61 10-6
Ca 467.9 6010 5560 7240 390
Cd 0.01 <0.10 0.03 0.19 10-5 - 5·10-5
Co <0.3 0.4 0.3 <0.1 10-4
Cr 0.1 0.1 0.26 0.07 0.2 - 1.0
Cu 0.6 0.8 0.6 0.01 10-4 - 10-3
Fe 3.78 5.93 66.09 nd 0.002 - 0.02
Hg <0.003 <0.003 <0.01 0.004 10-6 - 10-4
K 393.8 1048.2 199.6 266.1 380
Li 4.21 17.15 52.38 nd 0.1
Mg 711.7 816.2 445.7 994.4 1272
Mn 0.65 1.72 1.18 11.33 0.001 - 0.01
Na 1060 42909 8185 35484 11200
Ni 0.23 0.9 1.22 0.08 10 - 5·10-4
-4
Pb <0.05 <0.05 0.38 0.84 10-5 - 6·10-5

Sb nd nd nd 0.26 10-4
Se nd nd nd 0.002 0.004
Sn nd nd nd 0.07 0.003
Sr 29.75 393 65.56 154.27 13
V <0.10 0.1 0.07 <0.1 0.0003
Zn 0.84 4.59 0.2 68.96 5.5·10-4 - 43 ·10-4
nd - not determined
The cationic composition of produced waters from gas/condensate platforms followed a pattern
generally comparable to that described above for oil platforms (see Tables 3.1). However, here the
earlier demonstrated differences between almost fresh – condensed - water and very salty formation
water is confirmed: with very low quantities of all metals in the condensed water to very high
concentrations of alkaline, earth and alkaline-earth metals, but also some heavy metals, in formation
water. The longer the time that gas reservoirs are in production, the greater will be the relative
contribution of formation water in the effluent streams and the higher the concentrations of inorganics
therein. These relationships were most clear for the alkaline and alkaline-earth metals. For the other
metals this relationship was not so marked.
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Table 3.2 summarises the typical concentrations of heavy metals in produced waters and seawaters.
Table 3.2 General concentrations of heavy metals (µg/l) in produced water discharges
Element Concentration in oil and gas fields Concentration in

seawater
Typical (µg/l) Range (µg/l) Typical (µg/l)
Cd 50 0-100 0.02
Cr 100 0-390 0.001
Cu 800 0-1500 0.2
Pb 500 0-1500 0.03
Hg 3 0-10 0.001
Ni 900 0-1700 0.3
Ag 80 0-150 0.3
Zn 1000 0-5000 0.6
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4 Toxic effects of heavy metals
(References: Alloway and Ayres, 1997; Beger, 1994; Bowen, 1979; Kazantis, 1980; Langard, 1980;
Manahan, 1992a; Manahan, 1992b; Manahan, 1993; Rainbow, 1993; Rainbow and White, 1989;
Solheim, 1994.)
4.1 Toxicity
Living organisms require trace amounts of some heavy metals (essential metals), including cobalt,
copper, iron, manganese, molybdenum, vanadium, strontium, and zinc.
Non-essential heavy metals of particular concern to surface water systems are cadmium, chromium,
mercury, lead, arsenic, and antimony. The most likely metals to be encountered in produced water are
lead, zinc, copper, nickel, tin and iron. At trace levels, many of these elements are necessary to
support life. However, at elevated levels they become toxic, may build up in biological systems, and
become a significant health hazard.
Acidified or saline water enhances metal mobility, so drawing more lead or other metals into a form
more readily absorbed and stored in living tissues, thus amplifying the toxic effects of heavy metal
pollution. The heavy metals have so far affected water quality only on a local or regional - rather than
global - scale, though pollution from lead now occurs globally in coastal and marine environments.
Since offshore limits for discharge of heavy metals into the aquatic environment have not yet been set,
we have used on-shore limits as a guidance. It should be noted though that if off-shore limits were to
be introduced in the future, they might be more strict than on-shore limits since saline sea water
enhances environmental effects of discharged heavy metals.
National regulations on the quantity of heavy metals permitted in on-shore effluents vary, often by a
factor of 10 or more. The most dangerous pollutants, lead salts, have regulatory limits in most
countries between 0.1 and 1.0 mgl-1. It should be noted that the concentration which is permitted is
that of the metal alone and not of the salt. As an example, lead forms only 86.6% of the weight of the
more common form of lead oxide. One unit weight of lead can therefore be found in approximately
1.15 unit weight of lead oxide: this is an important distinction when measuring the metal content of
wastewater by analysis.
Heavy metals may be adequately removed in traditional domestic wastewater treatment plants for
effluent disposal but this may result in subsequently high concentrations in the wastewater sludges. In
some industrial wastewater treatment plants, treated wastewater may still contain large quantities of
heavy metals, requiring further treatment . Furthermore, although lead is highly toxic, small amounts
of other metals such as copper or iron have no apparent negative effect to humans and other
mammals. This may be true as far as the ingestion by mammals is concerned, but many metal salts
are highly toxic to the bacteria that are essential to the biodegrability of effluents in the sea. In
particular, copper in very low concentrations is a strong bactericide.
ERT F98/244/F005B
As a general rule, elements which are rare on earth tend to be toxic to some degree to organisms.
Heavy metals, such as lead, mercury and cadmium are elements rarely encountered due to their low
abundance or inaccessible forms. Because most organisms have had little evolutionary contact with
these elements, adverse effects may occur if ingested. Certain organisms have experienced a greater
degree of contact with toxic elements and have evolved defence mechanisms to increase their chance
of survival.
Single celled organisms do not have a very discriminate selectivity. Multi-cellular organisms,
however, do have improved selectivity due to the development of several barriers that metal ions must
pass prior to reaching target cells. The first line of defence organisms possess to minimise the adverse
effects of toxic elements is the capability to discriminate which elements are absorbed or ingested,
through selective uptake. The second type of defence mechanism involves minimising the adverse
effects of toxic elements once they have entered the organism.
Metal ions in an aqueous form can be taken up either as a cation or as an oxy-anion. The exception to
this is the direct absorption of a metal species, as in the case of Fe(II), which binds to a cell-secreted
agent allowing entry into the cell. Cell membranes are virtually impermeable to metallic cations and
oxy-anions; they require binding to a bio-molecule (eg- binding to a carrier protein that allows entry in
to the cell).
Some cells have ionophores on the surface of the cell membrane, which allow the passage of certain
elements into the cell based on their size and electric charge. Cd(II), Hg(II) and Pb(II) can enter a cell
by this mechanism, due to their similarity to essential cations, such as Ca(II). Heavy metals can also
gain entry into the cell by forming stable organometallic compounds, such as mercury’s formation of
mono- [(CH3)Hg]+ or dimethyl mercury [(CH3)2Hg]. Such complexes pass indiscriminately through
cellular membranes.
Toxicity of heavy metals at the molecular level cause the following to occur:
 blockage of essential enzymatic activity;

 modification of enzymes (conformational changes, making them non-functional);
 binding to cellular membranes, disrupting cellular integrity;
 displacement of essential metal ions from bio-molecules;
 displacement of essential cations from bio-minerals (eg Pb(II) and Cd(II) replacing Ca(II) in bone
due to similarity in size, ultimately affecting bone strength).
'Safe' levels of metal concentration are hard to establish and vary according to type and degree of
exposure and the state and toxicity of the metal in question. Toxicity is particularly difficult to
measure because effects may not show up for years, or levels may become toxic to humans only
through bioaccumulation in aquatic organisms. For instance, trace levels of elements such as lead,
zinc and cadmium may cause damage to human health through long-term exposure. The consumption
of sea food that has absorbed concentrated methylated mercury to a level toxic to humans could have
a serious effect within months if eaten exclusively.
Biological defences have evolved in organisms to minimise the effect of toxic elements upon cellular
function. However, the increase of toxic elements due to human activity pose a problem by exceeding
the limits natural defence mechanisms can withstand. An example of an evolved adaptation to deal
with toxic elements are metalothionein (MT) proteins. They are widely distributed among organisms,
ranging from bacteria to plants to mammals. Mammalian forms of the protein bind to Hg(II), Pb(II)
and Cd(II). Such toxic elements cannot exhibit their adverse effects on cellular function when bound
ERT F98/244/F005B
to metalothionein proteins. Thus, MT proteins serve as a protective mechanism to control, to some
degree, the level of free heavy metals within an organism.
So, life has adapted to combat the natural presence of adverse elements upon their survival. However,
the effect of industry and other anthropogenic sources upon the environment has led to an inability for
organisms to resist elevated (i.e.-toxic) levels of heavy metal pollutants.
Acute human intoxication from heavy metal pollution is not yet common. One of the most compelling
examples of aqueous heavy metal pollutants occurred during the mid-part of the twentieth century, in
central Japan. Inhabitants along the lower stream of the Jinzu River suffered from an undiagnosed
disease. The victims experienced intense bone pain, which led to the disease’s name, itai-itai, meaning
"ouch-ouch". The onset of the disease was long and painful, and the victims became progressively
worse over a period of about a decade. Final stages of the deadly disease resulted in any slight-
pressure movement causing bone fractures. The itai-itai disease victims were found at autopsy to
contain extremely high levels of heavy metals within their bone and tissue. After an extensive
investigation by the Japanese government, the cause was found to be the release of cadmium from
mining operations upriver of the villages of itai-itai victims. Cadmium, lead and other metals released
from mining operations were absorbed by inhabitants along the Jinzu River, as this river system was
their sole source of water for irrigation and drinking.
4.2 Health effects
Ingestion of metals such as lead (Pb), cadmium (Cd), mercury (Hg), arsenic (As), barium (Ba), and
chromium (Cr), may pose great risks to human health. Trace metals such as lead and cadmium will
interfere with essential nutrients of similar appearance, such as calcium (Ca 2+) and zinc (Zn2+).
 Lead: Because of size and charge similarities, lead can substitute for calcium and be included in
bone. Children are especially susceptible to lead because developing skeletal systems require high
calcium levels. Lead that is stored in bone is not harmful, but if high levels of calcium are ingested
later, the lead in the bone may be replaced by calcium and mobilised. Once free in the system, lead
may cause nephrotoxicity, neurotoxicity, and hypertension.
 Cadmium: Cadmium may interfere with the metallothionein's ability to regulate zinc and copper
concentrations in the body. Metallothionein is a protein that binds up an excess of essential metals
to render them unavailable. When cadmium induces metallothionein activity, it binds to copper
and zinc, disrupting the homeostasis levels. Cadmium is used in industrial manufacture and is a
by-product of the metallurgy of zinc.
 Mercury: Mercury poses a great risk to humans, especially in the form of methylmercury. When
mercury enters water it is often transformed by micro-organisms into the toxic methyl mercury
form. Symptoms of acute poisoning are pharyngitis, gasteroenteritis, vomiting, nephritis, hepatitis,
and circulatory collapse. Chronic poisoning is usually a result of industrial exposure or a diet
consisting of contaminated fish (mercury is the only metal that will bioaccumulate). Chronic
poisoning may cause liver damage, neural damage, and teratogenesis.
 Arsenic: Arsenic ingestion can cause severe toxicity through ingestion of contaminated food and
water. Ingestion causes vomiting, diarrhoea, and cardiac abnormalities.
ERT F98/244/F005B
 Chromium: The presence of abundant chromium anions in the water is generally a result of
industrial waste. The chronic adverse health effects are respiratory and dermatological.
4.3 Environmental effects
Aquatic organisms may be adversely affected by heavy metals in the environment. The toxicity is
largely a function of the water chemistry and sediment composition in the surface water system (see
"Environmental Fate/Mode of Transport").
Slightly elevated metal levels in natural waters may cause the following sub-lethal effects in aquatic
organisms: 1) histological or morphological change in tissues; 2) changes in physiology, such as
suppression of growth and development, poor swimming performance, changes in circulation; 3)
change in biochemistry, such as enzyme activity and blood chemistry; 4) change in behaviour; 5)
changes in reproduction.
Many organisms are able to regulate the metal concentrations in their tissues. Fish and crustacea can
excrete essential metals, such as copper, zinc, and iron that are present in excess. Some can also
excrete non-essential metals, such as mercury and cadmium, although this is usually met with less
success.
Research has shown that aquatic plants and bivalves are not able to successfully regulate metal
uptake. Thus, bivalves tend to suffer from metal accumulation in polluted environments. In estuarine
systems, bivalves often serve as biomonitor organisms in areas of suspected pollution. Shellfishing
waters are closed if metal levels make shellfish unfit for human consumption.
In comparison to freshwater fish and invertebrates, aquatic plants are equally or less sensitive to
cadmium, copper, lead, mercury, nickel, and zinc. Thus, the water resource should be managed for
the protection of fish and invertebrates, in order to ensure aquatic plant survivability. Metal uptake
rates will vary according to the organism and the metal in question. Phytoplankton and zooplankton
often assimilate available metals quickly because of their high surface area to volume ratio. The
ability of fish and invertebrates to adsorb metals is largely dependent on the physical and chemical
characteristics of the metal. With the exception of mercury, little metal bioaccumulation has been
observed in aquatic organisms.
Metals may enter the systems of aquatic organisms via three main pathways:
 Free metal ions that are absorbed through respiratory surface (eg gills) are readily diffused into
the blood stream.
 Free metal ions that are adsorbed onto body surfaces are passively diffused into the blood stream.
 Metals that are sorbed onto food and particulates may be ingested, as well as free ions ingested
with water.
ERT F98/244/F005B
4.4 Irrigation
Irrigation water may transport dissolved heavy metals to agricultural fields. Although most heavy
metals do not pose a threat to humans through crop consumption, cadmium may be incorporated into
plant tissue. Accumulation usually occurs in plant roots, but may also occur throughout the plant.
Most irrigation systems are designed to allow for up to 30 percent of the water applied not to be
absorbed and to leave the field as return flow. Return flow either joins the groundwater or runs off the
field surface (tailwater). Sometimes tailwater must be re-routed into streams because of downstream
water rights or a necessity to maintain streamflow. However, usually the tailwater is collected and
stored until it can be reused or delivered to another field.
Tailwater is often stored in small lakes or reservoirs, where heavy metals can accumulate as return
flow is pumped in and out. These metals can adversely impact on aquatic communities. An extreme
example of this was the Kesterson Reservoir in the San Joaquin Valley, California, which received
subsurface agricultural drainwater containing high levels of selenium and salts that had been leached
from the soil during irrigation. Studies in the Kesterson Reservoir revealed elevated levels of selenium
in water, sediments, terrestrial and aquatic vegetation, and aquatic insects. The elevated levels of
selenium were cited as relating to the low reproductive success, high mortality, and developmental
abnormalities in embryos and chicks of nesting aquatic birds.
Sources:
1 Nonpoint sources
Natural: Chemical and physical weathering of igneous and metamorphic rocks and soils often
release heavy metals into the sediment and into the air. Other contributions include the
decomposition of plant and animal detritus, precipitation or atmospheric deposition of airborne
particles from volcanic activity, wind erosion, forest fire smoke, plant exudates, and oceanic
spray.
Anthropogenic: Surface runoff from mining operations usually has a low pH and contains high
levels of metals such as iron, manganese, zinc, copper, nickel and cobalt. The combustion of
fossil fuels pollutes the atmosphere with metal particulates that eventually settle to the land
surface. Urban stormwater runoff often contains metals from roadways and atmospheric
fallout. Currently, anthropogenic inputs of metals exceed natural inputs.
2 Point sources
Domestic wastewater effluent contains metals from metabolic wastes, corrosion of water pipes,
and consumer products. Industrial effluents and waste sludges may substantially contribute to
metal loading.
ERT F98/244/F005B
4.5 Environmental fate/mode of transport
Transport in water: Water can transport metals that are bound to sediment particles. The primary
route for sediment-metal transport is overland flow.
Water also transports dissolved metals. Although dissolved metals are primarily transported in
overland flow, some underground transport is possible. Metals that are introduced to the unsaturated
zone and the saturated zone will most likely not be transported a long distance. Dissolved metals that
are carried below the land surface will readily sorb to soil particles or lithic material in the unsaturated
zone and the saturated zone.
Transport in air: Metals introduced into the atmosphere may be carried to the land surface by
precipitation and dry fallout. Additionally, because metals readily sorb to many sediment types, wind-
borne sediment is a potential route for metal transport.
ERT F98/244/F005B
5 Assessment of treatment technologies
In order to accumulate as much information as possible on technologies available to treat heavy metal
contaminated water, a comprehensive data search was conducted. Searches were carried out on ERT's
own library/database, using library searches, requesting vendor information, contacting research
institutions and by using on-line search methods such as the 'Inside' British Library search function
and Internet search engines, combing with IBM's patent search database.
From these methods, the following list of available technologies was generated:
 adsorption and absorption;

 advanced affinity chromatography;
 biological treatment;
 chemical treatment;
 distillation;
 electrochemical treatment;
 liquid/liquid membranes;
 ion exchange;
 reverse osmosis.
In addition, methods utilising combinations of the above technologies were also considered.
In general, response from equipment vendors was disappointing despite regular contact via telephone,
fax and e-mail. Therefore, the internet sites for these vendors were located and as much information
as possible was extracted in this way.
This section summarises and evaluates the technology information contained in Appendix 1 of this
report. For each treatment technology, three different status areas were identified:
1 vendor systems commercially available;

2 research currently undertaken;
3 patents available.
The discussion section for each treatment technology is subdivided into these three status areas.
ERT F98/244/F005B
5.1 Adsorption and absorption
Table 5.1 Summary of vendor and research products
Vendor/Researcher Process Applicability to Oil Further investigation

and Gas Production
Waters
VENDORS
ATA Technologies Corp. 'Aqua-Fix' Possible Yes
Biomin Incorp. 'EC-M / EC-MBC / Yes No
Clayfloc'
Colloid Environmental 'Quik-Solid' Yes No
Technologies Comp.
(Cetco).
Chitosan. 'Chitosan' Possible No
Dynaphore Inc. 'FORAGER' Possible Yes
Pacific Northwest Metaporous silica Possible Yes
National Lab. (PNNL). process
Selective Environmental 'Mag*Sep' Possible Yes
Technologies Inc.
(Selentec).
RESEARCH
Western Product 'CCBA' No n/a
Recovery Group Inc.
Filter Flow Technology 'CPFM' No n/a
5.1.1 Adsorption and absorption; vendors
5.1.1.1 ATA Technologies Corporation
ATA Technologies Corporation manufacture the 'Aqua-Fix', which they claim to be able to reduce
heavy metal contaminants to non-detectable levels. Patents are pending in the US and overseas.
Basically, the process uses a carbon-based material and a 'proprietary' additive, which is not described
in company information. So far only mercury, copper, zinc, chromium, cadmium, lead, iron and nickel
have been tested on this system, although work is ongoing to determine applicability to other metallic
and organic contaminants.
5.1.1.2 Biomin Incorporated
Biomin manufacture two filter media which they claim are suitable for the removal of heavy metals:
EC-M and EC-MBC.
EC-M (zeolite) removes ammonia and heavy metals for industrial water and soft ground water. EC-M
is a granular product for filter vessels and is claimed to remove lead, copper, zinc, and cadmium.
ERT F98/244/F005B
EC-MBC (bone char) is also a granular product for filter vessels but is suitable for hard waters. EC-
MBC is claimed to remove lead, zinc and nickel.
Biomin also manufacture Clayfloc, a bentonite based flocculating agent. This is not further
considered here as a suitable process for the offshore industry because it requires bulk volume
flocculation followed by a filter press.
5.1.1.3 Colloid Environmental Technologies Company
Cetco (Colloid Environmental Technologies Company) market the 'Quik-Solid' polymer for removal of
heavy metals.
Quik-Solid is a solid, granular, cross-linked polyacrylate that is claimed to absorb large volumes of
aqueous solutions. This product is used in the nuclear industry for wastewater treatment.
Cetco also manufacture 'Quick-Solid' absorbent pads for aqueous treatment in the nuclear remediation
area. Both products have potential for use in the oil and gas industry (small volumes only).
5.1.1.4 Chitosan
Chitosan is a natural polycationic polymer, soluble in solutions of most acids, which has metal
recovering properties. It is derived from the shells of crabs and shrimps.
An extract from Water Engineering & Management is contained in Appendix 1 and describes an
experiment undertaken to determine whether chitosan could remove copper from water. The
experiment concluded that copper concentrations decreased but high concentrations of copper require
large amounts of chitosan.
The amount of chitosan required, and its biodegradability tendencies suggest it may not be directly
suitable to the offshore industry.
5.1.1.5 Dynaphore Inc
Dynaphore manufacture the 'FORAGER' sponge, an open celled cellulose sponge with an amine
containing polymer which has an affinity for aqueous heavy metals in both anionic and cationic states.
The 'FORAGER' sponge can be used in columns, fishnet type enclosures or in rotating drums.
When used in a column, flowrates of up to three bed volumes per minute have been achieved using
less than 1m of hydrostatic pressure. The column can then be regenerated by a process similar to the
regeneration of ion exchange columns. The technology has been used to remove cadmium, copper,
lead, chromium, chromate and silver from aqueous streams.
5.1.1.6 Pacific Northwest National Laboratory
In this system, metaporous silica is used which has a honeycomb-like structure with pores nanometers
wide. PNNL have coated the walls of metaporous silica with sulphur compounds that absorb
mercury, silver and lead. The media can then be acid-regenerated.
ERT F98/244/F005B
Although this silica based media costs 50% more than conventional filter material, it is claimed to
absorb 30-1000 times more metals. However, further tests on a larger range of heavy metals are
required to determine applicability to the oil industry.
5.1.1.7 Selective Environmental Technologies Inc (Selentec)
Selentec produce the 'Mag*Sep' technology for removal of heavy metals. In this system, contaminants
are absorbed onto resin-coated magnetic particles. These particles are magnetically removed and
regenerated using an acid wash system.
The Mag*Sep process is claimed to remove titanium, copper, cadmium, arsenic, cobalt, molybdenum,
platinum, selenium, chromium, zinc, gold, iodine, manganese, technetium, mercury, strontium, iron,
ruthenium, thallium, caesium, cobalt, palladium, lead, radium, nickel, silver, bismuth, antimony,
zirconium, palladium, cerium and all actinides. This list is indeed impressive suggesting this may be
an attractive technology.
However, further investigation is required as some pre-treatment may be required, such as water, pH
adjustment and particle filtration, prior to Mag*Sep treatment; making this a potentially expensive
system.
5.1.2 Adsorption and absorption; research
5.1.2.1 Western Product Recovery Group Inc
The Western Product Recovery Group have recently developed the CCBA (co-ordinate, chemical
bonding and adsorption) process for removing heavy metals from soils, sediments and sludges.
This particular technology uses clays with specific cation exchange capacity as sites for physical and
chemical bonding of heavy metals to the clay. Although this is a continuous flow process, it is
particularly suited to the treatment of solids, sludges or slurries. Treatment takes place at high
temperatures (2,000 ºF) where organic compounds are oxidised, suggesting this process may be
suitable for cuttings pile treatment if heavy metals contamination is a concern.
However the batchwise, slurrified inlet stream required suggests this is not a suitable treatment
technology for a continuous aqueous inlet flow. However, as previously mentioned, this is a potential
technology for cuttings pile treatment, should this become legislatively necessary.
5.1.2.2 Filter Flow Technology Inc
The CPFM (colloid polishing filter method) uses an inorganic, oxide-based compound of granular
pellets to remove colloidal and ionic forms of heavy metals and non-tritium radionuclides from water.
As with some other adsorption systems, some pre-conditioning of the waste stream may be necessary
to induce colloid forms of pollutants. The waste stream is treated in a filter press containing the
pellets, Filter Flow 1,000, which adsorbs heavy metals in the water. Treated water exiting the filter
press may require pH adjustment.
ERT F98/244/F005B
Although this technology is claimed to reduce heavy metals concentrations down to ppm or, indeed,
ppb, levels, the careful pre-treatment required suggests this particular technology is not suitable to the
oil industry. This is especially the case when considering the varied organic, solids and chemical
compounds present in oily water discharges.
5.1.3 Adsorption and absorption; patents
All patents identified for this treatment technology are contained in Appendix 1 of the report.
Patent 5538645 describes a system for removing metallic ions by yeast cell walls. Selected yeasts are
first treated by a water soluble aldehyde prior to removing metal ions. The yeast walls can then be
regenerated by a mineral acid or other solutions mentioned in the report.
Patent 5578547 describes a bead for removing heavy metal contaminants. This bead consists of peat
moss or other non-living biomass immobilised by sodium silicate. These beads are claimed to remove
a feed stream containing less than 10 ppm of either silver, iron, chromium, cobalt, uranium, mercury,
nickel, arsenic, aluminium, cadmium, lead, manganese, copper or zinc.
Patent 5602071 again uses beads consisting of peat moss immobilised by a chemical binder. This is
the same patent applicant as for the previous patent.
Patent 5626765 describes an adsorption method using a tannin adsorbent. The system uses a
combination of pH changes to selectively adsorb heavy metal contaminants onto the adsorbent.
Patent 5647991 uses waste cast steel shot blast fines to remove heavy metals from aqueous streams.
These fines are sieved to collect particles of size 80 mesh or greater, which are then located as a filter
bed. pH adjustment of the feed stream to between pH 4 and 7 allows removal of cadmium, zinc,
copper, mercury, chromium and lead. These fines can then be acid regenerated.
Patent 5658450 removes heavy metal contaminants by passing wastewater through a vessel in which
small particles of insoluble cathodes interact with anodes to form galvanic couples. A flotation effect
is achieved by passing compressed air through the vessel. Hydroxides and ions are formed during the
process which act as coagulating agents, absorbing impurities.
Patent 5667694 uses organically modified smectite clay to remove heavy metals. Alternatively,
organoclays can be used which are the reaction product of smectite clays and quaternary ammonium
compounds. Heavy metals are sorbed onto the clay, forming an organically modified smectite
clay/heavy metal complex which can be removed by methods such as flotation and air sparging.
Patent 5681447 removes trace amounts of heavy metals using a cylindrical vessel divided into two
compartments. The waste streams flows through the inner section while a gas flows concurrently in
the outer, annular section. The flowing fluids charge the separating material, attracting and adsorbing
heavy metal ions.
Patent 5738791 uses a porous, hydrophobic polymer of size 0.1 to 10 mm and pores of 0.1 to 50 m.
This polymer can then be used for heavy metals removal, although this patent only applies to the
manufacture of the polymer.
ERT F98/244/F005B
Patent 5279745 also describes the production of adsorbent material for heavy metals removal. Water
insoluble beads consisting of, essentially, polysulfone are absorbed onto catived carbon, forming a
material which is capable of absorbing metal ions of less than 1 mg/l concentration in water.
Patent 5770090 uses a tank containing material such as activated carbon. The feedwater requires pH
adjustment to between 1.5 to 2.5 to allow heavy metal adsorption. A stripping solution containing
sulphuric acid removes the adsorbed metal ions, which are recovered using electrolytic recovery onto a
cathode.
Patent 5789204 describes the preparation, from biomass, of a biosorbent suitable for heavy metals
removal. The main ingredient of this biosorbent is polyaminosaccharide sodium phosphate.
5.2 Advanced affinity chromatography
Vendor/Researcher Process Applicability to Oil and Further investigation

Gas Production Waters
VENDORS
Affiniti Water AAC System Possible Yes
Technologies
Hydrokinetic Systems AAC System Possible Yes
Inc.
RESEARCH
No information - -
5.2.1 Advanced affinity chromatography; vendors
5.2.1.1 Affiniti Water Technologies
Affiniti Water Technologies were formed as a joint venture between Reilly Industries Inc and NTEC
Solutions Inc. Affiniti’s water treatment processes use advanced affinity chromatography (AAC) to
polish out low levels of heavy metals from aqueous solutions. AAC is claimed to be more cost
effective than chemical precipitation, activated carbon adsorption, ion-exchange and reverse osmosis.
Little information was available for this particular technology through all search methods.
5.2.1.2 Hydrokinetic Systems Inc
Hydrokinetic’s advanced affinity chromatography (AAC) system is claimed to have a much higher
capacity (10-500 times) than conventional ion exchange resins.
AAC is claimed to remove heavy metal contaminants down to concentrations below 1 ppb. AAC
systems are generally smaller than conventional ion exchange systems and in some instances will
provide over 1,000 cycles before replacement is necessary.
ERT F98/244/F005B
Columns are regenerated with around one bed volume of either dilute acid or dilute base. This low
volume regeneration makes for easy disposal or metal recovery, if desired. Hydrokinetic systems
claim they can set up their AAC system to selectively remove certain contaminants.
Further investigation into this technology’s applicability to the oil and gas industry may prove useful.
5.2.2 Advanced affinity chromatography; research
No research information was found.
5.2.3 Advanced affinity chromatography; patents
No relevant patents were found.
5.3 Biological treatment
Vendor/Researcher Process Applicability to Oil and Further

Gas Production Waters investigation
VENDOR
Biorecovery Systems 'AlgaSORB' Yes Yes
Inc.
Montana State Biopolymer gel process Possible No
University
NTBC Research Corp. Biosulphide process Possible No
Thiopaq 'ThiopaqR' Possible No
RESEARCH
UCLA Pollution Biomimetic process Possible n/a
Prevention
LINK Programme Biosulphide process Possible n/a
(DTI/MAFF)
Purdue University Phytoremediation process No n/a
ERT F98/244/F005B
5.3.1 Biological treatment; vendors
5.3.1.1 Biorecovery Systems Inc
Biorecovery Systems Inc manufacture the AlgaSORB sorption process which uses algae for heavy
metals removal. This process takes advantage of the natural affinity of algal cell structures to heavy
metals.
The AlgaSORB medium consists of dead algal cells immobilised in a silica gel polymer which protects
the cells from degradation and produces a hard material for packing into separation columns. The
column acts similarly to an ion exchange column but divalent cations such as calcium and magnesium
or monovalent cations such as sodium and potassium do not interfere with heavy metal removal. In
addition, anions such as chlorides or sulphates are claimed to be only weakly bound, if at all. This
suggests that AlgaSORB will not be affected by typical marine salts, making it an attractive option for
oil and gas operation.
At this moment, the AlgaSORB process may be available in a commercialised form but available
information relates to pilot plant tests.
5.3.1.2 Montana State University
This particular technology uses biopolymers to remove heavy metal contaminants from wastewater.
Work was undertaken to develop a system capable of removing more than one heavy metal
contaminant as waste water streams often contain combinations of two or more such metals.
Proving trials have been conducted on biopolymer gel bead binding to heavy metals. Results have
shown that alginate is much more selective for copper than zinc and that maximum binding capacity
for alginate is independent of metal type.
However, from the company information received (see Appendix 1), it is apparent that an effective
bead regeneration system has not been developed. Therefore this technology is no longer considered.
5.3.1.3 NTBC Research Corporation
The NTBC Research Corp have developed the biosulphide process for water treatment applications.
This process utilises SRBs (sulphate reducing bacteria) to convert sulphate in the water to sulphide,
whilst simultaneously raising pH. Sulphide is then stripped into the gas phase as H 2S (hydrogen
sulphide) and applied to the water in the chemical circuit.
In this chemical circuit, the sulphide and alkalinity generated in the biological stage encourage
precipitation of heavy metals as metal sulphides. As the precipitation of metals as sulphides varies
according to the solubility of the sulphide compounds, selective removal can be achieved.
Usually this system will be operated using a number of precipitation stages; one stage per metal ion to
be removed. However a final ‘clean up’ stage is recommended.
ERT F98/244/F005B
Although pilot studies have shown this system to be effective, there are a number of concerns
regarding applicability to an offshore environment, namely:
 use and presence of H2S, a gas normally avoided because it is very toxic and highly corrosive;
 this technology produces heavy-metal contaminated sludge which will require disposal.
For these reasons the NTBC system is no longer considered.
5.3.1.4 Thiopaq
The Dutch company Thiopaq are a wholly owned subsidiary of Paques and manufacture a biological
treatment process for heavy metals removal. This system, the ThiopaqR process, utilises similar
technology to the NTBC system described previously.
In the ThiopaqR process, wastewater is treated in biological stages, complemented with solids
separation steps. In the anaerobic stage, sulphate is reduced to H 2S again using SRBs while another
compound, the ‘reductant’ is oxidised. This ‘reductant’ could be hydrogen, ethanol or other organic
waste streams. Sulphides are formed and react with metal ions present forming metal sulphide
precipitates.
In the aerobic stage, excess sulphide is oxidised by aerobic micro-organisms to form elemental sulphur
which can be removed by sedimentation.
Pilot tests using the ThiopaqR system have shown good heavy metal reduction performance. However
these have been from processes such as zinc refining and copper mining. Therefore, as with the
NTBC system, its applicability to the oil industry is questionable.
5.3.2 Biological treatment; research
5.3.2.1 UCLA Pollution Prevention
The UCLA Centre for Clean Technology (CCT) have developed a number of innovative processes for
wastewater treatment. They have developed biomimetic (biological mimicking) metal sorbing vesicle
media for selective recovery of toxic heavy metal ions such as copper, cadmium and lead from dilute
aqueous solutions in a continuous process.
These metal sorbing vesicles are sub-micron in diameter and are surfactant bi-layer membrane
capsules which mimic biological membranes in structure and function. UCLA have engineered these
to scavenge and concentrate metal ions by a lipophillic metal carrier in the vesicle wall and a water
soluble, metal chelating agent dissolved in the aqueous vesicle interior.
This system works by facilitating transport of the charged metal ion across the lipid bi-layer while the
encapsulated chelating agents encourage metal ion uptake.
Development is now underway to determine feasibility of this process and to determine methods of
continuous operation with vesicle regeneration. Polymerisation of these vesicles has also been
undertaken for improved stability.
ERT F98/244/F005B
5.3.2.2 LINK Programme
Members of the LINK programme are the DTI, Ministry of Agriculture, food and fisheries and
research councils.
One objective of this research programme is to determine means of treating aqueous heavy metal
contaminants with sulphate reducing bacteria (SRBs). As previously mentioned in this section, SRBs
are used to precipitate out toxic heavy metal ions as metal salts. The LINK programme tested
heterotrophic bacteria to ensure that toxic compounds were degraded to non-toxic intermediates.
In addition, work has been undertaken to optimise a bioluminescence-based assay of water quality
where freeze dried cells of bacteria are resuscitated and exposed to water samples. Such bacteria has
been tested on whisky distillery effluent which is contaminated with copper.
5.3.2.3 Purdue University
The company Purdue use a ‘phytoremediation’ system for wastewater treatment. Phytoremediation
uses a combination of plants and soil organisms in a ‘wastewater garden’ to reduce levels of heavy
metal contaminants.
However, this treatment process uses fixed plants to degrade heavy metals contaminating land.
Therefore this technology is better suited to land remediation and is no longer considered.
5.3.3 Biological treatment; patents
5.4 Chemical treatment
Chemical treatment of heavy metals usually consists of flocculants or metal precipitates.
Flocculants are high to very high molecular weight polyelectrolytes that can be either anionic, cationic
or non-ionic in charge. With some notable exceptions, commercially available flocculants are based
on polyacrylamide and its copolymers and derivates. The high reactivity of acrylamide monomer
leads to products with average molecular weights between 1,000,000 and 20,000,000. High
molecular weight means long chains of molecules that have the capability of physically bridging from
one microscopic particle to another.
In practice, wastewater is often treated with a coagulant to neutralise negative surface charges to near
zero. This process lowers the electrical repulsive barrier preventing microscopic particles in water
from coalescing. The system is then treated with a flocculant which acts to bridge the neutralised
primary particles. A single high molecular weight flocculant molecule is large enough to bridge to
several primary particles simultaneously. The loops and tails that extend from these microflocs can
further interact with other microflocs thereby creating macroscopic floc structures. Relative to
ERT F98/244/F005B
coagulation alone, flocculation results in larger, more shear resistant structures that settle faster with
less pinfloc and carryover in the supernatant water.
Flocculants are also used in sludge de-watering applications to assist in the release of water and
production of higher solids, lower volume material that is easier to handle. When added to the sludge,
the flocculant bridges from particle to particle and creates large flocs with free water between the flocs
that can be easily separated. Biological sludges, for example, contain 95% or more water even after
being concentrated as much as possible by gravity settling. Conversely, this is only 5% solids. De-
watering can produce a sludge cake of 25% solids that is 1/5 the original volume. Industrial sludge
generators use a wide variety of de-watering equipment to achieve this goal. Most popular are belt
presses, centrifuges, plate and frame presses, vacuum filters, screw presses and drying beds, all of
which require the addition of a flocculant for maximum performance.
Each type of sludge and each type of de-watering equipment require a polymer that is optimised for
that application. For example, biological sludges almost always require a highly charged, molecular
weight flocculant, but the optimum molecular weight and degree of polymer branching will depend on
whether the application uses a belt press or a centrifuge. Inorganic sludges, such as those found in
coal preparation plants and mining applications, normally require an anionic or non-ionic, high
molecular weight flocculant. Paper mills, which have a mixture of biological and inorganic sludges,
can use flocculants with lower cationic charges. In all cases, the choice of product depends on the
type of sludge, the de-watering equipment in use and the results desired. Selection of flocculants for
de-watering is both an art and a science.
Metals precipitants are compounds that show a strong affinity for metals in solution. These products
are often used with coagulants and/or precipitate from suspension.
Historically, lime and/or caustic has been used to bring the pH of the system to where the target metal
hydroxides are the most insoluble. The metals are then removed by settling.
ERT F98/244/F005B

VENDOR
Argonne National Lab. Photocatalyst process Possible Yes
(ANL).
Ashland Chemicals Inc. Coagulant / flocculant Yes Yes
chemicals (not process) (with other system)
British Nuclear Fuels pH adjustment process Possible Yes
Ltd. (BNFL).
Colloid Environmental 'Accofloc' Possible No
Technologies Comp.
(Cetco).
Environmental 'CBTS' Possible No
solutions Inc. (ESI).
Geochem Technologies 'MetaLuck 300 / Possible Yes
Chrom Con 346'
KBF Pollution 'SST' Possible No
Management Inc.
KDF Fluid Treatment REDOX Possible Yes
Inc.
Keeco 'KB.1' Possible No
Martin Marietta 'FloMag / MagneClear' Possible No
Materials Inc. (MMM).
Metre General Inc. 'Octolig' Possible No
(MGI).
WMEC Ltd. 'Sentinel Systems' Possible No
RESEARCH
Centre for Hazardous Thermosulphide process No n/a
Materials Research.
Los Alamos National Polymer binding Possible n/a
Lab.
ERT F98/244/F005B
5.4.1 Chemical treatment; vendors
5.4.1.1 Argonne National Laboratory (ANL)
ANL have been developing and testing photocatalysts which, they claim, both sequester and convert
heavy metal ions from aqueous solutions to recoverable metallic forms.
Successful tests have been carried out removing lead and mercury ions using cysteine modified TiO 2
colloids. These photocatalysts can be used for both wastewater and ground remediation applications.
5.4.1.2 Ashland Chemicals Inc
Drew Industrial, through Ashland, offer a range of treatment chemicals such as coagulants,
flocculants and metal precipitants.
Coagulants commonly available are polydiallydimethyl ammonium chloride (Poly-DADMAC) and

epichlorohydrin dimethylamine polymers (Epi/DMA). Poly-DADMAC is available in molecular
weights between 50,000 and 1,500,000, while Epi/DMA is available in molecular weights from
10,000 to 100,000. Careful selection of molecular weight is required for efficient operation.
Drew Industrial manufacture three inorganic based coagulants such as Chargepac (polyquaternary
amines with inorganic compounds), Amersep (polyquaternary amine with ferric salts) and the all-
organic Amerfloc (quaternary and tertiary amines).
Other chemicals available from the company are Drewfloc flocculants and Amersep metal
precipitants.
All products from Drew Industrial are chemical agents and therefore do not constitute a treatment
process, they facilitate the removal of heavy metals in an overall treatment system.
5.4.1.3 British Nuclear Fuels Limited (BNFL)
BNFL have utilised ‘process intensification’ to develop a treatment method for removal of heavy
metals. BNFL use pH adjustment for water treatment and their plant at Sellafield regularly processes
effluents with flowrates ranging from 0 to 400 m3/hr.
This neutralisation plant uses a two stage process of static mixers and control algorithms which
allows continuous pH adjustment during periods of fluctuating flowrates. One component of this
system is the vortex mixer which gives residence times between 0.2 and 0.002 seconds. BNFL claim
these vortex mixers ensure a homogenous stream with a tight particle size distribution.
This system, with its vortex mixers, should be relatively small in size which suggests suitability to the
offshore oil and gas industry. However pH adjustment-driven precipitation is metal selective
suggesting a process system is required for each metal ion an operator wishes to remove. However
further investigation into this system is recommended.
ERT F98/244/F005B
5.4.1.4 Colloid Environmental Technologies Company (Cetco)
Cetco manufacture Accofloc, a range of high swelling pure sodium bentonite clays found in the Black
Hills region in the western US. These Accofloc clays have ion exchange capabilities and are therefore
suitable for removal of trace heavy metal contaminants. The Accofloc clays have to be used in
conjunction with polymers and/or flocculating agents as they, alone, will not generate a floc.
Cetco also supply the chemical RM-10 for wastewater treatment systems. RM-10 is available as 20
different dry powder formulations for wastewater applications. RM-10 works by precipitating metal
hydroxides and binding metallic ions to the clay platelets by electrostatic forces. RM-10 is added to
the treatment system as a single dose.
As this is a bulk sludge sedimentation process, its applicability to the oil and gas industry is
questionable given the size and weight considerations as well as contaminated sludge disposal
requirements.
5.4.1.5 Environmental Solutions Inc (ESI)
ESI manufacture the concentrated bath treatment system (CBTS) for removal of heavy metal ions,
including chelated and complexed compounds.
The CBTS system consists of a conical bottomed reaction tank into which the wastewater is added
batchwise. A mixing pump is used to generate a consistent chemical reaction environment while a pH
electrode monitors the solution pH. A neutralising agent is added until the pH is balanced and
controlled with reference to an ion-specific electrode which ensures precipitation end-point is
achieved.
The treated waste stream then passes through a filter press to remove precipitated solids. If necessary
the ‘clean’ water can be passed through a polishing filter (eg diatomaceous earth) to remove trace
solids. ESI distribute a number of such process systems depending on required throughput and
desired effluent quality. Again, contaminated sludge is generated from these processes which should
be considered when assessing this technology.
ESI also manufacture a number of wastewater treatment chemicals such as metal precipitants,
flocculants and other special application chemicals. Details are contained in the vendor information in
Appendix 1.
5.4.1.6 Geochem Technologies
Geochem produce two speciality chemicals for the treatment of heavy metals. MetaLuck 300 is a
powdered treatment reagent designed to precipitate and stabilise heavy metal contaminants. Chrom
Con 346 is, again, a powdered treatment reagent for specific removal of toxic hexavalent chromium
Cr6+.
Geochem also produce the Aqua-Fix Technology for wastewater treatment applications. This process
uses packed bed columns which can remove metals such as aluminium, arsenic, cadmium, cobalt,
copper, chromium, iron, lead, manganese, mercury, molybdenum, nickel, silver, selenium, tin,
uranium, vanadium and zinc. This technology is claimed to reduce contaminants to drinking water
standards.
ERT F98/244/F005B
However, as an element of ion-exchange is used in the treatment process, its applicability to saline
produced water is undetermined. Further investigation is recommended as this seems an attractive
treatment option.
5.4.1.7 KBF Pollution Management Inc
KBF produce the SST (selective separation technology)-Toxicure system for removal of heavy metals.
SST-Toxicure is, again, a selective precipitation technology which requires no chemical manipulation
prior to treatment.
KBF’s patented SST system selectively removes harmful metal contaminants while leaving others
behind. KBF claim that their SST system is not as pH dependant as some other technologies; however
in some cases acids, bases or flocculants may be required. Hydrocarbon based insoluble components
have to be removed, as with most chemical precipitation systems, thus limiting the applicability to the
oil and gas industry.
5.4.1.8 KDF Fluid Treatment Inc
KDF produce process media of high purity copper-zinc granules for wastewater treatment. KDF
media operate on a REDOX principle (Reduction/Oxidation) by exchanging electrons with
contaminants. In this process, toxic heavy metal cations are claimed to bond to the KDF media.
These REDOX media are claimed to remove up to 98% of water soluble cations. An example of the
process is the reduction of lead cations which are reduced to insoluble lead atoms, which are
electroplated onto the surface of the media by the following equation
Zn - 2 electrons  Zn2+ in solution (oxidation)
Pb2+ + 2 electrons  Pb on media (reduction)
Other heavy metals are bonded to the media surface and are recovered when the exhausted media pass
through a copper smelter. This technology seems attractive considering no waste sludge is generated.
However the filter media requires onshore regeneration and effect of hydrocarbon contaminants
requires further investigation.
5.4.1.9 Keeco
KB.1 was designed by Keeco for the treatment of waters containing heavy metals. KB.1 precipitates
out heavy metals as salts. The precipitated heavy metals are permanently encapsulated in a tight
matrix of silica. Keeco claim the process only takes minutes, making this a cost effective solution.
Again, this is a chemical precipitation process which requires disposal of contaminated

sludge/precipitants and is therefore no longer considered.
ERT F98/244/F005B
5.4.1.10 Martin Marietta Materials Inc (MMM)
MMM market a range of chemical precipitants under the company Martin Marietta Magnesia
Specialties Inc. Their precipitants are FloMag and MagneClear magnesium hydroxide based.
MMM claim that magnesium hydroxide is a relatively safe alkali compared to lime and caustic soda,
making it more attractive from an occupational health standpoint. However, a waste sludge is still
generated, thus dismissing this particular treatment technology.
5.4.1.11 Metre General Inc (MGI)
MGI produce the Octolig metal removal system (MGI Octolig MRS) for heavy metals removal from
an aqueous stream. This process removes the cations cadmium, cerium, chromium (IU), cobalt,
copper, iron, gold, lead, manganese, mercury, nickel, silver, uranium and zinc, and the anions arsenic,
chromium, molybdenum and selenium. MGI claim that the cations sodium, potassium, calcium and
magnesium are not removed thus allowing the system to operate with saline waters.
Initially, some pH adjustment may be necessary prior to the fluid entering the fixed bed or fluidised
Octolig column. In some cases two columns in series may be necessary to reduce contaminant levels.
The Octolig is regenerated by passing a dilute acid, then dilute base solution through it. If desired the
regenerated liquid can precipitate out the metal hydroxides formed, which can be filtered out. The
filter cake, it is claimed, is of a high enough quality to be onward shipped for metal recovery.
The MGI Octolig MRS is better at removing heavy metals from water with very few organic
impurities. Therefore pre-treatment to remove hydrocarbon contaminants is necessary, making this
system seem less attractive.
5.4.1.12 WMEC Ltd
WMEC manufacture the Sentinel range of wastewater treatment systems. Both chemical and
biological systems are available; although in this study only chemical processes were investigated.
As with many chemical-treatment systems, the wastewater is treated on a batchwise basis. Water is
added to a main sentinel tank, to which a pre-weighed amount of ‘reagent’ is added to being the
flocculation process. This normally takes under an hour, after which the supernatant water is passed
through columns of activated carbon, prior to discharge. Tracer dye is added prior to the carbon
filters to determine ‘breakthrough’ of the columns. Sludge collected in the main sentinel tank is treated
in a filter press to dry out. WMEC claim that 5 kg of sludge is generated per cubic metre of influent
water.
However, as with many chemical flocculation systems, gross oil contamination is not removed,
making a separate oil removal plant necessary. This, together with necessary sludge disposal,
discounts this technology for oilfield applications.
ERT F98/244/F005B
5.4.2 Chemical treatment; research
5.4.2.1 Center for Hazardous Materials Research
The main purpose of this study was destruction of hazardous organics contained in soils while also
stabilising metals and metal ions. Contaminants are contacted with elemental sulphur at elevated
temperatures. In this process, heavy metals are converted to sulphides and therefore stabilised.
However, this technology is aimed at contaminated soil remediation and is not directly applicable to
this study.
5.4.2.2 Los Alamos National Laboratory
This technology was originally intended for treatment of radioactive wastewater and uses water
soluble chelating polymers for heavy metal ion removal.
The basis of this system is to use water soluble chelating polymers to selectively bind with metal ions
in aqueous solutions. These polymers have a sufficiently large molecular weight to be removed by
ultrafiltration.
Although this technology’s ability to remove selected ions is attractive, the use of ultrafiltration may
prove problematic in an offshore environment due to the oil concentration and presence of suspended
solids in produced water.
5.4.3 Chemical treatment; patents
Patent 5266210 uses a multi-stage process for the removal of heavy metals. This process involves pH
adjustment, sodium carbonate addition and use of a polymer coagulant to precipitate heavy metals as
a sludge.
Patent 5298168 is, again, a multi-stage process. Wastewater is first treated with a source of ferrous
ion and dithionite ion at low pH to condition the waste. The following stages use sludge addition and
chelating agents to precipitate heavy metals.
Patent 5320759 is a metal-ion selective method. In this system, heavy metal ions are reacted with a
xanthate and by controlling the pH of the reaction, selected ions can be removed. The author’s claim
that the xanthate can be recovered from the heavy metal/xanthate reaction product.
Patent 5332509 again describes a system that is claimed to remove selected heavy metal
contaminants. In this system the process utilises a combination of a transition metal (selected from a
group containing nickel, copper, iron and zinc) and an electropositive metal (selected from a group
consisting of magnesium and aluminium) to remove organonetallic compounds. The authors claim
that heavy metals are removed whether in ionic or non-ionic form.
Patent 5338460 describes a process for removing heavy metals with a water-soluble inorganic
sulphide or hydrosulphide. At elevated temperatures and, under controlled pH conditions, heavy metal
contaminants are precipitated out.
ERT F98/244/F005B
Patent 5344566 is specifically intended for removing lead from aqueous waste stream. This process
involves a precipitation stage followed by reverse osmosis filtration.
Patent 5370827 is again a precipitation process. The feed wastewater stream is treated with silicate
and ammonium hydroxide precipitants and then with an acid gas. This gels or precipitates the
contaminant containing silica matrix which can be filtered out.
Patent 5385653 describes a chemical process for heavy metals removal. In this process a vessel is
loaded with metal particles through which wastewater passes which has had coal particles added.
These coal particles interact with metal to form galvanic couple which produce ions of Fe which are
then involved in the reduction of heavy metal ions and formation of a coagulating agent.
Patent 5389262 uses ferrous dithionite in acidic aqueous solution. Heavy metal ions are reduced to
metallic particles while chelating agents are deactivated with bonding to the ferrous ions. Remaining
heavy metals are precipitated using an alkali metal hydroxide.
Patent 5395532 uses a water in oil micro-emulsion for heavy metals removal. Waste streams are
contacted with a solvent containing such a micro-emulsion wherein the inverted micelles contain the
extracted metal. A silicon alkoxide is added to encapsulate the extracted metals.
Patent 5395534 describes a water filtration medium for removing heavy metals. This medium
comprises manganese dioxide particles treated with a reducing agent such as ferrous sulphate. This
patent further describes the chemical treatment required prior to achieving the filtration medium,
which can then be housed in a suitable vessel.
Patent 5397500 describes a composition containing natrolite, montmorillonite, calcium hydroxide,

aluminium sulphate and magnesium oxide catalyst for removing heavy metals. Authors claim this
composition is particularly effective at treating copper, nickel, zinc, iron, lead, chromium and cyanide
contaminated wastewater streams.
Patent 5415778 describes a method for removing heavy metals by chemical precipitation. A waste
sludge is generated requiring disposal.
Patent 5433864 uses acorns for removing heavy metals. Acorns and nuts from the Eagaceae group
are dried at room temperature in the sun and acornic acid is extracted. This acid is filtered until
colourless and added to a waste stream maintained at pH 8-11.5. Ca 2+ ions are then added and the
heavy metal ions are either precipitated or filtered out.
Patent 5434331 is for treatment of contaminated soil or sludge and is therefore discounted.
Patent 5441648 uses a fluid containing sulphur trioxide to form heavy metal sulphates. A leaching
agent is then used to extract these sulphates.
Patent 5505857 uses a selective precipitation method to remove heavy metals. A combination of
oxidising agents, pH adjustments and sulphur compound addition are used to precipitate out metal
ions. The authors claim that if aluminium and/or arsenic are present in the feed waste stream, high
grade magnetic spinel ferrite can be recovered.
Patent 5478540 uses sulphur trioxide, again, to form heavy metal sulphates which can be leached and
separated for removal.
ERT F98/244/F005B
Patent 5512526 removes heavy metals by passing the aqueous feed stream through a system
containing expanded organophilic clay (such as montmorillonite), a fatty quaternary ammonium
compound and a fatty mercaptan. No further information is contained in the patent data concerning
operation of such a system.
Patent 5518633 describes a process for removal of metal ions with valances of 2 + and higher. Ions
with valances of at least 3 + are converted to hydroxides while ions with valances of 2 + form metal
carbonate precipitants.
Patent 5545331 utilises iron particles in acid aqueous solutions to form heavy metallic particles which
can be either disposed of or recovered. Chelating agents present in the process are deactivated by
bonding to ferrous ions from the iron particles. Remaining heavy metal ions are precipitated using an
alkali metal hydroxide.
Patent 558775 describes a portable water treatment system. High flux rates are used within a filter
assembly to minimise solids accumulation and give good mixing conditions. Sequential chemical
dosing in this filter system to precipitate solids prior to UV treatment and further filtration/ionisation.
Patent 5587079 uses sulphate reducing bacteria (SRBs) to form hydrogen sulphide gas. From this,
hazardous metals precipitate out as metal sulphides. Control of H2S dosing can allow selective
precipitation of certain heavy metal ions.
Patent 5635073 removes heavy metal contaminants by passing wastewater through a particulate
carrier material in the presence of ferrous iron and an oxidising agent. The flux rates are sufficiently
high to fluidise the carrier material particles and metal containing coatings are formed on the surfaces
of the carrier material particles. The contaminated carrier material particles are then removed.
Patent 5651895 describes a method for removal of heavy metals from wastewater containing
oxygenated hydrocarbons and organic acids suggesting a possible applicability to produced water use.
Iron salt is added to the wastewater under controlled pH conditions and metal ions precipitate out of
solution. This precipitate is removed by filtration.
Patent 5685993 utilises magnetically susceptible ferrite crystals which, in this process, are
continuously formed from an aqueous solution. The heavy metal contaminants are, the authors claim,
incorporated into the lattice points of the spinal ferrite structures and these precipitates can then be
magnetically removed. Again, controlled pH conditions are required.
Patent 5744045 involves the preparation of an alloy containing tin, copper and zinc which is used as a
filtration medium. Wastewater flow through this filter bed in a one-pass operation and the different
redox potentials cause the simultaneous removal of heavy metal contaminants. There is no mention of
whether this filter bed can be regenerated or whether new filter beds are required.
Patent 5750033 uses coagulating sedimentation for the removal of heavy metal ions. Again pH
adjustment is required in order to obtain efficient chemical coagulation and subsequent heavy metal
precipitation.
Patent 5762807 uses elemental sulphur with an alkali and/or alkaline earth metal hydroxide in the
presence of water. The authors also state that alkali sulphite salts can be added to the compound to
reduce H2S emissions. Heavy metals will be removed as precipitated metal salts.
ERT F98/244/F005B
Patent 5807486 utilises high flux rates within a filter system. This is similar to patent 5558775 as
this patent describes chemical treatment within a filter assembly prior to further treatment methods
such as UV or reverse osmosis.
5.5 Distillation treatment

Evaporation is being considered as an alternative process in an increasing number of wastewater
treatment applications. It can be effective for concentrating or removing salts, heavy metals and a
variety of hazardous materials from solution. Also, it may be used to recover useful by-products from
a solution, or to concentrate liquid wastes prior to additional treatment and final disposal. Most
applications of the technology also produce a high quality, reusable distillate; a very important feature
where water conservation is a priority.
During evaporation, a solution is concentrated when a portion of the solvent, usually water, is
vaporised, leaving behind a saline liquor that contains virtually all of the dissolved solids, or solute,
from the original feed. The process may be carried out naturally in solar evaporation ponds, or
through the use of commercially available evaporation equipment.
Solar evaporation ponds are usually limited by land availability and cost, potential odour problems, or
meteorologic and climatological conditions, whereas mechanical evaporators are relatively compact,
reliable and efficient.
Vendor/Research Process Applicability to Oil and Further investigation

VENDOR
Complience Systems Low temperature vacuum Possible No
Inc. (CSI). distillation
Greenwood Low temperature vacuum Possible No
Environmental Inc. distillation
RESEARCH
No information - -
5.5.1 Distillation treatment; vendors
5.5.1.1 Compliance Systems Inc (CSI)
CSI manufacture a distillation system to reduce contaminants in wastewater. This is an alternative

option which simply reduces the volume of contaminated fluid and therefore increasing the
concentration. Either high temperature evaporation or low temperature vacuum distillation (LTD) can
be used. The CSI system operates on an LTD principle.
CSI claim that LTD treatment reduces the water boiling point down to 65-70 ºF which reduced
operating costs and makes vapour recovery easier. However the large volumes of produced water
encountered offshore eliminates this system on practicability grounds alone.
ERT F98/244/F005B
5.5.1.2 Greenwood Environmental Inc
The heat pump evaporator from Greenwood is a totally enclosed vacuum evaporation system. This
system operates under the same principle as the previous vendor and is therefore not suitable for
produced water applications.
This is further proved true when considering the maximum unit throughput available is 20,000 gallons
of water per day.
5.5.2 Distillation treatment; research
No research material was found.
5.5.3 Distillation treatment; patents
Patent 5783084 uses distillation as a polishing stage intended for use downstream of chemical
treatment system for removal of heavy metals.
Water containing sodium sulphate is distilled to remove the ‘clean’ water leaving a concentrated brine
of sodium sulphate.
5.6 Electrochemical treatment

VENDOR
Andco Environmental Electrochemical No No
Processes Inc. chromate reduction
RESEARCH
Electrokinetic Inc. Ion migration No n/a
Fraunhofer Institute. Galvanic metal No n/a
deposition
ERT F98/244/F005B
5.6.1 Electrochemical treatment; vendors
5.6.1.1 Andco Environmental Processes Inc
Andco have developed a system intended for groundwater applications using electrochemical in-situ
chromate reduction and heavy metal immobilisation.
This process uses electrochemical reactions which generate ions for removal of hexavalent chromium
(Cr6+) and other heavy metals. Chromium Cr 6+ is removed by passing contaminated water through a
treatment cell containing electrodes. Current passing between these electrodes release ferrous and
hydroxyl ions which reduce the hexavalent chromium.
Although this treatment method claims to have favourable results, it is more applicable, as mentioned,
to groundwater applications and therefore is not considered any further for produced water treatment.
5.6.2 Electrochemical treatment; research
5.6.2.1 Electrokinetic Inc
Electrokinetics is a developing technology for treatment of contaminated soils and groundwater.

Basically, the principle of electrokinetic remediation is as follows:
Direct current is applied and the subsequent voltage gradient in a porous media leads to two
transport phenomena:
 ionic species (ie heavy metal ions) in the soil water mix will migrate to the opposite charged
electrode (electromigration);
 the bulk flow of soil water is induced towards the cathode (electro-osmosis).
The combination of these two effects moves contaminants ions towards one of the electrodes. Non
ionic species are transported along with the electro-osmosis induced water flow.
As mentioned, this technology is being developed specifically for contaminated groundwater
remediation and its applicability to produced water applications is questionable. In addition, the paper
enclosed in Appendix 1 states that efficiency drops when the target ion concentration is significantly
lower than the non target ion concentration. As this is the case for saline produced water (eg
concentration of Na+ and Mg+ ions will be much higher than heavy metals concentration), and
considering this technology’s difficulty to remove heavy metals in their metallic form, it is discounted
from this study.
5.6.2.2 Fraunhofer Institute
The Fraunhofer Institute are currently developing an electrochemical process for removal of heavy
metals from wastewater.
A prototype reactor has been developed which operates under the principles of galvanic metal
deposition along with direct or indirect anodic oxidation of organic compounds. In this reactor the
ERT F98/244/F005B
surface of the cathode is continuously scraped to remove deposited metals. Therefore the reactor can
be operated on a continuous basis, collecting deposited metals from the bottom of the vessel or
filtering them out.
However, further investigation is required to determine whether this technology is suitable for
treatment of produced water.
5.6.3 Electrochemical treatment; patents
Patent 5587064 removes heavy metal contaminants by deposition onto a cathode or cathodes, which
are mechanically removed. Contaminants deposited on the cathode are then removed using a
mechanical cutting device. The principle of operation seems similar to the second technology in the
research section.
5.7 Reverse osmosis
Even though reverse osmosis and ultrafiltration are both membrane-based separation methods, reverse
osmosis is distinctly different. By applying a pressure higher than osmotic pressure, reverse osmosis
separates water from both the suspended and dissolved contaminants in it. The pressure forces water
through the membrane, leaving the impurities behind.
Improvements in both equipment design and membrane fabrication have reduced the operating
pressures necessary to achieve the desired separation to below 200 psi. Because of the nature of the
process, clean water flow can be relatively slow. While not a critical concern for most residential
needs, for higher volume applications, the membrane area must be boosted accordingly.
Significantly, reverse osmosis not only rejects particles and large molecules, but it also excludes much
smaller dissolved salts and metal ions (ionic in nature) and low molecular weight species based on a
charge phenomenon action. The semipermeable membrane actually works better on polyvalent ions
(ions with more than one positive or negative charge, such as Ca 2+, Mg2+, or SO42-) than it does on
monovalent (single-charge) ions such as Na + or Cl-. Typically, reverse osmosis can remove greater
than 99 percent of all polyvalent ions and greater than 95 percent of all monovalent ions.

VENDOR
No information - -
RESEARCH
No information - -
5.7.1 Reverse osmosis; vendors
ERT F98/244/F005B
Although reverse osmosis is a potentially efficient method for removal of heavy metal components,
little to no information was available on treatment systems using such technology.
The only information found detailed a Biomin Inc system which focussed on an organoclay adsorber
intended for placement upstream of an RO filter membrane. This was to allow longer RO run times
as the purpose of the organoclay is to remove contaminants which may block up or foul the RO
membrane.
As mentioned, reverse osmosis is a potentially efficient system for use on water containing no oils;
therefore for the purpose of this study it is discounted.
5.7.2 Reverse osmosis; research
No relevant research information was found
5.7.3 Reverse osmosis; patents
No relevant patents were found
5.8 Ion exchange
Many impurities in water and other liquids exist as dissolved ionic species that can be removed by ion
exchange processes. Ions are either positively charged cations or negatively charged anions. Ion
exchange resins remove undesirable ions from solution by an exchange process in which impurities are
removed or immobilised by the resin and desirable ions are released into solution. The water softening
process is an example of this process: "hardness" made up of calcium and magnesium cations in the
water is exchanged for the sodium cations on the resin.
The first ion exchange resins were developed to remove the naturally occurring ions found in most city
water supplies such as calcium, magnesium, sodium, sulphates, chlorides, bicarbonates, carbonates
and silica.
For impurities or contaminants to be removed by ion exchange, they must be:
 ionized or charged;
 exchanged with ions of the same charge, and/or;
 attracted to the resin more strongly than the host ion.
As a result of growing industries such as electroplating, semiconductor, and printed circuit boards,
there was a need to remove metal ions from wastewater. Examples of metals requiring removal from
wastewater include cadmium, chromium, mercury, nickel, copper, gold, lead, silver, zinc and cyanide
complexes.
Today, ion exchange resins are being used to remove toxic and precious metals from industrial
wastewater streams. Industries are removing metals from their wastewater because of new regulatory
ERT F98/244/F005B
discharge limits on metals to the environment, the economic benefits derived by recovering the metals,
and because water reuse reduces waste volumes.
Ion exchange is a viable method of removal when the metals in the solution are ionized, when the ionic
strength of solution is not too high, and when volumes to be treated are large and the metals
concentrations are low.
Metals exist as either cations or complexed anions, and are either monovalent or polyvalent.
Therefore, a variety of ion exchange resins must be considered for each application. Ion exchange
resins for metal removal generally fall into four categories. The categories are determined by the
resin's functional group.
1 Strongly acidic cation exchange resins have sulphonic acid groups.

2 Weakly acidic cation exchange resins have carboxylic acid groups.
3 Strongly basic anion exchange resins have quaternary ammonium groups.
4 Weakly basic anion exchange resins have polyamine groups.
There is also a specialised category of resins known as chelating resins. Chelating resins are more
selective than standard resins due to their chelating functional groups. Examples of chelates are
iminodiacetate, thiouronium and aminophosphonic.

VENDOR
Bayer Corporation 'Lewaitt' No No
Environmental IO Resins No No
Solutions Inc.
RESEARCH
Oak Ridge Lab. Inorganic sorbent media No n/a
5.8.1 Ion exchange; vendors
5.8.1.1 Bayer Corporation
Bayer Corporation is a research based company which produce, among other things, ion exchange
resins. Bayer's own ion exchange resin is entitled 'Lewaitt', a chelating macroporous resin for
selective removal of heavy metal contaminants.
Lewaitt is claimed to have an ultra high chelating capacity offering higher operation capacities and
improved kinetics. These resins are also claimed to have high mechanical and osmotic stabilities
giving higher unit flowrates and longer expected operational lifetimes.
However the sometimes high salinity associated with produced water suggests this may not be a
suitable technology for this particular application and is therefore no longer considered.
5.8.1.2 Environmental Solutions Inc
ERT F98/244/F005B
As with the previous vendor, Environmental Solutions produce a range of treatment systems utilising
ion exchange resins for removal of heavy metals.
However, as described previously, the saline nature of produced water discounts this particular
technology.
Other manufacturers of ion exchange systems identified were Resintech Inc and Thermax Ltd. Details
of these companies are contained in the vendor information section.
5.8.2 Ion exchange; research
5.8.2.1 Oak Ridge National Laboratory
The Lockhead Martin Energy Systems division of Oak Ridge are developing spheroidal inorganic
sorbents for use as ion exchange media.
The authors of the paper contained in the vendor information section claim that inorganic ion
exchangers have high selectivities and efficiencies for separating and removing elements such as
radionuclides, actinide and heavy metals.
Such inorganic ion exchangers are claimed to have improved flow dynamics as the manufacturing
process eliminates the need for 'binders', which are commonly used to produce pellets from powder
form. These 'binders' tend to block pores within the resin, thus reducing efficiency.
However, as with traditional ion exchange methods, the salinity associated with produced water will
have a detrimental effect on expected performance.
5.8.3 Ion exchange; patents
Patent 5368632 describes a system using redox polymers to remove heavy metal contaminants.
Polymers such as polypyrroles, polyanilines and polythiophenes are used with this system and can be
regenerated, thus recovering metal contaminants.
Patent 5525315 describes a system using a cation exchange column, first washed with acid to remove
all sodium ions. The column is then washed with water of pH between 1 and 6 and can then be used
for heavy metals removal by chelating cation exchange.
Patent 5595666 uses magnetic polymer resins for heavy metals removal. The exchange resin consists
of resin beads with ferrites attached to the beads' surfaces. This resin is then used in the presence of a
magnetic field and is claimed to offer improved performance over methods employing ordinary ion
exchange resins or ferrites taken separately.
Patent 569882 describes a system for removing heavy metals utilising an extraction material which
has an activated surface which has an affinity for heavy metals and heavy metal ions. The patent
describes in detail the method of producing this activated surface.
ERT F98/244/F005B
Patent 5702611 describes a system which uses a mixture of a chelating ion exchange resin (with
sodium ions removed) and an anion exchange resin. This system is intended to remove heavy metal
contaminants from organic solutions. This patent references Patent 5525315 which is described
earlier in this section.
5.9 Filtration
Vendor/Research Process Applicability to Oil and Further investigation

VENDOR
E1 DuPont de 'Tyvek T980' Possible Yes
Namours / Oberlin
Filter Comp.
Sterling Air and Water 'Ecolyte' Possible No
Inc.
RESEARCH
No information - -
5.9.1 Filtration; vendors
5.9.1.1 E1 DuPont de Namours/Oberlin Filter Company
This system uses an automatic pressure filter with a spun-bonded olefin filter material (Tyvek T980).
The fabric has a pore size of 0.1 µm. The system is comprised of an upper feed water chamber and
lower filtered water chamber, separated by this fabric filter.
Claimed applications are:
 hazardous waste suspensions (containing heavy metals and cyanides);

 contaminated groundwaters;
 landfill leachates;
 process wastewaters (containing uranium).
The contaminated water to be treated is required to contain less than 5,000 ppm solids though oily
wastes are acceptable.
Demonstrations (1990) on groundwaters containing dissolved cadmium, lead and zinc showed zinc
removal efficiencies of 99.75 to 99.99%, though removal efficiency of other components is not
indicated.
Commercial installation of systems began in 1991, though treatment of saline waters was not
mentioned.
ERT F98/244/F005B
5.9.1.2 Sterling Air & Water Inc
Manufacturers of residential, commercial and industrial air and water filtration systems. The 'Ecolyte'
filter media is claimed to remove lead and other heavy metals as well as other components such as
chlorine, hydrogen sulphide and organics.
No performance data or effects of salinity are indicated.
5.9.2 Filtration; research
No research information was found.
5.9.3 Filtration; patents
5.10 Combined systems

VENDOR
Cognics Inc. Biological / chemical Yes Yes
process
Epoc Water Inc. 'EXXFLOW / Possible No
EXXPRESS'
Great Lakes Wastewater Treatment Possible No
Environmental inc.
Wheelaborator Clean PO*WW*ER Possible No
Air Systems Inc.
Techtran Complexing / sorption Possible Yes
Environmental Inc. process
RESEARCH
Atomic Energy Agency Chemical / filtration Possible n/a
of Canada Ltd. (AECL). process
New Jersey Institute of Chemical / desorption Possible n/a
Technology. process
ERT F98/244/F005B
5.10.1 Combined systems; vendors
5.10.1.1 Cognics Inc
Combined biological/chemical treatment, primarily for soil and sediment treatment. Heavy metals are
removed in the chemical leaching stage. Metals in the aqueous phase (leachate from contaminated
soils or contaminated waters) are separated using liquid ion exchange, resin ion exchange or reduction.
The second biological stage is used to remove organics.
The process is claimed to treat lead, zinc, cadmium, copper, petroleum hydrocarbons and polynuclear
aromatic hydrocarbons. Modifications allow removal of mercury and other metal, and halogenated
hydrocarbons.
5.10.1.2 Epoc Water Inc
The Epoc water system uses precipitation followed by microfiltration (with sludge dewatering).
Precipitation is undertaken by pH adjustment (EXXFLOW). The metal oxide and hydroxides. These
metal precipitates and other solids form a dynamic membrane when the contaminated water is
subsequently passed through a tubular, woven polyester filter (EXXPRESS).
The system is claimed to remove solids above 0.2 µm in size, though no heavy metal efficiency is
indicated and the effects of hydrocarbons and salinity are not stated.
5.10.1.3 Great Lakes Environmental Inc
This wastewater treatment system is claimed to remove free and emulsified oils, solids, heavy metals
and BOD in industrial waters.
The method of treatment and salinity effects are not indicated.
5.10.1.4 Wheelabrator Clean Air Systems Inc
The PO*WW*ER system is claimed to treat complex mixtures of:
 inorganic salts;
 metals;
 volatile and non-volatile organics;
 radionuclides.
The process combines evaporation and catalytic oxidation. Wastewaters are evaporated, passed over
a catalytic bed and recondensed, with the oxidised pollutants separated during oxidation and treated in
a scrubber.
Where large volumes of water and low levels of heavy metals are involved large systems would be
required thus application to produced water treatment would be limited.
ERT F98/244/F005B
5.10.1.5 Techtran Environmental Inc
This system uses a complex mixture of binding agents to remove heavy metals and radionuclides, in a
contaminated stream. This complexing and sorption process form flocculants and colloids which are
removed through filtration.
Treatment is claimed to reduce contaminants to drinking water standards.
Areas of treatment include:
 contaminated water, sludges and soils;

 groundwater from mining operations;
 water from petroleum operations;
 remediation of stored radionuclides.
5.10.2 Combined systems; research
5.10.2.1 Atomic Energy of Canada Ltd (AECL)
The AECL process combines chemical pretreatment and ultrafiltration to remove trace levels of
dissolved metals from wastewater, contaminated groundwater and leachate.
The wastewater to be treated passes through an initial prefilter to the conditioning tanks. Here, pH
adjustment is carried out and macromolecular compounds added to form heavy metal complexes.
Following the addition of polymer coagulants the wastewater passes through a crossflow
ultrafiltration system to remove the precipitated heavy metals.
Applications include:
 industrial processes;
 base metal production and processing;
 smelters;
 electrolysis operations;
 battery manufacturing.
The system is claimed to remove cadmium, lead, mercury, uranium, manganese, nickel, chromium and
silver from initial levels of several to 100 ppm down to required discharge levels.
5.10.2.2 New Jersey Institute of Technology
The GHEA Associates Process uses surfactant addition to remove organic and metal contaminants (in
soil washing) and treatment of the aqueous phase by desorption.
Applications include soil, sludge, sediments, slurries, groundwater, surface water, end of pipe
industrial effluents and in situ soil flushing.
ERT F98/244/F005B
The system is claimed to remove 96.8% of chromium and 99.4% total hydrocarbons, though treatment
of low level heavy metal contamination and saline waters is not indicated.
5.10.3 Combined systems; patents
ERT F98/244/F005B
6 Analytical techniques
(References: Alloway and Ayres, 1997; Manahan, 1992b; Okland, 1993.)
6.1 Atomic Absorption Spectrometry (AAS)
Atomic Absorption Spectrometry was first used in the late 1930's to measure mercury in air but it was
not until the late 1960's that AAS and later Atomic Emission Spectrometry (AES) began to be widely
used. The theory of the AAS is based on the 19th century line spectra observations by Fraunhofer's
and Kirchhoff and Bunsen's principle that matter absorbs light at the same wavelength as it emits it.
In AAS devices a solution containing the metal ions is introduced as fine droplets into a gas stream
entering a heating source, eg a furnace or flame. The metal ions become excited and are reduced to
neutral atoms through electron capture. The required electrons for this transition are produced by a
hollow cathode tube. The incident beam from the tube is focused at the point that the metal ions are
come in contact with the heat source. Light of the relevant wavelength that is passed through the
flame is absorbed by the relevant element and measured by a light detector. The amount of light
absorbed at that wavelength is directly related to the amount of that element.
6.1.1 Flame Atomic Absorption Spectrometry (F-AAS)
In F-AAS the sample is aspirated into a flame and atomised, a method similar to flame emission
photometry. In F-AAS though a light beam is directed through the flame to a monochromator and
onto a detector that can measure the amount of light absorbed by the atomised elements in the flame.
Thus the amount of energy absorbed by the flame at the wavelength appropriate to the element is
directly proportional to the amount of that element. F-AAS uses air-acetylene or nitrous oxide-
acetylene mixtures as the flame gas.
Because many elements have their own characteristic wavelengths, by using a light source utilising the
element to be tested for, spectral and radiation interference, is minimised, and thus accurate
measurements at low concentrations may be obtained.
6.1.2 Cold-Vapour Atomic Absorption Spectrometry (CV-AAS)
This method is used exclusively for the analysis of mercury. The method uses a 'cold' cell through
which air used to aspirate a sample is passed. The absorbed light source used is a hollow cathode
mercury lamp and as with the other AA methods an AA detector and recorder are used. No ionisation
flame or heat source is required.
This method of analysis is simple and accurate, though specific to mercury.
ERT F98/244/F005B
6.1.3 Electrothermal Atomic Absorption Spectrometry (E-AAS)
The method of analysis is similar to that for F-AAS except the flame is replaced by a heated atomiser
or graphite furnace. This method allows the temperature of heating to be varied and may be
undertaken over a number of stages, such as drying, charring and atomisation stages.
This method allows the ground-state atoms to remain in the optical path for a longer period of time
than in F-AAS. This results in more accurate results at low concentrations. Another benefit is that
this method allows small, solid samples to be analysed. The method though is more prone to
interferences than F-AAS due to the longer analysis time.
6.1.4 Hydride Generation/Atomic Absorption Spectrometry (HG/AAS)
HG/AAS is specific for the analysis of Arsenic and Selenium. Prior to analysis, samples are digested
to convert the Arsenic and Selenium to there hydrates using sulphuric-nitric-perchloric or sulphuric-
nitric acid. These elements can then be separated and measured in an AAS using a hydrogen-oxygen
flame.
This method is very accurate for Selenium and Arsenic as the elements are removed from any
potentially interfering elements.
6.2 Plasma Emission Spectrometry (PES)
First developed in the mid 1960's, Plasma Emission Spectrometry utilises an Inductively Coupled
Plasma (ICP) to measure very small concentrations of metals. Argon gas flows through a radio
frequency field oscillating at 27.1 to 40.68 MHz (depending on unit design) which sends an alternating
current through water cooled coils, initiated by sparks from a Tesla coil. This field excites the gas
causing electrons in the plasma to collide with argon atoms causing ionisation and producing an argon
plasma. A quartz 'torch' is situated inside the coil which supports and confines the plasma. The
temperature of the plasma is between 7000 and 9000 K. Following solvent stripping the argon/sample
passes through the argon plasma where the sample is ionised and through the viewing zone. Samples
are injected into the argon gas feed stream where first the solvent is stripped at 4000 to 5000 K. The
ionised sample then continues to the measurement device (AAS or OES). Liquid samples may be
introduced directly but solid samples require solvent extraction prior to testing.
6.2.1 Inductively Coupled Plasma Mass Spectrometry (ICP-MS)
Of the two methods of measurement in ICP systems the mass spectrometer is the most accurate. The
stream of ions produced by the ICP is focused on a slit prior to entering a strong magnetic field. The
ion stream is then split within the magnetic field into its different constituents because of their different
masses and are then measured using an EM detector. All of the analysis is carried out within a
vacuum.
This method of detection is very accurate at very low concentrations but requires a skilled operator to
undertake the analysis. Because the analysis is dependant on the mass of the elements within the
ERT F98/244/F005B
sample, some interference may occur from constituents of the same or similar mass. Thus as shown
in table 6.1 other methods of analysis may be more accurate for some elements.
6.2.2 Inductively Coupled Plasma Optical Emission Spectrometry (ICP-OES)
Due to the conditions in the viewing zone, AAS is not suitable for measuring the concentration of
elements, thus OES is used as an alternative to MS. The light produced by the sample in the ICP is
passed through a prism in the OES. The high excitation temperature of the sample results in a spectra
of many emission lines from each element which can then be analysed and the composition of the
sample calculated.
Though this method of measurement is simpler than mass spectrometry, it is less accurate. Because
many spectra lines are produced by each element, interference may occur where the sample contains a
number of elements.
6.3 High Pressure Liquid Chromatography (HPLC)
The use of chromatography relies on the difference in speed of molecules of different weights through
a medium when carried in a flowing fluid (eluent). When the sample is passed through this medium
the molecules of different weights are split into separate bands which can then be independently
measured and compared to a standard. In low pressure liquid chromatography this process takes a
great deal of time, is subject to eddy diffusion and requires large volumes of solvent. The use of high
pressure (6000 psi) systems was thus developed to remove these problems. In such systems columns
of up to 50 cm in length and 4 to 6 mm in diameter are used to separate elements. These bands of
elements travel through the column and finally exit the column with the eluent. As each element leaves
the column, it is measured using a suitable detector. There are a large number of detectors available
including refractive index, UV and electrochemical units. The simplest method is to measure the
conductivity of the exiting eluent, relying on an appropriate column medium to separate the molecules.
A series of peaks is thus produced, each relating to a specific molecule type.
ERT F98/244/F005B
Table 6.1 Methods of analysis for metals and semi-metals below 1000 ppb (AAS, PES and
HPLC)
Method of Analysis Elements Tested Lowest Detectable Concentration (ppb)

AAS (F-AAS) Mg <0.1
Cd, Li, Ag, Zn, Ca, Cu, Mn <1
Pb, Tl, Ba, Co, Au, Ni, Fe, Cr <10
As, Sn, Se, Si, Ti, Pt, V, Al, Sb, Mo, Bi, Te <100
AAS (CV-AAS) Hg <0.5
AAS (E-AAS) Zn <0.01
Co, Cu, Fe, Mo, Al, Cr, Mn, Ag, Mg, Cd <0.1
Sb, Bi, Au, Ni, Si, Te, Tl, Ca, Pb, Ba <1
Se, Ti, Li, As, Pt, Sn, V <10
Hg <100
AAS (HG/AAS) As, Se <5
PES (ICP-OES) Ba, Ca, Mn, Mg, Be, Bi, Sr, Ti, Zn <1
Cd, Li, Cu, Fe, B, Zr, Cr, V, Ag, Co, Mo, <10
Si, Ni, Au
Al, Nb, Ta, W, As, Sn, Na, Pb, Sb, P, Se, S, <100
Pd, Pt, Tl
PES (ICP-MS) Ce, Ho, In, Lu, Pr, Bi, Cs, La, Hf, Ir, Re, <0.001
Eu, Co, Er, Nb, Au, Dy, Ga, Pb
Ba, Gd, Mn, Nd, Pt, Ag, Cu, Ge, Mo, Pd, <0.01
Rb, Hg, Al, As, Ni, Mg, Cd
Cr, Be, Li, Na, B <0.1
Br, P, Fe, K, Ca <1
HPLC Li, Na, K, Ni, Zn Co, Mg, Ca, Al, Cd, Pb, <10
Se, Cr, Ni, Sb, Cu, Hg, Ag, Fe, Mn, Ti, Tl,
This method of analysis is quite accurate down to the 10 ppb level but some problems may be
encountered. Firstly, the concentration of elements in the eluent may be required to be low for
accurate analysis and thus dilution of the sample may be required. Contaminates such as oil must be
removed prior to analysis, as these may contaminate the chromatography medium, resulting in
permanent damage, while other contaminants may be eluted with a specific element that is being
tested. Finally, where a number of elements are being analysed for in a single column, the peak from
large concentrations of a single element may interfere or completely hide peaks from other elements.
ERT F98/244/F005B
6.4 Other Methods
6.4.1 Flame Emission Photometry (FEP)
In flame photometry the sample to be tested is sprayed into a gas flame under carefully controlled
conditions. Light produced from the excitation of the molecules in the sample causes spectral lines to
be produced. The line relevant to the element tested can be isolated (at the relevant wavelength) using
interference filters, prisms or gratings. The intensity of the spectral line is then measured using a
phototube or potentiometer.
This method is accurate (in terms of % error) at high concentrations (0.1 ppm or above) but is
relatively inaccurate at lower concentrations (Table 6.2), when compared to the methods above due to
interference of other elements.
Table 6.2 Methods of analysis for metals and semi-metals below 1000 ppb (FEP and
colorimetry/spectrophotometry)
Method of Analysis Elements Tested Lowest Detectable Concentration

(ppb)
Flame Emission Photometric Method K <0.1
Li, Sr <0.5
Na <10
Dithizone Method Cd, Ag <0.5
Pb, Hg, Zn <1
Colorimetric Method Se <10
Cr <150
Eriochrome Cyanide R Method Al <10
Silver Diethyldithiocarbamate Method As <1
Aluminon Method Be <5
Neocuproine Method Cu <1
Bathocuproine Method Cu <20
Phenenthroline Method Fe <10
Persulphate Method Mn <50
Fluorimetric Method Se <10
Gallic Acid Method V <0.05
Zincon Method Zn <500
6.4.2 Colorimetry/Spectrophotometry
The remaining methods in Table 6.2 use colorimetry to measure element concentration. These
methods use a variety of chemicals to produce a colour change or colour intensity to indicate the
presence of a specific element, which can then be compared with a blank using spectrophotometry.
ERT F98/244/F005B
This method of analysis is the cheapest, though depending on the method, may not necessarily be the
easiest. These methods may also be inaccurate, especially at low ranges, due to interference from
other elements and inaccuracies during testing.
ERT F98/244/F005B
7 References
Alloway, B .J and Ayres D C (1997). Chemical Principles of Environmental Pollution. 2nd Edition.
Blackie Academic and Professional.
Beger, M (1994). Heavy metals in the environment - selected methods of their removal from urban
and industrial waste waters. MSc Thesis.
Bowen, H J M (1979). The environmental chemistry of the elements. Academic Press.
Brown, B, Colling, A, Park, D, Phillips, J, Rothery, D and Wright, J (1989). Seawater: Its
composition, properties and behaviour. 1st Edition. Wheaton and Co.
Fergusson, J E (1990). The heavy elements, environmental impact and health effects. Pergamon
Press.
Kazantis, G (1980). Metals in the environment (Ch 8). Academic Press.
Langard, S (1980). Metals in the environment (Ch 4). Academic Press.
Manahan, S E (1992a). Toxicological Chemistry. 2nd Edition. Lewis Publishers.
Manahan, S E (1992b). Environmental Chemistry. 5th Edition. Lewis Publishers.
Manahan, S E (1993). Fundamentals of Environmental Chemistry. 1st Edition. Lewis Publishers.
Marlow, D R (1993). The occurrence of Arsenic and Mercury in oil and gas deposits in various
regions throughout the world.
Okland, M (1993). A review of problems in oil and gas exploration and production created by
mercury. MSc Thesis.
Rainbow, P S (1993). Ecotoxicology of metals in invertibrates. CRC Press.
Rainbow, P S and White, S L (1989). Comparative strategies of heavy metal accumulation by

crustaceans: zinc, copper and cadmium in a decapod, an amphipod and a barnacle. Hydrobiologia,
174, 245-262.
Ray, J P and Engelhardt, F R (Ed) (1992). Produced water : Technical/environmental issues and
solutions. 1st Edition. Plenum Press.
Sarrazin, P, Cameron, C J, Barthel, Y and Morrison, M E (1993). Processes prevent detrimental

effects from As and Hg in feedstokes. Oil & Gas Jour., Jan. 25, 86-90.
Solheim, A (1994). Biological removal of heavy metals from municipal sludge. MSc Thesis.
ERT F98/244/F005B
Tibbetts, P J C, Bucnanan, I T, Gawel, L J and Large, R (1989). A comprehensive determination of

produced water composition.
Wilding, T A (1993). The world wide occurrence and discharge of mercury and arsenic in oil and gas
exploration, production and refining operations.
ERT F98/244/F005B

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SIEP 99­5266 ­ ii ­ Restricted

 adsorption and absorption,

 vendor systems commercially available;

 adsorption and absorption,

2 DEFINITION OF HEAVY METAL 2

3 CHEMISTRY OF HEAVY METALS 3

3.1 Sources of heavy metals in aquatic environments 3

3.2 Types of heavy metal compounds in the aquatic environment 4

3.3 Behaviour of heavy metals in the aquatic environment 6

3.4 Heavy metals in North Sea produced water 7

4 TOXIC EFFECTS OF HEAVY METALS 10

4.2 Health effects 12

4.3 Environmental effects 13

4.5 Environmental fate/mode of transport 15

5 ASSESSMENT OF TREATMENT TECHNOLOGIES 16

5.1 Adsorption and absorption 17

5.2 Advanced affinity chromatography 21

5.3 Biological treatment 22

5.4 Chemical treatment 25

5.5 Distillation treatment 35

5.6 Electrochemical treatment 36

5.7 Reverse osmosis 38

5.8 Ion exchange 39

5.10 Combined systems 43

6.1 Atomic Absorption Spectrometry (AAS) 47

6.2 Plasma Emission Spectrometry (PES) 48

6.3 High Pressure Liquid Chromatography (HPLC) 49

6.4 Other Methods 51

APPENDIX (See SIEP 99-5282)

2 Definition of heavy metal

Table 2.1 Important metals and semi-metals (metalloids) (CAS version)

Series Symbol Element Atomic Atomic

3 Chemistry of heavy metals

3.1 Sources of heavy metals in aquatic environments

3.2 Types of heavy metal compounds in the aquatic environment

1) hydroxides, oxides, silicates, or sulphides; or

3.2.1 Inorganic heavy metal compounds

3.2.2 Organically bound metals and metalloids

3.3 Behaviour of heavy metals in the aquatic environment

Pb <0.05 <0.05 0.38 0.84 10-5 - 6·10-5

Element Concentration in oil and gas fields Concentration in

4 Toxic effects of heavy metals

 blockage of essential enzymatic activity;

4.2 Health effects

4.3 Environmental effects

4.5 Environmental fate/mode of transport

5 Assessment of treatment technologies

 adsorption and absorption;

1 vendor systems commercially available;

5.1 Adsorption and absorption

Table 5.1 Summary of vendor and research products

Vendor/Researcher Process Applicability to Oil Further investigation

5.1.1 Adsorption and absorption; vendors

5.1.1.1 ATA Technologies Corporation

5.1.1.2 Biomin Incorporated

5.1.1.3 Colloid Environmental Technologies Company

5.1.1.5 Dynaphore Inc

5.1.1.6 Pacific Northwest National Laboratory

5.1.1.7 Selective Environmental Technologies Inc (Selentec)

5.1.2 Adsorption and absorption; research

5.1.2.1 Western Product Recovery Group Inc

5.1.2.2 Filter Flow Technology Inc

5.1.3 Adsorption and absorption; patents

SIEP 995266 ii Restricted