3.

04 Emerging Contaminants
K Kümmerer, Leuphana University, Lüneburg, Germany
& 2011 Elsevier B.V. All rights reserved.

3.04.1 Introduction 69
3.04.2 General Aspects: What Are the Emerging Contaminants and Micro-Pollutants? 69
3.04.3 Parent Compounds, Metabolites, and Transformation Products 70
3.04.4 A High Diversity of Chemicals Is Present in the Aquatic Environment 71
3.04.5 Sources and Fate 72
3.04.6 Examples of Individual Groups 73
3.04.6.1 Aryl Sulfonates 73
3.04.6.2 Flame Retardants 74
3.04.6.2.1 Organobromine compounds 74
3.04.6.2.2 Organophosphorus compounds 74
3.04.6.3 Pesticides 75
3.04.7 Endocrine Disrupting Chemicals 75
3.04.8 Anticorrosive Additives – BT and TT 75
3.04.9 Gasoline Additives – Methyl tert-Butyl Ether 76
3.04.10 Perfluorinated Surfactants – PFOS and PFOA 77
3.04.11 Personal-Care Products 77
3.04.12 Fragrances and Odorants 77
3.04.13 Disinfectants 78
3.04.14 UV Filters 78
3.04.15 Pharmaceuticals 78
3.04.15.1 Active Pharmaceutical Ingredients 78
3.04.15.2 Illicit Drugs 80
3.04.15.3 Metabolites 81
3.04.16 Engineered Nanoparticles 81
3.04.17 Artificial Sweeteners 82
3.04.18 Cyanotoxins 82
References 83

3.04.1 Introduction Population growth and climate change will place great
pressure on water resources in the future. Even now, several
The history of chemistry and the pharmaceutical sciences is an regions of this planet suffer surface water shortage as an
impressive success story. The products of the chemical and everyday challenge, because water is necessary for agricultural,
pharmaceutical industries are ubiquitous in everyday life. They industrial, recreational, laundry, personal care, and drinking
help us to define the modern way of living. They contribute to purposes. Therefore, the quality and quantity of water have to
our health and high living standards. The production of be carefully surveyed and managed. Artificial recharge can
chemicals and pharmaceuticals, their usage, and application contribute to groundwater resources. However, quality control
was associated over a long period with heavy pollution of the of the waters to be used must ensure that the groundwater is
environment and serious health effects. During the second not contaminated by the water used for charging, so the re-
half of the last century, tremendous progress was made to charge water must itself meet high standards. The presence of
prevent the pollution of environment and to reduce the im- organic pollutants such as medicines, disinfectants, contrast
pact of such pollution on health. Nowadays, proper and media, personal care products, laundry detergents, surfactants,
effective treatment and the prevention of emissions into air, pesticides, dyes, paints, preservatives and food additives, and
water, and soil is in place in developed countries and will their metabolites and transformation products is of growing
spread woldwide. However, it has also been learned since the interest in this context. Chemicals, like many of the xenobiotic
end of the last century that products of the chemical and organic compounds, are of increasing concern in urban water
pharmaceutical industries themselves such as medicines, dis- management, because water supply, urban drainage, and
infectants, contrast media, personal care products, laundry wastewater-treatment systems were expressly designed origin-
detergents, surfactants, pesticides, dyes, paints, preservatives ally to solve other problems (supply of potable water, flooding
food additives, and personal care products, to name a few, also prevention, and sanitation). Thus, there is a need to under-
constitute a new type of environmental pollution and a pos- stand, in an integrated manner, the sources, flow paths, fates,
sible health risk for the consumer. and effects of hazardous chemicals on both humans and

69
70 Emerging Contaminants

ecosystems. In this chapter, a very brief overview is given of micro-pollutants, chemicals with similar structures can be
our present knowledge about the presence of emerging pol- found. However, often groups of chemicals with very different
lutants in the aquatic environment. With respect to the vast structures and properties belong to the same category in terms
amount of literature available, only a rough overview for some of application and usage. Pharmaceuticals are often classified
groups of emerging contaminants will be given here for the according to their purpose and biological activity. The same
sake of demonstration rather than claiming an exhaustive hold for other groups such as insecticides, biocides, dyers,
elaboration and full overview of the topic. Instead, some plasticizers, antibiotics, analgesics, and anti-neoplastics. Clas-
typical examples and results are presented to demonstrate sification according to chemical structure is often used within
general principles and important issues and the diversity of subgroups of chemicals, for example, within the group of
chemicals involved. Therefore, after some general consider- antibiotics or the subgroups within the antibiotics such as
ations referring to the term ‘emerging contaminants’, some b-lactams, cephalosporins, penicillins, or quinolones. Other
selected examples will be presented in the following. The classifications refer to the mode of action (MOA), for example,
purpose of this chapter is not, and cannot be, to review all the anti-metabolites or alkylating agents within the group of
available results as the literature is vast. Instead, typical and cytotoxics/anti-neoplastics. In the case of classification ac-
illustrative examples and facts will be presented to demon- cording to MOA, the structures of molecules within the same
strate the underlying issues. group can be very different and, hence, so can their environ-
The reader interested in more detailed data and findings mental fates. Sometimes authors summarize a certain group of
will find help in the numerous books and reviews that have chemicals according to their chemical structure (e.g., bromi-
already been published. As for analysis, for example, only re- nated diphenyl ethers) and sometimes according to their use
cently two extensive reviews were published (Richardson, (e.g., pharmaceuticals and flame retardants) or both at the
2009; Giger, 2009). Therefore, analytical issues are not ad- same time. As some chemicals with a certain chemical struc-
dressed here. Instead, the interested reader is advised to seek ture such as the nyphtylsulfonates are applied for different
help in these articles and the ones cited in this chapter. purposes, such chemicals are often referred to in terms of their
Phthalates, polychlorinated dioxins, polychlorinated bi- chemical structure only. In general, there is no clear differen-
phenyls (PCBs), polycyclic aromatic hydrocarbons, the older tiation, and overlaps of different classification schemes are
pesticides such as the chlordienes, dichlorodiphenyltri- common. Depending on the class of compounds, the emer-
chloroethane, and others, surfactants such as linear alkylsul- ging contaminant is the chemical itself or it may only be the
fonates and nonylphenol and nonylphenol ethoxylates, their transformation products or metabolites (e.g., pesticides or
transformation products, and other compounds have long some surfactants). It is the transformation products, for others
been known to be present in the aquatic environment. Hence, such as pharmaceuticals it is the parent compounds and, since
they will not be included here. only recently, the transformation products too. Often authors
used the term ‘emerging contaminant’ to emphasize the nov-
elty of the detection of a certain chemical in the (aquatic)
3.04.2 General Aspects: What Are the Emerging environment. However, how ‘first’ is first enough is judged
Contaminants and Micro-Pollutants? differently by different authors and readers. Therefore, the
expression ‘emerging contaminant’ is not only loosely defined
The presence of certain chemicals at the lower mg l1 level in and used. The chemicals included may change from one
the aquatic environment has become evident with the im- author to another and within time. Furthermore, generally, it
provement of analytical techniques (Reemtsma and Jekel, does not mean that these compounds have only recently ap-
2006; Barceló and Petrovic, 2008; Kümmerer, 2008a). The peared in the environment; sometimes, it does not even mean
broader availability of liquid chromatography–mass spec- that there have been no earlier reports on their presence, be-
trometry (LC–MS) and LC–MS/MS, in particular, permits the cause in some cases older literature has not been searched for
detection of polar compounds such as most pharmaceuticals, or cited. In some other cases, these substances may have been
metabolites, and transformation products that have not pre- introduced into the environment long ago but had not been
viously been amenable to analysis. Some will never be de- detected because they had not been searched for or their
tected. This is one reason why these chemicals are often called concentration is so low (mg l1 and below) that until recently
emerging contaminants. However, there is neither a general they were undetectable. In cases where findings had been re-
definition nor a complete list of compounds available that are ported earlier but not noticed by the researches and the
in general included by the term ‘emerging contaminant’. The compounds are of interst now (again), the term ‘emerging
environment is contaminated by myriads of ‘merging con- contaminant’ is applied by some authors despite this earlier
taminants’, that is, chemicals present in the aquatic environ- findings. Emerging contaminant is a more or less loosely de-
ment in the mg l1 range and below. Because of this fined subgroup of the micro-pollutants. The list given here
concentration range, they are often called organic micro- reveals that the emerging contaminants are not a homo-
pollutants too. They are released from urban, industrial, geneous group of chemicals. On the contrary, they are very
agricultural, and other anthropogenic activities. Many of these different and they can be grouped according to chemical
have been and are currently undetected. structure, properties, purpose of application, or effects, re-
As most of the chemicals applied by consumers will end spectively. The composition of the types of compounds con-
up in sewage, ‘emerging contaminants’ is a term that des- stituting the whole bunch of emerging contaminants
cribes nowadays often the pollution of the aquatic environ- undergoes subtle change with time, as compounds that have
ment. Within the groups of emerging contaminants and/or been named emerging contaminant years ago may not be in
 Emerging Contaminants 71

the focus of the researches anymore after some time for several 2002; Zühlke et al., 2004; Li et al., 2008a; Méndez-Arriaga
reasons. Instead, other groups of chemicals may be included. et al., 2008). The resulting substances are often referred to as
The presence of such pollutants in the aquatic environment, metabolites by authors. However, this is confusing as metab-
however, is one of the big challenges for a sustainable water olism is linked to living organisms. Chemicals resulting from
future in any case (DFG, 2003; Schwarzenbach et al., 2006; nonbiotic transformation in the environment should there-
Ledin and Patureau, 2008; Fatta-Kassinos et al., 2010). fore be referred to as transformation products. When con-
Summarizing, there is no clear definition of emerging sidering pharmaceuticals and other chemicals in the
pollutants. In contrast, the term ‘micro-pollutants’ refers environment that are transformed by living organisms, it is
clearly to a nonambiguous criterion, that is, to such com- advisable to be even more restrictive. One should only refer to
pounds that are detected in the environment in the mg l1 those substances as metabolites that have been altered in their
range and below, independently of their chemical structure, chemical structure within a target organism (Längin et al.,
usage, or MOA, whereas the term emerging contaminant 2008; Figure 1). All other compounds should be referred to as
seems to be most helpful in the press room, not in science. transformation products. Their origin can be indicated in
Therefore, the author recommends to abandon the term designation by adding the process of formation, for example,
‘emerging contaminant’ and to stick with ‘micro-pollutant’. phototransformation product. Generally, such a structural
change results in new chemical entities with new properties.
Normally, it is assumed that metabolism and transformation
3.04.3 Parent Compounds, Metabolites, and of pharmaceuticals and other chemicals lead to decreased
Transformation Products toxicity. In some cases, however, metabolism (e.g., in the case
of pro-drugs) and transformation lead to more active com-
Many pharmaceuticals undergo a structural change in the pounds. The same has been found for phototransformation
bodies of humans and animals. The results of such processes and other oxidizing processes.
are metabolites. After their excretion and release into the en- Nowadays, several European regulations require the in-
vironment, both parent compounds and metabolites can clusion of transformation products in environmental risk as-
undergo structural changes by a variety of biotic and nonbiotic sessment and monitoring (e.g., Drinking Water Directive,
processes, including photolysis, hydrolysis, and bio- 1998; European Commission, 2003). The exposure to trans-
transformation. Pharmaceuticals and other chemicals are formation products can be relevant as has been indicated, for
often incompletely transformed, that is, they are not fully example, for pesticides in groundwater (Boxall et al., 2004;
mineralized by organisms such as bacteria and fungi in the Kolpin et al., 1997, 2004; Hanke et al., 2007). In these studies,
environment (Haiß and Kümmerer, 2006; Gröning et al., several pesticide metabolites (e.g., well known from the
2007; Trautwein et al., 2008) as well as by light and other extensively applied pesticide metolachlor) were found in
nonbiotic chemical processes. Structural transformations of higher concentrations in groundwater than the parent com-
chemicals may also be a result of technical processes such as pounds (see also the case of tolylfluanid described in this
effluent treatment by oxidation and photolysis (Ravina et al., chapter).

Active
pharmaceutical
(parent compound)

Nonbiological metabolism Humans

(hydrolysis in the stomach)
Metabolites Human metabolism Microbial metabolism
(liver, mucosa, etc.) (skin and gut)

Sewage
Transformation Water
products Soil
Manure
Biological Nonbiological
(air)
transformation transformation
(organisms) (light, oxidation, hydrolysis, etc.)

Technical transformation (Water)

(ozonolysis, photolysis, chlorination, etc.) treatment

Figure 1 Metabolites and transformation products of pharmaceuticals. For other compounds only transformation products are of interest. From
Kümmerer K (ed.) (2008a) Pharmaceuticals in the Environment: Sources, Fate, Effects and Risks, 3rd edn. Berlin: Springer.
72 Emerging Contaminants

3.04.4 A High Diversity of Chemicals Is Present in the 1,7-dimethylxanthine (16%, caffeine metabolite), and tri-(2-
Aquatic Environment chloroethyl)phosphate (12%, fire retardant). A median of four
compounds was detected per site, indicating that chemicals
In a study, more than 100 individual water samples from over generally occur in mixtures in the aquatic environment and
100 European rivers from 27 European Countries were ana- are likely to originate from a variety of natural origin, animal
lyzed for 35 selected compounds, comprising pharma- and human uses, and waste sources. In another study, four
ceuticals, pesticides, fluorinated surfactants, benzotriazoles wells down-gradient from a landfill were investigated for the
(BTs), hormones, and endocrine disrupters. Around 40 la- presence of waste-indicator and pharmaceutical compounds
boratories participated in this sampling exercise. The com- in groundwater affected by landfill leachate. The compounds
pounds most frequently detected and at the highest identified included detergent degradation products, plasti-
concentration levels were BT, caffeine, carbamazepine, tolyl- cizers (ethanol-2-butoxy-phosphate and diethyl phthalate),
triazole (TT), and nonylphenoxyacetic acid (Loos et al., 2009a, BPA, triclosan, an antioxidant (5-methyl-1H-benzotriazole),
2009b). Only about 10% of the river water samples analyzed fire-retardant compounds, and several pharmaceuticals and
could be classified as very clean in terms of chemical pol- their metabolites (Buszka et al., 2009).
lution. Rodil et al. (2009), for example, described a method for
the simultaneous determination of 53 multiclass compounds,
which they call emerging organic pollutants (e.g., acidic 3.04.5 Sources and Fate
herbicides, ultraviolet (UV) filters, insect repellents, organo-
phosphorus flame retardants, bactericides, pharmaceuticals, Numerous studies have shown that a variety of organic com-
and metabolites). The authors found 31 pollutants in waste- pounds such as pharmaceuticals, steroids, surfactants, flame
water with concentrations up to 10 mg l1 in the case of retardants, fragrances, plasticizers, and other chemicals often
the active pharmaceutical ingredient (API) ibuprofen. In total, associated with wastewaters have been detected in the vicinity
13 compounds were detected in tap water with concentra- of municipal wastewater discharges and agricultural livestock
tions up to 0.13 mg l1 for tri(chloropropyl)phosphate. The facilities, as these are an important source for the introduction
five most frequently detected chemicals in surface water of chemicals into the aquatic environment. There they may
in a study performed in the USA were cholesterol (59%, undergo different distribution and transformation processes
natural sterol), metolachlor (53%, herbicide), cotinine (51%, (Figure 2). More detailed information on the (incomplete)
nicotine metabolite), beta-sitosterol (37%, natural plant removal of some groups of emerging contaminants by differ-
sterol), and 1,7-dimethylxanthine (27%, caffeine metabolite), ent effluent treatment technologies was addressed by Barceló
whereas, in groundwater, the most frequently detected and Petrovic (2008).
were tetrachloroethylene (24%, solvent), carbamazepine The presence of the micro-pollutants in the aquatic en-
(20%, pharmaceutical), bisphenol A (BPA; 20%, plasticizer), vironment demonstrates that technical emission treatment is

Municipal or industrial
sewage discharge

Volatilization
to atmosphere Photolysis

por tHydrolysis
rans
o lved t
s Biodegradation
Dis
and
Sorption
transformation
onto sediments

p or t
ns
tra Dilution
e
cl

and
r ti
Pa

diffusion
n io

Biocencentration
Deposit

Deposition and
resuspension

Deposition and
accumulation

Figure 2 The fate of pollutants in the aquatic environment. From US Geological Survey, http://toxics.usgs.gov/regional/emc/transport_fate.html.
 Emerging Contaminants 73

not sufficiently effective. The presence of micro-pollutants in Union Emission Trading System (EU ETS; EU, 2003). In
water is currently leading to much research and development January 2008, the European Commission proposed a number
effort being directed toward advances in municipal wastewater of changes to the scheme, including the inclusion of other
treatment. The advanced treatment of effluents has been in- greenhouse gases, such as nitrous oxide and perfluorocarbons.
vestigated using (photochemical) oxidation processes (e.g., It is also under consideration whether to extend the EU ETS to
Qiting and Xiheng, 1988; Zwiener and Frimmel, 2004; Ravina other industries. Clark (2006) has described other drivers for
et al., 2002; Kiffmeyer, 2003; Ternes and Joss, 2006; Watkinson green chemistry.) Ozonation, for example, can consume an
et al., 2007; Isidori et al., 2007; Putschew et al., 2007; Lee et al., equivalent amount of energy to that needed to run a muni-
2007), filtration (Schröder, 2002; Drewes et al., 2002; Heberer cipal STP.
and Feldmann, 2008), application of powdered activated Wenzel et al. (2008) investigated the advantages and dis-
charcoal (Metzger et al., 2005; Nowotny et al., 2007), and advantages of advanced wastewater treatment for micro-
constructed wetlands (Matamoros and Bayona, 2006). Re- pollutants using environmental life-cycle assessment (LCA)
views are available describing the advantages and disadvan- and a literature review of advanced treatment performance.
tages of the different technologies (Schulte-Oehlmann et al., The LCA evaluation involved sand filtration, ozonation, and
2007; Jones et al., 2007; Wenzel et al., 2008; Ternes and Joss, membrane bioreactors, and assessed the effect of extending
2006). However, the approach of effluent treatment has some existing tertiary treatment with these technologies on a variety
limitations in principle and may not in the end be a sustain- of micro-pollutants (heavy metals, endocrine disruptors,
able solution. Some of these limitations may also apply for the polycyclic aromatic hydrocarbons (PAH), phthalates, and de-
treatment of solid waste and the chemical treatment of ex- tergents, flame retardants, and others). The authors assessed
haust air, some not in the case of the application of biofilters the environmental break-even point where the removal of
for the treatment of exhausts: micro-pollutants and reduction in (eco-)toxicity will outweigh
the increased resource and energy consumption. It was found,
• Efficiency may depend strongly on the type of compound to in some of the scenarios considered, that more environmental
be removed. impact may be induced than removed by the advanced treat-
• None of the technologies can remove all of the compounds ment. Furthermore, advanced treatment of effluent and ex-
(Ravina et al., 2002; Schröder, 2002; Wenzel et al., 2008). hausts is not available and affordable worldwide. Therefore,
• Will the now so-called advanced treatment technology other approaches are necessary. (Green and sustainable are
work for new compounds in the future? sometimes used synonymously by authors; however, they are
• Reaction products of (photo)oxidation processes have been not synonymous. Green chemistry is focused on the product/
found themselves to possess mutagenic and toxic properties chemical/pharmaceutical itself, whereas sustainable includes
(Isidori et al., 2005, 2007; Lee et al., 2007; Wei-Hsiang and all aspects of a product related to sustainability, e.g., the
Young, 2008). shareholders, the stakeholders, and the people applying and
• Prolongation of the hydraulic retention time in sewage using the compounds when seeking for solutions that will
treatment plants (STPs) results in only a little improvement work. (First International Conference on Sustainable Phar-
of the elimination rates. It may, however, cause high costs macy, Osnabrück, 24/25 April 2008).) It has been learned that
because of the necessity to enlarge the STPs. the source of micro-pollutants is often not a focus source.
• Resistance in bio-membrane reactors: Is the enrichment of These molecules end up in the environment not because of
antibiotics and resistant bacteria causing increasing resist- their improper use, but rather as a result of their proper use.
ance? (No information is available on this topic.) Furthermore, one has to be aware that especially in the case of
• Resistant material will not fully be retained by membranes. consumer products it is not only a single chemical compound
• Combined sewer overflow: no treatment of storm water. that is involved. Most often, it is a complex mixture of com-
• Sewage from leaking from drains is not treated since it pounds that constitute a product such as a shampoo, a
soaks into the ground before it reaches the STP. medicine, a disinfectant, a pesticide, a cleaning agent, or
• The advanced treatment processes depend on a high energy facade paint. Often, it is not feasible to assess the substance
input and a minimum water flow. Therefore, they are often flow of compounds that are ingredients of such products as
not possible/affordable in less developed countries. not all of the ingredients have to be declared in terms of
• Costs are not clear and whether they are affordable is not quantity. Some are not even declared at all. If the chemicals
known. As for the costs, different authors present different and pharmaceuticals, their metabolites, and transformation
data depending on the assumptions made. It is question- products are not eliminated during sewage treatment, they
able whether the additional costs are acceptable (Jones enter the aquatic environment and eventually reach drinking
et al., 2007). water. Going back to the beginning of the pipe, the products of
chemical industries – the molecules themselves – come into
In principle, the advanced treatment processes are not com- focus. Therefore, it is reasonable to think about emission
patible with a sustainable development as they are end-of-the- management directly related to the properties of the molecules
pipe technologies, not affordable and/or applicable in all themselves and to focus on the whole life cycle of products
countries, and costly for manufacturers and the public. Energy and substances. This is addressed by the concepts of green and
demand causes high emissions of CO2 (Jones et al., 2007) and sustainable chemistry (Anastas and Warner, 1998; Clark and
other green house gases cause additional costs for consumers Smith, 2005; Clark, 2006) and, more recently, by the concept
and companies, as well as for the general public in the future. of green and sustainable pharmacy (Kümmerer, 2009a).
(See, for example, the Kyoto-Protocol and the European Green and sustainable are sometimes used synonymously by
74 Emerging Contaminants

authors. However, they are not synonymous. Green chemistry flame retardants, for example, for textiles. Synthetic materials,
is focused on the product/chemical/pharmaceutical itself, usually halocarbons, include organochlorine compounds such
whereas sustainable includes all aspects of a product related to as PCBs, chlorendic acid derivates (most often dibutyl chlor-
sustainability, e.g., the shareholders, the stakeholders, and the endate and dimethyl chlorendate), and chlorinated paraffins.
people applying and using the compounds when looking for Nowadays, compounds such as organobromine compounds
solutions that will work (Kümmerer and Hempel, 2010). A key and organophosphates are also of interest.
point is the benign-by-design concept (Daughton, 2003;
Boethling et al., 2007; Kümmerer, 2007, 2008b).
3.04.6.2.1 Organobromine compounds
Organobromine compounds such as polybrominated diphe-
3.04.6 Examples of Individual Groups nyl ethers (PBDEs) are one of the important groups of organic
chemicals used as flame retardants. PBDEs are used as flame
3.04.6.1 Aryl Sulfonates
retardants in polymeric materials such as furnishing foam,
Aryl sulfonates are used as precursors for sulfonated azo dyes, rigid plastics, and textiles. PBDEs are technical, that is, loosely
wetting agents, leveling agents, dispersants, optical bright- defined mixtures. Many of these chemicals are considered
eners, pesticides, ion-exchange resins, pharmaceuticals, and harmful, having been linked to liver, thyroid, reproductive/
concrete plasticizers (Knepper et al., 1999; Reemtsma, 1999; developmental, and neurological effects. The EU has included
Arslan-Alaton et al., 2010). Sulfonated azo dye formulations the PBDEs on a list of chemicals to be phased out of use in
used in the tannery and textile industry are one major source electrical and electronic equipment (e.g., personal computers
of sulfonated aromatic amines in water. Dye production today and mobile phones). The main source of the organobromine
takes place mainly in Asian countries such as China and India. compounds in the aquatic environment is textiles. The com-
It is estimated that during the dyeing process, up to 10–30% of pounds are washed out during the washing cycles. The
sulfonated dyes end up in the exhausted dye bath (Arslan- manufacture of textiles may be another important source for
Alaton et al., 2010). Hence, aromatic sulfonates can be present their introduction into the environment.
at high concentrations in industrial wastewater in these PBDEs are included in Annex X of the Water Framework
countries. Recently, the discharge into receiving water bodies Directive (EU, 2000) and pentabromodiphenyl ether (pen-
has led to serious environmental pollution problems and the taBDE) is a priority hazardous substance. The EU risk assess-
production of aryl sulfonates, such as H-acid, has been re- ment of tetraBDE, sometimes also called tetrabromobisphenol
stricted in some countries. Sulfonates are strong organic acids; A (TBBPA), suggests the classification ‘‘Very toxic to aquatic
hence, they are anions over a wide range of pH and cannot be organisms, may cause long-term adverse effects in the aquatic
effectively trapped by conventional adsorbents such as RP 18 environment.’’ In the USA, decaBDE manufacturers have
materials. In the aquatic environment, they do not signifi- successfully petitioned for an exemption for decaBDE
cantly sorb on biosludge or sediments (Zerbinati et al., 1997). from this ban in the USA (Illinois EPA, 2007). A different
Sulfonated aromatic amines can be formed during the re- chemical structural class of flame retradand is hex-
duction of sulfonated azo dyes under anaerobic/anoxic con- abromocyclododecane (HBCD). The EU risk assessment of
ditions (Knepper et al., 1999). These are potentially toxic and/ HBCD (ECB, 2007) recommends that HBCD be considered a
or carcinogenic (Oh et al., 1997). The fate of aryl sulfonates persistent, bio-accumulative, and toxic (PBT) substance, al-
and their degradation products in the aquatic ecosystem and though there is no official classification yet.
in biological treatment facilities is still not very clear, since Amounts used may be different in different countries. Im-
until now only limited attention has been paid to their oc- portant subgroups of PBDEs are pentaBDE, octaBDE, and dec-
currence and degradability in the natural environment and in aBDE. tetraBDE, sometimes also called TBBPA, has the biggest
engineered systems (Jandera et al., 2001). Laboratory testing of share (Thuresson, 2006) in most countries. Over 40% of the use
organic sulfonates has revealed them to be nonbiodegradable of decaBDE occurs in North America. The US has historically led
(Sütterlin et al., 2008). Depending on their molecular structure the world production of these chemicals (50% of the total global
or other physical–chemical properties, aryl sulfonates may be demand in 2001). High pentaBDE, also called tetrabromobi-
biodegradable in engineered biological treatment systems at sphenol (A), PBDE (A), levels in the US marine environment
very slow rates and after acclimation (O’Neill et al., 1999; reflect that over 90% of the pentaBDE global production has
Rieger et al., 2002). Tan et al. (2005) reported concentrations been utilized in the USA (Yogui and Sericano, 2009).
in the ng l1–mg l1 levels in European rivers and they are PBDEs are ubiquitous in all compartments, including
detectable at ng l1–mg l1 levels in surface waters. However, water, sediment, and biota. Contamination is higher in ur-
their concentrations in industrial wastewater-treatment plants banized regions. The organobromine compounds are lipo-
(WWTPs) can be in the mg l1–mg l1 range (Tan et al., 2005). philic, bioaccumulative (log Kow often six and above), and
adsorptive. Therefore, only a minor proportion will pass STPs
and reach the surface water. It was found that the mean con-
3.04.6.2 Flame Retardants
centrations of decaBDE, pentaBDE, HBCD, and TBBPA in STP
Minerals such as asbestos, compounds such as aluminum sludge were 0.12, 0.11, 0.045, and 0.040 mg kg1 dry weight
hydroxide, magnesium hydroxide, antimony trioxide, various (d.w.), respectively (Nylund et al., 2002). This confirms the
hydrates, red phosphorus, and boron compounds, mostly significance of elimination by sorption.
borates are applied as flame retardants. In addition to these Another emerging brominated flame retardant, marketed
inorganic compounds, organic compounds are also used as as a replacement for decaBDE, is decabromo-diphenyl ethane
 Emerging Contaminants 75

(deBDethane). DeBDethane has a chemical structure similar pollutants. However, transformation products formed from the
to decaBDE and would accordingly have similar properties applied parent compounds in the environment (e.g., soil)
concerning bioaccumulation and persistence. Recently, a sur- came into focus in a broader range only recently. Nowadays,
vey was conducted on decaBDE and deBDethane in sludge data on the fate of the pesticide itself and the possible products
from 42 WWTPs in 12 different countries around the world of biotransformation (often called ‘metabolites’) in soil and
(Ricklund et al., 2008a, 2008b). The authors found decaBDE sediments have to be presented and assessed by the applicant
in concentrations from 0.003 mg kg1 dry matter (d.m.) to a before pesticides are authorized. Hence, these compounds are
maximum of 19 mg kg1d.m. in all samples. DeBDethane was the subject of a great deal of study. The following is a typical
present in all samples but two, in levels from 0.001 to example. The transformation product chloridazon-methyl-
0.22 mg kg1 d.m. The highest deBDethane/decaBDE ratios desphenyl is formed from chloridazon (5-amino-4-chloro-2-
were found in Germany and neighboring countries, whereas phenylpyridazin-3(2H)-one) in soil by biotransformation
the lowest ratios were found in the USA and the UK. The data (Roberts and Hutson, 2002), which is further transformed to
reflect the use patterns of the substances, that is, the known chloridazon-methyl-desphenyl. The transformation product
high imports of deBDethane into Germany and the largest chloridazon-methyl-desphenyl was detected at concentrations
market demands for decaBDE in the USA and the UK. up to several hundreds of nanograms per liter in many of the
Chemically applied nonhalogen decaBDE substitutes are groundwater samples investigated. Weber et al. (2007) detected
available for natural cellulose fibers such as cotton, wool, this compound in surface-ground-, and drinking water in
rayon, and linen. They include: Germany. The transformation product was often found in
higher concentrations than the parent compound. Knowledge
• dimethylphosphono (N-methylol)propionamide;
on the fate of the transformations product, for example, in the
• phosphonic acids such as (3-{[hydroxymethyl]amino}-
aquifer or drinking-water treatment is little. Transformation
3oxopropyl)-dimethyl ester; and
products may give rise to further concerns. This can be illus-
• tetrakis(hydroxymethyl)phosphonium urea ammonium
trated by the case of the pesticide tolylfluanid. Application and
salt.
microbial degradation of the fungicide tolylfluanid in soil re-
The future will show whether these will be part of the next- sult in a transformation product, N,N-dimethylsulfamide
generation emerging contaminants. (DMS). DMS was found in groundwater and surface water
with typical concentrations in the range of 100–1000 and
3.04.6.2.2 Organophosphorus compounds 50–90 ng l1, respectively. DMS itself is not of toxicological
Another important group of flame retardants already heavily concern. However, it exhibits high mobility in soils and water.
applied is organophosphates in the form of halogenated Hence, it can enter the drinking-water-treatment process.
phosphorus compounds such as phosphates and phospho- Laboratory-scale and field investigations concerning its fate
nium salts, for example, tri-o-cresyl phosphate, tris(2,3- during drinking-water treatment revealed that DMS cannot be
dibromopropyl)phosphate (TRIS), bis(2,3-dibromopropyl)- removed via riverbank filtration, activated carbon filtration,
phosphate, tris(1-aziridinyl)-phosphine oxide, tris(2-chloro-1- flocculation, and oxidation or disinfection procedures based
methylethyl)phosphate (TCPP), tris(2-chloroethyl)phosphate on hydrogen peroxide, potassium permanganate, chlorine
(TCEP), and tris(2-chloro-1-chloromethyl-ethyl)phosphate dioxide, or UV irradiation (Schmidt and Brauch, 2008). Even
(TDCP). The main source of these organophosphates is nanofiltration does not provide adequate removal efficiency.
probably construction materials (Bester et al., 2009). The Disinfection with hypochlorous acid converts DMS to so far
phosphates are slightly less polar (log Kow 4 and below) than unknown degradation products but not to N-nitrosodimethy-
the organobromine compounds. Organophosphates have lamine (NDMA) or 1,1-dimethylhydrazine. However, most
been found in the effluents of WWTPs (Marklund et al., 2005). important, during ozonation about 30–50% of DMS is con-
Potential risks to groundwater have been reported for tetra- verted into the carcinogenic NDMA (Figure 3). Wei-Hsiang
kis(hydroxymethyl) phosphonium chloride (Illinois EPA, and Young (2008) have described the NDMA formation during
2007). The concentrations of TCPP and related compounds in chlorination and chloramination of aqueous diuron solutions.
five WWTPs in the Rhine/Ruhr region ranged from a few NDMA is biodegradable and can be at least partially removed
hundred to 410 000 ng l1, depending on the respective ac- by subsequent biologically active drinking-water-treatment
tivities within the catchment area (Bester et al., 2009). Because steps, including sand or activated carbon filtration.
these compounds are not usually eliminated in wastewater
treatment, the effluent concentrations are identical to the in-
flow concentrations (Marklund et al., 2005; Bester, 2007). 3.04.7 Endocrine Disrupting Chemicals
Several wastewater-related organic micro-pollutants such as
chlorinated and nonchlorinated organophosphates have been Endocrine-disrupting chemicals (EDCs) are chemicals of nat-
detected in a spring. TCPP was found in concentrations up to ural or synthetic origin that may interfere with the endocrine
0.13 mg l1 in tap water in the United States (Rodil et al., system. They may have estrogenic, anti-estrogenic, androgenic,
2009). anti-androgenic, and other hormone-like effects. For example,
the egg yolk protein vitellogenin, only produced under normal
circumstances in mature female fish (Sumpter and Jobling,
3.04.6.3 Pesticides
1995) was found in male fish that have been exposed to such
Some pesticides have been detectable in the aquatic environ- substances. The same phenomenon has been observed down-
ment for decades. Hence, they cannot be called emerging stream in rivers receiving STP effluent (Purdom et al., 1994;
76 Emerging Contaminants

O O
O O
S
N N S O
S H2N N N
Cl N
Cl
F

N,N-Dimethylsuklfamid
Tolylfluanid NDMA
(DMS)
Figure 3 Formation of NDMA by ozonation of the transformation product (DMS) of the pesticide tolyfluanid by ozonation in drinking-water treatment.

Vethaak et al., 2006; Sumpter et al., 2006). Recently, an aquatic TT is a mixture of 4- and 5-methyl isomers. The BT and the
predicted no-effect concentration (PNEC) for ethinylestradiol TT possess good water solubility, low vapor pressure, and low
(EE2) has been derived based on a large number of studies on octanol water distribution coefficients (log Kow 1.23 and 1.89,
the effects of EE2 on aquatic organisms. Caldwell et al. (2008) respectively). BT is toxic and not biodegradable (Hem et al.,
recommended the use of a PNEC of 0.35 ng EE2 l1 in order to 2003), and it can be degraded by UV irradiation at pH values
adequately protect organisms in surface waters. Evidence that below 7 in laboratory testing. Approximately 65% reduction in
environmentally relevant concentrations of estrogens in sur- the BT concentration was achieved at a dose of 320 mW s cm2,
face waters can impact the sustainability of wild fish popu- and almost 90% reduction was achieved at 1070 mW s cm2
lations has been presented in the study by Kidd et al. (2007). (Hem et al., 2003). BT is transformed into several compounds
In the last 15 years, the discovery of the estrogenic nature of instead of full mineralization. Aniline and phenazine were
STP effluents (Purdom et al., 1994) has resulted in a vast public identified as main compounds. The authors report that the
concern and a huge amount of scientific literature in order to transformation products show toxic effects, but that they are not
better understand and identify EDCs, their occurrence, fate, as toxic as BT itself; hence, UV irradiation brings about a general
and their biological effects on wildlife. The naturally occurring decrease in toxicity (Hem et al., 2003). However, aniline itself is
estrogenic hormones (i.e., 17b-estradiol (E2) and estrone a confirmed animal carcinogen with unknown relevance to
(E1)) have been studied extensively (Desbrow et al., 1998; humans (IARC, 1987). The overall summary evaluation of car-
Routledge et al., 1998) in the 1990s. Together with EE2, the cinogenic risk to humans refers to group 3: the agent is not
synthetic active ingredient in many contraceptive pills, they classifiable as to its carcinogenicity to humans (HSDB, 2009).
were identified as the main contributors to estrogenicity of Weiss et al. (2006) noted 2.1 mg l1 of BT and 13 mg l1 of
effluents of STPs. As fish feminization was one of the most TTs in untreated municipal wastewater. BT and TT were found
striking of their effects, they were also referred to as gender in the lower mg l1 range in the samples of primary and sec-
benders. In the years that followed, an increasing number of ondary effluents STPs (Voutsa et al., 2006; Weiss et al., 2006).
chemicals were classified as EDCs. Compounds or compound The elimination rate of BT in WWTP is only 30–40% (Weiss
classes that had been detected in the environment in the last et al., 2006) and lower for TTs. Accordingly, these compounds
two decades such as BPA, phthalates, alkylphenols and their are found in receiving waters. Concentrations of TT in re-
ethoxylates, some pesticides, dioxins and PCBs, tributyltin ceiving rivers were lower than 80 mg l1. In an EU-wide re-
compounds, and others were shown to be endocrine active connaissance of the occurrence of polar organic persistent
(e.g., Jobling et al., 2006; Blair et al., 2000; Silva et al., 2002). pollutants in European river waters, more than 100 individual
Brominated organic flame retardants are also on the list now. water samples from over 100 European rivers from 27 Euro-
In the last decade, a great deal of research has been dedi- pean countries were analyzed for 35 selected compounds,
cated to the technological improvement of the various stages including BTs among other substances. BT and TT were among
of sewage treatment in terms of removal efficiency of micro- the most frequently detected compounds and also had the
pollutants, and especially estrogenic chemicals, in municipal highest concentration levels (Loos et al., 2009b).
STPs. Removal of EE2 in particular is often nowhere near Because of extensive de-icing activities, BT was found in the
complete, as demonstrated by the findings of Kanda and groundwater below de-icing platforms at airports (Cancilla et al.,
Churchley (2008), Esperanza et al. (2007), Vethaak et al. 2003a, 2003b) and in the subsurface waters at airports at con-
(2006), and Lamoree et al. (2009). centrations up to 126 mg l1 for BT and 198 mg l1 for total TT.

3.04.8 Anticorrosive Additives – BT and TT

3.04.9 Gasoline Additives – Methyl tert-Butyl Ether
BT and TT are widely used as anticorrosive additives. They are
also components of cooling and hydraulic fluids, antifreezing Methyl tert-butyl ether (MTBE) is a common gasoline additive
products, aircraft de-icer, and anti-icing fluid. The main input often found in drinking water. On account of its physico-
of BT into the aquatic environment stems from their use as chemical properties, it can contaminate large water volumes. It
dishwasher detergent additives where they are used for silver is to be phased out. The MTBE situation in the USA differs
protection. From there, they are discharged in municipal significantly from the one in Europe where the concentrations
wastewaters (Ort et al., 2005). measured in river water and drinking water are approximately
 Emerging Contaminants 77

two to three orders of magnitude lower than the USA, where lengths. They are also applied in the electroplating industry to
MTBE was detected first. This example demonstrates the im- prevent volatilization of chemicals from the electroplating
pact of use patterns on the presence of contaminants. The bath. PFOA and PFOS are discussed as end products of many
detection limits of analytical instruments and the volumes of fluorochemical compounds in the natural environment
samples used and the location of sampling determine when (Nakayama et al., 2005). In a study, more than 100 individual
and where a specific compound or a group of compounds water samples from over 100 European rivers from 27 Euro-
‘emerges’ as a contaminant. MTBE concentrations in German pean countries were analyzed for 35 selected compounds,
river water, for example, show a tendency toward increasing comprising pharmaceuticals, pesticides, PFOS, PFOA, BTs,
concentrations since 1999 (Achten et al., 2002). It is not clear hormones, and endocrine disrupters. The rivers responsible
when the phasing out of these compounds will result in de- for the major aqueous emissions of PFOS and PFOA from the
creasing concentrations in drinking water because the resi- European continent could be identified (Loos et al., 2008).
dence time of contaminants in groundwater is often not Nakayama et al. (2005) gave a review on the distribution of
known. Kolb and Püttmann analyzed 83 finished drinking- PFOA and PFOS in Japan and their toxicities. PFOA and PFOS
water samples from 50 cities in Germany for MTBE. The de- had a low order of toxicity in an acute toxicity study in ro-
tection frequency was 46% at a detection limit of 10 ng l1. dents; however, they exhibited versatile toxicities in primates.
The concentrations ranged from 17 to 712 ng l1 (100– Both chemicals are carcinogenic in rodents, causing repro-
200 ng l1 range in rivers for example). MTBE was detected at ductive toxicity, neurotoxicity, and hepatotoxicity (Nakayama
concentrations lower than 100 ng l1 in bank-filtered drinking et al., 2005). Nakayama et al. (2005) reported an epidemi-
water from the rivers Rhine and Main and at 43–110 ng l1 in ological study conducted by a manufacturer that revealed an
drinking water (Achten et al., 2002). All the MTBE concen- increase in prostate cancer mortality among workers exposed
trations measured were below the proposed limit values for to PFOA. Another study conducted by the same manufacturer
drinking water (Achten et al., 2002). The occurrence of MTBE showed an increase in bladder cancer mortality among
and gasoline hydrocarbons was examined in three types of workers exposed to PFOS. In addition, peroxisome prolifer-
studies of groundwater in the USA conducted by Moran et al. ation and calcium channel modulation are demonstrated ef-
(2005). The detection frequency of MTBE was highest on fects. There are large interspecies differences in toxicokinetics.
monitoring wells located in urban areas and in public supply Perfluorinated surfactants (e.g., PFOS and PFOA) have shown
wells. Only 13 groundwater samples from all study types, or different potentials for reproduction toxicity and carcinogenity
0.3%, had concentrations of MTBE that exceeded the lower in animal experiments as well as partly long half-lives in
limit of the US EPA’s Drinking-Water Advisory Board. The humans (Guruge et al., 2006; Zhang et al., 2010). They possess
probability of detecting MTBE in groundwater was strongly compound-dependent persistence in the environment. As they
associated with population density, use of MTBE in gasoline, are nonpolar compounds, they tend to bioaccumulate in
and recharge. Groundwater in areas with high population animals and humans (Houde et al., 2006). Accordingly,
density, in areas where MTBE is used as a gasoline oxygenate, Nakayama et al. reported that the concentrations of PFOA and
and in areas with high recharge rates had a greater probability PFOS in the sera of Japanese people may reach 57.7 mg l1.
of the presence of MTBE. In addition, groundwater from Many studies in recent years have reported the ubiquitous
public supply wells and shallow groundwater underlying distribution of this group of perfluorinated substances, espe-
urban land-use areas had a greater probability of MTBE oc- cially PFOS and PFOA in surface and drinking waters
currence than groundwater from domestic wells and ground- (Skutlarek et al., 2006; Hoelzer et al., 2008). When measure-
water underlying rural land-use areas. ments were made on samples from the Rhine, Ruhr, Moehne,
In a review on the MTBE production, use, properties, and and some of their tributaries, the Rhine-Herne Canal and
its behavior in the environment and occurrence in ground- the Wesel-Datteln Canal, the concentrations (sum of seven
water, surface water, drinking water, and wastewater, it was components usually detected) measured in the river Rhine
concluded that the conventional methods to remove volatile and its main tributaries (at the confluences) were below
organic compounds from drinking water – air stripping and 100 ng l1. The highest concentration (94 ng l1) was detected
adsorption on granular active carbon – are not effective in the in the river Ruhr (tributary of the Rhine). The pattern here was
case of MTBE with concentrations of 100 mg l1 or more. Peer- different, PFOA was the major component in contrast to the
reviewed laboratory data on the application of nine different other tributaries and the river Rhine. This may indicate a
advanced oxidation processes (AOPs) to the degradation and specific source. Remarkably, high concentrations of PS were
mineralization of MTBE in water revealed that the most found in the upper catchment of the river Ruhr (up to
promising seem to be UV/H2O2 and O3/H2O2 processes, from 446 ng l1) and the river Moehne (tributary of the Ruhr, up
both the technical and economic point of view (Siminiceanu, to 4385 ng l1). Illegal waste dumping was discussed as a
2007). However, data on possibly formed transformation possible source. Dilution effects were held responsible for
products were not given. decreasing downstream concentrations of PS in surface waters
of the rivers Moehne and Ruhr.
C-7–C-11 perfluorinated carboxylates and PFOS have been
3.04.10 Perfluorinated Surfactants – PFOS and PFOA analyzed in selected stretches of the river Po and its major
tributaries. Concentrations of about 1.3 mg l1 of PFOA were
Perfluorooctanesulfonate (PFOS) and perfluorooctanoic acid detected in the Tanaro River close to the city Alessandria.
(PFOA) are perfluorinated surfactants used to produce poly- Below this tributary, levels between 60 and 337 ng l1 were
mers and telomers whose carbon chains can be of various measured in the Po River on several occasions. A mass load of
78 Emerging Contaminants

about 2.6 tons per year is discharged into the Adriatic Sea being aware of it, humans are also affected by human info-
according to these data. PFOS concentration levels in the Po chemicals (Bhutta, 2007). Every substance which can be
River at Ferrara were around 10 ng l1 (Loos et al., 2008). smelled by the human nose can be used as a scent. It is as-
Concentrations of 0.4–123 ng l1 for PFOS and 4.2– sumed that humans can distinguish up to 10 000 different
2600 ng l1 for PFOA were measured in the Yodo River basin scents. Of these 10 000 compounds, more than 2100 sub-
(Japan). The highest concentrations were found in effluents of stances representing 22 chemical groups are listed as scents in
some STPs and tributary streams. The PFOA concentration was the Research Institute for Fragrance Materials (RIFM) database
often higher than that of PFOS, but their profiles in the basin (Salvito et al., 2002; Salvito et al., 2004). As different as they
were somewhat similar. Load estimates revealed that the main are with regard to their chemical structure, they also differ in
sources of the contaminants in Katsura River were three STP their physical and chemical properties such as vapor pressure,
effluents, whereas the sources in Uji River could be from Lake water solubility, and partition coefficient between octanol and
Biwa. It is suggested that wastewaters other than domestic water (log Pow).
wastewater contributed significant loads of PFOS and PFOA in Fragrances such as the musk fragrances HHCB (galaxolide),
highly contaminated STP effluents (Lien et al., 2008). In an- AHTN (tonalide), OTNE (tso-E-Super), and others are used in
other study from Japan, PFOA and PFOS concentrations in washing processes, especially in softeners, in cosmetics, and in
surface water were in the ranges 0.1–67 000 and 0.1– perfumery (Reiner and Kannan, 2006). According to their use,
526 ng l1, respectively. Although the origin of PFOS in surface most of these compounds end up in wastewater. The musk
water in Japan remains unknown, PFOA present in surface fragrances are often lipophilic, as they are tailored to sorb onto
water is very likely to have been released from a few industries fabric. Hence, they can bioaccumulate (Schmid et al., 2007).
according to the authors. Some of the polycyclic musks are under discussion, because
In the study performed for the river Ruhr area, the major they are assumed to act as endocrine disruptors (Seinen et al.,
component PFOA was determined in many drinking-water 1999; Bitsch et al., 2001). Influent concentrations in STPs are
samples as well as in the surface water of the same area. There in the lower mg l1 range (Simonich et al., 2000, 2002; Bester,
the water supplies are mainly based on bank filtration and 2005). Effluent concentrations are only little lower indicating
artificial recharge. Maximum concentrations in drinking-water little elimination on sewage treatment. The elimination of
samples were 598 ng l1 (major component PFOA: HHCB and AHTN is mainly due to sorption. Because of their
519 ng l1). persistence in the aquatic environment, HHCB and AHTN
have been used as markers for wastewater discharge into sur-
face waters. Other mechanisms might also be relevant in the
3.04.11 Personal-Care Products case of OTNE (Ternes and Joss, 2006; Andresen et al., 2007).
Other fragrances such as musk xylene and metabolites
Personal care involves products as diverse as deodorant, eye (amines) as well as the musk ketone are found in the range
liner, facial tissue, lipstick, lotion, makeup, mouthwash, po- 10–100 ng l1 in the inflow of the WWTPs in European
made, perfumes, personal lubricant, shampoo, shaving cream, countries (Bester et al., 2009). Newer fragrances such as the
skin cream, and toothpaste, to give a few examples. Some macrocyclic musks (e.g., habanolide, cyclopentadecanolide,
personal-care products such as shampoos and washing lotions and ethylenebrassylate) have not been detected in wastewater
can include up to 10–20 different ingredients such as sur- yet – this may be because of low usage, low dosage, or ready
factants, preservatives, dyes, fragrances and odorants, and degradability (Gautschi et al., 2001). Terpenoid chemicals such
others. During or after their use, a more or less big share of it is as linalool are also used as fragrances and scents. Knowledge
washed off from the skin or hair into sewage. on their significance is still scarce, especially as there are nat-
ural source of their origin and as they may act as infochemicals
(Bolek and Kümmerer, 2010).
3.04.12 Fragrances and Odorants

Humans depend very much on visual and acoustic stimuli to 3.04.13 Disinfectants
get along in their everyday life, whereas the role of scents is
considered to be of secondary importance. For fish, insects, Compounds that kill micro-organisms (bacteriocides) or at
and other organisms, however, they are much more import- least prevent their growth (bactriostatics) are employed to
ant. As they transport information for living organisms, such meet hygienic standards in medicine and food processing as
chemicals are also called infochemicals (Klaschka, 2008). well as for the preservation of certain chemical products such
Today, we distinguish between several classes of different as paints or glues (Russell et al., 1992). Some of these com-
infochemicals. Pheromones transfer information in which the pounds such as alcohols (e.g., ethanol and isopropyl alcohol)
sender and the receiver are both from the same species, are readily biodegradable preservatives. Others such as tri-
whereas allelochemicals contain interspecific information. chlosan form stable transformation products (methyltri-
Allelochemicals are further divided into allomones (only the chlosan). Others are less biodegradable and they are not fully
sender takes advantage of the information), kairomones (only removed in sewage treatment, including some quaternary
the receiver takes advantage of the information), and syno- ammonium compounds (QACs, e.g., benzalkonium chloride).
mones (sender and receiver take advantage of the infor- QACs are cationic microbiocidal substances. They are used
mation) (Dicke and Sabelis, 1988). The relationship of the as surfactants, anti-electrostatics, and phase-transfer catalysts.
different infochemicals can be seen in Figure 3. Although not They are also important ingredients in disinfectants. They are
 Emerging Contaminants 79

surface active compounds consisting of a hydrophobic alkyl Pharmaceuticals and disinfectants can be classified ac-
chain and a hydrophilic group carrying a positively charged cording to their purpose and biological activity (e.g.,
quaternary nitrogen atom. QACs are emitted via effluents antibiotics, analgesics, anti-neoplastics, anti-inflammatory
from hospitals, households, and industries and finally end up substances, antibiotics, antihistamines, X-ray contrast media,
in municipal sewage where they can reach surface water and surface disinfectants). The classification of small molecule
(Kümmerer et al., 1997; Martı́nez-Carballo et al., 2007a; APIs by their chemical structure is used mainly for the active
Sütterlin et al., 2008). Because of their positive charge, QACs substances within subgroups of medicines, for example,
adsorb strongly to the negatively charged surfaces of sludge, within the group of antibiotics, or subgroups within the
soil, and sediments (Ferrer and Furlong, 2002; Sun et al., antibiotics such as b-lactams, cephalosporins, penicillins, or
2003). Their widespread use and sorption behavior imply that quinolones. In this case, one might expect that the com-
they are expected to be present in many environmental com- pounds could be treated as groups with respect to chemical
partments (Martı́nez-Carballo et al., 2007b). Only recently, it behavior. However, even small changes in the chemical
has been found that QACs are weakly mutagenic (Ferk et al., structure may have a significant impact on solubility and po-
2007). larity as well as other properties that govern their environ-
mental fate to some extent (Cunningham 2008, Figure 4).
Other classifications refer to the MOA, for example, anti-
3.04.14 UV Filters metabolites or alkylating agents within the group of cyto-
toxics/anti-neoplastics. In the case of classification according
Typical compounds used in sun screens are benzophenone to MOA, chemical structures of molecules within the same
(BP), benzhydrol, 4-hydroxybenzophenone, 2-hydroxy-4- group can be very different and, hence, their environmental
methoxybenzophenone (HMB), 2,4-dihydroxybenzophenone fate can also differ. Therefore, these compounds cannot be
(DHB), 2,20 -dihydroxy-4-methoxybenzophenone, and 2,3,4- treated as a group with respect to environmental issues.
trihydroxylbenzophenone. Some of these compounds have Compared with most bulk chemicals, pharmaceutically active
endocrine effects (Schlumpf et al., 2008). UV filters applied in compounds are often complex molecules with specific prop-
sun screens are directly emitted into surface water after ap- erties, for example, dependence of the octanol–water partition
plication when people go bathing and swimming. Accord- coefficient (Kow) on pH (Cunningham, 2008; Kümmerer,
ingly, they have been detected in water samples (Giokas et al., 2009a).
2004, 2005). Analysis of wastewater in Spain revealed the Some medicines contain molecules based on protein
systematic presence of HMB (BP 3) and DHB (BP 1) in raw (biopharmaceuticals). Biopharmaceuticals may be defined as
samples with maximum concentrations close to 500 and medical drugs produced using biotechnology by means other
250 ng l1 (Negreira et al., 2009). Analysis of seven BP-type UV than direct extraction from a native (i.e., nonengineered)
filters in water in Korea (Jeon et al., 2006) revealed concen- biological source. Examples include proteins (including anti-
trations of 500–18 380 ng kg1 in soil samples of and of 27– bodies) and nucleic acids. The first and best-known example
204 ng l1 in water samples. was recombinant human insulin. Biopharmaceuticals are not
typically regarded as biopharmaceuticals by the industry.
Probably, not all naturally occurring compounds that are used
3.04.15 Pharmaceuticals as drugs are biopharmaceuticals. For example, estrogen is not
regarded as a biopharmaceutical. The environmental relevance
3.04.15.1 Active Pharmaceutical Ingredients
of biopharmaceuticals is not yet clear and they are not
The presence of pharmaceuticals for human use in the en- the focus of environmental research and risk management.
vironment has been a topic for several years now. Though the One view is that they are not relevant because they are closely
study of pharmaceuticals in the environment is still a fairly re- related to natural products and are therefore expected to be
cent, a vast amount of literature has already been published, quickly biodegraded or are denatured, that is, inactivated in
making it impossible to cover all topics and issues in this chapter. the environment. The other view is that naturally occurring

HN

N N

OH
F
O O

Figure 4 Zwitterionic character of ciprofloxacin. Depending on pH additional different chemical species can be formed by internal protonation, i.e., the
shift of protons between the basic amino functions and acidic carboxyl groups. Calculator Plugins were used for structure property prediction and
calculation, Marvin 4.1.1, 2006, ChemAxon (http://www.chemaxon.com).
80 Emerging Contaminants

compounds are not always easily biodegraded, and modified vary from country to country. Antimicrobials are among the
natural compounds even less so. Structurally related com- most widely used pharmaceutical compounds in animals
pounds such as plasmids have been found in the environment (Boxall et al., 2003a, 2003b; Sarmah et al., 2006). These drugs
(Schlüter et al., 2007; Kümmerer, 2009a). Furthermore, it is are used in animal husbandry for veterinary purposes, or as
known that the protein structures known as prions are growth promoters (particularly in large-scale animal farming
very stable. A prion (proteinaceous infectious particle, -on by and intensive livestock treatment).
analogy to virion) is an infectious agent composed only of The active compounds as well as excipients may enter
protein.) They cause a number of diseases in a variety of the environment by different routes via several different
animals and Creutzfeldt–Jakob disease in humans. Prions are nonpoint sources such as effluents of STPs, waste, and landfill
believed to infect and propagate by refolding abnormally into effluent or treatment of animals. Because of good manu-
a structure which is able to convert normal molecules of the facturing practice (GMP) regulations (required for the manu-
protein into the abnormally structured form. This altered facturing of pharmaceuticals) and the frequent high economic
structure renders them quite resistant to denaturation by value of the active substances, the amount of emissions oc-
chemical treatments and physical agents (proteases, heat, ra- curring during manufacturing had been thought to be neg-
diation, and formalin) making disposal and containment of ligible. Indeed, such emissions are assumed to be low in
these particles difficult. Prions can be denatured by subjecting Europe and the North Americas. However, manufacturers
them to a temperature of 134 1C in a pressurized steam have not yet published data. It has only recently been
autoclave. Besides the active substances, formulations may found that in Asian countries, concentrations for single
also incorporate excipients and, in some instances, pigments compounds up to several mg l1 can be found in effluents
and dyes. They are often of minor importance for the en- (Larsson et al., 2007; Li et al., 2008a, 2008b). However, even
vironment. Some medicines contain EDCs as excipients. in Norway the input from a local manufacturer was high
For data and findings that are more detailed, the reader is (Thomas, 2008).
advised to seek help from the numerous books and reviews As expected, pharmaceuticals are present in hospital
that have already been published (e.g. Kümmerer, 2001a, wastewater (Brown et al., 2006; Steger-Hartmann et al., 1996;
2001b, 2004, 2008b, 2009a, 2009b, 2009c; Heberer, 2002; Kümmerer and Helmers, 1997; Hartmann et al., 1999;
Williams, 2005; Ternes and Joss, 2006). Pharmaceutically Kümmerer, 2001a, 2001b; Hädrich, 2006; Gómez et al.,
active compounds (sometimes called active pharmaceutical 2006; Seifrtová et al., 2008; Kümmerer, 2008a). The concen-
ingredients or APIs) are complex molecules with various trations of pharmaceuticals in hospital wastewater are higher
functionalities and physico-chemical and biological prop- (up to 100 mg l1 in some cases) than in municipal sewage
erties. They are developed and used because of their more or (often in the range of a few up to 20 mg l1). However, the total
less specific biological activity on human and/or organisms substance flow is much lower because of the much lower share
that may cause illness such as bacteria and other micro- of effluent from hospitals in municipal effluent in developed
organisms. Therefore, they are of special scientific and public countries. The dilution of hospital wastewater by municipal
interest. wastewater is by much more than a factor of 100 (Kümmerer
Most pharmaceutically active compounds are polar com- and Helmers, 1997, 2000). In terms of volume, the public
pounds in order to make them orally available. Their mo- (households) is the main source for pharmaceuticals in
lecular weights range typically from 200 to 500/1000 Da. Such households (Kümmerer, 2009a). Concentrations in municipal
APIs are called small molecules. These are the ones currently wastewater are typically in the lower mg l1 range. Another, but
being researched and detected in the environment. They are minor, source is effluents from landfills as date-expired med-
among the compounds called micro-pollutants, because they icaments are often disposed of with household waste (Eckel
are often found in the mg l1 or ng l1 range in the aquatic et al., 1993; Holm et al., 1995; Ahel and Jeličic, 2001; Metzger,
environment. They are often complex molecules with different 2004). Systematic studies of the occurrence of pharmaceuticals
functionalities and physico-chemical and biological prop- in the environment are now available for several countries.
erties. There is no data available about the total worldwide Meanwhile, there is evidence of the occurrence of some 180
use of pharmaceuticals. The consumption and application different drugs in STP effluent, surface water, and groundwater.
of pharmaceuticals may vary considerably from country to Probably, there are many more, however, validated methods
country (Verbrugh and de Neeling, 2003; Goossens et al., not yet available for the analysis of most of the APIs in the
2005, 2007; Schuster et al., 2008). If there are legislative environment. The concentrations of pharmaceuticals in sur-
changes imposed on the health system, it may happen that face waters have been shown to lie most often in the ng l1
some compounds are not used any more or others gain more range, in rare cases in the low mg l1 range. The findings of
importance, for example, for economical reasons. According recent years have been confirmed for various countries and
to United Nations’ figures, 2.3% of Japanese women of different environmental compartments (Kümmerer, 2009a).
reproductive age take a contraceptive pill containing EE2 as Compared to the free water phase, the analysis of APIs is
the main active compound, compared to 16% in North difficult in biosolids and sewage sludge, despite the fact that
America and up to 59% in Europe (United Nations, 2004). information about pharmaceuticals in sewage sludge and
Some pharmaceuticals are sold over the counter without pre- biosolids is necessary for a proper understanding of fate and
scription in some countries, whereas in others they are only for risk assessment (Jones-Lepp and Stevens, 2007). APIs have
available by prescription. Some antibiotics such as strepto- also been detected in the arctic environment (Kallenborn
mycins are used in the growing of fruit (pomology) whereas et al., 2008). Some pharmaceuticals are used by hydrologists
others are used in bee-keeping. Again, the situation may as tracers for anthropogenic impact on waters (Möller et al.,
 Emerging Contaminants 81

2000, 2002; Elbaz-Poulichet et al., 2002; Verplanck et al., wastewaters at concentrations ranging from 4 to 4700 ng l1
2005; Buerge et al., 2006). Some APIs have even been detected and from 9 to 7500 ng l1, respectively (Huerta-Fontela et al.,
in drinking water (Heberer, 2002; Kümmerer, 2008a). 2008). Compounds of the amphetamine type, morphine, or
methadone were detected in the influents and effluents of two
Italian WWTPs and in several Spanish ones (2–688 ng l1).
3.04.15.2 Illicit Drugs
Removal rates for cocaine and benzoylecgonine were higher
Around 200 million people in the world are estimated to have than 88%, whereas those for amphetamine type compounds
used illicit drugs at least once during the last year (United varied, ranging from 40% to more than 99%. Cannabis (THC)
Nations Office of Drug and Crime, 2010). They are of special has been detected as its main carboxylic metabolite (THC-
concern because of their psychoactive properties. Cannabis is COOH) at concentrations from 0.5 to 7 ng l1 in Italian rivers
the one most consumed, involving far more than 4% of the and at 1 ng l1 in one UK River.
global population aged between 15 and 64 years old. Next Huerta-Fontela et al. (2009) described the removal of illicit
come opiates (especially heroin) and cocaine, which are the drugs through drinking-water treatment. Drinking-water
two second most consumed illicit drugs on the global level treatments achieved the complete removal of all the illicit
(United Nations Office of Drug and Crime, 2010). Recently, drugs or metabolites detected in the raw water except for
psycho-active and illicit drugs such as amphetamine, cocaine benzoylecgonine, a cocaine metabolite, methadone, and a
and its metabolite benzoylecgonine, morphine, 6-acet- methadone metabolite. Amphetamine-type stimulants (except
ylmorphine, 11-nor-9-carboxy-delta-9-tetrahydrocannabinol, MDMA) were completely removed during prechlorination,
methadone and its main metabolite 2-ethylidene-1,5-dime- flocculation, and sand filtration steps. Granulated activated
thyl-3,3-diphenylpyrrolidine, and amphetamines have been carbon filtration removed cocaine (100%), MDMA (88%),
detected in surface water and wastewater. The high con- and benzoylecgonine (72%). Post-chlorination resulted in the
sumption rates reported for these compounds explain their complete elimination of MDMA. However, no information
relatively high concentration levels in the aquifer. In some was reported for reaction by-products.
studies, the measured concentrations were employed to esti-
mate the use of these drugs. Seasonal variations have been
3.04.15.3 Metabolites
found in several studies (Kasprzyk-Hordern et al., 2008).
Maximum levels of cocaine, ecstasy, and methamphetamine In general, little is known about the occurrence, fate, and ac-
values were found in winter but high loads were also detected tivity of metabolites of pharmaceuticals. An important ques-
in summer. There was a significant increase in the concen- tion to be addressed is whether the glucoronides, methylates,
trations of these compounds during the last days of December glycinates, acetylates, and sulfates are still active. It has been
and the first days of January, corresponding to the Christmas found that some compounds (e.g., conjugates of sulfa-
and New Year holidays. methoxazole and ethinlyestradiol) can be cleaved back by
Up to now, drugs of abuse have been detected in waste- bacteria during sewage treatment (D’Ascenzo et al., 2003;
waters and surface waters in the USA, Italy, Germany, UK, and Göbel et al., 2005). This results in the active compound being
Spain. One goal of several studies was to estimate the levels set free again. Bendz et al. (2005) detected human ibuprofen
abused drugs discharged. Most of the main illicit drugs con- metabolites not only in the WWTP but also in the receiving
sumed are excreted unaltered or as slightly transformed me- river, and carbamazepine metabolites were found in WWTP
tabolites, which reach the sewage system. The detection of effluent and even in drinking water (Hummel et al., 2006;
these drugs shows that the parent compound or conjugates Miao et al., 2005). Other types of metabolites are excreted too
can pass STPs and reach receiving waters that may be used for and can be detected in wastewater (Miao et al., 2005). Their
drinking-water production. effects on environmental organisms may be less than that of
Daily and seasonal variability was examined and revealed the parent. However, in the case of pro-drugs the situation is
fluctuations in the concentrations of nicotine, paraxanthine, probably different as it may also be for the metabolites of
amphetamine, cocaine, and ecstasy during the week. Estima- several other pharmaceuticals as has been shown, for example,
tions of consumption were made using the total concen- for norfluoxetin.
trations found in wastewater (Zuccato et al., 2008a, 2008b;
Hummel et al., 2006; Boleda et al., 2009; Huerta-Fontela et al.,
2007, 2008, 2009; Jones-Lepp et al., 2004). Studies are avail- 3.04.16 Engineered Nanoparticles
able for Italy (Zuccato et al., 2005; Castiglioni et al., 2006),
Germany (Hummel et al. 2006), USA (Jones-Lepp et al., 2004), Nanomaterials are of increasing technological and economical
Ireland (Bones et al., 2007), Belgium (Gheorghe et al., 2008; importance, and, in turn, contribute to higher standards of
van Nuijs et al., 2008), UK (Kasprzyk-Hordern et al., 2007; living. Important properties include size, shape, surface
Zuccato et al., 2008a, 2008b), Poland (Kasprzyk-Hordern properties, aggregation state, solubility, structure, and chem-
et al., 2008), and in Spain (Boleda et al., 2009). Concen- ical composition. According to chemical composition and
trations of methamphetamine were 0.8 and 0.5 ng l1 for shape, for example, there are several classes of engineered
MDMA in effluent samples from three WWTPs in the USA. The nanoparticles (ENPs) such as inorganic particles (e.g., TiO2,
presence of cocaine (42–120 ng l1) and its major metabolite, SiO2, and ZnO), organic ones such as fullerens, and multi-
benzoylecgonine (390–750 ng l1), in wastewaters and in the and single-walled carbon nanotubes. Some of them are
Po River (2 and 25 ng l1, respectively) was demonstrated. chemically modified, that is, they carry organic functionalities
Cocaine and its metabolite were detected in Spanish on their surface. Insoluble material such as fullerens may
82 Emerging Contaminants

become soluble by such a modification. As a result of their status of surface waters. In this context, ‘priority substances’
widespread use, their exposure to the human body is in- are set up. Braun et al. (2009) concluded that it is impossible
creasing, for example, by ingestion or application onto skin to set limit values for ENPs in surface waters now and
(e.g., use of sun screens), or through the use or handling of in the foreseeable future. This is not only due to the extensive
materials or products containing them. Some of them can also lack of knowledge in relation to unknown toxic effects, de-
reach the environment via production processes (emissions gradability, and bioaccumulation of ENPs in the aquatic en-
into air and wastewater) and even more likely as a result of the vironment, but also due to the questionable validity of test
routine use of products containing nanoparticles (e.g., sun systems and methods to establish environmental quality
screens). Others are the result of wash off, for example, from standards (EQS).
facades of buildings (Kaegi et al., 2008). These authors found The limitations in our knowledge are partly due to the lack
evidence that synthetic nanoparticles are released from urban of methodology for the detection and characterization of en-
applications into the aquatic environment. They investigated gineered nanoparticles in complex matrices, that is, water, soil,
TiO2 particles as these particles are used in large quantities in or food (Tiede et al., 2008; Perez et al., 2009; Frimmel and
exterior paints as whitening pigments and are, to some extent, Nießner, 2010). Methods have been developed for the de-
also present in the nano-size range. Analytical electron mi- tection of natural or engineered nanomaterials in simple
croscopy revealed that TiO2 particles are detached from new matrices, which could be optimized to provide the necessary
and aged facade paints by natural weather conditions and are information, including microscopy, chromatography, spec-
then transported by facade runoff and are discharged into troscopy, centrifugation, as well as filtration and related tech-
natural, receiving waters. niques. A combination of these is often required. A number of
Some of the ENPs are used for the remediation of en- challenges will arise when analyzing environmental materials,
vironmental pollution too such as the treatment of effluents including extraction challenges, the presence of analytical ar-
and wastewater (e.g., photocatalysis by TiO2). In such cases, tifacts caused by sample preparation, problems of distinction
the introduction of nanomaterials is intended; however, the between natural and engineered nanoparticles, and lack of
focus of an LCA of such materials is indispensable for the reference materials.
sustainable use of these nanoparticles. There is an increasing
concern over the safety of ENPs to humans and the environ-
ment and it is likely that the environmental risks of these 3.04.17 Artificial Sweeteners
particles will have to be tested under regulatory schemes such
as REACH. However, to date, little is known about the oc- Artificial low-calorie sweeteners are consumed in considerable
currence, fate, and toxicity of ENPs. Knowledge on tox- quantities with food and beverages. After ingestion, some
icological issues of nanomaterials is almost nonexistent sweeteners pass through the human metabolism largely un-
(Albrecht et al., 2006; Landsiedel et al., 2009) and still less as affected, are quantitatively excreted via urine and feces, and
far as the environment is concerned. Frequently, genotoxicity thus reach the environment associated with domestic waste-
seems to be associated with nanomaterials (Landsiedel et al., water. Typical sweeteners are sucralose, acesulfame, cyclamate
2009). (banned in the US), and saccarin. Their presence in the
Predicted environmental concentrations (PECs) of ENPs in aquatic environment came into focus only recently and
water arising form their use in consumer products range from knowledge is still little.
o0.1 ng l1 (CeO2) to 310 ng l1 for fullerenes up to 76 mg l1 Concentrations in two influents of German STPs were up
for ZnO (Tiede et al., 2009). Gottschalk et al. (2009) calculated to 190 mg l1 for cyclamate, about 40 mg l1 for acesulfame and
PECs based on a probabilistic material flow analysis from a saccharin, and less than 1 mg l1 for sucralose (Scheurer et al.,
life-cycle perspective of ENP-containing products. The simu- 2009). Buerge et al. (2006) detected acesulfame consistently in
lated modes (most frequent values) range from 0.003 ng l1 untreated and treated wastewater (12–46 mg l1). Removal in
(fullerenes) to 21 ng l1 (TiO2) for surface waters and from the STPs was limited for acesulfame and sucralose and 494%
4 ng l1 (fullerenes) to 4 mg l1 (TiO2) for sewage treatment for saccharin and cyclamate (Scheurer et al., 2009). In German
effluents. These data demonstrate that there is still only surface waters, acesulfame was the predominant artificial
knowledge on usage and introduction of ENPs into the en- sweetener with concentrations exceeding 2 mg l1. Other
vironment. Gottschalk et al. (2009) concluded that risks to sweeteners were detected up to several hundred ng l1 in the
aquatic organisms may currently emanate from nano-Ag, order saccharin approximate to cyclamate higher than sucra-
nano-TiO2, and nano-ZnO in sewage treatment effluents for lose (Scheurer et al., 2009). The analysis of 120 river surface
all considered regions and for nano-Ag in surface waters and water samples from 27 European countries showed that
that for the other environmental compartments for which sucralose, which is in use in Europe since the beginning of
ecotoxicological data were available, no risks to organisms are 2005, can be found in the aquatic environment, at concen-
presently expected. However, the aggregation of ENPs plays an trations up to 1 mg l1. Sucralose was predominately found in
important role in the environmental fate and effects because samples from the UK, Belgium, the Netherlands, France,
the size and shape of nanoparticles will determine the mag- Switzerland, Spain, Italy, Norway, and Sweden, suggesting
nitude of any potentially toxic effect. Aggregation is affected by an increased use of the substance in Western Europe (Loos
pH, ionic strength, and ionic identity (inorganic and organic) et al., 2009a). In North American coastal and open ocean
of aqueous suspensions (Sharma, 2009). waters, the concentration of sucralose varied over several
In Europe, the Water Framework Directive (WFD) is re- orders of magnitude in these environmental samples with
sponsible for maintaining a good chemical and ecological the greatest abundance in a WWTP effluent (120 mg l1).
 Emerging Contaminants 83

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