CHARACTERISTICS AND TREATMENT
OF PHARMACEUTICALS
AND PERSONAL CARE PRODUCTS
IN WASTEWATER

Jfc U.S. Environmental Protection Agency
^4*2^ l*iOffice of Wastewater Management
^1 M "1 EPA-830-S-24-001


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CHARACTERISTICS AND TREATMENT
OF PHARMACEUTICALS AND PERSONAL CARE
PRODUCTS IN WASTEWATER

TABLE OF CONTENTS

SECTION	PAGE

INTRODUCTION
PPCP SOURCES AND EFFECTS

CHEMICAL PROPERTIES AND CONSIDERATION FOR MONITORING
CONVENTIONAL TREATMENT

ADSORPTION TECHNOLOGY

O

e
©
©
e

OXIDATION TECHNOLOGIES	0

MEMBRANE TECHNOLOGIES	0

CONSTRUCTED WETLANDS	fli)

PPCP TREATMENT TECHNOLOGY SUMMARY TABLE	0

REFERENCES

This report does not attempt to address the holistic management of PPCPs nor any
current or future policy decisions related to these chemicals. The discussion herein is
not exhaustive in describing the extent and effects of PPCPs, but rather introduces this
complex class of chemicals which may pose newly identified or re-emerging risks to
human health, aquatic life, or the environment, along with technologies that can be
used to treat them at wastewater treatment plants (U.S. EPA, 2022a). This report was
developed to support EPA's Searchable Clearinghouse of Wastewater Technology
(SCOWT) and to encourage the use of EPA funds for emerging contaminants projects.


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Introduction

Pharmaceuticals arid personal care products (PPCPs) encompass a diverse group of chemicals, including all drugs
(prescription and over the counter) and non-medicinal consumer chemicals (i.e., fragrances in lotions and soaps,
ultraviolet [UV] filters in sunscreens) (U.S. EPA, 2013). PPCPs vary in their intended applications and chemical
composition, making it challenging to monitor and treat these compounds. When detected in wastewater or the
environment, PPCPs are usually present at low concentrations (parts per billion or trillion). Even at low
concentrations, however, PPCPs may have adverse effects on aquatic organisms, including effects on antibiotic
resistance, endocrine disruption, and bioaccumulation (Dhangar & Kumar, 2020). The PPCPs most studied in
wastewater include analgesics (pain relievers), antihypertensives (blood pressure medications), psychoactives,
antibiotics, hormones, stimulants, UV filters (sunscreen), and fragrances due to their high consumption volume
and persistence in the environment.

Conventional municipal wastewater treatment facilities (WWTFs), defined as facilities using solids removal
(primary treatment) and biodegradable organics removal (secondary treatment), are not currently designed to
specifically target PPCPs. However, primary and secondary treatment can partially remove many PPCPs to varying
degrees depending on the physicochemical properties of specific PPCPs, treatment operational variables, and
climatic conditions. There are additional physical, chemical, and biological wastewater treatment technologies
that can treat PPCPs. These technologies may be most appropriate for moderate- to large-scale facilities with
more sophisticated operator capabilities and resources to support the operation, maintenance, and monitoring of
PPCP removal technologies. This technology brief aims to provide preliminary information on the treatment of
PPCPs in municipal wastewater and inform the initial identification of PPCP treatment technology. An important
first step to discussing technology options is to understand the characteristics of PPCPs that make them resistant
to removal in conventional WWTFs.

EXAMPLES OF
PHARMACEUTICALS

EXAMPLES OF PERSONAL
CARE PRODUCTS

UV filters (sunscreen agents)

Detergents

Preservatives

Insect repellents

Cosmetics

Blood pressure medications

Bactericides

Antimicrobials

Growth promoters

Animal drugs

Hormones

Characteristics arid Treatment of Pharmaceuticals arid Personal Care Products (PPCPs) in Wastewater / August 2024


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PPCP Sources and Effects

One of the primary ways that PPCPs enter the environment is through
municipal WWTF effluent. Municipal WWTFs are not designed to treat these
contaminants but receive them continuously. Many studies link the presence
of PPCPs in surface water to effluents from WWTFs that are not designed to
remove PPCPs (Al-Baldawi et al., 2021; Dhangar & Kumar, 2020; Tarpani &

Azapagic, 2018; Tijani et al., 2013; U.S. EPA, 2013). Pharmaceuticals from
residential sources are introduced to the municipal system through two
primary mechanisms: 1) through the improper direct disposal of unused or
expired medications to the sanitary sewer and 2) as waste following the
incomplete metabolization of pharmaceuticals in the body (Al-Baldawi et al., 2021). Personal care products (e.g.,
soaps, cosmetics, fragrances) are discharged into municipal wastewater through regular household activities such
as bathing and laundry (U.S. EPA, 2009). This technology brief does not focus on additional pathways for PPCPs to
enter the environment such as through hospital-specific wastewater, pharmaceutical manufacturing wastewater,
or agribusiness.

The presence of PPCPs in the environment may pose both an environmental and public health concern. Some
PPCPs have been shown to bioaccumulate in aquatic organisms such as fish (U.S. EPA, 2013). PPCPs can also cause
behavioral changes in aquatic organisms (Brodin et al., 2014). Long-term exposure to some PPCPs has been
correlated with endocrine disruption in fish and humans, leading to hormonal abnormalities and cancer (Tijani et
al., 2013). Antimicrobial resistance is also a significant concern. As pathogens and bacteria are exposed to PPCPs
such as antibiotics, they develop drug resistance, which may inhibit the treatment of certain pathogenic diseases
(Kumar et al., 2023). Preventing and reducing the release of PPCPs to the environment protects both human
health and the environment.

Source Control

Source control is the most effective means to keep PPCPs out of wastewater
and the environment. Best management practices such as sewer bans and
drug take-back programs help to reduce the amount of PPCPs that enter
municipal wastewater. This technology brief is focused on how to treat and
remove PPCPs once they are already in the wastewater.

More information on how EPA is reducing the amount of hazardous waste
pharmaceuticals entering our waterways.

Photo Credit: Lance Cpl. Kirstiri Merrimarahajara for the United States Marine

Chemical Properties and Considerations
for Monitoring

PCPPs are a category of chemicals defined by their intended use, not their chemical properties. This leads to
variability in the behavior of PPCPs and the effectiveness of different wastewater treatment technologies for
PPCPs. For example, compounds that have a high tendency to sorb onto solid material are likely to be adsorbed
onto sludge and may be effectively removed through conventional treatment methods. Table 1 provides a few
examples of PPCPs and their chemical properties. When addressing a chemical of concern in a community or
WWTF, the unique properties of that chemical should be identified before determining the best treatment option.

EPA has developed and
validated Method 1694 for
74 PPCPs and Method 1698
for 27 steroids and
hormones in water, soil,
sediment and biosoiids.

More information on EPA
analytical methods for
PPCPs.

Characteristics arid Treatment of Pharmaceuticals arid Personal Care Products (PPCPs) in Wastewater / August 2024

2


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Table 1. Chemical properties of select PPCPs."







Probability











Compound

Probability

Probability





Probability

Will

Compound

Compound





Compound

Dissociate

Will Adsorb

will





Will Dissolve

into Smaller

onto Solid

Biologically

Compound

Application

in Waterb

Molecules0

Material

Degrade6

Galaxolde

Fragrance

Low

—

High

Low

Fluoxetine

Antidepressant

Moderate

High

Moderate

—

17(B-Estradiol

Hormone

Low

High

Moderate

High

17a-

Hormone

Low

High

Low

Moderate

Ethinylestradiol











Roxithromycin

Antimicrobial

Low

High

Low

Low

Trimethoprim

Antimicrobial

High

Moderate

Low

—

Triclosan

Antimicrobial

Low

Moderate

Moderate

—

aThis table contains summarized information from Table 2 in Suarez et al., 2008 and Table 1 in Ohoro et al., 2022. Categories
assigned are based on numerical ranges provided in the reference table and should only be used to compare the
characteristics of each compound to the others in this table.
bSolubility in water, s.
c Dissociation constant, pKa.
d Octanol-water partition coefficient, K0w.
e Pseudo first-order degradation constant, kbioi.

If you would like more detailed information on what chemical characteristics these constants describe, please
see "Phvsiochemical Properties and Environmental Fate" in A Framework to Guide Selection of Chemical
Alternatives (National Research Council, 2014).

Conventional Treatment

This section provides a brief discussion of the treatability of PPCPs using
conventional wastewater treatment, which is defined here as only primary and
secondary treatment. Conventional treatment is not designed to remove PPCPs
but may have the co-benefit of removing select PPCPs without the addition of
tertiary treatment processes. Figure 1 summarizes how PPCPs move through a
WWTF and how they can potentially be treated and removed. Compounds that
are likely to sorb onto solids, such as fragrances, are readily removed in
conventional treatment at efficiencies between 60 and 90 percent (Suarez et al., 2008). Compounds that are
unlikely to sorb and are resistant to biodegradation, such as the antiepileptic drug carbamazepine, are removed at
0 to 45 percent efficiency (Suarez et al., 2008).

The goal of primary treatment is to remove settleable matter and solids. PPCPs that readily dissociate or adsorb
are likely to be removed during primary treatment. Just as with other suspended particles, the removal of PPCPs
may be enhanced by the addition of chemical coagulants or flocculants (Suarez et al., 2008). This may lead to
some removal of less sorbent PPCPs, but mainly improves the removal of sorbent compounds.

For more information on
conventional wastewater
treatment, see How
Wastewater Treatment
Works... The Basics (EPA
833-F-98-002).

Characteristics and Treatment of Pharmaceuticals and Personal Care Products (PPCPs) in Wastewater / August 2024

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In secondary treatment, bacteria break down organic matter
and adsorbent compounds sorb onto biological floe. Actual
PPCP removal during secondary treatment depends on several
factors, such as biomass concentration, the type of process
used, operating conditions such as solids retention time and
hydraulic retention time, and local conditions such as
temperature and sunlight intensity. The success of removal
also depends on PPCP compound chemical characteristics and
the extent of biotic degradation and adsorption onto solids
(Blair et al., 2013). Most pharmaceuticals are designed to be
resistant to biodegradation and thus do not easily degrade in
conventional activated sludge processes (Kumar et al., 2023).

Studies on PPCP removal in activated sludge treatment plants
report inconsistent removal rates across study locations. For
example, fragrances were removed at 50 to 75 percent
efficiency and hormones were removed at 49 to 99 percent
efficiency in two different case studies of PPCP removal in activated sludge treatment (Suarez et al., 2008). This is
likely due to differences in operating conditions (with the intent to improve secondary treatment) between
systems, such as dissolved oxygen levels, sludge age, and overall wastewater characteristics (Yang et al., 2011).
The complex nature of PPCPs further limits the removal efficiency of secondary treatment. While research
suggests that conventional treatment may have the co-benefit of removing some PPCPs, conventional treatment
alone may not be capable of treating all the PPCPs that may be present in a WWTF's influent.

Influent	Primary Treatment	Secondary Treatment	Tertiary Treatment

<3S> Degradation byproducts

Figure 1. How PPCPs move through a WWTF (DBPs: degradation byproducts).

Potable Reuse

As natural water resources in some areas become increasingly stressed, potable reuse may be an effective
option to increase drinking water availability. The advanced technologies needed to treat wastewater for
potable reuse have the co-benefit of removing PPCPs. Those exploring potable reuse should consider the
potential for targeted treatment of PPCPs.

The sections that follow describe a few of the technologies available for PPCP treatment in wastewater. There is
limited research on these technologies operating at full scale where PPCPs are specifically monitored, but
evidence at the pilot- and lab-bench scale indicates that these technologies are likely to achieve greater removal
of PPCPs than conventional treatment alone at full scale. The removal efficiencies presented are likely dependent
on the characteristics of the influent and concentration of each PPCP discussed. A table summarizing the
applications, considerations, and performance of these technologies is provided at the end of this document.

PPCPs in Biosolids

The presence of PPCP compounds in
biosolids is one of the potential routes of
human and ecological exposure. To date,
EPA has found 243 PPCP compounds in
biosolids through nine biennial reviews of
public literature and three national sewage
sludge surveys (Richman et al., 2022; U.S.
EPA, 2022b). These compounds, in addition
to the other chemicals that have been
found in biosolids, will be evaluated for risk
by EPA. Chemicals that present risk above
EPA's level of concern may be regulated in
biosolids.

Characteristics and Treatment of Pharmaceuticals and Personal Care Products (PPCPs) in Wastewater / August 2024

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Adsorption Technology

Description

Adsorption is sometimes called "phase-changing
technology" because it removes dissolved organic
and inorganic compounds from wastewater by
adhering them to binding sites on a solid adsorption
media. As seen in Figure 2, contaminants like PPCPs
can be removed from wastewater through
adsorption to sorbents like activated carbon.

Advanced adsorption media is specifically sourced
and designed to be more effective than the
adsorption that occurs in conventional primary
treatment. The most common adsorption media is
activated carbon, either in a granular (GAC) or
powdered (PAC) form, because of its high efficiency
relative to other adsorbents (Baskar et al., 2022).

GAC is often used in a bed form, where the
adsorption media remains in place while wastewater flows through it, while PAC is fed into the waste stream and
must be removed along with other sludge solids (U.S. EPA, 2000).

Over time, binding sites on the adsorption media are filled and the material becomes unable to remove additional
dissolved compounds. When used in a bed form, adsorption media can be backwashed to remove adsorbed
particulates, but the spent media will eventually need to be removed and replaced (U.S. EPA, 2000). Spent
adsorption media can be regenerated through various methods, including solvent washing, sonication, and most
commonly, thermal treatment (Baskar et al., 2022). Regeneration may need to occur off site at a different facility.
Solid adsorption media can be regenerated multiple times but does become less effective with each regeneration.

Applicability

Adsorption technology is available in a variety of configurations, making it easier to integrate into existing
facilities. The type of adsorption media a facility uses can be tailored to the needs of the system and the targeted
PPCP compounds. Highly soluble PPCPs that are unlikely to sorb onto solids will not be efficiently removed with
adsorption. An additional treatment step prior to GAC, such as filtration or use of additional GAC columns, would
further reduce organics in the water that would otherwise bind to the adsorbent media and occupy binding sites
needed for PPCP removal (Snyder et al., 2007).

Considerations

Advantages of Adsorption Technology

Disadvantages of Adsorption Technology

•	Adsorption technology removes a
wide range of PPCPs.

•	Adsorption technology does not form
potentially harmful degradation
products.

•	GAC media can be backwashed,
regenerated, and reused.

•	Adsorption technology does not degrade PPCPs; they remain
in their original form.

•	GAC systems must be monitored and backwashed frequently
to prevent clogging and breakthrough.

•	GAC media regeneration requires significant energy and may
need to be done off site.

•	GAC media regeneration produces a concentrated waste
stream that must be handled appropriately.

Organic pollutants

> Inorganic pollutants

Sorbents

Figure 2. Illustration of the removal of wastewater
contaminants using sorbent (Baskar et a I., 2022).

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Performance

Several laboratory-scale studies of activated carbon using spiked aqueous solutions have shown removal
efficiencies of more than 90 percent for four nonsteroidal anti-inflammatory drugs, three antibiotics, and caffeine
(Dhangar & Kumar, 2020). This technology has shown similar efficiencies at full scale surface water treatment and
water reuse plants, but efficiencies can vary greatly between systems (Snyder et al., 2007). The source of the
adsorption media affects the removal efficiency of PPCPs. In one study at the laboratory scale using aqueous
solutions, acetaminophen had a greater than 90 percent removal efficiency when using activated carbon from a
wood source, but only 60 to 87 percent removal efficiency when using activated carbon from herbaceous plants
(Dhangar & Kumar, 2020). It can be helpful to do bench-scale testing with samples from the WWTF of interest to
ensure that the most appropriate adsorption media is selected for installation.

Oxidation Technologies

Description

Oxidation is a chemical process in which chemical agents react
with target pollutants and oxidize them into a different
chemical that is distinct from but related to their parent
compound. The oxidation processes include chlorination,
photolysis (UV radiation), and ozonation; each of these are
defined by the agent used to initiate the process (Dhangar &

Kumar, 2020; Kumar, 2023). Ozone is a strong chemical
oxidant that can be used to treat a variety of organic
pollutants, including PPCPs, and can be combined with other
physical or chemical agents in advanced oxidation (Ikehata et
al., 2008). Each of the oxidants in these processes react either
directly or indirectly (i.e., through their degradation products)
with the chemical structure of PPCPs to break them down, as
outlined in Figure 3.

Some chemical agents are more effective than others; for
example, ozone is a much stronger oxidation agent than
chlorine or UV. These chemicals are also used for conventional
wastewater disinfection but are applied at a lower dose than
is required to oxidize complex chemicals such as PPCPs.

Unfortunately, oxidation does have the potential to form
harmful byproducts along with non-harmful byproducts (Dhangar & Kumar, 2020). There is little information on
the presence and effects of the degradation products of oxidized PPCPs because there are no EPA-validated
analytical methods to detect or analyze them.

Applicability

Oxidation technology is appropriate for moderate- to large-scale facilities with the capacity for chemical handling.
It is best used after secondary treatment to reduce the competing species in the process water that could also be
oxidized by the chemical agent. Decisions on which oxidation process(es) to use for PPCP removal are based on
several factors, including the facility's overall treatment goals and the specific pollutants within the water to be
treated. Regardless of which oxidation process is used, when the chemical agent is applied at a higher dose or for
a longer contact time, a wider range of PPCPs are oxidized at a higher rate. The chemical agent dose or reaction
time applied is expected to be higher than that required for standard disinfection (Paucar et al., 2018).

Oxidation technologies

V

1

Ozonation I Photolysis (UV) I Chlorination

Hydroxyl radicals

PPCP

PPCP

HiO

Degradation products

CO2

Unknown byproducts

Figure 3. Diagram of oxidation processes
(modified from Krishnan et al., 2021).

Characteristics and Treatment of Pharmaceuticals and Personal Care Products (PPCPs) in Wastewater / August 2024

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To choose the most appropriate chemical agent, facilities must consider the balance between their performance
goals and the risk of creating harmful byproducts. Chlorination is not as effective and has greater challenges than
photolysis and ozonation; chlorination is also likely to form harmful byproducts (Dhangar & Kumar, 2020).
Photolysis is most effective when paired with a photosensitizer such as hydrogen peroxide and can effectively
degrade many PPCPs, including antibiotics, analgesics, and hormones (Ngumba et al., 2020). Ozone is a strong
oxidant that can degrade many PPCP compounds, including antibiotics, hormones, and beta blockers, but it is
energy intensive to produce (Dhangar & Kumar, 2020). Ozone decomposes rapidly and must be generated on site
(U.S. EPA, 1999). Byproducts of ozonation include bromate and nitrosamines (such as N-nitrosodimethylamine
[NDMA]), which have been classified as probable human carcinogens and are not related to the presence of PPCPs
(Lim et al., 2022).

Considerations

Advantages of Oxidation Technologies

Disadvantages of Oxidation Technologies

•	Oxidation technologies effectively degrade
resistant PPCPs.

•	Oxidation technologies chemically transform,
not simply phase change, PPCPs.

•	Oxidation technologies treat for pathogens and
metals (Tarpani & Azapagic, 2018).

•	Oxidation technologies produce no additional
waste stream.

•	Chemical transformation of PPCPs can form
potentially harmful degradation products that are
challenging to monitor.

•	Byproducts of the oxidant itself may be potentially
harmful.

•	Chemical agents may need to be produced on site
and may be energy intensive.

•	Chemical agents can be hazardous to handle.

Performance

A laboratory scale study of UV photolysis on municipal wastewater effluent containing six PPCPs showed removal
efficiencies of over 90 percent for two antibiotics and one antiviral, all of which strongly absorbed UV light
(Ngumba et al., 2020). The removal efficiencies of the other two antivirals and one antibiotic that did not strongly
absorb UV light all increased with the addition of hydrogen peroxide but remained at or below 70 percent
removal (Ngumba et al., 2020). Ozonation is highly effective and effectively removes most types of PPCPs,
especially hormones, at an efficiency of 90 to 100 percent (Dhangar & Kumar, 2020). However, ozonation is less
effective on compounds without reactive groups in their chemical structure, such as ibuprofen (Suarez et al.,
2008).

Case Study: Pilot Scale Test of Ozonation at Different Doses and Contact Times (Paucar et al., 2018)

Conventionally treated municipal wastewater effluent was used as feed wastewater in this laboratory study
performed at the pilot scale. Three 35-liter stainless steel ozone reactors were connected in series to model
full-scale ozone treatment with ozone monitors placed before and after each reactor. Operating conditions of
the ozone treatment unit, including ozone dose (1 to 9 milligrams per liter) and contact time (five to 15
minutes), were analyzed for their PPCP removal efficiency.

Thirty-seven PPCPs were detected in the feed wastewater effluent, including antibiotics and anticonvulsants.
All 11 antibiotics detected in the feed wastewater were degraded to concentrations that could not be detected
when treated at the highest ozone dose and longest contact time. The anticonvulsant carbamazepine was
degraded to undetectable levels at the lowest ozone dose and medium contact time. The other anticonvulsant
detected, primidone, was one of the three chemicals that was resistant to ozone (i.e., not removed below the
limit of detection) even at the highest ozone dose and longest contact time. The other ozone-resistant
chemicals were DEET, an insect repellant, and ketoprofen, an analgesic. All three of these ozone resistant
chemicals, though not removed below the limit of detection, were still significantly reduced (92 to 99 percent)
at the highest ozone dose, showing that even the most resistant PPCP compounds can be removed significantly
using ozone.

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Membrane Technologies

Description

Membrane separation processes remove PPCPs
through size exclusion, electrostatic repulsion, and
adsorption. High pressure pushes water and
molecules with low molecular weight through the
membrane while solid particles and molecules
with high molecular weight remain behind in a
concentrated waste stream (Dhangar & Kumar,
2020). Nanofiltration (NF, pore size ~1-10
nanometers) and reverse osmosis (RO, pore size
<1 nanometers) membranes vary in pore size,
charge, molecular weight cut-off, and
hydrophobicity/hydrophilicity, which influence the

(a)

(b)

Figure 4. MBR system in (a) submerged and (b) side-
stream configurations (Melin et a!., 2005).

removal efficiency of specific PPCPs (Couto et al., 2018; Loganathan et al., 2023). The PPCPs themselves exist in a
range of properties (e.g., size, charge, hydrophobicity), so it is not possible to generalize their performance based
on membrane type or PPCP compounds in general.

Membrane bioreactors (MBRs) combine microfiltration (MF, pore size 0.1-1 micrometers) or ultrafiltration (UF,
pore size 0.01-0.1 micrometers) with biological treatment. Figure 4 provides schematics of the two primary
configurations of MBR systems. As with NF and RO membranes, water is forced across the membrane surface, but
instead of a pressurized system, MBRs use a vacuum so that the water outside is at ambient pressure (U.S. EPA,
2007). The microbes at the membrane surface then work to biodegrade the retained compounds and transform
them into smaller, less harmful compounds (Kumar et al., 2023).

MBRs work well for PPCPs that sorb onto solids and PPCPs that biodegrade. MBRs are less effective on dissolved
trace organic compounds, including PPCPs, that are unlikely to biodegrade or sorb and may pass through the
membrane pores. The addition of advanced membrane size exclusion methods, such as RO, increases PPCP
removal when used in combination with an MBR (Wang et al., 2018). A downside of membrane technologies is
that they form a concentrated waste stream that contains the contaminants removed from the water that were
not biodegraded.

Applicability

Membrane separation processes effectively remove low molecular weight organic pollutants, such as PPCPs, from
wastewater (Couto et al., 2018). Membranes and MBRs can be added to a conventional treatment system as a
tertiary treatment step or MBRs can replace secondary biological treatment (U.S. EPA, 2007). The integration of
an MF or UF membrane with a biological reactor in an MBR system allows for an increase in the solids retention
time, resulting in improved efficiency in removing trace organics such as PPCPs (Couto et al., 2018).

Proper operation and maintenance are essential to avoid membrane obstruction and fouling. Regular cleaning
with chemicals such as bleach or citric acid also helps to avoid clogging (U.S. EPA, 2007). Most MBR systems use
an air-scour technique which blows air around the membrane to reduce material buildup on the pore surface
(U.S. EPA, 2007). Membrane technology requires the management of concentrated waste streams consisting of
PPCPs extracted from the wastewater along with other pollutants (Kumar et al., 2023). This concentrated effluent
can be challenging to treat or dispose of in a way that mitigates ecological ramifications.

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Considerations

Advantages of Membrane Technologies

Disadvantages of Membrane Technologies

•	Membranes technologies do not alter the chemical
structure of PPCPs, thus avoiding the production of
potentially harmful byproducts.

•	Membrane technologies have small footprint
requirements.

•	Membrane technologies can be used to treat other
emerging contaminants, not just PPCPs.

•	Membrane technologies make minimal use of dangerous
chemicals.

•	MBRs combine physical and biological removal of PPCPs.

•	Membrane technologies can have issues
with clogging and fouling if improperly
operated.

•	RO/NF membranes create concentrated
waste streams that must be disposed of or
treated appropriately.

•	Membrane technologies are complex to
operate and maintain.

Performance

UF and RO were studied in combination at the pilot scale using conventionally treated secondary effluent (Snyder
et al., 2007). The UF unit did not achieve significant PPCP removal and was used mainly as pretreatment for the
RO unit. All 21 PPCPs identified in the secondary effluent, besides caffeine, were removed at over 90 percent
efficiency using the UF/RO system (Snyder et al., 2007). Many PPCPs, including carbamazepine (anticonvulsant),
DEET (insect repellent) and meprobamate (antianxiety) were removed at over 99 percent efficiency with the
UF/RO system (Snyder et al., 2007).

Pilot scale testing of an MBR system was performed on primary effluent from a municipal WWTP. Four membrane
modules with a pore size of 0.2 micrometers were in operation during the study (Snyder et al., 2007). Several
compounds were removed at 85 to 95 percent efficiency, including caffeine, carbamazepine (anticonvulsant),
gemfibrozil (cholesterol medication), and hydrocodone (analgesic) (Snyder et al., 2007). Other compounds, such
as ibuprofen and the antianxiety medication meprobamate, increased in concentration through the MBR (Snyder
et al., 2007). Some trace organic contaminants may increase through an MBR due to potential precursor
compound transformation in the wastewater treatment process.

Case Study: Integrated Membrane System for Municipal Wastewater (Wang et al., 2018)

This pilot-scale system treated municipal sewage using a primary settling tank prior to treatment in an MBR
reactor using an MF membrane. The MBR reactor was followed by a precision filter (to remove suspended
solids), UV light, and either RO or NF. The full treatment train is outlined in Figure 5. Twenty-seven PPCPs were
detected in the raw wastewater and were monitored throughout the system.

Removal efficiency across the 27 contaminants was variable and highly dependent on their chemical
characteristics. Removal efficiency through the MBR system alone was high for the hormone estriol (95
percent) and caffeine (88 percent) but was lower for the anticonvulsant carbamazepine (41 percent) and the
beta blocker metoprolol (47 percent). The MBR system showed limited removal of hydrophilic PPCPs and those
resistant to biodegradation. The downstream use of a smaller pore size NF/RO membrane more effectively
removed these types of compounds. The combination of the MBR and NF membrane removed 13 of the 27
compounds to below their detection limit, while MBR and RO membrane removed 20 of the 27 compounds to
below their detection limit. Using MBR and membrane filtration in combination can target a wide range of
PPCP compounds and remove them effectively.

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Case Study: Integrated Membrane System for Municipal Wastewater, cont. (Wang et al., 2018)

Inhibitor

(T) Primary setting tank (2) MBR reactor (3) Precision filter	(4) Ultraviolet light (5) RO membrate module

© NR membrane	(7) Pump	(§) Blast blower	(9) High-pressure pump

Figure 5. Schematic of pilot-scale treatment train (Wang et a!., 2018).

Constructed Wetlands

Description

Constructed wetlands mimic natural wetlands but are specially designed to meet treatment goals. As shown in
Figure 6, several removal pathways occur in constructed wetlands, including biodegradation, sorption, and
chemical oxidation (Al-Baldwai et ai., 2021). The most effective mechanisms of PPCP removal in constructed
wetlands are plant absorption and microbial degradation. Plants are primarily responsible for biodegradation in
the form of phytodegradation. In phytodegradation, plants and their associated root microbes convert both
inorganic and organic contaminants to less toxic forms, including complete mineralization to nontoxic inorganic
end products (e.g., carbon dioxide, water) (Al-Baldwai et al., 2021). If PPCPs become embedded in plant tissues,
they are rendered unattainable and will not return to soluble forms. Pretreatment of wastewater is needed to
remove competing compounds that the plants may prefer, such as sucrose (Al-Baldwai et al., 2021). Unlike
biodegredation, sorption and chemical oxidation mainly occur in the soil matrix where there are binding sites for
PPCPs to sorb to and chemicals that could potentially oxidize them as well (Dhangar & Kumar, 2020).

•	Pollutant
+ Nutrients and oxygen
I Evaporable form

*	C02 + H20and/or
metabolites

Degradation

Volatilisation -

: s

Extraction

Stabilisation

Rhizofiltration

Stimulation

Figure 4. Major phytoremediation processes (Al-Baldwai et al., 2021).

Characteristics arid Treatment of Pharmaceuticals arid Personal Care Products (PPCPs) in Wastewater / August 2024

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Applicability

Constructed wetlands have low energy requirements, have simple operation and maintenance requirements, and
are environmentally friendly. However, they do require a large footprint and are highly climate dependent as the
activity of microbes decreases significantly in colder months (Kumar et al., 2023). They require occasional
maintenance to remove built-up solids and exhausted biomass (Kumar et al., 2023).

The flow regime of wastewater through the constructed wetland is a critical design element in addition to the
appropriate plant and soil substrate. Horizontal flow, vertical flow, and subsurface/surface flow are examples of
regimes that could be used (Al-Baldwai et al., 2021). All flow regimes must provide a long hydraulic residence time
such that there is ample contact time between microbes, substrates, and the contaminants. Over time, the
accumulation limit of the plants is reached, and they must be harvested. These plants could potentially be used in
compost or biofuels, however, the recalcitrance of PPCPs through different treatments and their pathways of
rerelease are still within the research phase and more studies are needed (Al-Baldwai et al., 2021).

Considerations

Advantages of Constructed Wetlands

Disadvantages of Constructed Wetlands

•	Constructed wetlands have low
energy requirements.

•	Constructed wetlands are simple to
operate and maintain.

•	Constructed wetlands have large land requirements.

•	Constructed wetlands are climate dependent.

•	Constructed wetlands are prone to clogging issues.

•	It is difficult to monitor removal pathways in a constructed
wetland.

•	Constructed wetlands necessitate the harvesting and disposal
of vegetation which may contain PPCPs.

Performance

The performance of constructed wetland systems is highly dependent on their design and function, especially
since these factors can vary widely between systems. The growth and activity of plants and microorganisms are
significantly affected by water, soil, and air temperatures (Hu et al., 2021). A full-scale study of a constructed
wetland treating municipal wastewater in Spain reported ibuprofen removal at 42-99 percent and caffeine
removal at 83-96 percent, whereas a full-scale study of a constructed wetland treating wastewater in the Czech
Republic reported ibuprofen removal at 55 percent and caffeine removal at 84 percent (Al-Baldwai et al., 2021). In
the Spain study, ibuprofen was assumed to be aerobically biodegraded, as was caffeine in the Czech Republic
study. In constructed wetlands, it can be difficult to know which degradation pathway a chemical has taken
because there are several possibilities.

Characteristics and Treatment of Pharmaceuticals and Personal Care Products (PPCPs) in Wastewater / August 2024

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Case Study: Full-Scale Application of Integrated Conventional, Membrane, Adsorption, and

Oxidation Treatment (Yang et al., 2011)

Combining processes to treat PPCPs takes advantage of the different mechanisms specific to each process that
are synergistic or complementary. The following case study is an example of this principle in action. The F.
Wayne Hill Water Resources Center (WRC) is an advanced water reclamation plant that employs several of the
technologies described above to treat approximately 60 million gallons per day of municipal wastewater. The
WRC's treatment process consists of conventional treatment (primary clarification and activated sludge
treatment) followed by membrane microfiltration, activated carbon adsorption beds, and ozonation, as seen in
Figure 7.

Grit chamber

Screen Primary
darifier

Chemical
addition

Membrane

Aeration
tanks

Secondary
darifier

95%

^ Composite sampling location: Monthly sampling for 12 months
9 Composite sampling location: Monthly sampling forfour months

filtration





A,





~







GAC

contactor

Chemical
darifier

Granular
media filter

Figure 7. Schematic diagram of the wastewater reclamation plant (Yang et al., 2011).

Sixteen PPCPs were monitored throughout the WRC to determine which treatment units were removing
specific compounds. Acetaminophen, ibuprofen, and caffeine were removed at over 99 percent removal
efficiency in the activated sludge treatment. The concentration of DEET was reduced by several orders of
magnitude after passing through activated sludge treatment and membrane microfiltration, but was largely
unaffected by the GAC and ozone. Two antibiotics and one anti-inflammatory that were resistant to biological
treatment were removed by GAC. One antibiotic that increased in concentration through the GAC on average
showed 88 percent removal efficiency through the ozone contactor. Only DEET, caffeine, an antibiotic, and an
anticonvulsant were detected consistently in the final effluent. Except for one antibiotic and one
anticonvulsant, which were reduced in concentration by about 50 percent, all compounds were removed at an
efficiency of over 95 percent between the primary effluent and the final effluent.

Implementing tertiary treatment after the conventional treatment steps improves removal beyond what can be
achieved by clarification and activated sludge treatment. What isn't removed in those initial steps is targeted
more specifically in adsorption and ozonation treatment units. A multi-step approach that incorporates a
combination of processes removes a range of PPCPs. Note that this study did not include an analysis of the
sludge handling, which is critical when designing PPCP wastewater treatment decisions.

Call for Projects! Interested in piloting one of these technologies at your facility or have a different project
planned to address PPCPs in your area? We'd love to hear from you!

To learn how to have your project featured in EPA's Searchable Clearinghouse of Wastewater Technology
(SCOWT), contact EPA (cwsrfECffiepa.gov) to provide project details. Contributing information about your
project helps EPA build a library of case studies to serve as examples for future projects. Be a part of
advancements in the treatment and removal of emerging contaminants.

Characteristics and Treatment of Pharmaceuticals and Personal Care Products (PPCPs) in Wastewater / August 2024

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Pharmaceuticals and Personal Care Products (PPCPs)
Treatment Technology Summary Table

(Note: This table is not comprehensive and is intended to be complementary to this technology brief.)

Conventional
Treatment

Further reading: Suarez
et al., 2008

Non-targeted
treatment.

Does not require
changes to the current
system.

Removal can be
enhanced with
coagulants/flocculants.

Not designed to
specifically target
PPCPs.

Primary treatment:
fragrances (60-90%
removal);

carbamazepine (0-
45% removal).

Secondary treatment:
fragrances (50-75%
removal); hormones
(49-99% removal).

Sludge is likely to contain
PPCPs and should be
properly used or
disposed of.

Adsorption
Technologies

Further reading: Baskar
et al., 2022; Dhangar &
Kumar, 2020; Kumar et
al., 2023; Snyder et al.,
2007; Suarez et al.,
2008; Tarpani &
Azapagic, 2018; U.S.
EPA, 2000; Yang et al.,
2011

Some PPCPs
likely to sorb
onto solids.

Removes a wide range
of PPCPs.

Granular activated
carbon (GAC) media can
be backwashed,
regenerated, and
reused.

Does not form
potentially harmful
degradation products.

GAC systems must be
monitored and
backwashed
frequently to prevent
clogging and
breakthrough.

GAC media
regeneration requires
significant energy and
may need to be done
off site.

Laboratory scale:
>90% removal of
select PPCPs.

Full scale: more
variable, system
dependent.

Dependent on
adsorbent media, can
be targeted to specific
compounds.

Media regeneration and
replacement required
(for GAC).

Solids removal and
handling required (if
using powder).

Characteristics and Treatment of Pharmaceuticals and Personal Care Products (PPCPs) in Wastewater / August 2024

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Targeted







Operation and

Treatment

PPCP

Type(s)

Advantages

Disadvantages

Performance

Maintenance
Considerations







GAC media

regeneration produces
a concentrated waste
stream that must be
handled
appropriately.

Adsorption technology
does not degrade
PPCPs; they remain in
their original form.





Oxidation
Technologies

Further reading:

Dhangar & Kumar, 2020;
Kumar et a!., 2023;
Ngumba et al., 2020;
Paucar et al., 2018;
Suarez et al., 2008; Sui
et al., 2013; Tarpani &
Azapagic, 2018; Tijani et
al., 2013; U.S. EPA,
1999; Yang et al., 2011

Dependent on
type of

chemical agent
used.

Effective on
PPCPs resistant
to sorption and
biodegradation.

Effectively degrades
resistant PPCPs.

PPCPs are chemically
transformed, not simply
phase changed.

Also treats for
pathogens and metals
(Tarpani & Azapagic,
2018).

Produces no additional
waste stream.

Chemical
transformation of
PPCPs can form
potentially harmful
degradation products
that are challenging to
monitor.

Byproducts of the
oxidant itself may be
potentially harmful.

Chemical agents may
need to be produced
on site and may be
energy intensive.

Chemical agents can
be hazardous to
handle.

Ultraviolet (UV)
photolysis: >90% for
two antibiotics and
one antiviral.

Ozonation: >90%
removal of most
PPCPs, especially
hormones.

Dependent on
chemical agent, can
be targeted to specific
compounds.

Chemical handling may
be required, especially if
generated on site.

Characteristics and Treatment of Pharmaceuticals and Personal Care Products (PPCPs) in Wastewater / August 2024

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Treatment

Targeted
PPCP

Type(s)

Advantages

Disadvantages

Performance

Operation and
Maintenance
Considerations

Membrane
Technologies

Further reading:

Dhangar & Kumar, 2020;
Kumar et al., 2023;
Snyder et al., 2007;

Tijani et al., 2013; U.S.
EPA, 2007; Wang et al.,
2018

PPCPs likely to
sorb onto
solids.

PPCPs likely to
biodegrade.

Membranes do not alter
the chemical structure
of PPCPs, thus avoiding
the production of
potentially harmful
byproducts.

Small footprint
requirements.

Can be used to treat
other emerging
contaminants, not just
PPCPs.

Minimal use of
dangerous chemicals.

Membrane bioreactors
combine physical and
biological removal of
PPCPs.

Issues with clogging
and fouling if
improperly operated.

Reverse

osmosis/nanofiltration
creates a concentrated
waste stream that
must be disposed of or
treated appropriately.

Complex to operate
and maintain.

Pilot scale: 85-95%
removal of several
different PPCPs.

Laboratory scale: high
removal of hormones
and triclosan, low
removal of pesticides
and pharmaceuticals.

Regular air-scouring of
membranes is required
to remove adhered
solids.

Regular chemical
cleaning is needed to
reduce fouling.

Characteristics and Treatment of Pharmaceuticals and Personal Care Products (PPCPs) in Wastewater / August 2024

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Targeted







Operation and

Treatment

PPCP

Type(s)

Advantages

Disadvantages

Performance

Maintenance
Considerations

Constructed

PPCPs likely to

Low energy

Large land

Full scale, Spain: 42-

Regular solids removal is

Wetlands

sorb onto

requirements.

requirements.

99% removal of

required to reduce

Further reading: Al-
Baldawi et a!., 2021;
Dhangar & Kumar, 2020;

solids.

PPCPs likely to
biodegrade.

Simple operation and
maintenance.

Climate dependent.

Prone to clogging
issues.

ibuprofen, 83-96%
removal of caffeine.

Full scale, Czech
Republic: 55%

clogging.

Removal and disposal of
biomass is required.

Kumar et a!., 2023





Difficult to monitor
removal pathways.

Harvesting and
disposal of vegetation
which may contain
PPCPs is required.

removal of ibuprofen,
84% removal of
caffeine.



Characteristics and Treatment of Pharmaceuticals and Personal Care Products (PPCPs) in Wastewater / August 2024

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For more information, please contact us at:

United States Environmental Protection Agency
Clean Water Technology Center

Office of Water, Office of Wastewater Management
1200 Pennsylvania Avenue, NW (mail code 4204M)
Washington, DC 20460

EPA 830-S-24-001
August 2024

www.epa.gov/sustainable-water-irifrastructure/cleari-water-technology-center


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