During the last decade the occurrence of engineered nanoparticles (NPs), pharmaceuticals and personal care products (PPCPs) in the environment have been well documented. Nanoparticles are released from different nanomaterials used in our household and industrial commodities whereas PPCPs are a diverse group of chemicals comprising all human and veterinary drugs, diagnostic agents and cosmetics such as fragrances and sun-screen agents which enter into environment by excretion of humans and domestic animals, disposal of unused or expired PPCPs to drain and ultimately contaminate the sewage sludge and soil. Toxicity of many nanoparticles in wastewater and sludge and their fate to soil are the unanswered question (Brar et al., 2010). The phytotoxicology of nanoparticles (multi-walled carbon nanotube, aluminum, alumina, zinc and zinc oxide) on seed germination and root growth of radish, rape, ryegrass, lettuce, corn, and cucumber are reported by Lin and Xing, 2007 and Oleszczuk et al., 2011. Application of higher doses of ZnO-NPs inhibited the production of methane, respiration and also nitrification during anaerobic digestion of waste activated sludge (Liu et al., 2011; Mu and Chen, 2011). Some of the nanoparticles like Fe3O4, FeS, CeO2, etc. are used for removal of pollutants from wastewater and sludge. The pharmaceuticals like ibuprofen, naproxen, ketoprofen, diclofenac, phenazone, bezifibrate, erythromycin, sulfamethazine, trimethoprim, triclosan, musk compounds, etc. are identified in wastewater and sludge (Daughton and Ternes, 1999). These PPCPs react with other organic molecules to produce Phase I and Phase II compound which are more toxic than parent compounds. Bioremediation by fungus Trametes versicolor is one of the option to reduce pharmaceuticals to toxicity from sewage sludge (Rodríguez-Rodríguez et al., 2011).

1. Nanoparticles, pharmaceutical and personal care
products in sewage sludge
Pravash Chandra Moharana
Roll No. 9905
Division of Soil Science & Agricultural Chemistry
Indian Agricultural Research Institute
New Delhi-110 012

2. Presentation Outline
Introduction
Nanoparticles in sewage sludge
Pharmaceutical and personal care products (PPCPs) in
sewage sludge
Remediations
Conclusions
Future steps

3. News

4. Nanoparticles in sewage sludge

5. Environmental release pathways of nanoparticles to sewage
sludge
Nanoparticles are about 1 to 100 nm in size
Increased application of nanotechnology in the
past decade has raised concerns about both
human health and safety and environmental
impacts resulting from exposure to engineered
nanoparticles (ENPs).
ENPs products through normal use enter into
the wastewater streams. A significant portion
of ENPs in wastewater are expected to be
present in sewage sludge. Depending on local
practices sewage sludge are disposed in
landfills, incinerated, or applied to agricultural
lands as biosolids.

6. Research on Nanoparticles in Wastewater sludge and
Biosolids
Number of publications in different
disciplines of nanoparticles, until
December 2008.
(Number of publications for the
possibility of nanoparticle
contamination in wastewater
sludge are really minimal)
Survey done by Science direct (2008)

7. Release of nanomaterials from different products into waste
water treatment plants (WWTPs)
Product type Amount (g/pc/d)
Antiperspirant 0.35
Body lotion 1.2
Body wash 0.32
Cleaners 0.3
Deodorants 0.08
Face cream 1.64
Hair styling products 0.10
Paint 0.09-0.36 (ml/pc/yr)
Laundry detergents 10.1-20.5
Oral hygiene products 0.7
Perfume 0.05
Shampoo 1.83-6.30
Shaving foam 0.07
Soap 2.5
Nano-silver in Bandages & socks
Fullerene in “revitalizing” night creams
Nano-Aluminum in cosmetics
Brar et al., 2010 (Waste Management )

8. Nanoparticles found in wastewater and sewage sludge
Source Type of nanoparticle Application /uses
Metals and
alkaline
earth metals
Ag Antimicrobials, paints, coatings, medical use,
food packaging
Fe Water treatment
Sn Paints
Se, Ca, Mg Nutraceuticals, health supplements
Metal oxides TiO2, ZnO, SiO2, Al2O3 Cosmetics, paints, coatings
Carbon materials Carbon black Substrate bound, but released with tyre wear
Carbon nanotubes Used in a variety of composite materials
Fullerenes (C60-C80) Medical and cosmetics use
Miscellaneous Nanoclay Plastic packaging
Ceramic Coatings
Organic nanoparticles Vitamins, medicines, carriers for medicines and
cosmetics, food additives and ingredients
Brar et al., 2010 (Waste Management )

9. Nanoparticle toxicity
in sewage sludge

10. Toxicity of Nanoparticle found in wastewater and sewage-sludge
Type of
nanoparticles
Test organisms Effects References
TiO2, SiO2 and
ZnO
Gram-positive
Bacillus subtilis and
Gram negative
Escherichia coli
Antibacterial
activity increasing
with particle
concentration
US EPA (2005);
Adams et al.
(2006)
Multi-walled
carbon
nanotube,
aluminum,
alumina, zinc,
and zinc
oxide
Seed germination
and root growth of
plant species (radish,
rape, ryegrass,
lettuce, corn, and
cucumber)
Inhibition on root
and plants.
Suspensions of
2000 mg L-1 nano-
Zn or nano-ZnO
practically
terminated root
elongation of the
tested plant
species
Lin and Xing (2007)
C60 fullerene Salmonella
thyphimurium
Antimutagenic Babynin et al.
(2002)

11. Type of
nanoparticles
Test organisms Effects References
A mixture of
nanoscale SiO2
and TiO2
Soybean
(Glycine max)
Increases nitrate
reductase, enhances its
abilities of absorbing
and utilizing water and
fertilizer, stimulate its
antioxidant system,
and apparently hasten
its germination and
growth
Lu et al. (2002)
C60-nano-particles
(Buckminster
fullerenes)
Algae
(Pseudokirchneriella
subcapitata) and
crustaceans
(Daphnia magna)
On interaction with
other organic
compounds,
the toxicity was
magnified
Baun et al. (2007)
Cont…

12. Evidence for Bioavailability of Nanoparticles from Soil to food
chain
Gold-nanomaterials can be absorbed by
earthworms and biodistributed to
tissues and trophic transfer when
assessing the ecological risks of
Nanomaterials (Unrine et al., 2010).
Gold nanoparticles built up in
tobacco leaf tissue, and tobacco
hornworms that ate the plants
accumulated concentrations of
the nanomaterials about 6 to 12
times higher than in the plant
(Judy et al., 2011).
Predatory microbes also built up
concentrated levels of cadmium
selenide nanoparticles after
eating smaller microbes that
ingested them (Werlin et al.,
2011).

13. Mechanisms of nanoparticle accumulation and degradation in sewage
sludge
Brar et al., 2010 (Waste Management )

14. Effects of nano-ZnO, bulk ZnO, and soluble Zn on nitrificaton of the activated
sludge
Nitrificaton Chemicals IC50
(mg-Zn L-1)
Ammonium
oxidation
Nano-ZnO 13
Bulk ZnO 7.5
Zn ion (II) 6.5
Nitrite
oxidation
Nano-ZnO 476
Bulk ZnO ND
Zn ion (II) 71
Liu et al., 2011 (Science of the Total Environment )

15. Effects of nano-ZnO, bulk ZnO, and soluble Zn on activated
sludge respiration
(a) Oxygen uptake rate (OUR) under different concentrations of nano-ZnO.
(b) Plots of the inhibition rate as a function of added nano-ZnO, bulk ZnO, and soluble
Zn concentration
Liu et al., 2011 (Science of the Total Environment )

16. Effect of ZnO nanoparticles on methane production during anaerobic digestion
of waste activated sludge (WAS)
Mu et al., 2011 (Water Research)
81.7%
24.9%
Scanning electron micrographs imaging of
sludge long-term exposed to 0 mg/g-TSS
(A), 1 mg/g-TSS (B), 30 mg/g-TSS (C), and
150 mg/g-TSS (D) of ZnO NPs during WAS
anaerobic digestion
90.6%
36.2%

17. Effects of ZnO NPs on the reactive oxygen species (ROS) production and
biomass viability during anaerobic digestion of WAS.
ROS, including superoxide, H2O2,
and hydroxyl radical are
produced in the presence of
oxygen (Murphy, 2009).
However, it has been reported
that H2O2 can also be produced
under anaerobic conditions
(Degli-Esposti and McLennan,
1998).
The increase of ROS in the
sludge exposed to higher
dosages of ZnO NPs was a likely
reason for their adverse effect
on sludge anaerobic digestion.
Mu et al., 2011 (Water Research)

18. Phytotoxicity of the sewage sludges containing multiwalled carbon
nanotubes (MWCNTs)
Effect of CNT aging in sewage sludges
on root growth of Cucumis sativus
Lepidium sativum root growth inhibition in
soil amended by sewage sludge containing
MWCNTs
Oleszczuk et al., 2011 (Journal of Hazardous Materials)
Root growth inhibition (%)

19. Decontamination of wastewater and
sludge using nanoparticles

20. Removal processes of nano-particles in WWTPs
(1) Collection system: use of products
such as, cosmetics, fragrances,
pharmaceuticals etc. which comprise
nanoparticles;
(2) Bar screen
(3) Grit removal
(4) Primary sedimentation system
(5) Secondary treatment systems
(6) Secondary sedimentation
(7) Sludge thickener: concentration of nanoparticles; digester: via microbial
interactions; organic matter interactions; sludge dewatering; landfills (adsorption,
leaching leading to groundwater and sub-surface water contamination)
(8) Disinfection process
(9) Release into the receiving waters
(10) Advanced tertiary treatment
Brar et al., 2010 (Waste Management )

21. Removal of contaminant from sewage sludge using nano-particles
1) NPs that degrade contaminants in situ
(e.g., photocatalysis of organic matter using TiO2 NPs).
Fe3O4 NPs :Sludge =1:1
Sa´nchez et al., 2011 (Trends in Analytical Chemistry)
2) NPs that adsorb contaminants
(e.g., CaCO3 adsorbs Ni, and Fe3O4 adsorbs As and Cr).
Adsorbed metals lose their toxicity. Moreover, NPs can be
separated from media using magnetic or gravitational
fields.
3) NPs conjugated to molecules that adsorb contaminants
(e.g., NPs conjugated to cyclodextrins that adsorb persistent organic pollutants).

22. Application of nanoparticles in decontamination of wastewater and sludge
Pollutant Nanoparticle Mechanism Reference
Acetone, benzene,
In(OH)Photocatalytic
3 and toluene
degradation (UV)
Yan et al. (2010)
Trichloroethylene Bimetallic particles of
nickel on iron,
supported on
functionalized carbon
nanotubes
Catalytic
breaking of C–Cl
bond
Jasper et al. (2010)
Anthracene-9-
carbonxylic acid
CdSe Photocatalytic
degradation
(green
monochromatic
light)
Yang et al. (2010)
Cr(VI) Zero-valence iron Reduction Xu et al. (2007)
Pb(II) Titanium phosphate Adsorption Jia et al. (2009)
Hg(II) FeS Adsorption Xiong et al. (2009)

23. Removal of engineered nanoparticles
(ENPs) from sewage sludge ???
ENPs is itself toxic to the ecosystem
There is too many unanswered questions regarding the
fate and impact of ENPs to environment

24. Pharmaceutical and Personal care
products (PPCPs) in Sewage sludge

25. What is pharmaceuticals and personal
care products (PPCPs) ???
“Any product used by individuals for personal health or cosmetic reasons or used
by agribusiness to enhance growth or health of livestock.” (U.S. EPA)
PPCPs are a diverse group of chemicals comprising all human and
veterinary drugs (available by prescription or over-the-counter; including
the new genre of “biologics”), diagnostic agents (e.g., X-ray contrast
media), “nutraceuticals” (bioactive food supplements such as huperzine
A), and other consumer chemicals, such as fragrances (e.g., musks) and
sun-screen agents (e.g., methylbenzylidene camphor); also included are
“excipients” (so-called “inert” ingredients used in PPCP manufacturing
and formulation).
Daughton and Ternes, 1999 (Environmental Health Perspectives )

26. Common Contaminants in waste water and sewage sludge
Chemical Group
EDC (Endocrine Disrupting Chemical)
PBT (Persistent, Bioaccumulative Toxic)
POP (Persistent Organic Pollutant)
OWC (Organic Wastewater Contaminant)
PPCP (Pharmaceuticals
and Personal Care
Product)
Priority Pollutant
ECC (Emerging Compound of Concern)
Xenobiotics
HPV (High Production Volume) chemical
POHO (Pollutant Of Human Origin)
PPCPs as “Emerging”
Risks?
There is no reason to believe
that PPCPs have not existed in the
environment for as long as they
have been used commercially
It has only become
more widely evident in the last
decade because continually
improving chemical analysis
methodologies have lowered
the limits of detection for a
wide array of xenobiotics in
environmental matrices

27. PPCPs Sources
Manufacturing process waste
Wastes from the distributor, pharmacy, hospital
and healthcare facility
Wastes from residential care facilities
Pharmaceuticals from the consumer
Excreted metabolites entering wastewater

28. Pathways of PPCP Source to sewage sludge
• Ingested then excreted
• Discharged during bathing
• Discharged during medication
disposal
• 50% of all unused prescriptions
• 80% of all unused antibiotics

29. Research reports
on
PPCPs in sewage sludge

30. Research trends in PPCPs
Survey done by Science direct (2010)

31. PPCPs identified in environment
Compound Use/Origin Environmental occurrence
Acetaminophen Analgesic Removed efficiently by WWTS,
max. conc. in effluent 6μg l-1
Benzafibrate Lipid regulator Removal efficiency 83%, max. conc.
in effluent 4.6μgl-1
Chloroxylenol Antiseptic In influents and effluents <0.1μg l-1
Clofibric acid Metabolite of clofibrate Removal efficiency 51%,
Diatrizoate X-ray contrast media Resistant to biodegradation
Diclofenac-Na Analgesic Removal efficiency 69%, max. conc.
in effluent 2.1 μg l-1
Fluoxetine Antidepressant No studies
Fluvoxamine Antidepressant No studies
Gentisic acid Metabolite of
acetylsalicylic acid
Efficiently removed by WWTS
Meclofenamic acid Anti-inflammatory Not detected in WWTS
Daughton and Ternes, 1999 (Environmental Health Perspectives )

32. Fate of pharmaceutical compounds
Halling-Sorensen, 1998 repotred that chloramphenicol glucoronide and N-4-
acetylated sulphadimidine (phase II metabolites of the antibiotics chloramphenicol
and sulphadimidine, respectively), are reactivated in liquid manure
Penicillin antibiotics are eliminated rapidly and have short half-lives in the body,
usually 30-60 minutes, and very high concentrations are excreted in urine: it has
been determined that up to 40% of penicillin V is excreted unchanged (Christensen,
1998).

33. Risk of PPCPs
The antibiotics like fluoroquinolones ciprofloxacin and norfloxacin are
substantially eliminated in wastewater treatment (80–90%) by sorption
transfer to sewage sludge and in sludge treated soil (Giger et al., 2003).
Triclosan acts as an antibacterial, having particular enzymatic targets
(lipid synthesis). Bacteria could develop resistance to triclosan. So, this
could lead to development of resistance and change in microbial
community structure (Mc Murry et al., 1998)
Musk xylene has proved carcinogenic in a rodent bioassay and is
significantly absorbed through human skin; from exposure to combined
sources, a person could absorb 240 μg/day (Bronaugh et al., 1998).
Critical role of production of "multixenobiotic resistance” which harm to
soil as well as aquatic environments (Daughton and Ternes, 1999)

34. Antibiotics problem in biological treatment processes of WWTPs
Antibiotic Excretion (%)
Unchanged Other Metabolites
Amoxicillin 80-90 10-20
Penicillin V 40 60
Penicillin G 50-70 30-50
Sulphamethoxasole 15
Trimethoprim 60
Erythromycin >60
Roxithromycin >60
Clarithromycin >60
Minocycline 60 40
Alcock et al., 1999
Antibiotics leave humans
unchanged by the body
metabolism and it has been
determined that up to 90% of
the parent compounds are
excreted unchanged. These
active products can be excreted
either as unchanged compounds
or as conjugates; 30-90% of
administered antibiotics are
excreted via urine as active
substances.
This introduces the problem at the WWTS of disruption of biological treatment
processes, as pharmaceutical compounds, particularly antibiotics, can potentially
affect bacteria.

35. Antusch, 1999
Musk Compounds in Sewage Sludge
Musk compounds use in cosmetic and detergent products
Persistent, bioaccumulative pollutants and sometimes highly toxic
Compound
(mg/kg)
N>
LOD
Sediment:
industrial area
Sediment:
residential area
Sewage sludge
Musk-xylene 6 <0.005-0.20 0.066-0.134 < 0.005
Musk-ketone 7 <0.01-1.78 0.15-0.36 <0.01-0.06
Celestolide 12 <0.01-0.28 0.19-0.52 0.12-0.29
Galoxolide 17 0.08-5.2 9.1-21.8 4.3-13.4
Tonalide 17 0.13 - 8.9 9.5 - 36.7 4.0 - 12.6
N = number of samples analysed
N>LOD number of samples over the limit of detection

36. 123
42
21
18 17
9
140
120
100
80
60
40
20
0
Media
Number of PCP Detected
No. of PPCP in Biosolids, Wastewater &
Treatment Related Media
Wastewater
Drinking water (tap)
Biosolids & Sludge
Agricultural Runoff
Raw drinking water
Animal waste
Daughton and Ternes, 1999 (Environmental Health Perspectives )

37. Amount of PPCPs in different units of Sewage treatment
plant
Ibuprofen (IBP), Naproxen (NPX), Diclofenac (DCF), Galaxolide (HHCB), Tonalide (AHTN)
Reif et al., 2010 (Journal of Environmental Monitoring )

38. Frequency of detection of pharmaceuticals in wastewater
influent (WWI), effluent (WWE) and sewage sludge
Jelic et al., 2011 (Water Research )

39. Partition of pharmaceuticals in sewage water and sludge during
wastewater treatment
Jelic et al., 2011 (Water Research )

40. PPCPs removal efficiencies during anaerobic
digestion of sludge
Higher removal
efficiencies of
PPCPs at lower
sludge retention
time (SRT)
Carballa et al., 2007 (Water Research )

41. Aerobic biodegradation of pharmaceuticals inoculated
with diluted waste activated sludge
Yu et al., 2006 (Agricultural Water Management )

42. Interaction between Diclofenac and Soil Humic Acids
UV-Vis curves of titration of 1 μM Na-diclofenac with HAs. (a) Normalized
absorbance values of diclofenac recorded at the two characteristic λmaxAbs
Margon et al., 2009 (Soil and Sediment Contamination )

43. Removal of pharmaceuticals from the Sewage sludge by fungus
Trametes versicolor
Rodríguez-Rodríguez et al., 2011 (Bioresource Technology )

44. Removal efficiency of carbamazepine by Typha spp.
Dordio et al., 2011 (Bioresource Technology )

45. Uptake of the pharmaceutical Fluoxetine Hydrochloride from growth
medium by cauliflower
Fluoxetine uptake to cauliflower tissue
cultures and amounts in residual media.
(A)Fluoxetine μg per gram of wet cauliflower
tissue;
(B)Fluoxetine μg per milligram of lipid of
tissue;
(C)% uptake of initial Fluoxetine added (9.8 μg)
and percentage residue in media.
Redshaw et al., 2008 (Phytochemistry )

46. Most visual effect of PPCP in environment
Decline of Vultures in Pakistan and India –
Possible Link with Diclofenac
At the 6th World Conference on Birds of
Prey and Owls (Budapest, Hungary, 18-23
May 2003), Prof. J. Lindsay Oaks
(Washington State University) presented
evidence that the die-offs may have
resulted from diclofenac poisoning.

47. Management of PPCPs
 Public awareness
 Unused PPCPs return to manufacturer for disposal
 Incineration
 Highly engineered sanitary landfill
 Frequent monitoring in aquatic body

48. Conclusions
NPs and PPCPs enters wastewater streams and significant portion of NPs
in wastewater are expected to partition between sewage and sludge
which is ultimate fate to food chain.
Nanoparticles contaminated sewage sludge inhibited the seed
germination and root growth of radish, rape, lettuce and cucumber.
Application of higher doses of ZnO-NPs inhibited the production of
methane, respiration and also nitrification during anaerobic digestion of
waste activated sludge.
Many of PPCP compounds have the potential to bioaccumulate that why
there is concern about their presence in wastewater and sewage sludge.
Use of Trametes versicolor and Typha spp. as a potential agent for the
degradation of pharmaceuticals at environmentally relevant
concentrations in sewage sludge.

49. Future steps
Development of cohesive National or International
guidance for disposal/recycling of PPCPs
Development of integrated industry-consumer
stewardship programs for minimizing the introduction of
PPCPs to the environment (pollution prevention, source
control)
Safety limit of PPCPs in wastewater, sewage sludge and
soil
Study the ecotoxicity effect of PPCPs and NPs
contaminated sewage slugde in agroecosystem

50. 50