nanoparticles, pharmaceutical and personal care products in sewage sludge
DESCRIPTION
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).TRANSCRIPT
Nanoparticles, pharmaceutical and personal care products in sewage sludge
Pravash Chandra MoharanaRoll No. 9905
Division of Soil Science & Agricultural ChemistryIndian Agricultural Research Institute
New Delhi-110 012
Presentation Outline
Introduction
Nanoparticles in sewage sludge
Pharmaceutical and personal care products (PPCPs) in
sewage sludge
Remediations
Conclusions
Future steps
News
Nanoparticles in 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.
Environmental release pathways of nanoparticles to sewage sludge
Survey done by Science direct (2008)
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)
Research on Nanoparticles in Wastewater sludge and Biosolids
Brar et al., 2010 (Waste Management )
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
Fullerene in “revitalizing” night creams
Nano-silver in Bandages & socks
Nano-Aluminum in cosmetics
Brar et al., 2010 (Waste Management )
Nanoparticles found in wastewater and sewage sludge
Source Type of nanoparticle Application /uses
Metals and alkalineearth 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
Nanoparticle toxicity in sewage sludge
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 negativeEscherichia coli
Antibacterialactivity increasing with particle concentration
US EPA (2005); Adams et al.(2006)
Multi-walled carbon nanotube,aluminum, alumina, zinc, and zincoxide
Seed germination and root growth ofplant species (radish, rape, ryegrass, lettuce, corn, and cucumber)
Inhibition on root and plants. Suspensions of2000 mg L-1 nano-Zn or nano-ZnO practicallyterminated root elongation of the tested plantspecies
Lin and Xing (2007)
C60 fullerene Salmonella thyphimurium
Antimutagenic Babynin et al. (2002)
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 andfertilizer, stimulate its antioxidant system, and apparently hasten its germination and growth
Lu et al. (2002)
C60-nano-particles (Buckminsterfullerenes)
Algae (Pseudokirchneriella subcapitata) andcrustaceans (Daphnia magna)
On interaction with other organic compounds,the toxicity was magnified
Baun et al. (2007)
Cont…
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).
Mechanisms of nanoparticle accumulation and degradation in sewage sludge
Brar et al., 2010 (Waste Management )
Liu et al., 2011 (Science of the Total Environment )
Effects of nano-ZnO, bulk ZnO, and soluble Zn on nitrificaton of the activated sludge
Nitrificaton Chemicals IC50
(mg-Zn L-1)
Ammoniumoxidation
Nano-ZnO 13
Bulk ZnO 7.5
Zn ion (II) 6.5
Nitrite oxidation
Nano-ZnO 476
Bulk ZnO ND
Zn ion (II) 71
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 )
Mu et al., 2011 (Water Research)
Effect of ZnO nanoparticles on methane production during anaerobic digestion of waste activated sludge (WAS)
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%
Mu et al., 2011 (Water Research)
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.
Oleszczuk et al., 2011 (Journal of Hazardous Materials)
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
Root
gro
wth
inhi
bitio
n (%
)
Decontamination of wastewater and sludge using nanoparticles
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 )
Sa´nchez et al., 2011 (Trends in Analytical Chemistry)
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). 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).
Fe3O4 NPs :Sludge =1:1
Application of nanoparticles in decontamination of wastewater and sludge
Pollutant Nanoparticle Mechanism Reference
Acetone, benzene, and toluene
In(OH)3 Photocatalytic degradation (UV)
Yan et al. (2010)
Trichloroethylene Bimetallic particles of nickel on iron,supported on functionalized carbonnanotubes
Catalytic breaking of C–Cl bond
Jasper et al. (2010)
Anthracene-9-carbonxylic acid
CdSe Photocatalytic degradation (greenmonochromatic 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)
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
Pharmaceutical and Personal care products (PPCPs) in Sewage sludge
Daughton and Ternes, 1999 (Environmental Health Perspectives )
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).
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
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
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
Research reports on
PPCPs in sewage sludge
Survey done by Science direct (2010)
Research trends in PPCPs
Daughton and Ternes, 1999 (Environmental Health Perspectives )
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 ofacetylsalicylic acid
Efficiently removed by WWTS
Meclofenamic acid Anti-inflammatory Not detected in WWTS
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).
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)
Alcock et al., 1999
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
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.
Antibiotics problem in biological treatment processes of WWTPs
Antusch, 1999
Musk Compounds in Sewage Sludge
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 analysedN>LOD number of samples over the limit of detection
Musk compounds use in cosmetic and detergent products Persistent, bioaccumulative pollutants and sometimes highly toxic
123
42
2118 17
9
0
20
40
60
80
100
120
140
Media
Nu
mb
er
of
PP
CP
De
tec
ted
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 )
Reif et al., 2010 (Journal of Environmental Monitoring )
Ibuprofen (IBP), Naproxen (NPX), Diclofenac (DCF), Galaxolide (HHCB), Tonalide (AHTN)
Amount of PPCPs in different units of Sewage treatment plant
Jelic et al., 2011 (Water Research )
Frequency of detection of pharmaceuticals in wastewater influent (WWI), effluent (WWE) and sewage sludge
Jelic et al., 2011 (Water Research )
Partition of pharmaceuticals in sewage water and sludge during wastewater treatment
Carballa et al., 2007 (Water Research )
PPCPs removal efficiencies during anaerobic digestion of sludge
Higher removal efficiencies of PPCPs at lower sludge retention time (SRT)
Yu et al., 2006 (Agricultural Water Management )
Aerobic biodegradation of pharmaceuticals inoculated with diluted waste activated sludge
Margon et al., 2009 (Soil and Sediment Contamination )
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
Rodríguez-Rodríguez et al., 2011 (Bioresource Technology )
Removal of pharmaceuticals from the Sewage sludge by fungus Trametes versicolor
Removal efficiency of carbamazepine by Typha spp.
Dordio et al., 2011 (Bioresource Technology )
Redshaw et al., 2008 (Phytochemistry )
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.
Uptake of the pharmaceutical Fluoxetine Hydrochloride from growthmedium by cauliflower
Decline of Vultures in Pakistan and India – Possible Link with Diclofenac
Most visual effect of PPCP in environment
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.
Public awareness
Unused PPCPs return to manufacturer for disposal
Incineration
Highly engineered sanitary landfill
Frequent monitoring in aquatic body
Management of PPCPs
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.
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
Future steps
50