Addressing the pharmaceutical problem in hospital wastewaterlifepharmdegrade.arhel.si/wp-content/uploads/... · 2016-05-27 · - Pharmaceutical (e.g. laxatives, analgesics, anti-inflammatory,

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Addressing the pharmaceutical problem in hospital wastewater

Maja Zupančič Justin, Arhel d.o.o.

LIFE Water Platform Meeting24th- 25th May, 2016, Manchester, UK

LIFE13 ENV/SI/000466

http://lifepharmdegrade.arhel.si



« LIFE PharmDegrade »

- Demonstration of technology for removal of PH from the wastewater effluents

- Electrochemical oxidation in electrolytic cell - Diamond electrodes

Degradation of pharmaceuticals (PH) in wastewaters from nursing homes and hospitals

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Specifics of hospital wastewater



- Specific contaminants - micro pollutants / emerging pollutants:- Pharmaceutical (e.g. laxatives, analgesics, anti-inflammatory, antibiotics, cytostatic)- Disinfectants- Detergents (personal care, laundry, washing)

- X-ray contrast media, other diagnostic agents- Microbiological load (multi-resistant microbes)

- Organic load with potential low biodegradability (BOD5/COD range)- pH shocks (disinfection)- Seasonal/daily/regional variation of effluent composition (seasonal diseases)

*P. Verlicchi, M. Al Aukidy, E. Zambello, 2015, What have we learned from worldwide experiences on the management and treatment of hospital effluent? An overview and a discussion on perspectives, Science of the total Environment

Main chemical characteristics of hospital effluent*

Impact of PH in wastewater on the environment



Environmental concern:• Persistence in the environment:

• High polarity of substances:• Easy discharge from the body• Resistant to biological degradation in treatment plant

• Development of antibiotic resistant microorganisms; antibiotic resistant genes• Toxicity to aquatic organisms – (ciprofloxacin - algal growth inhibition; diclofenac -

alters the kidney functions in fishes and birds; cytostatics - genotoxicity)• Endocrine disruptors – affect the reproduction of organisms• Bioaccumulation

Difficulties in municipal wastewater treatment plants:- pH shocks, toxicity inhibitor / disintegration of activated sludge low

treatment efficiency- Low biodegradability reduction of removal efficiency

Presence in drinking water, irrigation water

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Commonly adopted hospital wastewater treatment



Outflow to municipal sewage system

Treatment: Preliminary treatment, (primary clarification) Secondary biological treatment (conventional activated sludge process) Polishing treatments (chemical disinfection / rapid filtration + UV disinfection)

• Is treatment in municipal wastewater treatment plant (WWTP) adequate to reach high removal efficiencies for wide spectrum of micro pollutants ?

• Is load of PH from hospitals significant compared to total urban load?

• Should dedicated treatment be adopted for hospital WW?

• Which kind of WWT would be appropriate?

• Is the risk of PH residuals in the environment appropriately addressed?

Households Sewage

?

?

?

Do hospitals contribute a significant amount of PH to urban load?



*Daouk et al., 2016: Dynamics of active pharmaceutical ingredients loads in a Swiss university hospital wastewaters and prediction of the related environmental risk for the aquatic ecosystems. Sci. Tot. Env.

Swiss University hospital case*:- 15 PH analysed:

• Only consumed in hospital: piperacilin, cisplatin, gadopentetic acid • Relatively important contribution from hospital: codeine, morphine, metronidazole,

sulfamethoxazole• Mainly consumed in households: mefenamic acid, diclofenac, carbamazepine, ..

- all PH participate to the environmental hazard (HQ > 1),

- Risk for the aquatic environment after dilution in urban network, receiving water body and WWTP (activated sludge):

- Hospital load:- Ciprofloxacin high (RQ>1)- Sulfamethoxazole moderate (1>RQ>0,1)- API mixture toxicity >1

- Total urban load:- gabapentin, sulfamethoxazole, ciprofloxacin, piperacillin, ibuprofen, diclofenac, mefenamicacid (RQ > 1)

- On-site advanced treatment proposed- Municipal WWT should be improved

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Do hospitals contribute a significant amount of PHtourban load? (cont.)



Portuguese case*:

Santos et al., 2013: Contribution of hospital effluents to the load of pharmaceuticals in urban wastewaters: Identification of ecologically relevant pharmaceuticals. Sci. Tot. Env.

- 78 PHs considered- PH widespread pollutants in hospital and public WW- Hospital WW contained higher PH concentrations- Public WWTP effluent contribute the higher mas load of PH - Therapeutic groups with highest input from hospitals: NSAID, analgesics, antibiotics- Therapeutic groups with highest input from public WW: antihypertensive, psychiatric drugs, lipid regulators- 90% removal efficiency (activated sludge):

- Acetaminophen- Ibuprofen

- No removal fficiency:- Beta-blockers- antihelmintics- Sulbutamol

- Antibiotics (ciprofloxacin, ofloxacin, sulfamethoxazole, azithromycin, clarithromycin) pose ecotoxicological risk to algae –special attention needed

- Need to assess ecotoxicity of mixture of PHs- Co-treatment of hospital and public WW should be improved

Pharmaceuticals: legislative backgroundA Blueprint to Safeguard Europe`s Water Resources (COM(2012) 673:

2.2 Chemical status and pollution of EU waters: problems and solutions:- Pharmaceutical residues is an emerging problem- Human and veterinary medicinal products need for:

- Environmental risk assessment- Case-by-case consideration of the need for protective measures

Proposal for directive .. Amending the Directives 2000/60/EC and 2008/105/EC as regards priority substances in the field of water policy (COM/2011)876)

- 3 pharmaceuticals proposed on the list:

Directive 2013/39/EU amending Directives 2000/60/EC and 2008/105/EC as regards priority substances in the field of water policy

- Pharmaceuticals not on the list The First Watch list created (JRC)

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Pharmaceuticals: legislative background (cont.)

Development of the first Watch List under the Environmental Quality Standards Directive (JRC, 2015)

- Watch list of compounds which need further monitoring before listing to Env. Quality Standard Directive- It will contain 10 compounds; 3 already listed:

- Diclofenac*; - 17-beta-esrtadiol (E2)**; - 17-alpha-ethnylestradiol (EE2)**

- Candidate compounds (7 will be selected): - trichlorfon, cyclododecane, imidacloprid, diflufenican, oxadiazon, tri-allate, methiocarb, 2,6-di-tert-butyl-4-

methylphenol, thiacloprid, aminotriazole, clothianidin, chromium trioxide, thiamethoxam, 2-ethylhexyl 4-methoxycinnamate, dichlofluanid, formaldehyde, dimethenamid-P, triphenyl phosphate, acetamiprid, ofloxacin***, erythromycin***, clarithromycin***, ciprofloxacin***, tolylfluanid, azithromycin*** and free cyanide

Pharmaceuticals:* anti-inflammatory , analgesic** Estrogenic hormone*** antibioticsOther compounds: UV stabilizer and fuel antioxidant, insecticides, pesticides, sun screen ingredient

Underlined – most recommended for the first Watch List

Adopted Commission Decision 2015/495 – watch list- EE2, E1, diclofenac- Macrolide antibiotics (erythromycin, clarithromycin, azithromycin)

Pharmaceuticals detected in short screening in LIFE PharmDegrade project

MWWTP NH 1 NH 2 NH 3 NH 4 H 2014 H 2015Priority

substance Watch listCandidate

compounds* Initial list*

Critical predicted environmental concentration*

ng/L ng/L ng/L ng/L ng/L ng/L ng/L ng/L

beta blockersbisoprolol 14,3 391,9 164,7 484,4 378,4 134,2 414,10

metoprolol 492,5 371,0 156,9 714,2 87,8 88,8 81,43

anti-epileptic carbamazepine 216,9 18,1 555,1 77,7 345,8 9,6 573,25 x

antibiotic (human, veterinary)

ciprofloxacin772,2 22417,9 38078,0 < LOQ 8154,6 10321,6 3560,65 x x 0,54

cholesterol treatmentclofibric acid < LOQ < LOQ < LOQ < LOQ < LOQ < LOQ

atorvastatin 65,41

anti-inflammatory diclofenac 2244,5 581,9 < LOQ < LOQ 323,3 248,2 3247,50 X

anti-depressantfluoxetine 6,3 < LOQ < LOQ < LOQ < LOQ < LOQ

setraline 61,60

citostatic imatinib < LOQ < LOQ < LOQ < LOQ < LOQ 1,9 7,67

plant protectionatrazine 2,5 < LOQ < LOQ < LOQ 11,5 < LOQ x

simazine < LOQ < LOQ < LOQ < LOQ < LOQ < LOQ x

MWWTP – municipal wastewater treatment plantNH – Nursing HomeH - Hospital

* Development of the first Watch List under the Environmental Quality Standards Directive (JRC, 2015)

- Similar concentrations in municipal sewage and sewage with hospital WW load- Nursing home – lower concentration (incontinence – other disposal routes)

More results on preliminary project activities (analytical metods used, first treatment trials with boron doped electrodes) presented on poster by J. Trontelj on the LIFE Water Platform Meeting:A. Klančar, J. Trontelj et al.: I. Optimisation of LC-MS/MS method for quantification of selected pharmaceuticals in wastewater effluent II. Evaluation of electrolytic cell performance under various conditions

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Environmental classification of found pharmaceuticals



According to: Environmentally classified pharmaceuticals, 2009; Stockholm Country Council

max conc found* (ng/L) risk TBT P B T

beta blockersbisoprolol 484,4

metoprolol 714,2 insignificant 4 3 0 1

anti-epileptic carbamazepine 573,3 insignificant 4 3 0 1

antibiotic (human, veterinary) ciprofloxacin 38078,0 Can nnot be excl. 5 3 0 2

cholesterol treatmentclofibric acid < LOQ

atorvastatin 65,4 insignificant 4 3 0 1

anti-inflammatory diclofenac 3247,5 insignificant 4 3 0 1

anti-depressantfluoxetine 6,3 low 6 3 0 3

setraline 61,6 moderate 6 3 0 3

citostatic imatinib 7,7 insignificant 5 3 0 2

P = PERSISTENCE: ability to resist biodegradation (0-3)B = BIOACCUMULATION: accumulation in adipose tissue (0 –3)T = TOXICITY: potential to poison aquatic organism (fish, Daphnia, algae) (0 – 3)

BPT index - total of B, P, T (0-9)

PEC = Predicted Environmental ConcentrationPNEC = Predicted No Effect Concentration; the highest

concentration of the substance that does not have harmful effect in the environment

* Max concentration found in PharmDegrade short survey

Are risks higher as indicated?Development of resistance as additional concern?

Ciprofloxacin case



- We detected so far 0,038 mg/L in WWTP outflow – toxic level for algae (cyanobacteria)

- Most frequently detected fluoroquinolone antibiotic in hospital WW- 0,164 and 6,5 mg/L median and maximum concentration in water- Not biodegradable (0% degradation over 40 day incubation)- Found concentrations in WW potential environmental concern

Source: Development of the first Watch List under the Environmental Quality Standards Directive (JRC, 2015)

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Approaches to reduce pharmaceuticals from wastewater



Approaches:

• Activated sludge process• Membrane bioreactors• Treatment wetlands• Chlorination• UV disinfection• Ozonation• Ultrafiltration• Nano filtration• Activated carbon filtration• Advanced oxidation processes:

• Fenton process, electrochemical oxidation, H2O2 + UV• Combination of these

Issues:

Removal/degradation efficiency

Disinfection efficiency

Retention times

Investment & operation costs; land requirement

By-products development (Eco-toxicological effects)

Electrochemical oxidation and diamond electrodes



• Boron-doped diamond electrodes (BDD) was used• Formation of HO• radicals directly from water with the use of

electric power• Complete mineralisation of organic compounds or converting them

to more hydrophilic molecules

• very effective degradation observed for ciprofloxacin, imatinib, fluoxetine, sertraline, diclofenac and atorvastatin

• less effective: metoprolol, bisoprolol and clofibric acid

Further work on:• Self cleaning of electrodes• Control of electrode activity• Optimisation of treatment efficiency (contact times, combining

treatment systems)

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The technology used should not necessarily lead to complete removal of PH but to reduction of ecotoxicological effect

Synergistic toxicity of PH mixtures is often neglected Antibiotics are of a high importance due to ecotoxicity and resistance development

Nursing homes have different PH disposal ways than hospitals and public WW Hospitals important from the point of view of release of:

High concentrations of specific groups of PH Multi-resistant pathogenic microbes

Public WW are important from the high mass load of PH WWT should be improved In areas with WWTP receiving high effluent contribution from hospitals on-site treatment should

be considered

Some conclusions



L. & T. ROZINA

We expect to provide soon new results from LIFE PharmDegrade project


[email protected]

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Addressing the pharmaceutical problem in hospital wastewaterlifepharmdegrade.arhel.si/wp-content/uploads/... · 2016-05-27 · - Pharmaceutical (e.g. laxatives, analgesics, anti-inflammatory,