emerging compounds in wastewater reuse compounds, effect

Emerging compounds in wastewater reuse – compounds, effect evaluation and removal technologies – an overview

Dr. Norbert Kreuzinger

Technische Universität WienInstitute for Water Quality and Resource Management

Karlsplatz 13/226-1

1040 Vienna – Austria

[email protected] - XIV Jornadas Tecnicas de ESAMUR - Kreuzinger

Emerging compounds in wastewater reuse – compounds, effect evaluation and removal technologies – an overview

• “emerging compounds” – what are they?

– CECs: Compounds of emerging concern

– Chemicals and other substances that have no regulatory standard and not currently included in routine monitoring programs

– have been recently “discovered” in natural streams (often because of improved analytical chemistry detection levels)

– potentially cause deleterious effects in aquatic life at environmentally relevant concentrations.

– CECs are not necessarily new chemicals. They include pollutants that have often been present in the environment, but whose presence and significance are only now being evaluated.

2018.11.21 - XIV Jornadas Tecnicas de ESAMUR - Kreuzinger

Photo: EPA

CECs - Compounds of emerging concern

• Organic compounds in < µg/l range in waters– Industrial chemicals

solvents; fuels; components; explosives; dyes; plasticisers; …

– Consumer relatedcontrast agents; personal care products; detergents; sweeteners; ...

– Industrial productsrefrigerants; lubricants; surfactants; flame retardants; preservatives; ...

– targeted bioactivitypesticides; biocides; disinfectants; antibiotics, pharmaceuticals; …

• Antibiotic resistance– Bacteria

– Genes 2018.11.21 - XIV Jornadas Tecnicas de ESAMUR - Kreuzinger


Is the topic of CECs in the water a matter of “fear mongering” in science?



IncreasingDiversity ofChemicals

> 140,000

substances on

global market;

30,000 water

relevant


Source: CAS

CECs

“Synthetic chemicals as agents of global change”

Bernhardt et al. Front Ecol Environ 2017; 15(2): 84–90

ΔX = (Xt −Xref) ∕ Xref


Modified from Bernhardt et al. Front Ecol Environ 2017; 15(2): 84–90


• CECs are found in wastewater and receiving waters due to

– More sensitive LODs in chemical analysis – Yes; but

– we have a whole lot of “new” chemicals and substances that were not present 20; 30; 40 years ago

• Question:

– When were the criteria / parameter used today for describing water quality and wastewater treatment defined?

• UWWD: 1991 (-> “young” in terms of reinvestment periods for wwtps)

• WFD: 2000 (later on: review of hazardous substances + watch list)

– Fit for purpose? Still sufficient? Protection targets? Parameters?2018.11.21 - XIV Jornadas Tecnicas de ESAMUR - Kreuzinger

Effects of CECs – organic trace compounds

• Effects of “traditional” makro - pollutants (C/N/P)

– Oxygen depletion in environmental waters

– Eutrophication

– Acute toxicity (e.g. NH3)

• Effects of “emerging” mikro – pollutants (CECs)

– First indication: hormones • estrogenic activities

• Population stability of fish, molluscs, makro-invertebrates

– No acute effects; rather long-term subtle effects• Not reflected by conventional acute and chronical in vivo tests

• New effect based in vitro tests with various biological endpoints



• Effect based in vivo assays

– Advantages:• Same sample preparation as for chemical analysis (e.g. SPE extraction)

• Suitable for high throughput analysis (robotics)

• Fast and cheap (compared to chemical analysis and in vivo tests)

• No ethical issues

– Selection of possible endpoints:• General toxicity (cytotoxicity always is accessed due to test setup)

• Hormone active (estrogenicity; anti-estrogenbicity; androgenicity, anti-androgenicity, Progesterone receptor; Glucocorticoid receptor …)

• Oxidative stress response; genotoxicity; response to Polycyclic aromatic hydrocarbons; Xenobiotic sensing; Repression of constitutive transcriptional activation


Example:

Assessment of 12 WWTPs by in vitro tests in the frameof the Joint Danube Survey



3-10 x EBT >10 x EBT1-3 x EBT< EBT

WWTP ERα anti-AR GR PPARγ PAH Nrf2 PXR

1

2

3

4

5

6

7

8

9

10

11

12

Bioassay Parameter

anti-AR Anti-androgens

GR Glucocorticoid receptor

ERa Estrogens

Nrf2 Oxidative stress

PPARy Peroxisome proliferator

PAH Polycyclic aromatic hydrocarbons

PXR Xenobiotic sensing

EBT Effect based trigger value

Nikiforos Alygizakis, Characterisation of wastewater effluents in the Danube River Basin with target and non-target chemical screening techniques,

in vitro bioassays and antibiotic resistant genes analysis NORMAN – ICPDR Joint Danube Survey 4 (JDS4)


• Chemical analysis– What substances?

– Looking at parent-substances only. Transformation products?

• Effect based in vivo assays– Broad variety of endpoints available nowadays (not only estrogenicity)

• Combination of both approaches suggested– Whole effluent assessment -> mixture toxicities (substances with same effect)

– Chemical monitoring of tracer substances -> technology working

– Chemical analysis to investigate reason for toxicological effect

In vivo biotests: “New experience” for WWTP regulators and operators

Not suitable for operation control to prove the proper operation of an installed technology but the suitability


CECs – antibiotic resistance

• Clinical relevant pathogenic bacteria get resistant to new antibiotics

• Antimicrobial resistance (AMR) is one of the largest health-related issues worldwide, recently acknowledged by the General Assembly of the United Nations in the A/RES/71/3/2016

• Wastewater treatment:

– Close contact between environmental & clinical bacteria

– High density of bacteria

– Resistance genes get exchanged from clinical bacteria to environmental bacteria -> genpool


CECs – antibiotic resistance - sewer

Abundance of various antibiotic resistance genes in sewers -Case Study

• Hospital waste water

• Municipal wastewater without hospital

• Similar / same pattern

• Except: 2 ARGs in hospital wastewater only:blaKPC & VanB

2018.11.21 - XIV Jornadas Tecnicas de ESAMUR - KreuzingerPM Gabriela Karina Paulus – ANSWER project – KWR – water Cycle Institute – The Netherlands

CECs – antibiotic resistance - wwtp

12 wwtps in Danube catchment

attention: compare results to results from municipal / hospital sewer!


Concentration of ARGs [Gene copies/16S rRNA]

PM Nikiforos Alygizakis – ANSWER project – Environmental Institute Slovakia

CECs – removal technology

• Tertiary CAS treatment according to BAT (low loaded AS Systems) does remove target substances to a certain extend; some substances very well –despite not being designed for CEC removal!

• Effluent concentrations for CEC nevertheless > EBT (effect based trigger values)

• Technologies for further elimination are not “new”, but mostly adopted from drinking water treatment

– Membrane technologies - MBR (NF)

– Activated carbon application – AC (PAC, GAC)

– Chemical oxidation – Ozonation – O3 2018.11.21 - XIV Jornadas Tecnicas de ESAMUR - Kreuzinger

CECs – organic micro pollutants - wwtp


• CAS (conventional activated sludge plant)– Same wastewater (=same

location of plant)!

– High loaded C-removal only

– Low loaded Ni/Deni

– Subsequent Ozonation step (zspec 0,7 mg O3/ mg DOC)

Schaar, et al. 2010, Environmental Pollution 158, 1399-1404

CECs – organic micro pollutants - advanced technology

• Options for advanced wwttechnologies “ready to use”

– PAK: powdered AC

– GAK: granular AC filter

– Ozonung: O3 (zspec +/- 0.5)

• Suggested for Austria:Multibarrier with O3 & GAK


CECs – organic micro pollutants - ozonation

• Removal of organic trace pollutancs is depending on specific ozone dose!

• zspec = mg O3 / mg DOC

• Competition of organic matrix (mg/l) with trace pollutants (µg/l)


CECs – removal of pathogens - ozonation

• removal for pathogens not as dependant on specific ozone dose!

• Similar results for zspec > 0.2 mg/mg

• No removal for C. perfringens spores


CECs – organic micro pollutants – GAC Filter

• Breakthrough behaviour Acesulfame K

• Competition of organic matrix (mg/l) with trace pollutants (µg/l)

• Competition adsorption kinetics between substances


Bed volumes treated [m3 m

-3]

0 2000 4000 6000 8000 10000 12000

c/c

0 [-]

0.0

0.5

1.0

1.5

2.0

2.5

3.0GAC stand-aloneGAC post-treatment

CECs – response to in vitro biotests - wwtp


CALUX-Assays

EBTBEQ LOQ **

FK-AB O3-OUT* N GAC-N FK-AB O3-OUT N GAC-N

Cytotox n.a. 0.51 0.54 0.64 0.53 0.51 0.54 0.64 0.53

ERa 0.3 0.49 0.07 0.05 0.08 0.04 0.06 0.05 0.05

anti-AR 14.4 6.0 5.3 7.2 5.5 5.3 5.3 7.2 5.5

Nrf2 21 107 127 107 64 27 27 27 27

p53 n.a. 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.01

p53 +S9 n.a. 220 243 300 240 220 243 300 240

PAH 6.2 170 70 45 55 1.0 1.2 1.0 1.0

PXR 54 53 18 20 65 10.2 6.0 6.2 5.9

If BEQ < LOQ LOQ assumed as result* ± 0.7 g O3/g DOC ** average LOQ of single measurements

CECs – antibiotic resistance - wwtp

FC – CFUsfor 2 C/N/DN/P CAS plants in Austria

• Sul resistance

• Average over 4 samplings

• Inflow (Zulauf) & effluent(Ablauf) 24h samples

• ~ 0,5% resistant FC in inflow

• ~ 0,05% resistant FC in effluent


qPCR; results in copies/100ng DNA Culture based


CECs – antibiotic resistance – advanced wwtp

Reduction in absolute number of bacteriarelative abundance of genes (ARG & 16s) +/- constant

„in“ = effluent of CAS = inflow of advanced steps

treatment

Summary

• We are living in a changing world; more and more chemicals and substances found in wastewater.

• Todays topics

– Organic trace pollutants

– Antibiotic resistance

• We can neither measure them all in chemical analysis nor access their toxicological potential individually - > whole effluent in vivo assays

• Direct reuse of treated ww & indirect reuse via receiving waters face the same challenges


Conclusion

• CAS (conventional activated sludge) aren’t that bad in CEC removal!

• Compared to high loaded C-removal plants, CAS with nitrification have a significant removal of CECs and toxic / biological effects (no significant further removal with Denitrification)

– (They have installed a system immanent online toxicity measurement: nitrification ;-)

• Even advanced treatments do not remove all CECs! (Multibarrier Concept)

• BAT (as low loaded AS plants) are an absolute requirement for implementation of further steps!

– Removal of competing matrix (“DOC”; COD; e.g. humic acids)

– Reduction of O3 depleting substances (e.g. NO2)


Conclusion

• Advanced ww treatment by ozonation and GAC-filtration is applicable even on smaller plants with limited personel resources


Thank you

For your attention


The ANSWER project has received funding from the European

Union’s Horizon 2020 research and innovation programme under

the Marie Skłodowska-Curie grant agreement No 675530.

Dr. Norbert Kreuzinger

Technische Universität WienInstitut für Wassergüte und Ressourcenmanagement

Karlsplatz 13/226-1

1040 Wien

[email protected]

emerging compounds in wastewater reuse compounds, effect

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