Micro-pollutants in water circulationThe wastewater treatment plant of the future with ozone!

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Pharmaceutical substances in water circulation

The elimination of micro-pollut-ants from our water is a chal-lenge which more and more responsible providers and disposers have to set them-selves. While biological treat-ment processes do not remove them completely, oxidation with ozone is proving to be one of the most efficient methods.

Pharmaceuticals help many people and animals when fighting diseases, keeping healthy or improving quality of life. Nonetheless, a large propor-tion of pharmaceutical agents end up in the environment via sewage from bodily excretion.

Although they do not constitute an immediate hazard there, it is the long-term dangers that are becom-ing ever more significant. The effects of micro-pollutants or of pharma-ceutical substances in surface waters have already been proven on numer-ous occasions in large-scale stud-ies and lead to negative changes in the ecosystem and therefore to problems.

Problem I: Persistence

Not all approved substances in the area of pharmacy, agriculture and in-dustry as well as in the area of daily consumption are completely biode-gradable. This means they cannot be fully removed with conventional clarification technology. As a result, the number of contaminants in our water circulation and its consumers is creeping upwards (bioaccumula-tion). This means a constant rise in water pollutants and further negative ef-fects for the aquatic environment for the future, unless appropriate mea-sures are taken.

Problem II: Endocrine effect

Some micro-pollutants (e.g. the active ingredient of the pill (ethi-nylestradiol)) has an effect on the hormonal system of humans and animals. These so-called endocrine substances (EDCs) are effective from the lowest of concentrations and are classified by science as particularly critical. In connection with negative environmental influences on living creatures, EDCs are currently being considered as elicitors: Negative effects on the reproduc-tion of certain kinds of fish are being observed (including the “feminisa-tion” of male fish)

The fertility decrease in humans and animals due to reduced sperm quality is going up

The increase of certain types of cancer which could be related to a disturbance of the hormonal system

Micro-pollutants in water circulation

They are persistent

Thus they are only biodegradable to a limited extent

Have a negative effect on organisms

Cause endocrine effects

Are highly mobile in aqueous solution

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Sources of drinking water such as ground water or surface water have different micro-pollutant concentra-tions, depending on the degree to which they intermix with the influx paths, via which the substances get into the water.

The main influx paths or “hot spots” of persistent micro-pollutants in sur-face waters are municipal waste-water treatment plants, drainage from the pharmaceutical industry, animal breeding grounds or medical centres.

Further indirect influx paths result from the improper disposal of unused pharmaceuticals and agricul-tural application of animal excre-ments or of sewage sludge.

IndustrialWastewater

MunicipalWastewater

HospitalWastewater

TreatmentSystem

WWTP TreatmentSystem

Surface WaterGround Water

Drinking WaterTreatment

Influx paths

High concentrations of endocrine disruptive substances get into our ground water and surface water via the clarification plant process

The main influx paths of endocrine disruptive sub-stances in waste waters. = possibility of trea-ting with ozone

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3The effects of endocrine substanc-es and persistent micro-pollutants on our ecosystem mean that more extensive purification is necessary. Many wastwater treatment plants reach their limits in eliminating the pollutants to a sufficient extent with existing purification technology. Numerous pilot tests with ozone as a further treatment step have shown that ozone is a suitable means for eliminating persistent pollutants. This means that micro-pollutants present in water can be effective-ly removed with ecologically and economically worthwhile doses of ozone.

How does OZONE work?

Ozone reacts quickly with micro-pol-lutants containing accessible amino groups, double bonds or aromatic systems. Alongside these pollutant-specific attributes, the efficiency of the reactions also depends on the pH value and on the dissolved or-ganic carbon (DOC). The extent to which a pollutant can be eliminated can be estimated by looking at its reaction rate constants with ozone.

The special agent: Ozone

Agents k= [M-1·s-1]

Ethinylestradiol ~3,0 x 106

Bezafibrat ~0,6 x 103

Carbamazepine ~0,3 x 106

Diclofenac ~1,0 x 106

Ibuprofen ~9,6 x 103

Sulfamethoxazol ~2,5 x 106

[Source: Project Poseidon, EAWAG, Huber et al.]

Pollutants with reaction constants of > 105 M-1·s-1 can be assumed to react very quickly with ozone. For comparison: The colourant indigo (which is used for the quantitative detection of ozone among other things) shows a constant of ~107 M-1·s-1 and hydrogen sulphide of ~3x104 M-1·s-1 for the reaction with ozone.

The varying reaction constants result mainly from the different points of action of the ozone on the mole-cules. 17α ethinylestradiol is acted on for example at the phenol group. In the case of carbamazepine, ozone reacts with a double bond. Diclofenac and sulfamethox-azole have functional amino groups which can be oxidised by ozone. Bezafibrate and Ibuprofen have no such functional groups and there-fore react considerably more slowly with ozone. [Schuhmacher]

The table shows the reaction constants of the reactions of various pharmaceuticals with ozone

Ozone introduction: As soon as ozone is intro-duced into water, any hazardous pollutants present are effectively degraded through oxidation

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Active Ingredients Agent Disposal [kg/a] Concentration [µg/l] Effect Reaction

Total disposal in Germany in the year 2001

Highest concentration measured in surface waters

Effects on various water organisms

Reaction in the environ-ment (poorly degradable)

Antibiotics

Sulfamethoxazol 53.600 1

Erythromycin 19.199 1,7

Trimethoprim 11.427 0,2

Clarithromycin 7.159 0,003

Pain Killers

Diclofenac 85.801 2

Ibuprofen 344.885 1,5

Phenazone 24.843 0,95

Propyphenazone 28.140 0,31

Antiepileptics Carbamazepine 87.605 6,1

AntilipemicsBezafibrat 33.476 3,1

Clofibric acid 2 1,1

Beta-blockers Atenolol 13.594 0,22

Antirheumatic Indometacin 3.721 0,7

HormonsEstradiol 1.098 0,0006

Ethinylestradiol 48 0,002

X-ray contrast media

Iomeprol 83.377 0,89

Iopamidol 42.994 2,8

Iopromid 64.056 8,5

Diatrizoat 60.687 15,8

CytostaticsCyclophosphamide 385 0,1

Ifosfamid 170 0,18

Source: MUNLV 2008

Pharmaceuticals and their effect

A total of over 2700 dif-ferent agents are used in Germany in human medi-cine and over 600 agents in animal medicine. The table shows the pollu-tants with the highest concentrations in surface water and their effect.

Terms and what they mean

Micro-pollution: Pollution by substances in relatively low concentrations, which are persistent against conventional treatment.

EDC: Endocrine Disrupting Compounds, pol-lutants with undesired effects on the hormonal system of humans and animals. These effects can be caused by pharmaceuticals or even other substances.

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WEDECO ozone systems have al-ready been used for several national as well as international projects for reducing micro-pollution and tested on an industrial scale: EU project POSEIDON, Braunschweig wastewater treatment plant January 2001 – June 2004 (Project No. EVK1-CT-2000-00047)

National project of Switzerland “Strategy MicroPoll”, Wüeri wastewater treatment plant in Regensdorf, July 2007 – October 2008

Successful pilot tests with ozone

“PILOTOX” project, Technical University of Berlin, Berlin Ruhleben wastewater treatment plant, December 2004 – July 2005

EU project POSEIDON, EAWAG, Zürich/Opfikon wastewater treat-ment plant, November 2003

Trim

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Sulfam

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Erythro

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Clarith

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Roxith

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Atenolol

Sotalol

Metopro

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Propranolol

Carbam

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Clofibricac

Ibupro

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Nap

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Ketopro

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Diclofenac

Tonalide

Galax

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Iopam

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Iopro

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Diatrizoate

Con

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µg/

L

0.01

0.10

1.00

10.00 WWTP effluent5 mg/L Ozone

10 mg/L Ozone15 mg/L Ozone

Antibiotics Beta-blockersAnti-epileptics Antilipemics Musks

X-ray contrast media

The graphic shows the results achieved at the wastewater treatment plant in Brunswick with an ozone dosage of 5 to 15 g ozone per m³ sewage. They illustrate the high degrees of degradation (not shown = under the detection limit) which can be attained in this way.

Research project at the University of Stuttgart, Büsnau wastewater treatment plant, December 2003 – May 2005

“KomOzon” project, Technical University of Vienna, Vienna waste-water treatment plant, 2007 – 2009

WEDECO ozone plant at the Wüeri was-tewater treatment plant in Regensdorf, Switzerland

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ADVANTAGES OF OZONE

Ozone eliminates bacteria, viruses and most other organic and inorganic contaminants

Ozone can significantly reduce levels of critical chemicals such as chlorine

Ozone acts as a microflocculant aiding in the removal of minerals such as iron and manganese

Ozone leaves neither chlorinated byproducts nor unpleasant chemical taste or smell

Ozone is generated on site and on demand from air/ oxygen and energy

No storage & handling of chemicals

Ozone is one of the most power-ful technically produced, gaseous oxidants. It is eminently suitable fortreating water and industrial pro-ducts. Its great advantage is its envi-ronmentally friendly mode of action.Pollutants, coloured substances, odours and microorganisms are di-rectly destroyed by oxidation, without creating harmful by-pro-ducts or significant residues.

By decomposing to oxygen as it reacts, ozone provides a costeffective and environmentallyfriendly alternative to oxidation with chlorine, absorption (i.e. activatedcarbon) or separation processes (i.e.reverse osmosis).

Ozone in Use

DRINKING W

ATER

WA

STE WA

TER

PROCESS WATER

PRO

DU

CT

POLI

SHIN

GBL

EACH

ING PROCESS

Improvement of flocculation; Decoloration; Taste/odor control; Fe/Mn elimination;

Disinfection, Algae removal, Elimination of persistant substances

Decolouration; Elimination of tensides, phenols, COD, cyanides, AOX and endocrine

substances; Sludge reduction

Cooling water (i.e. power plants), Swimming pools; Rinsing water in beverage

industry

Chemical modification of starch, Shelf-life improvement of food; Surface treatment

(i.e. laminating, ozonolysis, coating)

Pulp bleaching (pulp & paper industry); China clay (Kaolin)

PRODUCT POLISHING

The Oxidative Action of Ozone

Ozone reacts quickly with a large number of compounds. In doing so these com-pounds are attacked either directly by the ozone molecule or indirectly by the intermediately occurring hydroxyl radicals. Preferable the ozone is completely con-sumed in this reaction process, releasing only oxygen. In case of remaining ozone in the off-gas these residues are converted to oxygen by a residual ozone destructor. By combinating ozone with UV or peroxid advanced oxidation processes are formed which are able to mineralize even most persistent substances. These advanced oxidation processes (AOP) help to render other, previously nondegradable,water pollutants harmless.

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WEDECO AGBoschstr. 432051 Herford, GermanyTel +49 (0)5221 930 0Fax +49 (0)5221 930 222wedeco.de@itt.comwww.wedeco.com

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