THE ‘HYDROGEN PEROXIDE METHOD’From lab scale to full scale, new developments

and perspectives

U.S. Algal Toxin Conference 2016, Akron Ohio

Geert WijnArcadis NLMay 11 2016

© Arcadis 2016

Content

Introduction

The Achilles heel of Cyanobacteria: Hydrogen peroxide?

Scaling up: From lab to full scale

Research Projects 2009 – 2015

How did we do it?

Regulatory aspects

The Future: Extend and improve our method

© Arcadis 2016

IN-SITU SOIL REMEDIATION

IN-SITU TREATMENT SYSTEMS

BLUE ALGAE TREATMENT

GEERT WIJNSenior specialist

Summary 22 years environmental contracting business

5 yrs BioSoil, Biological Soil remediation 7 yrs A&G Environmental Technology 10 yrs Arcadis InSitu, Soil and ground water remediation

Arcadis Consultant and contractor(!)

Sector Europe North

Business Line Environment

Value Proposition Environmental Construction Services

7 years in water business with Blue algae treatment

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HANS MATTHIJS

PETRA VISSER

JEF HUISMAN

Team University of Amsterdam

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In Memoriam Hans Matthijs (1951 - 2016)

The Achilles heel of Cyanobacteria?

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Selective killing of cyanobacteria

Drabkova, Matthijs, Admiraal and Marsalek, 2007

Research by University of Amsterdam

Cyanobacteria appeared 5-10 times more sensitive to H2O2 than green algae

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HP breaks down in 1-2 days (2H2O22H20 + O2)

Microcystins break down in 1-2 days (!)

Cyanobacteria are a lot more sensitive for HP (Drabkova et al., 2007)

Selective killing of cyanobacteria, other phytoplankton are hardly affected. Cyanobacteria appeared 5-10 times more sensitive to H2O2 than green algae in lab tests.

Effective in very low concentration: equal to a 3% solution (used for mouth rinsing) diluted 15.000x

Effects on fish and aquatic plants haven’t been expected: treatment with a 15 fold higher concentration is a common method in aquaria

Fast, selective and environmentally safe!

A chemical in open water?

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Toxic algae blooms are an increasing problem in the Dutch surface water. Various organizations are interested in our method. In general, organizations who are responsible for water quality, but for different reasons:

Recreational entrepreneurs

Drinking water industry

Water managers

Municipalities

Food Industry

Increasing problem

From lab tests to field study

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Proof of Principle

Surface area 12 ha

Phosphate concentration 0.1 mg P/L

Since 2007: Planktothrix agardhii dominated

Lake was often closed for recreation

Lake Koetshuis, Veendam

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Method 8 enclosures 0, 2, 4, 6 mg/l (duplicate)

Results 2 mg/l is sufficient! Matthijs et al., 2012.

Step 1: Enclosures

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Step 2: Whole lake Strong decrease of

cyanobacteria

Microcystins rapidly degraded

Remedy lasts for several weeks

Research projects 2009 – 2015

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Site Year Surface (ha) volume (m3) Type of Water Cyanobacteria

Lake Koetshuis 2009 12,0 240.000 swimming lake Planktothrix, Woronichinia

Lake Koetshuis 2010 12,0 240.000 swimming lake Planktothrix, Woronichinia

Born 2009 0,2 3.000 city pond Microcystis

Lake Veer 2009 10,0 450.000 swimming lake Planktothrix

Lake Kotermeerstal 2011 16,0 1.920.000 swimming lake Aphanizomenon, Anabaena

Ouwerkerk 2012 8,5 456.800 Creeks, canal, pond dinoflagellate Alexandrium ostenfeldii

Troelstraweg 2015 0,6 12.850 city pond Woronichinia

Lake Krabbe 2015 3,0 52.500 swimming lake Aphanizomenon

Lake Delftse Hout 2015 23,5 705.000 swimming lake Anabeana

Reservoir ‘De Grote Rug’ 2015 60,0 3.300.000 drinking water

basin Microcytis

Research projects 2009 - 2015

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Alexandrium (D)-99,9%

Mussels saved

Pla/Wor-99,9%7 weeks

Aphanizomenon-95%

Season

Ana/Aph-99,7%/-97,3%

6 weeks

Microcystis-95%

Full Intake

Microcystis -98%

>4 weeks

Wor/Pla/Mic/Ana-92%

2 days!

Aphanothece/Wor -95%/-33%

8 weeks=Season

Pla-99,8%Season

Swimming waterCity pondDrinking water

Food production

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Treatment time 1 – 2 days

HP disappeared within 2 days

Toxins are not always produced/present by toxic algae

No effects on higher biota (including macrofauna) observed at low H2O2 concentrations

Temporarily effects on zooplankton measured (diversity & motility) – population recovered within 8 days

Population of cyanobacteria suppressed for at least 6 weeks, up to a whole summer season (regarding Anabaena, Aphanizomenon, Planktothrix & Microcystis)

Results and effect strongly depends on site specific conditions

In general

How did we do it?

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Boat from local fire brigade

Custom made pump and dosing system ’water harrow’ installed on site

Fixed depth at 2 m, width approx. 5 m

Equal distribution in full water column

HP Storage in cubic container

GPS system onboard

For max. 20 ha

Low speed

Prototype 2009 - 2011

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Large HP stock and dosing unit on board and tow boat

Adaptable harrow in depth (6 m) and width (6 m)

GPS

Low speed, large volumes

Small lakes

Used for Alexandrium ostenfeldii treatment

Pontoon

Successful saving of mussel production threatened with

Paralytic Shellfish Poisoning due to Saxitoxines

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Aluminium ProWorker

Adaptable harrow in depth and width

7,5 m width and 6 m depth

HP storage build in

GPS and depth sonar

Up to 100 ha

High speed

Spray for scum

The ‘Hans Matthijs’

Successfully cleaning of 60 ha drinking water reservoir

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Equipment - Storage Double walled

containers

Pontoon for off shore refilling

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Fencing

Signs

Toolbox meeting

Personal protection

HAZOP and CE

Health & Safety

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Treatment time/cruising speed/engine power

Stability and balancing the load

Stock storage and refilling

Accessibility of stock

Treatment depth and dosing speed

Structures, lines, aquatic flowers

Mobilizing and demobilizing boat and pontoon

It is a job for skilled technicians with professional equipment!

Also to keep in mind…

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With current vessel

<100 hectare (250 acres)

<6 m depth

Highly impacted and ‘matured’ blooms e.g. small ponds

Potential resistance of some types?

Treatment time

Permit: Only available in The Netherlands

LimitationsYes! It is still not the silver bullet!

H2O2

Regulatory Aspects

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Applying chemicals in surface waters in Europa is regulated by European Chemicals Agency (ECHA) in the Biocidal Products Regulation (BPR)

Arcadis is the only organization licensed by CTGB (Dutch partner ECHA) to apply H2O2 in surface waters in the Netherlands

Application of hydrogen peroxide is allowed for conducting experiments or trials

Experiments by University of Amsterdam, execution by Arcadis

Basic monitoring:

Phytoplankton Zooplankton Toxins Abiotic water quality Supervision

Under research: Apply for product authorization

Approved biocide?

More research

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Extend and improve our method

Applicability for different types of cyanobacteria

Early application: Develop a new method to suppress the springtime recruitment of cyanobacteria from lake sediments with a slow-release peroxide formulation.

P-reduction: Harvesting of the floating biomass of lysing Microcystis cells as a cost-effective and non-invasive alternative for existing P-reduction programs

Hidden risks (such as adaptation and change in toxicity)

Biodegradation/chemical oxidation of cyanotoxins released from lysing cells

Multiple lake treatments in the coming years (approx. 7 for 2016)

Recent potential new lakes for this program:

1 ha swimming lake nearby Nantes (France) 100 ha recreational area in The Netherlands (Rotterdam)

4 years of research is about to start!

Wrap-up

© Arcadis 2016

Very low and (environmentally) safe hydrogen peroxide concentrations

Selective killing of cyanobacteria

0,2 – 60 ha treated, up to 100 ha possible (with current technology)

10 sites treated since 2009

Treatment by trained and experienced technicians with safe and professional equipment

Arcadis is licensed by CTGB (Dutch partner European Chemicals Agency) to apply H2O2 in surface waters in NL (for research projects)

4 – >>8 weeks of proven effect after treatment. Depends on site specific conditions

UvA and Arcadis: A solid research combination for a very promising algaecide

Fundamental questions still remain unsolved: The limits of the ‘hydrogen peroxide’ method haven’t been reached

Wrap-up

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Soon available in the US?

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WHO TO CONTACT?GEERT WIJNSenior specialist

Arcadis Europe NorthConstruction Services+31 64667260Arnhem geert.wijn@arcadis.com

RENEE TALENSCommercial manager/senior consultant water

Arcadis Europe North Watermanagement & Landscape +31 627060141Arnhem, NLrenee.talens@arcadis.com

JASPER ARNTZConsultant watermanagement & ecology

Arcadis Europe NorthWatermanagement & Landcape+31 646036504Den Bosch, NLJasper.Arntz@arcadis.com

PETRA VISSERAssistant Professor,Aquatic Microbiology

University of AmsterdamFaculty of Science+31 0205257073Amsterdam, NLP.M.Visser@uva.nl

© Arcadis 2016

© Arcadis 2016

Arcadis.Improving quality of life.