Sampling, monitoring and source tracking of dioxins

in the environment of an incinerator in the Netherlands

A. Arkenbout and K.H. Esbensen

Environmental Sampling and Monitoring

May 9-11, 2017

Situated near the UNESCO Wadden Sea,

mostly agricultural economy

Harlingen, North of the Netherlands

2011: Incinerator ‘REC’ (Waste to Energy-concept)

‘state of the art’ incinerator, the best of Europe

Incinerator, Harlingen, the Netherlands

Waste

Waste

Dioxins

Unintended Persistent Organic Pollutants (UPOPs)

Extreme toxic in extreme low concentrations (pbb) 7-10 years lifetime carcinogenic

Incineration

• Best Available Techniques (BAT)

• Best Environmental Practise (BEP)

• Elimination/reduction emissions of hazardous pollutants to the environment (Stockholm/Basel Conventions)

Dioxins under control?

Stockholm Convention, regulations

• What does Stockholm convention say about - sampling?

• Heterogeneity is a serious issue (grab sampling is unacceptable)

• Heterogeneity - and how to counteract its effects when sampling

• ALL samples (for analysis) must be representative !!!

• And where is the Stockholm ‘police’?

‘New Sheriff in Town’ Theory of Sampling (TOS)

More importantly: WHAT does TOS say about - sampling?

New Sheriff in Town’ Theory of Sampling (TOS)

Incorrect sampling errors (ICS)

IDE

IEE

IPE

IWE

FSE

GSE

Correct sampling errors (CSE) Process sampling errors (PSE)

PIE2

PIE3

PIE1

Theory of Sampling (TOS)

Measurement Uncertainty (MU)

Theory of Sampling (TOS)

Total Analytical Error (TAE) Total Sampling Error (TSE)

Incorrect sampling errors (ICS)

IDE

IEE

IPE

IWE

FSE

GSE

Correct sampling errors (CSE) Process sampling errors (PSE)

PIE2

PIE3

PIE1

Theory of Sampling (TOS)

Measurement Uncertainty (MUanalysis)

Error Uncertainty

Risk?

• Soil

• Feed

• Waste

• Bottom ash

• Fly ash

• Flue gas

• Digestate

• Sewage sludge

• Water

• Combustion temperatures

• Sheep liver • Here liver • Cow milk • Goat milk • Birds eggs • Backyard chicken eggs • Grass • Human blood serum • Earthworm • Tree bark • Sheep

Organic Inorganic Persistent Organic Pollutants

• 7 Dioxins, Polychlorinated dibenzodioxins (PCDD)

• 10 Furans, Polychlorinated dibenzofurans (PCDF)

• 12 dioxin-like PolyChlorinatedBiphenyls (dl-PCB)

• 5 PolyBrominated Dibenzo-Dioxin (PBDD)

• 6 PolyBrominated Dibenzo-Furans (PBDF)

• PBDE, PBB • PFOA, PFOS

Sampling & Analysis

Biomarkers

Dioxins

Grass Eggs of backyard chicken

Incinerator

Amesa

Biomarkers

Standard approach (BEP):

One sample milk,

5 kilometers away from the incinerator: …

everything is wrong with this approach

ToxicoWatch approach: At 15 locations (1 – 25 km), a composite sample of 10 eggs of backyard chickens: local and areal coverage = counteracting heterogeneity

Biomonitoring paradigma

Eggs of backyard chicken as biomarkers of local dioxin/PCB pollution

Bioaccumulation Biomagnification Biotransformation Xenobiotical metabolism

Eggs of backyard chicken as biomarkers of local dioxin/PCB pollution

DR CALUX

Local composite sampling of ten eggs of backyard chicken

Results analytical bioassay eggs

pg BEQ/g fat

10,9

5,0

13,8

5,7

8,8

> 3,4

1,7

< 1,7

DR CALUX

Results analytical bioassay eggs

DR CALUX

> 3,4 pg BEQ /g fat

1,7 pg BEQ /g fat

< 1,7 pg BEQ /g fat

T Verification by GC/MS

10 km

Harlingen

Wadden Sea

*

*

*

*

*

*

*

Mapping eggs backyard chicken

BEQ: Bioanalytical EQuivalents

Mapping eggs backyard chicken

8,1

5,8

Rijnmond

Harlingen Friesland

National

5,2

6,1

n: comply n: not complying

Dioxines pg TEQ/gram

52% comply

Governmental research shows 52% comply the limit of dioxins, but exact sample locations were not given

Levels of dioxins in eggs of backyard chicken in the Netherlands

Media attention ‘Dioxin eggs’

Dioxin emissions according to EU norm (0,1 ng TEQ/Nm3)

…....but only 12 hrs/365 days (0,1 % production time)

Only analyses of dioxins (PCDD) and furans (PCDF)

Other compounds with dioxin-like properties (TEQ) are not in the regulatory frameworks

Only measurements under stable combustion conditions

And only pre-announced visits

Flue gas incinerator

• This mandate is an extreme grab sampling in the time domain.

• Absolutely insufficient ... A laughing matter (if it wasn’t so serious!)

Short-term: Extreme grab sampling; 0.14 % of a year

• For the first time in the history of the Netherlands a long-term continuous sampling of flue gas in the chimney of the incinerator

• Analysis of regulated dioxins and furans (PCDD/F) and also the non-regulated dioxin-like PCBs, brominated and fluorinated compounds

• All results publicly accessible

Long-term sampling flue gas

2012-3T

2012-10T

2013-3T

2013-9S

2014-3T

2014-3S

2014-6S

2015-3T

2015-8A

2015-9A

PCDD 0% 0% 95% 0% 34% 73% 19% 0% 67% 70%

PCDF 0% 0% 4% 0% 66% 27% 81% 0% 33% 30%

0%

20%

40%

60%

80%

100%

120%

% T

EQ P

CD

D/F

Short-term % TEQ PCDD/F

Sampling: 2 x 6 hours/year Sampling under ‘normal’ operation conditions; variable PCDD/F and congeners patterns, 50% dioxins 0,0 4 years no elevated dioxins

Sampling: 12 x 672 hours/year* Measurements during start-ups, shut-downs and unstable combustion. Most congeners detected, always results.

REC01

REC02

REC03

REC04

REC05

REC06

REC07

REC08

PCDD 63.4% 67.2% 45.8% 48.0% 54.1% 57.6% 56.3% 61.8%

PCDF 32.7% 28.9% 44.0% 43.6% 38.3% 36.9% 34.1% 28.6%

PCB 3.9% 3.9% 10.2% 8.4% 7.6% 5.5% 9.6% 9.6%

0.0%

10.0%

20.0%

30.0%

40.0%

50.0%

60.0%

70.0%

80.0%

% T

EQ P

CD

D/F

Long-term % TEQ PCDD/F/dl-PCBs

Comparing short- vs. long-term sampling of flue gas incinerator

A dioxins eruption.. 17 x the permitted TEQ emission limit during a start-up

UNESCO herity, The Wadden Sea

More than 42 times start-ups have taken place since 2011. Analyses show structural impairments of the incinerator.

Unexpected dioxin emissions

-0.50

0.00

0.50

1.00

1.50

2.00

2.50

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21

Emission during start-ups

Permitted emission

Failure

Incomplete measurement dioxins

5 x exceeding the permitted limit for dioxins

L Long-term sampling PCDD/Fs (log)

Juridical status

Max. PCDD/F cattle feed

2015-March

1 km

REC

2015 December 2014-March

6 weeks 20 weeks 20 weeks

Polluted grass near the incinerator

Spatial sampling of grasses

0.00%

5.00%

10.00%

15.00%

20.00%

25.00%

30.00%

PCDD/Fs

Egg

Incinerator

Grass

% TEQ Egg (n=8) Grass (n=40) Incinerator (n=12)

Similar patters of congeners

• The elevated dioxins in eggs of backyard chicken shows clearly an environment under stress

• In a broad area around the incinerator eggs of backyard chicken all exceeding the limit values of dioxins

• Long-term sampling of flue gas gives a more reliable picture of emissions of dioxins

• Samples of grass show elevated levels near the incinerator

• Fingerprints congeners of dioxins and furans in eggs, flue gas and grass have similar patterns

Summary

• Theory of sampling offers guidance how to make representative samples.

• Long-term sampling of flue gas shows the incinerator is a potential source of dioxins.

• The Stockholm Convention set up guidelines to eliminate the unintentional production of dioxins, but when sampling isn’t representative and the governmental enforcement fail, POPs still keep a growing health hazard to the environment and human health.

Conclusions

So it was a good idea to use eggs of backyard chicken as biomarkers of dioxin pollution, the dark side is however, there’re no chickens anymore in Harlingen and that was not the aim of this research.

NGO ToxicoWatch Foundation stands for

# DETOX the future

By TOS the sample rules

Thank you

At last..