Andreja Žgajnar Gotvajn

University of Ljubljana, Slovenia

Faculty of Chemistry and Chemical Technology

Chemical, Biochemical and Environmental Engineering

Subject: Environmental Chemistry and

Technology

Topic: PERSISTANT POLLUTANTS

PRESENTATION OUTLINE

Persistent/resistant organics

Problems?

Legislation: EU REACH

Biodegradability testing

Ecotoxicity testing

DEFINITION

Persistent organic pollutants (POPs) are organic compounds that are resistant to environmental degradation:

chemical

biological

photolytic

Their characteristics:

Persist in the environment

Long-range transport (atmosphere, hydrosphere),

Bioaccumulate in human and animal tissue,

Biomagnify in food chains,

Significant impacts on human health

Significant impact on the environment.

PERSISTENCY/RESISTANCY ?

Biodegradation of XENOBIOTICS:

MO with different metabolic/cometabolic pathways

Induction of enzymes in MO

Mutation

Evolution

Other possibilities:

Physico-chemical processes

Biodegradation

DDT

dichloro-diphenyl-trichloro-ethane

For ever or for a long time ?

http://www.planet-lepote.com/forum/viewtopic.php?t=6122&start=30/?registracija=nov_uporabnik, 24. 8. 2012

DAILY USE OF CHEMICALS?

ZERO WASTE MANAGEMENT,GREEN CHEMISTRY ?

(Pichtel, 2005).

http://www.cas.org/cgi-bin/cas/regreport.pl

All registred organic and inorganic substances

Commercially available substances.

% of commercially available substances

2000 2001 2003 2004 2005 2006 2007 2008 2009 2010

17.108.155 18.766.082 22.176.046 24.267.905 26.752.587 30.009.658 32.687.772 37.966.182 50.269.830 55,501,670

960.312

6 %

2.872.816

15 %

6.299.284

28 %

8.143.833

34 %

8.974.433

34 %

11.509.742

38 %

15.965.596

56 %

24.033.991

63 %

35.479.919

71 %

48.807.771

78 %

83,546,456

70,516,747

85%

2014

No. of regulated: 309,061 —> 0,4% !

DAILY USE OF CHEMICALS?

THE IMPACT OF SUBSTANCES ?

RISK ASSESSMENT OF SUBSTANCES?

Hazard

Identification

Dose/Response

Assessment

Actual

Concentrations ?

Risk Assessment

Risk Management

DIRECTIVE 93/21/EEC:

new+existing substances

When ? production, transport, removal

For ? chemicals/mixtures/products

Why ? producers/users/importers

Labeling/regulation:

- physico-chemical properties (explosive…)

- toxicological properties (toxic, harmfull…)

- imapct on human (cancerogenic…)

- environmental impact:

* water

* terrestial (soil, plants…)

New European REACH legislation ?REACH:

Registration

Evaluation,

Authorisation and

Restriction of

CHemical substances

REACH is a new European Community Regulation on chemicals and their safe use (EC

1907/2006).

The new law entered into the force on 1st of June, 2007.

The aim of REACH is to improve the protection of human health and the environment

through the better and earlier identification of the properties of chemical substances.

At the same time, innovative capability and competitiveness of the EU chemicals industry

should be enhanced.

The benefits of the REACH system will come gradually, as more and more substances are

phased into REACH – 11 Years.

The need to fill the data gaps would result in an increased use of laboratory animals for the

next 10 years. To minimise the number of animal tests, the REACH Regulation provides a

number of possibilities to adapt the testing requirements and use existing data and

alternative assessment approaches instead.

New European REACH legislation ?Covers all substances (Minor exceptions).

Manufacturers and importers are required to obtain relevant

information - preregistration.

Data from toxicity testing should be shared.

Information on hazards and risks will be passed down by supply

chain.

According to their quantities:

- 1 to 10 tonnes

- 10 to 100 tonnes

- more than 100 tonnes

CMRs: Carcinogenic, mutagenic or

toxic to reproductionhttp://www.google.si/search?sourceid=navclient&aq=0h&oq=REACH&ie=UTF-

8&rlz=1T4ADFA_enSI411SI413&q=reach+legislation

New European REACH legislation ?

Source: European Chemicals Agency, http://echa.europa.eu/

SUBSTANCES OF VERY HIGH CONCERN - 46

(banned in the next few years?)

Trichloroethylene Carcinogenic

Boric acid Toxic for reproduction

Disodium tetraborate Toxic for reproduction

Tetraboron disodium heptaoxide Toxic for reproduction

Potassium dichromate Carcinogenic, mutagenic, reproduction

Ammonium dichromate Carcinogenic, mutagenic, reproduction

Potassium chromate Carcinogenic and mutagenic

Sodium chromate Carcinogenic, mutagenic, reproduction

2,4-Dinitrotoluene Carcinogenic

Acrylamide Carcinogenic and mutagenic

.....

New European REACH legislation ?Source: European Chemicals Agency, http://echa.europa.eu/

CRITERIA FOR THE IDENTIFICATION OF PERSISTENT, BIOACCUMULATIVE AND

TOXIC SUBSTANCES

Substance fulfils the persistence criterion when:

the half-life in marine water is higher than 60 days,

the half-life in fresh- or estuarine water is higher than 40 days,

the half-life in soil is higher than 120 days.

Substance fulfils the bioaccumulation criterion when:

the bioconcentration factor (BCF) is higher than 2 000.

Substance fulfils the toxicity criterion when:

the long-term no-observed effect concentration (NOEC) for marine or freshwater

organisms is less than 0,01 mg/l,

the substance is classified as carcinogenic (category 1 or 2), mutagenic (category 1

or 2), or toxic for reproduction (category 1, 2, or 3), according to other directives

there is other evidence of chronic toxicity, as identified by the classifications:

T, R48, or Xn, R48 according to Directive 67/548/EEC

New European REACH legislation ?Source: European Chemicals Agency, http://echa.europa.eu/

DESCRIPTION FOR THE SUBSTANCE

Hexachloroethane

CAS No 67-72-1

EINECS No 200-6664

Shall not be used in the

manufacturing or

processing of non-ferrous metals.

Azocolourants

1. Azodyes which, by reductive cleavage of one or more azo groups, may release one or

more of the aromatic amines listed in Appendix 8, in detectable concentrations,

i.e. above 30 ppm in the finished articles or in the dyed parts thereof, according to the

testing methods listed in Appendix 10, shall not be used in textile and leather articles

which may come into direct and prolonged contact with the human skin or oral cavity,

such as:

– clothing, bedding, towels,hairpieces, wigs, hats, nappies and other sanitary items,

sleeping bags,

– footwear, gloves, wristwatch straps, handbags, purses/wallets, briefcases, chair

covers, purses worn round the neck,

– textile or leather toys and toys which include textile or leather garments,

– yarn and fabrics intended for use by the final consumer.

2. Furthermore, the textile and leather articles referred to in paragraph 1 above shall not

be placed on the market unless they conform to the requirements set out in ...

CHARACTERISTICS OF

PERSISTENT ORGANICS

Low water solubility

High lipid solubility

High molecular masses

Low volatility

Biologically active?

Soil, sediments.

Uptake till equilibrium is reached, possible leaching.

Possible consequence: A rise in soil and sediment toxicity.

BIOLOGICAL ACTIVITY

http://www.elsevierimages.com/image/33239.htm, 29. 10. 2010

TRANSPORT PATHWAYS

(EDCs)

CHARACTERSTICS OF

SUBSTANCES ?Structure

Physico-chemical properties: volatility, solubility, miscibility, etc.

Transport pathways

Environmental concentrations

Environmental impact

HOW TO ASSESS RESISTANCY ?

Biodegradability studies.

Chemicals, wastewaters.

Biodegradability is dependent upon:Structure and concentration of the substance

Source and type of MO

Physico-chemical conditions: pH, T, oxygen, etc.

Nutrients: N, P, etc.

A A*CO2 + H2O + Inorganic components

+ E

+ biomass

MO

BIODEGRADABILITY

EXPERIMENTAL SETUP ?

Standardised and non-standardised tests

How ?

Change of parameter vs. time

Basic idea:

Directly: concentration of chemicals biodegradation

Non-directly: non-specific parameters:- O2 consumption- CO2 production- TOC, TC, IC...

Sample

Nutrients

Buffer Water

MO

Xv/t

-

X B /t

=Nutrients

Buffer

MO

Water

Sample

BIODEGRADABILITY TESTING IN EU

Multilevel protocol

Not only quantity, but also other environmental characteristics

(toxicity, mutagenicity, bioaccumulation potential, etc.)

OECD = EU ISO

Level

of testing Test name Annual production (t) Production in 5 years (t)

0 Ready biodegradability 1 5

1 Potential biodegradability:

- on demand: 10 - 100 50

- regulatory: 100 – 1000 500

2 Simulation tests 1000 /

EVALUATION OF

BIODEGRADABILITY

EVALUATION OF

BIODEGRADABILITY

EVALUATION OF

BIODEGRADABILITY

Different aquatic environments: WWTP, rivers, lakes, sediments….

Test

design

Real

processes:

-evaporation

-adsorption

-dillution

-transport

pathways

-...

Possibilities:

-knowledge

-tehnical

-price

-...

? In situ ?

Ecotoxicology – science describing the toxic effectof various agents on living organisms, especially onpopulations and communities within ecosystems.

ECOTOXICITY

Response of tested organisms during the exposition of toxic compound depend on dose of this compound as well as time of the exposure.

Paracelsus (15th century) "All things are poison and nothing is without poison,

only the dose permits something not to be poisonous."

Aquatic ecosystem

TOXICITY TEST

TOXICITY TEST

Physico-chemical analyses

and/or?

Biotests

LC (lethal concentration)

Concentration, causing death of certain amount of tested organisms

48h LC50 = 0.1 mg/l

EC (effective concentration)

Concentration, causing specific response of tested organisms

96h EC50= 0.2 mg/l

RESULTS OF TOXICITY TEST

Most often

found

parameters

BACTERIA Activated sludge

Vibrio fischeri (Photobacterium phosphoreum)

Pseudomonas putida

ALGEA Scenedesmus subspicatus

Selenastrum capricornutum

WATER FLEAS Daphnia magna

Daphnia pulex

Ceriodaphnia dubia

FISH Oncorhynchus mykiss

Brachydanio rerio

Cyprinus carpio

Pimephales promelas

Salvenius fontinalis

TEST ORGANISMS

FUTURE OF POPs?

Synthesis/development.

Increased use over large areas.

Restricted use.

Reduced emissions, as well as bans and controls.

SOME REFERENCES USED/FUTURE READING

Vesilind, P. A., Morgan, S. M.: Introduction to Environmental Engineering, 2nd

Ed., Thomson Brooks/Cole, London, 2004.

Davis, M. L, Masten, S. J.: Principles of Environmental Engineering and

Science, McGraw-Hill, 2004.

Masters G.M., Wendel E: Introduction to Environmental Engineering and

Science. 3rd Ed., Prentice-Hall International, London, 2008.

Baird,C., Cann, M.: Environmental Chemistry, 4th Ed., W.H. Freeman and

Company, New York, 2008.

Sawyer C.N., McCarty P.L., Parkin G.F.: Chemistry for Environmental

Engineering, 5th Ed. McGraw-Hill, New York, 2003.

Society of Environmental Toxicology and Chemistry (SETAC), Ecological Risk

Assessment, Technical Issue Paper, Pensacola, Florida, 1997.

Struijs, J., Van der Berg, R.: Standardized biodegradability tests: Extrapolation

to aerobic environments, Water Research, 29, 1995, 255-262.

Rand, G.M., Fundamentals of Aquatic Toxicology, Effects, Environmental Fate,

and Risk Assessment, 2nd Edition, Taylor and Francis Publishers, London, 1995.

REACH: Regulation (EC) No 1907/2006 of the European Parliament and of the

Council of 18 December 2006 concerning the Registration, Evaluation,

Authorisation and Restriction of Chemicals (REACH).

.....