ENVIRONMENTAL CHEMISTRY

PART 2

ASSOC. PROF. JAN TŘÍSKAISBE AS CR, ČESKÉ BUDĚJOVICE

DISTRIBUTION OF COMPOUNDS BETWEEN WATER AND AIR

HENRY LAW CONSTANT (H)

Pi = Hi . xi

Pi = yi . P = xi . Pi0

Hi = yi . P/ xi

FUGACITY (f)

dG = VdP = RT dln f

Gibbs function dG = VdP = RT dlnP

RT dln f = RT dln P

f/P = 1

FUGACITY CAPACITY (Z)

C = f . Z

K12 = C1/C2 = f1.Z1/f2.Z2 = Z1/Z2

FUGACITY CAPACITY (Z)

Fugacity capacity for air

Zi,G = RT1

Fugacity capacity for soil

Zi,S = i

SoCS

HdKoC )..(

R….....gas constantT..........temperature in oKoCS......content of organic carbon in soil [%/100]KoC.......=0.411 KOW

KOW.....distribution coefficient octanol-water for given compoundsdS........ density of wet soil [kg/m3]Hi ........Henry law constant for given compound [Pa.m3.mol]

FUGACITY CAPACITY (Z)

Z is like C (heat capacity) At equilibrium, all phases will have same fugacity (temperature)

C (heat capacity) = amount of heat (energy in J/unit volume)/Temperature

Z = amount of chemical (moles per unit volume)/fugacity

ENVIRONMENTAL MODELLING

• UNIT WORLD (Mackay, 1979)• Surface 1 km2 (water depth 10 m, 70% of area)• Soil (depth 15 cm, 30% of area)• Air (height 6 000m)• Sediment (depth 3 cm, 70% of area)• Sedimented particles (5g/m3 of water)• Biota (fishes - 1g/m3 of water)

EXAMPLE OF COMPOUNDS DISTRIBUTION IN BIOTA

ECOLOGICAL RISK ASSESSMENT(Regulation of Ministry of Environment No. 306/1998 Sb.)

GENERAL INFORMATION• name of the compound (IUPAC, CAS)

• synonyms• purity

• impurities• summary formula• structural formula

• member of the chemical group• state

• identification of the author of data• amount of the compound (higher than 1000 t)

• means of usage• the possibilities of disposal

ECOLOGICAL RISK ASSESSMENT

PHYSICO - CHEMICAL PROPERTIES• melting point• boiling point • density

• vapour pressure • log Kow

• water solubility• flash point

• inflammability• explosiveness

• oxidative properties• additional data

ECOLOGICAL RISK ASSESSMENT

COMPOUND FATE AND TRANSPORTATION• stability

• fotogedradation• stability ve water• monitoring data

• distribution in exposed compartments• biodegradation• bioaccumulation• additional data

EKOTOXICITY

• BACTERIAL BIOLUMINISCENCE TEST (Microtox) (Photobacterium phosphoreum)

• TEST ON CRUSTACEANS (Daphnia magna according ISO 6341)

• TEST OF PHYTOTOXICITY (Sinapsis alba according OECD 208)

• TEST ON FISHES (Poecilia reticulata and Brachydanio

rerio according ISO norms: ČSN EN ISO 7346-1 (statical method)

• TEST ON ALGAE (Scenedesmus subspicatus, Selenestrum capricornutum) according ISO 8692

• AMES TEST, Salmonella typhimurium TA 98, TA 100

BACTERIAL BIOLUMINISCENCE TEST (Microtox) (Photobacterium phosphoreum)

HACH-LANGE LUMINOMETER

TEST ON CRUSTACEANS (Daphnia magna according ISO 6341)

TEST OF PHYTOTOXICITY (Sinapsis alba according OECD 208)

TEST ON FISHES (Poecilia reticulata and Brachydanio rerio according ISO norms: ČSN EN ISO 7346-1 (statical method), ČSN EN ISO 7346-2 and ČSN EN ISO 7346-3

(flow method)

TEST ON ALGAE (Scenedesmus subspicatus, Selenestrum capricornutum) according ISO 8692

• non toxic 48hEC50 higher than 10 000 mg·l-1 • very weak toxic 48hEC50 in the range of 1 000 mg·l-1 to 10 000 mg·l-1• weak toxic 48hEC50 in the range of 100 mg·l-1 to 1 000 mg·l-1• middle toxic 48hEC50 in the range of 10 mg·l-1 to 100 mg·l-1• strong toxic 48hEC50 in the range of 1 mg·l-1 to 10 mg·l-1• very trong toxic 48hEC50 in the range of 0.1 mg·l-1 až 1 mg.l-1• extremely toxic 48hEC50 less than 0.1 mg·l-1

CLASSIFICATION OF TOXICANTS

FLOW METHODS

BIOMARKERS, BIOINDICATORS

• FYTOCHELATINS• METALLOTHIONEINS

• NEEDLES• MOSSES

AMES TEST

The indicator strains of Salmonella typhimurium used in the test are mutants in the genes for biosynthesis of the amino acid histidine. Hence, this amino acid must be added to the cultivation medium. In the course of the test back mutations induced by the tested mutagens are going on, causing a change of phenotype and induction of revertants colonies. An important property of the Ames testing system is, that it allows a metabolic activation in vitro using the microsomal fraction S9 of rat liver. In this way a biological proof of indirectly acting chemical mutagens (promutagens) can be given.

ECOLOGICAL RISK ASSESSMENT

MONITORED SUBJECTS

•  population of animal or plant species• community species• ecosystem model• region model

ECOLOGICAL RISK ASSESSMENT

EVALUATION OF DOSE RESPONSE RELATION

  (NOEC)

• estimation of the likely local concentration PEC (L)

(emission inventory, monitoring, models)• estimation of the likely regional concentration

PEC (R) (mass transfer balance)

ECOLOGICAL RISK ASSESSMENT

ECOLOGICAL RISK ASSESSMENT

EXPOSURE ASSESSMENT

• PEC(L)/NOEC and PEC(R)/NOEC ≤ 1

• PEC(L)/NOEC and PEC(R)/NOEC > 1