CORRELATIONS IN POLLUTANTS AND

TOXICITIES

Kovanic P. and Ocelka T.Kovanic P. and Ocelka T.

The Institute of Public Health, The Institute of Public Health, Ostrava, Czech RepublicOstrava, Czech Republic

DATADATA

Actions: Regular monitoring of Czech and Moravian Actions: Regular monitoring of Czech and Moravian riversrivers

Period: 2002 – 2007Period: 2002 – 2007 Profiles: Profiles: 21 locations of rivers 21 locations of rivers Bečva, Berounka, Bílina, Dyje, Bečva, Berounka, Bílina, Dyje,

Jihlava, Jizera, Jihlava, Jizera, Labe, Labe, Lužická Nisa, Lužnice, Morava, Odra, Lužická Nisa, Lužnice, Morava, Odra, OhOhře, ře, Opava, Otava, Sázava, Svratka, Opava, Otava, Sázava, Svratka, VltavaVltava..

Field activity: Institute of Public Health, Ostrava Field activity: Institute of Public Health, Ostrava (IPH)(IPH) (The National Reference Laboratory)(The National Reference Laboratory) Chemical analyses: Laboratories of theChemical analyses: Laboratories of the IPH, Fr IPH, Frýdek-Místekýdek-Místek Mathematical Mathematical (Gnostic) (Gnostic) analysisanalysis: IPH: IPH Particular problem: Particular problem:

Are there any interactions Are there any interactions between pollutants?between pollutants?

““NATURAL” NATURAL” ASSUMPTIONS ?ASSUMPTIONS ?

Contaminations are generated, polluted and Contaminations are generated, polluted and accumulated mostly simultaneously, hence accumulated mostly simultaneously, hence the more contaminants, the higher the more contaminants, the higher contamination and opposite.contamination and opposite.

The The moremore pollutant A, the pollutant A, the moremore polutant B. polutant B. PositivePositive and and significantsignificant interactions interactions

betweenbetween concentrations of pollutants are expected.concentrations of pollutants are expected.

IS IT TRUE?IS IT TRUE?

COMMENTSCOMMENTS

Concentrations of groups of pollutantsConcentrations of groups of pollutants

differ by orders of magnitude.differ by orders of magnitude. Distributions differ not only by meanDistributions differ not only by mean

levels but also by their forms.levels but also by their forms. Distributions are non-Gaussian Distributions are non-Gaussian

(“normal”):(“normal”):

domains are domains are finitefinite, densities , densities asymmetric.asymmetric. DataData variability is strong, robust analysisvariability is strong, robust analysis

must be applied.must be applied.

TWO APPROACHES TWO APPROACHES TO INTERACTIONSTO INTERACTIONS

Robust correlation coefficients:Robust correlation coefficients: interdependence of deviations interdependence of deviations

from the mean valuefrom the mean value Robust regression models:Robust regression models: interdependence of variablesinterdependence of variables

The former does not imply The former does not imply the latter automatically !the latter automatically !

ROBUST ROBUST CORRELATIONSCORRELATIONS

Robust estimate: low sensitivity Robust estimate: low sensitivity

to “bad” datato “bad” data

Non-robust estimates: point statisticsNon-robust estimates: point statistics

(sample estimates of statistical (sample estimates of statistical moments)moments)

Many robust estimates exist producingMany robust estimates exist producing

different resultsdifferent results

DIVERSITY OF DIVERSITY OF ESTIMATESESTIMATES

In the past: lack of robust methodsIn the past: lack of robust methods

Recently: abundance of robust Recently: abundance of robust methodsmethods

Diversity of results: Diversity of results:

IN WHICH METHOD TO IN WHICH METHOD TO BELIEVE?BELIEVE?

INFERENCEINFERENCE Significant interactions between groupsSignificant interactions between groups of pollutants have been of pollutants have been confirmedconfirmed.. Assumption of positive interactions wasAssumption of positive interactions was falsifiedfalsified: there exist negative interactions.: there exist negative interactions. Group HCH initiates Group HCH initiates negativenegative effects. effects. Interactions of groups implie interactions Interactions of groups implie interactions

between individual congeners. between individual congeners. Which congeners interact negatively Which congeners interact negatively

and how much?and how much?

DEPENDENCE OF POLLUTANTS DEPENDENCE OF POLLUTANTS (“Y”) (“Y”)

ON THE GAMMAHCH (“X”)ON THE GAMMAHCH (“X”) Title Title L(Y)[L(X)]L(Y)[L(X)] is to be read as ‘natural is to be read as ‘natural

logarithm of the pollutant Y presented as a logarithm of the pollutant Y presented as a linear function of the natural logarithm of the linear function of the natural logarithm of the pollutant X (gammaHCH)’pollutant X (gammaHCH)’

GRAPHS:GRAPHS:

Straight line is the robust linear model.Straight line is the robust linear model.

Points depict the data values (X, Y)Points depict the data values (X, Y)

NOTE:NOTE: Vertical scalings (of Y) differ, the horizontal Vertical scalings (of Y) differ, the horizontal scale (of X) remains unchangedscale (of X) remains unchanged

x

y

5.0 5.5 6.0 6.5 7.0

-4.5

-4.0

-3.5

-3.0

Y=Ln(OCDD){Ln(gammaHCH)}

x

y

5.0 5.5 6.0 6.5 7.0

-5-4

-3-2

-1

Y=Ln(TCDD){Ln(gammaHCH)}

x

y

5.0 5.5 6.0 6.5 7.0

-5-4

-3-2

Y=Ln(PeCDD){Ln(gammaHCH)}

x

y

5.0 5.5 6.0 6.5 7.0

-4.0

-3.5

-3.0

Y=Ln(HxCDD){Ln(gammaHCH)}

x

y

5.0 5.5 6.0 6.5 7.0

-5-4

-3-2

Y=Ln(HpCDD){Ln(gammaHCH)}

x

y

5.0 5.5 6.0 6.5 7.0

-5-4

-3-2

-10

Y=Ln(OCDF){Ln(gammaHCH)}

x

y

5.0 5.5 6.0 6.5 7.0

-1.5

-0.5

0.5

1.0

1.5

Y=Ln(TCDF){Ln(gammaHCH)}

x

y

5.0 5.5 6.0 6.5 7.0

-3-2

-10

Y=Ln(PeCDF){Ln(gammaHCH)}

x

y

5.0 5.5 6.0 6.5 7.0

-4-3

-2-1

01

Y=Ln(HxCDF){Ln(gammaHCH)}

x

y

5.0 5.5 6.0 6.5 7.0

-4-3

-2-1

0

Y=Ln(HpCDF){Ln(gammaHCH)}

x

y

5.0 5.5 6.0 6.5 7.0

34

56

7

Y=Ln(alfaHCH){Ln(gammaHCH)}

x

y

5.0 5.5 6.0 6.5 7.0

23

45

67

Y=Ln(betaHCH){Ln(gammaHCH)}

x

y

5.0 5.5 6.0 6.5 7.0

12

34

5

Y=Ln(deltaHCH){Ln(gammaHCH)}

x

y

5.0 5.5 6.0 6.5 7.0

-2-1

01

23

Y=Ln(PBDE28){Ln(gammaHCH)}

x

y

5.0 5.5 6.0 6.5 7.0

23

45

6

Y=Ln(PBDE47){Ln(gammaHCH)}

x

y

5.0 5.5 6.0 6.5 7.0

-10

12

34

Y=Ln(PBDE100){Ln(gammaHCH)}

x

y

5.0 5.5 6.0 6.5 7.0

-4-2

02

4

Y=Ln(PBDE99){Ln(gammaHCH)}

x

y

5.0 5.5 6.0 6.5 7.0

-4-2

02

Y=Ln(PBDE154){Ln(gammaHCH)}

x

y

5.0 5.5 6.0 6.5 7.0

-4-2

02

Y=Ln(PBDE153){Ln(gammaHCH)}

x

y

5.0 5.5 6.0 6.5 7.0

-2-1

01

23

Y=Ln(PBDE183){Ln(gammaHCH)}

PARAMETERS OF THE FUNCTIONPARAMETERS OF THE FUNCTIONlognatlognat((Y) = Intercept + Y) = Intercept + Coef Coef lognat(lognat(gammaHCH)gammaHCH)

Pollutant (Y) Intercept STD(Intct) Pollutant (Y) Intercept STD(Intct) Coeff. Coeff. STD(Coef)STD(Coef)

OCDD -1.01 0.23 OCDD -1.01 0.23 -0.376-0.376 0.040 0.040TCDDTCDD 0.00.088 0.30.34 4 -0.424-0.424 0.0570.057PeCDDPeCDD -0.94 -0.94 0.28 0.28 -0.454-0.454 0.0480.048HxCDDHxCDD -2.5-2.588 0.160.16 -0.082-0.082 0.0270.027HpCDDHpCDD -1.53 -1.53 0.27 0.27 -0.312-0.312 0.0460.046OCDFOCDF -1.55 -1.55 0.28 0.28 -0.344-0.344 0.047 0.047TCDFTCDF 2.01 2.01 0.35 0.35 -0.446 -0.446 0.0580.058PeCDFPeCDF 0.36 0.36 0.33 0.33 -0.319-0.319 0.055 0.055HxCDF -1.58 HxCDF -1.58 0.27 0.27 -0.249-0.249 0.045 0.045HpCDFHpCDF -2.07 -2.07 0.25 0.25 -0.184 -0.184 0.0410.041

PARAMETERS PARAMETERS FOR THE HCH AND PBDEFOR THE HCH AND PBDE

Pollutant (Y) Intercept STD(Intct) Pollutant (Y) Intercept STD(Intct) Coeff. Coeff. STD(Coef)STD(Coef)alfaHCHalfaHCH 2.14 2.14 0.38 0.38 0.3730.373 0.064 0.064betaHCHbetaHCH -2.39 0.57 -2.39 0.57 1.0541.054 0.096 0.096deltaHCHdeltaHCH -3.47 0.52 -3.47 0.52 1.057 1.057 0.089 0.089HCBHCB 9.19.155 0.60.611 -0.666 -0.666 0.102 0.102 PBDE28 9.66 0.73 PBDE28 9.66 0.73 -1.603 -1.603 0.123 0.123PBDE47 15.30 0.69 PBDE47 15.30 0.69 -2.019-2.019 0.116 0.116PBDE100PBDE100 11.40 0.56 11.40 0.56 -1.698 -1.698 0.0950.095PBDE99PBDE99 13.39 0.71 13.39 0.71 -1.826 -1.826 0.119 0.119PBDE154PBDE154 11.42 0.77 11.42 0.77 -2.004 -2.004 0.130 0.130PBDE153PBDE153 9.92 0.71 9.92 0.71 -1.700 -1.700 0.119 0.119PBDE183PBDE183 2.77 0.64 2.77 0.64 -0.534 -0.534 0.105 0.105

RELATIVE IMPACTS OF gammaHCHRELATIVE IMPACTS OF gammaHCHImpact/mean(pollut.concentr.)Impact/mean(pollut.concentr.)

(How many times is the mean exceeded)(How many times is the mean exceeded)

PollutantPollutant Rel.ImpactRel.Impact PollutantPollutant Rel.ImpactRel.Impact

OCDDOCDD --0.880.88 alfaHCHalfaHCH 0.49 0.49

TCDDTCDD --0.890.89 betaHCHbetaHCH 2.27 2.27

PeCDDPeCDD --0.880.88 deltaHCHdeltaHCH 2.28 2.28

HxCDDHxCDD -0-0.21.21 HCBHCB --0.63 0.63

HpCDDHpCDD --0.680.68 PBDE28PBDE28 --2.222.22

OCDFOCDF --0.53 0.53 PBDE47PBDE47 --3.203.20

TCDFTCDF --0.750.75 PBDE100PBDE100 --2.82 2.82

PeCDFPeCDFHxCDFHxCDF

--0.570.57 -0.33-0.33

PBDE99PBDE99PBDE154PBDE154

--3.063.06-3.33-3.33

HpCDFHpCDF --0.31 0.31 PBDE153PBDE153 --2.37 2.37

PBDE183PBDE183 --0.200.20

POLLUTANT’S TOXICITY

Four methods to measure toxicity:

1. Daphnia Magna2. Vibrio Fischeri3. Desmodemus subspicatus4. Saprobita

“NATURAL” ASSUMPTIONS

A) Methods measuring the same give the same results or

B) Results of measuring the same are at least similar (correlated) C) The more pollutant’s concentration,

the more toxic effects

SIGNIFICANT CORRELATIONS WITH TOXICITIES

Correlation Cor. Coef.

Prob{0}

(Vibrio F., Desm. Subsp.) 0.524 0.022

(sumPAH, Desm. Subsp.) 0.643 0.010

(sumDDT, Daphnia Magna)

0.501 0.035

Other correlations are not significant.“Natural” assumptions A) through C) are not supported by the data.

Let us try the MD-models !

WORTHWHILE

MD-models confirm the existence of „contrary toxic effects“.

The group PCB affects the toxicity contrary to other groups of pollutants in 3 of 4 MD-models in spite of the positiveness of all correlations

(pollutant, toxicity).

SUMMARYSUMMARY

Statistically significant (mostly positive) Statistically significant (mostly positive) correlations in organic pollutants exist.correlations in organic pollutants exist.

Negative correlations exist as well.Negative correlations exist as well. The most negatively “active” is The most negatively “active” is gammaHCHgammaHCH.. Its strongest negative effects are manifested Its strongest negative effects are manifested

by the congeners of by the congeners of PBDEPBDE.. ContraryContrary toxicity impacts of pollutants toxicity impacts of pollutants exist. exist.

HYPOTHESES MUST BE TESTED !HYPOTHESES MUST BE TESTED !

OPEN PROBLEMSOPEN PROBLEMS

Are these effects Are these effects caused by somecaused by some real real chemical or physical chemical or physical rreeactions of the actions of the substances or only substances or only by by different rates of different rates of their production and pollution?their production and pollution?

Are theyAre they worth of further investigation? worth of further investigation?

EXPERIENCE:EXPERIENCE:

DATA TREATMENT MUST BE ROBUSTDATA TREATMENT MUST BE ROBUST

AND HYPOTHESES MUST BE AND HYPOTHESES MUST BE TESTED !TESTED !

FUNDINGFUNDING

European Commission Sixth Framework Program, Priority 6 (Global change and ecosystems), project 2-FUN (contract#036976)