Emission and fate of lead in the European environment, 1958-1995

Hans von StorchHelmholtz Zentrum Geesthacht

4. December 2012 - Case Studies in Environmental Chemistry, Kemisk Institut, København Universitet

Hans von Storch• Klimaforsker• Speciale: kystklima, dvs storme, stormfloder, bølger, Vesterhavet, Østersøen, Nordatlanten• Kooperation også med socialvidenskabsfolk• Direktør af Institut for Kystforskning ved Helmholtz-Zentrum Geesthacht• Medlem af KlimaCampus „CliSAP“ Hamburg

Jeg vil genere høre hvad I sznes om aktuelle spørgsmål vedrørende klima forsckning of klimapolitik

1. Hver får sådan en afstemmingsdims2. I skal ikke tænde dimsen.3. Når I ænsker at afstemme, bare trykker den apssende

nummer. Hvis du ikke ønsker at deltage, lad være.4. Når afstemmningen er færdige, vil resultatet vises på

skærmen5. Det er en anonym afstellning. Det er ikke mulitgt at

finde ud hvem har afstemt hvordan – vi ved ikke hvem har brugt hvilket dims.

Anonymt survey med Turning Technology

Inforstået med Undersøgelsen?

1. Jo2. Nej3. Ligeglad.

0% 0%0%

Menneskeskabt Klimaforandringer?

1. Jeg er overbevist om, at vi i øjeblikket oplever primært menneskeskabte klimaforandringer.

2. Jeg har alvorlige tvivl om, at vi har at gøre med primært menneskeskabte klimaforandringer.

3. Ingen udtalelse.

0% 0%0%

Energipolitik1. Jeg støtter energipolitikken som

sænker grug af olie og kul med mindst x % indtil 2030 (Hedegaard planen)

2. Jeg finde sødan en plan umodne og forbundet med for høje omkostninger.

3. Jeg sznes ikke, at den videnskaelige vides kan legitimere sådan en energipolitik.

4. Jeg foretrækker en anden klimapolitik, f.x., tilpassning, kortvarig justering efter behov eller geoengineering

5. Ingen udtalelse

0% 0% 0%0%0%

Extreme vejrhændelser1. Jeg opfatter i det sidste årti enf forstærkning

af regionale stormbegivenheder.2. Vores storme har altid været farligt, men en

systematisk ændring i retning af mere eller kraftigere storme kan jeg ikke afgøre.

3. Ingen udltalese.

0% 0%0%

Videnskabens rolle1. Videnskaben bør gøre politiske anbefalinger

til at håndtere problemer, hvis første tegn er synlige, at der er et alvorligt problem.

2. Videnskaben bør gøre politiske anbefalinger til at håndtere problemer, hvis en konsensus er lavet i videnskaben om emnet.

3. Videnskaben bør ikke være nogen anbefalinger, men kun beskrive problemet og mulige løsningsstrategier.

4. Ingen udtalelse 0% 0%0%0%

Om bly I miliøetA. Det var et problem.B. Der var og stadigvæk er et

problem.C. Ved ikke.

0% 0%0%

Kemisk Institut, København, 29.April 2004

Miljøbelastning med anthropogene stoffer

Eksempel „bly“, emissioner og deponering i Europa, 1958- 1995

Hans von StorchInstitut für Küstenforschung, GKSS Forschungszentrum

Motivation1. Prototypical example of a reconstructing of flow

and deposition of anthropogenic matter on the regional scale (50 - 1000 km).

2. Lead is chosen because the substance is during its aerial transport almost inert – that is, the problem is technically less challenging than with, say, mercury or POPs.

3. Lead is also chosen because of the highly variable emissions, with an unabated increase until about 1970 and several political regulations in the 1970s and 1980s, which ended with the out-phasing of lead in gasoline.

Lead emission

Total gasoline sale

Consumption of gasoline in Germany (mio.litres) and associated lead emissions (tons)

Political regulation in 1971, 1975 and 1985.

Overview• General analysis of lead pollution• Accumulation in eco-systems and humans • Reconstructed emissions• Simulation of transport and deposition of emitted lead, 1958-1997• Conclusions

ANTHROPOGENIC EMISSIONS OF LEADIN EUROPE 1955–1990

Petersen (1998)

Sources of lead emissions, 1955-1995

Costa-Cabral, 2001

General overview of lead pollution

Hagner, C., 2000: European Regulations for Reducing Lead Emissions from Automobiles - Did they have an Economic Impact on the German Gasoline and Automobile Markets? Regional Environmental Change 1: 135-152

Source: Umweltbundesamt 2001

Atmospheric Lead Concentration in German Urban and Rural Areas 1970-1989

Data source: Pb – monitoring of the German Environmental Ministry (1998) and Landesamt Nordrhein –Westfalen(1998).

Atmospheric Lead Concentrations in German Conurbation and Rural Areas 1986 –1995

Accumulation in eco-systems and man

Hagner, C., 2000: Regional and long-term patterns of lead concentrations influvial, marine and terrestrial systems and humans in Europe. Water, Soil and Air Pollution, in press.

Data source: Heinzow 1998

Blood-lead levels (mg/l) from various studies in Germany, 1979–1997

Data source: Umweltprobenbank 1999b

Lead concentrations (mg/g) in spruce (Picea abies) sprouts and poplar (Populus nigra) leaves in urban areas in Saarland, 1985-1996

Data source: Umweltprobenbank, Research Center Karlsruhe, 1999

Lead concentration in annual beech leaves in German forest areas 1989-1997

Lead concentration (mg/kg) in Blue Mussels (Mytilus Edulis) in the North Sea, 1982-1997

Data source: Ministry of Ecology of Niedersachsen 1999

* Sample stations: Bantsbalje ( 53°34’/ 7°01’); Borkum ( 53°35.4’/ 6°47.84’); Cuxhaven Leitdamm ( 53°53.05’/ 8°41.03’); Elmshörn Rinne ( 53°29.05’/ 6°54.00’);

Mellumbalje ( 53°41.09’/ 8 °08.08’)

Lead concentrations in muscles and livers of Breams.

muscles

livers

Space/time details of Emissions

Pacyna, J.M., and E.G. Pacyna, 2000: Atmospheric emissions of anthropogenic lead in Europe: Improvements, updates, historical data and projections. GKSS report 2000/31.

European Gasoline Lead Content RegulationsInitial Regulations

Germany

– 1971, the ”German Environmental Programm” was passed

Increasing automobile emissions were considered to be a latent danger for humans, animals and plants

– 1972, legal max. lead content of gasoline: 0.4 g Pb/l

– 1976, legal max. lead content of gasoline: 0.15 g Pb/l

European Union

– 1978, the first EU-regulation of lead in gasoline was adopted:

– Gasoline with more than 0.4 g Pb/l was banned on EU-markets

Further Regulations

Germany

– 1984, unleaded gasoline was introduced on the German market, complemented by tax incentives

– Justified by widespread damage to forests due to NOx, CO and CxHy

– 1988, low-emission cars become obligatory

European Union

– 1989, obligation to offer super-unleaded gasoline in all member states

– lead in gasoline should be reduced to max. 0.15 g Pb/l

Data source: German Environmental Ministry ,1998

Annual Lead Emissions in Different EU–Nations 1980 –1996

Emissions

1955 1965

Emissions

1975 1985

Emissions

1990 1995

Simulation of Transport and Deposition of Emitted Lead, 1958-1995

Costa-Cabral, M. C., TUBES: An exact solution to advective transport of trace species in a two-dimensional discretized flow field using flow tubes, submitted

Atmospheric concentration

deposition

Calculated depositions

1995

Validation

Mean annual Pb air concentration at Schauinsland, Germany.

1970 1975 1980 1985 1990 1995 2000

0

50

100

150

200

250lead concentration in the air

waldhof obswaldhof simwesterland obswesterland sim

Analysis

model estimate

Chemical / ecological dimension

Overland transport

Schulte-Rentrop, A., M.Costa-Cabral, R. Vink, 2005: Modelling the overland transport of lead deposited from the atmosphere in the elbe catchment over four decades (1958-1995), Water , Air and Soil Pollution, Vol. 160, 1-4, pp.271-291

Estimated deposition of lead in the Elbe catchment

Flux of lead into the Elbe, 1958-1997

total

erosion runoff

Direct deposition

Estimated lead concentration in the soil

Change from 1958-1995

Lead concentration in the Elbe water

Conclusions1. Reconstruction of regional environmental change is

doable with dynamical regional environmental models.

2. The environmental impact of past political and economic evolutions may be assessed quantitatively by a retrospective analysis. Scenarios of environmental impact of possible future socio-economic developments are possible to be constructed.

3. Lead reduction in gasoline was successful in reducing the presence of lead in the atmosphere, in terrestrial ecosystems and in men.

4. In aquatic ecosystems the increase of concentrations has been halted at a level well above the natural level. (How long is the residence time in sediment?)

Kemisk Institut, København, 29.April 2004

Miljøbelastning med anthropogene stoffer

Eksempel „bly“:

konsekvenser, iagttagelser og helbred

Hans von StorchInstitut für Küstenforschung, GKSS Forschungszentrum

1. Enhanced levels of lead in human blood- detailed study for Germany- rest of the world

2. Attention cycles in Germany, France and Great Britain (Kolb)

3. Short discussion of economic implications of lead regulations (Hagner)

Enhanced levels of lead in human blood

The case of Germany

Questions

• Is it doable to estimate lead concentrations in the atmosphere and in human blood with a simple regression-type model?

• What were the levels of lead concentration in human blood in Germany in the 196s and 1970s (a time for which no measurements are available)?

• How can we design scenarios of lead levels in human blood conditional upon alternative political regulations?

Annual gasoline sales and lead emissions in Germany. Volume of gasoline sold (millions of liters per year; solid) and of leaded gas (after 1985; red crosses); amount of lead added to gasoline (in tons; yellow).

We have two data sets with time series of lead concentrations in human blood (LHB), beginning in the late 1970s. No reliable earlier data about lead in the human blood in Germany is available.

Data set “G” (“Germany”; Heinzow, 1998) is unsystematically collected, with samples at different locations, different methods, different age and gender groups.

The second data set “M” (“Münster”; Human-Probenbank Münster 2002;) is better, as it is derived from a controlled sampling strategy – for groups of students living in the industrial town of Münster (51.5oN, 7.4oE) in Nordrhine-Westfalia, close to the Ruhr area with heavy industry and intensive road traffic.

1980 1983 1986 1989 1992 1995 1998 2001

0

40

80

120

mg/l

lead in human bloodaccording to G and M data sets

G childrenG adultsM

Data set G (“Heinzow”) and M (“Münster”) with lead concentration in human blood (in mg/l). The G data are split into adults and children.

2 0 4 0 6 0 8 0 1 0 0 1 2 0M sam ples (mg/l)

2 0

4 0

6 0

8 0

1 0 0

1 2 0G

sam

ples

(mg/

l)

0 5 10 15 20 25

0

5

10

15

20

25

Similarity of lead concentration in human blood sampled in the same year.Based on G and M data.

0 0.04 0.08 0.12 0.16lead concentration in gasoline (g/l)

0

40

80

120

lead

con

cent

ratio

n in

blo

od (m

g/l)

lead concentrationin gas (g/l) and in human blood (mg/l)

MG adults

Lead concentration in gasoline and in blood in Germany. Heinzow (G) and Münster (M) data sets. The lead concentration in 1985 to 1995 is an "effective" concentration for West Germany, by proportionally weighting the concentrations in of leaded (0.015 g/l) and unleaded (0.013 g/l) gasoline

Data set G: There is a linear relationship between the mean concentration and the dispersion of the sample distributions.

standard deviation = 0.43 mean – 3.9, (1)95% quantile = 1.63 mean + 10.9 (2)

0 40 80 120 160m e a n

0

40

80

120

stan

dard

dev

iatio

n an

d 95

%ile

Scatter diagrams of sample means (horizontal axis) and sample standard deviations

(dots, red) and 95% quantiles (diamonds, green) in lead concentrations in human

blood in data set G. In mg/l.

Data set G: According to (1), if the mean blood concentration is 150 mg/l, then on average one sixth of the population will have more than 200 mg/l or less than 100mg/l. This rough estimate is based on the assumption of a normal distribution, which is not really valid as the distribution of lead levels is skewed, with a long tail towards large values

. Thus, it is more appropriate to use percentiles:

If the mean concentration is 150mg/l, then according to (2)

5% of the population may have a concentration of

more than 250 mg/l.0 100 200

0

200

400

600

800frequency distribution of LH B (mg/l)

in adults in 1991/1992 in the M dats set

Critical Values of Lead Concentration in Human Blood

Category 1: unobstrusive valueCategory 2: no health risks are expected but monitoring is recommendedCategory 3: health hazards are possible, clarification and mitigation is needed

category value (μg//l)

children (6-14 years)women* (25-45 years)

123

≤ 100100 – 150

> 150

other adults 123

≤150150 – 250

> 250

Source: Krause et al. 1996

Defined by the `Human-Biomonitoring-Kommission´ in Germany

* women in child-bearing age

In case of data set M, the 90% and 95% quantiles are given. Also in this case, a clear linear relationship between the mean and the quantiles is emerging with

90% quantile = 1.46 mean – 2.2 (3)95% quantile = 1.75 mean – 4.6. (4)

According to (3) and (4), a mean concentration of 150mg/l is associated with 5% (10%) of the population having more than 258 mg/l (217 mg/l) lead in their blood.

0 20 40 60 80 100

0

40

80

120

160 Sam ple statisticsmean vs. 90% quantilemean vs. 95% quantile

Scatter diagrams of sample means (horizontal axis) and sample 95%

(diamonds) and 90% (dots) quantiles (vertical axis) in lead concentrations in human blood in data set M. In mg/l.

A simple dynamical relationship between three variables, namely the emission of lead LEt in an area AE in the year t, the atmospheric concentration LCt in an area AC in the year t and the mean concentration of lead in human blood LHBt in the year t in the area AC.

LCt+1 = LCt + LEt+1 (5)LHBt+1 = LHBt + LCt+1 + (6)

Equation (6) is equivalent to(LHBt+1 - ) = (LHBt - ) + LCt+1 (7)

with = /(1-). Formulation (7) describes the dynamics of “anomalies” LHBt- relative to a “normal” state towards which the system converges as soon as the forcing LCt ceases if <1. For 0 < <1 the air concentration approaches asymptotically with a time scale of 1/(1-) if LCt=0.

1955 1960 1965 1970 1975 1980 1985 1990 1995 2000

0

2000

4000

6000

8000

10000

12000estimates of lead emissionrelated to use in gasoline (g/l)

MW V estimatePacyna estim ate

Estimates of emitted lead in Germany in tons/year.Dots: Linearly interpolated estimates by Pacyna and Pacyna (2000).Crosses: Estimates based on volume of gasoline sold in West Germany, according to MWV (1998, 2002)

1960 1970 1980 1990

-200

0

200

400

600B est guess of emissions in A E Muenster case

Pacyna linearly interpolatedbest guess according to (8)difference

Best guess of lead emissions in the 6-grid box AE surrounding Münster in tons/year. The times with an estimate from Pacyna is given by a big dot. The blue time series is used as input in the reconstruction 1955-1995 of lead concentrations in the air (5) and in the blood (7).

Equation 5/6LCt+1 = α LCt + β LEt+1

LC = lead concentration in the atmosphereLE = total lead emissionLHB = lead concentration in human blood

LHBt+1 = γ LBHt + δ LCt+1 + ε

1960 1970 1980 1990

0

200

400

600

modelling lead concentrationin air using (5)

6 cell AElinearly interpolated LCannual series LC

Lead concentration LCt in the air, in ng/m3, in the 50 50 km2 grid cell containing the

town of Münster as simulated in the reconstruction, and as

estimated using the linear model (5) (red) Münster

emissions LEt.LCt+1 = LCt + LEt+1 (5)

Fit of equation (7) and test of equation (4) for data set M.. The upper two curves refer to the 95%-iles, and the lower two to the means. The estimated mean curve is derived by using simulated air concentrations in Münster and the 1981 observed blood level as initial value; the curve for the estimated 95%-iles is obtained by using the estimated means and applying formula (4).

(LHBt+1 - ) = (LHBt - ) + LCt+1 (7)95% quantile = 1.75 mean – 4.6. (4)

1955 1960 1965 1970 1975 1980 1985 1990 1995

0

100

200

300

400lea

d co

ncen

tratio

n in

blo

od (m

g/l)

means

90%-iles

95%-iles

Estimated mean, 90%ile and 95%ile lead concentrations in human blood in Münster, according to (6/7) and (3/4 (red solid lines, M). Additionally the mean level estimated with the Germany model is given as dotted blue curve (G). A level of more than 150 mg/l are considered in Germany as potentially harmful for children and women in child-bearing age (HBM 3). For other adults the limit for serious concern is set to 250 mg/l.

Three scenarios of reduction of lead used as anti-knock in gasoline in Germany. The big black symbols describe the actual concentrations.

1950 1960 1970 1980 1990 2000

0

100

200

300

400lea

d con

cent

ratio

n in b

lood,

mg/l

lead concentrations in human b loodadults in Münster

scenario 1: m eansscenario 1: 90% ilesscenario 1: 95% ilesscenario 2: 90% ilesscenario 3: 90% iles

Scenarios for mean lead concentrations (mg/l) in human blood, as derived by the Münster model (M, red, continuous) and for the Germany model (G, blue, dashed). Scenario 1 describes an evolution without regulation (i.e., ongoing use of 0.6 g/l lead in gasoline in Germany, upper curves). In scenario 2 no unleaded gasoline has been introduced in Germany in 1985 (middle curves), and in scenario 3, regulation was instituted in Germany already in 1961 (lower curves). The reconstructed lead levels in blood are also given as open (Germany model) and full circles (Münster model).

Conclusions

• It is possible to reconstruct atmospheric lead concentrations and blood lead levels using a simple regression model

• It is possible to estimate lead concentrations in human blood using only lead emissions

• Reducing the lead content in gasoline was a successful environmental policy to limit human health risks

Rest of the world

USA

After Kitman, Nation 270, March 20, 2000

May 8, 2001

New Warnings on Lead and ChildrenBy ERIC NAGOURNEYnew study raises questions about whether the current measure used to define lead poisoning is stringent enough.

Lead poisoning has been redefined over the years, as doctors have decided that smaller and smaller amounts are acceptable. It is now considered to occur at 10 micrograms of lead per deciliter of blood.

But researchers told a recent gathering of the Pediatric Academic Societies of evidence that even at levels lower than that, lead in the bloodstream appears dangerous.

The primary researcher, Dr. Bruce Lanphear of the Children's Hospital Medical Center of Cincinnati, said that in the children he and his colleagues had studied, I.Q. declined in those with less than 10 micrograms of lead per deciliter of blood. The findings, he said, suggest that millions more children in the United States than previously suspected may be at risk.

"This is clearly a major public health crisis, and there really is too much complacency about this as a public health issue," he said.

The researchers studied 276 children born in five hospitals in Rochester, N.Y., and then kept track of them for five years, measuring their lead levels and then their I.Q.'s at age 5.

The researchers reported finding an inverse relationship between I.Q. and lead levels. Among all the children, they said, there was an average 5.5 percent reduction in I.Q. for every 10-microgram increase in lead.

Lead Use in Gasoline in 1996

Country Western Europe

Lead Content in Gasoline (g/l)

Market Share of Leaded Gasoline (%)

Austria 0 0 (since 1993)

Belgium 0.013 26

Denmark 0 0

Finland 0 0

France 0.013 38

Germany 0.013 3

Greece 0.4 (0.15 in Athens) 67 (since 1995)

Iceland 0.013 15

Ireland 0.013 35

Italy 0.013 56

Luxembourg 0.013 18

Netherlands 0.013 14

Norway 0.013 2

Portugal 0.4 61

Spain 0.4 77

Sweden 0 0 (since 1994)

Switzerland 0.013 13

Turkey 0.4 82

United Kingdom 0.013 33

Country Central and Eastern Europe

Lead Content in Gasoline (g/l)

Market Share of Leaded Gasoline (%)

Bulgaria 0.15 95

Croatia 0.6 70

Czech Republic 0.15 45

Hungary 0.15 36

Moldova 0.4 100

Poland 0.15 30

Romania 0.6 94

Russian Federation 0.6 50

Slovak Republic 0 0 (since 1995)

Source: modified from World Bank 1997

Thomas and Kwong, 2001

Source: World Bank (1997), Heinzow et al. (1998)

Blood Lead Levels in Different Cities in 1980s and 1990s

US- scientists expect health dangers for children above a blood lead level of 100mg/l.German experts are convinced there can be health dangers above 150mgPb/l.

bloo

d le

ad le

vel (

mg/l)

years of sampling