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Identification of particulate heavy metal pollution sources in urban river sediment using scanning electron microscopy coupled with energy dispersive spectrometer (SEM-EDS) Cindy Rianti PRIADI Laboratoire des Sciences du Climat et de

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Identification of particulate heavy metal pollution sources in urban river sediment using scanning electron microscopy coupled with energy dispersive spectrometer (SEM-EDS)

Cindy Rianti PRIADI

Laboratoire des Sciences du Climat et de l’Environnement (LSCE) CEA-CNRS-UVSQ/IPSL, Gif-sur-Yvette

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www YES 13-16 May 2008

Presentation plan

  • Watershed and heavy metal
  • Urban river sediment: the Seine River case
  • Scanning Electron Microscopy
  • Results
  • Conclusion and Prospectives
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Multiple natural and anthropogenic sources of heavy metals… Cd Cu Cr Hg Pb Ni Zn As Se

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Urban metal particles

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…..Reflecting in human

  • Small amount =

useful or useless; beyond = toxic

  • Bioaccumulate
  • Form (speciation)

dependent

Air Food and water contact Air Food and water contact

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Multiple natural and anthropogenic sources…

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….In the Seine Riv

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  • 25% agricultural activities
  • 25-30% industries
  • Upper Seine: up to 30 p/km
  • Lower Seine: 250 p/km2

12% of France Metropolitan Territory, but…

QuickTime™ et un décompresseur TIFF (non compressé) sont requis pour visionner cette image.

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High metal content in SPM and Sediment

Estuary sediment Background SPM Flood deposit (Horowitz et al 1994, Grosbois et al 2006) Sediment deposit 5RNB 2003) Oise Sediment (Dessery 1982)

  • M. Meybeck et al., 2007

(- -)

  • European Water Framework Directive demands a good ecological

level for water bodies

  • Priority substances including Nickel, Plomb, Mercure, Cadmium and

urban metals including Copper, Chrome, Zinc

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Particulate binding phase

  • Iron oxyde
  • Sulfide
  • Calcite…

Precipitation Metal Metal n+ Metal n+ Source

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Common Methodology: Tessier Method

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Common Methodology: Tessier Method

Chemical analysis by ICP-AES/MS

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Direct observations

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Direct observations

Scanning Electron Microscopy coupled with Energy Dispersive Spectrometry

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A B

Depth 12-14 cm

Depth 25-30 cm 45-50 cm

Sam pling site of Seine sedim ent

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Pb (µg/g) Zn (µg/g) Cu (µg/g) Cr (µg/g) Ni (µg/g) V (µg/g)

Sediment A 12-14

188,51 572 109,33 105,62 39 133,58

Sediment B 25-30

286,75 604 156,02 91,06 32,47 14,13

Sediment B 45-50

383,61 695 232,1 95,59 34 32,31

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Zn

20 40 60 80

Fe3O4 BaSO4 SiO2 Ca

  • ther

fractions non- identified

Pourcentage

)A 12-14(38 )B 25-30 (48 )B 45-50 (50

Percentage Zn

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Zn

20 40 60 80

Fe3O4 BaSO4 SiO2 Ca

  • ther

fractions non- identified

Pourcentage

)A 12-14(38 )B 25-30 (48 )B 45-50 (50

Barite from road and automobile pollution vs Zinc from roof and gutter runoff (El Samrani et al, 2004)

Percntage Zn

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V

5 10 15 20 25 30 35 40 45

Fe3O4 Fe2TiO4 FeS2 SiO2 Ca non- identified Pourcentage

)B 25-30 (36

Calcium, SIlicon, Iron, Vanadium and Chromium compose basic oxygen furnace steel slag, partially reused for road construction (Chaurand et al., 2007)

Percentage V

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Cu

10 20 30 40 50 60 70 80

Fe3O4 BaSO4 FeS2 SiO2 Ca d'autres fractions non- identifiˇ

Pourcentage A 12-14(16) B 25-30 (20) B 45-50 <50 µm (42) B 45-50 <50 µm FM (40)

?

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Sulfurized copper

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Pb

10 20 30 40 50 60 70

Fe3O4 BaSO4 FeS2 SiO2 Ca non- identified

pourcentage

)A 12-14(32 )B 25-30 (22 )B 45-50 (12

Sulfide as anImportant binding phase in reducing

  • condition. A higher

percentage of association in deeper sediment as forms are crystallized and well detected by the MEB

Percentage Pb

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Ni (non spinelle)

10 20 30 40 50 60 70 80 90 100

FeS2 Ca non-identified

pourcentage

)A 12-14(28 )B 25-30 (27

Nature of nickel to be associated with iron sulfide in fresh water lake sediment (Canavan et al.2007) and combined sewer overflow (El Samrani et al.2004)

Percentage Ni

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Conclusion:

  • Microscopic analysis as a powerful tool in

analyzing heavy metal association with sediment

  • Urban surface runoff = Zn, V
  • Preferably Sulfide associated = Pb, Ni

Perspective: Focus on particles controlling mobility and dissolution towards the dissolved fraction Calcite (Bonte et al 2002, Pepe et al., 2008) Iron oxyde (Elbaz-Poulichet et al., 2006)

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Thank you!