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St. Louis, Mo 1-4 December 2009 Meri Barbafieri ISE-CNR 1 Metal phyto-extraction technology as a remediation step in the redevelopment of an Italian industrial site Ambrosini P., Patata L. Saipem/RISAMB – Fano - Italy Pedron F., Petruzzelli G., Barbafieri M. CNR - Institute for Ecosystem Studies – Pisa - Italy [email protected] 6° International Phytotechnologies Conference 2009

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St. Louis, Mo 1-4 December 2009 Meri Barbafieri ISE-CNR

1

Metal phyto-extraction technology as a remediation step in the redevelopment

of an Italian industrial site

Ambrosini P., Patata L.Saipem/RISAMB – Fano - Italy

Pedron F., Petruzzelli G., Barbafieri M.CNR - Institute for Ecosystem Studies – Pisa - Italy

[email protected]

6° International Phytotechnologies Conference 2009

St. Louis, Mo 1-4 December 2009 Meri Barbafieri ISE-CNR

2

The Brindisi areaThe industrial site is an oil refinery located in Brindisi

(southern Italy) and belongs to a multi-company.

St. Louis, Mo 1-4 December 2009 Meri Barbafieri ISE-CNR

3

Solving the problem

In the redevelopment process it was necessary to proceed with the remediation of soil moderately

contaminated mainly by hydrocarbons and metals (Hg, Pb, Cu, Zn)

Following applicability tests, on-site phytoextraction was selected as a viable technology approved by the Italian

Ministry of the Environment.

Italian legislation supports remediation technologies such as in-situ and matrix recovery

St. Louis, Mo 1-4 December 2009 Meri Barbafieri ISE-CNR

4

Remediation

The site remediation was planned in different steps and in sub-areas.

Reclamation comprehends two phases:

Phase 1 (2003 – 2008): excavation, selection, transport and sieving of the materials and subsequent deposit in the phytoremediation area

Phase 2: ( 2007- present) phyto-treatment of the selected materials (soil)

St. Louis, Mo 1-4 December 2009 Meri Barbafieri ISE-CNR

5

Phytoremediation plant

Areas of intervention

Excavation, selection, transport and sieving of the materials and subsequent deposit in the phytoremediation area

The remediation: phase 1

St. Louis, Mo 1-4 December 2009 Meri Barbafieri ISE-CNR

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The remediation: phase 2Started in 2007 and still

running: with the phyto-treatment of the selected materials (soil)

The phytoremediation plant is located inside the

industrial area It covers 15,000 m2 and is

about 0.7m high

St. Louis, Mo 1-4 December 2009 Meri Barbafieri ISE-CNR

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Some pictures

Waterproof basin to contain contaminated soils

Anti-bird intrusion net at 5m high

Irrigation system to assure the spread of water and of metals mobilizing additives

St. Louis, Mo 1-4 December 2009 Meri Barbafieri ISE-CNR

8

Some pictures

Tank for chemical additives

Water drainage system to collect leachates into a controlled tank.

St. Louis, Mo 1-4 December 2009 Meri Barbafieri ISE-CNR

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Cooperation

The process is assisted by ongoing experimental research to implement the technology

CNR - Institute for Ecosystem Studies – Pisa - Italy

Saipem/RISAMB – Fano - Italy

St. Louis, Mo 1-4 December 2009 Meri Barbafieri ISE-CNR

10

Site SpecificFeasability test

St. Louis, Mo 1-4 December 2009 Meri Barbafieri ISE-CNR

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Increased bio-accessibility of metals following addition of mobilizing agents

We screened different additives for increasing Hg mobilization; the most effective were ammonium

thiosulfate (TS) and potassium iodide (KI)

Hg contamination is of major concern with a contentof about 15 mgkg-1

St. Louis, Mo 1-4 December 2009 Meri Barbafieri ISE-CNR

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Increased metal concentration in the crop plants used

Ammonium thiosulfate was tested in microcosm to

verify its effectiveness in increasing Hg uptake by

plants

It was effective!

eg. in Poa annua Hg uptake increased 400-fold in the aerial part (140 mg kg-1) and in Brassica

increased 70-fold (100 mgkg-1)

St. Louis, Mo 1-4 December 2009 Meri Barbafieri ISE-CNR

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Test microcosm – some observationsBiomass– Hg uptake – Translocation - Phytoextraction

TS treated plants show toxic symptoms

TS treatment showed good effectiveness in increasing Hg uptake and translocation

TS increased Hg phytoextraction

St. Louis, Mo 1-4 December 2009 Meri Barbafieri ISE-CNR

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Test in scale-up - Mesocosm

Most successful protocols: plants + additive are tested on mesocosm scale

St. Louis, Mo 1-4 December 2009 Meri Barbafieri ISE-CNR

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Test in scale-up – field test

Moreover, field tests are carried out in a portion of the field subdivided into 5 plots

St. Louis, Mo 1-4 December 2009 Meri Barbafieri ISE-CNR

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Trend in decreased metal concentration in the soil under phyto-treatment.

How things are going!In the first period, the on-site phytoremediation plant showed very good results, in particular regarding:

Increased bio-accessibility of metals following addition of mobilizing agents

Increased metal concentration in the crop plants used (alfalfa, corn, sunflower, mustard plants)

St. Louis, Mo 1-4 December 2009 Meri Barbafieri ISE-CNR

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One result from field-test

4.860.142

4.50.129

4.130.261 0.0886

7.240.527 0.0853

38 36.831.5

11.3

170

38.4

16.4

51.7

103

20.6

0

20

40

60

80

100

120

140

160

180

Parcella 5mais

IPOGEA

Parcella 5mais

Epigea(foglie +

fusto)

Parcella 4mais

IPOGEA

Parcella 4mais

Epigea(foglie +

fusto)

Parcella 3girasoleIPOGEA

Parcella 3girasoleEpigea

(foglie +fusto)

Parcella 3girasoleEpigea(fiore)

Parcella 2girasoleIPOGEA

Parcella 2girasoleEpigea

(foglie +fusto)

Parcella 2girasoleEpigea(fiore)

Hg

(mg/

kg s

.s.)

Hg content in Corn and Sunflower plants before and after TS treatment.

Before treatment

After treatment

St. Louis, Mo 1-4 December 2009 Meri Barbafieri ISE-CNR

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A Field result: alfalfa

Hg content in alfalfa plants before and after TS treatment.

0.40

5

0.53

6

0.19

4

0.27

1

0.41

5

0.26

6

0.32

0.21

3

0.42

9

0.33

4

0.37

2

0.41

3

0.23

5

0.27

1

0.49

3

1.5

0.33 1.27

0.11

4

0.91

3

0.16

1

0.77

9

0.25

2

0.91

6

0.25

9

0.92

0.27 0.92

6

72.8

17.6

12.6

62.1

36.8

75.8

24.8

42.1

12.6

16.8

41.8

17.3

25.5

47.8

0

10

20

30

40

50

60

70

80

Erbamedica AB

(foglie-fusto)

Erbamedica AB

(radici)

Erbamedica CF

(foglie-fusto)

Erbamedica CF

(radici)

Erbamedica DE

(foglie-fusto)

Erbamedica DE

(radici)

Erbamedica GH

(foglie-fusto)

Erbamedica GH

(radici)

Erbamedica IN(foglie-fusto)

Erbamedica IN(radici)

Erbamedica LM

(foglie-fusto)

Erbamedica LM

(radici)

Erbamedica OP

(foglie-fusto)

Erbamedica OP

(radici)

mg/

Kg

s.s.

1° harvest not treated

Before treatment

After treatment

St. Louis, Mo 1-4 December 2009 Meri Barbafieri ISE-CNR

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Trend in decreased of mercury concentration in the soil under phyto-treatment

St. Louis, Mo 1-4 December 2009 Meri Barbafieri ISE-CNR

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Phytoremediation

The reclamation of contaminated site with low environmental impact and cost is the main objective of phyto-technologies.

Phytoremediation study implies different levels of scale test: microcosm, mesocosm and field test.

The efficiency of phytoremediation is complex and depends on the nature of contaminants, the additive if used, plant characteristics and local environmental conditions.

St. Louis, Mo 1-4 December 2009 Meri Barbafieri ISE-CNR

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Difficulties in field operation

Heterogeneous physical soil characteristics and contaminant concentrationHeterogeneous plant growthHeterogeneous treatment applicationUncertain weather conditions ?????????

So data from field operations are sometimes non-predictive

St. Louis, Mo 1-4 December 2009 Meri Barbafieri ISE-CNR

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Future implementation of the Hg - phytoextraction

Study the use of PGR to increase metal translocation by foliar application. Products currently used in flori- and horticulture could be of benefit for phytotechnology

Test crop plant (eg. corn, sunflower) at high biomass production selected for bio-energy goal

Implement additive addition in dose and timing to increase metal uptake and translocation

Study of other additives to increase metal mobilization and consequently metal phytoextraction

St. Louis, Mo 1-4 December 2009 Meri Barbafieri ISE-CNR

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Acknowledgement:

Eliana Tassi (ISE-CNR)Irene Rossellini (ISE-CNR)Giorgio Poggio (ISE-CNR)Virginia Giansoldati (ISE-CNR)Rosario Cigna (Enipower Brindisi)Gian Stefano Cecca (Saipem)

Thanks to everybody!!!

as I am very busy……