Carbon in Brownfield, Urban and Contaminated Soils

Interactions between carbon and pollutants in heavy metal contaminated urban soils in N.W. England Luke Beesley, Rafael Clemente, Marianna Bandiera & Nicholas Dickinson
School of Biological and Earth Sciences, Liverpool John Moores University, Byrom Street, Liverpool L3 3AF

Significance

Soil Science
Quantity of Carbon sequestered in brownfield soils

Land remediation
Mobility and transport of pollutants in response to soil characteristics

Effects of organic amendments on Carbon storage and fluxes

Management of soil contamination by organic amendment

What are the effects of organic amendments on carbon storage and mobility in brownfield soils? What is the fate of pollutants in brownfield soils as a response to organic amendments?

Context
Organic Matter content of typical brownfield soils

Former agricultural land As/Pb brownfield Old style landfill Disused canal
Source: Hartley (2005)

Soil Organic Matter % 5.72 7.89 9.59 26.77

Poorly managed, degraded soils Amount of carbon in brownfield soils is unknown

The addition of recycled greenwaste compost may increase carbon sequestered in brownfield soils

Addition of recycled greenwaste may influence mobility and environmental dispersal of contaminants

Experimental sites
Prescot and Enchanted Forest, Merseyside. Heavy metal contaminated urban woodland sites Sustainable vegetation established without remediation or human intervention Variations in soil physico-chemical characteristics

Cross Lane, Wirral. Created soils consisting of subsoil materials mixed with recycled greenwaste (PAS 100 compost) Mixtures of 15-65% compost (by volume) Mulch treatment 30% compost

Methods
Total Organic Carbon (TOC) in solid soil samples Water Soluble Organic Carbon (WSOC)

Total metals measured by digestion and ICP-MS/AAS Dissolved Organic Carbon (DOC) in soil porewater/leachate

In-situ Soil Respiration by open chamber respirometry

Initial findings
12

Manufactured soils compost application trialsafter 4 months

200 8.5

Total organic and Inorganic carbon

10 TC IC

180 160 140 WSOC (ppm) 120 100 80 60 40 20

8 %C

Water Soluble Organic Carbon (WSOC) and pH WSOC pH

8.3 8.1 7.9 7.7 7.5 7.3 7.1 6.9 6.7 6.5 pH

0 0% 15% 30% 45% 50% 66% 30% Mulch

0 0% 15% 30% 45% 50% 66% 30% Mulch

Volume Compost

Volume Compost

Most OC in soil with largest compost volume Most WSOC with largest compost volume pH increase with compost volume

Dissolved Organic carbon (DOC) mobilizes metals by forming strong complexes with metals in solution, whereas solid organic matter immobilizes metals Zhao et al (2007)

Prescot Urban woodland soils

TOC (%) 0 10 20 30 40 50

10

20

Selected soil physico-chemical data at 0-10cm (values in mg kg-1DW) Prescot woodland pH 4.44 OM (%) 81 TOC (%) 39.5 Cu 2184 Zn 95 Pb 881 As 45

30 Depth (cm) 40

Cu (ppm)

TOC shows non uniform decrease with depth History of aerially deposited Cu did not explain elevated TOC

50

60

70

500

1000

1500

2000

2500

Mean Total Organic Carbon and soil Cu at Prescot.

Prescot Urban woodland soils- Metals depth distribution

TOC (%) 0 0 10 20 Depth30 (cm) 40 50 60 70 0 500 1000 1500 2000 2500 5 10 15 20 25 30 35 40 45

Metals not uniformly distributed within soil profile

Pb (ppm) Zn

Pb shows decrease with depth (as Cu)

Zn and As pooling in 1030cm depth

Enchanted Forest Urban woodland soils Birch (Betula) and tall grassland established within the last 60 years Vegetation showing no signs of toxicity

Large variation in TOC, pH and metals over small spatial area

Metals 4x higher values in soil pH 6.1 As 9x higher values in soil pH 6.1

Selected physico-chemical properties of three heavy metal contaminated urban woodland soils (values in mg kg-1DW). Enchanted Forest A Enchanted Forest B pH 4.32 6.11 OM (%) 40.82 7.67 TOC (%) 31.1 13 Cu 419 1531 Zn 525 2845 Pb 9388 31914 As 104 911

Enchanted Forest Urban woodland soils-Dutch Leaching column experiment

As
150 800

Cu

r2 =2 0.905 r = 0.905

Percentage of contaminant removed by leaching after 3 weeks.

pH 4.3 Cu 1.01 3.38 0.11 0.15 Zn As Pb pH 6.1 0.15 0.27 0.09 0.01

ng ml

100

ng ml

Soil pH 4.3 Soil pH 6.1

600 -1

-1

400
2 rr2= 0.803 = 0.803

50

200

Pb
2000 1500 -1 -1 1500

Zn

ng ml

1000

ng ml

1000

r2r2 = 0.961 = 0.961

500

2 r2 = 0.857

500

Zn appears most mobile of the metals

70 80 90

0 20 30 40 50 60 70 80 90

20

30

40

50

60

DOC (mg l-1)

DOC (mg l-1)

Cu was positively correlated with DOC at soil pH 4 and pH 6 Zn and Pb removal was only correlated with DOC at higher pH

Higher pH soil retains/immobilizes metals more effectively

Conclusions & Limitations

Created soils contain less carbon than non-remediated brownfield soils

The distribution and dispersal of heavy metals and arsenic in soils are impacted by carbon storage and mobility

Comparability between created soils and non-remediated soilslack of litter input, time and soil contamination

Correlations between DOC and metals may be due only to time leached

The relationship between C and metals mobility is pH dependent Amendment may reduce metal mobility by increasing pHbut mobility may be increased by increases in DOC

References & Acknowledgements

Hartley, W. 2005. Brownfield soil Physico-Chemical data. (Pers. Comm) Zhao, L, Y, L et al, Coupled mobilization of dissolved organic matter and metals (Cu and Zn) in soil columns. Geochim. Cosmochim. Acta (2007) in press