Organic compounds in biochar: strong binding and limited bioavailability

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1 Organic compounds in biochar: strong binding and limited bioavailability Gerard Cornelissen Norwegian Geotechnical Institute (NGI), Oslo, Norway Norwegian University of Life Sciences (NMBU), Ås, Norway Stockholm University, Sweden

2 Black Carbon including biochar Biomass Fossil fuel Incomplete combustion Black Carbon (soot, charcoal) pollutant source pollutant sink ph and GHG effect Health risk Stronger binding (soil) Soil improvement (biochar)

3 Janus face? Not really Pollutant sink Pollutant source

4 Part I PAHs in biochar: a perceived problem?

5 Polycyclic aromatic hydrocarbons 90% of total! naphthalene, C 10 H 8 phenantrene, C 14 H 10 most toxic pyrene, C 16 H 10 benzo(a)pyrene, C 20 H 12

6 PAH contents from 0.05 to 100 mg/kg Acceptable levels 1 to 6 mg/kg Bucheli, T.D Contribution to Biochar for Environmental Management, 2 nd Edition, (Lehmann, Ed.), chapter 22.

7 Contaminant bioavailability Contaminants on soil particles Contaminants in dissolved organic matter Freely dissolved in pore water Organisms

8 Porewater concentrations better predictors of toxicity than total concentrations! Hawthorne et al, ETC 2007 Toxicity to Hyalella azteca

9 Strong binding to BC (Black Carbon- BioChar) WATER slow desorption rapid desorption Amorphous organic humic matter OC soot BC slow biodegradation rapid biodegradation low uptake high uptake MICROBES ORGANISMS Cornelissen Gustafsson Bucheli Jonker Koelmans Van Noort, Environ. Sci. Technol. 2005,

10 Oslo Harbour total concentrations PCB µg/kg

11 Oslo Harbour porewater concentrations PCB µg/kg PCB ng/l

12 Why are risk limits often still based on total contents? Impossible to measure porewater concentrations in 1980s Soil quality criteria derived from aquatic tox tests! Nowadays easy to measure free concentrations and compare to water quality criteria Let s not make the same mistake as soil and sediment regulators.

13 In situ PAHs in harbor sediments containing soot and charcoal: Binding can be 100 times stronger than for organic matter! log KOC (L/kg) Stockholm Koc humic matter Oslo Bergen Tromsø Drammen log K OW Cornelissen Breedveld Kalaitzidis Christanis Oen, Environ. Sci. Technol. 2006, 40,

14 PAH-contaminated harbor sediments with BC: Stronger binding less uptake in organisms binding Sediment, no BC Oslo sediment Bergen sediment Tromsø sediment uptake uptake Sorption coefficient BSAF Nereis worm BSAF Hinia snail Cornelissen et al, Environ Toxicol Chem, 2006; Environ Sci Technol, 2006

15 Early evidence: charcoal sorbs PAHs x stronger than soil organic matter! K = d C C SOLID WATER Jonker, Michiel TO, and Albert A. Koelmans. "Sorption of polycyclic aromatic hydrocarbons and polychlorinated biphenyls to soot and soot-like materials in the aqueous environment: mechanistic considerations." Environmental Science & Technology (2002):

16 Literature overview biochar sorption (n=507) Soil organic matter Soil with 5% organic matter Hale, S.; Arp, H.P.H.; Kupryianchyk, D.; Cornelissen, G. A synthesis of parameters related to the sorption of organic compounds to charcoal. Chemosphere 2015.

17 Higher biochar formation temperature higher surface area stronger binding to 800 C Hale, S.; Arp, H.P.H.; Kupryianchyk, D.; Cornelissen, G. A synthesis of parameters related to the sorption of organic compounds to charcoal. Chemosphere 2015.

18 Total PAH concentrations in 60 biochars Biochars: Max Tolerable Risk soil (95% species protected): Digested dairy manure Food waste Paper mill waste Corn stover Rubberwood saw dust µg/g 8 µg/g Materials produced in the field Hot toluene extraction Hilber, I., Blum, F., Leifeld, J., Schmidt, H. P., & Bucheli, T. D. (2012). Quantitative determination of PAHs in biochar: a prerequisite to ensure its quality and safe application. Journal of agricultural and food chemistry, 60(12), Hale, S. E.; Lehmann, J.; Rutherford, D.; Zimmerman, A. R.; Bachmann, R. T.; Shitumbanuma, V.; O'Toole, A.; Sundqvist, K. L.; Arp, H. P. H.; Cornelissen, G., Quantifying the Total and Bioavailable Polycyclic Aromatic Hydrocarbons and Dioxins in Biochars. Environ. Sci. Technol

19 Total PAH concentrations in 60 biochars Biochars: Biochars: Max Tolerable Risk soil (95% species protected): Max Tolerable Risk soil (95% species protected): Digested dairy manure Food waste Paper mill waste Corn stover Rubberwood saw dust µg/g µg/g 8 µg/g 8 µg/g Materials produced in the field Hot toluene extraction Hilber, I., Blum, F., Leifeld, J., Schmidt, H. P., & Bucheli, T. D. (2012). Quantitative determination of PAHs in biochar: a prerequisite to ensure its quality and safe application. Journal of agricultural and food chemistry, 60(12), Hale, S. E.; Lehmann, J.; Rutherford, D.; Zimmerman, A. R.; Bachmann, R. T.; Shitumbanuma, V.; O'Toole, A.; Sundqvist, K. L.; Arp, H. P. H.; Cornelissen, G., Quantifying the Total and Bioavailable Polycyclic Aromatic Hydrocarbons and Dioxins in Biochars. Environ. Sci. Technol

20 Bioavailable concentration of PAHs in biochars Pure Biochars: Max Tolerable Risk water: ng/l 500 ng/l 12.5 sec HP flash char: 162 ng/l Decreased as pyrolysis time NORGES GEOTEKNISKE INSTITUTT NGI.NO

21 Bioavailable «leachable» PAH contents (max tolerable risk 500 ng/l) Sample number Sample Temperature of production Prepared by Replicates Concentration available PAHs (ng/l) 1 Wheat straw 550 UKBC Wheat straw 700 UKBC Switch grass 400 DA Switch grass 550 DA Pine chip 400 DA Pine chip 550 DA Eucalyptus wood 400 Sydney Eucalyptus wood 550 Sydney Poultry litter 550 NSW Digestate biochar 700 Germany Municipal greenwaste 550 NSW Rice husk 550 UKBC Rice husk 700 UKBC Miscanthus straw 550 UKBC Miscanthus straw 700 UKBC Mixed softwood 550 UKBC Mixed softwood 700 UKBC Greenhouse waste 550 Sydney Durian shell 400 BKK Rice straw Chestnut wood «Australian» ring trial biochars

22 PAHs in 21 ring trial biochars: 400 times more strongly bound than in «average» soil log K OC and log K biochar (L/kg) Biochars Organic matter «Average» soil 5% OC log K OW

23 Total dioxins in biochar Biochar Dioxin concentration (pg/g) Food waste 400 C 92 Food waste 600 C 84 Manure 600 C 86 Wood 900 C 92 Wod 500 C 86 MTR soil (95% protection) 250 Bioavailable concentrations: all below detection Hale, S. E.; Lehmann, J.; Rutherford, D.; Zimmerman, A. R.; Bachmann, R. T.; Shitumbanuma, V.; O'Toole, A.; Sundqvist, K. L.; Arp, H. P. H.; Cornelissen, G., Quantifying the Total and Bioavailable Polycyclic Aromatic Hydrocarbons and Dioxins in Biochars. Environ. Sci. Technol

24 So bioavailability is low.. How about bioaccessibility?

25 Only low PAH amounts released from biochar Even if you pull hard (with infinite sink sorbents) = PAH remaining after release to water Hilber et al., Setac Barcelona, 2015: Assessing the exposure of PAHs in biochars and biochar mixtures Mayer et al., ES&T, 2011: A contaminant trap as a tool for isolating and measuring the desorption resistant fraction of soil pollutants

26 Pulling hard with supercritical fluid extraction releases very little PAH > 1000 y Jonker, M. T., Hawthorne, S. B., & Koelmans, A. A. (2005). Extremely slowly desorbing polycyclic aromatic hydrocarbons from soot and soot-like materials: evidence by supercritical fluid extraction. Environmental science & technology, 39(20),

27 Strong sorption of monoterpenes (C 10 H 16 ) by biochar: Influence on C and N cycles? Lignite coke Coal Biochar graphite Soil Peat 5% biochar: α-pinene and limonene bioavailability reduced by factor (Nitrification stimulated?) Hale, S.E.; Endo, S.; Arp, H.P.H.; Zimmerman, A.R.; Cornelissen, G. Sorption of the monoterpenes α-pinene and limonene to soil and carbonaceous geosorbents including biochar. Chemosphere 2015, 119,

28 Part II Biochar for soil and sediment remediation

29 The concept of active sorbent amendment (Activated) Biochar particle Sediment organic matter Transfer of pollutants to biochar Hale, S.; Cornelissen, G.; Werner, D Contribution to Biochar for Environmental Management, 2 nd Edition, (Lehmann, Ed.), chapter 23.

30 Native BC, biochar and activated carbon if native BC binds too strongly, biochar will have no effect! Soils and sediments contain native, «environmental» BC at 5-10% of organic carbon (0.1-1 % of total mass) Biochar can be added on purpose to bind contaminants Biochar can be activated to get extra strong binding Activated Carbon (AC)can be made from biomass/biochar or anthracite coal

31 Effect of strong binding to biochar on pollutant risk Binding stronger Freely dissolved porewater concentrations lower Uptake in organisms lower Actual risk lower

32 Contaminant bioavailability Contaminants on soil particles Contaminants in dissolved organic matter Freely dissolved in pore water Organisms

33 Contaminant bioavailability Contaminants on soil particles + BIOCHAR Contaminants in dissolved organic matter Freely dissolved in pore water Organisms

34 Biochar: much stronger pesticide binding than soil (diuron) Biochar Soil Yang, Yaning, and Guangyao Sheng. "Enhanced pesticide sorption by soils containing particulate matter from crop residue burns." Environmental science & technology (2003):

35 Freely dissolved sum of 13 PAHs content (ng/l) Activated carbon better than biochar in reducing PAH risk in sewage sludge Risk A 0% 0.5% 2% 5% 10% Activated carbon dose (%) BP2 Activated coal CP1 Activated biochar Risk B 0% 0.5% 2% 5% 10% Biochar dose (%) MSB Corn BC PMW Paper Mill waste BC Oleszczuk, P.; Hale, S.; Lehmann, J.; Cornelissen, G. Bioresour. Technol. 2012, 111,

36 Some biochars sorb (almost) as well as AC Biochar type Phenanthrene Log K D at 1 µg/l PCB-52 Non-activated Pinewood 700 C Activated Switchgrass 700 C Coconut (commercial) Wood 600 C (self-activated) POM passive sampler Kupryianchyk Hale Rumpel Schmidt Rutherford Zimmerman Knicker Harvey Cornelissen. Sorption of hydrophobic organic compounds to a diverse suite of carbonaceous materials with emphasis on biochar. Chemosphere 2015.

37 Biochar characteristics and sorption Recalcitrance compared to graphite Kupryianchyk Hale Rumpel Schmidt Rutherford Zimmerman Knicker Harvey Cornelissen. Sorption of hydrophobic organic compounds to a diverse suite of carbonaceous materials with emphasis on biochar. Chemosphere 2015.

38 Sulfamethazine sorption to biochar: much weaker in presence of soil Factor 500! Pure BC BC + soil TeixidóM, Hurtado C, Pignatello JJ, Beltrán JL, Granados M, Peccia J Predicting Contaminant Adsorption in Black Carbon (Biochar)-Amended Soil for the Veterinary Antimicrobial Sulfamethazine. Environ Sci Technol 47:

39 Pore blockage by natural organic matter (NOM) Oen A.M.P., B. Beckingham U. Ghosh, M.C. Elmquist Kruså, R.G. Luthy, T. Hartnik, T. Henriksen, G. Cornelissen, Sorption of Organic Compounds to Fresh and Field-Aged Activated Carbons in Soils and Sediments. Environ. Sci Technol 2012, 46,

40 Less severe effect of soil on sorption of pyrene to biochar (factor 1-10) Material Log K D at 1 ng L -1 Measured BC+soil mixture Predicted BC+soil mixture Biochar+soil 4.95 ± Hale SE, Hanley K, Lehmann J, Zimmerman A, Cornelissen G Effects of Chemical, Biological, and Physical Aging As Well As Soil Addition on the Sorption of Pyrene to Activated Carbon and Biochar. Environ Sci Technol 45:

41 Slow mass transfer under unmixed conditions (PCBs) Werner D, Ghosh U, Luthy RG Modeling polychlorinated biphenyl mass transfer after amendment of contaminated sediment with activated carbon. Environ Sci Technol 40:

42 Sorption of perfluorated substances to biochar: a solution for a large-scale problem? K D = 1000 to L/kg Kupryianchyk Hale Breedveld Cornelissen. Treatment of sites contaminated with perfluorinated compounds using biochar amendment. Chemosphere, 2015.

43 PFC-contaminated airport soils: AC works, biochar does not 4% AC No sorbent & 4% biochar Reason is pore clogging by organic matter Kupryianchyk Hale Breedveld Cornelissen. Treatment of sites contaminated with perfluorinated compounds using biochar amendment. Chemosphere, 2015.

44 Overall picture of biochar and activated biochar as pollution immobilizers Process Sorption strength Pore blockage by organic matter Incomplete mass transfer Quantitative effect x stronger than humic OC Factor weaker Factor 1-10 weaker Strong sorption to sediment BC Factor weaker Overall: sorption to biochar can range from weaker than soil sorption to x stronger than soil sorption! Hale, S.; Cornelissen, G.; Werner, D Contribution to Biochar for Environmental Management, 2 nd Edition, (Lehmann, Ed.), chapter 23.

45 Activated Biochar amendment in soil, field study, Drammen, Norway bentonit foil PAH contaminated soil (urban soil) Mixing in 2% Activated Biochar Plots: Reference plot Powdered AC (0.02 mm) Granulated AC ( mm) Concrete element clay soil (and AC ) asphalt D rainage pipe Concrete element

46 Leaching from soil after 1 year with activated biochar C water (ng/l) Untreated Granular AC Powdered AC 60-90% reduction phenanthrene anthracene fluoranthene pyrene Hale, S. E.; Elmquist, M.; Brändli, R.; Hartnik, T.; Jakob, L.; Henriksen, T.; Werner, D.; Cornelissen, G., Activated carbon amendment to sequester PAHs in contaminated soil: A lysimeter field trial. Chemosphere 2012, 87 (2),

47 Reduced bioavailability to plants and worms Jakob L., T. Hartnik, T. Henriksen, M. Elmquist, R. Brändli, S.E. Hale and G. Cornelissen, (2012) Activated carbon amendment to a PAH-pollutedsoil: Effects on earthworm and plant growth and bioaccumulation, Chemosphere 2012, 88,

48 Avoidance test E. Fetida: biochar favoured over other amendment materials 20 worms were added and allowed to move between the two sides Soil without amendment (all amendments tested against each other) Soil with amendment (all amendments tested against each other) Primary amendment Number of E. fetida Comparison amendment Number of E. fetida Biochar 2% 13 ±3 *** Unamended 8 ±2 Biochar 2% 16 ±4 *** Fe 2 O 3 2% 5 ±3 Biochar 2% 13 ±1 *** GAC 2 % 7 ±1 Biochar 2% 17 ±2 *** PAC 2% 5 ±1 SOIL SOIL + BIOCHAR Hale Sarah E, John Jensen, Lena Jakob, Patryk Oleszczuk, Thomas Hartnik, Thomas Henriksen, Gudny Okkenhaug and Gerard Cornelissen. The effect of the soil amendments; activated carbon, biochar and ferric oxyhydroxide, on bacteria and invertebrates. Environmental Science & Technology, 2013.

49 Field test in Grenlandsfjords: Does activated BC reduce dioxin bioavailability? From 0.1 g carbon in the lab to 80 tons carbon on the seafloor..

50 Mixing AC and clay Dredging clean clay Placement with reverse hopperdredging

51 Sediment Profile Imaging Limestone Clay Clay+AC Reference Gerard Cornelissen, Katja Amstaetter, Audun Hauge, Morten Schaanning, Bjørnar Beylich, Jonas S. Gunnarsson, Gijs D. Breedveld, Amy M.P. Oen, and Espen Eek. Environ. Sci. Technol., 2012, 46,

52 Dioxin flux from sediment to water Ormerfjord Eidangerfjord Gerard Cornelissen, Katja Amstaetter, Audun Hauge, Morten Schaanning, Bjørnar Beylich, Jonas S. Gunnarsson, Gijs D. Breedveld, Amy M.P. Oen, and Espen Eek. Environ. Sci. Technol., 2012, 46,

53 Passive capping material: less effective over time - Settling particles slightly contaminated Gerard Cornelissen, Morten Schaanning, Jonas S. Gunnarsson, Espen Eek. Long-term effects of thin-layer capping of PCDD/F-contaminated sediments on sediment-to-water fluxes in a large-scale field trial in Grenlandfjords, Norway. Integrated Environmental Assessment and Management, 2015.

54 Activated biochar: more effective over time Gerard Cornelissen, Morten Schaanning, Jonas S. Gunnarsson, Espen Eek. Long-term effects of thin-layer capping of PCDD/F-contaminated sediments on sediment-to-water fluxes in a large-scale field trial in Grenlandfjords, Norway. Integrated Environmental Assessment and Management, 2015.

55 Thank you for your attention IBI white papers (May 2015)