Biochar: climate saving soils - Biochar Testing Protocol

Version 1.0, October 2013

1. Introduction This document provides a set of test criteria for biochar materials and products. It includes analysis of biochar itself with respect to safety and possible toxicants (section 2) as well as measurement of potentially beneficial properties (section 3). This information allows the user to describe and define the properties of the biochar product. Information is also provided on the effects of biochar on receiving soils and on the measurement of effects of biochar on plant growth. As far as practicable, information is provided on the analytical methods which can be used for measuring the different criteria identified. At the time of writing (October 2013), there are three main schemes available for assessment of biochar products. The International Biochar Initiative (IBI)1 and the European Biochar Certificate (EBC)2 both published guidelines in 2012. In 2013, the Biochar Quality Mandate (BQM)3 was issued for consultation and, at the time of writing, is in process of finalisation; pending further discussions within the EU (see Table 1). A major difference between IBI and EBC is in the definition of biochar. IBI sets out three categories of biochar with respect to their carbon content: low carbon (>10<30%C), medium carbon (>30<60%C) and high carbon (>60%C). EBC meanwhile defines biochar as having a minimum

carbon content of 50%. There is a fair degree of overlap between the two schema with respect to Maximum Permissible Limits (MPLs) of potentially toxic elements (heavy metals) which is not surprising since both rely upon existing experience and practice in setting regulatory limits for possible toxicants in major jurisdictions, including Europe, North America and Australia. IBI provided a range of values which reflects the range of values internationally. The EBC provided a two-tier system of Basic and Premium Grade biochar with different MPLs for some toxicants as the distinguishing aspect. The BQM followed the EBC in adopting a two tier system (Standard and High Grade biochar) though the upper MPLs used were from the top end of the IBIs range as well as from the UK PAS100 composts standard. The lower MPLs (i.e. defining High Grade biochar) were derived by analysis of naturally occurring quantities of potentially toxic elements (PTEs) in a range of non-poisonous plant materials. Values were collected from databases including the Phyllis database4 and Plant Analysis 5 and averaged. The rationale is that if X concentration of a PTE is naturally-occurring in non-poisonous plant material it should be regarded as environmentally acceptable. Since, on average, 3kg of plant material produce 1kg of biochar, it was decided to multiple the mean concentration in plant matter by three times. Table two compares the proposed MPLs for the three schemes for elements and organic compounds. Table One: Comparison of the three schemes for biochar quality Name International Biochar Initiative (IBI): Standardized Product Definition and Product Testing Key Requirements Material definition; basic utility material properties; Toxicants (metals, organic contaminants, seed germination) ; optional advanced property testing; clean production; protocol for consistent testing ; details of accredited and modified analytical tests. Comparison of guidance Ensures safe production of a consistent biochar that is not contaminated or an environmental hazard when added as a soil amendment. Minimum 10% C content. Status, Certification and Labelling IBI Biochar Certification Program is a voluntary certification program for biochar manufacturers. IBI Certified Biochar Seal Due to be launched 2013.

European Biochar Certificate As for IBI but also includes (EBC) sustainability assessment of feedstocks and production operation; positive list. Biochar Quality Mandate (BQM) As for IBI and EBC but more comprehensive sustainability assessment; more detailed end of waste to biochar product process outlined.

Applies positive list of biomass (excludes dirty wastes); requires 50% carbon content. Basic and Premium Grades. Applies to waste and nonwaste feedstocks. Standard and Premium Grades.

Now incorporated into Swiss Law. Third party accreditation process established.

Published and currently under consultation and finalization anticipated late 2013. Certification process planned.

Table Two: Comparison of the Maximum Permissible Limits (MPLs) with respect to Elements and Compounds for Three Schema: IBI, EBC and BQM Heavy Metal IBI MPL (mg/kg dry matter), 1.1 (issue: 11.04.2013; IBI-STD-01.1) PAS 100 (for composts) MPL (mg/kg dry matter) (UK-based standard) European Biochar Certificate basic biochar (mg/kg dry matter) n/a 1.5 90 European Biochar Certificate premium biochar (mg/kg dry matter) n/a 1 80 Biochar Quality Mandate High Grade (mg/kg dry matter) Biochar Quality Mandate Standard Grade (mg/kg dry matter)

Arsenic Cadmium Chromium

12-100 1.4-39 64-1200

n/a 1.5 100

10 3 15

100 39 100

Cobalt Copper Lead Mercury Manganese Molybdenum Nickel Selenium Zinc Boron Chloride Sodium Organic compounds PAHs

40-150 63-1500 70-500 1-17 n/a 5 - 20 47-600 1-36 200-7000 Declaration Declaration Declaration

200 200 1 n/a n/a 50 n/a 400

100 150 1 n/a n/a 50 n/a 400

100 120 1 n/a n/a 30 n/a 400

40 60 1 3500 10 10 5 150

1500 500 17

20 600 36 2800

6 - 20

12

20

20

PCBs PCDDs (dioxins) / PCDFs (furans

0.2 0.5 9 ng/kg

0.2 20 ng/kg

0.2 20 ng/kg

0.5 20 ng/kg

0.5 20 ng/kg

Note: The BQM advocates testing for PCBs, PCDDS and PCDFs only in the situation where there is a reasonable risk of sufficient chlorine in the feedstocks to constitute a risk that these chemicals could be produced during pyrolysis or gasification.

2. Suggested Necessary Basic Biochar Testing It is advised that all biochar samples should be tested against the criteria set out in Table Three. This includes properties which allow a basic characterisation of the material to be made, as well as those properties likely to be beneficial as well as potentially negative properties. The methods proposed are not definitive but rather indicative and it is suggested that those requiring testing talk to potential providers to establish the most suitable options. The table includes variables from all the published biochar standards but they are not necessarily required by all three approaches. Table Three: Criteria Recommended for Basic Biochar Testing STANDARD BIOCHAR PROPERTIES pH Moisture at time of delivery Organic Carbon (Corg) CRITERIA Declaration Declaration 10%, irrespective of the quality biochar grade (IBI basic) Declaration UNIT pH % by dry mass % of dry mass Indicative methods DIN 10390; BS EN13037; TMECC6 modified by Rajkovich et al. (2011)7; ASTM D1762-84 (105c); BS EN 13040BS EN 13040 (105 C for 24 hours) ASTM D4373-02. Organic C calculated as Total C Inorganic C; BS EN 13039 BS EN 13039 As calcium carbonate BS 7755-3.10, ASTM D4373-02. or Inorganic carbon calculated as Total C-Organic C (after HCl pre-treatment BS EN 15104; ASTM D5291 Elemental analyser by dry combustion
0

Inorganic Carbon

% of dry mass

Total Carbon (C)

Declaration

% of dry mass

Hydrogen (H) Oxygen (O) H:Corg

Declaration Declaration 0.7 (maximum) irrespective of the quality biochar grade H/C ratio <0.6 8 O/C ratio <0.4, 8

% of dry mass % of dry mass Molar ratio

BS EN 15104; ASTM D5291 Elemental analyser by dry combustion 15104 BS EN 15104; ASTM D5291 Elemental analyser by dry combustion C and H ratio elemental analyser by dry combustion, BS EN 15104, ASTM D5291. Degree of carbonization (Chun et al., 2004) as described by Schimmelpfennig & Glaser (2012)8. maturity and decomposition rate Hammes et al., 2006) as described by Schimmelpfennig & Glaser (2012)8 BS EN 15104; SASTM D5291 Elemental analyser by dry combustion BS EN 15104; ASTM D4239 (Method B) ; Elemental analyser by dry combustion Total C and N BS EN 15104; ASTM D5291. Elemental analyser by dry combustion ) ASTM D1762-84 (750c); BS EN 13039; ASTM D4442 (Method a) Modified dry ashing method followed by ICP (Enders and Lehmann 2012)9 BS EN 13650 Modified dry ashing method followed by ICP (Enders and Lehmann 2012)9; BS EN 13650

oxygen (O)/C ratios (Van Krevelen diagrams) Total Nitrogen (N) Total Sulphur (S) Carbon / nitrogen ratio

Molar ration

Declaration Declaration Declaration

% of dry mass % of dry mass Molar ratio

Total Ash

Declaration

% of dry mass

Total Phosphorus (P)

Declaration (IBI Advanced)

% of dry mass

Total Potassium (K)

Declaration (IBI Advanced)

% of dry mass

Potentially toxic elements (PTEs) (as listed in Table Two).

Declaration

mg kg-1

PAHs

Declaration

mg kg-1

Dioxins and Furans PCBs Water holding capacity

Declaration Declaration Declaration (EBC Premium) Declaration Declaration

ng kg-1 ng kg-1 ml g_1

DIN EN ISO17294-2 (E29); Modified dry ashing method followed by ICP (Enders and Lehmann 2012)9 BS EN 13650; aqua regia extraction (BS7755) followed by ICPAES (BS ISO 22036) ; Also see sludge code of practice10 and EU waste and fertilizer report 11 DIN/BS EN: 15527:2008-09; DIN ISO 13877: 1995-06 (principle B with GC-MS; Toluene with accelerated solvent extraction (ASE) (recommended Hilber et al, 2012)12. AIR DF 100 HMRS; BS EN 1948 series AIR DF 100 HMRS; BS EN 1948 series Funnel and filter paper method; Hilgard paper cup method; DIN 51718; TGA 701 D4C Mass and volume determination Progressive dry sieving with 4760m, 2380m and 420m sieves, as outlined in ASTM D2862-10 Method for activated carbon. TIMECC13 TIMECC13 ASTM E776 (Cl)

Bulk density Particle size distribution

t m-3 mm and m

Boron Sodium Chlorine

Declaration Declaration Declaration

mgkg-1 mg kg-1 dry wt % of dry mass

3. Suggested Additional Testing Criteria Listed in Table Four are a range of other biochar properties which might be measured as part of product development. Table Four: Additional properties of biochar which may provide additional beneficial information to product developers ADDITIONAL BIOCHAR PROPERTIES
Micro-nutrients (Zn, Ca, Fe, Ni, Se, Mo, Mg, Mn, Fe, etc.)

CRITERIA Optional

UNIT mg kg-1

INDICATIVE METHOD DIN EN ISO 17294 2 (E29); EPA method 3053 (microwave digestion followed by AA) Rayment & Higginson (1992) ASTM D 4373 Rajkovich et al. (2011) BS EN 13038; TIMECC (modified) Ammonium-acetate (EPA 9080)(extraction) then ICP-OES e.g. mercury intrusion porosimetry N2 gas adsorption method (e.g. BET) ; ASTM D 6556-10; ISO 9277

Neutralising Capacity (liming if pH above 7) Liming (carbonate value) Electrical Conductivity Cation Exchange Capacity (K, Ca, Mg, Na) Porosity Specific Surface area / total surface area Labile carbon content / volatile matter Long-term stable carbon

(IBI basic) Declaration (IBI basic) Optional Optional Optional (EBC Premium)

% CaCO3 % CaCO3 dSm-1 cmol+kg-1

% of dry mass % of dry mass

Incubation studies (Cross & Sohi, 2011)14 / ASTM D1762-84 Accelerated ageing (oxidative) method (Cross & Sohi, 2013)15

Available P

mg/kg

Mineral N (NO3-N)

(IBI Advanced) Declaration

% of dry mass or mg/kg

Release dynamics of nutrients (P, K, N) Impact on soil aggregation Soil water potential (available water content) Priming potential (impacts on SOC) Thermal analysis Optional stability indices Exo1 and Exo2 g/g or g/cm3 %/% ratio

2% formic acid followed by spectrophotometry as described by Wang et al (2012)16 after Rajan et al (1992)17 and AOAC (2005)18 KCl xtraction followed by spectrophotometry/ ICP (Rayment and Higginson 1992)19 Soil column leaching experiments modified by Angst & Sohi 201320 Tension table and pressure plate Incubation studies Thermogravimetric analysis (TGA); Thermogravimetry-differential scanning calorimetry (TG-DSC) % labile (exo1)and % recalcitrant C (exo2) over % OC (% weight loss under oxidation contitions)21,22 Rayment and Higginson 1992

Ammonia (NH4-N)

Declaration

mg kg-1

4. Properties of Soils In many cases it will be useful and important to know about the properties of the soil in to which biochar is added, either or both prior to and after biochar addition. Table Five lists some of the dimensions of the soil which may be useful to characterise. Table Five: Testing Soil Properties Variable Unit Test method

Soil organic carbon pH Total Nitrogen

% dry weight

e.g. ISO 13878 - Dumas dry combustion (with HCl pretreatment for calcareous soils) In de-ionised water(Allen, 1989).ISO 10390

% dry weight or mg/kg mg/kg

ISO 13878 - Dumas dry combustin BS EN 15104

Extractable Mineral nitrogen (nitrate, nitrite, ammonium) Extractable Phosphorus Soil moisture CEC (exchangeable K, Na, Ca, Mg)

e.g. 0.5 KCl extraction; ISO 14256-2 Olsen Method

% dry weight cmol+/kg

Dry at 105oC for 24 hours Ammonium-acetate then ICP-OES 23

Saturated hydraulic conductivity (SHC) Soil water potential / available water content Soil texture (clay, fine silt, coarse silt, fine sand, coarse sand)

m/s g/g

soil water movement (using Darcys law)24 Tension table and pressure plate 24

Separation by sieving (ASTM) and sedimentation(Pipette method 25

5. Measuring the Plant Response Some possible measures of plant responses to biochar soil amendment are presented in Table Six. Table Six: Measuring Plant Response to Soil Amendments such as Biochar Variables : Basic Unit Indicator Total plant response Detail

Total biomass yield - above and kg (DW) per m2 below ground Harvestable biomass kg (DW) per m2

grain, vegetable leaves, edible stems, edible roots Indicates chlorophyll content Crude protein ? Starch water uptake by plant

Useable / saleable part of crop

Leaf chlorophyll Nitrogen content Crude fibre Starch Xylem sap flow (XSF) Micro-nutrients Other nutriitional properties and indicators

SPAD meter % % %

Leaves / stems Leaves / stems Tubers

mg per kg (DW)

e.g. Zn, Mn, B, Mg, Na, Fe e.g. nutritional value per kg or area ?

In edible parts of plant

References 1. the International Biochar Initiatives (IBI) Guidelines for biochar that is used in soils. http://www.biocharinternational.org/characterizationstandard (version 1.1, published May 2012, updated 11th April 2013, accessed on 16th October 2013) 2. The European Biochar Certificate (EBC). (Delinat Institute, Switzerland). http://www.european-biochar.org/en/ct/1-Guidelines-for-theEuropean-Biochar-Certificate (4.6 version, published 2nd April 2013, accessed on 16th October 2013) 3. Biochar Quality mandate (BQM), v.1 (2013). http://biocharbraf.files.wordpress.com/2013/06/bqm-v-1-0-version-for-publicconsultation1.pdf (published 15.06.2013, accessed on 16th October 2013) 4. Phyllis database (ECN, 2007) https://www.ecn.nl/phyllis2/ 5. Reuter, D., Robinson, J.P. (editors), Plant Analysis An Interpretation Manual, CSIRO, Australia. . 6. US Composting Council and US Department of Agriculture (2001) Test methods for the 29 examination of composting and compost. (TMECC) Thompson W.H. (ed.) http://compostingcouncil.org/tmecc/. (Accessed January 2012). 7. Rajkovich, S., Enders, A., Hanley, K., Hyland, C., Zimmerman, A.R., and Lehmann, J. (2011).Corn growth and nitrogen nutrition after additions of biochars with varying properties to a temperate soil.BiolFertil Soils.DOI 10.1007/s00374-011-0624-7.Published Online. 8. Schimmelpfennig S.; Glaser B. (2012). One Step Forward toward Characterization: Some Important Material Properties to Distinguish Biochars. J. Environ. Qual. 41: 1001-1013 (doi:10.2134/jeq2011.0146) 9. Enders, A. and Lehmann, J. (2012) Comparison of wet digestion and dry ashing methods for total elemental analysis of biochar. Communications in Soil Science and Plant Analysis. 43:10421052. 10. Sludge Code of Practice, available at: http://archive.defra.gov.uk/environment/quality/water/waterquality/sewage/documents/sludgecop.pdf. Methods as listed in Index of Methods for the Examination of Waters and Associated Materials 1976 -1992 (ISBN 011752669X). 11. Amlinger, F., Faroino, E., and Pollack, M. (2004) EU Heavy Metals and Organic Compounds from Waste Used as Organic Fertilizers Final Report. ENV.A.2./ETU/2001/0024 REF.NR.: 12. Hilber, I, Bucheli, TD, Blum, F, Leifeld, J, Schmidt, HP Quantitative determination of PAHs in biochar a prerequisite to assure its quality and safe application. J. Agric. Food Chem. 2012 13. US Composting Council and US Department of Agriculture (2001) Test methods for the examination of composting and compost. (TMECC) Thompson W.H. (ed.) http://compostingcouncil.org/tmecc/. (Accessed January 2012).

14. Cross, A., Sohi, S.P. (2011) The priming potential of biochar products in relation to labile carbon contents and soil organic matter status, Soil Biology & Biochemistry, 43: 2127-2134 15. Cross, A., Sohi, S.P. (2013) A method for screening the relative long-term stability of biochar, GCB Bioenergy, 5:215-220 16. Wang, T., Camps Arbestain, M., Hedley, M., and Bishop, P. (2012) Predicting phosphorus bioavailability from high-ash biochars. Plant and Soil. DOI 10.1007/s11104-012-1131-9. Published Online. 17. Rajan, S.S.S., Brown, M.W., Boyes, M.K., and Upsdell, M.P. (1992) Extractable phosphorus to predict agronomic effectiveness of ground and unground phosphate rocks. Nutrient Cycling in Agroecosystems. 32(3):291-302. 18. AOAC (Association of Analytical Communities) International (2005) AOAC Official 1 Methods of Analysis. 18th 2 Edition. Latimer, G. (Ed.) www.eoma.aoac.org (accessed September 3 2011). 19. Rayment, G.E. and Higginson, F.R. (1992). Australian Laboratory Handbook of Soil and Water Chemical Methods. Reed International Books, Australia/ Inkata Press, Port Melbourne. 20. Angst, T.E., Sohi, S.P. (2013) Establishing release dynamics for plant nutrients from biochar, GCB Bioenergy, 5:221-226 21. Lopez-Capel, E.; Sohi, S. P.; Gaunt, J. L.; Manning, D. A. C. Use of thermogravimetry-differential scanning calorimetry to characterize modelable soil organic matter fractions. Soil Sci. Soc. Am. J. 2005, 69,136140. 22. Plante, A. F.; Fernandez, J. M.; Leifeld, J. Application of thermal analysis techniques in soil science. Geoderma 2009, 153, 110. 23. Sparks, L.S. (1996) Methods of soil analysis: chemical methods. Part 3. Soil Science Society of America Book series. 24. Soil Survey Division Staff. 1993. Soil survey manual. United States Department of Agriculture, Soil Conservation Service, Agricultural Handbook No. 18. U.S. Government Printing Office, Washington, D.C. 25. Sheldrick BH and C Wang. 1993. Particle Size Distribution. p. 499-511. In MR Carter (ed.) Soil Sampling and Methods of Analysis. Canadian Society of Soil Science. Lewis Publishers. Ann Arbor.