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BIOCHAR AND ORGANIC WASTES
G. Gascó (1), A.M. Tarquis(2), A. Méndez (3)
(1) Edafología. E.T.S.I. Agrónomos. Email: [email protected]
(2) Matemáticas. ETSI Agrónomos
(3) Ingeniería de Materiales. ETSI Minas.
International Conference “Protection of soil functions – challenges for the future”
Definition of biochar
-Biochar is a carbon-rich solid obtained by the thermal decomposition of organic matter
under a limited supply of oxygen and at relatively low temperatures (Lehmann and
Joseph, 2009)
- Biochar is defined as char produced by pyrolysis for use in agriculture in an
environmentally sustainable manner.
Raw materials
Pyrolysis: Thernal process
Without O2 (<2% )
300-700ºC
Biochar
Sewage sludge treated at
400ºC
Lehmann, J., Joseph, S., 2009. Biochar For Environmental Management. Earthscan, London.
Feedstock (Schmidt et al., 2012): Guidelines from biochar production
Schmidt H.P., Abiven S., Kammann C., Glaser B., Bucheli T., Leifeld J. 2012. Guidelines from biochar production. Delinat
Institute und Biochar Science Network, Switzerland
- Biodegradable waste with waste separation: biodegradable waste with kitchen waste
and leftovers
- Garden waste: leaves, flowers, roots, pruning from trees, vines and bushes, clippings
from nature conservation measures, hay, grass
- Agriculture and forestry: bark, bark and chippings, sawdust, wood shavings, wood wool
-Vegetable production : material from washing, cleaning, peeling, centrifuging and
separation processes. Pulp, pips, peelings, shreds or pomace (from oil mills, spent grain)
-Waterway maintenance : flotsam, fishing residues
-Kitchens and canteens : Kitchen, canteen and restaurant leftovers
-Animal by-products: bones, hides , skins
-Materials from food production and confectionary production: oilseed residues,
mushroom substrates, fish residues
-Textiles: cotton, cellulose
-Paper production: paper fibre sludge
-Biogas plants: fermentation residues
Pyrolysis conditions
Temperature
- Carbon content increases with temperature (Okimori et al., 2003): 56 % (300ºC)
to 93% (800º)
- Biochar surface area (Day et al., 2005): 120 (400 ºC) to 460 m2 g-1 (900 ºC)
- Surface area, pH and total surface charge (Ippolito et al., 2012): Switchgrass.
Increase from 250 to 500 ºC.
Day, D., Evans, R.J., Lee, J.W., Reicosky, D., 2005. Energy 30, 2558–2579..
Ippolito, J.A., Novak, J.M., Busscher, W.J., Ahmedna, M, Rehrah, D., Watts, D.W., 2011. J. Environ. Qual. 41, 1123-1130.
Okimori, Y., Ogawa, M., Takahashi, F., 2003. Mitigat. Adaptat. Strateg. Mitig. Adapt. Strateg. Glob. Chang. 8, 261-280.
Pyrolysis conditions
Temperature
- H/C ratio, cation exchange capacity (Kloss et al., 2012): Straw and woodchips.
Decrease from 400 to 525ºC.
- Low temperatures: controlling the release of nutrients in soils, hydrophobic
properties and limit the capacity for soil water storage.
Song, W., Guo, M., 2012.. J. Anal. Appl. Pyrol. 94, 138-145..
Kloss S., Zehetner, F., Dellantonio, A., Hamid, R., Ottner, F., Liedtke, V., Schwanninger, M., Gerzabek, M.H., Soja, G.,
2012. J. Environ. Qual. 41, 990-1000..
Optimal temperature treatment for soil amendment
(Song and Guo, 2012)
300-600 ºC
Influence of temperature on biochar properties (Méndez et al., 2013)
Sewage sludge CAP-400ºC CAP-600ºC
pH (1:2.5) 6.33 7.76 8.72
EC (1:2.5 (dS m-1, ) 3.6 3.04 1.46
TOM (%) 20.10 17.49 11.95
SOM(%) 0.15 ip ip
CEC (cmol(+) kg-1) 45.23 29.90 11.67
BET Surface Area (m2/g) 6.81 33.44 37.18
Cu (mg kg-1) 545 632 740
Ni (mg kg-1) 102 129 134
Cd (mg kg-1) 7.54 9.67 9.76
Zn (mg kg-1) 2398 2983 3922
Pb (mg kg-1) 189 239 253
A. Méndez, M. Terradillos, G. Gascó .2013. Physicochemical and agronomical properties of biochar from sewage sludge at
different temperatures. Journal of Analytical and Applied Pyrolysis 102: 124-130
SL 400ºC 600ºC
Proximate analysis of SL, CAP-400 and CAP-600 (by thermal analysis)
A. Méndez, M. Terradillos, G. Gascó .2013. Physicochemical and agronomical proeprties of biochar from sewage sludge at
different temperatures. Journal of Analytical and Applied Pyrolysis 102: 124-130
Sample VM (%) FC (%) Ash (%) FC/(FC+VM)
SL 35.89 6.99 57.12 16.30
CAP-400 23.34 4.64 72.02 16.58
CAP-600 16.70 4.77 78.53 22.23
VM: Volatile matter, FC: Fixed carbon
-1,0
-0,5
0,0
0,5
1,0
1,5
0 100 200 300 400 500 600 700 800 900
Temperature (ºC)
DT
A (
uV
/mg)
SL
CAP-400
CAP-600
exo DTA curves
-The exothermic band is more intense in
the original feedstock (SL) due to their
higher organic matter content
- Pyrolysis reduces organic matter content
- Temperature at which combustion starts
and finishes moves to higher temperatures
from SL to CAP-400 and CAP-600. These
results indicate that as the pyrolysis
temperature increases, the biochar
obtained was thermally more stable.
- This fact is according to the reduction of
VM(%) during pyrolysis.
Sewage sludge
CAP-400ºC CAP-600ºC
Fibers from pruning waste added in the sewage sludge composting process can be
observed in images from raw samples. Some fibers are still in the biochar pyrolyzed at
400ºC but completely disappear at 600ºC.
Optical micrographs of sewage sludge and biochar samples
Influence on soil properties
1. The soil emissions of CO2 and greenhouse gases for long term.
2. Physical, chemical and biological soil properties.
Formulation of growing media
3. Hydrophysical characteristics of the substrates
Soil and water remediation
4. Soil contaminated by Ni
5. Water contaminated by metals and organic compounds
Soil CO2 emissions: biochar and carbon sequestration (Méndez et al., 2013)
“Biochar contribute to carbon sequestration due to carbon stability of biochar materials”
A. Méndez, A.M. Tarquis, A. Saa-Requejo, F. Guerrero, G. Gascó.
2013. Influence of pyrolysis temperature on composted sewage
sludge biochar priming effect in a loamy soil. Chemosphere 93:
668-676
Treatments
Selected soil (T) was amended with sewage
SL and biochars (CAP-400 and CAP-600) at
8%wt
CO2 evolved was evaluated during 80 days at
a temperature of 28 ºC
101a
139d
123c
95a
0
20
40
60
80
100
120
140
0 20 40 60 80C
um
ula
tive
CO
2 e
volv
ed
(m
g C
-CO
2/
10
0 g
)
Time (Days)
T
SL
B400
B600
The application of biochar prepared from
sewage sludge reduced the CO2 evolution by
11 and 32% with respect to sewage sludge
treatment after the incubation experiment
Soil CO2 emissions: biochar and carbon sequestration
Double first-order kinetic model (Jenkinson, 1977)
)1()1( 21
2121
tktkeCeCYYY
Y1 is the cumulative evolved C–CO2 (mg CO2/100 g of soil)
from labile C and Y2 is the cumulative evolved C–CO2 (mg
CO2/100 g of soil) from relatively recalcitrant mineralizable C.
Young Carbon
(C1)
Old Carbon (C2)
CO2
r K1 C1
r K2 C2
r= factor summarising external influence. In our case r=1.
i=Carbon input . In our case i=0.
Jenkinson, D.S. 1977. Studies on the decomposition of plant material in soil. J. Soil Sci. 28, 424-434.
Reduction of CO2 emissions
between 301 and 932 kg CO2 ha-1
with respect to the direct application
of raw sewage sludge after 10 yr.
Physical and chemical properties
-Field capacity (FC) followed the order C=SL4<B4<SL8<B8 .
- Wilting point (WP) followed the order C<B4<SL4<B8<SL8.
-Available water (AW) increased in the soil treated with biochar according to Beck et al. (2011).
-Biochar did not improve soil aggregation according to Peng et al. (2011).
- SL8 improved soil aggregation .
Treatments
Biochar (B) was prepared by pyrolysis of selected sewage sludge (SL) at 500ºC.
Haplic Cambisol was amended with the sewage sludge (SL) and the biochar (B) at two different
rates in mass: 4 and 8%, leading to SL4, SL8, B4 and B8 treatments.
Soil
sample
FC (%) WP (%) AW (%) Soil aggregates (%)
(> 2 mm)
T 10.65±0.07a 5.05±0.04a 5.60±0.09 b 22.2±3.1ab
SL4 10.85±0.08b 5.48±0.04c 5.37±0.06 b 27.2±2.1bc
SL8 12.68±0.12 c 7.76±0.06e 4.92± 0.15a 29.0±1.9c
B4 12.32±0.12 b 5.25±0.07b 7.07±0.06c 20.4±2.27a
B8 13.83±0.10 d 6.01±0.07d 7.83±0.14d 18.3±1.50a
Soil aggregates (%)
Total organic carbon (TOC), cation exchange capacity (CEC), pH and electrical conductivity
(EC) of control and amended soils after the incubation experiment
Soil sample TOC (%) CEC (cmol(c) kg-1) pH (1:2.5) EC (1:2.5)
(µS cm-1, )
T 0.66±0.05 a 6.76±0.16a 7.84±0.04 b 73±7a
SL4 1.30±0.04 b 7.94±0.28 b 7.80±0.08 b 978±8 c
SL8 2.42±0.05 d 9.97±0.13 c 7.44±0.05a 1124±9 c
B4 1.28±0.07 b 7.11±0.04a 7.83±0.02 b 293±7 b
B8 1.74±0.08 c 7.16±0.06a 8.01±0.02 c 304±6 b
Méndez A, A. Gómez, J. Paz-Ferreiro, G. Gascó. 2012. Effects of sewage sludge biochar on plant metal availability after
application to a Mediterranean soil. Chemosphere 89 (2012) 1354–1359.
-The largest increase in both TOC at the end of the incubation happened when adding SL8 which
resulted in a 3.5 fold increase in TOC to the control soil. The order of TOC at the end of the
incubation was SL8 > B8 > B4 = SL4 > C.
-Biochar increased soil pH by 0.2 units when a high dose (B8) according with the biochar pH
(9.5) while sewage sludge (SL8) decreased pH to 7.44.
-Sewage sludge (1055 µS cm-1) amendment multiplied EC value by 15 in the soil,
Physical and chemical properties
Soil sample TOC (%) CEC (cmol(c) kg-1) pH (1:2.5) EC (1:2.5)
(µS cm-1, )
T 0.66±0.05 a 6.76±0.16a 7.84±0.04 b 73±7a
SL4 1.30±0.04 b 7.94±0.28 b 7.80±0.08 b 978±8 c
SL8 2.42±0.05 d 9.97±0.13 c 7.44±0.05a 1124±9 c
B4 1.28±0.07 b 7.11±0.04a 7.83±0.02 b 293±7 b
B8 1.74±0.08 c 7.16±0.06a 8.01±0.02 c 304±6 b
Total organic carbon (TOC), cation exchange capacity (CEC), pH and electrical
conductivity (EC) of control and amended soils after the incubation experiment
Méndez A, A. Gómez, J. Paz-Ferreiro, G. Gascó. 2012. Effects of sewage sludge biochar on plant metal availability after
application to a Mediterranean soil. Chemosphere 89 (2012) 1354–1359.
- Sewage sludge increased the value of CEC while Biochar did not.
- CEC of biochar is scarce after low pyrolysis temperatures, increasing at higher temperatures
(Lehmann, 2007).
- Our results agreed with other studies reporting biochar to have a minimal CEC when compared
to soil organic matter (Lehmann, 2007; Cheng et al., 2006; Cheng et al, 2008).
- It is admitted that the effect of biochar addition on CEC is dependent on the type of biomass
pyrolyzed (Jha et al., 2010).
Metal content in sewage sludge and biochar: leaching experiment (mg L-1) and after
extraction with CaCl2 or DTPA (mg kg-1) (Méndez et al, 2012)
Méndez A, A. Gómez, J. Paz-Ferreiro, G. Gascó. 2012. Effects of sewage sludge biochar on plant metal availability after
application to a Mediterranean soil. Chemosphere 89 (2012) 1354–1359.
Metal content after leaching experiment (mg L-1)
Sample Cu Ni Zn Cd Pb
L 0.300 0.085 a 0.081 0.004 a 0.071 0.005 a 0.008 0.001 a 0.0022 0.0006 a
B 0.012 0.006 b 0.029 0.015 b 0.034 0.001 b 0.002 0.001 b 0.0013 0.0004 a
Plant-available metals (DTPA) (mg kg-1)
Sample Cu Ni Zn Cd Pb
L 85.18 4.10 a 31.04 1.21 a 90.05 2.13 a 0.503 0.175a 68.60 3.78a
B 43.55 2.47 b 0.63 0.12 b 29.60 1.27 b 0.321 0.112 b 8.82 0.07 b
Mobile forms (CaCl2) (mg kg-1)
Sample Cu Ni Zn Cd Pb
L 34.24 4.31 a 5.45 0.42 a 247.54 7.60a 0.350 0.107a 12.540 0.107a
B 14.8 2.55 b 4.10 0.31b 24.52 2.33b 0.302 0.101a 2.452 0.072b
Mobile and available forms of metals reduced after pyrolysis (Méndez et al, 2005)
The plant bioavailability (DTPA) of Ni, Zn, Cd and Pb were 57%, 30%, 29% and 31% of those
in SL8 (Méndez et al, 2012).
Advantages of sewage sludge pyrolysis
-It removes pathogens
- The risk of metals lixiviation is reduced
Available Metals (DTPA) in soils (mg kg-1)
0,00
1,00
2,00
3,00
4,00
5,00
6,00
7,00
8,00
Cu Ni Zn Cd Pb
T
SL8
B8
Bio
aval
ible
met
al
(mg/k
g)
Biochar and soil enzyme activities
“Use of soil biochemical properties as indicators of soil quality”
Treatments
Umbrisol with a pH of 6.5. Sandy-loam
Biochar from sewage sludge: 650ºC at a rate of 10º
C min-1 and the final temperature was maintained for
2 h
Biochar and sewage sludges were added to soil at a
rate of 4 % and 8 % (w/w) obtaining the following
treatments: B4, B8 for biochar; SL4 and SL8 for
sewage sludge. 60 % of water holding capacity
(WHC). Incubation: 70 days.
Biochar and soil enzyme activities
J. Paz-Ferreiro, G. Gascó, B. Gutierrez, A. Méndez2.. 2012. Soil activities and the geometric mean of enzyme
activities after application of sewage sludge and sewage sludge biochar to soil. Biology and Fertility of Soils
48:511–517.
The geometric mean of enzyme activities (GMea) was used as a soil quality
index
GMea = (DH x Glu x Phos x Aryl )1/4
Where DH, Glu, Phos and Aryl are dehydrogenase, b-glucosidase,
phosphomonoesterase and arylsulphatase activities, respectively
-Individual biochemical properties showed a different response to the treatments
Advantages of sewage sludge pyrolysis
GMea showed an increase in the quality of soils amended with the high biochar dose and a
decrease in those amended with a high sewage sludge dose.
High doses of sewage sludge are harmful for the soil microorganisms
J. Paz-Ferreiro, G. Gascó, B. Gutierrez, A. Méndez2.. 2012. Soil activities and the geometric mean of enzyme
activities after application of sewage sludge and sewage sludge biochar to soil. Biology and Fertility of Soils
48:511–517.
Treatment Dehydrogenase -glucosidase Phosphomonoesterase Arylsulphatase Gmea
Control 0.11±0.02 a 2.64±.0.86 a 2.57±0.54 a 0.19±0.06 a 0.59±0.05 a
SL4 0.12±0.02 a 1.98±0.22 ab 4.39±1.46 bc 0.16±0.06 a 0.61±0.02 ac
SL8 0.10±0.08 a 0.58±0.10 c 5.24±0.21 c 0.19±0.06 a 0.49±0.05 b
B4 0.16±0.08 a 1.71±0.19 b 2.94±0.54 ab 0.23±0.04 a 0.63±0.05 ac
B8 0.29±0.05 b 1.22±0.20 bc 2.67±0.32 a 0.26±0.04 a 0.70±0.03 c
Enzyme activities (units are expressed as mmol product g dry soil-1 h-1)
Germination index (watercress): Zucconi phytotoxicity test
Zucconi phytotoxicity test
-The germination test was carried out on
filter paper in petri dishes.
- 5 mL of aqueous extract (1/10 w/v) from
different treatment (8%), soil, sewage
sludge and biochar (650ºC)
-10 seeds of watercress (Lepidium sativum)
were placed on the filter paper and dishes
placed in the dark at 28 ºC.
-Germination percentages (Ge) with respect
to control (distilled water) and root lengths
(Lm) were determined after 48 hours.
Germination index (IGe)
IGe = %Ge * Lm/Lc,
where %Ge is the percentage of germinated seeds in each
extract with respect to control; Lm is the mean total root
length of the germinated seeds in each extract and Lc is
the mean root length of the control (Zucconi et al., 1985).
The control GI value is considered as 100%.
Soil contaminated by Ni
Methods
-Vertisol was artificially contaminated by Ni2+ at a concentration of 1000 mg Ni kg-1 soil
- Biochar was prepared by pyrolysis of de-inking sewage sludge (HP) at 500ºC (HP-500).
- HP and HP500 were added to polluted soil at a rate of 5% (w/w) and soils were incubated
during during 80 days at a temperature of 28ºC.
Treatment Ni H2O
(mg kg-1)
Ni CaCl2
(mg kg-1)
Ni DTPA (mgkg-1)
S - 1.30a 0.60a
S1000 1.34b 15.46b 64.70c
S1000+HP 1.87b 15.52b 73.40d
S1000+HP500 0.15c 10.85c 43.60e
HP500 addition to the polluted soil reduced the quantity of mobile, leached and bioavailable Ni
Water contaminated by metals and organic compounds
Activated carbon or carbon based adsorbent
Reinoso and Marsh (2000)
Type of
pore
Diámetro
(nm)
Micropore d < 2
Mesopore 2 < d <5
Macroporoe d > 5
Removal of contaminants
-Introduction in the pores
- Superficial charge density
- Precipitation
Malachite green removal from water (mg L-1)
Initial concentration of MG (mg/kg)
MG
Re
mo
va
l (%
)
0
20
40
60
80
100
Removal of malachite green (%)
HP-3
HP-10
CAC
ORGANIC WASTES
Sewage sludges
Deinking sludge and other paper wastes
Prunning waste
Growing media
Organic
amendments
Soils
Pyrolysis
Biochar
Carbon-based
adsorbents
Soil flushing Wastewater
treatment Gabriel Gascó Guerrero
Email: [email protected]
Soil Department (Edafología)
Universidad Politécnica de Madrid (Spain)