sabiene et al.presentation2
TRANSCRIPT
HEAVY METALBIOAVAILABILITY IN THE BIOFERTILIZER
DERIVED FROM SEWAGE SLUDGE
Prof. dr. Valdas Paulauskas, [email protected]
*Assoc. prof. dr. Nomeda Sabiene, [email protected]
Dr. Ernestas Zaleckas, [email protected]
Aleksandras Stulginskis University,Institute of the Environment and Ecology,
LITHUANIAhwww.asu.lt/me/en/15320
October 17-20, Bari
Rationale
• Sewage sludge composting can form an important part of acomprehensive, integrated waste management system thatemphases resource conservation through source reduction, recyclingand reuse.
• There is no universally accepted and used sewage sludge treatmenttechnology still:– sewage sludge can be treated using aerobic composting,
anaerobic digestion or both methods can be used sequently.• Composting provides a simple but cost effective alternative
treatment method for waste disposal by decomposing organicmatter, producing a pathogen free, stabilised and nutrient richproduct:– quality of the final product (biofertilizer) can be improved by
adding nutrient additives and stabilizing heavy metals.
The aim and objectives
• To find an optimal solution for the sewagesludge composting by producing a high qualityand environmentally friendly product –compost or bio-fertilizer:
– to create suitable technologies for aerobic and anaerobiccomposting of sewage sludge what concern high nutritionalvalue and low heavy metal bioavailability;
– to evaluate heavy metal bioavailability in the compostedproducts by chemical analyses and vegetative pot experiments.
Methods of sewage sludge quality evaluation
• CEN/TC 308 standards on characterization of sewage sludge where used:
– EN 12832:1999. Utilisation and disposal of sludges –vocabulary.
– EN ISO 5667-13:2011. Sampling of sludges.
– EN 12176:2000. Determination of pH-value.
– EN 12879:2000. Determination of the loss of ignition of dry mass.
– EN 12880:2000. Determination of dry residue and water content.
– EN 13342:2000. Determination of Kjeldahl nitrogen.
– EN 3346:2000. Determination of trace elements and phosphorous.
Aqua regia extraction methods.
• Sequential extraction of heavy metals (Emmerich at al., 1982; Lin et al., 1999)
Methods of compost quality evaluation
• CEN/TC 223 standards on characterization of composts:
– EN 12579:2000. Sampling.
– EN 13040: 2007. Sample preparation for chemical and physical tests,
determination of dry matter content, moisture content and laboratory
compacted bulk density.
– EN 12580: 2000. Determination of a quantity.
– EN 13039:2011. Determination of organic matter content and ash.
– EN 13037: 2011. Determination of pH.
– EN 13654-1:2002. Determination of nitrogen - Part 1: Modified Kjeldahl
method.
– EN 13650:2001. Extraction of aqua regia soluble elements.
– EN 13652:2001. Extraction of water soluble nutrients and elements.
• Sequential extraction of heavy metals (Emmerich at al., 1982; Lin et al., 1999)
Object of the research (1)
• Sewage sludge from the Min-Shen municipal sewagetreatment plant (MSTP), Taiwan, R.O.C.
0
1
2
3
4
N P K
3.70
2.01
0.15
%
175
64 46 25 <2 <0.020
200
400
Zn Cu Pb Mn Ni Cr Cd
mg kg-1
907
LT, LAND 20:2005
300 75 140 - 50 140 1.5
EU, EC, 2001
200 100 100 - 50 100 0.7N:P:K – 1:1:1
Object of the research (2)
• Sewage sludge from the Kaunas and Šiauliai municipalsewage treatment plant (MSTP), Lithuania.
N:P:K – 1:1:1LT, LAND 20:2005
300 75 140 140 50 1.5 1.0
EU, EC, 2001
200 100 100 100 50 0.7 0.5
0
2
4
6
N P K
3.202.21
0.56
5.16
2.74
0.54
%Sewage sludge(Kaunas)Sewage sludge(Šiauliai)
257,98108,7594,96
35,85 21,65 1,77115,8 68,4 28,80
15,40 2,9 0,050
200
400
600
800
1000
Zn Cu Pb Cr Ni Cd Hg
Sewage sludge(Kaunas)Sewage sludge(Šiauliai)
14221158
COMPOSTING PROCEDURES1. AEROBIC COMPOSTING
Methodology of the aerobic composting
• The composting was carried out in 13 m-3
aerated piles in the pilot-scale compostingplant at the Pa-Li MSTP in Taipei, Taiwan,R.O.C.
• Composition of the mixture:
– sewage sludge 62% (5490 kg),
– bulking agent (sawdust) 24% (2122 kg),
– recycled compost (obtained from previous studies
and used as inoculants) 14% (1265 kg).
• Air flow rate was controlled by a computer-regulated solenoid valve and was measured bya flow meter. The average air flow rate was13.85 m-3h-1
• The composted mixture was turned once aweek during the first month of the compostingcycle and twice a week during the secondmonth.
• The composted mixture was sampled weeklyduring the 2-month period.
Roller door
Compost bin A
Roller door
Compost bin D
Compost bin B
Compost bin E
Compost bin C
Compost bin F
Deo-doringVessel
Pretreatment operational area
Roller door
14 m
8m
7
m
4 m 4 m
Changes in characteristics of composted mixture during composting
0
20
40
60
80
0 7 14 21 28 35 42 49 56
days
Temperature, oC
5055606570
0 7 14 21 28 35 42 49 56
Moisture, %
8688909294
0 7 14 21 28 35 42 49 56
days
Organic matter, %
Material Ash, % C/N N, % P, % K, % pH
Sewage sludge 25.40 7.4 3.70 2.01 0.15 7.70Sawdust 0.38 420.0 0.14 n.d. n.d. 5.60Recycledcompost 15.50 19.4 2.46 n.d. n.d. 5.80
Raw composted mixture 7.80 30.5 1.74 n.d. n.d. 7.20
Final compost 11.20 19.4 2.64 1.57 0.33 6.20Changes +3.40 -11.1 +0.90 -1.00
Changes in chemical composition of mixture during composting
COMPOSTING PROCEDURES2. ANAEROBIC COMPOSTING
Methodology of the anaerobic composting
• Biofertilizer was produced by anaerobic treatment of sewage sludgefrom Kaunas and Raseiniai MSTP (200 g) and meat-bone mass mixture(100 g). Nutrients ratio N:P:K was adjusted to 1:1:1 (total amountreaching to about 6 %):– P content was increased before anaerobic digestion by acidic (45 % H3PO4)
meat-bone mass treatment ( ratio 1:5),
– K amount was increased after anaerobic digestion by adding to digestate30% of cement kiln dust and K2SO4 mixture.
• For biological activation of digestion process pig manure (5 % fromtotal mixture mass) was added.
• Anaerobic digestion was performed in the laboratory anaerobic reactor(volume 18 l) under mesophilic conditions (at temperature 38.5-39.5oC)for 8 days until gas emission stopped.
1
2 3
4 5
Fee
dsto
ck
Bio
gas
Effluent
Scheme: 1 – level of liquid, 2 – electricaldriver, 3 – mixer, 4 – insulation, 5 –heating coil
View of the laboratory anaerobicdigester (biogas reactor) with ameasurement/control panel
Equipment of the anaerobic composting
• Sterilization of organic waste mixture(killing of pathogenic microorganisms andparasite eggs) was carried out in 3 stages:
– initial chemical sterilization by acidicwaste treatment with phosphoric acid;
– sterilization during anaerobicdigestion process in a biogas reactor;
– thermal pasteurization during bio-fertilizer drying process.
• Already after second stage (anaerobictreatment) bio-product met sanitaryrequirements for sewage sludge appliedon agricultural land as fertilizer (LAND20:2005).
17,900,000
184,222 324,500
Before treatment
12,127,777 (decrease
32.2%)
117,555 ( decrease
36.2%)
236,777 (decrease
27.0%)
After treatment
Total bacteriaamount,CFU g-1
Faecalstreptococci,CFU g-1
Enterobacter,CFU g-1
Changes in microbiological composition of composted mixture during composting
• amount and calorific value of the received biogas could nearly satisfy the energy needs forthe mesophilic anaerobic digestion and drying processes.
• Life Cycle Analysis showed that simultaneous biogas-bio-fertilizer production and directusage of bio-energy make this waste utilization process more energetically effective andenvironment friendly.
Characteristic
Raw stuff for compostingSewagesludge
(Kaunas) (200g)
Sewagesludge
(Šiauliai) (200g)
Sewage sludge(Kaunas)+ Meat-
bone mass(200+100g)
Sewage sludge(Šiauliai)+ Meat-
bone mass(200+100g)
Biogas output, l 7.2 7.5 34.7 36.85
Relative biogasgeneration rate, l kg-1 DM 217.0 150.8 443.2 384.3
Content of biogas, %
− CH4
−CO2
−O2
61.830.72.0
51.321.92.8
68.525.71.40
64.225.21.60
Changes in gas emissions during composting
Effect of cement kiln dust (30%) onsewage sludge properties
0,0
0,5
1,0
1,5
2,0
2,5
3,0
N 0,02 2,72 1
P 0,039 2,47 0,99
K 2,38 0,99 1,52
CKD (30%) SSCKD(30%)
+SS
7
9
11
13
0 10 20 30 40 50
pH
CKD + SS
0
20
40
60
80
0 10 20 30 40 50
Moisture, %
Composition, %
CKD+SS
%
1:1:1.5
0% 20% 40% 60% 80% 100%
CKD
SS
CKD(30%)+SS
CKD
SS
CKD(30%)+SS
CKD
SS
CKD(30%)+SS
CKD
SS
CKD(30%)+SS
7.7
1.7
4.6
55.4
5.7
32.5
26.1
48.3
33.3
48.2
956.6
508.8
0.7
1.2
0.6
2.9
9.7
6.6
2.5
67.5
29.2
0.5
201.438.4
Immobile HM, mg/kg Mobile (EDTA extractable) HM, mg/kg
Zn
Cu
Cd
Ni
Effect of cement kiln dust on heavy metal mobility in sewage sludge
Changes in chemical composition of mixture during composting
Material N, % P, % K, % pH
Sewage sludge (Kaunas), 200 g
3.20 2.21 0.56 7.66
Sewage sludge (Šiauliai), 200 g
5.16 2.74 0.54 7.20
Meat-bone mass, 100 g5.26 10.60 - 4.65
Cement kiln dust + K2SO4, 30%
0.02 0.04 2.38+2.57
13.60
Raw composted mixture 8.52 7.50 6.05 8.25
Final product 5.92 6.25 6.02 7.45
Changes -2.60 -1.25 -0.03 -0.80
EVALUATION OF THEHEAVY METAL BIOAVAILABILITY
1. Aerobically processed compost
Heavy metals in the aerobically processed compost
MaterialCu Mn Ni Pb Zn Cd Cr Hg As
Sewage sludge 175 46 25 64 907 <0.02 <2.0 - -
Recycled compost
88 102 23 50 509 <0.02 <2.0 - -
Sawdust 5 13 8 13 50 <0.02 <2.0 - -
Raw composted mixture
71 76 21 47 315 <0.02 <2.0 - -
Final compost 85 78 23 39 403 <0.02 <2.0 1.5 1.3
EU EC, 2001 100 - 50 100 200 0.70 100 0.5 -
EC No. 889/2008 70 - 25 45 200 0.70 70 0.4 -*Exceed MPC
Sequential extraction of heavy metals
Exchangeable Fraction F1
Bound to Carbonates FractionF2
Bound to Fe-Mn Oxides FractionF3
Sample, 1g
1M CH3COONa (pH 5), 6h, 20oC
1M MgCl2(pH7), 1h, 20oC
0,04M NH2OH·HCl, 5h, 96oC
0,02M HNO3+30% H2O2, 3h,85oC
30% H2O2, 2h, 85oC
3,2M CH3COONH4, 0,5h, 20oC
HNO3+HF+HCl, microwave digestion
Bound to Organic Matters/ Sulphides Fraction F4
Residual Fraction F5
Lin,J.G.,Chen,C.Y.,Chen,S.Y.,1999. Effects of pH on metals specification in a contaminated sediment. Journal ofthe Chinese Institute of Environmental Engineering 9,49–56.
Heavy metal chemical speciation
0%
20%
40%
60%
80%
100%
Zn Pb Mn Cu
Heavy metals in sewage sludge
0%
20%
40%
60%
80%
100%
Zn Pb Mn Cu
Heavy metals in compost
F5
F4
F3
F2
F1
Mn (38-37%) F1 exchangeable > Zn (45-40%) F3 Fe-Mn oxides >Cu (90-99%) F4 organic compounds > Pb (70-19%) F5 sulphides, minerals
Heavy metals in compost and soil mixturesSample Clay,
%OM, %
pH Cu,
mg kg-1
Pb,mg kg-1
Mn, mg kg-1
Zn mg kg-1
Compost - 82.2 5.80 88.00 49.82 101.86 509.32
Sandy soil 4.5 2.01 6.51 8.99 14.11 173.01 33.10
Sandy soil-compost (20:1) 0.45 5.57 6.25 11.09 16.10 194.41 55.34
Sandy soil -compost (5:1) 0.23 15.89 6.02 13.08 17.18 191.17 101.06
Clay soil 32.5 2.14 6.12 10.78 20.36 318.18 42.67
Clay soil - compost (20:1) 6.5 9.14 6.07 11.13 21.46 327.34 62.33
Clay soil -compost (5:1) 1.6 17.95 5.92 16.33 22.75 361.20 108.56
MPC (HN 60:2004) - - - 100 100 1500 300
MPC (86/278/EEC) - - - 50-140 50-300 - 150-300
Heavy metal mobile/stabile fractions incompost and soil mixtures
0%
20%
40%
60%
80%
100%Zn
0%
20%
40%
60%
80%
100%Pb
F4-F5
F1-F3
0%
20%
40%
60%
80%
100%Mn
0%
20%
40%
60%
80%
100% Cu
SampleRatio (F1-F3)/F4-F5
Pb Cu Zn Mn
Sewage sludge 0.22 0.03 1.83 2.02Compost 0.24 0.07 2.84 7.22Sandy soil 0.42 0.39 1.54 1.43Sandy soil-compost (20:1) 0.71 0.12 2.17 2.10Sandy soil-compost (5:1) 0.65 0.12 2.31 1.81Clay soil 0.37 0.21 0.22 0.37Clay soil-compost (20:1) 0.50 0.12 0.56 0.50
Clay soil-compost (5:1) 0.43 0.08 0.93 0.58
Potential heavy metal biovailability
Compost Mn >>Zn> Pb>> Cu Mixture:Sandy soil Zn> Mn>>Pb > Cu Zn>Mn >Pb > CuClay soil Mn = Pb > Zn ≈ Cu Zn>Mn >Pb>>Cu
EVALUATION OF THEHEAVY METAL BIOAVAILABILITY
2. Anaerobically processed bio-fertilizer
MaterialCu Ni Pb Zn Cd Cr Hg
Sewage sludge (Kaunas), 200 g 258.0 35.9 108.8 1422.0 21.70 95.0 1.77
Sewage sludge (Šiauliai), 200 g 115.8 15.4 68.4 1158.0 2.90 28.8 0.05
Meat-bone mass, 100 g - - - - - - -
Cement kiln dust+ K2SO4, 30% 24.3 - 184.1 54.4 9.50 - -
Final product 137.2 23.4 61.3 990.4 2.72 37.9 0.10
EU EC , 2001 100 50 100 200 0.50 100 0.50
EC No. 889/2008 70 25 45 200 0.70 70 0.40
Heavy metals in the anaerobically processed compost
*Exceed MPC
Sequential extraction of heavy metals
(F1) – exchangeable fraction
(F2) – adsorbed fraction
(F3) – oxidizable fraction (bound to organic matter)
(F4) – acid soluble fraction (bound to carbonates)
(F5) – residual fraction (bound to silicates and detritus materials
Emmerich,W. E., Lund, J. L., Page, A. L. and Chang, A. C. (1982). Solid phase form of heavy metal in sewage sludge in sewage sludge treated soils. Journal of Environmental Quality. 11, pp. 178–181
0
20
40
60
80
100
Cr Cd Ni Pb Cu Zn
Che
mic
al f
ract
ion,
%
.
F1 F2 F3 F4 F5
0
20
40
60
80
100
Cr Cd Ni Pb Cu Zn
Che
mic
al f
ract
ion,
% .
F1 F2 F3 F4 F5
before anaerobic treatment after anaerobic treatment
Heavy metal speciation
F1-F2 (0.3-18.6%) : Ni ≥ Zn > Cu ≥ Cd >Pb >Cr; Ni ≥ Zn ≥ Cu > Cd ≥Pb ≥Cr F3-F5 (81.4-99.7%): Cr>>Pb>Ni > Cd ≥ Cu ≥ Zn; Cr>>Pb≥Ni > Cd > Zn ≥ CuF5 (15-75%): Cr>> Pb >Ni>Cd ≥Cu ≥Zn; Cr>> Ni≈ Pb> Cd> Zn ≥ Cu
PbCu
Zn
F1-F3
F4-F50
1020304050607080
90100
Perc
enta
ge, %
.
a
CrCd
Ni
F1-F3
F4-F50
1020304050607080
90
100
Perc
enta
ge, %
.
a
CrCd
Ni
F1-F3
F4-F50
1020304050607080
90100
Perc
enta
ge, %
.
b
PbCu
Zn
F1-F3
F4-F50
1020304050607080
90100
Perc
enta
ge, %
.
b
before anaerobic treatment before anaerobic treatment
after anaerobic treatment after anaerobic treatment
Heavy metal mobile/stabile fractions
SampleRatio (F1-F3)/F4-F5
Cr Cd Ni Pb Cu Zn
Before treatment
0.09 0.43 0.51 0.14 0.80 0.50
After treatment
0.14 0.47 0.53 0.11 2.50 0.40
Change ratio +1.6 +1.1 1.0 -1.3 +3.1 -1.3
Potential heavy metal biovailability
Cu>>Ni≈Zn>Cd>>Pb≈Cr
Vegetative pot experiment
NutrientsK
Commercial compost
I Compost-perlite
1:1
II Compost-perlite
1:2
III Compost-perlite
1:3
N, % 0.48 2.91 1.89 1.41
P, % 0.22 3.08 2.01 1.48
K, % 0.54 2.97 1.96 1.45
Heavy metal, mg/kg DM
Growth medium
EU E
C, 2
001 Leaves of salad
Lim
it
**
Con-trol I II III Con-
trol I II III
Chromium (Cr) 6.2 24.3 16.2 12.2 100 1.30 2.50 2.81 2.25 5
Cadmium (Cd) 0.2 0.7 0.5 0.4 0.7 0.04 0.11 0.08 0.10 0.2*
Lead (Pb) 4.3 14.3 9.5 7.2 100 0.01 0.07 0.06 0.04 0.3*
Nickel (Ni) 3.9 14.1 9.4 7.1 50 1.60 3.75 3.31 3.50 10
Copper (Cu) 29 156 104 78 100 5.30 12.6 10.0 10.5 20
Zinc (Zn) 57 254 169 127 200 35 85 59 74 100
Heavy metals in growth mediumand salad leaves
* MPC, Lithuanian legislative document HN 54:2003. ** Kabata Pendias A., Pendias H. 1992. Trace elements in soils and plants, CRC Press.
Heavy metal bioaccumulation factor and potential bioavailability
Mixture/Element
Control
(Commercial
compost)
I Compost-
perlite
1:1
II Compost-
perlite
1:2
III Compost-
perlite
1:3
Potential
bioavai-
lability
Cr 0.21 0.10 0.17 0.18 0.14
Cd 0.20 0.16 0.16 0.25 0.47
Pb 0.002 0.005 0.006 0.006 0.11
Ni 0.41 0.27 0.35 0.49 0.53
Cu 0.18 0.08 0.10 0.13 2.50
Zn 0.61 0.33 0.35 0.58 0.40
Conclusions (1)
It is important to take into account amounts ofnutrients and contaminants when producingcomposts and bio-fertilizers from sewage sludge.
It is recommended:
– to optimize nutrient amounts and ratios(N:P:K 1:1:1) using amendments of otherwastes;
– to reduce HM bioavailability immobilizingthem when increasing pH, content ofcarbonates and organic matter.
Conclusions (2)
• During aerobic composting total HM amounts as well as theirpotential availability increased (Pb 0.22-0.24; Cu 0.03-0.07; Zn 1.83-2.84; Mn 2.02-7.22) due to their transfer to more mobile fractions (F1-F3 - exchangeable, carbonates and Fe-Mn oxides bound fractionsexcepting Cu which was generally bound to the organics fraction F4).
• During anaerobic sewage sludge treatment only Cu potentialavailability increased markedly (0.8-2.5) due to its’ affinity to theorganic matter while insignificant increase of Cd (0.43-0.47) and Ni(0.51-0.53) as well as decrease of Pb (0.14-0.11) and Zn (0.5-0.4) wasobserved.
• Obtained differences are due to different methods of sequentialextraction and interpretation of mobile-stable fractions as well ascould be due to different methods of sewage sludge composting.
Conclusions (3)
• Amendment of the aerobically processed compostincreased HM potential availability excepting Cu due toits’ affinity to the organic matter and behavior in thesoils due to changes in speciation:
• In the soil-compost mixtures potential heavy metal availabilityranked in the order Zn > Mn > Pb > Cu while in
• compost Mn>>Zn>Pb>> Cu,
• sandy soil Zn >Mn>>Pb > Cu,
• clay soil Mn = Pb > Zn ≈ Cu.