J. Anal. Appl.

Pyrolysis 68
/69 (2003) 561
/575

www.elsevier.com/locate/jaap

Pyrolysis of sewage sludge: nitrogenated

compounds and pretreatment effects
Andres Fullana *, Juan A. Conesa, Rafael Font,
Ignacio Martı́n-Gullón
Department of Chemical Engineering, University of Alicante, Apartado 99, Alicante, Spain
Received 7 October 2002; accepted 7 March 2003

Abstract

Pyrolysis at high temperature (850 8C) of different sewage sludge has been studied in a
horizontal laboratory reactor. Volatile and semivolatile organic compounds from pyrolysis of
seven different samples have been identified and quantified. Results show that yields of several
compounds are similar to those obtained from other wastes in similar conditions.
Nitrogenated aromatic compounds have been identified as characteristic compounds in
sewage sludge pyrolysis due to their nitrogenous constitution. The origin and formation of
these compounds are discussed. The effect of different pre-treatment methods of sewage sludge
in the composition of pyrolysis gases has also been discussed.
# 2003 Elsevier Science B.V. All rights reserved.

Keywords: Sewage sludge; Pyrolysis; PAH; Nitrogenated PAH

1. Introduction

In the two last decades, wastewater treatment has been a very important
development probably due to the increasing limitations in water disposal. Due to
this increase, the amount of sewage sludge has also increased in accordance with this
development. In the European Union the amount of sewage sludge is expected to
increase by 50% to at least 11.2 millions tones dry solid by 2005.

* Corresponding author. Tel.: /34-9-6590-3400x3003; fax: /34-9-6590-3828.

E-mail address: andres.fullana@ua.es (A. Fullana).

0165-2370/03/$ - see front matter # 2003 Elsevier Science B.V. All rights reserved.
doi:10.1016/S0165-2370(03)00052-4
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Agricultural use of raw sludge or other composting practices are the best way for
using this waste. However, an important amount of sewage sludge cannot be used as
fertilizer due to the high heavy metal content. For this type of sewage sludge, land
disposal is the only possible application. Before disposal, sewage sludge has to be
treated to eliminate the bacteria, viruses and organic pollutants. Thermal treatment
(pyrolysis, gasification or combustion) is an interesting technique to stabilize sewage
sludge for disposal. Thermal treatments sometimes have been classified as a method
of disposal but in fact, it is a method of stabilization because the final destination of
ashes generated is the landfill.
Formation of organic compounds during pyrolysis and combustion could be a
limitation in the use of these materials in waste treatment. Identification and
quantification of products from pyrolysis plays an important role in exploitation
development of industrial pyrolysis devices. On the other hand, pyrolytic compounds
could be the major hazardous organic pollutant formed in incinerator systems due to
possible low local oxygen ratios. Therefore the knowledge of the possible formation
of these compounds could be an important tool in the design of clean air devices for
sewage sludge incinerators.
The direct study of incineration pollutant in industrial boilers is a complicated
task. The hazardous air pollutants (HAPs) in stacks are usually present in low yield
and the analyses of these compounds have to be conducted with target analysis,
requiring a previous identification of pollutants. In this sense, The Environmental
Protection Agency of the USA [1] has studied the emission factor for some organic
compounds (around 20) in industrial sewage sludge incinerators.
Some authors [2
/5] have studied pyrolysis of sewage sludge at temperatures
between 400 and 700 8C. The principal objective of these studies was the production
of fuel derived from this waste. Tirey et al. [6] have studied the sewage sludge
combustion in a laboratory system with a CDS Pyroprobe apparatus. The
experiments have been performed without considering an afterburner zone or
secondary chamber. Nowadays, governmental incineration regulations require an
afterburner or secondary chamber with a temperature higher than 850 8C and more
than 2 s of residence time. In the University of Dayton during the 1980s and 90s [7,8]
an extensive work about thermal degradation of some of hazardous pollutants
(added into the sludge) in incineration processes was carried out. Mascolo et al. [9]
have studied incineration of sewage sludge considering afterburner zone. The
authors have identified lineal hydrocarbon, aromatic and nitrogenated compounds
such as pyrroles, pyridines and nitriles. In this paper the author also studied the
effect of temperature, residential time and ratio of oxygen in the yield of organic
compounds formed during combustion.
In the incinerator, the major pollutants (excluding those formed in postcombus-
tion zones) are a consequence of low local oxygen concentration in high temperature
zones called ‘pyrolysis pockets’. The study of pyrolytic products would show a larger
quantity of possible pollutants from incineration. Obviously incineration will
produce lower yields of these products but the pyrolysis study could be an
interesting tool to identify the organic pollutant leading to subsequent posterior
research in combustion.
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Although the study of pollutants in laboratory system with oxygen is apparently

better that the study of pyrolysis (absence of oxygen) the major problem of this is the
control of grade of mixing between air and pyrolytic gases. Bad mixing produces a
large number of ‘pyrolysis pockets’ but if the system has good mixing the number of
‘pyrolysis pockets’ decrease and consequently quantity of pollutants. In this sense,
the pyrolysis study gives better information because it is independent of quality of
mixing. On the other hand, it is necessary to mention that pyrolysis does not show
pollutants that need oxygen for the formation.
In this work, pyrolysis products at 850 8C of seven different types of sewage
sludge have been studied. A large secondary reactor with 5
/7 s of residence time was
used to simulate reactions in the secondary chamber of the sewage sludge boilers.
The main objective of this work has been the identification of the major number of
possible hazardous organic pollutants in sewage sludge combustion and to find a
relation between these compounds and the treatment that has been performed to the
waste prior to pyrolysis.

2. Equipment and experimental procedures

2.1. Material

Seven sewage sludges from different plants were studied corresponding to

wastewater treatment plants from the Valencian Community (Spain). The sludges
were dried and grounded before its use. Table 1 shows the different origins of the
sewage, with the previous treatment and the physical aspect. Table 2 shows ultimate
analysis and concentration of hazardous metals.

Table 1
Origin and physical aspect of the sludge

Treatment in the water line Treatment in the sludge line Physical aspect

Sludge Physical
/chemical/primary se- Mechanical dehydratation Fibrous reddish

1 dimentation
Sludge Activated sludge Anaerobic digestion/mechanical Fine particulate gray
2 dehydratation
Sludge Physical
/chemical/activated Anaerobic digestion/mechanical Fine particulate gray
3 sludge dehydratation
Sludge Physical
/chemical Aerobic digestion/mechanical de- Fine particulate dark
4 hydratation gray
Sludge Physical
/chemical/activated Aerobic digestion/mechanical de- Fine particulate
5 sludge hydratation brown
Sludge Activated sludge Aerobic digestion/mechanical de- Fine particulate gray
6 hydratation
Sludge Physical
/chemical Chemical softening/mechanical de- Fibrous brown
7 hydratation
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Table 2
Ultimate analysis and major metal concentration in dry matter percentage

Ultimate analysis

Sludge 1 Sludge 2 Sludge 3 Sludge 4 Sludge 5 Sludge 6 Sludge 7

C 29.6 29.2 30.6 33.6 35.3 33.6 32.2

H 4.7 4.7 4.9 5.1 5.5 5.2 5.3
S 1 B/1 B/1 3 B/1 B/1 B/1
N 1.4 2.9 3.0 5.4 6.2 4.2 0.85
Major metals concentration
Cr 0.05 0.01 0.01 0.04 2.6 0.03 0.30
Fe 2.7 0.73 0.72 1.3 4.5 2.3 4.7
Ni nd 0.15 0.02 nd 0.01 nd 0.44
Cu nd 0.24 0.24 nd nd 0.15 1.3
Zn 0.22 0.59 0.22 1.0 0.03 0.38 0.8
Sr 0.43 0.57 0.43 0.33 0.19 0.38 0.28
Pb 0.01 0.01 1.2 0.05 0.82 0.03 0.11

The characterization of the sewage sludge waste was done in a previous paper [10].
The use of these sludges as agricultural fertilizer [11] is not possible due to high
contents of transition metals and consequently they are a potential incinerable waste.
For the particulate sludges, the sample is powdered with particle diameters less
than 0.1 mm. For the fibrous sludges, the size of the fibers was less than 0.5 mm.

2.2. Experimental procedure

A horizontal reactor furnace was used. The reactor used was a quartz cylinder,
where the sample was introduced inside the cylinder boat. The volatiles evolved were
cracked and burnt inside the reactor. The sample in the small boat was introduced at
constant velocity (0.5 mm s 1) into the furnace. The gas flow used was 280 ml
min 1 at 25 8C and 1 atm. For this flow the residence estimated time was 5
/7 s.
An experiment in pyrolysis was performed for each sewage sludge at 850 8C. The
volatiles evolved were collected in a TedlarTM bag for analysis of light hydrocarbon
compounds and the small tube containing the resin (XAD-2) was used to collect the
heavy volatile compounds. More details of reactor and sampling procedure can be
found elsewhere [12,13].

2.3. Analytical methods

The gases collected in a Tedlar† bag were analyzed by gas chromatography. The
Capillary Alumina-KCL PLOT column and FID detector were used to analyze light
hydrocarbon compounds: methane, ethane, ethylene, propylene, butane, acetylene,
benzene, toluene. . . On the other hand, the AllTech CTR1 column with TCD was
used in the analysis of O2, N2, CO2 and CO.
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The volatiles absorbed in the XAD-2 resin (around 3 g) were extracted with 100 ml
of dichloromethane, following the EPA 3540C method. An internal deuterate
standard (1,4-dichlorobenzene-d4, naphthalene-d8, acenaphthene-d10, phenathrene-
d10, chrysene-d12 and pyrene-d12) was added before the extraction. The deuterate
compounds are used to estimate quantitative analysis. Then the extract was
concentrated to 2 ml with a micro Kuderma-Danish.
Semivolatile organic compounds were analyzed by gas chromatography/mass
spectrometry (GC/MS). The capillary column DB-5 MS was used and the
compounds were identified by MS (15
/450 a.m.u., 70 eV). The qualitative
identification of compounds was performed comparing sample mass spectrum
with NIST database reference spectrum. The Lee and Kovad index [14,15] was used
to identify compounds with a similar spectrum. A semiquantitative estimation of the
yields was obtained using factors obtained for the deuterate internal standards (EPA
method 8270 section 7.7.3).

3. Results and discussion

Table 3 shows the yields of different pollutants identified in the pyrolysis of

sewage sludge. In Table 3, three types of compound have been classified: CO2, light
hydrocarbons and semivolatile compounds.
CO2 and CO yields are indicators of the oxygen present in the sample in pyrolysis
processes. The oxygen present could originate from two different sources: decom-
position of inorganic salts as carbonates or from pyrolytic decomposition of partially
oxygenated organic compounds such as cellulose, lignin, lipids or carbohydrates.
The results obtained correspond to an oxygen concentration between 7 and 12%,
indicative of an important amount of carbonates and oxygenated compounds in
sewage sludge. No relevant differences were found between the pretreatment of
sludge and CO
/CO2 yields.
Thirteen light hydrocarbons have been identified with a total yield between 8 and
12%. Although these compounds are the major yield of organic compounds
analyzed, their relevance, as pollutants is low. Only benzene and 1,3-butadiene are
HAPs, due to their carcerigen effects. The high concentration of these compounds in
the analysis suggests that they will be present in the incinerator devices.
A previous qualitative analysis with HRGC/MS using a GS-Q as column also
shows the presence of ammonia, hydrogen cyanide, acetonitrile and propanonitrile.
Unfortunately the Alumina-KCL PLOT column is too polar and retains these
compounds.
About 100 semivolatile compounds were identified. The total yield of these
compounds is between 1.8 and 3%. The compounds with higher yields are: styrene
(0.4%) benzonitrile (0.26%), propynylbenzene (0.22%), naphthalene (0.54%), ben-
zoacetonitrile (0.15%), acenaphthylene (0.13%) and phenanthrene (0.09%).
The majority of compounds identified are aromatics very similar to those
identified in previous work with different wastes [12,16,17]. This similarity is
expected because at a high temperature (850 8C) all compounds resulting from
 566
Table 3
Yields of compounds analyzed

Sludge 1 Sludge 2 Sludge 3 Sludge 4 Sludge 5 Sludge 6 Sludge 7

mg 100 mg 1 sludge
CO2 11.7 10.4 6.3 8.5 9.3 12.8 9.8

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CO 7.9 6.7 4.6 5.8 6.4 5.1 6.4
Methanea 3.13 2.83 2.8 2.9 3.37 3.21 3.13
Ethanea 0.2 0.16 0.17 0.13 0.15 0.14 0.22
Etylenea 4.86 3.43 3.77 2.79 3.5 3.35 4.9
Propanea 0.008 0.005 0 0.006 0.005 0 0.001
Propylenea 0.33 0.33 0.33 0.31 0.39 0.34 0.3178
Acetylenea 0.28 0.22 0.2 0.21 0.24 0.26 0.28
Butanea 0 0 0.028 0.022 0.035 0.019 0
Butenea 0.004 0.005 0.003 0.005 0.004 0.003 0.005
1,3-Butadienea 0.35 0.3 0.31 0.26 0.32 0.28 0.34
Butynea 0.025 0.023 0.02 0.02 0.026 0.013 0.0229
Hexanea 0.1 0.071 0.066 0.064 0.071 0.075 0.12
Benzenea 1.79 1.53 1.51 1.11 1.62 1.53 1.82
Toluenea 0.15 0.17 0.15 0.15 0.22 0.31 0.17
Total light hydrocarbons 11.227 9.074 9.357 7.977 9.951 9.53 11.3267
mg kg 1 sludge
Pyridine, 2-methyl-b,d 180 160 100 280 270 340 360
4-Pyridinaminec 82 50 21 64 37 nd nd
1-Hepthane, 2,4-dimethyl-b 4 28 nd 36 409 92 46
Pyridine, 3-methyl-b,d 150 68 85 290 140 420 300
m-Xyleneb 390 210 190 240 280 460 320
Phenyl acetyleneb 390 190 130 180 270 220 400
Styreneb 4500 2300 1700 1400 2400 1500 4100
Benzomethiolc 24 13 16 16 13 37 nd
Azidobenzeneb 64 29 21 14 32 4 11
Pyridine, 2-ethenyl-b 340 140 130 250 180 330 120
Pyridine, 3-ethenyl-b 130 84 42 94 65 83 85
3-Pentanone, 2,2,4,4-tetramethylb 160 47 190 390 100 620 nd
Anilineb,d 140 42 61 74 58 88 15
Phenolb 270 120 150 210 140 373 264
Benzonitrileb 2600 1300 100 1300 1400 1400 950
Styrene, m-methylb 470 280 280 300 260 440 460
Table 3 (Continued )

Sludge 1 Sludge 2 Sludge 3 Sludge 4 Sludge 5 Sludge 6 Sludge 7

p-Vinyltoluenob 140 46 52 223 84 85 17

Benzene, 1-ethenyl-3-methyl-b 48 23 25 19 26 22 60
Benzene, ethenylmethyl-b 24 13 11 0 18 11 55
Benzene, 1-propynylb 2200 1200 990 690 1130 790 2500

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4-Pyridinecarbonitrileb 96 33 34 115 55 171 17
Benzonitrile, 2-methyl-b 290 150 120 260 180 320 100
Benzonitrile, 3-methyl-b 260 120 110 230 140 310 66
c
Benzene, 1-methyl-2-(2-propenyl) 24 17 17 18 15 24 34
Benzene, divinylb 107 51 62 57 58 57 82
Indoleb 150 67 71 133 83 230 43
Azuleneb 204 96 120 110 99 160 180
Naphthalenea 10300 6200 5300 3000 5000 3600 9900
Benzo[b]tiopheneb,d 220 150 2300 210 120 nd 17
Cinnamonitrilec 110 52 26 9 77 440 37
Quinoxilinab 140 68 72 100 67 110 nd
Quinolineb,d 1200 610 560 770 690 920 410
1h-Benzimidazoleb 78 32 36 nd 36 18 13
Isoquinolineb,d 410 170 190 360 190 420 130
2-Nitro-6-picolinec 10 31 34 210 0 83 18
Benzeneacetonitrileb 1500 680 650 980 910 860 1500
Naphthalene, 2-methyl-b,d 880 550 590 240 460 1800 67
Quinoline, 2-methyl-b 96 47 48 nd 47 49 22
Naphthalene, 1-methyl-b,d 609 450 480 370 370 590 520
Biphenylb,d 610 310 320 210 330 260 410
Naphthalene, 1-azido-c 160 72 74 118 78 130 50
Biphenyleneb 180 46 65 46 49 99 53
2-Vinylnaphthaleneb,d 150 79 100 69 80 120 94
Naphthalene, dimethyl-b,d 74 46 55 18 43 72 25
1-Vinylnaphthaleneb,d 530 340 370 210 290 310 450
2,3-Dimethylnaphthaleneb,d 20 13 17 19 52 nd nd
Acenaphthylenea 2400 1600 1100 590 1200 820 2300
Pyridine, 3-phenyl-b,d 190 35 55 91 93 71 13
Acenaphthenea 69 33 37 42 37 53 64
1-Naphthalenecarbonitrileb,d 600 350 280 320 330 420 190
Dibenzofuraneb,d 15 8 8 8 8 11 16

567
2-Naphthalenecarbonitrileb 460 240 210 280 270 330 190
 568
Table 3 (Continued )

Sludge 1 Sludge 2 Sludge 3 Sludge 4 Sludge 5 Sludge 6 Sludge 7

Naphthalene, 1-(2-propenyl)-b 120 55 59 98 80 104 52

1h-Phenaleneb 60 47 54 38 42 57 54
Fluorenea 800 550 500 270 450 330 1200
Fluorene, methyl-b 240 170 170 150 160 220 230

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Carbazoleb 73 29 32 58 50 87 22
Naphthaleneacetonitrilec 44 43 31 48 32 58 26
Diphenylethyneb 68 48 51 36 40 36 61
9h-Fluorene, 9-methylethyleneb 48 26 30 30 25 32 21
Anthracene, 9,10-dihydro-b 68 36 46 42 46 87 44
Dibenzothiopheneb,d 98 59 96 115 80 150 27
Phenanthrenea 640 440 330 150 340 210 540
Anthracenea 280 200 210 100 160 120 250
p-Phenylbenzonitrileb 40 18 23 19 19 53 nd
Phenanthridineb 85 44 50 64 49 89 29
Carbazol-9-methanolb 79 42 39 63 52 86 45
Anthracene, ethenyl-b 14 64 77 73 74 97 65
Phenanthrene, methyl-b 53 27 34 37 39 49 39
9h-Fluorene-2-carbonitrileb 23 12 13 13 13 22 11
Phenanthrene, 3-methyl-b,d 66 95 54 42 38 57 51
Phenanthrene, 2-methyl-b,d 120 69 78 70 57 110 36
Benzo[def]fluoreneb 44 95 16 0 22 43 27
Anthracene, 9-methyl-b 29 88 14 27 93 nd 50
Phenanthrene,9-methyl-b 82 198 33 83 nd 116 nd
9h-Fluorene-2-carbonitrileb 20 13 12 48 28 43 23
2-Phenylnaphthalenec 140 68 83 51 79 74 94
Fluorene, 2-carbonitrileb 21 12 11 22 13 17 10
Benzonitrile, 3-(2-phenylethene)c 18 10 14 12 9 14 10
Naphthalene, 2-phenyl-b 36 23 29 25 19 29 27
2-Phenylnaphthaleneb 75 77 45 0 35 67 0
Fluoranthenea 87 110 250 100 160 120 120
Naphtalene, 2-benzylb 36 14 16 18 13 25 11
Acenaphtho(1,2-b)pyridineb 44 94 29 27 25 58 0
2,3-Dihydrofluoranteneb 130 97 92 74 72 126 89
Pyrenea 430 390 390 160 250 290 470
Indene(1,2,3-ij)isoquinolineb 32 20 56 78 82 151 11
11h-Benzo[a]fluoreneb 80 61 69 35 52 84 84
Table 3 (Continued )

Sludge 1 Sludge 2 Sludge 3 Sludge 4 Sludge 5 Sludge 6 Sludge 7

11h-Benzo[b] fluoreneb 82 94 61 42 63 84 150

Pyrene, methyl-b 53 95 75 28 42 73 76
Benzo c phenanthreneb 51 53 40 22 31 48 61
Naphtaceneb 19 16 13 12 12 20 16

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Benzo(a) anthracenea 121 105 99 57 71 101 120
Crysenea 92 80 77 40 50 91 73
Benzo(a)pyrenea 86 75 64 35 46 72 91
Benzo(b)fluoranthenea 20 17 15 8 11 16 21
Benzo(k)fluoranthenea 63 57 52 27 34 52 65
Indeno (1,2,3-cd) pyrenea 9 7 6 4 5 6 8
Benzo(g,h,i)perylenea 7 6 5 3 4 4 7
Total semivolatile compounds 39 880 23 441 20 665 18 171 22 257 23 564 33 445

P qffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi2ffi
(ILib × IUnk )
 Forward value 100 P P
ILib × IUnk
where: Ilib refers to the intensity of the method spectrum at a given mass; IUnk refers to the intensity of the ‘unknown’ sample spectrum at a given mass.
a
Target analysis standard.
b
Forward values* larger than 90 and quantification using internal standard.
c
Forward values* between 80 and 90 and quantification using internal standard.
d
Difference in Lee and Kovad’s index lesser than 5% respect index published in [11,12].

569
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primary decomposition react to form similar thermal stable compounds in secondary

reactions. In this case, nitrogenated aromatic compounds were also identified due to
the fact that nitrogen is present in the original waste. Similar compounds have been
identified in wastes with a high nitrogen content [13,18,19].
An appreciable amount of nitrogen is present in sewage sludge due to the proteins
and nucleic acids from original waste and dead microorganisms [20]. A detailed
analysis of the compounds in Table 3 shows that the major yields of nitrogenated
compounds are cyano compounds and heteroaromatic ring. Only aniline was
identified as an amino compound. This fact is very interesting because the nitrogen
functionalities in proteins are amino and in lessen quantity heteroaromatic ring.
Fig. 1 compares the molecular structure of nitrogenated aromatic compounds
obtained from sewage sludge 1 with their homologue. Nitrogenated organic
compounds have a high analogy with non-nitrogenated PAH which suggests that
pathways of formations of these kinds of compounds are very similar.
Cyano aromatic compounds could be formed in two different ways: from
dehydrogenation of amino group present in proteins, and from hydrogen cyanide
addition of light aromatic hydrocarbons formed in primary decomposition.
Probably, both processes are simultaneous in the pyrolysis of sewage sludge. Recent
studies [21
/23] about formations of ammonia and hydrogen cyanide in the pyrolysis
of nitrogenated fuels concluded that waste decomposes firstly to ammonia and
nitrogenated light compounds and secondly cracking reactions provide hydrogen
cyanide. Furthermore, yields of HCN increase with temperature, but curiously as
residence time increases at 800 8C, the yield of HCN decreases. This result shows
that HCN is probably incorporated at organic compounds during secondary
reactions. Fig. 2 shows a scheme of the process described in the formation of
HCN and ammonia.
On the other hand, Ricca et al. [24] suggested pathways where nitrogen is
incorporated in aromatic organic compounds with the addition of HCN forming
cyano aromatic compounds similar to those found in the present work. A similitude
can be found between this pathway and the acetylene addition described by Bitter
and Howard [25].
The different compounds with heteroaromatic ring found in this work can have
two origins: firstly the decomposition of nucleic and amino acid with heteroaromatic
ring can produce this kind of compound, and on the other hand, the cyclation
reactions of cyano aromatics compounds. Indole and piridine found in this work
could be formed directly by decomposition of amino acid with heteroaromatic ring
(proline, tryptophan and histidine). Heteroaromatics structures such as those present
in nucleic acids (pyrimidine and purine) have not been identified.
However, the major part of the compounds with heteroaromatic ring found in this
work are 6-atoms ring whilst 5-atoms ring are usually present in biological matter.
The 6-atoms ring could be formed by cyclation of cyano compounds. Ricca et al. [24]
also proposed a plausible cyclation mechanism of cyano aromatic compounds.
Fig. 3 shows the relation between light aromatic compounds (benzene, pyridine
and toluene) with some semivolatile compounds identified in this work considering
acetylene and the HCN addition.
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Fig. 1. Comparison between aromatic hydrocarbons and nitrogenated aromatic compounds. Numbers
under the structures are yield in mg kg1 for sludge 1.

A relationship between the pretreatment of each sludge and the yields of the
different compounds produced by pyrolysis has been sought. Fig. 4 shows the
percentage (from total semivolatile compounds) of major compounds for each
sample, and it can be observed that shapes of distributions are not very different.
Only sludges with aerobic pretreatment show some lower concentration in
naphthalene. This suggests that treatment in sludges is not very important in the
composition of pyrolysis gas at 850 8C. This result can also be extrapolated to
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Fig. 2. A schematic diagram showing major routes of pyrolysis organic compounds with nitrogen.

Fig. 3. Relation between nitrogenated and non-nitrogenated compounds in pyrolysis of sludge.

compounds with lower yields. However, the total amount of semivolatile organics
can be correlated with the pretreatment of sewage sludge. Fig. 5 shows the total
yields of semivolatiles compounds for each sludge. It can be observed that sludge
with anaerobic and aerobic digestion has lower total yield than undigested sludges.
Sludge treated by physical
/chemical treatment and aerobic digestion presents lower
yields.
Nitrogen present in semivolatile compounds has been plotted in Fig. 6a. This
figure is quite similar to Fig. 5 with the exception of sludge 7 that presents a lower
yield than the other sludge. This behavior is probably due to the physical
/chemical
treatment performed with sludge 7 that produces the reduced microbial activity and
consequently organic nitrogen. This data is in contrast with total nitrogen found
with ultimate analysis. Fig. 6b shows the percentage of nitrogen (total nitrogen basis)
found in organic compounds. In this figure it can be appreciated that percentage of
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Fig. 4. Percentage of major compounds in each sewage sludge studied.

Fig. 5. Effect of sewage sludge treatment in total semivolatile compounds.

total nitrogen that it is incorporated in the organic structure is lower in the sludges
with some digestion. Differences between two figures are due to high concentration
in total nitrogen in digested samples that it is not extrapolated to organic nitrogen
present in semivolatile compounds. During digestion of fresh sewage sludge,
microorganisms digest nitrogenated organic matter forming mineral nitrogen such
as NH4 and NO3. This process is showing at same time that decomposition of
organic matter to CO2 or methane results in an increase in the concentration of total
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Fig. 6. Effect of sewage sludge treatment in total nitrogen as semivolatile compounds.

Fig. 7. Yield of total PAH (16 PAH considered as priority pollutants by EPA).
 A. Fullana et al. / J. Anal. Appl. Pyrolysis 68
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nitrogen, but this inorganic nitrogen it is not able to form HCN and add to aromatic
structures.
The yields of 16 PAH considered as priority pollutants by EPA have been
quantified using target analysis. Results of this analysis (Fig. 7) show a good
correlation with semivolatile compounds (Fig. 5).

Acknowledgements

Financial Support for this work was provided by CYCIT-Spain, Research project
AMB99-420.

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