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J. Anal. Appl.

Pyrolysis 80 (2007) 61–76


www.elsevier.com/locate/jaap

Thermal degradation of pesticides under oxidative conditions


Osvalda Senneca a,*, Fabio Scherillo b, Alfredo Nunziata b
a
Istituto di Ricerche sulla Combustione-Consiglio Nazionale delle Ricerche, P.le V. Tecchio 80, 80125 Napoli, Italy
b
B.A.T. Italia S.p.A. Ricerca & Sviluppo, c/o Università degli Studi di Napoli ‘‘Federico II’’, Dip. di Chimica Organica e Biochimica,
Complesso di Monte S. Angelo, Via Cinthia, 45-80126 Napoli, Italy
Received 2 November 2006; accepted 8 January 2007
Available online 12 January 2007

Abstract
The paper addresses thermal decomposition under oxidative conditions of 16 pesticides. Within the scope of the paper such 16 substances have
been divided in four groups:

(1) Pesticides with linear molecule belonging to the family of aldoxime carbamates.
(2) Benzimidazolylcarbamates.
(3) Pyrethroids.
(4) Pesticides containing one aromatic (heterocyclic in one case) ring within their structure.

The experimental work consists of non isothermal thermogravimetric analysis with 5% oxygen in helium, using a TG–DSC–MS system
equipped with a Skimmer device that ensures the simultaneousness of thermogravimetric analysis with the analysis of evolved gas and rules out the
possibility of secondary reactions in the gas phase.
Results have been analyzed in order to highlight similarities and differences in the modes of decomposition of pesticides within and among the
four mentioned groups. The influence of oxygen and the yield in gaseous products has also been addressed.
# 2007 Elsevier B.V. All rights reserved.

Keywords: Thermal decomposition; Combustion; Pesticides; Pyrolysis

1. Introduction massive use in agriculture. The possibility of accidents has also


received some attention in the literature [6–13].
Thermal decomposition and combustion of pesticides can A third field of application for studies on thermal
occur in different situations. First of all during the processing of decomposition of pesticides lies in the newly born problem
vegetables and foods poisoned by traces of pesticides. The of the disposal of unused stocks. Indeed over the last years
possibility that pesticides residues in food break down and form several pesticides and chemicals have been withdrawn or
chemical species harmful for human health has indeed been restricted from use in agriculture because of environmental
addressed in the last years [1–3]. An interesting case is that of concerns. Available stocks of these chemicals are temporarily
tobacco [4,5] because during cigarette smoke temperatures as stored in warehouses, but their final destination is uncertain at
high as 900 8C can be encountered, enabling the break down of the moment. Thermal/inceneration processes may be consid-
chemicals present in the formulation. ered as an option for the disposal of this very particular type of
The study of thermal decomposition/combustion of pesti- wastes, provided that this process can be run safely and with no
cides is also relevant to the assessment of risk of heat up and harm for public health and environment [14,15].
fires at warehouses. Very large amounts of pesticides are indeed Thermal degradation of some pesticides has already been
stored in magazines every day as a consequence of their addressed in past literature [16–26] in particular that of
aldoximes [17–20] and chlorine pesticides [21]. The latter
indeed received special attention because of the possibility of
* Corresponding author. Tel.: +39 081 7682969; fax: +39 081 5936936. formation of very toxic chlorine containing species in case of
E-mail address: senneca@irc.na.cnr.it (O. Senneca). chemical fires. For other pesticides the degradation in crop
0165-2370/$ – see front matter # 2007 Elsevier B.V. All rights reserved.
doi:10.1016/j.jaap.2007.01.002
62 O. Senneca et al. / J. Anal. Appl. Pyrolysis 80 (2007) 61–76

storage and in the environment is well documented but the allows better comprehension of the modes of decomposition and
effect of heat treatment on degradation has been little of the yield in gaseous products.
investigated. Sixteen pesticides have been investigated. They have been
Available literature to date reports quite different patterns of divided in four groups according to their chemical structure:
thermal decomposition of pesticides. Some chloroorganic
pesticides undergo simple evaporation and sublimation, while (1) Aldoxime carbamates, characterised by a linear molecule;
others devolatilise with chemical changes in the system. Some (2) Benzimidazolylcarbamates;
aldoximes decompose by an intramolecular cyclic mechanism (3) Pyrethroids;
leading to nitriles, carbon dioxide and amine, others instead (4) Pesticides containing one aromatic (heterocyclic in one
follow a thermal Beckmann rearrangement. Apparently the case) ring within their structure.
presence of a benzenic ring in the molecule plays an important
role in the thermal feature of pesticides. This has been observed Notably all these substances are commonly used in
for organophosphorous compounds by Nageswara et al. [22] agriculture. However some of them, in particular those in
who reported a different behaviour between CPP, an the first two groups, are known to be highly toxic for humans
organophosphorous compound with a benzenic ring in its and the environment, therefore it is likely that an official ban
structure, and MCP, an organophosphorous compound with for their use will be made in Europe and around the globe as
linear structure. Differences regarded in particular the soon as effective alternative substances are available. The
relevance of combustion versus decomposition, the combustion disposal of stocks will then become an important issue.
products being more abundant in CPP. Experimental results are analyzed in order to highlight
The present work aims to gather information on the character similarities and differences in the modes of decomposition of
and pathways of the thermal processes occurring upon heating different pesticides. In particular results are discussed in order
different types of pesticides in an oxygen containing atmosphere. to identify a relation between the chemical structure and the
Experimental work consists of non-isothermal thermogravi- mode of thermal decomposition of pesticides.
metric experiments coupled with differential scanning calori-
metry and with mass spectrometric analysis of the gaseous 2. Materials
products. The main strength of the work lies in the experimental
apparatus: a TG–DSC–MS equipment with only 12 mm transfer Experiments have been carried out on chemicals produced
path between the sample and the gas analysis device. This rules by Sigma–Aldrich. Reagents consisted in 98% purity solid or
out condensation and secondary reactions in the transfer line and liquid samples.
Table 1
Pesticides of group 1 (pesticides with linear molecule)
Name Formula CAS MW (g/mol) MR (8C)

Aldicarb C7H14N2O2S 116-06-3 190.27 100.3–101.1

Aldicarb sulfoxide C7H14N2O3S 1646-87-3 206.26 106.4–107.0

Aldicarb sulfone C7H14N2O4S 1646-88-4 222.26 130.3–130.6


O. Senneca et al. / J. Anal. Appl. Pyrolysis 80 (2007) 61–76 63

Table 2
Pesticides of group 2 (benzimidazolylcarbamates)
Name Formula CAS MW (g/mol) MR (8C)

Benomyl C14H18N4O3 17804-35-2 290.32 –

Carbendazim C9H9N3O2 10605-21-7 191.19 307.0–310.4

2.1. Aldoxime carbamates (pesticides with linear replaced by a 2-methyl-3-benzyl propane, moreover the
molecule) benzilic group is chlorinated in Fenvalerate and is chlorinated
and additionally linked to a CF3 group in t-Fluvalinate.
Three aldoxime carbamates have been investigated:
Aldicarb, Aldicarb sulfone and Aldicarb sulfoxide. Their 2.4. Pesticides containing one aromatic (heterocyclic in
chemical structure and properties are reported in Table 1. one case) ring within their structure
Aldicarb is a systemic carbamate pesticide, nematicide and
acaricide traded under the name of Temik. Aldicarb sulfone Five pesticides with an aromatic ring and one with an
and aldicarb sulfoxide are biodegradation byproducts of heterocyclic ring within their structure have been chosen:
Aldicarb itself. Aldicarb and its metabolites have indeed Iprodion, Chlorothalonil, Procymidone, Butralin, Maleic
similar linear chemical structure. Hydrazide. Their structure, chemical formula and properties
are reported in Table 4. It can be noted that Iprodione,
2.2. Benzimidazolylcarbamates Chlorothalonil and Procymidone are chloro-organic pesticides;
Iprodione and Procymidone contain a dichlorophenyl dicar-
Two widely used benzimidazolylcarbamates have been boximide group; Butralin contains a dinitrobenzenamine but no
used, namely Benomyl and Carbendazim. Their chemical chlorine; Maleic hydrazide is the only pesticide within the
structure and properties are reported in Table 2. group which does not contain a benzenic ring, but rather a
pyridazinic ring.
2.3. Pyrethroids
3. Experimental
A set of six pyrethroids has been investigated: Permethrin,
a-Cypermethrin, Deltamethrin, l-Cyalothrin, Fenvalerate and 3.1. Apparatus
t-Fluvalinate. All are synthetic substances developed in order
to increase the stability of the natural mixtures of pyrethrins Experiments have been carried out with a thermal analysis
(esters derived from dried chrysantemum). The chemical instrument Netzsch STA 409 CD TG/DSC connected to a
structure and properties of the pyrethroids investigated are Balzers quadrupole Mass Spectrometer QMG422 (0–300 amu)
reported in Table 3. It can be noted that the structure of by a special Coupling System, which insiders call Skimmer.
Permethrin contains a diphenil ether and a ciclopropane; it is This special apparatus is described in Fig. 1. Notably the
also chlorinated to increase stability. a-Cypermethrin is similar coupling system is made up of two orifices in tandem, which are
to Permethrin with the addition of a cyano group. The structure held at the same temperature as the sample. The coupling
of l-Cyhalothrin resembles that of a-Cypermethrin but one of system lies indeed right inside the thermobalance furnace,
the chlorines is replaced by a CF3 group. Deltamethrin is also which is tailor made for this purpose. The first orifice serves as a
very simlilar to a-Cypermethrin, but chlorine is substituted by divergent nozzle and creates a compression zone into which the
bromine. Fenvalerate and t-Fluvalinate are somewhat different second orifice, the so-called Skimmer, extends and creates a
in structure from the previous four: they contain a diphenil ether parallel molecular beam, which is directed at the ion source of
as the other four and a cyano group as a-Cypermethrin, the QMS.
Deltamethrin and l-Cyhalothrin. On the contrary, Fenvalerate The short transfer path (only 12 mm) of the gas particles
and t-Fluvalinate do not contain a ciclopropane, which is through the two orifices, which are located directly above the
64 O. Senneca et al. / J. Anal. Appl. Pyrolysis 80 (2007) 61–76

Table 3
Pesticides of group 3 (pyrethroids)
Name Formula CAS MW (g/mol) MR (8C)

Permethrin C21H20Cl2O3 52645-53-1 391.29 41.2–44.0

a-Cypermethrin C22H19Cl2NO3 67375-30-8 416.30 82.1–83.1

Deltamethrin C22H19Br2NO3 52918-63-5 505.21 100.2–101.0

l-cyhalothrin C23H22ClNO3 91465-0-6 449.86 49.8–50.8

t-fluvalinate C26H22ClF3N2O3 102851-06-9 502.92 Liquid at room temperature

Fenvalerate C25H22ClNO3 51630-58-1 419.91 54.5–57.8


O. Senneca et al. / J. Anal. Appl. Pyrolysis 80 (2007) 61–76 65

Table 4
Pesticides of group 5 (pesticides containing one aromatic (heterocyclic in one case) ring within their structure)
Name Formula CASRN MW (g/mol) MR (8C)

Butralin C14H21N3O4 32629-47-9 295.34 59.9–60.8

Chlorothalonil C8Cl4N2 1897-45-6 265.91 252.7–253.2

Maleic hidrazide C4H4N2O2 123-33-1 112.09 292.6–296.0

Iprodion C13H13Cl2N3O3 36734-19-7 330.17 134.3–134.6

Procymidone C13H11Cl2NO2 32809-16-8 284.14 165.4–166.1

sample, guarantees a short response time and thus a perfect increase in sensitivity (depending on the mass number, the
temperature–time correlation. Holding the sample and orifice intensity of the measurement signal is increased by up to over
system at the same temperature eliminates the disadvantageous 100 times). At the same time the special design of this apparatus
condensation (for non-permanent gases) which usually occurs rules out the possibility of secondary pyrolysis reactions as well
with capillary coupling systems and which is more or less as of oxidation reactions in the transfer line and therefore
dependent on the mass number. The result is a considerable guarantees that species detected by the MS are really primary
66 O. Senneca et al. / J. Anal. Appl. Pyrolysis 80 (2007) 61–76

Fig. 1. Skimmer TG–MS apparatus.

products. This feature is most important in the present work and without confirmation by complimentary methods such as py/gc/
allows to regard the MS spectra as a finger print of the chemical ms, therefore a detailed analysis of the chemical composition of
products that are produced in the reaction chamber at a known the gaseous products of decomposition has not been attempted.
temperature. The comparative analysis of TG–MS–DSC results has been
rather directed to characterise the extent of degradation of the
3.2. Procedure pesticides molecules as a function of temperature and the
presence of oxidative reactions.
The experimental procedure was as follows: the temperature
was increased from ambient temperature to 850 8C with heating 4. Results
rate of 10 8C/min. Small amounts of sample (1–10 mg) were
used for each experiment in order to reduce the effects of side 4.1. Aldoxime carbamates (pesticides with linear
reactions and mass and heat transfer limitations. Gases of molecule)
chromatographic grade were used. Tests were carried out at
atmospheric pressure with a gas flow rate of 50 ml/min. All Aldicarb, Aldicarb sulfoxide and Aldicarb sulfone exhibit
samples were tested with an atmosphere of 5% oxygen in similar TG–DTG curves. The TG, DTG and DSC curves of
helium. Some samples were additionally tested in 100% helium Aldicarb are shown in Fig. 2A. The MS curves obtained for
in order to compare the pyrolythic behaviour under oxidative Aldicarb are also reported in Fig. 2B. Notably the experimental
and purely inert conditions, however the number of tests under curves obtained for Aldicarb sulfoxide and Aldicarb sulfone
inert conditions was kept to a minimum in order to avoid have not been reported for sake of brevity, but results will be
excessive fouling and damage of the skimmer apparatus. taken into account in the foregoing analysis.1 Aldicarb and its
Thermogravimetric data have been worked out in order to oxides melt around 100 8C (140 8C at the most) and
obtain TG-curves, reporting the weight loss as a function of immediately after experience a 100% weight loss. Around
time/temperature and DTG curves, reporting the derivative of 150 8C the DTG and the MS curves present a single peak and
the weight loss with respect to time. DSC curves as a function of the DSC reveals a moderately exothermic reaction. The
time/temperature have also been obtained. Notably DSC results bargraph spectrum obtained for Aldicarb at 150 8C is reported
obtained within the TG-Skimmer tests are not quantitatively in Fig. 2D. The spectrum of Aldicarb published in NIST library
accurate, however they provide valuable qualitative informa- is also reported in Fig. 2 for comparison. Notably major
tion such as the occurrence of melting and the exothermic/ differences exist in these spectra as regards both the m/z values
versus endothermic nature of the processes. detected and their intensity. This indicates that thermal
Results of the MS analysis have been worked out in order to degradation occurs upon heating in the thermogravimetric
obtain bargraph spectra (at selected temperature) and MS apparatus already at 150 8C. From a more detailed analysis of
curves, which report the profiles of ion current intensity as a
function of temperature for a selection of m/z. Notably it is
1
difficult to assign individual m/z values to a single compound Additional figures are available as supplementary material.
O. Senneca et al. / J. Anal. Appl. Pyrolysis 80 (2007) 61–76 67

Fig. 2. Experimental results of Aldicarb. (A) TG and DTG; (B) selected MS curves; (C) mass spectrum at T = 154 8C; (D) mass spectrum at T = 267 8C. NIST
spectrum is reported for comparison.

the spectrum in correspondence with the DTG peak it can be molecule. It can also be noted that m/z 44 is released mainly at
noted that the fragment detected with highest intensity is m/z 41 150 8C, whereas at higher temperatures its release appears
followed by m/z 44. Although no electron density estimations negligible, this suggests that m/z 44 arises from a primary
have been made within this work to assess the most probable decomposition product, possibly CH2NO or CO2. Also m/z 27
fragmentations, m/z 41 can be tentatively attributed to a C3H5 and 68 are detected for all the three samples investigated
group arising from the fracture of the right hand side of the suggesting that the cyano group –C N produces HCN (27 amu)
68 O. Senneca et al. / J. Anal. Appl. Pyrolysis 80 (2007) 61–76

and C4H6N (68 amu). m/z 48, 100, 115 are also observed in case of Benomyl m/z 29 peaks at 235 and 250 8C, m/z 16 peaks
Aldicarb, reasonably associated to sulphur products CH4S, at 250 8C, m/z 28 at 280 8C suggesting that CH3 (MW 15) and
C4H6NS and C5H9NS. m/z 64 is instead obtained from Aldicarb CHO (MW 29) are released first, followed by CO (MW 28). In
sulfoxide and may be associated to CH4SO (64 amu); m/z 80 is the case of Carbendazim m/z 29, 15 and 31 peak at 235 and
observed in Aldicarb sulfone and can be possibly attributed to 280 8C, possibly due to the release of CH3 (MW 15) and CH3O
CH4SO2 (80 amu). (MW 31).
If this interpretation is valid, it is be concluded that thermal Above 400 8C the MS curves reveal m/z 44, 28, 18, 30 which
degradation of Aldicarb and its oxides around 150 8C is caused can be easily attributed to oxidized species. The abundance of
by the fracture of the parent molecules at different points. The oxidized species released at this stage suggest that oxidative
fragmentation of the left side of the molecule produces similar reactions aid the rupture of the benzymidazol group. This is
species for the three samples, while the fragmentation of the supported also by results of DSC that in this temperature range
right hand side of the molecule produces somewhat different show a marked heat production. Under this hypothesis a weight
sulphur containing species. The process is moderately loss of 46% is expected for Benomyl and of 67% for
exothermic but the abundance of hydrocarbons suggests that Carbendazim, which is indeed consistent with experimental
degradation products prevail over combustion products and that results. Oxidized species remain abundant up to 750 8C when
the presence of oxygen in the reaction environment dos not residues of thermal decomposition have been fully consumed
affect the course of pyrolysis of these pesticides. by oxidative/combustion reactions.

4.2. Benzimidazolylcarbamates 4.3. Pyrethroids

Fig. 3 reports the TG–DTG–DSC and the MS curves of Common features have been observed also in the behaviour
Benomyl as well as a selection of spectra. Results obtained for of the six pyrethroids investigated. Experimental results of a
Carbendazim are not reported for sake of brevity1 however the selection of three of them are reported in Figs. 4–6. Other
two benzymidazolyl carbamates examined in the present work results have not been reported for sake of brevity, but will
both undergo multiple stages of weight loss. More in detail however be taken into account in the foregoing analysis (see
Benomyl exhibits three marked DTG peaks at 120, 235 and Footnote 1). All pyrethroids melt at low temperature (50–
340 8C and a shallow shoulder around 400 8C. The MS and the 100 8C), then they lose weight in one abrupt step. The DTG,
DSC curves are similar to the DTG curves up to 400 8C. Three DSC and MS curves exhibit a marked peak at temperatures
endothermic peaks are indeed observed in this temperature comprised between 280 and 320 8C. As the temperature is
range. However at higher temperature the MS and the DSC further increased very modest or negligible weight loss is
reveal the existence of two additional exothermic processes registered by the TG, nevertheless the MS curves exhibit a
with peaks at 400 and 550 8C. Results obtained for second important peak and the DSC shows the occurrence of an
Carbendazim are quite similar but peaks occur at 235, 340, exothermic process.
410 and 610 8C. The appearance of peaks in the MS and in the DSC when the
Comparison of the spectra obtained throughout the weight loss is negligible needs to be examined thoroughly. This
experiments with those available in NIST library reveals circumstance was not expected because the Skimmer TG–MS
marked differences, suggesting that benzymydazolycarbamates apparatus used in the present work was purposely designed to
undergo thermal degradation. Notably the early peak at 120 8C ensure negligible transfer time of the gaseous products from the
is observed only for Benomyl and accounts for 35% weight TG to the MS. In fact the DTG and the MS curves did exhibit
loss. It can be hypothesised that this peak is due to the similar patterns as regard the number and position of peaks
fragmentation of the side chain C5H10NO of Benomyl, which is when the same experimental apparatus and experimental
indeed absent in Carbendazim. On the basis of the molecular procedure was applied to pyrolysis of the previous two groups
weight this fragmentation should cause the loss of 33% sample of pesticides as well as to other materials such as coal and
mass in good agreement with experimental results. cellulosic materials [27,28]. It is therefore believed that the
After this process both Benomyl and Carbendazim have one appearance of MS peaks when the weight loss is negligible is
linear side chain. In the intermediate temperature range in fact related to some peculiar feature of pyrethroids. It is possible
the two substances exhibit very similar behaviour, both having that upon heating at approximately 300 8C pyrethroids produce
two DTG peaks at 235 and 340 8C. It could be hypothesized some chemical species that do not pass effectively through the
that in this temperature range the other linear side chain starts to Skimmer orifice and partly stick to the walls of the apparatus.
break up producing low molecular weight species. However the This is suggested also by the observation of some degree of
detachment of the entire chain would bring about a loss of 25% fouling of the apparatus and of some instability of the pressure
and 39% of the initial weight for Benomyl and Carbendazim, inside the Skimmer, so much so that after each experiment with
respectively, against an experimental value of only 16% for pyrethroids extensive cleaning of the apparatus was necessary
Benomyl and 20% for Carbendazim. This discrepancy may to restore its original performance. When the temperature is
indicate that not all the chain is broken, but only its terminals. further raised the products stuck inside the apparatus undergo a
As a matter of fact the MS curves of both Benomyl and second exothermic reactive process, which is detected by the
Carbendazim exhibit a multitude of very close peaks: in the MS and DSC but not by the thermobalance.
O. Senneca et al. / J. Anal. Appl. Pyrolysis 80 (2007) 61–76 69

Fig. 3. Experimental results of Benomyl. (A) TG and DTG; (B) selected MS curves; (C) mass spectrum at T = 120 8C; (D) mass spectrum at T = 235 8C. NIST
spectrum is reported for comparison.
70 O. Senneca et al. / J. Anal. Appl. Pyrolysis 80 (2007) 61–76

Fig. 4. Experimental results of a-Cypermethrin. (A) TG and DTG; (B) selected MS curves; (C) mass spectrum at T = 290 8C; (D) mass spectrum at T = 497 8C. NIST
spectrum is reported for comparison.
O. Senneca et al. / J. Anal. Appl. Pyrolysis 80 (2007) 61–76 71

Fig. 5. Experimental results of Deltamethrin. (A) TG and DTG; (B) selected MS curves; (C) Mass spectrum at T = 300 8C; (D) mass spectrum at T = 508 8C. NIST
spectrum is reported for comparison.
72 O. Senneca et al. / J. Anal. Appl. Pyrolysis 80 (2007) 61–76

Fig. 6. Experimental results of t-Fluvalinate. (A) TG and DTG; (B) selected MS curves; (C) mass spectrum at T = 310 8C. NIST spectrum is reported for comparison.

Comparison of the spectra obtained at different temperature associated production of CO, CO2, H2O, dominates as the
with NIST published spectra can turn helpful to understand the temperature is raised above 400–500 8C.
nature of the processes that take place at the different stages of
reaction. The experimental spectra obtained around 300 8C 4.4. Pesticides containing one aromatic (heterocyclic in
moderately differ from NIST ones, differences lying only in the one case) ring within their structure
higher intensity of low molecular mass fragments and in the
presence of m/z 28, 44, 18. This finding suggests that in the first Figs. 7–9 report the TG–DTG–MS curves and the spectra at
step the main process is evaporation accompanied by some given temperatures for a selection of pesticides containing one
decomposition and oxidation. In the spectra obtained at higher aromatic (heterocyclic in one case) ring within their structure.
temperature differences are more marked denoting a greater Results of the other pesticides investigated within this category
extent of decomposition and the progression of oxidation. as well as the DSC results have not been reported for sake of
Oxidation species dominate the MS spectra above 500 8C. The brevity (see Footnote 1).
DSC results also show marked heat production above 500 8C. For all these samples two different temperature regions can
Altogether results suggest that pyrethroids undergo evapora- be distinguished across 300 8C. The TG indicates 100% of
tion, oxidative pyrolysis and char combustion. Oxidation, and weight loss below 300 8C. Above 300 8C the TG registers little
O. Senneca et al. / J. Anal. Appl. Pyrolysis 80 (2007) 61–76 73

Fig. 7. Experimental results of Chlorothalonil. (A) TG and DTG; (B) selected MS curves; (C) mass spectrum at T = 230 8C. NIST spectrum is reported for
comparison.

or negligible weight loss, nevertheless the MS still detects the Major differences are observed between the experimental and
release of several chemical species. This phenomenon, already NIST spectra. The abundance of m/z 109 and of several species
observed for pyrethroids, has been attributed to the formation in with m/z in the range 30–133 clearly indicates the occurrence of
a first instance of some heavy and sticky products that deposit pyrolythic breakage of the carbon ring.
on the furnace and on the Skimmer walls to be further Results of Maleyc Hydrazide, Procymidone, Butralin and
decomposed or oxidized as the temperature is increased. Iprodion are similar to results of Chlorothanolin as regards the
Fig. 7 shows the results obtained for Chlorothalonil. The shape of the DTG curves. Figs. 8 and 9 report results relative to
weight loss starts above 150 8C, well below the nominal melting Maleyc Hydrazide and Iprodion. Results of Procymidone and
temperature of 253 8C, producing a DTG peak at T = 230 8C. In Butralin are not reported for sake of brevity. In the case of Maleyc
this event over the 95% of the sample weight is lost. The remnant hydrazide the weight loss starts above 220 8C and occurs in
few percent is lost slowly up to 500 8C. The DSC curve shows an parallel with melting with DTG and DSC peaks at T = 300 8C.
endothermic peak at 230 8C. The MS curves peak also at Follows the slow loss of the residual 5% weight. Procymidone
T = 230 8C, but the peak is very broad and long tails are observed. melts at 166 8C, loses 95% of its weight between 180 and 280 8C
74 O. Senneca et al. / J. Anal. Appl. Pyrolysis 80 (2007) 61–76

Fig. 8. Experimental results of Maleic Hydrazide. (A) TG and DTG; (B) selected MS curves; (C) mass spectrum at T = 300 8C; (D) mass spectrum at T = 400 8C.
NIST spectrum is reported for comparison.
O. Senneca et al. / J. Anal. Appl. Pyrolysis 80 (2007) 61–76 75

Fig. 9. Experimental results of Iprodion. (A) TG and DTG; (B) selected MS curves; (C) mass spectrum at T = 270 8C; (D) mass spectrum at T = 360 8C. NIST
spectrum is reported for comparison.
76 O. Senneca et al. / J. Anal. Appl. Pyrolysis 80 (2007) 61–76

with DTG peak at T = 246 8C, the other 5% weight is lost before the Skimmer and stick on the furnace wall. Further pyrolysis
T = 350 8C. Butralin melts at approximately 58 8C and loses and oxidation determine fragmentation of these products as the
almost 100% of the weight between 120 and 300 8C with a DTG temperature is increased above 300–400 8C.
peak at T = 228 8C, very close to the boiling point of 228 8C.
Iprodion melts at 134 8C and loses 100% weight between 200 Acknowledgments
and 340 8C with a DTG peak at T = 270 8C.
The MS curves of Maleyc Hydrazide, Butralin and Support by MS Anna Maria Scamardella, Mr Giovanni
Procymidone exhibit a very broad peak in correspondence Lionetti, Mr Stefano Ciaravolo is gratefully acknowledged. The
with the DTG peak, followed at higher temperature by a peak in work has been financially supported by B.A.T. Italia S.p.A.
the curves of m/z 44, 28,18, 30, possibly associated with species
such as CO, CO2, H2O, NO. Iprodion after the first MS peak in Appendix A. Supplementary data
correspondence with the DTG one exhibits two more MS peaks
at 350 and 430 8C. For all these samples differences are Supplementary data associated with this article can be
observed between experimental and NIST spectra as regards found, in the online version, at doi:10.1016/j.jaap.2007.01.002.
the abundance of low molecular and of oxidized species,
confirming that in the present experiments extensive rupture of References
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