ALI-7

PEDOT MODIFIED ELECTRODES FOR THE DETERMINATION OF

COLOUR INDEX AND POLYPHENOL CONTENT IN WINES

L. Pigani, C. Rioli, R. Seeber, C. Zanardi, B. Zanfrognini

Dipartimento di Scienze Chimiche e Geologiche, Università degli Studi di
Modena e Reggio Emilia, via G. Campi 103, 41125 Modena

Polyphenols are naturally occurring compounds found largely in the fruits,

vegetables, cereals and beverages, among which wines. In this last case, many of
the sensory attributes, such as colour and mouthfeel, are affected by the
polyphenolic content; furthermore, the determination of this group of compounds
can help to identify variants on type and differences in winemaking and
maturation processes. The characterization of a wine by its total phenolic content
(TPP) and by its colour index (CI), which is determined by the presence of a
specific class of polyphenols, i.e., anthocyanin, is hence of great importance. The
setup of new devices and methods for rapid, cheap and reliable analysis of TPP
content represents an emerging topic, to which electrochemistry can give
important contributions.
In this presentation, we show the first results collected by using poly-
ethylenedioxythiophene (PEDOT) modified electrodes for the estimation of TPP
content and of CI in different samples of wines. Among the several advantages
offered by PEDOT-coated electrodes, the possibility to work properly in aqueous
media make them attractive for direct analyses of food matrices, as already
demonstrated in our previous studies and in Refs. [1,2]. In the preliminary part of
this study, differential pulse voltammetry (DPV) and spectrophotometric
measurements have been performed in model wine solutions containing different
amounts of red grape skin extract powder (oenocyanin - EC). PEDOT-modified
electrodes used in properly diluted wine solutions, buffered at different pH values,
give rise to repeatable DPV signals in which a well-defined current peak related to
the EC content is detectable. A good correlation is found of the current intensity
with the TPP content, as well as with the CI measured by spectrophotometric
methods.
In the second part of the study, the correlation curves previously cited have been
used for the determination of TPP content and of CI in commercial wines. The
comparison between TPP and CI values obtained by the electrochemical and by
the spectrophotometric methods is definitely satisfactory, giving sound reasons to
go forward in this study.

[1] L. Pigani, A. Culetu, A. Ulrici, G. Foca, M. Vignali, R. Seeber, Food

Chemistry 129 (2011) 226-233.
[2] L. Pigani, R. Seeber, A. Bedini, E. Dalcanale, M. Suman, Food Analytical
Methods 7 (2014) 754-760.

91
 AMBG-1

QuEChERS METHOD IN THE DETERMINATION OF

POLY(HYDROXYALKANOATES) IN BACTERIA BY ANALYTICAL
PYROLYSIS: TOWARD AN ON-LINE MONITORING OF
BIOTECHNOLOGICAL PROCESSES

C.Torri1,2, C. Samorì2, F. Abbondanzi2, G. Carvalho3, D. Fabbri1,2

1
Dipartimento di Chimica “G. Ciamician”, Università di Bologna
2
Centro Interdipartimentale di Ricerca Industriale Energia e Ambiente, Università
di Bologna.
3
Department of Chemistry, Faculdade de Ciencias e Tecnologia, Universidade
Nova de Lisboa.

Poly(hydroxyalkanoates) (PHAs) are polyesters produced by several bacterial

strains and formed by saturated short chain hydroxyacids. From a practical point
of view, the need to obtain effective, stable and high quality PHAs production
usually requires long microbial acclimatization times. Consequentially, a huge
number of systematic determinations of PHAs content and microbial community
characterization are needed; therefore it is important to identify fast and reliable
analytical procedures able to provide both of these parameters for a real time
monitoring of the production process.
The aim of this work is the development of a fast method for the quantitative
determination of PHAs and their monomeric composition by using pyrolysis
coupled with GC-MS analysis. In fact, under pyrolysis, PHAs are degraded in
high yield (>40%, w/wPHA) into the corresponding 2-alkenoic acids (e.g.
crotonic acid from polyhydroxybutyrate) [1]; moreover, under these conditions,
other bacterial-strain specific markers (e.g. long chain fatty acids) can be detected
[2]. In the developed protocol, the sample was directly subjected to low
temperature thermal treatment (300°C for 30 min) in a closed vial and reaction
products were analyzed by GC–MS. The method was firstly optimized on pure
polymers and then applied to bacterial samples deriving from both mixed
microbial cultures or selected strains, containing various types and amounts of
PHAs.
The QuEChERS method provided RSD <15% range, limit of detection of 100 µg
(1% PHAs in biomass), and results comparable to that of conventional methods
(R2 = 0.9855), but with minimal sample pretreatment.

[1] C. Torri, H. Cordiani, C. Samorì, L. Favaro, D.Fabbri. Journal of

Chromatography A. 1359 (2014) 230–236.
[2] F. Basile, K. J. Voorhees, T. L. Hadfield. Appl. Environ. Microbiol. 61 (1995)
1534-1539.

92
 AMBG-2

ANALYSIS OF ANTITHYROID DRUGS IN SURFACE WATER BY

USING LIQUID CHROMATOGRAPHY TANDEM MASS
SPECTROMETRY

V. Pérez-Fernández1, S. Marchese1, A. Gentili1, M.A. García2, R. Curini1, F.

Caretti1, D. Perret1.
1
Department of Chemistry, Faculty of Mathematical, Physical and Natural
Science, Sapienza University of Rome, Piazzale Aldo Moro 5, 00185 Rome, Italy
2
Department of Analytical Chemistry, University of Alcalá, Ctra.Madrid-
Barcelona, Km. 33.600, 28871, Alcalá de Henares (Madrid), Spain

Antithyroid drugs (ATDs) are heterocyclic compounds containing a thionamide

functionality able to produce a decrease in the production of thyroid hormones T3
and T4. For this reason, ATDs have been in use for more than half a century in
human medicine for the management of hyperthyroidism as well as in veterinary
medicine to treat companion and farm hyperthyroid animals. Moreover, in the last
decade there has been a strong suspicion about their illicit administration to obtain
a quick fattening with commercial purpose.
ATDs are associated with a variety of minor side effects and potentially life-
threatening. The FDA has categorized these drugs as class D agents because of the
potential for foetal hypothyroidism. For these reasons, there is a world-wide
agreement on the ban of these drugs in animal husbandry.
Humans and animals excrete un-metabolized ATDs in urine or faeces; thence,
these drugs can reach sewage treatment plants and enter surface waters if they
escape degradation. Although the number of human prescriptions is steadily
increasing, currently, there are not analytical methods to verify the potential
contamination of the different environmental compartments. Certainly, the unique
physico-chemical properties of ATDs (high polarity, amphoteric nature, small
molecular weight and tautomeric forms) make this a demanding task to be
undertaken.
This work describes development and validation of a new method for the
simultaneous determination of six antithyroid drugs in surface waters using liquid
chromatography–triple quadrupole mass spectrometry (LC–MS/MS). Sensitivity
and selectivity of the multiple reaction monitoring (MRM) analysis allowed
applying a simple preconcentration procedure and “shooting” the sample into the
LC-MS/MS system without any other treatment with recoveries higher than 75%.
The adequate values obtained for all the validation parameters studied allowed its
successful application to the analysis of ATDs in surface water samples collected
from the Tiber river basin and three lakes of Lazio (central Italy), selected on the
basis on the different anthropic impact. The most frequently detected compound
was tapazole, one of the most common ATDs used in human medicine but also
thiouracil and mercaptobenzimidazole were detected in some of the analysed
samples.

93
 AMBG-3

ALTERNATIVE RENEWABLE BIOFUEL: CHARACTERIZATION OF

VINE SHOOTS

M. Cantamessa, M. Ginepro, J. Tafur Marinos, V. Zelano

Dipartimento di Chimica, Università di Torino, Via P. Giuria, 7 - 10125 Torino

The issues of global warming and depletion of fossil fuels have reemphasized the
importance of energy recovery from wastes [1]. Biomass is the organic matter
derived from trees, agricultural crops and other living plant material. The use of
biomass for energy does not increase carbon dioxide emissions and does not
contribute to the risk of global climate change. In addition, using biomass to
produce bioenergy is often a way to dispose of waste materials that otherwise
would create environmental risks.
Vine shoot is the major sub-product of vineyards, as it is produced from the
annual pruning, with production of approximately 2–4 tons/ha in Piedmont. They
are generally shredded and then buried, or burned directly on the sideline,
constituting an additional charge for the farmer. This solution is the fastest one but
not the best one, economically and environmentally. Thus, one of the biggest
challenges for wine-producing regions is to create alternatives for processing the
vast amount of grape waste generated during harvest season [2].
The present study has characterized vine shoots to reevaluate them as biofuel.
Two samples of vine shoots from Asti (moscato) and Sardinia (cannonau,
cagnulari e vermentino) were analyzed. Proximate analysis (ash content, volatile
matter, fixed carbon), elemental composition (Al, Ca, Cd, Cl, Co, Cr, Cu, Fe, Hg,
K, Mg, Mn, Na, Ni, Pb, Zn, S, P e Si) and higher heating value (HHV) were
determined.
Proximate analysis results were similar for both vine shoots. The ash content and
the HHV were approximately 3% and 4518 kcal/kg for both of them. These two
parameters make biomass suitable for using it as a biofuel despite its medium
quality. S, Cl and heavy metal contents were low. In particular, the element
contents were higher for Asti vine shoots than Sardinia ones except for the Na, Cl,
Cr and As contents.
One of the best ways of using this waste is to convert it into fuel for generating
heat and electricity on a small scale, to supply the needs of vinegrowers
themselves or nearby locations.

[1] I-H. Hwang, J. Kobayashi, K. Kawamoto. Waste Management 34 (2014) 402–

410.
[2] JMV Nabais, C Laginhas, PJM Carrott, MMLR Carrott. Journal of Analytical
and Applied Pyrolysis 87 (2010) 8–13.

94
 AMBG-4

ICP-MS-BASED ISOTOPIC ANALYSIS OF ENVIRONMENTAL

SAMPLES COLLECTED FROM POLAR REGIONS

M. Grotti1, A. Bazzano1, F. Ardini1, K. Latruwe2, F. Vanhaecke2

1
Dipartimento di Chimica e Chimica Industriale, Università di Genova, Via
Dodecaneso, 31 – 16146 Genova, Italy.
2
Department of Analytical Chemistry, Ghent University, Krijgslaan, 281-S12 –
9000 Ghent, Belgium.

Isotope ratio data of appropriate analytical quality are able to provide valuable
information in different fields of research, including archaeometry, geochemistry,
forensics and environmental sciences.
In particular, the measurement of lead isotope ratios in environmental samples is
very useful for assessing its origin and long-range transport pathways and to
distinguish the relative contributions of natural and anthropogenic sources. The
accurate measurement of these isotope ratios can, however, be quite challenging
when the analytical concentration is low and the sample size limited, as frequently
occurs in polar environmental studies.
Recently, we have developed different analytical protocols, enabling us to
measure lead isotope ratios in a number of environmental sample types, including
atmospheric particulates, surface snow, marine suspended particulate matter and
sediment. Single- and multi-collector inductively coupled plasma-mass
spectrometry (ICP-MS) were employed in this context, in combination with
conventional and high-efficiency sample introduction systems. The analytical
methods were optimized using multivariate approaches, and the procedures
developed were characterized in terms of analytical working range, interferences
and uncertainty accompanying the measurement data. Finally, the methods were
applied in the context of polar studies addressing both the Arctic (Ny-Ålesund,
Svalbard Islands) and Antarctica (Terra Nova Bay and Dome Concordia) [1-3].
The main features of the analytical procedures developed and representative
results for the marine environment and the atmosphere will be presented and
discussed.

[1] A. Bazzano, P. Rivaro, F. Soggia, F. Ardini, M. Grotti, Marine Chemistry, 163

(2014) 28-35.
[2] A. Bazzano, F. Soggia, M. Grotti, Environmental Chemistry 12 (2015) 245-
252.
[3] A. Bazzano, F. Ardini, S. Becagli, R. Traversi, R. Udisti, D. Cappelletti, M.
Grotti, Atmospheric Environment 113 (2015) 20-26.

95
 AMBG-5

PASSIVE SAMPLING AND STIR BAR SORPTIVE EXTRACTION: TWO

INNOVATIVE APPROACHES FOR THE DETERMINATION OF
NONSTEROIDAL ANTI-INFLAMMATORY DRUGS AND OTHER
POLAR CONTAMINANTS IN WATER

E. Magi, M. Di Carro, Shivani Tanwar, Francisco Ardini

Dipartimento Chimica e Chimica Industriale, Università di Genova, via
Dodecaneso, 31 – 16147 Genova

The protection of the aquatic environment requires a constant monitoring activity

and new, more effective sampling/preconcentration techniques are necessary. In
fact, besides well known pollutants as pesticides, new compounds used in
everyday life, the “emerging pollutants”, need to be determined. For example
pharmaceuticals are not entirely absorbed by human body, reaching the aquatic
compartment through the effluents from wastewater treatment plants. The very
low concentration level and possible matrix interferences represent the main
analytical problems; so, highly sensitive and selective detection techniques must
be preceded by reliable sampling and preconcentration steps.
Two different innovative approaches have been developed in our laboratory for
the determination of polar contaminants in water such as nonsteroidal anti-
inflammatory drugs (NSAIDs): stir bar sorptive extraction (SBSE) and passive
sampling, followed by liquid chromatography-tandem mass spectrometry.
SBSE was developed by comparing classical PDMS stir bars with new polar
phases (Polyacylate and EG-Silicone); main SBSE parameters optimized to attain
high enrichment, then analytes were back-extracted using liquid desorption under
ultra sonication. The SBSE-LC-MS/MS method provided satisfactory figures of
merit (NSAIDs showed LODs in the range 7.5 - 71 ng L-1) and was successfully
applied to real samples collected from river water and wastewater effluents.
The passive sampling approach was carried out by using Polar Organic Chemical
Integrative Sampler (POCIS); samplers were deployed for two weeks in river and
tap water, allowing the detection of analytes at the ultra-trace level. Using the
sampling rates values obtained by means of a simple calibration system developed
in our lab, Time Weighted Average concentration of NSAIDs in river water was
estimated in the range 0.33-0.46 ng L-1.

E. Baltussen, P. Sandra, F. David, C. Cramers J. Microcol. Sep. 11 (1999) 737–

747
D.A. Alvarez, J.D. Petty et al., Environ. Toxicol. Chem. 23 (2004) 1640–1648.
S. Tanwar, M. Di Carro, E. Magi. J. Pharm. Biomed. Anal. 106 (2015) 100–106
M. Di Carro, L. Bono, E. Magi Talanta, 120 (2014) 30-33

96
 AMBG-6

HINTS ON PAST SEA ICE CHANGES AND SOLAR ACTIVITY FROM

TALOS DOME SITE (EAST ANTARCTICA)

R. Traversi, S. Becagli, L. Caiazzo, D. Frosini, M. Severi and R. Udisti

Dipartimento di Chimica “U.Schiff”, Università degli Studi di Firenze, Via della
Lastruccia, 3, I -50019 Sesto F.no (Firenze).

The site of Talos Dome (TD - East Antarctica, 159° E 72° S, 2316 m a.s.l.),
revealed to yield relevant information on past environmental and climatic
variability on different timescales due to favourable features such: high
accumulation rate (allowing the chemical species preservation) and geographical
location (sensitive to atmospheric transport processes occurring on the regional to
global scale). Here we show two chemical records from TD site, sea salt Na+
(ssNa+) and nitrate, focusing on their potentiality of providing information on past
sea ice and solar activity.
Although sea ice is a key component of the polar climate, a direct knowledge of
its variability is limited to the satellite monitoring era and, for earlier times, one
has to rely on proxy data. ssNa+ record from ice cores has been long proposed as
such a proxy but, in order to reliably use it, a validation with the available direct
data for current times is mandatory. At this purpose, ssNa+ record from TD firn
cores was compared with satellite data of Sea Ice Extent (SIE) in the whole
Antarctic Ocean and in different sectors in the 1978-2003 time period. A good
agreement was observed especially considering the Ross Sea and Indian Ocean
sector, which appears to control ssNa+ concentration in the marine aerosol
reaching TD during selected periods.
As concerning solar activity, a better knowledge of its long-term variability is
crucial for solar physics, as well for environmental and climate sciences.
Continuous direct records are limited to the past four centuries, so that for longer
timescales one has to rely on indirect proxies, such as cosmogenic nuclides 14C
and 10Be, stored in natural archives. Nonetheless, a difficulty in such a
reconstruction by using cosmogenic isotopes is due to the complex signal they
provide (containing information on production rate and also on geochemical
system effects) and to significant discrepancies on millennial time scales,
hindering the knowledge of solar activity at this time scale. At this regard, a
significant positive correlation between nitrate content in TD (TALDICE) ice core
and the flux of galactic cosmic rays, as reconstructed from radiocarbon INTCAL
14
C and GRIP 10Be records, was found along the Holocene on multi-centennial
and millennial timescales. Moreover, Schwabe (11 yr) and Gleissberg (55-100 yr)
solar cycles were shown to be present in the last two centuries of nitrate dataset.
These evidences support TALDICE nitrate record as a potential new proxy of past
solar activity.

97
 AMBG-7

SOURCES, TRANSPORT PROCESSES AND CLIMATIC IMPACT OF

POLAR AEROSOL. A MULTI-YEAR ITALIAN EXPERIENCE.

R. Udisti, on behalf of the Italian Aerosol Research Group.

Dept. of Chemistry, Univ. of Florence, 50019 Sesto F.no (FI), Italy.

The aerosol plays a key role in the local to global distribution of natural and
anthropogenic chemical components emitted into the atmosphere from marine and
terrestrial environmental sectors. In particular, the size distribution and chemical
composition of aerosol particles affects the climate through complex feedback
processes between climate forcings and environmental responses, by the
interaction with the solar irradiation (scattering and absorption processes) and as
CCN sources. Besides, anthropogenic pollutants can be quickly transported from
the source areas to the deposition sites that could have a very higher vulnerability
for the atmospheric contaminants. Due to the large uncertainties on the knowledge
of the quantitative and qualitative effects of the aerosols in the Polar Regions and
the high vulnerability of the polar ecosystems, with particular attention to the
effect of the present climate change in the Arctic, several measurements and
sampling campaigns were carried out both in Antarctica and in the Arctic since
2005 by the Italian aerosol community.
In order to understand the main atmospheric processes possibly leading anthropic
and natural aerosol components in inner Antarctica, a continuous all-year-round
sampling of size-segregated aerosol were carried from 2005 to 2013 at Dome C
(East Antarctica; 75° 60’ S, 123° 200’ E, 3220 m a.s.l. and 1100 km away from
the nearest coast). In the Arctic, a continuous all-year-round sampling campaign is
ongoing since 2010 at Thule (North Greenland). Contemporaneously, “summer”
(March to September) aerosol was annually collected at Ny Alesund (Svalbard
Islands, Norway; 78°56’ N, 11°56’E; 50 m a.s.l.), together with size-distribution
measurements in the nano- and micro-metric ranges. Besides, shorter
measurement and sampling campaigns were carried out by using a tethered
balloon, up to about 1.000 m altitude, in order to study the effect of the PBL
dynamics on the aerosol atmospheric load and chemical composition.
Chemical analysis includes: Ion Chromatography (inorganic anions and cations,
selected organic anions); elemental analysis (PIXE, ICP-AES and ICP-MS for
selected metals, including REEs); Pb isotopic composition; thermo-optical
analysis (Elemental/Organic Carbon fractions - EC/OC).
Besides, continuous measurements of particle size-distribution (TSI-SMPS and
TSI-APS; 6 nm – 20 um; 10 min resolution) and Black Carbon (by Particle Soot
Absorption Photometry – PSAP) were carried out during the sampling periods.
Here, we report the most relevant results obtained from the sampling campaigns
carried out in Antarctica and in the Arctic.

98
 AMBG-8

PYROLYSIS AND GASIFICATION OF WOODSTOCKS: ANALYSIS OF

ORGANIC COMPOUNDS

M. Cantamessa, M. Ginepro, J. Tafur Marinos, V. Zelano

Dipartimento di Chimica, Università di Torino, Via P. Giuria, 7 - 10125 Torino

Lignocellulosic biomass is currently attracting much attention as a renewable

energy source. Thermochemical processes commonly used to produce energy
from biomass are pyrolysis and gasification [1]. Solid (biochar), liquid (biooil and
tar) and gaseous products derived from these processes may contain hazardous
organic compounds, such as phenols and PAHs, depending on experimental
conditions [2].
Since biochar can be used as a soil amendment to improve soil functions and may
concurrently act as carbon sequestrator, and biooil is regarded as an alternative to
fossil fuels, they can release organic compounds in the environment.
The aim of this work is to assess the formation of organic compounds in relation
to the main process parameters: temperature, residence time, presence of oxygen
[2].
The analysis of biooil and tar, and biochar extracts was made by GC-MS, while
qualitative identification of main sorbed volatile organic compounds (VOCs) on
biochar was conducted by purge and trap desorption coupled to GC-MS [2].
Some samples were obtained in laboratory from the same feedstock (woody
biomass) at different temperature, in a range between 400 and 900°C, both in
anaerobic and aerobic conditions. Others derived from commercial or industrial
plants; in these cases exact production parameters were not always known.
Preliminary results showed that commercial/industrial biochar samples have more
VOCs than ones obtained in laboratory, e.g. methylnaphthalene was not found in
the laboratory char samples [3]. Biooil samples produced in laboratory at different
temperatures have similar qualitative composition. However, some organic
compounds, which were found in all biooil samples, were in different percentage
depending on temperature, such as alkylphenols and alkoxy phenols.

[1] K.A. Spokas, J.M. Novak, C.E. Stewart, K.B. Cantrell, M. Uchimiya, M.G.
DuSaire, K.S. Ro, Chemosphere 85 (2011) 869-882.
[2] M.I. Schnitzer, C.M. Monreal, G. Jandl, P. Leinweber, P.B. Fransham, Journal
of Environmental Science and Health Part B 42 (2007) 79-95.
[3] N. Jendoubi, F. Broust, J.M. Commandre, G. Mauviel, M. Sardin, J. Lédé,
Journal of Analytical and Applied Pyrolysis 92 (2011) 59-67.

99
 AMBG-9

SYSTEMIC INSECTICIDES FROM CORN COATED SEEDS. A LC-

HRMS STUDY ON METHIOCARB AND ITS METABOLITES IN
GUTTATION DROPS

A. Lentola1, S. Bogialli1, V. Girolami2, A. Tapparo1

1
Dipartimento di Scienze Chimiche, Università degli Studi di Padova, via Marzolo
1 - 35131 Padova
2
Dipartimento di Agronomia Animali Alimenti Risorse Naturali e Ambiente,
Università degli Studi di Padova, Agripolis, viale Università 16 - 35020 Legnaro,
Padova

The seed coating with systemic pesticides is a worldwide used agronomic

practice. Recently, in EU some neonicotinoids (and fipronil) have been banned as
seed coating insecticides in crops that are attractive for honey bees [1]. As a
consequence, the methylcarbamate methiocarb has been authorized and largely
used as an alternative pesticide for the corn seeds coating.
It is well established that guttation drops of plants obtained from treated seeds
might contain high concentration of systemic pesticides [2]. In the case of corn
seeds coated with neonicotinoids, highly contaminated guttations (10-1000 mg/L
of insecticide) are released in the first weeks after the seedling emergence [3].
These levels can cause acute toxicity in insects, included pollinators like honey
bees. Therefore, guttation drops must be carefully considered in the assessment of
the environmental impact of systemic pesticides.
Unfortunately, data from literature on pesticide residue levels in guttations are still
unreliable, and very limited information on the environmental variable affecting
this contamination is available. Moreover, no data regarding the presence of
methiocarb and its metabolite in corn guttations are accessible. This gap is of
environmental and health concern as methiocarb and its metabolites (in particular
methiocarb sulfoxide and the related hydrolysis products) may be toxic also for
vertebrates and mammals.
In the present study a LC-HRMS (Q-TOF) methodology has been optimized for
the direct determination of methiocarb and its degradation product in guttation
drops. The analysis of corn guttations obtained both in field and in greenhouse
allowed us to better clarify the metabolic pathway of this insecticide that should
be considered in the related environmental risk assessment. In particular, the high
concentrations of methiocarb sulfoxide and methiocarb sulfoxide phenol found in
guttations confirmed the potential toxicity of drops produced from corn seeds
coated with methiocarb.

[1] Regulation (EU) n. 485/2013 and Regulation (EU) n. 781/2013.

[2] V. Girolami, L. Mazzon et al., J. Econ. Entomol. 102 (2009) 1808-1815.
[3] A. Tapparo, C. Giorio et al., J. Environ. Monit. 13 (2012) 1564-1568.

100