Water, Air, & Soil Pollution

Statistical Analysis and Mathematical Models for dissipation of Volatile Organic

Compounds from Romanian Littoral
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Manuscript Number: WATE-D-15-00040

Full Title: Statistical Analysis and Mathematical Models for dissipation of Volatile Organic
Compounds from Romanian Littoral

Article Type: Full research paper

Keywords: volatile organic compounds; gas-chromatography; GRNN; sampling

Corresponding Author: Lucica Barbes

Ovidius University of Constanta
Constanta, ROMANIA

Corresponding Author's Institution: Ovidius University of Constanta

First Author: Alina Barbulescu

Order of Authors: Alina Barbulescu

Lucica Barbes

Abstract: Last decade, preserving the air quality in the northern part of the Romanian Littoral has
become a national priority. In order to monitor the pollution in this zone, volatile organic
compounds (cumulated values of benzene, toluene, ortho- , meta-, and para-xylene,
ethyl-benzene, and styrene) have been collected in six monitoring sites (three
industrial and three urban zones). The sampling was done by the active sampling
method, and the analysis, by gas chromatography. The statistical analysis emphasized
that the concentrations of the volatile organic compounds were under the limits
established by the European Union's laws and the pollutants' distributions are
asymmetric. We also propose models for the series of the concentrations of the volatile
organic compounds, using the General Regression Neural Network (GRNN) method,
with the wind speed, the variation of air temperature, and the humidity as regressors.
The models fit well the data, proving that GRNN is a good alternative to the classical
methods

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Statistical Analysis and Mathematical Models for dissipation of Volatile Organic

Compounds from Romanian Littoral

Alina Brbulescu 1, Lucica Barbe 2*

1
Technical University of Civil Engineering, Doctoral School, 122 124, Lacul Tei Blvd., Bucharest, Romania,
e-mail: alinadumitriu@yahoo.com
2
Ovidius University of Constanta, 124, Mamaia Blvd, Constan a, Romania
e-mails: lucille.barbes2009@gmail.com, lbarbes@univ-ovidius.ro

Abstract. Last decade, preserving the air quality in the northern part of the Romanian Littoral has
become a national priority. In order to monitor the pollution in this zone, volatile organic compounds (cumulated
values of benzene, toluene, ortho- , meta-, and para-xylene, ethyl-benzene, and styrene) have been collected in
six monitoring sites (three industrial and three urban zones). The sampling was done by the active sampling
method, and the analysis, by gas chromatography. The statistical analysis emphasized that the concentrations of
the volatile organic compounds were under the limits established by the European Unions laws and the
pollutants distributions are asymmetric. We also propose models for the series of the concentrations of the
volatile organic compounds, using the General Regression Neural Network (GRNN) method, with the wind
speed, the variation of air temperature, and the humidity as regressors. The models fit well the data, proving that
GRNN is a good alternative to the classical methods.
Key words: volatile organic compounds, gas-chromatography, GRNN, sampling

INTRODUCTION
Volatile organic compounds, sulphur and nitrogen oxides (SOx; NOx) and the particulate matter (PM10;
PM2.5) are major air pollutants that produce environmental damage. Recent epidemiological studies (Berenjian et
al. 2012; Alvarez-Hornos et al. 2008, Rappaport and Kupper 2004; Huang et al. 2014) prove the serious effects
of environmental pollution on the human health, the accumulation of volatile organic compounds in atmosphere
being one of the main causes of some types of diseases, including cancer.
According to the European Directive 2008/50/EC (European Parliament and Council 2008), the volatile
organic compounds are defined as organic compounds from anthropogenic and biogenic sources, other than
methane, that are capable of producing photochemical oxidants by reactions with nitrogen oxides in the presence
of sunlight. They are precursors of a number of secondary pollutants such as ozone, aldehydes, peroxyacyl
nitrates and secondary organic aerosols (European Environment Agency 2013). Examples of toxic air pollutants
include benzene and other aromatics (found in gasoline) or methane, ethane, tetrachloroethane, methyl chloride
and various chlorohydrocarbons, perfluorocarbons, styrene and naphthalenes (Hellen et al. 2008; European
Parliament and Council 2004). Benzene, which is the most monitored toxic air pollutant, is emitted by cars,
trucks, oil refineries and chemical processes (Pandya et al. 2006). The petrochemical, metal finishing, electronics
and paint industries generate volatile organic compounds, as solvents, lubricants, liquid fuels, degreasers and

*
Corresponding author: E-mail: lucille.barbes2009@gmail.com, alinadumitriu@yahoo.com
cleaners (De Nevers 2000). In urban zones, the atmospheric pollutants originate mainly in the road traffic,
combustion processes and industrial sources.
From 2011, Romania has adopted a new legislation regarding the technical conditions applicable to
vehicles and installations used for depositing, loading, unloading and distribution of oil products (Rexeis and
Hausberger 2009), in accordance with European legislation. The Romanian air quality standards regulate the
maximum level of the benzene concentration in air, whose value was fixed at 10 g/m3 in January 2004, 5 g/m3
in January 2007 and was progressively reduced by 1 g/m3 every year, from January 2010 (Romanian
Parliament 2011).
The mathematical modeling is the main tool used in the development of monitoring air pollutants
programs by estimating pollution levels in various hypothetical scenarios. It remains the safest method that can
reveal the connection between the emission source and the receiver situated in the lower atmospheric layer
(European Parliament and Council 2008). Designing models for the pollutants dispersion in crowded zones is a
complex process, due to the configuration of antropic and natural structures (as urban constructions, forestry
fund, waters etc.), of their different dynamic and radiative properties (Kalabokas et al. 2001), and of the
evolution of atmospheric factors that must be modeled by appropriate techniques (Barbulescu and Barbes 2014).
Starting to 1990 a big variety of models was elaborated and developed for modeling the pollutants dissipation,
as: Gaussian processes for the environmental impact assessments and ozone concentration evaluation (Grasic et
al. 2006; Olesen et al. 2007; Petelin et al. 2013); linear simple and multiple models for pollutants correlation in
the Romanian Littoral (Barbes et al. 2014; Barbulescu and Barbes 2014); Artificial Neural Networks for
forecasting the concentration of some airborne pollutants in urban areas and modeling the dissipation of some
inorganic pollutants in urban and industrial zones (Barbes et al. 2009; Barbulescu and Barbes 2013); fuzzy
systems for forecasting the ozone concentration (Lin and Cobourn 2007; Nebot et al. 2008); generalized
autoregressive linear models for PM10 dispersion (Hrdlickova et al. 2008) etc. Also, different integrated
modeling systems (CALPUFF, AERMOD, ADMS Urban, UDM-FMI) for simulation and prediction of
atmospheric pollution dispersion (Macintosh et al. 2010; Zou et al. 2010; Carruthers et al. 2008; Owen et al.
2000; Karppinen et al. 2000) or for air quality simulation have been built, as, for example, CMAQ (Appel et al.
2011; Matthias 2008) and CALIOPE (Pay et al. 2012; Pay et al. 2010; Paatero 2004). In this context, the interest
in monitoring and modeling the dispersion of volatile organic compounds in atmosphere is continuous
increasing, a number of articles treating these aspects (Bereznicki et al. 2012; Kabir and Kim 2010; Li et al.
2001; Wei et al. 2014).
Last period, the artificial neural networks have became an important tool for solving problems related to
the time series modeling and forecasting, especially of those that present high variations in time or for which
different classical methods fail to give satisfactory results, due to the restrictive hypotheses imposed to the data.
They can also be used, together with Box Jenkins methods, providing alternative better results than the
classical methods (Zhang 2003; Terasvirta et al. 2005). In order to choose an adequate dispersion model one has
to take account of the chemism of the pollutants involved, the complexity of the pattern of emission sources, the
homogeneity or stationarity of weather conditions (Barbulescu and Deguenon 2014b) in the monitored areas.
Often this is a difficult decision that requires modifications or adaptations of the considered models, and/or
reintegration in the analysis system (Leuchner and Rappengluck 2010).
 The aim of this study was to investigate the concentrations, composition and sources of emission of
some volatile organic compounds in ambient air of urban and industrial areas in the North Romanian Littoral, as
a first step of the process of individual risks removal for workers and civil population. In this paper we propose
mathematical models for the dispersion in atmosphere of aromatic hydrocarbons with moderate solubility range
(including benzene, toluene, ortho-, meta- and para - xylene (X), ethyl - benzene and traces of styrene), whose
concentrations were obtained by gas chromatography analysis. Our approach is based on the use of general
regression neural network (GRNN), techniques that gave good results for solving other problems of the same
type (Barbulescu and Barbes 2013). If, typically, GRNN is used to model the evolution in time (t) of some series
(Yt), considering as regressor Yt-1, , Yt-h (h N*), here we considered as explained variable, (Yt), the
concentrations series, and we had to determine the explanatory variables, knowing that the atmospheric
conditions could influence the pollutants dissipation. After performing different tests and building various
models, the pollutants lag one concentration, Yt-1, the temperature variation (dT), the logarithm of humidity
(lnH), and the wind speed (v) were chosen as explicative variables. This approach is important because the
evolution of the pollutants concentrations is not considered function of time (that is not a significant influence
factor in the problem at hand), but function of the pollutants concentration in the previous period (considering
that the pollutants emission is a continuous process and its dissipation is not complete between the measuring
moments) and some atmospheric factors. Far as we know, after a systematic search on the literature, such an
approach wasnt used for describing the dissipation of different types of atmospheric pollutants. Moreover, this
approach can be successfully used for forecasting the pollutants evolution in a region with a relative climatic
stability, as Dobrogea.

MATERIAL AND METHOD

Sampling and measurement techniques for the concentrations of volatile organic compounds
Data was collected at six monitoring sites from the Romanian Black Sea Littoral (Fig. 1). They are
situated in three urban areas - Site 1 - Navodari Summer Camp (4418'54.36"N, 2837'36.96"E, elevation of 4.6
m), Site 2 - Navodari city (4419'21.46"N, 2837'04.25"E, elevation of 10 m), Site 6 - Corbu village
(4422'29.91"N, 2839'49.60"E, elevation of 5.5 m) and three industrial points - Site 3 (4420'18.42"N,
0
28 3812.27"E, elevation of 3 m), Site 4 (4420'45.62"N, 2838'40.36"E, elevation of 3 m), and Site 5
(4421'09.05"N, 2839'29.82"E, elevation of 3 m). The numbering of the monitoring sites has been done from
south to north.
The study area was selected because the last 15 years the population number increased in the northern
part of the Romanian Black Sea Littoral, due to the development of the oil platform in Navodari area and of
Constanta shipyard. Also, Navodari Summer Camp and Corbu village became popular tourists destinations,
more calm, and quiet, but also close to Mamaia resort and Constanta city. Therefore, preserving the air quality
became a priority, due to the influence of the pollution on the human health. The monitoring sites were selected
very close to the main sources of volatile organic compounds emission, which are mainly the processes of
primary and secondary distillation of brute petroleum from the oil refinery situated near Site 4 and the
petrochemical plant situated near Site 3. The distance between the northernmost site (Site 6) and the
southernmost site (Site 1) is of 10 km.
 Figure 1. Monitoring sites
The first step in monitoring the volatile organic compounds was the air samples acquisition, by the
active sampling method, that consisted of drawing an air volume through a dual packing adsorbent tube
(manufactured by Supelco, in this case). The air was pumped with a constant flow rate of 500 mL/min, for 5 - 6
hours. Gas samples were collected every two weeks from January 2006 to December 2009.
The second step was the chemical desorption. The charcoal tubes were sealed and extracted in
laboratory with carbon disulphide (CS2), followed by the quantitative transfer into acetonitrile.
The third step was the analysis of the volatile organic compounds, that has been done using a gas
chromatography equipment - Perkin Elmer - Clarus 500, possessing a thermo - desorption system (TDS) with the
following characteristics: the carrier of He with the flow rate of 30-50 mL/min; the column - HP-1 (Cross-
Linked Methyl Silicone) with the dimensions of 50m x 0.32 mm x 1.0 m; the detector - FID, the injection split -
1L; and the set points for heated zones - 2000C. The laboratory procedure was performed according to EPA
TO-17 Method (U.S. Environmental Protection Agency 1999).
The sample flow rates of volatile organic compounds were checked before and after each sampling
period using a Gill flowmeter. The calibration curves for aromatics were done using standard solutions (Supelco
- EPA TOX-MIX 1A) at different concentrations between 1g/mL and 100g/mL. Using these calibration
curves, the concentrations of volatile organic compounds (g/m3) were determined by the formula:
cm = mVOC/Vsample (g/m3),
where:
cm - the concentration of volatile organic compounds in the air sample,
mVOC - the organic compounds weight, measured by chromatographic analysis (ng),
Vsample - the air samples volume (L).
The forth step was the comparison of the resulted concentrations of volatile organic compounds with the
accepted limits (given in regulations).

Mathematical method
Firstly, some statistical analyses have been performed, in order to extract the characteristics of the series
registered at the monitoring sites. They consisted in: (a) calculation of basic statistics (minimum, maximum,
average, variance, skewness, kurtosis); (b) estimation of autocorrelation function (ACF), (c) testing the
homoscedasticity hypothesis (the homogeneity of variance), by the Levene test (Levene 1960), for each data
series.
For the study of the correlation between some volatile organic compounds (benzene, toluene and
styrene) the correlation coefficients were determined.
Secondly, General Regression Neural Network (GRNN) was used to perform mathematical modeling.
In the following we shall shortly present this method.
GRNN, introduced in by Specht (1991) belongs to the class of probabilistic neural networks, being a
feedforward network that allows the estimation of a response vector (Yi)i=1,..,n function of other vectors,
containing the predictors values, obtained by measurement. The GRNN structure consists of four layers
(Input layer, Hidden layer, Summation layer, Output layer), formed by neurons. A neuron is the elementary
processing unit of a neural network whose structure consists of: (a) a set of synapses, characterized by a
weight, (b) a function with the role of computing a linear combination of the inputs, using the weights from
(a); (c) an activation function, that limits the amplitude of the neuron.
The Input layer of GRNN is formed by one neuron for each predictor variable. The Hidden layer
contains many neurons, each of them corresponding to a case from the training data set. The Summation
layer is formed of two neurons: the numerator and the denominator. The former contains the result of the
addition of the weighted values stored in the Hidden layer. The second one contains the result of the
addition of the weighted values stored in the Hidden layer, multiplied by the actual target value corresponding
to the neurons from the hidden layer. The Output Layer contains only a neuron, that stores the value obtained by
dividing the values stored by the numerator and the denominator neurons.
In order to be used, the neural network must be trained for estimating the networks parameters from the
input data. Typically, the series is divided in two parts, one for training and one for validation. In this study the
splitting ratio of the data for training and validation was 90:10 (%), as suggested in (Chatfield 2001). The
training method was the conjugate gradient descent algorithm (Shewchuk 1994).
For the model selection, different approaches can be used, as information - based criteria (Akaike - AIC,
Bayesian Information Criteria - BIC, Schwarz - SCH), or criteria based on different indices, as the proportion of
variance explained by the model (R2), the root mean squared error (RMSE), the mean absolute error (MAE), the
mean absolute percentage error (MAPE), the correlation between the actual and predicted values. If MAPE is a
dimensionless parameter, measuring the average of absolute values of the ratio between the modeling errors and
the registered data, the measure unit for RMSE and MAE are those of the variables (g/m3, in our case). In all
the cases, the best model corresponds to the lowest index value.
Remember that:

1 n 1 n 1 n yt yt*
MAE t t
n t 1
y y *
, RMSE t t
n t 1
( y y * 2
) , MAPE
n t 1 yt
,

where: yt , yt* are respectively the actual and the computed values and n is the sample volume.
The response vector was formed by the registered concentrations of volatile organic compounds
(denoted by Yt). The predictor variables were: the lag 1 concentration of volatile organic compounds
(denoted by Yt-1), the temperature variation (dT), the logarithm of the air humidity and the wind speed.
These predictor variables have been chosen after performing the analysis of the dependence of volatile
organic compounds on each variable (temperature, humidity, and the wind speed) and by physical
considerations, knowing that these atmospheric parameters also influences the dissipation of other
pollutants (Hrdlickova et al. 2008).
The software used for calculations were: R and DTREG.

RESULTS AND DISCUSSIONS

Data included measurements of the concentrations of benzene, toluene, ortho-, meta- and para-xylene,
ethyl-benzene and styrene done in the morning, starting to 8 a.m. The meteorological parameters were
simultaneously measured at the study sites. The values of the mean temperature, mean wind speed and mean air
humidity are presented in Table 1. The wind direction was from east to west (from the Sea to the continent) at
the measurements moments. From Table 1 we remark that the mean parameters didnt significantly differ, their
highest values being registered at Site 3.
Table 1. Mean temperature, mean wind speed and mean humidity recorded in the study period

The quantified volatile organic compounds were separated into chemical families according to their
chemical structure. The values of concentrations taking into consideration for modeling were the cumulated
concentrations of the seven individual volatile organic compounds, whose maxima are presented in Table 2.
Between the maximum concentrations of the quantified compounds, the highest was that of benzene.
Table 2. The highest concentrations of individual volatile organic compounds

During the sampling period, the average and the highest concentrations of benzene, toluene, ethyl-
benzene and xylene didnt exceed the EPA 2006 - 24 hour air quality standard for benzene (20 g/m3), toluene (2
g/m3) and xylene (2 g/m3) and WHO-24 hour quality guidelines for benzene (0.338 g/m3) (European
Environment Agency 2013; World Health Organization 2005).
To study the correlations between the concentrations of toluene, benzene and xylene, we calculated the
correlation coefficients between: (a) the concentrations of toluene and benzene, (b) the concentrations of toluene
and xylene, (c) the concentrations of benzene and xylene. Since the values of these coefficient were between
0.85 and 0.92, we conclude that the correlation between the concentrations of toluene, benzene and xylene were
strong, indicating that these compounds had a common emission source.
The highest concentrations of meta- and para - xylene were registered in Site 6.
In the following we present the results of the statistical analysis of the data series of total concentrations
of the total volatile organic compounds studied. They are presented in Table 3, which contains: row 1: the
maximum value of concentration of the volatile organic compounds; row 2: the minimum concentration value of
the volatile organic compounds; row 3: the average of the concentrations of the volatile organic compounds; row
4: the variance of the concentrations of the volatile organic compounds; row 5: the skewness; row 6: the kurtosis.
Each column of this table contains the values corresponding to the pollutants concentrations registered at each
site.
From Table 3, we remark that the minima are comparable, but the maxima and the averages varied in
large limits, respectively 185 - 1080 g/m3, and 11.89 - 42.23 g/m3. For the series of volatile organic
compounds registered at each site, the average has been calculated. The values obtained prove that, in mean, the
concentrations recorded were under the maximum limits established by law, even if some particular extreme
events of pollution have been registered. The variance, that measures the deviations of the values of a data series
from its average, has heterogeneous values, the maximum being registered in Site 5. The values of variances are
due to some very high concentrations of the series of volatile organic compounds, registered, for example: in
June 2007 (278 g/m3), December 2006 (161.1 g/m3), January 2007 (160.2 g/m3) in Site 1, December 2006
(510 g/m3 and 182.5g/m3) in Site 6, in December 2006 (1080 g/m3), December 2007 (1080 g/m3),
November 2006 (313.7 g/m3), September 2006 (169.5g/m3) in Site 5 etc. The values of the skewness and
kurtosis emphasize asymmetric distributions of the series of volatile organic compounds registered at each site
(they are right - skewed) and their leptokurtic shape (the distributions have higher peaks around the mean and
fatter tails).
 Table 3. Basic statistics for pollutants series (concentrations of volatile organic compounds)

The comparison between the series of concentrations of the volatile organic compounds was also done
after removing the extreme values (maxima) from the data series registered at each site. It resulted that the
concentrations of volatile organic compounds recorded in the oil refinery area (Sites 3-5) were comparable, and
higher than those from Navodari city and Navodari Summer Camp (Sites 1 and 2) .
The results of the Levene test, performed for each series of volatile organic compounds, at the
confidence level of 0.95 reveal the series heteroskedasticity (the heterogeneity in variance).
The study of the autocorrelation functions emphasizes the existence of a first order autocorrelation
between the concentrations series registered in all sites, but Site 6. This is a very important aspect that was taken
into consideration for choosing a model that has as explicative variable the lag 1 concentrations. The existence of
such an autocorrelation can be explained by the persistence of some volatile organic compounds in the period
between the measurements because the wind speed wasnt high to dissipate the pollutants, and the emission
sources are very close to the monitoring sites, as we already mentioned. Since Site 6 is the northernmost
monitoring zone, it is supposed that it was less affected by pollution, fact emphasized by the absence of
pollutants accumulation (so, the inexistence of the first order autocorrelations in the data registered at this site).
To emphasize the performances of the GRNN models for the volatile organic compounds
concentrations, we present in Table 4 the following goodness of fit parameters: proportion of variance explained
by the model (R2 %), root mean squared error (RMSE), mean absolute error (MAE), mean absolute percentage
error (MAPE). As R2 is close to 100, the models explain very well the real data. This result is confirmed by the
values of RMSE and MAE, which are small for all the series. Considering the values of all the indicators, the
best model was obtained for the series registered in Site 4 and the worst, for those from Site 5 (RMSE, MAE and
MAPE are the highest) and Site 2 (R2 is the smallest). The lower quality of the model for the pollutants
concentration from Site 2 is due to the existence of some very high values (called outliers) registered at this site:
153.3 g/m3, 221.2 g/m3 and 125.7 g/m3 (registered respectively in October 2006, December 2006, and
February 2007), which are respectively 9.04, 6.3 and 5.2 times higher than the average of the concentrations
from Site 2. Analogous remarks are true for the values from Site 5, where, the values of the concentrations
recorded in December 2006 and December 2007 (1080 g/m3) and January 2007 (251.6 g/m3) were 24,
respectively 7 times higher than the mean concentration from this site.
From the statistics literature (Barnett and Lewis 1994), it is known that the outliers existence influence
the models quality (Barbulescu and Deguenon 2014a). In our particular case, the neural network learns some
data that will be used for prediction. If the learned data are close to those that will be predicted, the models
quality will be higher, otherwise, the prediction quality will be lower.
Table 4. Indicators of the models quality

In Figures 2 7 we represented, by dots, the values of concentrations estimated by the GRNN models
(called predicted values) vs. the recorded ones (called actual values). Therefore, the abscissa of a dot is its
recorded value, and the ordinate is its predicted value. When the registered and the estimated values are equal,
the dot is situated on the first bisectrix of the axes of coordinates, represented by the continuous line. If the
estimated value is less (greater) than the registered one, the dot is situated under (above) the first bisectrix and
the vertical line that connects the dot with the diagonal represents the estimation error.

Figure 2. Chart of predicted values vs. the actual values in GRNN model for the concentrations of volatile
organic compounds collected in Site 1- Navodari Summer Camp

Figure 3. Chart of predicted values vs. the actual values in GRNN model for the concentrations of volatile
organic compounds collected in Site 2 - Navodari city

Figure 4. Chart of predicted values vs. the actual values in GRNN model for the concentrations of volatile
organic compounds collected in the industrial Site 3

Figure 5. Chart of predicted values vs. the actual values in GRNN model for the concentrations of volatile
organic compounds collected in the industrial Site 4

Figure 6. Chart of predicted values vs. the actual values in GRNN model for the concentrations of volatile
organic compounds collected in the industrial Site 5

Figure 7. Chart of predicted values vs. the actual values in GRNN model for the concentrations of volatile
organic compounds collected in Site 6 - Corbu village

We chose the present these charts instead of representing on the same figure the chart of actual values
and that of the predicted ones function of time since the recorded and the estimated values are practically
superposed in the majority of cases, so it would be very difficult to distinguish between them on the same chart.
The advantage of our representation is that it also emphasizes the domain of values. For example, in Fig. 2 we
see that all the values are very well estimated, most of them being under 40 g/m3, and the maximum one is over
250 g/m3, so the estimation errors cannot be visualized. By comparison, in Fig.3, we can see the estimation
errors, so it is clear that the model for the concentrations series from Site 2 is worse than that from Site 1. We
also remark some similarities of the series from the industrial sites (3 and 4), due to the following factors: the
distance between them is of about 1 km, so atmospheric factors didnt significantly differ; both are close to the
emission sources, and the wind direction (from east to west) facilitates the dispersion of pollutants from the
emission points to these two monitoring sites. On the other part, the less polluted sites were 1 and 6, because
they are situated to the highest distance from the pollution sources and the wind direction didnt favor the
pollutants dissipation to their directions.

CONCLUSIONS
In this article we presented the results of our study concerning the series of the concentrations of volatile organic
compounds collected in six monitoring sites in the area of Navodari city. This approach is a part of our series of
studies concerning the environmental quality in the Constanta - Navodari area (Barbes et al. 2009; Barbes and
Barbulescu 2014; Barbulescu and Barbes 2013), which is the main industrialized zone situated on the Romanian
Black Sea Littoral, that also concentrates many tourist resorts, so maintaining the air quality is of main
importance for the population health. According to our previous studies on the pollutants dissipation in this
area, the aromatic compounds were the most abundant volatile organic compounds family detected in the oil
refinery samples. The analysis emphasized that the concentrations of this compounds were in the limits
established by the Romanian and European laws, even if the existence of some very high values of the
concentrations, registered especially in winter, have been emphasized, giving asymmetric shapes of the empirical
distributions of the data series.
The variations of the concentrations measured in the monitoring sites were modeled using GRNN. We
didnt follow the classical way of modeling the pollutants evolution function of time, since it wouldnt be
realistic, taking account of the dispersion phenomenon that is influenced by many factors. Therefore, we
considered a model in which some atmospheric factors were chosen as independent variables. But only these
physical factors were not enough for explaining the evolution of pollutants concentrations series, since the
pollutants continuous production and their persistence in atmosphere cannot be neglected. Therefore, the lag 1
pollutants concentrations, the wind speed, the temperature variation, and the logarithm of humidity were
considered as explanatory variables. The high quality of our models (quantified by four indicators) proved that
GRNN was a good choice for describing the evolution of the actual concentration of volatile organic compounds.
This approach gives a unifying perspective of the pollutants dissipation at all the monitoring sites,
function of the same variables and can be used for forecasting their concentrations. For example, the values of
the concentrations of the volatile organic compounds predicted for the period January February 2010 (called
forecasted values), for Site 1 were respectively 10.19, 11.66, 13.35 and 13.27, in concordance to the registered
ones (unused for modeling purposes). Knowledge on these values is important for issuing warning about the
pollution phenomena and taking measures for their control.
The main advantage of this methodology is that the variables and the residuals in the GRNN model are
not constrained to fulfill some specific distributions, as in the case of parametric ones. We also mention that the
modeling results are better than those obtained by parametric approaches, as, for example multiple linear
regression, for which the proportion of variance explained by the model is very low (0.344 - Site 1, 0.418 - Site
2, 0.373 Site 3, 0.257 - Site 4, 0.279 Site 5, 0.215 - Site 6). Further study will be dedicated to comparison of
our results with those obtained by other different approaches.

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Table 1. Mean temperature, wind speed and humidity in the in the experiments period
Site 1 Site 2 Site 3 Site 4 Site 5 Site 6
Mean temperature (0C) 14.9 14.9 15.8 15.7 14.4 14.4
Mean wind speed (m/s) 2.6 2.6 3.3 2.8 3.0 2.6
Mean humidity (%) 60.8 62.1 64.9 64.2 63.8 63.0
Table 2. The highest concentrations of individual volatile organic compounds
Compound Maximum (g/m3)
Benzene 850 17.02
Toluene 100 5.01
Ethyl benzene 58 1.16
Ortho - xylene 42 0.84
Meta - and para - xylene 22 0.44
Styrene 8 0.16
Table 3. Basic statistics for pollutants series (concentrations of volatile organic compounds)
Site 1 Site 2 Site 3 Site 4 Site 5 Site 6
minim (g/m3) 0.15 0.10 0.10 0.10 0.10 0.10
3
maxim (g/m ) 278.40 221.20 185.00 198.20 1080.00 510.00
average (g/m3) 28.53 24.34 16.52 11.89 42.23 22.07
variance 2042.64 1259.63 750.57 726.34 26854.90 3178.23
skewness 2.96 3.03 3.92 4.81 5.60 7.25
kurtosis 10.75 11.53 18.69 27.35 33.21 60.63
 Table 4. Indicators of the models quality
Site 1 Site 2 Site 3 Site 4 Site 5 Site 6
Proportion of variance explained 99.65 97.17 99.96 99.97 99.72 99.83
2
by the model (R ) (%)
Root mean squared error (RMSE) 2.66 5.93 0.47 0.41 8.51 2.27
Mean absolute error (MAE) 0.27 3.62 0.08 0.04 4.98 0.23
Mean absolute percentage error 15.97 227.69 9.53 0.92 360.39 100.41
(MAPE)
Figures captions

Figure 1. Monitoring sites

Figure 2. Chart of predicted values vs. the actual values in GRNN model for the concentrations of volatile
organic compounds collected in Site 1- Navodari Summer Camp

Figure 3. Chart of predicted values vs. the actual values in GRNN model for the concentrations of volatile
organic compounds collected in Site 2 - Navodari city

Figure 4. Chart of predicted values vs. the actual values in GRNN model for the concentrations of volatile
organic compounds collected in the industrial Site 3

Figure 5. Chart of predicted values vs. the actual values in GRNN model for the concentrations of volatile
organic compounds collected in the industrial Site 4

Figure 6. Chart of predicted values vs. the actual values in GRNN model for the concentrations of volatile
organic compounds collected in the industrial Site 5

Figure 7. Chart of predicted values vs. the actual values in GRNN model for the concentrations of volatile
organic compounds collected in Site 6 - Corbu village
Figure 1
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Figure 2
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Figure 3
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Figure 4
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Figure 5
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Figure 6
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Figure 7
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