Receptor Modeling Source Apportionment of PM10 and Benzo(a)pyrene in Krakow, Poland

The main energy source in Krakow, Poland is coal combustion, which is believed to be the reason for frequent winter episodes of extremely high ambient air concentrations of particulate matter (PM10) and associated benzo(a)pyrene B(a)P. Results are presented on the source apportionment of PM10 and B(a)P during two episodes of thermal inversion (14/1 ; 2/3, 2005) at four different air monitoring stations and four apartments (indoor) in the city of Krakow, The results are compared to the Zakopane mountain site selected due to its prominent domestic coal heating and little traffic. The source apportionment was based on receptor modeling of the total of 72 ambient PM samples and 21 individual PM sources, chemically characterised for a high number of organic and inorganic compounds including polyaromatics (15 PAH and 18 azaarenes) heavy metals and trace elements (28 compounds), major ions, soot and organic carbon. An array of multivariate receptor models was used i.e. chemical mass balance (CMB), constrained matrix factorisation (CMF), constrained physical receptor modelling (COPREM) positive matrix factorization (PMF), principle component analysis with multi-linear regression analysis (PCA-MLRA), edge analysis (UNMIX), cluster analysis (CA), and self organizing maps SOM). The variation in the receptor dataset (55 compounds, 60 outdoor and 12 indoor PM samples) allowed the models of the pure factor analysis type (PMF, UNMIX, PCA-MLRA) to identify 3-5 factors of mixed sources. The interpretation of the factors was not straightforward, but pointed to a dominating primary source contribution from coal combustion (>60%) and a minor contribution from traffic (<10%). The secondary PM sources (20-30%) comprised industry and traffic. The results of cluster analysis and self organizing maps supported these indications. PMF was able to disaggregate the coal combustion into three factors i.e. ~10% related to industrial activities, ~20% related to home heating by stoves (coal) and ~30% related to boilers. The chemical fingerprints of the receptor samples and the main PM sources in Krakow and Zakopane allowed the pure chemical mass balance; type model (EPA-CMB8.2) to estimate the major contributions from two primary source types i.e. residential heating by coal combustion in small stoves and low efficiency boilers (~45%) and boilers with rudimentary PM reductions techniques such as cyclones (~15%), one major secondary source deriving from industrial and traffic emissions of SO2 + NOx + possibly HCl (~20%). Five minor primary sources were also identified i.e. traffic 5%, biomass burning ~5%, coke/fuel combustion ~5%, industrial high efficiency coal combustion 3%, and road/salt/rock re-suspension ~2%. The indoor PM10 and B(a)P were found to have the same sources as outdoor PM10 and B(a)P The results obtained by the models CMF and COPREM - which are hybrids of factor analysis and chemical mass balance generally agreed with the CMB results. However, their source contribution estimates are slightly different: residential heating ~30%, boilers with rudimentary PM reductions techniques such as cyclones ~30%, industrial high efficiency coal combustion ~15% traffic 3-7%, secondary 13-21%, road/salt/rock re-suspension 2-8%. All receptor models calculated residential heating to be the principal PM source in Zakopane (70-80%).JRC.H.4-Transport and air qualit

How to Implement User-Friendly BLMs in the Absence of DOC Monitoring Data: A Case Study on Bulgarian Surface Waters

The metal bioavailability concept is implemented in the Water Framework Directive (WFD) compliance assessment. The bioavailability assessment is usually performed by the application of user-friendly Biotic Ligand Models (BLMs), which require dissolved metal concentrations to be used with the &ldquo;matching&rdquo; data of the supporting physicochemical parameters of dissolved organic carbon (DOC), pH and Cadissolved. Many national surface water monitoring networks do not have sufficient matching data records, especially for DOC. In this study, different approaches for dealing with the missing DOC data are presented: substitution using historical data; the appropriate percentile of DOC concentrations; and combinations of the two. The applicability of the three following proposed substitution approaches is verified by comparison with the available matching data: (i) calculations from available TOC data; (ii) the 25th percentile of the joint Bulgarian monitoring network DOC data (measured and calculated by TOC); and (iii) the 25th percentile of the calculated DOC from the matching TOC data for the investigated surface water body (SWB). The application of user-friendly BLMs (BIO-MET, M-BAT and PNEC Pro) to 13 surface water bodies (3 reservoirs and 10 rivers) in the Bulgarian surface waters monitoring network outlines that the suitability of the substitution approaches decreases in order: DOC calculated by TOC &gt; the use of the 25th percentile of the data for respective SWB &gt; the use of the 25th percentile of the Bulgarian monitoring network data. Additionally, BIO-MET is the most appropriate tool for the bioavailability assessment of Cu, Zn and Pb in Bulgarian surface water bodies

How to Implement User-Friendly BLMs in the Absence of DOC Monitoring Data: A Case Study on Bulgarian Surface Waters

The metal bioavailability concept is implemented in the Water Framework Directive (WFD) compliance assessment. The bioavailability assessment is usually performed by the application of user-friendly Biotic Ligand Models (BLMs), which require dissolved metal concentrations to be used with the “matching” data of the supporting physicochemical parameters of dissolved organic carbon (DOC), pH and Cadissolved. Many national surface water monitoring networks do not have sufficient matching data records, especially for DOC. In this study, different approaches for dealing with the missing DOC data are presented: substitution using historical data; the appropriate percentile of DOC concentrations; and combinations of the two. The applicability of the three following proposed substitution approaches is verified by comparison with the available matching data: (i) calculations from available TOC data; (ii) the 25th percentile of the joint Bulgarian monitoring network DOC data (measured and calculated by TOC); and (iii) the 25th percentile of the calculated DOC from the matching TOC data for the investigated surface water body (SWB). The application of user-friendly BLMs (BIO-MET, M-BAT and PNEC Pro) to 13 surface water bodies (3 reservoirs and 10 rivers) in the Bulgarian surface waters monitoring network outlines that the suitability of the substitution approaches decreases in order: DOC calculated by TOC > the use of the 25th percentile of the data for respective SWB > the use of the 25th percentile of the Bulgarian monitoring network data. Additionally, BIO-MET is the most appropriate tool for the bioavailability assessment of Cu, Zn and Pb in Bulgarian surface water bodies

Chemometric Assessment of Bulgarian Wastewater Treatment Plants’ Effluents

Surface water quality strongly depends on anthropogenic activity. Among the main anthropogenic sources of this activity are the wastewater treatment plant (WWTP) effluents. The discharged loads of nutrients and suspended solids could provoke serious problems for receiving water bodies and significantly alter the surface water quality. This study presents inventory analysis and chemometric assessment of WWTP effluents based on the mandatory monitoring data. The comparison between the Bulgarian WWTPs and previously reported data from other countries reveals that discharged loads from investigated WWTPs are lower. This is particularly valid for total suspended solids (TSS). The low TSS loads are the reason for the deviations of the typical calculated WWTP effluent ratios of Bulgarian WWTPs compared to the WWTPs worldwide. The performed multivariate analysis reveals the hidden factors that determine the content of WWTP effluents. The source apportioning based on multivariate curve resolution analysis provides detailed information for source contribution profiles of the investigated WWTP effluent loads and elucidate the difference between WWTPs included in this study

Statistic challenges in pharmacy education

The graduate programs in pharmacy education are designed to prepare students for teaching and research careers in academia, for pharmaceutical industry, for drugs controlling agencies and research institutes. The aim of this presentation is to discuss the necessity of including basic knowledge on statistic techniques in education of students from pharmaceutical faculties. Some practical examples of using statistics in quality control, particularly in validation of analytical procedures, will demonstrate the application of statistics in pharmaceutical analysis. The debate stays open concerning the optimal range of statistical methods, included in education programs. It is intended that the pharmacists after graduation will be capable to apply regulatory guidance documents, to develop statistical thinking within the pharmaceutical industry, to validate analytical procedures. Students are expected to use statistics in all pharmaceutical disciplines including medicinal chemistry, pharmacology, toxicology and pharmaceutics

Comparison of the variable importance in projection (VIP) and of the selectivity ratio (SR) methods for variable selection and interpretation

This study compares the application of two variable selection methods in partial least squares regression (PLSR), the variable importance in projection (VIP) method and the selectivity ratio (SR) method. For this purpose, three different data sets were analysed: (a) physiochemical water quality parameters related to sensorial data, (b) gas chromatography-mass spectrometry (GC-MS) chemical (organic compound) profiles from fossil sea sediment samples related to sea surface temperature (SST) changes, and (c) exposed genes of Daphnia magna female samples related to their total offspring production. Correlation coefficients (r), levels of significance (p-value) and interpretation of the underlying experimental phenomena allowed the discussion about the best approach for variable selection in each case. The comparison of the two variable selection methods in the first water quality data set showed that the SR method is more accurate for sensorial prediction. For the climate data set, when raw total ion current (TIC) GC-MS chromatograms were considered, variables selected using the VIP method were easier to interpret compared with those selected by the SR method. However, when only some chromatographic peak areas (concentrations) were considered, the SR method was more efficient for prediction, and the VIP method selected the most relevant variables for the interpretation of SST changes. Finally, for the transcriptomic data set, the SR method was found again to be more reliable for prediction purposes.Peer reviewe

Chemometric Evaluation of WWTPs’ Wastewaters and Receiving Surface Waters in Bulgaria

Wastewater treatment plant (WWTP) installations are designed and operated to reduce the quantity of pollutants emitted to surface waters receiving treated wastewaters. In this work, we used classical instrumental studies (to determine chemicals and parameters under obligations put with Directive 91/271/EEC), ecotoxicological tools (Sinapis alba root growth inhibition (SA-RG) and Heterocypris incongruens mortality (MORT) and growth inhibition (GRINH)) and multivariate statistical analysis to gain information on feature profiles of WWTPs’ effluents and the possible burden of surface water bodies receiving treated wastewaters in eleven locations of Bulgaria. Initial screening of results has shown that only phosphorus content exceeds the admissible level in 5 out 11 WWTP effluents, while As, Cr, Cu, Mn, and Zn show exceedance at several locations. The multivariate statistical analysis reveals the discriminating water quality parameters and outlines the ability of Heterocypris incongruens to evaluate the ecotoxicological potential of different groups of waters

Chemometric Evaluation of WWTPs&rsquo; Wastewaters and Receiving Surface Waters in Bulgaria

Wastewater treatment plant (WWTP) installations are designed and operated to reduce the quantity of pollutants emitted to surface waters receiving treated wastewaters. In this work, we used classical instrumental studies (to determine chemicals and parameters under obligations put with Directive 91/271/EEC), ecotoxicological tools (Sinapis alba root growth inhibition (SA-RG) and Heterocypris incongruens mortality (MORT) and growth inhibition (GRINH)) and multivariate statistical analysis to gain information on feature profiles of WWTPs&rsquo; effluents and the possible burden of surface water bodies receiving treated wastewaters in eleven locations of Bulgaria. Initial screening of results has shown that only phosphorus content exceeds the admissible level in 5 out 11 WWTP effluents, while As, Cr, Cu, Mn, and Zn show exceedance at several locations. The multivariate statistical analysis reveals the discriminating water quality parameters and outlines the ability of Heterocypris incongruens to evaluate the ecotoxicological potential of different groups of waters

Influence of Storage Time and Temperature on the Toxicity, Endocrine Potential, and Migration of Epoxy Resin Precursors in Extracts of Food Packaging Materials

The aim of the present study was to establish a standard methodology for the extraction of epoxy resin precursors from several types of food packages (cans, multi-layered composite material, and cups) with selected simulation media (distilled water, 5% ethanol, 3% dimethyl sulfoxide, 5% acetic acid, artificial saliva) at different extraction times and temperatures (factors). Biological analyses were conducted to determine the acute toxicity levels of the extracts (with Vibrio fischeri bacteria) and their endocrine potential (with Saccharomyces cerevisiae yeasts). In parallel, liquid chromatography-tandem mass spectrometry was performed to determine levels of bisphenol A diglycidyl ether (BADGE), bisphenol F diglycidyl ether (mixture of isomers, BFDGE), ring novolac glycidyl ether (3-ring NOGE), and their derivatives. The variation induced by the different experimental factors was statistically evaluated with analysis of variance simultaneous component analysis (ASCA). Our findings demonstrate the value of using a holistic approach to best partition the effects contributing to the end points of these assessments, and offer further guidance for adopting such a methodology, thus being a broadly useful reference for understanding the phenomena related to the impacts of food packaging materials on quality for long- and short-term storage, while offering a general method for analysis