A novel method for rapid and quantitative detection of bisphenol A in urine.

Bisphenol A (BPA) is classified as an endocrine disruptor (ED) and it can interact with variety of hormone receptors leading to hormonal disruption and increased risk of various adverse health effects. Reducing human exposure to BPA is one of the main challenges of public health, as it is constantly present in daily life. A low-cost and commonly applied method to enable determination of BPA in the patient's body has yet to be developed. Currently available techniques are expensive, time-consuming, and require access to highly equipped analytical chemistry laboratories. Here we describe a fast and cheap engineered lateral flow assay of our design, to detect of BPA in urine samples. The technology not only provides an opportunity to perform rapid medical diagnostics without the need for an access to the central laboratory but also a means for self-diagnosis by the patient. The addition of ß-glucuronidase improves the sensitivity of detection as it releases the free BPA from glucuronide complexes in urine. This invention may become a demonstrated analytical means for lowering human exposure to BPA and probably also to other EDs and consequently, may be useful in decrease of the risk for several lifestyle diseases.

Chemometric Assessment and Best-Fit Function Modelling of the Toxic Potential of Selected Food Packaging Extracts.

Food packaging materials constitute an ever more threatening environmental pollutant. This study examined options to specifically assess the ecotoxicity of packaged wastes, such as cans, subjected to various experimental treatments (in terms of extraction media, time of exposure, and temperature) that imitate several basic conditions of the process of food production. The extracts were studied for their ecotoxicity with bioluminescent Vibrio fischeri bacteria. The first objective of this study was to find patterns of similarity between different experimental conditions; we used multivariate statistical methods, such as hierarchical cluster analysis, to interpret the impact of experimental conditions on the ecotoxicity signals of the package extracts. Our second objective was to apply best-fit function modelling for additional data interpretation, taking into account, that ecotoxicity for various temperature conditions is time- and temperature dependent. We mathematically confirmed that chemometric data treatment allows for better understanding how different experimental conditions imitating the real use of food packaging. We also demonstrate that the level of ecotoxicity depends on different extraction media, time of exposure, and temperature regime.

Rapid assessment of the authenticity of limequat fruit using the electronic nose and gas chromatography coupled with mass spectrometry.

ABSTRACT: Citrus fruits are very popular food products. There are many species and varieties of them. There are also documented cases of some citrus fruits causing a severe allergic reaction. Some species of the citrus fruits, especially hybrid ones show a reduced allergenic effect due to the lack of seeds. There is a need for rapid methods for evaluation of citrus' botanical origin. During research, the headspace of three citrus fruits Citrus Aurantifolia, Citrus japonica, and Citrus × floridana was analysed using electronic nose based on ultrafast gas chromatography and gas chromatography with mass spectrometry. In the paper, two approaches were compared. The usefulness of an electronic nose to control the quality of hybrids was demonstrated. The results obtained during ultrafast gas chromatography analyses were subjected to statistical analysis. Four chemometric methods namely: principal component analysis (PCA), discriminant function analysis (DFA), soft independent modeling of class analogies (SIMCA), statistical quality control (SQC) were used to distinguish between limequat and its parent fruits. Electronic nose combined with chemometrics is a novel analytical tool for hybrid fruits' classification due to their botanical origin. It can supplement established techniques by providing results in a short time and at a low cost.

Assessment of ecotoxicity and total volatile organic compound (TVOC) emissions from food and children's toy products.

The development of new methods for identifying a broad spectrum of analytes, as well as highly selective tools to provide the most accurate information regarding the processes and relationships in the world, has been an area of interest for researchers for many years. The information obtained with these tools provides valuable data to complement existing knowledge but, above all, to identify and determine previously unknown hazards. Recently, attention has been paid to the migration of xenobiotics from the surfaces of various everyday objects and the resulting impacts on human health. Since children are among those most vulnerable to health consequences, one of the main subjects of interest is the migration of low-molecular-weight compounds from toys and products intended for children. This migration has become a stimulus for research aimed at determining the degree of release of compounds from popular commercially available chocolate/toy sets. One of main objectives of this research was to determine the impact of time on the ecotoxicity (with Vibrio fischeri bioluminescent bacteria) of extracts of products intended for children and to assess the correlation with total volatile organic compound emissions using basic chemometric methods. The studies on endocrine potential (with XenoScreen YES/YAS) of the extracts and showed that compounds released from the studied objects (including packaging foils, plastic capsules storing toys, most of toys studied and all chocolate samples) exhibit mostly androgenic antagonistic behavior while using artificial saliva as extraction medium increased the impact observed. The impact of time in most cases was positive one and increased with prolonging extraction time. The small-scale stationary environmental test chambers - µ-CTE™ 250 system was employed to perform the studies aimed at determining the profile of total volatile organic compounds (TVOCs) emissions. Due to this it was possible to state that objects from which the greatest amounts of contaminants are released are plastic containers (with emission rate falling down from 3273 to 2280 ng/g of material at 6 h of conditioning in elevated temperature).

Implementation of multicriteria decision analysis in design of experiment for dispersive liquid-liquid microextraction optimization for chlorophenols determination.

A novel and efficient approach to optimization of extraction step prior the chromatographic determination of nine chlorinated phenols is described. It is based on the combination of design of experiments and multicriteria decision analysis. Such an approach is used to optimize dispersive liquid-liquid microextraction procedure for the determination of 9 chlorophenols in water samples. Three parameters are optimized - sample volume, volume of disperser solvent and extraction solvent. Combination of the technique for order of preference by similarity to ideal solution with central composite design allows to perform multi-analyte procedure optimization. It gives information about the efficiency of the system for every experimental plan point in terms of closeness to ideal solution. The optimal conditions for extraction of chlorophenols are 76 µL of extraction solvent, 0.6 mL of dispersive solvent and 6.7 mL of water sample. The presented approach has the potential to be applied in variety of optimization systems.

Pre-selection and assessment of green organic solvents by clustering chemometric tools.

The study presents the result of the application of chemometric tools for selection of physicochemical parameters of solvents for predicting missing variables - bioconcentration factors, water-octanol and octanol-air partitioning constants. EPI Suite software was successfully applied to predict missing values for solvents commonly considered as "green". Values for logBCF, logKOW and logKOA were modelled for 43 rather nonpolar solvents and 69 polar ones. Application of multivariate statistics was also proved to be useful in the assessment of the obtained modelling results. The presented approach can be one of the first steps and support tools in the assessment of chemicals in terms of their greenness.

Portable Electronic Nose Based on Electrochemical Sensors for Food Quality Assessment.

The steady increase in global consumption puts a strain on agriculture and might lead to a decrease in food quality. Currently used techniques of food analysis are often labour-intensive and time-consuming and require extensive sample preparation. For that reason, there is a demand for novel methods that could be used for rapid food quality assessment. A technique based on the use of an array of chemical sensors for holistic analysis of the sample's headspace is called electronic olfaction. In this article, a prototype of a portable, modular electronic nose intended for food analysis is described. Using the SVM method, it was possible to classify samples of poultry meat based on shelf-life with 100% accuracy, and also samples of rapeseed oil based on the degree of thermal degradation with 100% accuracy. The prototype was also used to detect adulterations of extra virgin olive oil with rapeseed oil with 82% overall accuracy. Due to the modular design, the prototype offers the advantages of solutions targeted for analysis of specific food products, at the same time retaining the flexibility of application. Furthermore, its portability allows the device to be used at different stages of the production and distribution process.

Thermal degradation assessment of canola and olive oil using ultra-fast gas chromatography coupled with chemometrics.

ABSTRACT: Oil blending is often used to enhance the properties of vegetable oils. The admixture of a more thermally stable oil makes the resulting blend more suitable for use in frying. A new method of quality assessment of vegetable oils used in frying is presented in this paper. In this method, ultra-fast gas chromatography coupled with flame ionization detector and chemometrics is employed. Principal component analysis was used for data processing. The results obtained with this method were compared with the results of the Rancimat test and sensory evaluation. It is demonstrated that the addition of olive oil improves the stability of rapeseed oil, and also changes its flavour and aroma profile. In addition, it was found that ultra-fast GC coupled with chemometrics is an effective tool for the assessment of the quality of edible oils. The proposed method does not require sample preparation, and the total time of analysis is less than 2 min.

Electronic noses: Powerful tools in meat quality assessment.

Main factors that are considered by consumers when choosing meat products are colour and aroma, of which the latter is a more reliable indicator of quality. However, a simple sensory evaluation of hedonistic qualities is often not sufficient to determine whether protein is past its shelf life, and consumption of spoiled meat can lead to serious health hazards. Some volatile compounds can be used as spoilage indicators, and so a device equipped with a sensor sensitive to particular odorants would prove useful. Unfortunately, no such single compound has yet been identified, as the changes taking place in a sample of meat during storage are contingent on numerous factors. On the other hand, a combination of volatile compounds may form a unique 'fingerprint' which can be analysed pattern recognition algorithms with an electronic nose. It can supplement established techniques of meat quality assessment by providing results that correlate well with hedonic perception in a short time and at a low cost.

Novel fast analytical method for indirect determination of MCPD fatty acid esters in edible oils and fats based on simultaneous extraction and derivatization.

A novel method for indirect determination of MCPD esters levels in lipid samples has been developed. The method is based on combination of extraction and derivatization in the same sample preparation step. It is achieved by the application of diethyl ether as extraction solvent for isolation of analytes released from esterified forms from the water phase and as dilution solvent for solid PBA - the derivatization agent. It is a noteworthy improvement of recommended indirect approaches available in the literature because such steps as sample clean-up, multiple liquid-liquid extractions, and preconcentration are excluded in the proposed solution. In this way, the developed procedure is shortened and simplified. Such an approach also minimizes the utilization of organic solvents; therefore, it is in accordance with the principles of "green analytical chemistry." In spite of the fact that the step of sample clean-up is omitted, no deterioration in GC-MS system performance was observed. Equivalence testing of the developed procedure and AOCS cd 29b-13 official method (SGS) has been conducted. It was concluded that results obtained by both methods do not significantly differ statistically. The procedure has been applied to determination of MCPD esters concentrations in lipid fractions isolated by accelerated solvent extraction technique from such foodstuffs as bakery products, salty deep-fried snacks, and instant products. In all investigated samples, the level of bound MCPD was elevated. Additionally, for both procedures, the environmental impact (with the use of analytical Eco-scale) and uncertainty budget have been assessed and compared.

Assessment of Lipophilicity Indices Derived from Retention Behavior of Antioxidant Compounds in RP-HPLC.

Reverse phase high pressure liquid chromatography was employed in order to evaluate the lipophilicity of antioxidant compounds from different classes, such as phenolic acids, flavanones, flavanols, flavones, anthocyanins, stilbenes, xantonoids, and proanthocyanidins. The retention time of each compound was measured using five different HPLC columns: RP18 (LiChroCART, Purosphere RP-18e), C8 (Zorbax, Eclipse XDBC8), C16-Amide (Discovery RP-Amide C16), CN100 (Saulentechnik, Lichrosphere), and pentafluorophenyl (Phenomenex, Kinetex PFP), and the mobile phase consisted of methanol and water (0.1% formic acid) in different proportions. The measurements were conducted at two different column temperatures, room temperature (22 °C) and, in order to mimic the environment from the human body, 37 °C. Furthermore, principal component analysis (PCA) was used to obtain new lipophilicity indices and holistic lipophilicity charts. Additionally, highly representative depictions of the chromatographic behavior of the investigated compounds and stationary phases at different temperatures were obtained using two new chemometric approaches, namely two-way joining cluster analysis and sum of ranking differences.

Assessment of toxic and endocrine potential of substances migrating from selected toys and baby products.

Analysis of literature data shows that there is limited information about the harmful biological effects of mixture of compounds from the EDC group that are released from the surface of toys and objects intended for children and infants. One of the tools that can be used to obtain such information is appropriate bioanalytical tests. The aim of this research involved determining whether tests that use living organisms as an active element (Vibrio fischeri-Microtox®, Heterocypris incongruens-Ostrocodtoxkit F™ and the XenoScreen YES/YAS™ test of oestrogenic/androgenic activity) can be a tool for estimating the combined toxic effects induced by xenobiotics released from objects intended for children. To reproduce the conditions to which objects are exposed during their use, liquids with a composition corresponding to that of human bodily fluids (artificial sweat and saliva) were used. This research focused on the main parameters influencing the intensification of the migration process (temperature, contact time and composition of the extraction mixture). The studies aimed to estimate the endocrine potential of the extracts showed that compounds released from the surface of studied objects exhibit antagonistic androgenic activity. While on the basis of the results of Microtox® test, one can state that the largest quantity of toxic compounds are released in the first 2 h of using the object. The FTIR spectra analyses confirmed that no degradation of polymeric material took place. On the basis of the results obtained, it was unanimously concluded that contact of the object with bodily fluids may result in the release of a large number of xenobiotics, which has disadvantageous effects on the metabolic processes of the indicator organisms.

Environmental risk assessment of Polish wastewater treatment plant activity.

Wastewater treatment plants (WWTPs) play an extremely important role in shaping modern society's environmental well-being and awareness, however only well operated and supervised systems can be considered as environmentally sustainable. For this reason, an attempt was undertaken to assess the environmental burden posed by WWTPs in major Polish cities by collecting water samples prior to and just after wastewater release points. Both classical and biological methods (Microtox(®), Ostracodtoxkit F™ and comet assay) were utilized to assess environmental impact of given WWTP. Interestingly, in some cases, water quality improvement indicated as a toxicity decrement toward one of the bio-indicating organisms makes water worse for others in the systems. This fact is particularly noticeable in case of Silesian cities where heavy industry and high population density is present. It proves that WWTP should undergo individual evaluation of pollutant removal efficiency and tuned to selectively remove pollutants of highest risk to surrounding regional ecosystems. Biotests again proved to be an extremely important tool to fully assess the impact of environmental stressors on water bodies receiving effluents from WWTPs.

Application of multicriteria decision analysis in solvent type optimization for chlorophenols determination with a dispersive liquid-liquid microextraction.

This study presents a novel support tool for the optimization and development of analytical methods. The tool is based on multi-criteria decision analysis (MCDA), namely the Technique for Order of Preference by Similarity to the Ideal Solution (TOPSIS), that allows users to rank possible solutions according to their requirements. In this study, we performed rankings of pairs of eight extraction and three dispersive solvents used in DLLME for chlorophenols extraction from water samples. The first ranking involved sensitivity and precision of the method for each of the nine chlorophenols. The tool is a quantitative solution to the common analytical problem that the change of analytical performance results in better performance for some analytes and worse for others. The second ranking included the assessment of the greenness of each pair of solvents, based on toxicological, ecotoxicological and environmental persistence criteria. The third ranking was based on a combination of sensitivity, precision and greenness criteria. Heptane as an extraction solvent and acetone as a dispersive solvent were selected as the most appropriate ones. The TOPSIS tool is a successful, easy to implement, incorporation of green analytical chemistry values to analytical method optimization.

Green analytical chemistry introduction to chloropropanols determination at no economic and analytical performance costs?

In this study we perform ranking of analytical procedures for 3-monochloropropane-1,2-diol determination in soy sauces by PROMETHEE method. Multicriteria decision analysis was performed for three different scenarios - metrological, economic and environmental, by application of different weights to decision making criteria. All three scenarios indicate capillary electrophoresis-based procedure as the most preferable. Apart from that the details of ranking results differ for these three scenarios. The second run of rankings was done for scenarios that include metrological, economic and environmental criteria only, neglecting others. These results show that green analytical chemistry-based selection correlates with economic, while there is no correlation with metrological ones. This is an implication that green analytical chemistry can be brought into laboratories without analytical performance costs and it is even supported by economic reasons.

Novel approach to ecotoxicological risk assessment of sediments cores around the shipwreck by the use of self-organizing maps.

Marine and coastal pollution plays an increasingly important role due to recent severe accidents which drew attention to the consequences of oil spills causing widespread devastation of marine ecosystems. All these problems cannot be solved without conducting environmental studies in the area of possible oil spill and performing chemometric evaluation of the data obtained looking for similar patterns among pollutants and optimize environmental monitoring during eventual spills and possible remediation actions - what is the aim of the work presented. Following the chemical and ecotoxicological studies self-organising maps technique has been applied as a competitive learning algorithm based on unsupervised learning process. Summarizing it can be stated that biotests enable assessing the impact of complex chemical mixtures on the organisms inhabiting particular ecosystems. Short and simple application of biotests cannot easily explain the observable toxicity without more complex chemometric evaluation of datasets obtained describing dependence between xenobiotics and toxicological results.

Occurrence and levels of polybrominated diphenyl ethers (PBDEs) in house dust and hair samples from Northern Poland; an assessment of human exposure.

Polybrominated diphenyl ethers (PBDEs) are among most ubiquitous compounds to be found in indoor environment and ingestion of household dust is considered an important route of exposure to PBDEs, especially in toddlers and young children. The present work reported concentration levels of PBDE congeners (PBDE-28, -47, -99, -100, -153, -154, -183 and -209) in hair and dust samples from selected households from Northern Poland. The concentrations of PBDEs in dust ranged from

Ranking of ecotoxisity tests for underground water assessment using the Hasse diagram technique.

The present study deals with the novel application of the Hasse diagram technique (HDT) for the specific ranking of ecotoxicity tests capable of assessment of underground water quality. The area studied is a multi-municipal landfill in the northern Poland. The monitoring network of the landfill constitutes of 27 piezometers for underground water monitoring and two observation points at surface water courses. After sampling, chemical analysis of various water parameters was performed (pH, conductivity, temperature, turbidity (TURB), color, taste, smell and atmospheric conditions: temperature, precipitation and cloud cover, heavy metals content (Cu, Zn, Pb, Cd, Cr(6+), Hg), total organic carbon (TOC), sum of Polycyclic Aromatic Hydrocarbons (PAHs), Na, Mg, K, Ca, Mn, Fe, Ni, alkalinity (Alkal), general hardness, total suspended matter (SUSP), Biological Oxygen Demand (BOD), Chemical Oxygen Demand (COD), chlorides, fluorides, sulphides, sulphates, ammonium nitrogen, total nitrogen, nitrate and nitrite nitrogen, volatile phenols, ether extracts (ETHER), dry residues (DRY_RES), dissolved compounds). Parallel to the chemical parameters assessment six different ecotoxicity tests were applied (% root length(PG)/germination(PR) inhibition of Sorghum saccharatum (respectively PGSS/PRSS), Sinapis alba (respectively PGSA/PRSA), Lepidium sativum (respectively PGLS/PRLS), % bioluminescence inhibition of Vibrio fischeri (MT), % mortality of Daphnia magna (DM), % mortality of Thamnocephalus platyrus (TN)). In order to determine the applicability of the various ecotoxicity tests, a ranking of samples from different monitoring levels according to the test used (attributes) is done by using HDT. Further, the sensitivity of the biotests was determined and compared. From the sensitivity analysis of the both monitoring levels was evident that the choice of ecotoxicity tests could be optimized by the use of HDT strategy. Most reliable results could be expected by the application of root growth inhibition of Sorghum saccharatum (PGSS test). In order to clarify the relationship between the chemical parameters measured and each of the ecotoxicity tests a optimized similarity analysis between Hasse diagrams for the ecotoxicity tests for different levels of monitoring and Hasse diagrams obtained by the use of the chemical parameters was performed. Finally, it could be concluded that for reliable monitoring of underground waters passing a dump collector following chemical parameters are of significance: water hardness, dissolved matter, total nitrogen (ammonia and nitrate nitrogen), nickel, chlorides, alkalinity, total organic carbon and ether extract and the proper battery test could include PGSA, PGSS and PRSS.

A solid phase extraction-ion chromatography with conductivity detection procedure for determining cationic surfactants in surface water samples.

A new analytical procedure for the simultaneous determination of individual cationic surfactants (alkyl benzyl dimethyl ammonium chlorides) in surface water samples has been developed. We describe this methodology for the first time: it involves the application of solid phase extraction (SPE-for sample preparation) coupled with ion chromatography-conductivity detection (IC-CD-for the final determination). Mean recoveries of analytes between 79% and 93%, and overall method quantification limits in the range from 0.0018 to 0.038 µg/mL for surface water and CRM samples were achieved. The methodology was applied to the determination of individual alkyl benzyl quaternary ammonium compounds in environmental samples (reservoir water) and enables their presence in such types of waters to be confirmed. In addition, it is a simpler, less time-consuming, labour-intensive, avoiding use of toxic chloroform and significantly less expensive methodology than previously described approaches (liquid-liquid extraction coupled with liquid chromatography-mass spectrometry).

Toxicity assessment of sediments associated with the wreck of s/s Stuttgart in the Gulf of Gdansk (Poland).

The paper presents the results of toxicity determinations carried out on sediment samples collected in the vicinity of the wreck of the German s/s Stuttgart (the southern part of the Gulf of Gdansk, off the Polish coast) in relation to the determination of polycyclic aromatic hydrocarbons (PAHs). The toxicity of surface and core sediment samples was assessed using two biotest organisms-the bioluminescent bacteria Vibrio fischeri and the ostracod Heterocypris incongruens. PAH levels in these samples were determined by GC-MS. The surface sediments collected at W2 (ca. 34 m north of the shipwreck) and W4 (ca. 415 m north-east of the wreck) as well as the core sediments collected at WR3 (ca. 400 m north-east of the wreck) were the most heavily polluted with substances toxic to the biotest organisms. The chronic and acute toxicities in the case of most of the surface sediment samples studied are correlated. This may suggest that not only hydrophobic chemicals (like PAHs from fuel residues) but also more polar chemicals (resulting from the conversion of aromatic hydrocarbons) are responsible for the toxicity levels found. There is a clear dependence between the levels of chronic toxicity and PAH concentrations in the core sediment samples. In addition, a simultaneous decrease in the PAH content and chronic toxicity was noted in all the core sediment samples at depths below 80 cm.