Bioassays as one of the Green Chemistry tools for assessing environmental quality: A review.

For centuries, mankind has contributed to irreversible environmental changes, but due to the modern science of recent decades, scientists are able to assess the scale of this impact. The introduction of laws and standards to ensure environmental cleanliness requires comprehensive environmental monitoring, which should also meet the requirements of Green Chemistry. The broad spectrum of Green Chemistry principle applications should also include all of the techniques and methods of pollutant analysis and environmental monitoring. The classical methods of chemical analyses do not always match the twelve principles of Green Chemistry, and they are often expensive and employ toxic and environmentally unfriendly solvents in large quantities. These solvents can generate hazardous and toxic waste while consuming large volumes of resources. Therefore, there is a need to develop reliable techniques that would not only meet the requirements of Green Analytical Chemistry, but they could also complement and sometimes provide an alternative to conventional classical analytical methods. These alternatives may be found in bioassays. Commercially available certified bioassays often come in the form of ready-to-use toxkits, and they are easy to use and relatively inexpensive in comparison with certain conventional analytical methods. The aim of this study is to provide evidence that bioassays can be a complementary alternative to classical methods of analysis and can fulfil Green Analytical Chemistry criteria. The test organisms discussed in this work include single-celled organisms, such as cell lines, fungi (yeast), and bacteria, and multicellular organisms, such as invertebrate and vertebrate animals and plants.

Ionogel fibres of bis(trifluoromethanesulfonyl)imide anion-based ionic liquids for the headspace solid-phase microextraction of chlorinated organic pollutants.

Ionogels, a family of hybrid materials in which ionic liquids (ILs) are confined in a sol-gel network, are receiving much attention in a variety of scientific and technological fields. In this work, ionogels derived from three different ILs based on the anion bis(trifluoromethanesulfonyl)imide (TFSI), namely 1-butyl-3-methylpyridinium bis(trifluoromethanesulfonyl)imide ([C4C1Py][TFSI]), 1-butyl-1-methylpyrrolidinium bis(trifluoromethanesulfonyl)imide ([C4C1Pyrr][TFSI]), and 1-butyl-1-methylpiperidinium bis(trifluoromethanesulfonyl)imide ([C4C1Pip][TFSI]) were obtained on the outer surface of optical fibres by sol-gel technology. The obtained hybrid materials were characterized by scanning electron microscopy (SEM) and energy dispersive X-ray spectrometry (EDX), and subsequently evaluated as sorbent coatings for the headspace solid-phase microextraction (HS-SPME) of volatile chlorinated organic compounds in combination with gas chromatography with barrier ionization discharge detection (GC-BID). The ionogel based on [C4C1Pyrr][TFSI] exhibited the highest extractability for target analytes. The experimental parameters that affect the extraction process were optimized by means of a central composite design. Under optimal conditions, the proposed method yielded excellent enrichment factors (EFs) in the range 3889-20 919 and limits of detection (LODs) between 11 and 151 ng L(-1) for the target compounds. The inter-day repeatability, intra-day reproducibility and fibre-to-fibre reproducibility, were less than 8.5, 9.6 and 16.9%, respectively. Finally, the developed method was applied to the analysis of water samples, showing recovery values in the range 95-106%.

Concentration and sources of polycyclic aromatic hydrocarbons (PAHs) and polychlorinated biphenyls (PCBs) in surface soil near a municipal solid waste (MSW) landfill.

Due to a continuous demand of land for infrastructural and residential development there is a public concern about the condition of surface soil near municipal solid waste landfills. A total of 12 surface (0-20 cm) soil samples from a territory near a landfill were collected and the concentration of 16 PAHs and 7 PCB congeners were investigated in these samples. Limits of detection were in the range of 0.038-1.2 µg/kg for PAHs and 0.025-0.041 µg/kg for PCBs. The total concentration of ∑ PAHs ranged from 892 to 3514 µg/kg with a mean of 1974 µg/kg. The total concentration of ∑ PCBs ranged from 2.5 to 12 µg/kg with a mean of 4.5 µg/kg. Data analyses allowed to state that the PAHs in surface soils near a landfill were principally from pyrogenic sources. Due to air transport, PAHs forming at the landfill are transported outside the landfill. PCB origin is not connected with the landfill. Aroclor 1242 can be the source of PCBs in several samples.

Chemical pollution and toxicity of water samples from stream receiving leachate from controlled municipal solid waste (MSW) landfill.

The present study was aimed to determine the impact of municipal waste landfill on the pollution level of surface waters, and to investigate whether the choice and number of physical and chemical parameters monitored are sufficient for determining the actual risk related to bioavailability and mobility of contaminants. In 2007-2012, water samples were collected from the stream flowing through the site at two sampling locations, i.e. before the stream׳s entry to the landfill, and at the stream outlet from the landfill. The impact of leachate on the quality of stream water was observed in all samples. In 2007-2010, high values of TOC and conductivity in samples collected down the stream from the landfill were observed; the toxicity of these samples was much greater than that of samples collected up the stream from the landfill. In 2010-2012, a significant decrease of conductivity and TOC was observed, which may be related to the modernization of the landfill. Three tests were used to evaluate the toxicity of sampled water. As a novelty the application of Phytotoxkit F™ for determining water toxicity should be considered. Microtox(®) showed the lowest sensitivity of evaluating the toxicity of water samples, while Phytotoxkit F™ showed the highest. High mortality rates of Thamnocephalus platyurus in Thamnotoxkit F™ test can be caused by high conductivity, high concentration of TOC or the presence of compounds which are not accounted for in the water quality monitoring program.

Coacervative extraction as a green technique for sample preparation for the analysis of organic compounds.

One of the present trends in analytical chemistry is miniaturization, which is one of the methods of green analytical chemistry application. A particular emphasis is placed on the elimination of the use of large amounts of organic solvents which are toxic and harmful to the environment, maintaining high efficiency of the extraction process, high recovery values and low values of quantification (LOQ) and detection (LOD) limits. These requirements are fulfilled by coacervative extraction (CAE) technique. In this review, theoretical aspects of the coacervation process are presented along with environmental and bioanalytical applications of this technique, its advantages, limitations and competitiveness with other techniques. Due to its simplicity and rapidity, CAE is an excellent alternative for currently practiced procedures of sample preparation for the analysis of organic compounds.

Elucidation of transformation pathway of ketoprofen, ibuprofen, and furosemide in surface water and their occurrence in the aqueous environment using UHPLC-QTOF-MS.

The identification and determination of transformation products (TPs) of pharmaceuticals is essential nowadays, in order to track their fate in the aqueous environment and, thus, to estimate the actual pollution. However, this is a challenging task due to the necessity to apply high-resolution instruments enable to detect known and unknown compounds. This work presents the use of liquid chromatography quadrupole time-of-flight mass spectrometry (LC-QTOF-MS) as a powerful tool for the identification of three selected pharmaceuticals, furosemide (FUR), ibuprofen (IBP), and ketoprofen (KET), and their TPs in various water samples. Laboratory degradation experiments were performed using xenon lamp as a source of the irradiation in order to simulate phototransformation processes which may occur in the environment. Furthermore, the photodegradation kinetics of three selected compounds were assessed in a reactor equipped with xenon lamp in river water samples. Five TPs of IBP, seven of KET, and five of FUR were identified; some of them are presented here for the first time. Accurate mass measurements and fragmentation pattern obtained during an LC-QTOF-MS analysis allowed for structure elucidation of TPs followed by the creation of transformation pathway of selected pharmaceuticals. Finally, different water samples (wastewater influent and effluent, river water, untreated and treated water) were analyzed in order to estimate the presence of parent and transformed compounds. Only KET was detected in untransformed form in considered samples. Most of the TPs of selected drugs were found at least once in all water samples. Although IBP and FUR were not present in water samples as parent compounds, their different TPs occur. A great potential of LC-QTOF-MS in the identification and structural elucidation of TPs in the environment, allowing the recognition of the fate of pharmaceuticals in the environment through the determination of transformation pathway, has been presented.

Study of Cloud Water Samples Collected over Northern Poland.

The paper gives the results of the first studies on the chemistry of cloud water collected during 3 mo (Aug.-Oct. 2010) in the free atmosphere over the area to the south of the Tri-City (Gdansk-Sopot-Gdynia) conurbation on the Gulf of Gdansk, Poland. Taken from cumulus, stratus, and stratocumulus clouds by means of an aircraft-mounted collector, the water samples were analyzed for the following contaminants: anions (chlorides, fluorides, nitrates, sulfates, and phosphates), cations (lithium, sodium, potassium, ammonium, calcium, and magnesium), and trace metals. In addition, pH values were measured, and the type and composition of suspended particulate matter was determined. We discuss the relationship between the concentration of inorganic ions and the type of cloud from which water was sampled. The chemistry is also likely related to the circulation pattern and inflow of clean air masses from the Baltic Sea. Moreover, a relationship was found between the composition of the samples examined and the location of pollutant emission sources.

Development of laboratory reference material: Soil 1. Baseline and highly elevated concentrations of metals and polycyclic aromatic hydrocarbons.

Reference materials play a key part in systems of inspection and quality control of results of analytical measurements. The main limitation in using certified reference materials (CRM) is their high price, which results from the long and costly process of producing the reference material. An alternative to costly CRM materials is the employment of laboratory reference materials, particularly for interlaboratory control of measurement results and procedures. Under the auspices of the Chair of Analytical Chemistry at the Chemical Department of Gdansk University of Technology, research on the development of new reference materials is being conducted. At present, the research is aimed at producing a new laboratory reference material (LRM): 'Soil 1. Baseline and Highly Elevated Concentrations of Metals and Polycyclic Aromatic Hydrocarbons' - LRM soil 1. This paper presents the production stages of the developed laboratory reference material: acquisition of raw material from soil samples taken from the environment of the Tri-city (in Polish, Trójmiasto Gdansk, Sopot, Gdynia) bypass road, homogenization and subsequent dosage into appropriate containers, tests of homogeneity of sampled material within one container and between containers, based on the results of the determination of selected parameters (total carbon, content of optional metals - Hg, Fe, Cu Zn, Mn, Mg, water content, content of PAH-group analytes). The obtained results of homogeneity tests of the proposed future laboratory reference material have confirmed the homogeneity of soil samples within a container and between containers. Currently, interlaboratory tests are being carried out to determine the reference value.

Surface water quality assessment by the use of combination of multivariate statistical classification and expert information.

The present study deals with the assessment of surface water quality from an industrial-urban region located in northern Poland near to the city of Gdansk. Concentrations of thirteen chemicals including total polycyclic aromatic hydrocarbons (PAHs), halogenated volatile organic compounds (HVOCs) and major ions in the samples collected at five sampling points during six campaigns were used as variables throughout the study. The originality in the monitoring data treatment and interpretation was the combination of a traditional classification approach (self-organizing maps of Kohonen) with PAH diagnostic ratios expertise to achieve a reliable pollution source identification. Thus, sampling points affected by pollution from traffic (petroleum combustion products), from crude oil processing (petroleum release related compounds), and from phosphogypsum disposal site were properly discriminated. Additionally, it is shown that this original assessment approach can be useful in finding specific pollution source tracers.

Metal-coated fused silica fibers as a support for immobilized compounds yielding a volatile analyte (C2H4).

This paper presents the results of investigations of chemically modified fibers comprising an immobilized compound that yields ethene as the analyte in generated standard gaseous mixtures. Prior to chemical modification, the fibers were coated with a thin aluminum layer to improve their mechanical strength. Commercially available Al-coated fibers were used in this work. During thermal decomposition of the immobilized compound, reproducible quantities of the analyte per unit fiber length were obtained for all the investigated fibers (fiber diameter (microm)/outside diameter (microm) of the Al-coated fiber=110/146, 220/300, and 660/830), amounting to 0.685+/-0.032, 0.8300+/-0.0081, and 1.092+/-0.010 ng cm(-1), respectively. The proposed procedure can be used successfully for the generation of measured component of matrix-free reference materials.

Chemometrics in monitoring spatial and temporal variations in drinking water quality.

This case study reports multivariate techniques applied for the evaluation of temporal/spatial variations and interpretation of monitoring data obtained by the determination of chloro/bromo disinfection by-products in drinking water at 12 locations in the Gdansk area (Poland), over the period 1993-2000. The complex data matrix (1756 observations) was treated with various multivariate techniques. Cluster analysis (CA) was successful, yielding two different groups of similarity reflecting different types of drinking water supplied (surface and groundwater). The locations supplied in general with groundwater could be further classified into two subgroups, depending on whether the groundwater was mixed with surface water or not. Analysis of variance (ANOVA) was used to classify and thus confirm the groups found by means of cluster analysis and proved the existence of statistically significant differences between the concentration levels of CHCl3, CHBrCl2+C2HCl3, CHBr2Cl, and CH2Cl2 in the samples collected. Of all the variables evaluated, only three were characterized by statistically significant correlations (CHCl3, CHBrCl2+C2HCl3, CHBr2Cl). The analysis of correlation coefficients revealed that chloroform formed as the main chlorinated disinfection by-product and, furthermore, the natural presence of bromide in water (both ground and surface) results in the formation of brominated disinfection by-products (DBPs). Temporal variations of volatile organic chlorinated compounds (VOCls) were also evaluated by multidimensional ANOVA. Observation of temporal changes in the concentration of VOCls at the location supplied with both surface and groundwater reveals a steady improvement in drinking water quality. In general, the study shows the importance of drinking water monitoring in connection with simple but powerful statistical tools to better understand spatial and temporal variations in water quality.

Interspecific distribution and co-associations of chemical elements in the liver tissue of marine mammals from the Polish Economical Exclusive Zone, Baltic Sea.

Concentrations of Al, B, Ba, Cd, Co, Cr, Cu, Fe, Ga, Hg, Li, Mn, Mo, Ni, Pb, Se, Si, Sr, Tl, V, Zn, Ca, K, Mg, Na and P in the livers of marine mammals obtained from by-catches or stranded on beaches on the Polish Baltic coast were determined by ICP-MS or ICP-AES and CV AAS. Interspecific diversity with respect to the contents of these elements was found in cetaceans and pinnipeds. The diverse Cd contents in the livers of these mammals can be attributed to the variable concentrations of this element in their food. Mercury was correlated with age and can reach high concentration associated with higher level of Se in older specimens. No significant relationships were found between concentration of the chemical elements studied and nutritional status/condition of the Baltic harbour porpoises as well as between their concentration in specimens from the Gulf of Gdansk and open Baltic. It seems that the nutritional and health status of the specimens studied is generally enough good since the specimens studied were not stranded on beach because of starvation but almost incidentally caught in salmon gill nets. Strong correlations were found between the macroelements analysed, i.e. for the Ba-Ca-Sr, Ca-K, Ca-Mg, Mg-P, Zn-Mg and Zn-P assemblies. Significantly higher content of Al was found in males of harbour porpoises.

Sampling of atmospheric precipitation and deposits for analysis of atmospheric pollution.

This paper reviews techniques and equipment for collecting precipitation samples from the atmosphere (fog and cloud water) and from atmospheric deposits (dew, hoarfrost, and rime) that are suitable for the evaluation of atmospheric pollution. It discusses the storage and preparation of samples for analysis and also presents bibliographic information on the concentration ranges of inorganic and organic compounds in the precipitation and atmospheric deposit samples.

Partial characterization of proteins from mussel Mytilus galloprovincialis as a biomarker of contamination.

Preservation of a healthy environment is a very important task, especially in the time of the total industrial revolution. Therefore, attempts to find new additional biomarkers of contamination are welcomed. For this aim, the functional and antioxidant properties of mussel Mytilus galloprovincialis proteins and the heavy metals Cd and Pb were explored. Mussels were collected in contaminated and noncontaminated sites in the Varna area of the Bulgarian Black Sea coast. Proteins were extracted from mussel entire soft tissue and analyzed using instrumental (Fourier transform infrared [FT-IR] spectroscopy, fluorescence, atomic absorption spectrophotometry), and biochemical (2,2'-azinobis 3-ethylbenzothiazoline-6-sulfonate) radical cation [ABTS(.+)]) methods. It was found that mussel proteins from the contaminated sites had specific qualitative changes: partial unfolding of the alpha-helix, slight shift in amide I bands, increased hydrophobicity, and fluorescent intensity in native and denatured samples. In the same mussel samples, an increased radical-scavenging capacity and increased contents of Cd and Pb in entire soft tissue were registered. Therefore, the above-mentioned indices could be used as additional biomarkers of sea water contamination.

New procedure of silica gel surface modification preparation of gaseous standard mixtures for calibration purposes.

The new type of silica gel surface modification with using the trimethylamine as a reagent is described. The samples of chemically modified silica gel have been used for generation of gaseous standard mixtures (methyl chloride as a measurand) using the technique of thermal decomposition of the surface compound. The main aim of the research was to check the suitability of the new type of silica gel surface modification for obtaining methyl chloride as a measurand of gaseous standard mixture. The gaseous standard mixture obtained with using this technique was used for calibration of a thermal desorber-gas chromatography-flame ionization detector (TD-GC-FID) system. The homogeneity of coverage of silica gel surface with the immobilized compound has been evaluated. The full uncertainty budget of determination of liberated amount of methyl chloride has been calculated. The average amount of methyl chloride liberated from the unit sample of chemically modified silica gel is 3.59 +/- 0.13 mg g(-1). The influence of the modification way on the amount of liberated analyte has also been determined.

Solid-phase extraction clean-up of soil and sediment extracts for the determination of various types of pollutants in a single run.

A new sample clean-up procedure based on solid-phase extraction (SPE) sorbents was proposed for the determination of pesticides, polycyclic aromatic hydrocarbons and polychlorinated biphenyls in soils and sediments. The main purpose of the research was to find a combination of sorbents for the SPE method that would permit the determination of many types of analytes (polycyclic aromatic hydrocarbons, polychlorinated biphenyls, N-, P- and Cl-containing pesticides) in a single run. Elution profiles for both the analytes and the interfering components were determined for several types of SPE sorbents (alumina, silica and surface-modified silica) and combinations of them. The efficiency of the clean-up method developed was evaluated using real soil samples.

Preparation of samples of plant material for chromatographic analysis.

The selection, collection, and preliminary treatment of plant material samples are discussed. Stages of sample preparation and extraction techniques presently used are described, and the most recent examples of sample preparation for chromatographic analysis are reviewed. Recent applications of gas chromatography for the assessment of emission of volatile organic compounds by plants are also described.

Application of a catalytic combustion sensor (Pellistor) for the monitoring of the explosiveness of a hydrogen-air mixture in the upper explosive limit range.

A new technique is presented for continuous measurements of hydrogen contamination by air in the upper explosive limit range. It is based on the application of a catalytic combustion sensor placed in a cell through which the tested sample passes. The air content is the function of the quantity of formed heat during catalytic combustion of hydrogen inside the sensor. There is the possibility of using the method in industrial installations by using hydrogen for cooling electric current generators.